Smith - INTRODUCCION A LA TERMODINAMICA EN ING QUIMICA-Van Ness PDF

IntroduccIón a la
termodInámIca en
IngenIería químIca
00-SmithVanNess Preliminares.ind1 1 8/1/07 12:46:17

IntroduccIón a la
termodInámIca en
IngenIería químIca
SÉPtIma edIcIón
J. m. Smith
University of California, Davis
H. c. Van ness
m. m. abbott
Rensselaer Polytechnic Institute
reVISIón tÉcnIca
misael Flores rojas

Profesor de Termodinámica
ESIQIE, Instituto Politécnico Nacional
MÉXICO • AUCKLAND • BOGOTÁ • BUENOS AIRES • CARACAS • GUATEMALA

LISBOA • LONDRES • MADRID • MILÁN • MONTREAL • NUEVA DELHI • NUEVA YORK
SAN FRANCISCO • SAN JUAN • SAN LUIS • SANTIAGO
SÃO PAULO • SIDNEY • SINGAPUR • TORONTO

Director Higher Education: Miguel Ángel Toledo Castellanos
Director editorial: Ricardo A. del Bosque Alayón
Editor sponsor: Pablo E. Roig Vázquez
Editora de desarrollo: Lorena Campa Rojas
Supervisor de producción: Zeferino García García
Traducción: Efrén Alatorre Miguel

Esther Fernández Alvarado
Emilio Sordo Zabay
IntroduccIón a la termodInámIca en IngenIería químIca

Séptima edición
Prohibida la reproducción total o parcial de esta obra,

por cualquier medio, sin la autorización escrita del editor.
DERECHOS RESERVADOS © 2007, respecto a la séptima edición en español por

McGRAW-HILL/INTERAMERICANA EDITORES, S.A. DE C.V.
A Subsidiary of The McGraw-Hill Companies, Inc.
Edificio Punta Santa Fe
Prolongación Paseo de la Reforma 1015, Torre A
Piso 17, Col. Desarrollo Santa Fe,
Delegación Álvaro Obregón
C.P. 01376, México, D. F.
Miembro de la Cámara Nacional de la Industria Editorial Mexicana, Reg. Núm. 736
ISBN-13: 978-970-10-6147-3
ISBN-10: 970-10-6147-0
(ISBN edición anterior: 970-10-3647-6)
Traducido de la séptima edición en inglés de la obra: INTRODUCTION TO CHEMICAL ENGINEERING

THERMODYNAMICS, by J.M. Smith, H.C. Van Ness, M.M. Abbott. Copyright © 2005, 2001, 1996, 1987,
1975, 1959, 1949 by The McGraw-Hill Companies, Inc. All rights reserved.
ISBN 10: 0-07-310445-0
ISBN 13: 978-0-07-310445-4
1234567890 09865432107
Impreso en México Printed in Mexico

Contenido
lista de símbolos Ix
Prefacio xV
1 IntroduccIón 1
1.1 El panorama de la termodinámica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Dimensiones y unidades . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Medidas de cantidad o tamaño . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4 Fuerza . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.5 Temperatura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.6 Presión . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.7 Trabajo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.8 Energía . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.9 Calor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2 la PrImera ley y otroS concePtoS báSIcoS 21

2.1 Experimentos de Joule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2 Energía interna . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.3 La primera ley de la termodinámica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.4 Balance de energía para sistemas cerrados . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.5 Estado termodinámico y funciones de estado . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.6 Equilibrio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.7 Regla de las fases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.8 El proceso reersible . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.9 Procesos con V y P constantes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.10 Entalpía . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.11 Capacidad calorífica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.12 Balances de masa y energía para sistemas abiertos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3 ProPIedadeS VolumÉtrIcaS de FluIdoS PuroS 64

3.1 Comportamiento PVT de sustancias puras . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.2 Ecuaciones de estado iriales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.3 El gas ideal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

i
3.4 Aplicación de las ecuaciones iriales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

3.5 Ecuaciones cúbicas de estado . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.6 Correlaciones generalizadas para gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.7 Correlaciones generalizadas para líquidos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4 eFectoS tÉrmIcoS 125

4.1 Efectos del calor sensible . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4.2 Calores latentes de sustancias puras . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
4.3 Calor estándar de reacción . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
4.4 Calor estándar de formación . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
4.5 Calor estándar de combustión . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
4.6 Dependencia con la temperatura de ΔH ° . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4.7 Efectos térmicos de las reacciones industriales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5 la Segunda ley de la termodInámIca 159

5.1 Presentación de la segunda ley . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
5.2 Máquinas térmicas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
5.3 Escalas de temperatura termodinámica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5.4 Entropía . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
5.5 Cambios de entropía de un gas ideal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
5.6 Planteamiento matemático de la segunda ley . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
5.7 Balance de entropía para sistemas abiertos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
5.8 Cálculo del trabajo ideal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5.9 Trabajo perdido . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
5.10 La tercera ley de la termodinámica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
5.11 Entropía desde el punto de ista microscópico . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
6 ProPIedadeS termodInámIcaS de loS FluIdoS 199

6.1 Expresiones para la ealuación de una propiedad en fases homogéneas . . . . . . . . . . . . . . . . 199
6.2 Propiedades residuales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
6.3 Las propiedades residuales a partir de ecuaciones de estado . . . . . . . . . . . . . . . . . . . . . . . . . 215
6.4 Sistemas de dos fases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
6.5 Diagramas termodinámicos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
6.6 Tablas de propiedades termodinámicas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
6.7 Correlaciones generalizadas para la ealuación de una propiedad para gases . . . . . . . . . . . 230
7 aPlIcacIoneS de la termodInámIca a loS ProceSoS de FluJo 254

7.1 Flujo en conductos de fluidos compresibles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
7.2 Turbinas (expansores) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
7.3 Procesos de compresión . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
8 generacIón de PotencIa a PartIr del calor 290

8.1 Planta de energía de apor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
8.2 Motores de combustión interna . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
8.3 Motores de reacción: motor de propulsión . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
9 reFrIgeracIón y lIcueFaccIón 317

9.1 El refrigerador de Carnot . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317

ii
9.2 Ciclo de compresión de apor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318

9.3 La elección del refrigerante . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
9.4 Refrigeración por absorción . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
9.5 La bomba de calor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
9.6 Proceso de licuefacción . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
10 equIlIbrIo VaPor/líquIdo: IntroduccIón 338

10.1 La naturaleza del equilibrio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
10.2 Regla de fase . Teorema de Duhem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
10.3 EVL: Comportamiento cualitatio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
10.4 Modelos simples para el equilibrio apor/líquido . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
10.5 EVL mediante la ley de Raoult modificada . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
10.6 EVL a partir de las correlaciones del alor K . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
11 termodInámIca de SolucIoneS: teoría 378

11.1 Relación de una propiedad fundamental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
11.2 Potencial químico y equilibrio de fase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
11.3 Propiedades parciales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
11.4 Modelo de mezcla de gas ideal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
11.5 Fugacidad y coeficiente de fugacidad: especies puras . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
11.6 Fugacidad y coeficiente de fugacidad: especies en solución . . . . . . . . . . . . . . . . . . . . . . . . . 401
11.7 Correlaciones generalizadas para el coeficiente de fugacidad . . . . . . . . . . . . . . . . . . . . . . . . 407
11.8 El modelo de solución ideal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
11.9 Propiedades de exceso . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
12 termodInámIca de SolucIoneS: aPlIcacIoneS 430

12.1 Propiedades de fase líquida a partir de la información de EVL . . . . . . . . . . . . . . . . . . . . . . . 430
12.2 Modelos para la energía de Gibbs de exceso . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
12.3 Cambios en la propiedad de mezclado . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
12.4 Efectos térmicos de los procesos de mezclado . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
13 equIlIbrIo en reaccIón químIca 483

13.1 Coordenada de la reacción . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
13.2 Aplicación de criterios de equilibrio a las reacciones químicas . . . . . . . . . . . . . . . . . . . . . . 488
13.3 Cambio en la energía de Gibbs estándar y la constante de equilibrio . . . . . . . . . . . . . . . . . . 489
13.4 Efecto de la temperatura en la constante de equilibrio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 492
13.5 Ealuación de las constantes de equilibrio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 496
13.6 Relación de las constantes de equilibrio con la composición . . . . . . . . . . . . . . . . . . . . . . . . 498
13.7 Conersiones de equilibrio para reacciones únicas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
13.8 Regla de la fase y teorema de Duhem para sistemas con transformaciones químicas . . . . . 514
13.9 Equilibrios en reacciones múltiples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
13.10 Celdas de combustible . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529
14 temaS Sobre loS equIlIbrIoS de FaSe 545

14.1 Formulación gamma/phi del EVL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
14.2 EVL a partir de ecuaciones de estado cúbicas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
14.3 Equilibrio y estabilidad . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575

viii
14.4 Equilibrio líquido/líquido (ELL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581

14.5 Equilibrio vapor/líquido/líquido (EVLL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
14.6 Equilibrio sólido/líquido (ESL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
14.7 Equilibrio sólido/vapor (ESV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
14.8 Equilibrio de adsorción de gases en sólidos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
14.9 Equilibrio osmótico y presión osmótica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
15 Análisis termodinámico de procesos 635

15.1 Análisis termodinámico de procesos de flujo en estado estacionario . . . . . . . . . . . . . . . . . . 635
16 introducción A lA termodinámicA moleculAr 647

16.1 Teoría molecular de los fluidos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
16.2 Segundos coeficientes viriales a partir de las funciones potenciales. . . . . . . . . . . . . . . . . . . 654
16.3 Energía interna de gases ideales: punto de vista microscópico . . . . . . . . . . . . . . . . . . . . . . . 657
16.4 Propiedades termodinámicas y mecánica estadística. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
16.5 Enlace de hidrógeno y complejo de transferencia de carga . . . . . . . . . . . . . . . . . . . . . . . . . . 662
16.6 Comportamiento de las propiedades de exceso . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
16.7 Bases moleculares para el comportamiento de mezclas . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
16.8 EVL por simulación molecular . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
A Factores de conversión y valores de la constante de los gases 677
B propiedades de especies puras 679
c capacidades caloríficas y cambios de propiedad de formación 683
d programas representativos para computadora 688

d.1 Funciones definidas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688
d.2 Solución de problemas de ejemplo con Mathcad® . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
e tablas de correlación generalizada de lee/Kesler 695
F tablas de vapor 712

F.1 Interpolación . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712
G diagramas termodinámicos 788
H método uniFAc 791
i método de newton 798
Índice de autores 803
Índice analítico 807

Lista de símbolos
A Área
A Energía de Helmholtz molar o específica ≡ U − TS
A Parámetro, ecuaciones Empíricas, por ejemplo, en las ecuaciones (4 .4), (6 .76) y (12 .14)
a Aceleración
a Área molar de una fase adsorbida
a Parámetro en las ecuaciones de estado cúbicas
a-i Parámetros parciales en ecuaciones de estado cúbicas
B Segundo coeficiente irial, expansión en densidades
B Parámetro en ecuaciones empíricas, por ejemplo, en las ecuaciones (4 .4), (6 .76) y (12 .14)
B̂ Segundo coeficiente irial reducido, definido por la ecuación (3 .62)
B′ Segundo coeficiente irial, expansión en presiones
B0, B1 Funciones de la correlación generalizada del segundo coeficiente irial
Bij Interacción del segundo coeficiente irial
b Parámetro en ecuaciones de estado cúbicas
-
bi Parámetro pracial en ecuaciones de estado cúbicas
C Tercer coeficiente irial, expansión en densidades
C Parámetro, en ecuaciones empíricas, por ejemplo, ecuaciones (4 .4), (6 .76) y (12 .14)
Ĉ Tercer coeficiente irial reducido, definido en la página 103 .
C′ Tercer coeficiente irial, expansión en presiones
C 0, C1 Funciones, correlación generalizada del tercer coeficiente irial
CP Capacidad calorífica molar o específica, a presión constante
CV Capacidad calorífica molar o específica, a olumen constante
CP° Capacidad calorífica en el estado estándar, a presión constante
ΔCP° Cambio en la capacidad calorífica estándar de reacción
CPH Capacidad calorífica media para cálculos de entalpía
CPS Capacidad calorífica media para cálculos de entropía
CP°H Capacidad calorífica estándar media para cálculos de entalpía
ix

x
CP°S Capacidad calorífica estándar media para cálculos de entropía

c Rapidez del sonido
D Cuarto coeficiente irial, expansión en densidades
D Parámetro en ecuaciones empíricas, por ejemplo, en las ecuaciones (4 .4) y (6 .77)
D′ Cuarto coeficiente irial, expansión en presiones
Ei Niel de energía
EK Energía cinética
EP Energía potencial graitacional
F Grados de libertad, regla de las fases
F Fuerza
F Constante de Faraday
fi Fugacidad, especies puras i
f i° Fugacidad en el estado estándar
fˆi Fugacidad de la especie i en solución
G Energía de Gibbs molar o específica ≡ H – TS
Gi° Energía de Gibbs en el estado estándar de la especie i
–
Gi Energía de Gibbs parcial de la especie i en solución
GE Energía de Gibbs de exceso ≡ G – G i d
GR Energía de Gibbs residual ≡ G – G i g
ΔG Cambio en la energía de Gibbs por mezclado
ΔG° Cambio en la energía de Gibbs estándar de reacción
ΔGf° Cambio en la energía de Gibbs estándar de formación
g Aceleración local de la graedad
gc Constante dimensional = 32 .1740(lbm)(ft)(lbr)–1(s)–2
gi Degeneración
H Entalpía molar o específica ≡ U + PV
Hi Constante de Henry de la especie i en solución
Hi° Entalpía en el estado estándar de la especie pura i
–
Hi Entalpía parcial de la especie i en solución
HE Entalpía de exceso ≡ H – H i d
HR Entalpía residual ≡ H – H i g
(HR)0, (HR)1 Funciones en la correlación de la entalpía residual generalizada
ΔH Cambio de entalpía (“calor”) por mezclado; también calor latente de transición de fase
∼
Δ H Calor de solución
ΔH ° Cambio en el entalpía estándar de reacción
ΔH 0° Calor estándar de reacción a la temperatura de referencia T0
ΔH °f Cambio en la entalpía estándar de formación
h Constante de Planck
I Representa una integral definida, por ejemplo en las ecuaciones (6 .65)

xi
I Primer potencial de ionización

Kj Constante de equilibrio para la reacción química j
Ki Constante de equilibrio apor/líquido para la especie i ≡ yi / xi
k Constante de Boltzmann
L Fracción molar líquida del sistema
l Longitud
li j Parámetro de interacción de una ecuación del estado, ecuación (14 .101)
m Número de Mach
M Masa molar (peso molecular)
M Valor moral o específico, de una propiedad termodinámica extensia
–
Mi Propiedad parcial de la especie i en solución
ME Propiedad de exceso ≡ M – M i d
MR Propiedad residual ≡ M – M i g
ΔM Cambio en una propiedad por mezclado
ΔM ° Cambio en una propiedad estándar de reacción
ΔM f° Cambio en una propiedad estándar de formación
m Masa
ṁ Rapidez de flujo de masa
N Número de especies químicas, regla de las fases
NA Número de Aogadro
n Número de moles
ṅ Rapidez de flujo de moles
ñ Moles de solente por mol de soluto
ni Número de moles de la especie i
P Presión absoluta
P° Presión en el estado estándar
Pc Presión crítica
Pr Presión reducida
P 0r , P 1r Funciones, correlación generalizada apor-presión
P0 Presión de referencia
pi Presión parcial de la especie i
Pisat Presión de apor de saturación de la especie i
Q Calor
Q· Rapidez de transferencia de calor
q Rapidez de flujo olumétrico
q Parámetro en las ecuaciones de estado cúbicas
q Carga eléctrica
q-i Parámetro parcial en las ecuaciones de estado cúbicas
R Constante uniersal de los gases (tabla A .2)

xii
r Relación de compresión
r Separación intermolecular
r Número de reacciones químicas independientes, regla de fases
S Entropía molar o específica
–
Si Entropía parcial de la especie i en solución
SE Entropía de exceso ≡ S – S i d
SR Entropía residual ≡ S – S i g
(SR)0, (SR)1 Funciones en la correlación de entropía residual generalizada
SG Generación de entropía por cantidad unitaria de fluido
S·G Rapidez de generación de entropía
ΔS Cambio de entropía por mezclado
ΔS ° Cambio de entropía estándar de la reacción
ΔS °f Cambio de entropía estándar de la formación
T Temperatura absoluta en kelin o rankine
Tc Temperatura crítica
Tn Temperatura normal de ebullición
Tr Temperatura reducida
T0 Temperatura de referencia
Tσ Temperatura absoluta de los alrededores
Tisat Temperatura de saturación de la especie i
t Temperatura, °C o (°F)
t Tiempo
U Energía interna molar o específica
U Función del par potencial intermolecular
u Velocidad
V Volumen molar o específico
V Fracción molar del sistema que es apor
–
Vi Volumen parcial de la especie i en solución
Vc Volumen crítico
Vr Volumen reducido
VE Volumen de exceso ≡ V – V i d
VR Volumen residual ≡ V – V i g
ΔV Cambio de olumen por mezclado; también, cambio de olumen de la transición de fase
W Trabajo
·
W Rapidez de trabajo (potencia)
Wideal Trabajo ideal
·
Wideal Rapidez de trabajo ideal
Wperdido Trabajo perdido
·
Wperdido Rapidez de trabajo perdido

xiii
Ws Trabajo de flecha para procesos de flujo

·
Ws Potencia de flecha para procesos de flujo
xi Fracción molar de la especie i en general o en una fase líquida
xv Calidad
yi Fracción molar de la especie i en la fase apor
Z Factor de compresibilidad ≡ PV / RT
Zc Factor de compresibilidad crítica ≡ PcVc / RTc
Z 0, Z 1 Funciones en la correlación generalizada de factores de compresibilidad
Z Funcion de partición
z Factor de compresibilidad de fase adsorbida definida por la ecuación (14 .108)
z Eleación por encima de un niel de referencia
zi Fracción molar global o fracción molar en una fase sólida
Superíndices
E Denota una propiedad termodinámica de exceso

av Denota una transición de fase de la fase adsorbida a apor
R Denota una propiedad termodinámica residual
s Denota fase sólida
sl Denota transición de fase de sólido a líquido
t Denota un alor total de una propiedad termodinámica extensia
v Denota fase de apor
∞ Denota un alor a dilución infinita
Letras Griegas
α Función en las ecuaciones del estado cúbicas (tabla 3 .1, p .98)

α Polarizabilidad
α, β Como superíndices, identifican fases
αβ Como superíndices, denota una transición de fase de la fase α a la fase β
β Expansiidad del olumen
β Parámetro en las ecuaciones de estado cúbicas
l Constante de integración
γ Relación de las capacidades caloríficas CP / CV
γ l Coeficiente de actiidad de la especie i en solución
δ Exponente politrópico
 Constante en las ecuaciones de estado cúbicas

xi
 Profundidad del pozo en la función de potencial intermolecular

0 Permitiidad eléctrica en el acío
ε Coordenada de reacción
η Eficiencia
κ Comprensibilidad isotérmica
 Presión de dispersión en fase absorida
 Presión osmótica
π Número de fases, regla de las fases
µ Coeficiente de Joule/Thompson
µ Momento dipolar
µi Potencial químico de la especie i
νi Número estequiométrico de la especia i
ρ Densidad molar o específica ≡ 1/V
ρc Densidad crítica
ρr Densidad reducida
σ Constante en las ecuaciones de estado cúbicas
σ Diámetro de colisión molecular
τ Relación de temperatura ≡ T / T0 [En la ecuación (6 .77), τ ≡ 1 – Tr ]
i Relación de coeficientes de fugacidad, definida por la ecuación (14 .2)
φi Coeficiente de fugacidad de la especie pura i
φ̂i Coeficiente de fugacidad de la especie i en solución
φ0, φ1 Funciones en la correlación generalizada de coeficientes de fugacidad
,  constantes en las ecuaciones de estado cúbicas
ω Factor acéntrico
Notas
c Como subíndice, denota un olumen de control

fs Como subíndice, denota corriente de flujo
° Como superíndice, denota el estado estándar
– La sobrebarra denota una propiedad parcial
· El sobrepunto denota una rapidez
ˆ El circunflejo denota una propiedad en solucion
Δ Operador de diferencia

Prefacio
La termodinámica, uno de los temas centrales de la ciencia, está basada en leyes de aplicación universal. La
justificación para presentar el tema desde el punto de vista de la Ingeniería Química es que tenemos la convic-
ción de que es más efectivo pensar en el contexto de la disciplina que interesa y compromete al estudiante.
Aunque es de naturaleza introductoria, el material de este texto no se considera tan simple. En realidad,
no hay manera de hacerlo sencillo, ya que un estudiante que se inicia en el tema encontrará que tiene por
delante una tarea demandante de descubrimiento. Se presentan conceptos, términos y símbolos nuevos con
una frecuencia y rapidez desconcertantes, y en este punto resulta que la memoria tiene un papel significativo.
Un reto aún más difícil es la necesidad de desarrollar la capacidad de razonamiento y aplicar los principios de
la termodinámica en la solución de problemas prácticos. Por ello, mientras se mantiene el rigor característico
del análisis termodinámico integral, hemos hecho esfuerzos para evitar la complejidad matemática innecesa-
ria. Además, alentamos la comprensión al escribir frases simples y directas en voz activa y tiempo presente.
Existen los elementos para ofrecer la motivación requerida, pero nuestro objetivo, como ha sido en todas las
ediciones anteriores, también es proporcionar un método que pueda ser comprendido por cualquier estudian-
te dispuesto a ejercitarse con el esmero adecuado.
Los primeros dos capítulos del libro presentan las definiciones básicas y un desarrollo de la primera ley.
Los capítulos 3 y 4 tratan el comportamiento a través de la presión/volumen/temperatura de los fluidos y
ciertos efectos térmicos, lo cual permite la aplicación inicial de la primera ley a problemas reales. La segunda
ley y algunas de sus aplicaciones se consideran en el capítulo 5. Un tratamiento de las propiedades termodi-
námicas de los fluidos puros en el capítulo 6 permite la aplicación general de la primera y la segunda leyes, y
proporciona un amplio tratamiento de los procesos con flujo en el capítulo 7. Los capítulos 8 y 9 abordan
los procesos de producción de energía y de refrigeración. En el resto del libro, se hace referencia a mezclas
fluidas y se tratan temas que corresponden exclusivamente a la termodinámica de la ingeniería química. Los
capítulos 11 y 12 proporcionan una exposición detallada de la teoría y aplicación de la termodinámica de so-
luciones. El equilibrio de las reacciones químicas se cubre con detalle en el capítulo 13. El capítulo 14 se
ocupa de temas como el equilibrio de fase, en donde se incluye un tratamiento extenso del equilibrio vapor/
líquido, así como del equilibrio osmótico y de adsorción. El capítulo 15 considera el análisis termodinámico
de procesos reales, proporcionando una revisión de gran parte de los temas prácticos de interés para la termo-
dinámica.
xv

xvi
El material de estos capítulos es adecuado para un curso de un año a nivel licenciatura; no obstante, es
útil en otro tipo de cursos siempre y cuando se utilice con discreción y de manera condicionada por el conte-
nido de estos. Los primeros 13 capítulos incluyen material que es necesario en la formación del ingeniero
químico. Por lo tanto, cuando se proporcione un curso de termodinámica de Ingeniería Química con duración
de sólo un semestre, estos 13 capítulos representan el material suficiente.
Las leyes y los principios de la termodinámica clásica no dependen de algún modelo en particular de la
estructura de la materia; están libres de cualquier consideración a nivel molecular. Sin embargo, el comporta-
miento exhibido por la materia (gases, líquidos y sólidos) depende de su naturaleza en particular, por lo que
en el capítulo 16 presentamos una introducción a la termodinámica molecular, a la cual se hace referencia de
manera ocasional en capítulos anteriores.
Este libro fue realizado de manera detallada a fin de convertirlo en una referencia útil para los cursos a
nivel de posgrado y la práctica profesional. No obstante, debido a consideraciones de extensión, fue necesario
hacer una selección prudente del material. De este modo, no incluimos ciertos temas dignos de atención, pero
de naturaleza especializada. Éstos incluyen aplicaciones a polímeros, electrolitos y biomateriales.
Estamos en deuda con muchas personas, estudiantes, profesores, revisores, quienes han contribuido de
diversas maneras a la calidad de esta séptima edición, tanto en forma directa como indirecta, a través de pre-
guntas y comentarios, elogios y críticas a lo largo de 55 años y seis ediciones de evolución. A todos ellos
hacemos extensivo nuestro agradecimiento.
J. M. Smith
H. C. Van Ness
M. M. Abbott
Agradecemos en especial la valiosa contribución de los siguientes asesores técnicos para la presente
edición en español:
Alejandro J. Guzmán Gómez, Universidad Nacional Autónoma de México, FES Zaragoza

Margarita Hernández Alvarado, Universidad Tecnológica de México, campus Sur
Ma. del Carmen Doria Serrano, Universidad Iberoamericana, Ciudad de México
Luis Neri Vitela, ITESM, campus Estado de México
Rodolfo Gámez Aguilar, Instituto Tecnológico de Los Mochis
Hidelberto Hernández Frías, Instituto Tecnológico de Los Mochis
Fortunato Ramos Valenzuela, Instituto Tecnológico de Los Mochis
Pedro Rochín Angulo, Instituto Tecnológico de Culiacán
Guillermo Aguirre, Instituto Tecnológico de Mazatlán

Capítulo 1
Introducción
1.1 EL PANORAMA DE LA TERMODINÁMICA
La ciencia de la termodinámica nació en el siglo xix, cuando surgió la necesidad de describir el funcionamiento
de las máquinas de vapor y establecer los límites de lo que éstas podían realizar. Así, como su nombre lo indica, la
termodinámica es la potencia desarrollada por el calor, con aplicaciones obvias a las máquinas térmicas, de las
cuales la máquina de vapor representa el primer ejemplo. De cualquier modo, los principios observados, válidos
para las máquinas, se han generalizado sin dificultad y ahora se conocen como la primera y la segunda leyes de
la termodinámica. Estas leyes no tienen demostración en sentido matemático; su validez estriba en la ausencia
de experiencias contradictorias. Así, la termodinámica comparte con la mecánica y el electromagnetismo la base
sobre la que se sustentan las leyes básicas, que no se deducen de algo más.
Estas leyes conducen, mediante la deducción matemática, a un sistema de ecuaciones que encuentran
aplicación en todas las ramas de la ciencia y de la ingeniería. El ingeniero químico hace frente de manera
particular a una amplia variedad de problemas; por ejemplo, el cálculo de los requerimientos de calor y de
trabajo para los procesos físicos y químicos, así como la determinación de las condiciones de equilibrio para
las reacciones químicas y para la transferencia de especies químicas entre las fases.
Las consideraciones termodinámicas no establecen la rapidez de los procesos químicos o físicos. La
rapidez depende de las fuerzas impulsoras y de la resistencia; las fuerzas impulsoras son variables termodiná
micas, pero las resistencias no. Ninguna formulación termodinámica, es decir, de características macroscópi
cas, revela los mecanismos microscópicos (moleculares) de los procesos físicos o químicos. Por otra parte, el
conocimiento del comportamiento microscópico de la materia puede ser útil en el cálculo de las propiedades
termodinámicas. Los valores de las propiedades son esenciales para el uso práctico de la termodinámica. El
ingeniero químico se ocupa de muchas especies químicas y a menudo no cuenta con datos experimentales,
lo cual ha conducido al desarrollo de las “correlaciones generalizadas” que proporcionan estimaciones de la
propiedad cuando se carece de información.
La aplicación de la termodinámica a cualquier problema real comienza con la identificación de un agre
gado particular de materia como punto central de atención. Este agregado de materia se llama sistema y su
estado termodinámico está definido por algunas propiedades macroscópicas mensurables. Éstas dependen
de las dimensiones fundamentales de la ciencia, de las cuales la longitud, el tiempo, la masa, la temperatura y
la cantidad de sustancia son las de mayor interés.
Se presenta un tratamiento elemental en el capítulo 6.
01SmithVanNess.indd 1 8/1/07 12:47:11

CAPÍTULO 1. Introducción
1.2 DIMENSIONES Y UNIDADES
Las dimensiones fundamentales son primordiales, ya que son reconocidas por nuestras percepciones sen
soriales y no son definibles en términos de algo más simple. Sin embargo, su empleo requiere la definición
de escalas arbitrarias de medición, divididas en unidades de tamaño específico. Las unidades originales fue
ron establecidas mediante un acuerdo internacional, y codificadas como el Sistema Internacional de Unidades
(abreviado como SI, para el Système International).
El segundo, la unidad del tiempo del SI, cuyo símbolo es s, corresponde a la duración de 9 9 63 770
ciclos de radiación asociada a una transición específica del átomo del cesio. El metro, cuyo símbolo es m, es
la unidad fundamental de longitud que se define como la distancia que la luz viaja en el vacío durante
/99 79 458 de un segundo. El kilogramo, con el símbolo kg, es la masa de un cilindro de platino/iridio que
se conserva en la Oficina Internacional de Pesas y Medidas en Sèvres, Francia. La unidad de la temperatura
es el kelvin, cuyo símbolo es K, y es igual a /73.6 de la temperatura termodinámica del punto triple del
agua. En la sección .5 se hace un análisis detallado de la temperatura, que es la dimensión característica de
la termodinámica. El mol, cuyo símbolo es mol, es la cantidad de sustancia representada por tantas entida
des elementales (por ejemplo, moléculas) como el número de átomos que hay en 0.0 kg de carbono.
Esto es equivalente al “gramo mol” usado de manera común por los químicos.
Los múltiplos y fracciones decimales de las unidades del SI se designan mediante prefijos. Los de
uso más frecuente se enumeran en la tabla .. De esta manera, el centímetro está determinado como cm =
0 – m, y el kilogramo como kg = 0 3 g.
Tabla 1.1: Prefijos para unidades del SI
Múltiplo Prefijo Símbolo Múltiplo Prefijo Símbolo
0−5 femto f 0 hecto h

0− pico p 03 kilo k
0−9 nano n 06 mega M
0−6 micro µ 09 giga G
0−3 mili m 0 tera T
0− centi c 05 peta P
Otros sistemas de unidades, como el sistema inglés de ingeniería, utilizan unidades que están relaciona
das con las unidades del SI mediante factores fijos de conversión. Así, el pie se define como 0.3048 m, la libra
masa (lbm) como 0.4535937 kg y la libra mol (lb mol) como 453.5937 mol.
1.3 MEDIDAS DE CANTIDAD O TAMAÑO
Tres medidas de cantidad o tamaño son de uso común:
• Masa, m • Número de moles, n • Volumen total, V t
Para un sistema específico, estas medidas están en proporción directa una de otra. La masa, una medida pri-
mordial sin definición, se puede dividir entre la masa molar M, comúnmente llamada peso molecular, para

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of allofunits.
all units.
todas las unidades.

4 CHAPTER 1. Introduction
4 CAPÍTULO 1. Introducción
Weight properly refers to the force of gravity on a body, and is correctly expressed in
Elnewtons or in properly
peso Weight
se refierepounds force.
refersaUnfortunately,
propiamente to
la the force
fuerza ofstandards ofamass
gravitysobre
de gravedad on body,
un areand
cuerpo often
y is called “weights,”
se correctly
expresa manera and
deexpressed in
correcta en
newtonsuse
o enoflibras
newtons a balance
or fuerza.toDesafortunadamente,
in poundscompare masses is los
force. Unfortunately, called “weighing.”
standards
estándares ofmasa
de Thus,
mass aare one must
often
menudo discern
called
se from
“weights,”
denominan they al uso
and
“pesos”
context
de una balanza whether
use of apara
balance force or mass
to compare
comparar masas is llama
semasses
le meant when
is“para
called “weight”
Por isloused
“weighing.”
pesar”. incuando
Thus,
tanto, a one
casualse or
must informal
discern
emplea way. the
from
la palabra “peso” de
context
una manera whether
ocasional force oresmass
o informal is meant
preciso whendentro
distinguir “weight” is used in
del contexto a casual
si se trata deoruna
informal
fuerza oway.
de una masa.
Example 1.1
Ejemplo
An 1.1 weighs
Example
astronaut 1.1 730 N in Houston, Texas, where the local acceleration of gravity
is =pesa m −2
Angastronaut
Un astronauta 9.792730 Ns en.Houston,
weighs
−2 ? −2
What
730 Narein the donde
astronaut’s
Houston,
Texas, Texas, mass
whereand
la aceleración thelaweight
de local on local
the moon,
acceleration
gravedad where
es deofggravity
= 9.79 m s−2.
is
g =
g =
1.67 m
9.792s
¿Cuáles son la masa −2m s . What are the astronaut’s mass and weight
y el peso del astronauta en la Luna, donde g = .67 m s ? on
− the moon, where
g = 1.67 m s ?
Solución 1.1
Solution 1.1
Con aSolution
g, laaley
=With = de1.1
g, Newton es:
Newton’s law F is:
= mg.F =De donde,
mg. Whence,
With a = g, Newton’s law F is: F =730 N Whence,
mg. 2
m= = = 74.55 N m−1 s
F
g 730mNs−2
9.792 2
m= = −2
= 74.55 N m−1 s
g 9.792 m
−, s
Como elBecause
newton theN tiene
newtonunidades
N has de thekg m skg
units m s−2 ,
Because the newton N has the units kg m s−2 ,
m
m= = 74.55
74.55 kg kg
m = 74.55 kg
Esta masa
Thisdelmass
astronauta
of the es independiente
astronaut de la ubicación,
is independent perobut
of location, el peso
weightdepende de on
depends la aceleración
the
local delocal
la gravedad.
This mass of De
accelerationthe esta forma,isel
of gravity.
astronaut Thuspesoondel
theastronauta
independent moon the en labut
Luna
astronaut’s
of location, es:
weight
weight is: on the
depends
local acceleration of gravity. Thus on the moon the astronaut’s − weight is:
F(Luna) =
F(moon) mg(Luna) == 74.55
= mg(moon) 74.55kg kg ×× .67
1.67 mm ss−2
F(moon) = mg(moon) = 74.55 kg × 1.67 m s−2
or F(moon) = 124.5 kg m s−2 −= 124.5 N
o F(Luna) = 4.5 kg m s = 4.5 N
or F(moon) = 124.5 kg m s−2 = 124.5 N
Usesistema
El uso del of the English
inglés de engineering
unidades de system of units
ingeniería requiresdeconversion
requiere of thedelas-peso del
la conversión
tronaut’s −of −2 . With 1 N equivalent to
astronauta (lbf)ofweight
aUse y the
de los tovalores
(lbf )engineering
English and
de gthe values
a (pie)(s
system goftounits
). Puesto(ft)(s)
que N equivale
requires a 0.4809(lb
conversion of the as- f) y m
0.224809(lb
a 3.8084(pie):
tronaut’s weightf ) andto1 (lb
m fto the values of g to (ft)(s)−2 . With 1 N equivalent to
3.28084(ft):
) and
0.224809(lbf ) and 1 m to 3.28084(ft):
Weight of astronaut in Houston = 164.1(lbf )
El peso del astronauta en Houston = 64.(lb f)
Weight of astronaut in Houston = 164.1(lbf )
g(Houston) = 32.13 and g(moon) = 5.48(ft)(s)−2 −
g(Houston)
g(Houston) = 3.3
= 32.13 and y g(moon) = g(Luna) = 5.48(pie)(s)
5.48(ft)(s) −2
Newton’s law then gives:
Por esto,Newton’s
la ley de law
Newton
then da:
gives:
Fgc 164.1(lbf ) × 32.1740(lbm )(ft)(lbf )−1 (s)−2
m= =
Fg
gc 164.1(lbf ) × 32.1740(lb
32.13(ft)(s) )(ft)(lbf )−1 (s)−2
m −2
m= = −2
or g 32.13(ft)(s)
m = 164.3(lb m)
or m = 164.3(lbm )
o Thus the astronaut’s mass in (lbmm) and weight in) (lbf ) in Houston are numerically
= 64.3(lb m
almost
Thus thetheastronaut’s
same, but mass
on theinmoon
(lbm )this
andisweight
not theincase:
(lbf ) in Houston are numerically
De esta forma, la masa del astronauta
almost the same, but on the en (lbm) y (164.3)(5.48)
moon
mg(moon) this is su peso en (lbf) en Houston son casi numérica-
not the case:
mente iguales, pero enF(moon) = no es el caso:
la Luna éste = = 28.0(lbf )
mg(moon)
gc (164.3)(5.48)
32.1740
F(moon) = = = 28.0(lbf )
gc
mg.Luna/ 32.1740
.164:3/.5:48/
F.Luna/ H H H 28:0(lbf )
gc 32:1740

1.5. Temperatura 5
1.5 TEMPERATURA
La temperatura se mide por lo regular con termómetros de líquidos en capilares de vidrio, donde el fluido se
expande cuando se calienta. De este modo, un tubo uniforme que está parcialmente lleno de mercurio, alcohol
o algún otro fluido, indica el grado de “calentamiento” mediante la longitud de la columna del fluido. De
cualquier modo, se asignan valores numéricos a los diversos grados de calentamiento por medio de una defi
nición arbitraria.
Para la escala Celsius,3 el punto de hielo (punto de congelación del agua saturada con aire a la presión
atmosférica estándar) es cero, y el punto de vapor (punto de ebullición del agua pura a la presión atmosférica
estándar) es 00. Es posible asignar a un termómetro una escala numérica sumergiéndolo en un baño de hielo
y haciendo una marca correspondiente al cero en el nivel donde se encuentra el fluido, para después sumer
girlo en agua hirviendo y hacer una marca para el valor de 00 en este nuevo nivel del fluido. La distancia
entre las dos marcas se divide en 00 espacios equidistantes denominados grados. Para extender la escala del
termómetro se marcan otros espacios de igual tamaño por debajo del cero y por encima del 00.
Todos los termómetros, sin importar el fluido que contengan, proporcionan la misma lectura en cero y
en 00 si se calibran con este método, pero generalmente en otros puntos no corresponden las lecturas porque
los fluidos varían en sus características de expansión. De esta manera se requiere una elección arbitraria del
fluido, y la escala de temperatura en el sistema SI cuya unidad es el kelvin y su símbolo es K, se apoya en
el gas ideal como fluido termométrico. Puesto que la definición de la escala Kelvin depende de las propieda
des de los gases, se hará un análisis detallado hasta el capítulo 3. Sin embargo, se observa que la escala abso
luta depende del concepto de un límite inferior de la temperatura.
Las temperaturas Kelvin se indican con el símbolo T, en tanto que las temperaturas Celsius se designan
con el símbolo t, y se definen en relación a las temperaturas Kelvin mediante:
t °C = T K − 73.5
La unidad de temperatura Celsius es el grado Celsius, °C, que en magnitud equivale al Kelvin.4 No obstante, las
temperaturas en la escala Celsius son 73.5 grados menores que en la escala Kelvin. De esta forma el límite infe
rior de la temperatura, conocido como el cero absoluto en la escala Kelvin, se presenta en −73.5 °C.
En la práctica, la Escala Internacional de Temperatura de 1990 (ITS90) se utiliza para la calibración
de instrumentos científicos e industriales.5 La escala ITS90 se define de modo que sus valores difieren de las
temperaturas del gas ideal, pero que están en los límites de exactitud con los que actualmente se hacen las me
diciones. Se basa en valores asignados de la temperatura para un número de estados de equilibrio de fase
reproducibles de sustancias puras (puntos fijos) y en los instrumentos estándar calibrados a estas tempera
turas. La interpolación entre las temperaturas de punto fijo se proporciona mediante fórmulas que establecen
la relación entre las lecturas de los instrumentos estándar y los valores de la ITS90. El termómetro de resis
tencia de platino es un ejemplo de un instrumento estándar, que se utiliza para temperaturas que van desde
−59.35 °C (punto triple del hidrógeno) hasta 96.78 °C (el punto de congelación de la plata).
Además de las escalas Kelvin y Celsius existen otras dos que aún son utilizadas por los ingenieros de
Estados Unidos: las escalas Rankine y Fahrenheit.6 La escala Rankine es una escala absoluta que se relaciona
3 Anders Celsius, astrónomo sueco (70744).

4Adviértase que la palabra grado no se emplea en las temperaturas dadas en kelvins, y que la palabra kelvin entendida como una
unidad no se escribe con mayúsculas.
5 El texto en lengua inglesa de la definición de ITS90 está dado por H. PrestonThomas, Metrologia, vol. 7, pp. 30, 990.
6 Gabriel Daniel Fahrenheit, físico alemán (686736).

directamente con la escala Kelvin mediante:
T(R) = .8 T K
La escala Fahrenheit se relaciona con la de Rankine por una ecuación semejante a la relación entre las escalas
Celsius y Kelvin:
t(°F) = T(R) − 459.67
De este modo, el límite inferior de la temperatura en la escala Fahrenheit es −459.67(°F). La relación entre
las escalas Celsius y Fahrenheit está dada por:
t(°F) = .8 t °C + 3
Por consiguiente, el punto de congelación del agua es 3(°F) y el punto de ebullición normal del agua es
(°F).
El grado Celsius y el kelvin representan el mismo intervalo de temperatura, al igual que el grado Fah
renheit y el Rankine. Las relaciones entre las cuatro escalas de temperatura se ilustran en la figura .. En ter
modinámica, se da a entender una temperatura absoluta mediante una referencia informal de la temperatura.
Celsius Kelvin Fahrenheit Rankine
100(C) 373.15 K 212(F) 671.67(R) Punto de vapor
0(C) 273.15 K 32(F) 491.67(R) Punto de hielo
273.15(C) 0K 459.67(F) 0(R) Cero absoluto
Figura 1.1: Relaciones entre las escalas de temperatura.
1.6 PRESIÓN
La presión P ejercida por un fluido sobre una superficie se define como la fuerza normal ejercida por el fluido
por unidad de área de la superficie. Si la fuerza se mide en N y el área en m, la unidad es el newton por metro
cuadrado o N m−, llamado pascal y representado con el símbolo Pa, y es la unidad básica de la presión para
el SI. En el sistema inglés de ingeniería una unidad común es la libra fuerza por pulgada cuadrada (psi, por
sus siglas en inglés).
El estándar primario para mediciones de presión es la balanza de peso muerto, en la cual una fuerza
conocida se equilibra con una presión del fluido que actúa sobre un área conocida, donde P ≡ F/A. En la figu
ra . se muestra un diseño sencillo. El pistón se ajusta cuidadosamente al cilindro dejando una separación

1.6. Presión
1.6. Pressure 7 7
1.6. Pressure 7
muy pequeña.
clearance Se small.
ponen Weights
pesas en are
la bandeja
placed on hasta
the que
pan la presión
until del aceite,
the pressure queoil,
of the tiende
which a hacer
tends que el pistón se
to make
eleve, se equilibre
the pistonsmall.
clearance precisamente
rise, isWeights por
just balanced la
are placedfuerza
by on de
thethe gravedad
force
panof en
gravity
until el pistón
on the piston
the pressure y todo lo que
andwhich
of the oil, éste
all that soporta.
to makeCon esta
it supports.
tends
fuerza dada
the por
Withpiston la ley
this force de Newton
rise, given
is justby la presión
Newton’s
balanced del
by law, aceite es:
the pressure
the force of the
of gravity onoiltheis:piston and all that it supports.
With this force given by Newton’s law, the pressure F of the oil is:
mg
P= =
FA mgA
P= =
donde m es la masa del pistón, de la bandeja y de las pesas; gges
where m is the mass of the piston, pan, and weights;
A A is la
theaceleración local deof
local acceleration la gravity;
gravedad,andy A es el
área dewhere
sección
A is m transversal
the is the mass del
cross-sectional pistón.
area
of the of Los
the
piston, instrumentos
piston.
pan, Gauges
and weights; degmedida
in common de uso
is the local use, común, como
such as
acceleration Bourdon el manómetro
gauges,
of gravity; and de
Bourdon,aresecalibrated
A is calibran
the por comparación
by comparison
cross-sectional area of con
with las balanzas
thedead-weight
piston. Gauges de peso
gauges. muerto.use, such as Bourdon gauges,
in common
are calibrated by comparison with dead-weight gauges.
Weight
Pesa
Weight
Pan
Bandeja
Piston
Pan
Pistón
Piston
Cylinder
Cilindro Figure 1.2:1.2: Balanza
Cylinder Figura
Dead-weight
de peso
Figure gauge.
1.2: muerto.
Oil
Aceite Dead-weight gauge.
Oil
To pressure
A la fuentesource
To pressure
de presión
source
Because a vertical column of a given fluid under the influence of gravity exerts a pressure
at its base
Puesto que una
Becausein direct
columnaproportion
a vertical columntode
vertical ofitsaunheight,
fluido
given pressure
underisthe
determinado
fluid also expressed
que está of
influence as la
bajo theinfluencia
gravity equivalent deheight
la gravedad,
exerts a pressure
of
at a
its fluid
base column.
in direct This
proportionis theto basis
its for
height, the use
pressure of manometers
ejerce una presión en su base que va en proporción directa con su altura, la presión también se expresa
is also expressed for pressure
as the measurement.
equivalent heightcomo la
Conversion
altura equivalente
of deofuna
a fluid column. height to force
columna
This perbasis
isdethefluido.unitÉste areathe
for esfollows
eluse offrom
fundamento Newton’s
manometerspara el for lawpressure
uso applied
de to
manómetrosthe force of
en mediciones
measurement.
gravity acting on the mass of fluid in the column. The mass is given
de presión. La conversión de la altura a fuerza por unidad de área surge a partir de la ley de Newton aplicada
Conversion of height to force per unit area follows from Newton’s by:
law m =
applied Ahρ,
to where
the force A is
of a la
the cross-sectional
gravity acting on thearea
mass of the
of column,
fluid in the h is its
column. height,
The and
mass ρ is
is the
fuerza de la gravedad que actúa sobre la masa del fluido en la columna. La masa está dada por: m = Ahρ, donde
given fluid
by: density.
m = Ahρ,Therefore,
where A is
A es el área de sección transversal
the cross-sectional area of the de la columna,
column, F h ishmg es height,
its su altura
Ahρg and y ρρ es
is la
thedensidad del fluido.
fluid density. Por lo tanto,
Therefore,
P= = = = hρg
FA mgA AhρgA
P= = = = hρg
The pressure to which a fluid height A corresponds
A Ais determined by the density of the fluid
(which
La presión
The que depends
pressure to on
corresponde itsa identity
which una altura
a fluid and del
height temperature)
fluido andisthe
se determina
corresponds local
por la
determined acceleration
densidad
by the del of gravity.
mismo
density Thusfluid
of (que
the the
depende de
(torr) is the pressure equivalent of 1 millimeter of mercury at 0 ◦ C in a standard gravitational
su identidad
(whichy depends
temperatura)on itsyidentity
de la aceleración
and temperature) local deand la the
gravedad. Así, el (torr)
local acceleration ofes la presión
gravity. Thusequivalente
the
field, and
de milímetro
(torr) is de ismercurio
the equal to a133.322
pressure 0 °C enPa.
equivalent unofcampo gravitacional
1 millimeter of mercury at 0◦yCesinigual
estándar, a 33.3
a standard Pa.
gravitational
Otra Another
unidad
field, and isdeequal unit
presiónof pressure is
es la atmósfera
to 133.322 Pa. the standard atmosphere (atm),
estándar (atm), que es la presión the approximate averagepor
promedio ejercida pres-
la atmós
sure exerted
fera de la Tierra
Another by
a nivel the
unit earth’s
delofmar, atmosphere
y se is
pressure define at
como 0
the standard sea level,
35
atmosphere defined
Pa, 0.35as 101,325
(atm), thekPa, o Pa,
bien,
approximate 101.325
0.035 kPa,
average MPa. or El bar,
pres-
0.101325 SI5 unit 5 Pa, is equal to 0.986923(atm).
una unidad
sure del SI,MPa.
exerted seby The
define bar,
como
the earth’s an0 Pa ydefined
atmosphere es igual asa 10
at sea 0.98693
level, (atm).as 101,325 Pa, 101.325 kPa, or
defined
La
0.101325 Most
mayoría depressure
MPa. losThe gauges
manómetros
bar, an SIgive
deunit readings
presión
defined danas 105 Pa,
which
lecturasareque
isthe difference
representan
equal between the pressure
la diferencia
to 0.986923(atm). of
entre la presión de
interest
interés y la presiónand the pressure
atmosférica
Most pressure gaugesof the
de losgive surrounding
alrededores.
readings which atmosphere.
Estas lecturas These readings
se conocenbetween
are the difference are known
como presiones as gauge
manométricas
the pressure of
pressures,
y se pueden
interest andand
convertir theacan be converted
presiones
pressure ofabsolutas to absolute
the surrounding al sumarles pressures
la presión
atmosphere. by These
addition
barométrica.of theEn
readings barometric
losknown
are pressure.
cálculos
as termodinámi
gauge
Absolute
cos se deben pressures
utilizar
pressures, andpresiones must be used in thermodynamic calculations.
absolutas.to absolute pressures by addition of the barometric pressure.
can be converted
Absolute pressures must be used in thermodynamic calculations.

Example
Ejemplo 1.2 1.2
A dead-weight gauge with a 1-cm-diameter piston is used to measure pressures very
Se utiliza una balanza de peso muerto con un pistón de 1 cm de diámetro para medir presiones con
accurately. In a particular instance a mass of 6.14 kg (including piston and pan)
mucha precisión. En un caso particular, una masa de 6.14 kg (incluyendo el pistón−2 y la bandeja) alcan
brings it into balance. If the local acceleration of gravity is 9.82 m s , what is the
za el equilibrio. Si la aceleración local de la gravedad es 9.82 m s−, ¿cuál es la presión manométrica
gauge pressure being measured? If the barometric pressure is 748(torr), what is the
medida? Si la presión barométrica es 748(torr), ¿cuál es la presión absoluta?
absolute pressure?
Solución 1.2
Solution
La fuerza 1.2
ejercida por la gravedad sobre el pistón, la bandeja y las pesas es:
The force exerted by gravity on the piston, pan, and weights is:
F = mg = (6.4)(9.8) = 60.95 N
F = mg = (6.14)(9.82) = 60.295 N
F 60.295
Presión manométrica
Gauge pressure = = = 76.77 N cm−2
A (1/4)(π )(1)2
The
Por lo tanto absoluteabsoluta
la presión pressurees:
is therefore:
P = 76.77 + (748)(0.013332) = 86.74 N cm−2

P = 76.77 + (748)(0.0333) = 86.74 N cm–
or P = 867.4 kPa
o P = 867.4 kPa
Example 1.3
At 27◦ C the reading on a manometer filled with mercury is 60.5 cm. The local ac-
Ejemplo 1.3 of gravity is 9.784 m s . To what pressure does this height of mercury
celeration −2
correspond?
A 27 °C la lectura en un manómetro lleno de mercurio es de 60.5 cm. La aceleración local de la grave
dad es 9.784 m s −. ¿A qué presión le corresponde esta altura del mercurio?
Solution 1.3
Solución 1.3
Recall the equation in the preceding text, P = hρg. At 27◦ C the density of
Recuerde mercury
la ecuación cm−3anterior,
del gtexto
is 13.53 . Then, P = hρg. A 7 °C la densidad del mercurio es
−3
3.53 g cm . Por esto,
P = 60.5 cm × 13.53 g cm−3 × 9.784 m s−2 = 8,009 g m s−2 cm−2
P = 60.5 cm × 3.53 g cm−3 × 9.784 m s− = 8 009 g m s− cm−
or P = 8.009 kg m s−2 cm−2 = 8.009 N cm−2 = 80.09 kPa = 0.8009 bar
o P = 8.009 kg m s− cm− = 8.009 N cm− = 80.09 kPa = 0.8009 bar
1.7 TRABAJO
1.7 WORK
Se realiza Work
trabajoWWis siempre
performedquewhenever
una fuerza actúeacts
a force a través de auna
through distancia.
distance. Por definición,
By definition, la cantidad
the quantity of de
trabajo está dadaispor
work la ecuación:
given by the equation:
d W = F dl (1.1)
dW = F dl (.)

1.7. Work 9
1.7. Work
1.7. Trabajo
1.7. Work 99 9
where F is the component of force acting along the line of the displacement dl. When inte-
donde F es la componente
where de la fuerza que acting
actúa aalong lo largo thede la of
línea de desplazamiento dl. Cuando se inte
grated,FFthis
where isis the
the component
component
equation of
yieldsof force
workacting
force
the along
of a finite the line
line
process. of the
Bythe displacement
displacement
convention, work dl.
dl. When
is When
regarded inte-
inte-
as
gra, esta ecuación
grated,
grated, this proporciona
equation el trabajo
yields the para
work un
of aproceso
finite finito.
process. PorBy convención,
convention, el trabajo
work is se considera
regarded as como
as
positivethis when equation yields the work
the displacement is in theof asamefinitedirection
process.asBy theconvention,
applied force work
and is regarded
negative when
positivopositive
cuandowhen
positive el desplazamiento
when the displacement
the displacement estáisenin la
themisma
same dirección
direction que
as thela fuerza
applied aplicada,
force and y negativo
negative cuando se
when
they are in opposite directions. is in the same direction as the applied force and negative when
encuentratheyen direcciones
are
they areThe in opposite
in opposite opuestas.
directions.
directions.
work which accompanies a change in volume of a fluid is often encountered in
Con frecuencia,
The work enwhich
termodinámica
which accompanies el trabajo se acompaña
volumede ofun cambio en el volumen de un inlíquido.
The work
thermodynamics. A common exampleaais
accompanies change
change inin volume
the compression of
or aa fluid
fluid isisof
expansion often
often encountered
encountered
a fluid in a cylinderin
Un ejemplo común
thermodynamics.
thermodynamics. es la compresión
A common o expansión
example is de
the un fluido
compression en un
or cilindro,
expansion resultado
of a del
fluid in movimiento
a cylinder de un
resulting from theAmovement common example
of a piston. is theThe compression
force exerted or expansion
by the piston of aonfluid
the in a cylinder
fluid is equal
pistón. resulting
La fuerzafrom
resulting ejercida
from the por el pistón
movement ofsobre
a el
piston. fluido
The es
force igual al
exertedproducto
by the del área
piston ondel pistón
the fluid yisla presión
equal del
to the product the movement
of the of aand
piston area piston. The force
the pressure exerted
of the fluid.byThethedisplacement
piston on theoffluid the is equalis
piston
fluido. to
El
to desplazamiento
the product
the product of
of thethedel pistón
piston area
pistonchange es igual
and
area and the al cambio
pressure ofde
the volumen
fluid. Thetotal del fluido
displacement dividido
of the entre
piston is el área
equal to the total volume ofthe
thepressure
fluid dividedof theby fluid.
the The
area displacement
of the piston. ofEquation
the piston is
(1.1)
del pistón.
equal
equal Porto
to lothe
the tanto,
total
total la ecuación
volume
volume (.)of
change
change sethe
of convierte
the fluid
fluid en: by
divided
divided by the
the area
area of
of the
the piston.
piston. Equation
Equation (1.1)
(1.1)
therefore becomes:
thereforebecomes:
therefore becomes: Vt
d W = −P A dVVt t
ddWW= =−P −PAAdd A
AA
or, because A is constant, d W = −P d V tt (1.2)
o, debidoor,abecause
or, que A es
because AAconstante,
isisconstant,
constant, ddW W= =−P −PddVVt (1.2) (.)
(1.2)
� t
� V2t
Integrating, W = −� VV2t2 P d Vt tt (1.3)
Integrando,
Integrating,
Integrating, WW= =− − V1t PPddVV (1.3) (.3)
(1.3)
t
VV1t1
Los signos
The“negativos”
minus signseninestas theseecuaciones
equationssearehacenmadenecesarios
necessarypor bylathe
convención de signos
sign convention adoptada
adopted for para el
The
The minus
minus signs
signs in these
in these equations
equations arecylinder
are made necessary
made necessary byby the
the sign
sign convention
convention adopted
adopted for
for
trabajo. Cuando el pistón se mueve en el cilindro para comprimir el fluido, la fuerza aplicada y su desplaza
work. When the piston moves into the so as to compress the fluid, the applied force
work. When thepiston
piston moves into the cylinderthesoas
as tocompress
compress thepositive.
fluid,the
the applied force
mientowork.
and itsWhen
se encuentran the
displacement aremoves
en la misma in the into
samethe
dirección; cylinder
por so
lo tanto,
direction; el to
worktrabajo
is the
es positivo.
therefore fluid, applied
Se requiere
The el force
minus signo
sign menos
and
and its
its displacement
displacement are
are in
in the
the same
same direction;
direction; the
the work
work is
is therefore
therefore positive.
positive. The
The minus
minus sign
sign
porque el cambio de volumen es negativo. Para un proceso de expansión, la fuerza aplicada y su desplaza
is required because the volume change is negative. For an expansion process, the applied force
isrequired
requiredbecause
becausethe the volume change isisnegative.
negative. For an expansion process, theisapplied
appliedforce
force
mientoisand
estánitsendisplacement
direcciones volume
opuestas.
are change
El cambio
in opposite directions. TheFor
de volumen an
en expansion
volume este caso es
change process,
in the
positivo,
this case y positive,
se requiereandel signo
and
and its
its displacement
displacement are
are in
in opposite
opposite directions.
directions. The
The volume
volume change
change in
in this
this case
case is
is positive,
positive, and
and
menos para hacer negativo el trabajo.
the minus sign is required to make the work negative.
theminus
the minussign
signisisrequired
requiredto tomake
makethe
thework
worknegative.
negative.
2
P2
P 22
PP22
P
P
PP Figura 1.3: Diagrama que muestra
Figure 1.3: Diagramlashowing
trayectoria
a P de
vs.PVen función de V t .
t path.
Figure1.3:
Figure 1.3:Diagram
Diagramshowing vs.VVt t path.
showingaa PPvs. path.
P1 1
P
PP10
1 11
0
t 00 V2tt V1tt
V Vt
VV2t2 t VV1t1
t Vt
V t
VV
Equation (1.3) expresses the work done by a finite compression or expansion process. 7
LaFigure
ecuación
Equation (.3) expresa
(1.3) el trabajo
expresses the hecho
work por
done unbyproceso
a finite de compresión
compression o
or expansión
expansion finitas.
process. 777La figu
Equation (1.3) expresses the work done by a finite compression
1.3 shows a path for compression of a gas from point 1 with initial volume t Vt1t at or expansion process. t
ra .3 muestra
Figure
Figure una
1.3 trayectoria
1.3Pshows
shows aa path2 para
path forla
for compresión
Vt2tt at de
compression
compression of un
of aa gas
gas P del
from
from punto
point 1con
point volumen
1 with
with initialinicial
initial volume
volume V VVa presión
atat P
pressure 1 to point t 2 with volume pressure 2 . This path relates the pressure at11any
al punto con
pressure
pressure volumen
PP11 to
to V
point
point
a2 presión
with
with
point of the process to the volume. The P
volume.
volume Esta
V
V trayectoria
at
at pressure
pressure relaciona
PP22. . This
This la presión
path
path en
relates
relates cualquier
the
the
2 work required is given by Eq. (1.3) and is proportional
2 punto
pressure
pressure at
at del
any
any proceso
con el volumen.
point
point
to theof El trabajo
ofarea
the
the process
under requerido
processthe tothe
to curve está
thevolume.
volume. dado
of Fig. The
The por
1.3.workla
work
The ecuación
required
required
SI unitis (.3) y esby
isofgiven
given
work proporcional
by Eq.
isEq. (1.3)
the(1.3) al is
and
and área
newton-meter bajo
or la
isproportional
proportional curva de la
joule,
figura .3.
to La area
the
tosymbol
the unidad
area
J. InunderdelEnglish
under
the trabajo
the
the curve delof
curve SI Fig.
of es el1.3.
engineeringFig. newtonmetro
1.3.
system The
Thethe SI o often
unit
SIunit
unit joule,
of cuyois
work
of workused issímbolo
is the es J. Enforce
newton-meter
the foot-pound
the newton-meter el sistema
oror(ft lbfinglés
joule,
joule, ). de
ingeniería la unidad
symbol
symbol J.J.In
Inthepielibra
the English
English fuerza (pie lbf)system
engineering
engineering se emplea
system con
theunit
the mucha
unitoften
oftenused frecuencia.
used isisthe
thefoot-pound
foot-poundforce force(ft(ftlb
lbff).).
7 However, as explained in Sec. 2.8, it may be applied only in special circumstances.
77However,
However,asasexplained
explainedininSec.
Sec.2.8,
2.8,ititmay
maybe
beapplied
appliedonly
onlyininspecial
specialcircumstances.
circumstances.
7 Sin embargo, como se explica en la sección .8, sólo se aplica en circunstancias especiales.

10
10 1. Introduction
CHAPTER 1.
CHAPTER Introduction
1.8 ENERGÍA
1.8 ENERGY
1.8 ENERGY
ENERGY
1.8
El principio general de conservación de energía se estableció alrededor de 850. El germen de este principio,
tal comoThe
se general
The aplica aprinciple
general la mecánica,
principle of está implícito
conservation
of conservation
conservation of en los was
energy
of energy
energy trabajos
was de Galileo
established
established (56464)
about
about 1850. The
1850. The y de Isaac
germ
The germ
germ of thisNewton
this
of this
The
(6476). general
De as
principle as principle
hecho,
it es una
applies of
to consecuencia
mechanics wasof
directa
implicit was
de in
la the
in established
segunda
the work ley
of about 1850.
de Newton
Galileo of
sobre el movimiento,
(1564–1642) and Isaac una
principle it applies to mechanics was implicit work of Galileo (1564–1642) and Isaac
vez queprinciple
el trabajo
Newton
Newton
asesitdefinido
applies to
(1642–1726).
(1642–1726).
mechanics
como producto
Indeed,
Indeed, it
it
wasdeimplicit
follows
follows
in yfrom
ladirectly
fuerza
directly
the
el work
from
of Galileo
desplazamiento.
Newton’s
Newton’s
(1564–1642)
second
second law
law of
of
and Isaac
motion
motion once
once
Newton
work is (1642–1726).
defined as the Indeed,ofit force
product followsand directly from Newton’s second law of motion once
displacement.
work is
work is defined
defined as as the
the product
product of
of force
force and
and displacement.
displacement.
Energía cinética
Kinetic Energy
Kinetic Energy
Kinetic Energy
CuandoWhen
un cuerpo
When a body deof
masa
massm,m,
mass m,enacted
m, el que
acted uponactúabyuna
by a force fuerza
F, se desplaza
F,displaced
is una distancia
a distance dl during dl, durante un intervalo
a differential
When
diferencial de aatiempo
body
body of
of mass
el
acted
trabajo que
upon
upon
se by aa force
realiza
force
está
F, is
F,
dado
is displaced
displaced
por la aa distance
ecuación
distance dl during
dl
(.).
during
De manera aa differential
differential
conjunta
interval
interval of of time
of timedt,
dt,
time dt, the
dt, the work
the work done
work done
done is is given
is given
given by by Eq.
by Eq. (1.1).
Eq. (1.1).
(1.1). In In combination
In combination
combination with with Newton’s
with Newton’s
Newton’s second second con la
second
segundainterval
ley
law de
this
law this Newton,
equation
this equation esta ecuación
becomes:
equation becomes:
becomes: se convierte en:
law dW = ma dl
dd W
dW W === mama dl
ma dl
dl
By
By definition
definition the
the acceleration
acceleration is
is a
a ≡
≡ du/dt,
du/dt, where
where u is the velocity of
of the body. Thus,
By definition
Por definición, the acceleration
la aceleración is a ≡donde
es a ≡ du/dt, du/dt, where
u es uu is
is the
la velocidad
the velocity
velocity of
del cuerpo.the
the body.
body. Thus,
De este modo,
Thus,
du
du dl = m dl dl
dl du
d
d W
W =
= m
m du dl = m du
d W = m dt dt dl = m dt
dt du
dt dt
Because
Because the definition
the definition
definition of velocity
of velocity is
isuuu
velocityesis u≡≡≡
≡dl/dt,dl/dt,
dl/dt, the
the expression
expression for
for work becomes:
work becomes:
becomes:
Puesto que la definición
Because the de la velocidad
of dl/dt, la the
expresión
expression para for el trabajo
work es:
dW W ===
= mu mu du
dW
dd W mu du
mu du
This equation may now be integrated for a finite change in velocity from u to u :
Esta ecuación
This ahora semay
This equation
equation puede
may nowintegrar
now para unfor
be integrated
be integrated forcambio finitefinito
aa finite change
changeen la invelocidad
in velocity from
velocity de uuu111a to
from u:uu222::
to
� �
� u2 �
�
� uu 22
� � 22 uu 221 �
W = m u 2 u du = m u 2 − u 1 u 2 2
W=
W =m m u uu du du = =m m 22 − − 21
u1
u 11 22 22
�
� 2� �
�
mu 2 mu 2 �
mu 2
2 mu 2
1 mu
mu 2
o or
or W
W= =
= mu
2 −
2 − mu
2 2
1 =
=� �
� mu
2 (1.4)
(1.4) (.4)
or W 2
2 − 22 1 = 22 (1.4)
2 2 2
1 2 in Eq. (1.4) is a kinetic energy, a term introduced by Lord
Each of the quantities 1 mu 2 in Eq. (1.4) is a kinetic energy, a term introduced by Lord
en
Cada una Each
Each of the
de las
of the quantities
cantidades
quantities −¹ mu122 mu
mu 2 inla Eq.
ecuación
(1.4) is(.4) es unaenergy,
a kinetic energíaa cinética, un término
term introduced introducido
by Lord
Kelvin 8 in 1856. Thus, by ²
definition,
2
Kelvin8 8in
por lordKelvin
Kelvin 8 inen1856.
856.Thus,
1856. En estos
Thus, términos, por definición,
by definition,
by definition,
1 2
E
E K ≡≡
E K ≡ 22 mu
K
11 mu
mu22 (1.5) (.5)
(1.5)
(1.5)
La ecuación (l.4) muestra que elthat trabajo hechodone 2
sobreonuna cuerpo que se acelera aitpartir de una velocidad inicial u
Equation
Equation (1.4)
(1.4) shows
shows that the
the work
work done on a body
body in accelerating
in accelerating
accelerating from
itAfrom
from an initial
an initial
initial velocity
velocity
hasta una velocidad
Equation
u 1 to final
(1.4) u
shows es igual
that al
the cambio
work de
donela energía
on a bodycinética
in del cuerpo. it la inversa,
an si el cuerpo
velocityen movi
miento se to aaa final
uau11moving
final
desacelera
to
velocity
final por
velocity
la
velocity acción
u
u
is
u 22 is
is
de
equal
equal
una
equal
to
fuerza
to
the
to the change
theque
change
se
change opone,
in
in
kinetic
in kinetic
kinetic
el trabajo
energy
energy
hecho
energy
of
ofpor
of
the
the
body.
theelbody.
body.
cuerpo
Conversely,
Conversely,
es igual
Conversely, a
if
ifcambio
su
if
body is decelerated
2 by the action of aa resisting force, the work done by the body is
a moving
en energía moving
aequalcinética.
to
body
En
body
its
issistema
elis
change
decelerated
decelerated
in kinetic
by the
de unidades
by the action
energy.
action
SI
In con
the
of
laSIamasa
of resisting
en kg
resisting
system of
force,
yunits the work
workendone
la velocidad
force, the
with mass
done s −
m kg
in
by, the
by the body is
la energía
and body iscinética
velocity
E K tieneequal to
unidades its change
de kgenergyin −
kinetic
min kinetic
s E. Puesto energy.que In the SI system of units with mass in kg −
and velocity
equal
in m to
−1 ,its change energy. Inelthe
newton
SI m 2ess−2
system la of
unidad
units compuesta
with mass inkgiskg
mthes composite
and , velocity
EK se mide en
in m
newtonmetros
in m sss−1
−1 , kinetic
o, kinetic
joules.
kinetic
−2 Deenergy
acuerdo
energy EEKK con
has
has
the
has la
the
units
theecuación
units
of
units of kg
of(.4),
kg m
kg
2 s−2 .. Because
m2éstas −2es
. Because
la unidad
Because
the
the
del
the
newton
newton
trabajo.
newton is the
is the composite
composite
unit kg
unit kg
kg m m
m sss−2
−2 ,, E
EK is measured K in newton-meters or joules. In accord with Eq. (1.4), this is the
unit ,E K is measured in newton-meters or joules. In accord with Eq. (1.4), this is the
unit of work. K is measured in newton-meters or joules. In accord with Eq. (1.4), this is the
unit of
unit of work.
work.
8 Lord Kelvin
8 LordoKelvin,
William Thomson (84907) fue un físico
8 Lord Kelvin, or William Thomson (1824–1907), wasinglés que, junto
an English con who,
physicist el físico alemán
along Rudolf
with the Clausius
German (8888),
physicist
establecióRudolf
los8 Lord
fundamentos or William
para Thomson
la ciencia moderna(1824–1907), was an English physicist who, along with the German physicist
de la termodinámica.
Kelvin,(1822–1888),
Clausius or William Thomson
laid (1824–1907),
the foundations forwas
the an English
modern physicist
science who, along with the German physicist
of thermodynamics.
Rudolf Clausius (1822–1888), laid the foundations for the modern science of thermodynamics.
Rudolf Clausius (1822–1888), laid the foundations for the modern science of thermodynamics.

1.8. Energy
1.8. Energía
1.8. Energy 11
11
1.8. Energy 11
En el sistemathe inglés
In the Englishde engineering
ingeniería, lasystem,
energíakinetic
cinéticaenergy
se expresa como −¹ mu
is expressed
expressed as 2112/g
muc ,2donde gc tiene
2 /g , where gc el valor
In English engineering −system,− kinetic energy is ² as mu 2/g
c
c , where gc
3.740hasy las unidades
In the
the value (lb
English
value 32.1740 )(pie)(lb
engineering) (s)
system, . De este
kinetic modo,
−1
energy −2 la
is unidad de
expressed
m and the funits (lbm )(ft)(lbf )−1 (s)−2 . Thus the unit of
32.1740 la
asenergía
2 1
mu cinética
/g
kinetic en este
c energy gin
, where siste
has the and the units (lbm )(ft)(lbf ) −1(s) −2. Thus the unit of 2 kinetic energy inc
ma es: has
this system
system
the valueis:32.1740 and the units (lbm )(ft)(lbf ) (s) . Thus the unit of kinetic energy in
this is: −2
this system is: mu22
mu )(ft)22(s)
(lbm)(ft)
(lb (s)−2
E K =
E K = mu 2 = m 2 −1−2
= (ft lb )
−2 = (ft lbff)
2gc = (lbm (lb m )(ft)f )(s)
)(ft)(lb −1 (s) −2
E K = c = (lbm )(ft)(lbf ) −1(s) −2 = (ft lbf )
2g
Aquí, laDimensional
consistenciaconsistency
Dimensional dimensionalhere
consistency 2gc la inclusión
requiere
here requires (lbminclusion
the )(ft)(lb
defg) cof
. (s)
of
requires the inclusion ggcc..
Dimensional consistency here requires the inclusion of gc .
Potential
Energía Energy
potencial
Potential Energy
Potential Energy
If aa body
body of of mass
mass m m isis raised
raised from from an initialinitial elevation
elevation zz 1 to to aa final
final elevation
elevation zz 2,, an an upward
upward
Si un cuerpo
If de masa m se mueve desde unaanaltura inicial z a una 1 altura final z, se debe 2 ejercer una fuerza
force
If a at
body least
of equal
mass mto the
is weight
raised fromof the
an body
initial must be
elevation exerted
z 1 to on
a it,
final and this
elevationforce
z , must
an move
upward
ascendente
forcealatmenosleast equaligual to al the
pesoweight del cuerpo,
of the ybody esta must
fuerza bedebe
exertedmoverse
on it, aand lo largo de2lamust
this force distancia
move z − z.
through
force at the the distance
least distance
equal tozz 2the − weight
z 1.. Because
Because
of thethe the
bodyweight
mustof ofbethe
the body is
exerted is the
on forcethis
it, force
and of gravity
gravity
force muston it,
it, the
move
Puesto que el peso del
through cuerpo 2es−lazfuerza 1 de la gravedad weight sobre el body
mismo, the la fuerza mínima
of requerida
on está dada
the
minimum
through the force required
distance z 2 −isiszgiven
given by Newton’s
1 . Because Newton’s
the weight law:of the body is the force of gravity on it, the
por la ley de Newton:
minimum force required by law:
minimum force required is given by Newton’s law:
F= = ma = mg
FF = ma ma = mg
F = ma = mg
where g is the local acceleration of gravity. The minimum
minimum work work required
required to to raise
raise the the body
body is is
donde gwhere
the
where la gaceleración
es productg
is the locallocal
is of
the this
local
acceleration
force de
and
acceleration lathe of gravity.
gravedad.
change
of gravity.in
The
El elevation:
trabajo
The mínimo requerido
minimum work para to
required elevar
raise althecuerpo
body es
is el pro
ducto detheesta
product
fuerza ofporthiselforce
cambio anden thelachange
elevación: in elevation:
the product of this force and the change in elevation:
W= = F(z 2 − − z ) = mg(z mg(z 2 − − z1)
W W =F(z F(z2 − zz11) = mg(z 2− zz1))
W = F(z 2 − z 1 ) = mg(z 2 − z 1 )
or
or WW= = mz mz 2gg − − mzmz 1gg = = �(mzg)
�(mzg) (1.6)
(1.6)
2 1
o or W = mz 2 g − mz 1 g = �(mzg) (1.6) (.6)
We see
We see from from Eq.
Eq. (1.6)
(1.6)que that work
thatelwork done
done on a
on asobrebody
body el in raising
incuerpo,
raising it it is equal to
islevantarlo, the
equal to the change
change in the
En la ecuación
quantity We mzg.
see (.6)
from vemos
Conversely,
Eq. (1.6) if a body
that trabajo
work is done hecho
lowered on against
a body a
in resisting
raising al
itforce
is equal
equal to esits
to
the igual al in
weight,
change in
the
cambio
the en la
cantidadquantity
mzg. De mzg.maneraConversely,
inversa, ifsiaelbody
cuerpo is lowered
desciende against
con a resisting
una fuerza force
en equalcontrario,
sentido to its weight, pero the
igual a su
work
quantity done mzg. by the
the body is
Conversely, is equal
equal
if a bodyto the
the change
ischange
loweredin inagainst
the quantity
quantity mzg.force
a resisting Eachequal
of the
thetoquantities
quantities
its weight,mzg mzg
the
peso, elwork
intrabajo
work
done
Eq.done(1.6)by
by
hecho is atheporbodyel
a potential
potential cuerpoenergy.
body isenergy.
equal toes to
igual
9 Thus,
the
9 Thus,
al cambio the
en la cantidad mzg. Each of
Cada una
in the quantity mzg. Each of the quantities mzg mzg
by definition,
change definition, mzg. de las cantidades
in Eq.
en la ecuación (1.6)
(.6) ises una energía potencial.
9 9 De by esta forma, por definición,
in Eq. (1.6) is a potential energy. Thus, by definition,
E P ≡
E P ≡ mzg mzg (1.7)
(1.7)
EEPP ≡≡ mzg
mzg (1.7) (.7)
In the
In the SI system of units with mass in kg, elevation in m, and the acceleration of gravity in
−2 ,SI system of units with mass in kg, elevation in m, and the acceleration of gravity in
En el sistema
m
In sthe
−2 de
SI unidades
potential
system of SIunits
energy con has
m s −2, potential energy has the units of−
la the
with masa en in
units
mass kg,kg,
of kgla melevación
2 s−2 . This
elevation
2 −2 en m,
in m,
is y lanewton-meter
the
and aceleración
the de
acceleration
kg m 2 s −2. This is the newton-meter or joule, the unit or lajoule,
gravedad
of the
gravity in m s−,
en
unit
la energía
m potencial
of work,
swork, tiene
in agreement
agreement
, potential unidades
energy with
hasEq. de kg
Eq.
the (1.6).
units m ofs kg . Éste
m ses .elThis newtonmetro o joule, laorunidad
is the newton-meter joule, the del unit
trabajo, de
of in with (1.6).
acuerdoofcon la
work, ecuación
In thethe
in agreement (.6).
English engineering
engineering
with Eq. (1.6). system, potential
potential energyenergy is is expressed
expressed as as mzg/g
mzg/gc.. Thus Thus thethe
In English system, c
En el of
unit sistema
Inpotential
the inglés
English deengineering
energy ingeniería,
in this systemla energía
system, is: potencial
potential se expresa
energy is como mzg/g
expressed as mzg/gc . Así,
c . la unidad
Thus the de la
unit of potential energy in this system is:
energía unit
potencial en este sistema es:
of potential energy in this system is:
mzg (lbm)(ft)(ft)(s)
)(ft)(ft)(s)−2 −2
E P = mzg = (lb m −2−2 = = (ft
(ft lb
lbf))
E P = mzg g = (lb(lb )(ft)(lb −1
m )(ft)(ft)(s)
f))−1 (s)
(s)−2 f
E P = gcc = (lb m)(ft)(lb
m f = (ft lbf )
gc (lbm )(ft)(lbf )−1 (s)−2
De nuevaAgain,
cuenta,
Again, ggcc must
must
debe be be included
incluirse
included gc forfor dimensional
para dimensional consistency.
asegurar la consistency.
consistencia dimensional.
Again, gc must be included for dimensional consistency.
Energy Conservation
Conservation
Conservación
Energy de la energía
Energy Conservation
In any
any examination
examination ofof physical
physical processes,
processes, an an attempt
attempt is
is made
made to
to find
find or
or to
to define
define quantities
quantities
En cualquier
In
which examen
remain de procesos
constant físicos of
regardless se the
intenta encontrar
changes whicho occur.
definirOne
cantidades
such que permanezcan
quantity, early recog-constan
In any examination of physical processes, an attempt is made to find or to define quantities
tes, sinwhich
nized
remain
importar
in los constant regardless
cambios
the development
developmentque of the
ocurran. Una
of mechanics,
mechanics,
changes
de estaswhich
is mass.which
occur. One
cantidades,
The great
great
such quantity,
reconocida
utility of al early
principio
thequantity,
law of
recog-
del desarrollo
of conservation
conservation
whichin
nized remain
the constant regardless
of of the changes occur. One ofsuch early recog-
de la mecánica, es la masa. La gran utilidad deislamass.
ley deThe utility
conservación the
de masa law
sugiere que existen otros
nized in the development of mechanics, is mass. The great utility of the law of conservation
9 This term was proposed in 1853 by the Scottish engineer William Rankine (1820–1872).
9 9 This termpropuesto
was proposed in 1853 byingeniero
the Scottish engineer William Rankine (1820–1872).
Este término
9 This fue en 853 por el escocés William Rankine (8087).
term was proposed in 1853 by the Scottish engineer William Rankine (1820–1872).

CAPÍTULO 1. Introducción
of mass suggests that other conservation principles could be of comparable value. With re-
principios de conservación que podrían tener un valor comparable. Con respecto a la energía observamos que
spect to energy we observe that Eqs. (1.4) and (1.6) both show that work done on a body is
las ecuaciones (.4) y (.6) muestran que el trabajo realizado sobre un cuerpo es igual al cambio en una can
equal to the change in a quantity which describes the condition of the body in relation to its
tidad que describe la condición del cuerpo en relación con sus alrededores. En cada caso, el trabajo efectuado
surroundings. In each case the work performed can be recovered by carrying out the reverse
puede recuperarse realizando el proceso inverso y regresando el cuerpo a su condición inicial. Esta observa
process and returning the body to its initial condition. This observation leads naturally to the
ción conduce naturalmente a la idea de que, si el trabajo se efectúa sobre un cuerpo al acelerarlo o elevarlo,
thought that, if the work done on a body in accelerating it or in elevating it can be subsequently
éste se puede recuperar posteriormente; de esta manera, el cuerpo tiene la habilidad o capacidad de realizar
recovered, then the body by virtue of its velocity or elevation contains the ability or capacity
trabajo en virtud de su velocidad o elevación. Este concepto ha demostrado ser tan útil en la mecánica del
to do the work. This concept proved so useful in rigid-body mechanics that the capacity of a
cuerpo rígido, que a la capacidad que tiene un cuerpo para realizar trabajo se le dio el nombre de energía,
body for doing work was given the name energy, a word derived from the Greek and meaning
palabra derivada del griego, que significa “en trabajo”. Por lo tanto, se dice que el trabajo para acelerar un
“in work.” Hence the work of accelerating a body produces a change in its kinetic energy:
cuerpo produce un cambio en su energía cinética:
� �
mu 22
W = �E KK = �
2
y el trabajo realizado
and the para on
work done elevar un cuerpo
a body produce
in elevating un cambio
it produces en su energía
a change potencial:
in its potential energy:
W
W==E = Δ(mzg)
EPPP = �(mzg)
Si un cuerpo recibe
If a body is energía cuandowhen
given energy se eleva,
it is conserva
elevated, othen
retiene
the esa
body energía hasta or
conserves queretains
realizathis
el trabajo
del cualenergy
es capaz. Cuando
until un cuerpo
it performs se eleva
the work of ywhich
después
it issecapable.
le permiteAncaer libremente,
elevated body, gana en energía
allowed to fall cinéti
ca lo que pierde
freely, en energía
gains potencial,
in kinetic de manera
energy what it losesquein su capacidad
potential parasorealizar
energy that itstrabajo no for
capacity cambia.
doingPara un
cuerpo que
workcae libremente
remains esto significa
unchanged. que: falling body this means that:
For a freely
ΔEKK +
�E E P P==00
+�E
K P
mu 222 mu 212
2 − 1 + mz g − mz g = 0
o or 22 11
2 2
La validez
Thede esta ecuación
validity fue confirmada
of this equation has beenpor innumerables
confirmed experimentos.
by countless De este
experiments. modo,
Thus the el desarrollo del
develop-
concepto de energía
ment condujoof
of the concept deenergy
maneraled lógica al principio
logically de conservación
to the the de energía
principle of energy para todosfor
conservation losall
procesos
estrictamente mechanicalLa
purely mecánicos. amplia evidencia
processes. experimentalevidence
Ample experimental que justifica esta generalización
to justify this generalization fue obtenida
was sin
dificultad.
readily obtained.
Son posibles
Other otras
formsformas de energía
of mechanical mecánica,
energy besidesademás
kineticde la gravitational
and energía cinética y de laenergy
potential potencial
are gravi
tacional.possible.
La más evidente
The mostes la energía
obvious potencial
is potential de configuración.
energy Cuando
of configuration. When se acomprime un resorte, el traba
spring is compressed,
jo es hecho
workpor una fuerza
is done by anexterna.
externalPuesto
force. que el resorte
Because puede realizar
the spring can latermás tarde this
perform cierto trabajo
work contra una
against
fuerza de resistencia,
a resisting posee
force, thelaspring
capacidad para efectuarlo.
possesses capacity for Ésta es lawork.
doing energíaThispotencial de configuración.
is potential energy of Exis
te energía del mismo Energy
configuration. tipo tanto en una
of the sameligaformestirada
exists como en una barra
in a stretched rubberdebandmetal deformada
or in en la región
a bar of metal
elástica.deformed in the elastic region.
La generalidad del principio
The generality de conservación
of the principle de la energía
of conservation en mecánica
of energy in mechanics aumenta si consideramos
is increased if we al
trabajo mismo
look uponcomo
workunaitself
forma as adeform
energía. Esto esThis
of energy. claramente
is clearlyaceptable,
permissible,ya que
becauselos cambios tantoand
both kinetic- en la ener
gía cinética como en la changes
potential-energy energía potencial
are equal sonto theiguales al trabajo
work done hecho para
in producing themproducirlos
[Eqs. (1.4)[ecuaciones
and (1.6)]. (l.4) y
(.6)]. Sin embargo,
However, el trabajo
work is energy es energía
in transitenand
tránsito y nunca
is never se considera
regarded as residingcomoin residente en unwork
a body. When cuerpo.is Cuan
do se realiza trabajo
done and doesy not
no aparece simultáneamente
appear simultaneously as como trabajo en otra
work elsewhere, it is parte,
convertedse convierte en otra
into another formforma de
energía.of energy.
Al agregado o conjunto
The body sobre el que
or assemblage se concentra
on which attentionla atención
is focusedseislecalled
nombra system.AAll
thesistema. todo lo demás
else is se
le llamacalled
alrededores. Cuando se When
the surroundings. realizawork
trabajo, éste esit hecho
is done, is doneporbylos
thealrededores
surroundings sobre el sistema,
on the system, oorvicever
sa; en tanto, la energía
vice versa, se transfiere
and energy de los alrededores
is transferred al sistema, otodethe
from the surroundings manera
system, inversa.
or the La formaItdeisenergía
reverse.
conocida como trabajo sólo existe durante esta transferencia. En contraste, las energías cinética y potencial

1.8. Energy 13
1.8. Energía
only during this transfer that the form of energy known as work exists. In contrast, kinetic and 3
potential energy reside with the system. Their values, however, are measured with reference
to the
residen en surroundings;
el sistema. i.e., kinetic
Sin embargo, energy depends
sus valores se midenon velocity
con with
respecto respect
a los to the surroundings,
alrededores; es decir, la energía
and potential energy depends on elevation with respect to a datum level.
cinética depende de la velocidad con respecto a los alrededores, y la energía potencial Changes in kinetic
depende de la altura
and potential energy do not depend on these reference conditions, provided they are fixed.
con respecto a un nivel de referencia. Los cambios en las energías cinética y potencial, una vez fijados, no
dependen de estas condiciones de referencia.
Example 1.4
Ejemplo 1.4 with a mass of 2,500 kg rests at a level 10 m above the base of an eleva-
An elevator
tor shaft. It is raised to 100 m above the base of the shaft, where the cable holding it
Un elevador con The
breaks. una masa de falls
elevator 2 500freely
kg descansa en un
to the base ofnivel a 10 m
the shaft sobre
and la base
strikes del pozo
a strong de un ele
spring.
vador. Cuando se eleva a 100 m sobre la base del pozo, se rompe el cable que lo sostiene.
The spring is designed to bring the elevator to rest and, by means of a catch arrange- El elevador
cae libremente
ment, to hold the elevator at the position of maximum spring compression. Assuming para
hacia la base del pozo y golpea contra un fuerte resorte. El resorte está diseñado
poner althe
elevador en reposo
entire process to y,
bepor medio deand
frictionless, un diseño
taking gde= retención,
9.8 m s−2 ,mantener
calculate:al elevador en la po
sición de máxima compresión del resorte. Si se supone que todo el proceso es sin fricción, y tomando
− , calcule:
g = 9.8 m s(a) The potential energy of the elevator in its initial position relative to the base of
the shaft.
a) La energía potencial del elevador en su posición inicial con respecto a la base del pozo.
(b) The work done in raising the elevator.
b) El trabajo hecho al subir el elevador.
(c) The
c) La energía potentialdelenergy
potencial of the
elevador elevator
en su in its
posición máshighest position
alta con relative
respecto to the
a la base base
del pozo.
of the shaft.
d) La velocidad y la energía cinética del elevador justo antes de que golpee en el resorte.
(d) The velocity and kinetic energy of the elevator just before it strikes the spring.
e) La energía potencial del resorte comprimido.
(e) The
f) La energía delpotential energy
sistema que of the compressed
se compone del elevadorspring.
y el resorte: 1) al inicio del proceso, 2) cuan
do el(felevador alcanza su altura máxima, 3) justo antes
) The energy of the system consisting of the elevator de queand
el elevador
spring (1) incida enstart
at the el resorte,
4) después de que el elevador ha llegado al reposo.
of the process, (2) when the elevator reaches its maximum height, (3) just
before the elevator strikes the spring, (4) after the elevator has come to rest.
Solución 1.4
Suponga que el subíndice
Solution 1.4 denota las condiciones iniciales; el subíndice , las condiciones cuan
do el elevador está en su posición más alta, y el subíndice 3, las condiciones justo antes de que el
elevadorLet subscript
llegue 1 designate the initial conditions; subscript 2, conditions when the
al resorte.
elevator is at its highest position; and subscript 3, conditions just before the eleva-
tor strikes the spring.
a) Por la ecuación (.7), E P = mz g = ( 500)(0)(9.8) = 45 000 J
(a) By Eq. (1.7), E P1 = mz 1 g = (2,500)(10)(9.8) = 245,000 J
� z2 � z2
b) Por la(b)
ecuación
By Eq. (.),
(1.1), W = F dl = mg dl = mg(z 2 − z 1 )
z1 z1
whence W = (2,500)(9.8)(100 − 10) = 2,205,000 J
de donde W = ( 500)(9.8)(00 − 0) = 05 000 J
(c) By Eq. (1.7), E P2 = mz 2 g = (2,500)(100)(9.8) = 2,450,000 J
Note that
c) Por la ecuación (.7), EWP2==Emz
P2 −
gE 1 . 500)(00)(9.8) = 450 000 J
=P(
Observe que W = E P − E P .

4
14 14
14 CHAPTER
CHAPTER
1. 1.1. Introduction
CAPÍTULO
Introduction Introduction
1. Introducción
14 CHAPTER
CHAPTER 1. Introduction
d) Del principio
(d)
(d)From de the
From conservación
the principle
principle de
ofof energía mecánica
conservation
conservation of
of se puede energy,
mechanical
mechanical escribir
energy, que
one lamay
onemaysuma dethat
write
write los
thatcam
(d) From(d)the principle
From of conservation
the principle of mechanical
of conservation energy, energy,
of mechanical one mayone write
maythat
write that
bios de lastheenergías
thesum
sum ofofcinética
the
the y potencial
kinetic-
kinetic- and
and durante los procesos
potential-energy
potential-energy changes
changes desde
during
duringlasthe
condiciones
the process
process a con-
from
from 3con-
es cero;
the sum the
of the
sum kinetic-
ofthe and potential-energy
theprinciple
kinetic- and changes
potential-energy during the
changes process
during theonefrom
processcon-
from
writecon-
es decir,(d)ditions
From
ditions 22 toto 3 3is
iszero;
zero; of
thatconservation
that is,
is, of mechanical energy, may that
ditions 2ditions
to sum
the 3 is2zero;
to the
of 3 isthat is, that
zero;
kinetic- andis,potential-energy changes during the process from con-
ditions�E 2�E�E
to 3KKis ++
zero;=�E
�E
that Pis,
P2→3 ==00 E oror o −−EEKK2 E
EE+K3 3E ++EEP3P30−−EEP2P2==00
�E K 2→3 + �E +
2→3
2→3
K 2→3P2→3 �E 0P2→3 =or0
2→3 orK 3 − EEKK23 K− EPK3 2−+2EPP2 3 =− E P2 = 0
Sin embargo,
However, E K KyE
However,
EHowever,
�E EEP3
KK2+2son
and
and
�E cero.
EPE2→3 Por
3are
are0consiguiente,
= zero.
zero.Therefore,
P3PTherefore, Therefore,
or E K 3 − E K 2 + E P3 − E P2 = 0
K 2 andE
However, are zero.
2 3and E P3 are zero. Therefore,
2→3
KP
However, E K 2 and E
E P3 areEEzero.
K3 ==
E EEP=2P2=
EEK=K3Therefore, =450 000J JJ J
2,450,000
J2,450,000
K3 = E PK23 = EP
=32,450,000
P2 = 2,450,000
1 1 2 2 2E KE2K232E =2E2EEKPK23 3= 2,450,000 J

(2)(2,450,000)
(2)(2,450,000)
With
With
1 EEK2K3, 3=1=2 2mu2mu
2 3=,3 , 2u3u3= ==(2)(2,450,000)
K3 (2)(2,450,000)
==
Con EEK3
With K3 =
With E mu =
2 K 3 33 2 mu u
33, u = 3 mm = 2,500
2,500
m3 m 2,500 2,500
= 1 2, 2 = 2E K 3 = (2)(2,450,000)
With E
Whence,
Whence,
K3 2 mu 3 u 3 uu3m3==
s−1 44.27
44.27m ms−1
s−1
Whence,Whence, u3 = u 3m=
44.27 44.27 s−1
m 2,500
De donde, 44.7 m −
m ss−1
Whence,
(e)
(e)Because
Because the
the uupotential
= 44.27
33potential
=
(e) Because the
(e) Becausechanges inchanges
the changes
changes
the ininthe
potential the
energy
in the potential of energy
energy
the
energy
ofofthe
spring thespring
of theand
spring
the
spring
and
andthe
kinetic thekinetic
kineticenergy
and theenergy
energy
kinetic energy
ofofthe
theelevator
elevator must
must sum
sum totozero,
zero,
Puesto
e) the
of (e)que
elevator
of the los
mustcambios
elevator
Because sum
the toen
must
changes la in
zero,
sum energía
tothe
zero, potencial
potential del resorte
energy y en laand
of the spring energía cinética
the kinetic del elevador
energy
deben serof cero,
the elevator�E must(spring)
sum �E�E
to (spring)
zero,(spring)
PP �E (elevator) + + �E�E (elevator)
(elevator)
KK= 0 == 00
P �E P (spring) + K + �E K (elevator) =0
The initial TheTheinitial
Thepotential
initialenergy
initial potential
potential
potential of energy
�E energy
the
energy (resorte)
(spring)
Pspring ofofthe
of theand
the+spring
spring
spring
�Eand
the final(elevador)
K andand the
(elevator)
the
thefinal
final =
kinetic final 0kinetic
energy
kinetic
kinetic
of
energy
energy
energy
the ele- ofofthe
of the ele-
theele-ele-
vator arevator vator
vator
zero; are
are zero;
zero; therefore,
therefore, the
the final
final potential
potential energy
energy of
of the
the spring
spring must
must equal
equal the
the
The aretherefore,
initial zero;
potential theenergy
therefore, finalthe potential
of final
the energy
potential
spring and of
energythe final
the spring
of the must
spring
kinetic equal
energymustthe ofequal
the the
ele-
La energía
kinetic energy
kinetic potencial
kinetic
kinetic of energy
energy
energy
the inicial
elevator the del
ofof the
oftherefore, justresorte
the elevator
elevator
elevator before justyitbefore
just lastrikes
just energía
before
before it
it the cinética
itstrikes
strikes
strikes
spring. the final
the
the
Thus del
spring.
spring.
spring. elevador
theThus Thus
Thus
final the son cero;
the
po-equal
the
final
final
final
po-
po-
po-por lo
vator
tanto, energy
latential
energía
tential are
tential zero;
potencial
energy
energy final
ofofthe the del
springthe
spring isfinal
resorte potential
is2,450,000debe
2,450,000 ser energy
J.J.igual a of energía
la the spring cinética must del the justo
elevador
tential of the
energy spring is
of the spring 2,450,000 is 2,450,000J. beforeJ. it
antes dekinetic
que incida energy conofelthe elevator
resorte. Así,just la energía strikes the
potencial finalspring.
del resorteThusesthe 450 final000 po- J.
tential
(f (f
) ) If energy
Ifthe
the of theand
elevator
elevator spring
and the
the isspring
spring2,450,000 together
together J. are are taken
taken asas the
the system,
system, the
the initial
initial energy
energy
(f ) If the(felevator and the spring
) If the elevator and thetogetherspring together are takenare astaken
the system, the initial
as the system, theenergy
initial energy
of Si elsystem
f) the elevador
of
ofofthe
the is ysystem
thethe
system elpotential
system resorte
is
isisthe
the juntos
the potential
energy
potential seof
potential consideran
energy
energy
theenergy
elevator,
of the como
ofofthe the
or
elevator, el sistema,
elevator,
elevator,
245,000 or
orJ. la energía
or245,000
245,000
The
245,000 total
J. inicial
J.J.energy
The
The
The total
totaldel
total energy sistema es
energy
energy
la the
energía (f )
of If
of the
potencial
thethe elevator
system
systemdel and
elevador,
can
can the
change
change spring
o 45if
only
only together
000ifif J. La
work
work are
isis taken
energía
transferred
transferred as
total thedel system,
sistema
between
between itthe
itsólo
and
andinitial
cambia
the
the energy si se trans
surround-
surround-
of system
of the
ofings.
the can
system
system change can only
change if work
only is transferred
work is between
transferred it and
between theit surround-
and the surround-
fiere trabajo
ings. Asings.
the entre
ings. AsAsélthe
elevator
As yis
the
the elevator
the
islos
elevator potential
alrededores.
elevator
raised, is work
raised,
energy
isisraised,
raised, Conforme
isifwork
doneworkof the
workon
is
isis elevator,
sedone
done
the
done levanta
systemononor the
the
by
on the between
245,000
el elevador
system
system
system
the
J.by The
bysethe
surroundings
by the
thetotal
hace energysobre el
trabajo
surroundings
surroundings
surroundings
sistema ofpor the system can change only work is transferred it and the surround-
theacción de of los2,205,000
alrededores en unathe cantidad de the
05when 000 the J.when
De estatheforma, la energía
in the amount in in thethe amount
amount
of 2,205,000 ofof 2,205,000
2,205,000
J. isThus J.J. Thus
Thus the
the energy
energy ofof the
the system
system when
when the
the elevator
elevator
in
ings. amount
As the elevator raised,J.the Thusenergy
work is of
done theon
energy system
ofthe system
system by elevator
the elevator
surroundings
del sistema
reaches its
reaches cuando
reaches
reaches
maximum its
itsel height
its
maximum elevador
maximum
maximum is alcanza
height
height
245,000
height is su
isis
+
245,000altura
245,000
245,000
2,205,000 +máxima
+ + 2,205,000
=
2,205,000 es 45
2,205,000
2,450,000 =
= 000
= 2,450,000
J. 05
2,450,000
2,450,000+Subsequent J.
J.000 = 450 000 J.
J. Subsequent
Subsequent
Subsequent
Los cambiosin changes
the amount
siguientes ofocurren
2,205,000 por J. Thus
completo the
dentroenergy del of the
sistema, system
sin when
transferencia the elevator
thedesys-
trabajo
changes occurchanges entirelyoccur
occur entirely
withinentirelythe within
within
system, thethe
withsystem,
system,
no+withworkwith
with no no
transfer work
work transfer
transfer
between thebetween
between
sys- the
the sys- en
sys-
changes
reaches occur
its maximumentirely within
height isthe245,000
system, 2,205,000no work = transfer
2,450,000 between
J. Subsequent
tre eland
tem sistematemtem y los
and
surroundings.
tem and
and alrededores.
surroundings.
surroundings.
surroundings. Hence the Por
Hence
Hencetotallothe
Hence tanto,
the
energytotallaof
the total
totalenergía
energy
energy
the
energy total
system
of
of of
the del
the
the sistema
system
system
remains
system permanece
remains
remains
constant
remains at theconstante
constant
constant
constant at
atat en
450 000 changes occur entirely within the system, with no work transfer between sys-
2,450,000 J.J.and
2,450,000
tem ItÉsta
2,450,000
2,450,000
merelysólo J. J.cambia changes
It It
J. It changes
merely
merely
surroundings.
merely de
fromenergía
changes
changes
Hence potential
from potencial
from
from potential
energy
potential deof
potential posición
energy
energy
position
energy (elevación)
of
theofsystem
of position
position
(elevation)
position del elevador
(elevation)
(elevation)
of the
(elevation)
ofof
of the a energía
the
the
cinéticaelevator
elevator del
to elevador,
elevator
elevator
kinetic to
energy ykinetic
tokinetica energía
of energy
energy
the ofofthe
potencial
elevator thethe
to
total
de laenergy
elevator
elevator configuración
potential
of
totoenergy
potential
potential ofen energy
energy remains
el resorte.
configuration
constant
ofofconfiguration
configuration
of
atofof
2,450,000 to kinetic energy of the elevator to potential
J. It merely changes from potential energy of position (elevation) of the energy of configuration of
the spring. thethespring.
spring.
the spring.
elevator to kinetic energy
Este ejemplo ilustra el uso de laofley thedeelevator
conservación to potential energy of
de la energía configuration
mecánica. of
Sin embargo, se
supone the spring.
This queexample todo
This
This
This elexample
proceso
example
illustrates
example ocurre application
illustrates
illustrates
application
illustrates sinapplication
fricción;
application
of the law oflos
of ofthe
of
the resultados
thelaw obtenidos
lawofofconservation
conservation
law of conservation
conservation
of mechanical son
of
ofofexactos
mechanical
mechanical
mechanical sólo para
procesos
energy. tan
energy.
However, idealizados
energy. However,
However,
the como
entire the éste.
the
theprocess
entire
entire is process
processisisto
assumed assumed
assumed
occur totooccur
occur without
withoutthe friction;
friction; the the
energy. This However,
results
results example
obtained
obtained illustrates
are
are
entire
exact
exact only
process
application
only for
for
isofassumed
such
such anan law to
theidealized
idealized ofwithout
occur
conservation
process.
process.
friction;
without offriction;
mechanical the
results obtained
results
energy.obtained are exactare
However, onlyexact
the for suchprocess
only
entire an such
for idealized
isanassumedprocess.
idealized toprocess.
occur without friction; the
results obtained are exact only for such an idealized process.
Durantethe
During elDuring
During
During
periodo
period the
the period
del
theofperiod
period
developmentofofdevelopment
desarrollo development
ofdethe
of development la law
ley of
of de
ofthe
of thelaw lawofofconservation
conservación
theconservation
conservation
law of conservation ofdemechanical ofofmechanical
la energía mechanical
mecánica,
energy,
of mechanical
energy,
heatenergy,
en
energy,
heat
general heat
heat no se
reconocía was
was
alnotnot
not
calor generally
generally
como recognized
recognized asas a a form
form ofofenergy,
energy, but
but was
was considered
considered anan indestructible
indestructible fluid
fluid
was notwas
generally
called
called
generally
During
caloric.the una
recognized
caloric. period
This
This
forma
as of
recognized deasenergía;
a form of
development
concept
concept was
was
energy,
a form más
firmly
of
of the
firmly
bien,
but wasseof
energy,
law
entrenched,
entrenched,
leconservation
consideraba
considered
but
and
andmuchos
for
formany
como
of
many
an un
an indestructible
was considered mechanical
years
years
fluido
no
nohizo
indestructible
fluid
indestructible
energy,
connection
connection
fluid
heatwas
was
lla
mado caloric.
called calórico.
called
was Este
This
caloric.
not between concepto
concept
generally This estaba
was
concept
recognized firmemente
firmly
was entrenched,
asfromfirmly
afrom
form establecido,
and
entrenched,
of energy, for
but y
andpor
many
was foryears
many no
considered años
years no
connection
no
anofof se wasconexión
connection
indestructible was entre el
made
made between heat
heat resulting
resulting friction
friction and
andthe theestablished
established forms
forms energy.
energy. Thefluid
The law
lawofof
calor between
made resultante
made
called de
heat
between la
caloric. of fricción
resulting
heat
This y
fromlas
resulting
concept formas
friction
from
was establecidas
and
friction the
firmly limited and
entrenched, de
established
the la energía.
forms
established
and for many Por
of lo tanto,
energy.
forms of Thela
energy. ley
law
years no connection de
of
The la conservación
law of
was
conservation
conservation ofenergy
energy was
was therefore
therefore limitedininapplication
application totofrictionless
frictionless mechanical
mechanical pro-
pro-
de la energía
conservation estaba
of
conservation
made energy
between limitada
of was
energy
heat a was
procesos
therefore
resulting mecánicos
limited
therefore
from limited
friction sininthe
in application
and fricción. No to es forms
to frictionless
application
established necesaria talmechanical
mechanical
frictionless
of energy.limitación;
pro-
The law hoy
pro-of en día,
cesses.
cesses. No
No such
such limitation
limitation isisnecessary;
necessary; heat
heat like
like work
work is
is now
now regarded
regarded asas energy
energy inintransit,
transit,
tanto alcesses.
cesses. calor
No como
such No
conservation aloftrabajo
limitation
such sewas
limitation
energy lesisconsidera
is necessary; heat like
necessary;
therefore como energía
work
heat
limited en regarded
inisapplication
like now
work tránsito, un
as concepto
is nowtoregarded energy
frictionlessas in que ganó
transit,
energy aceptación
in transit,
mechanical pro- en
cesses. No such limitation is necessary; heat like work is now regarded as energy in transit,

Problemas 5
los años posteriores a 850, en gran parte por los experimentos clásicos de J. P. Joule. Estos experimentos
se consideran de manera detallada en el capítulo , pero primero examinaremos algunas de las caracterís
ticas del calor.
1.9 CALOR
Sabemos por experiencia que un objeto caliente que se pone en contacto con otro objeto frío tiende a enfriar
se, al mismo tiempo que este último se calienta. Una visión razonable es que algo se transfiere del objeto ca
liente al frío, y a ese algo le llamamos calor Q.0 En estos términos se dice que el calor siempre fluye de una
temperatura más alta a una más baja, lo cual nos lleva al concepto de temperatura como la fuerza impulsora
para la transferencia de energía como calor. Con más precisión, la rapidez de transferencia de calor de un
cuerpo a otro es proporcional a la diferencia de temperatura entre los dos cuerpos; cuando no existe diferen
cia de temperatura, no hay transferencia neta de calor. En sentido termodinámico, el calor nunca se considera
como algo que está almacenado dentro de un cuerpo. Al igual que el trabajo, solamente existe como energía
en tránsito desde un cuerpo hacia otro; o, en términos termodinámicos, entre un sistema y sus alrededores.
Cuando se agrega energía en forma de calor a un cuerpo, se almacena no como calor sino como energías ci
nética y potencial de los átomos y de las moléculas que constituyen el sistema.
A pesar de la naturaleza transitoria del calor, con frecuencia se le ve sólo desde el punto de vista de su
efecto sobre el cuerpo del cual o al cual se transfiere. De hecho, alrededor de 930 las definiciones de unida
des de calor estaban basadas en los cambios de temperatura de una masa de una unidad de agua. De esta
forma, la caloría se definió por mucho tiempo como la cantidad de calor que, al transferirse a un gramo de
agua, elevaba su temperatura un grado Celsius. Del mismo modo, la unidad térmica inglesa (o Btu, British
termal unit) se definió como la cantidad de calor que, al transferirse a una libra masa de agua, elevaba su
temperatura en un grado Fahrenheit. Aunque estas definiciones proporcionan una “sensación” de la magnitud
de estas unidades de calor, dependen de experimentos realizados con agua y, por lo tanto, están sujetas a cam
bios en la medida en que las mediciones se vuelven más precisas. En la actualidad se reconoce a la caloría y
al (Btu) como unidades de energía, y se definen con respecto al joule, la unidad de energía del SI, que es
igual a N m. Éste es el trabajo mecánico realizado por la fuerza de un newton que actúa a través de una
distancia de un metro. Todas las demás unidades de energía se definen como múltiplos del joule. El pielibra
fuerza, por ejemplo, es equivalente a .355879 J, la caloría es igual a 4.840 J, mientras que el (Btu) es igual a
055.04 J. La unidad SI para la potencia es el watt, cuyo símbolo es W y se define como una relación de
energía de un joule por segundo.
La tabla A. en el apéndice A proporciona una lista amplia de factores de conversión para la energía, así
como para otras unidades.
PROBLEMAS
1.1. ¿Cuál es el valor de gc y cuáles son las unidades en un sistema donde el segundo, el pie y la libra
masa están definidos como en la sección ., y el poundal es la unidad de fuerza requerida para que
a (lbm) se le dé una aceleración de (pie)(s)−?
0 Un punto de vista igualmente razonable sería considerar que se transfiere “frío” desde el objeto frío hacia el objeto caliente.

6 16
16 CHAPTER 1.
1. Introduction
CHAPTERCAPÍTULO 1. Introducción
Introduction
1.2.
1.2.LaElectric
1.2. corriente
Electric eléctrica
current
current is es fundamental
is the
the la dimensiónSI
fundamental eléctrica
SI fundamental
electrical
electrical dimension,enwith
dimension, el SI,
with y su unidad
ampere
ampere (A) asesunit.
(A) as el ampere (A).
unit.
Determine
Determine las unidades
units for the de las siguientes
following cantidades,
quantities, as como
combinationscombinaciones
of fundamental
Determine units for the following quantities, as combinations of fundamental SI units. de las
SI unidades
units. funda-
mentales del SI.
(a)
(a) Electric
Electric power;
power; (b)
(b) Electric
Electric charge;
charge; (c)
(c) Electric
Electric potential
potential difference;
difference;
Potencia
a)(d) eléctrica;
Electric b)
resistance; carga
(e) eléctrica;
Electric c) diferencia
capacitance.
(d) Electric resistance; (e) Electric capacitance. de potencial eléctrico;
d) resistencia eléctrica; e) capacitancia eléctrica.
1.3. sat
1.3.LaLiquid/vapor
1.3. Liquid/vapor saturation
saturationde
presión de saturación
pressure
pressure P sat is
P
un líquido/vaporis often
often represented as
Psatrepresented as aa function
con frecuencia function of
of temperature
se representatemperature
como una función de
by an equation of the form:
laby an equation
temperatura ofmedio
por the form:de una ecuación de la forma siguiente:
sat bb
log10 P
log 10 P /torr =
sat /torr = aa −− t/◦◦ C + c
t/ C + c
Here,
Aquí, parameters
Here,los parámetros
parameters a, b,
b, band
a, a, andy cccson
are substance-specific
are constantes constants.
específicas
substance-specific Suppose
Suppose it
de las sustancias.
constants. it is required
Suponga
is to
requiredque
to se requiere
represent P sat
sat by the equivalent equation:
representar P mediante la ecuación equivalente:
represent P sat by the equivalent equation:
sat B
B
ln
ln P /kPa =
P sat /kPa =A A−− T /K + C
T /K + C
Muestre
Show cómo
Show how
how theestán
the relacionados
parameters
parameters in the los
in the twoparámetros
two equations en las
equations are
are dos ecuaciones.
related.
related.
1.4.
1.4.¿AAt
1.4. Atqué temperatura
what
what absolute absoluta las do
absolute temperature
temperature escalas
do the Celsiusand
the Celsius
Celsius y Fahrenheit
and Fahrenheitdan
Fahrenheit el mismo valor
temperature
temperature scalesnumérico?
scales give
give ¿Cuál
esthe
esesame
the valor?
same numerical
numerical value?
value? What
What isis the
the value?
value?
1.5.
1.5.Las
1.5. presiones
Pressures
Pressures up superiores
up to
to 3,000 bara are
3,000 bar 3 000
are bar se with
measured
measured miden
with con una balanza
aa dead-weight
dead-weight gauge.deThe
gauge. peso
The muerto.
piston
piston El diámetro del
diameter
diameter
pistón
is 4 es deWhat
mm.
is 4 mm. 4 mm.
What is ¿Cuál
the
is the es la masamass
approximate
approximate aproximada
mass in kg ofen
in kg of thekgweights
the de las pesas
weights requeridas?
required?
required?
1.6.
1.6.Las
1.6. presiones
Pressures
Pressures up superiores
up to a 3 are
to 3,000(atm)
3,000(atm) 000(atm)
are se miden
measured
measured with aacon
with una balanza
dead-weight
dead-weight de peso
gauge.
gauge. The muerto.
The piston El diámetro del
piston diam-
diam-
pistón
eter es
is de 0.7
0.17(in). (pulg).
What is¿Cuál
the es la masa
approximate aproximada
mass in (lb m
eter is 0.17(in). What is the approximate mass in (lbm ) of(lb
) of ) de
the las pesas
weights requeridas?
required?
m the weights required?
◦ C (open to the atmosphere at one end)

1.7.
1.7.LaThe
1.7. Thelectura de un
reading
reading onmanómetro
on aa mercury de mercurioat
mercury manometer
manometer ata 25
5◦°C
25 (abierto
C (open to athe
la atmosphere
atmósfera enatuno
onede sus extremos)
end)
−2 . Atmospheric
esis
isde56.38
56.38cm.
56.38 cm.The
cm. TheLa aceleración
local local deof
local acceleration
acceleration oflagravity
gravedad
gravity is es de 9.83
is 9.832
9.832 m ss−2m
m s−. La presión
. Atmospheric atmosférica es de
pressure
pressure
0.78
is kPa.kPa.
is 101.78
101.78 ¿CuálWhat
kPa. es la is
What presión
is the absolutapressure
the absolute
absolute en kPa que
pressure in
in kPadebe
kPa medirse?
being
being La densidad
measured?
measured? The del mercurio
The density
density of
of a 5 °C
◦◦ C−3 −3
esmercury
de 3.534
mercury at g cm
at 25
25 is.13.534
C is 13.534 gg cm
cm−3 ..
◦◦ F) (open to the atmosphere at one end) is
l.8.
1.8.LaThe
1.8. lectura
The en un
reading
reading on manómetro
on aa mercury de mercurio
mercury manometer
manometer at a70(
at 70(°F)
70( (abierto
F) (open a laatmosphere
to the atmósfera at
enone
unoend)
de sus
is extremos)
−2 −. La
es25.62(in).
de 5.6 (pulg).
25.62(in). The La aceleración
The local
local accelerationlocal
acceleration of de la gravedad
of gravity
gravity is es de 3.43(pie)(s)
is 32.243(ft)(s)
32.243(ft)(s) −2 .. Atmospheric
Atmospheric presión atmosfé
pressure
pressure
rica
is es de 9.86
is 29.86(in
29.86(in (pulg
Hg).
Hg). What
What de is
Hg).
is the¿Cuál
the es lapressure
absolute
absolute presiónin
pressure inabsoluta
(psia) en (psia)
(psia) being
being que debeThe
measured?
measured? medirse?
The densityLa densidad
density
◦◦ F) is 13.543 g cm−3 −3
del
ofmercurio
of mercury aat70(°F)
mercury at 70( F)esis de
70( 3.543
13.543 g cm. .
g cm −3 .
1.9.
1.9. Liquids
1.9.Los that
líquidos
Liquids thatqueboil at
at relatively
boilhierven low
low temperatures
a temperaturas
relatively are
are often
relativamente
temperatures stored
bajas
often as
as liquids
liquids under
son almacenados
stored their
como
under líquidos bajo
their
vapor
sus
vapor pressures,
presiones which
de vapor,
pressures, which at ambient
lasatcuales
ambient seríantemperature
más grandes
temperature can
canabebe quite
temperaturalarge.
quite large. Thus,
ambiente. n-butane
Así, el nbutano al
Thus, n-butane
stored
stored as
macenado aa liquid/vapor
as como un sistema
liquid/vapor system is
is at
at aa pressure
líquido/vapor
system está aof
pressure 2.581
ofuna bar
bar for
presión
2.581 de aa.58
for temperature
bar paraof
temperature 300
ofuna K.
300temperatura
K. de
Large-scale storage (>50 m 33 ) of this kind is sometimes 3 done in spherical tanks. Sug-
300 K. El almacenaje
Large-scale de grandes
storage (>50 m ) of this cantidades (>50 m ) de
kind is sometimes estainclase
done de sustancias
spherical tanks. Sug-en ocasiones
segest
gest two
realiza
twoenreasons
tanques
reasons why.
esféricos. Sugiera dos posibles razones del por qué.
why.
1.10.
1.10.ElThe
1.10. first
primer
The accurate
accurate measurements
first instrumento preciso paraof
measurements the
the properties
ofmedir of
of high-pressure
las propiedades
properties gases
de los gases
high-pressure were
a alta
gases made
made by
werepresión fue creado en
by
E.
E. H.
H. Amagat
Francia por E. H.in
Amagat France
France between
inAmagat, entre 869
between 1869 and
and 1893.
y 893.
1869 Before
Antes de
1893. developing
desarrollar
Before the
the dead-weight
la balanza
developing de peso muerto, Ama
dead-weight
gauge,
gat trabajó
gauge, he
heenworked
el pozoin
worked indeaa mine shaft,
una mina
mine shaft, and
and used
y utilizó un aamanómetro
used mercury
mercury manometer
de mercuriofor
manometer measurements
forpara medir presiones mayo
measurements
resof
ofapressure
400 bar.to
pressure more
more than
Determine
to thanla400 bar.
altura
400 Estimate
bar.del manómetro
Estimate the
the height
height of
of manometer
manometer required.
requerido. required.

Problems 17
Problemas 7
1.11. An instrument to measure the acceleration of gravity on Mars is constructed of a spring

1.11. Un instrumento
from para mediralamass
which is suspended aceleración de la
of 0.40 kg. Atgravedad
a place onenearth
Marte está the
where construido con un resorte de
local acceler-
donde se suspende una
ation of gravity is 9.81 masa
m s , the spring extends 1.08 cm. When the instrument pack- local de la
−2de 0.40 kg. En un lugar de la Tierra donde la aceleración
gravedad es 9.8 m s −, el resorte se extiende .08 cm. Cuando el aparato desciende en Marte, la radio
age is landed on Mars, it radios the information that the spring is extended 0.40 cm.
informa
What isque
theelMartian
resorte acceleration
se extiende 0.40 cm. ¿Cuál es la aceleración de la gravedad marciana?
of gravity?
1.12.
1.12.LaThe
variación deof
variation la fluid
presión de un with
pressure fluidoheight
con laisaltura está by
described descrita por la ecuación
the differential diferencial:
equation:
dP
= −ρg
dz
Here,ρ ρes is
Aquí, la specific
densidaddensity and yggisesthe
específica local acceleration
la aceleración local deofla gravity.
gravedad.ForParaanun
ideal
gas ideal, ρ =
gas, ρ = MP/RT , where M is molar mass and R is
M P / RT, donde M es la masa molar y R es la constante universal de losthe universal gas constant.
gases. Modele la atmós
Modeling
fera como una thecolumna
atmosphere as an isothermal
isotérmica column
de un gas ideal of°C
a 0 ideal 10◦ C, estimate
gasdeatcalcular
a fin la presiónthe
ambiental en
ambientdonde
Denver, pressure= in(milla)
z −1 Denver,
conwhere z =al 1(mile)
respecto nivel delrelative to sea
mar. Para level.
el aire, ForMair,
tome = take
9 g mol−; los
M = 29 g mol ; values of
valores de R se dan en el apéndice A.R are given in App. A.
1.13. A group of engineers has landed on the moon, and they wish to determine the mass
1.13. Unofgrupo
some de ingenieros
rocks. ha aterrizado
They have a spring en la Luna
scale y desea
calibrated to determinar
read poundslamass
masaatdea algunas
locationrocas. Tiene
una escala de resorte calibrada
where the acceleration of para leer libras masa
−2 en una posición donde
gravity is 32.186(ft)(s) . One of the moon rocks givesla aceleración
a de la
gravedad es 3.86(pie)(s −). Una de las rocas lunares da una lectura de 8.76 en esta escala. ¿Cuál
reading of 18.76 on this scale. What is its mass? What is its weight −
on the moon?
esTake
la masa? ¿Cuál=es
g(moon) el peso en
5.32(ft)(s)−2la
. Luna? Tome g(Luna) = 5.3(pie)(s ).
1.14.
1.14.Una luz externa
A 70-watt de seguridad
outdoor de 70
security light wattsonseaverage,
burns, utiliza en
10 promedio
hours a day.0 A
horas
newalbulb
día.costs
Un foco nuevo
cuesta $5.00, y su tiempo de vida es de casi 000 horas. Si la electricidad cuesta
$5.00, and the lifetime is about 1,000 hours. If electricity costs $0.10 per kW-hour,$0.0 por kWhora,
¿cuál es el costo anual de “seguridad” por luz?
what is the yearly price of “security,” per light?
1.15.
1.15.UnAgas
gasseis encuentra confinado
confined in en un cilindro
a 1.25(ft)-diameter de .5by
cylinder (pie) de diámetro
a piston, por medio
on which rests adeweight.
un pistón, sobre el
cual descansa una pesa. La masa del pistón y la pesa en conjunto es de 50(lb
The mass of the piston and weight together is 250(lbm ). The local acceleration m). La aceleración
of local de
lagravity
gravedad es de 3.69(pie)(s)
−2 − y la presión atmosférica es de 30.(pulg de Hg).
is 32.169(ft)(s) , and atmospheric pressure is 30.12(in Hg).
a) (a)¿Cuál
Whatesislathe forceen
fuerza in(lb
(lbf))ejercida
f
exerted on thegas
en el gaspor
by la
theatmósfera,
atmosphere, the piston,
el pistón and the
y la pesa? Suponga que
weight, assuming no friction between
no existe fricción entre el pistón y el cilindro. the piston and cylinder?
b) (b)¿Cuál
Whatesislathe pressure
presión del of
gastheengas in (psia)?
(psia)?
(c) If the gas in the cylinder is heated,
c) Si el gas en el cilindro se calienta, se expande it expands, pushing
y empuja the piston
el pistón and weight
y la pesa hacia arriba. Si el
upward. If the piston and weight are raised 1.7(ft), what is the work
pistón y la pesa se levantan .7(pie), ¿cuál es el trabajo realizado por el gas en done by(pie
the lb )? ¿Cuál
f
gas in (ft lb )? What is the change in potential
es el cambio en la energía potencial del pistón y la pesa?
f energy of the piston and weight?
1.16. A gas is confined in a 0.47-m-diameter cylinder by a piston, on which rests a weight.

1.16. Un gas se encuentra confinado en un cilindro de 0.47 m de diámetro por medio de un pistón, sobre
The mass of the piston and weight together is 150 kg. The local acceleration of gravity
el cual descansa una pesa. La masa del pistón y la pesa en conjunto es de 50 kg. La aceleración
is 9.813 m s−2 , and atmospheric pressure is 101.57 kPa.
local de la gravedad es de 9.83 m s−, y la presión atmosférica es de 0.57 kPa.
(a) What is the force in newtons exerted on the gas by the atmosphere, the piston, and
a) ¿Cuál es la fuerza
the weight, en newtons
assuming ejercida
no friction sobrethe
between el gas porand
piston la atmósfera,
cylinder? el pistón y la pesa? Supon
(b)gaWhat
que no hay fricción entre el pistón y el cilindro.
is the pressure of the gas in kPa?
b) (c)¿Cuál
If thees gas
la presión
in the del gas eniskPa?
cylinder heated, it expands, pushing the piston and weight
c) Siupward.
el gas enIf elthecilindro
piston andse calienta, se raised
weight are expande
0.83y m,
empuja
what el
is pistón y la
the work pesabyhacia
done the arriba. Si
el gas
pistón y laWhat
in kJ? pesa se levantan
is the change0.83 m, ¿cuál energy
in potential es el trabajo
of therealizado
piston andpor el gas en kJ? ¿Cuál es el
weight?
cambio en la energía potencial del pistón y la pesa?

1.17. Verifique si el joule es la unidad en el sistema internacional para las energías cinética y potencial.
1.18. Un automóvil que tiene una masa de 50 kg se encuentra viajando a 40 m s−. ¿Cuál es la energía
cinética en kJ? ¿Cuánto trabajo debe efectuarse para detenerlo?
1.19. Las turbinas de una planta hidroeléctrica son alimentadas por una caída de agua de 50 m de altura.
Al suponer una eficiencia de conversión de la energía potencial en eléctrica de 9%, y 8% de pérdi
da de potencia resultante en la transmisión, ¿cuál es la rapidez de flujo de masa de agua requerida
para encender un foco de 00 watts?
1.20. A continuación se encuentra una lista de factores de conversión aproximados, que se emplean para
cálculos “rápidos”. Ninguno de ellos es exacto, pero en la mayoría hay un margen de error de ± 0%.
Haga uso de la tabla A. (apéndice A) para establecer los factores de conversión exactos.
• (atm) ≈ bar
• (Btu) ≈ kJ
• (hp) ≈ 0.75 kW
• (pulgada) ≈ .5 cm
• (lbm) ≈ 0.5 kg
• (milla) ≈ .6 km
• (cuarto) ≈ litro
• (yarda) ≈ m
Agregue sus propios términos a la lista. La idea es mantener los factores de conversión en una forma
simple que sea fácil de recordar.
1.21. Considere la siguiente propuesta para un calendario decimal. La unidad fundamental es el año de
cimal (año), igual al número convencional de segundos (SI) requeridos para que la Tierra complete
una órbita alrededor del Sol. Otras unidades son definidas en la tabla siguiente. Desarrolle, hasta
donde sea posible, factores para convertir unidades del calendario decimal a unidades del calendario
convencional. Analice los puntos a favor y en contra de esta propuesta.
Unidades del calendario decimal Símbolo Definición

Segundo Seg 0–6 Año
Minuto Min 0–5 Año
Hora H 0–4 Año
Día Día 0–3 Año
Semana Sem 0– Año
Mes Mes 0– Año
Año Año

Problemas 9
Problems 19
Problems 19
1.22. Los costos de la energía varían en gran medida con la fuente de energía: el carbón cuesta $5.00/to
nelada, la gasolina
1.22. Energy coststiene
vary un precio
greatly creciente
with energyde $.00/galón
source: coal @y$25.00/ton,
la electricidad vale $0.000/kWhora.
gasoline @ a pump
1.22. Energy costs vary greatly with energy source: coal @ $25.00/ton, gasoline @ a pump
En la práctica
price of es conveniente
$2.00/gal, expresarlos@en$0.1000/kWhr.
and electricity una base común en $ GJ−. practice
Conventional [Un gigajoule equivale
is to put
price of $2.00/gal, and electricity @ $0.1000/kWhr. Conventional practice is to put
aproximadamente
these on a commona 0 6 (Btu).]
basis by Para este propósito
expressing $−1GJ−1 . valores
them insuponga de calentamiento
[A gigajoule totales (sin
is approximately
these on a common basis by expressing them in $ GJ −3 . [A gigajoule is approximately
106 (Btu).]
corrección), de 9For kg−
MJthis para el carbón
purpose, assumeygrossde 37heating
GJ m values
para la 29 MJ kg−1 for coal and
ofgasolina.
106 (Btu).] For −3 this purpose, assume gross heating values of 29 MJ kg−1 for coal and
37 GJ m for gasoline.
37 GJ m−3 for gasoline. −
a) Clasifique en orden las tres fuentes de energía con respecto a los costos de energía −1 . en $ GJ .
(a)
b) (a)Explique Rank order
la notable the three
discrepancia energy sources
que hay with respect
enrespect
los resultadosto energy cost
numéricos in $ GJ
Rank order the three energy sources with to energy cost in $ del
GJ−1inciso
. a). Discuta las
(b) Explain
ventajas y the largededisparity
desventajas las tres in the numerical
fuentes de results of Part (a). Discuss the advan-
energía.
(b) Explain the large disparity in the numerical results of Part (a). Discuss the advan-
tages and disadvantages of the three energy sources.
tages and disadvantages of the three energy sources.
1.23. Los costos del equipo de una fábrica de especies químicas rara vez varían en proporción al tamaño.
1.23. Chemical-plant equipment costs
varíararely vary in proportion
S conforme to size. In the simplest case,
1.23.EnChemical-plant
el caso más sencillo, el costo
equipment costsCrarely con
varyelintamaño
proportion a la
to size. In theecuación
simplestalométrica:
case,
cost C varies with size S according to the allometric equation
cost C varies with size S according to the allometric equation
C = αSβ β
C = αS
C = αS β
La magnitud del exponente β por lo regular se encuentra entre 0 y . Para una amplia variedad de
equipos The size
valorexponent
su exponent es de β is typically between 0 and 1. For a wide varity of equipment types
aproximadamente
The size β is typically between0.6. 0 and 1. For a wide varity of equipment types
it is approximately 0.6.
it is approximately 0.6.
a) Para 0 < β < muestre que el costo por tamaño unitario disminuye con el incremento de tama
(a) For 0 < β < 1, show that cost per unit size decreases with increasing size. (”Econ-
(a)ñoFor
(“economía
0 < β < de escala”).
1, show that cost per unit size decreases with increasing size. (”Econ-
omy of scale.”)
b) Considere el caso de un tanque de almacenamiento esférico. El tamaño se mide regularmente
omy of scale.”)
(b) Consider the case of a spherical storage tank. The size is commonly measured by
(b)mediante
Consider el the
volumen
case ofinterno V it. Demuestre
a tspherical que The
storage tank. /3.is¿De
β = size qué parámetros
commonly measuredo propiedades
by se
internal volume V
t . Show . Show that β = 2/3. On what parameters or properties would
espera quevolume
internal dependaVila cantidad
i thatα?β = 2/3. On what parameters or properties would
you expect quantity α to depend?
you expect quantity α to depend?
1.24. Un laboratorio elabora un informe con la siguiente información de presión de vapor (P sat) para una
1.24. A laboratory reports the following vapor-pressuresat(P sat ) data for a particular organic
1.24.especie orgánicareports
A laboratory particular:
the following vapor-pressure (P ) data for a particular organic
chemical:
chemical:
t/◦ C P sat /kPa t/◦ C P sat /kPa
t/◦ C P sat /kPa t/◦ C P sat /kPa
−18.5 3.18 32.7 41.9
−18.5 3.18 32.7 41.9
−9.5 5.48 44.4 66.6
−9.5 5.48 44.4 66.6
0.2 9.45 52.1 89.5
0.2 9.45 52.1 89.5
11.8 16.9 63.3 129.
11.8 16.9 63.3 129.
23.1 28.2 75.5 187.
23.1 28.2 75.5 187.
Correlate the data by fitting them to the Antoine equation:
Correlate
Haga the data de
la correlación by la
fitting them to the
información Antoinelosequation:
ajustando datos a la ecuación de Antoine:
B
ln P sat /kPa = A − B
ln P sat /kPa = A − T /K + C
T /K + C
That is, find numerical values of parameters A, B, and C by an appropriate regression
EsThat
decir,is,encuentre los valores
find numerical valuesnuméricos de losA,parámetros
of parameters B, and C by B yappropriate
A, an C medianteregression
un procedimiento de
procedure. Discuss the comparison of correlated with experimental values. What is
regresión
procedure. apropiado.
DiscussTambién compareoflos
the comparison valores correlacionados
correlated with experimentalconvalues.
los experimentales.
What is ¿Cuál
the predicted normal boiling point of this chemical?
esthe
el punto
predictedde ebullición normal
normal boiling pronosticado
point para esta especie química?
of this chemical?
1.25. (a) In summer 1970, the pump price of gasoline was about $0.35(gal) −1 . Between
−1 . Between
−. Entre
1.25. a) (a)EnInelsummer
1.25. verano de 970,
1970, theelpump
precioprice
de laofgasolina
gasolineera
wasde about
$0.35(gal)
$0.35(gal) 970 y 000, la tasa
1970 and 2000, the average rate of inflation was about 5% per year. What might
promedio
1970 and de2000,
inflación fue de aproximadamente
the average 5% about
rate of inflation was por año.
5%¿Cuál es el What
per year. preciomight
esperado para el
be the expected pump price in summer 2000? What conclusion might one reach
verano
be thedelexpected
año 000?
pump¿A price
qué conclusión
in summerse2000?
puedeWhat
llegarconclusion
a partir de might
estos cálculos?
one reach
from this calculation?
from this calculation?

b) Un doctor en ingeniería inició su carrera en 970, con un salario de $6 000(año)−, se retiró en
−
(b)el A
año 000engineer
Ph.D. con un salario
startingdehis
$80career
000(año)
in 1970. ¿Qué tanto le
at a salary ofconvendrá mantenerse
$16,000(yr)−1 , retiredcon este sa
lario dada una tasa de inflación de 5%−1anual?
in 2000 at a salary of $80,000(yr) . How well did his salary keep up with an
c) Los incrementos
inflation rate ofen
5%lasper
matrículas
year? de las principales universidades privadas de Estados Unidos
presentan una tasa de inflación de aproximadamente 3% anual. Haga uso de esta observación
(c) Tuition increases at major private universities in the United States have led infla-
para sugerir estrategias de pago para la futura matrícula de un niño en una universidad privada.
tion rates by about 3% per year. Use this observation to suggest strategies for
Suponga la ausencia de ayuda económica, una tasa de inflación anual de 5% y una matrícula ac
paying the future tuition for a child at a private university. Assume no financial
tual de $5 000(año)−.
aid, an annual inflation rate of 5% per year, and a current tuition of $25,000(yr)−1 .
Recall the la
Recuérdese compound interest
fórmula de formula:
interés compuesto:
C(t2 )
= (1 + i)t2 −t1
C(t1 )
donde
whereC Cpuede
can simbolizar costos,
be cost, salary, salarios,
etc., t1 andetc., t y t representan
t2 indicate times, and itiempos,
is a ratey (inflation,
la i es una tasa (infla
ción, interés,
interest, etc.)etc.) expresada
expressed as acomo un número decimal.
decimal.

Capítulo 2
La primera ley y otros conceptos

básicos
2.1 EXPERIMENTOS DE JOULE
El concepto moderno de calor se desarrolló después de experimentos decisivos llevados a cabo por
James P. Joule1 (1818-1889), en el sótano de su casa cerca de Manchester, Inglaterra, durante la década
de 1840.
Los experimentos de Joule se caracterizaron por ser bastante simples en los aspectos esenciales, pero
tomó precauciones minuciosas para asegurar su exactitud. En su más famosa serie de mediciones colocó en
un recipiente aislado cantidades conocidas de agua, aceite y mercurio, y después mezcló el fluido con un agi-
tador giratorio. La cantidad de trabajo hecha sobre el fluido con el agitador fue medida con precisión y se
anotó cuidadosamente el cambio de temperatura del fluido. Joule encontró que para cada fluido se requiere
una cantidad fija de trabajo por unidad de masa, por cada grado de aumento en la temperatura causado por el
agitador, y que la temperatura original del fluido se puede restituir por la transferencia de calor a través
del simple contacto con un objeto más frío. De esta manera, Joule demostró finalmente que existe una rela-
ción cuantitativa entre el trabajo y el calor y que, por lo tanto, el calor es una forma de energía.
2.2 ENERGÍA INTERNA
En experimentos como los realizados por Joule, la energía que se agrega a un fluido en forma de trabajo se
transfiere posteriormente desde el fluido como calor. ¿Dónde se encuentra esta energía entre su adición al
fluido y la transferencia desde el mismo? Pensando de modo lógico se diría que está contenida en el fluido,
pero en otra forma llamada energía interna.
La energía interna de una sustancia no incluye la energía que ésta puede poseer como resultado de su
posición macroscópica o su movimiento. Más bien, se refiere a la energía de las moléculas internas de la sus-
tancia. Debido a su movimiento incesante, todas las moléculas poseen energía cinética de traslación y, excep-
tuando a las moléculas monoatómicas, también poseen energía cinética de rotación y vibración interna. La
1 Estos experimentos y su influencia en el desarrollo de la termodinámica fueron descritos por H. J. Steffens, James Prescott Joule
and the Concept of Energy, Neale Watson Academic Publications, Inc., Nueva York, 1979.
21
02-SmithVanNess.indd 21 8/1/07 12:48:40

22 CAPÍTULO 2. La primera ley y otros conceptos básicos
adición de calor a una sustancia aumenta su actividad molecular provocando un aumento en su energía inter-
na. El trabajo hecho sobre la sustancia puede tener el mismo efecto, como lo demostró Joule.
La energía interna de una sustancia también incluye la energía potencial que resulta de las fuerzas in-
termoleculares (véase la sección 16.1). En una escala submolecular la energía se asocia con los electrones y
los núcleos de los átomos, así como con la energía de enlace que resulta de las fuerzas que mantienen unidos
a los átomos como moléculas. Esta forma de energía se llama interna para distinguirla de las energías cinéti-
ca y potencial, las cuales se asocian con la sustancia debido a su movimiento o posición macroscópica y se
consideran formas externas de energía.
La energía interna no tiene una definición termodinámica concisa. Es un concepto básico en termodi-
námica. No se puede medir de manera directa ni existen medidores de energía interna. Como resultado, los
valores absolutos son desconocidos; sin embargo, esto no es una desventaja en el análisis termodinámico, ya
que sólo se requieren cambios en la energía interna.
2.3 LA PRIMERA LEY DE LA TERMODINÁMICA
El reconocimiento del calor y la energía interna como formas de energía hace posible generalizar la ley de la
conservación de energía mecánica (sección 1.8) que incluye el calor y la energía interna además del trabajo y
las energías externa, potencial y cinética. De hecho, la generalización se puede extender a otras formas, tales
como las energías superficial, eléctrica y magnética. La abrumadora evidencia de la validez de esta generali-
zación ha permitido elevar su categoría al nivel de una ley de la naturaleza, conocida como la primera ley de
la termodinámica. Un enunciado formal es:
Aunque la energía adopta muchas formas, la cantidad total de energía es constante, y

cuando la energía desaparece de una forma, aparecerá simultáneamente en otras formas.
Al aplicar la primera ley a un proceso dado, la esfera de influencia del proceso se divide en dos
partes: el sistema y sus alrededores. La región en la que ocurre el proceso está separada y se conoce como
sistema; todo aquello con lo que el sistema interactúa son los alrededores. Un sistema puede ser de cualquier
tamaño, y sus fronteras pueden ser reales o imaginarias, rígidas o flexibles. Con frecuencia, un sistema se
compone de una sola sustancia; en otros casos puede ser complejo. En cualquier situación, las ecuaciones
termodinámicas se escriben con referencia a un sistema bien definido. Enfocamos nuestra atención al proce-
so de interés particular, así como al equipo y material directamente involucrados en el proceso. De cualquier
modo, la primera ley se aplica al sistema y a sus alrededores, y no sólo al sistema. Para cualquier proceso,
la primera ley requiere:
Δ(Energía del sistema) + Δ (Energía de los alrededores) = 0 (2.1)
donde el operador diferencia “Δ” indica cambios finitos en las cantidades encerradas entre paréntesis. El sis-
tema puede cambiar en su energía interna, en su energía potencial o cinética, así como en las energías poten-
cial o cinética de sus partes finitas.
En el contexto de la termodinámica, el calor y el trabajo representan energía en tránsito a través de las
fronteras que separan al sistema de sus alrededores, que nunca se encuentra almacenada o contenida en el
sistema. Por otra parte, la energía potencial, cinética e interna reside y se almacena en la materia. En la prác-
tica, la ecuación (2.1) adopta formas especiales que son adecuadas para aplicaciones prácticas específicas. El
desarrollo de estas formas y sus posteriores aplicaciones son el tema del resto de este capítulo.

2.4. Balance de energía para sistemas cerrados 23
2.4 BALANCE DE ENERGÍA PARA SISTEMAS CERRADOS
Si la frontera de un sistema impide la transferencia de materia entre éste y sus alrededores, se dice que es un
sistema cerrado, y su masa es necesariamente constante. El desarrollo de los conceptos básicos en termodi-
námica se facilita con un examen cuidadoso de los sistemas cerrados, y por esta razón serán tratados con todo
detalle en las secciones siguientes de este capítulo. En la práctica industrial son más importantes los procesos
en los que la materia cruza las fronteras del sistema como corrientes que entran y salen del equipo de pro-
ceso. A estos sistemas se les llama abiertos, y se abordarán en este capítulo una vez presentado el material
necesario.
Dado que en un sistema cerrado no entran ni salen corrientes, no se transporta energía asociada con la
materia a través de la frontera que divide el sistema de sus alrededores. En ese caso todo intercambio de ener-
gía entre un sistema cerrado y sus alrededores aparecerá como calor y trabajo, y el cambio de energía total de
los alrededores equivaldrá a la energía neta transferida hacia o desde ellos como calor o trabajo. Por lo tanto
el segundo término de la ecuación (2.1) se puede sustituir por
Δ(Energía de los alrededores) = ± Q ± W
El calor Q y el trabajo W siempre se refieren al sistema, y la elección de los signos empleados con estas can-
tidades depende de la dirección de transferencia de energía con respecto al sistema, las cuales se consideran
positivas. La convención moderna de los signos hace que los valores numéricos de ambas cantidades sean po-
sitivos para la transferencia al interior del sistema desde los alrededores. Las cantidades correspondientes
tomadas con referencia a los alrededores, Qalrededores y Walrededores, tienen el signo opuesto, por ejemplo,
Qalrededores = –Q y Walrededores = –W. Con esto entendemos:
Δ(Energía de los alrededores) = Qalrededores + Walrededores = –Q –W (2.2)
La ecuación (2.1) ahora será:2
Δ(Energía del sistema) = Q + W (2.3)
Esta ecuación significa que el cambio en la energía total de un sistema cerrado es igual a la energía neta trans-
ferida como calor y trabajo hacia el sistema.
Los sistemas cerrados a menudo se someten a procesos durante los cuales cambia únicamente la energía
interna del sistema. Para tales procesos, la ecuación (2.2) se reduce a:
ΔU t = Q + W (2.3)
donde Ut es la energía interna total del sistema. La ecuación (2.3) se aplica a los procesos que involucran
cambios finitos en la energía interna del sistema. Para cambios diferenciales:
dU t = dQ + dW (2.4)
2 La convención del signo utilizado aquí es recomendada por la Unión Internacional de Química Pura y Aplicada. De cualquier modo,
la elección original del signo para el trabajo y el que se usa en las primeras cuatro ediciones de este texto es la opuesta, y el lado derecho
de la ecuación (2.2) se escribía entonces como Q – W.

En las ecuaciones (2.3) y (2.4) los símbolos Q, W y U t están relacionados con el sistema entero, que
puede ser de cualquier tamaño y debe estar definido con claridad. Todos los términos requieren expresiones
en las mismas unidades de energía. En el sistema SI la unidad es el joule. Otras unidades en uso son la caloría,
el (pie lbf) y la (Btu).
El volumen total V t y la energía interna total U t dependen de la cantidad de material en un sistema, y se
denominan propiedades extensivas. En contraste, la temperatura y la presión, las principales coordenadas
termodinámicas para fluidos homogéneos puros, son independientes de la cantidad de materia, y se conocen
como propiedades intensivas. Para un sistema homogéneo, un medio alternativo para expresar las propieda-
des extensivas, como V t y U t, es:
V t = mV o V t = nV y U t = mU o U t = nU
donde los símbolos simples V y U representan el volumen y la energía interna de una cantidad unitaria de
materia, ya sea una unidad de masa o un mol. Éstas se denominan respectivamente propiedades específicas o
molares y son intensivas, independientes de la cantidad de materia que en realidad está presente.
Aunque V t y U t para un sistema homogéneo de tamaño arbitrario son propiedades exten-
sivas, el volumen específico y molar V (o densidad) y la energía interna específica y molar
U son intensivas.
Observe que las coordenadas intensivas T y P carecen de contrapartes extensivas.

Para un sistema cerrado de n moles, las ecuaciones (2.3) y (2.4) se escriben ahora como:
Δ(nU) = n ΔU = Q + W (2.5)
d(nU) = n dU = dQ + dW (2.6)
En esta forma, dichas ecuaciones muestran de manera explícita la cantidad de sustancia contenida en el sistema.
Las ecuaciones termodinámicas con frecuencia se escriben para una unidad representativa de la canti-
dad de materia, ya sea unidad de masa o mol. Así para n = 1, las ecuaciones (2.5) y (2.6) serán:
ΔU = Q + W y dU = dQ + dW
La base para Q y W se da a entender siempre por la masa o número de moles asociado con el lado izquierdo
de la ecuación de energía.
La ecuación (2.6) es la fuente fundamental de todas las relaciones de una propiedad que une a la ener-
gía interna con las cantidades mensurables. No representa una definición de la energía interna, ya que ésta no
existe. Tampoco conduce a los valores absolutos para la energía interna. Lo que proporciona es la manera de
calcular los cambios en esta propiedad; sin ésta, la primera ley de la termodinámica no se podría formular. De
hecho, esa ley requiere de una afirmación previa de la existencia de la energía interna, la naturaleza esencial
que se resume en el siguiente axioma:
Existe una forma de energía, conocida como energía interna U, que es una propiedad in-
trínseca del sistema y que se relaciona mediante una función con las coordenadas mensu-
rables que caracterizan a dicho sistema. Para sistemas cerrados, que no están en
movimiento, los cambios en esta propiedad se dan por las ecuaciones (2.5) y (2.6).

2.4. Balance de energía para sistemas cerrados 25
Ejemplo 2.1
Fluye agua en una cascada de 100 m de altura. Considérese a 1 kg de agua como el sistema y supon-
ga que no hay un intercambio de energía con los alrededores.
a) ¿Cuál es la energía potencial del agua en la parte superior de la cascada con respecto a la base
de la misma?
b) ¿Cuál es la energía cinética del agua justo antes de llegar al fondo?
c) Después de que el kg de agua entra al río que corre bajo la cascada, ¿qué cambio ocurre en su
estado?
Solución 2.1
El kg de agua no intercambia energía con los alrededores. Por lo tanto, para cada parte del proce-
so la ecuación (2.1) se reduce a:
Δ(Energía del sistema) = ΔU + ΔE K + ΔE P = 0
a) De la ecuación (1.7), con g igual a su valor estándar,
E P = mzg = 1 kg × 100 m × 9.8066 m s –2

kg m 2
= 980.66 = 980.66 N m = 980.66 J
s2
b) Durante la caída libre del agua no existe un mecanismo para convertir energía potencial o ci-
nética en energía interna. Así, ΔU debe ser cero:
ΔE K + ΔE P = E K 2 – E K 1 + E P 2 – E P 1 = 0
Como una excelente aproximación, sea EK1 = EP2 = 0. Entonces,
E K 2 = E P 1 = 980.66 J
c) Conforme el kg de agua choca con el fondo y se mezcla con el agua que forma parte del río, la
turbulencia resultante tiene el efecto de convertir la energía cinética en energía interna. Durante
este proceso, ΔEP es esencialmente cero, y la ecuación (2.1) será:
ΔU + ΔE K = 0 o ΔU = E K 2 – E K 3
No obstante, suponiendo que la velocidad del río es baja, podemos despreciar a EK3. De este modo,
ΔU = E K 2 = 980.66 J
El resultado global del proceso es la conversión de la energía potencial del agua en energía
interna de la misma. Este cambio en la energía interna se manifiesta por un aumento de la tempe-
ratura del agua. Ya que se requiere una cantidad de energía de 4 184 J kg–1 para aumentar en 1 °C
la temperatura del agua, el incremento en la temperatura es de 980.66/4 184 = 0.234 °C, supo-
niendo que no hay transferencia de calor con los alrededores.

26
26
26 CHAPTER2.
CHAPTER
CHAPTER 2.2.The
TheFirst
The FirstLaw
First Lawand
Law andOther
and OtherBasic
Other BasicConcepts
Basic Concepts
Concepts
2.5
2.5 THERMODYNAMIC
2.5 THERMODYNAMICSTATE
THERMODYNAMIC STATEAND
STATE ANDSTATE
AND STATEFUNCTIONS
STATE FUNCTIONS
FUNCTIONS
2.5 ESTADO TERMODINÁMICO Y FUNCIONES DE ESTADO
The
Thenotation
The notationof
notation ofofEqs.
Eqs.(2.3)
Eqs. (2.3)through
(2.3) through(2.6)
through (2.6)suggests
(2.6) suggeststhat
suggests thatthe
that theinternal-energy
the internal-energyterms
internal-energy termson
terms ononthe theleft
the left
left
La notación de las ecuaciones (2.3) a la (2.6) sugiere que los términos de energía interna en el ladothe
are
are
are different
different
different in
ininkind
kind
kind from
from
from thethe
the quantities
quantities
quantities on
onon the
the
the right.
right.
right. Those
Those
Those on
on on the
thethe leftleft
left reflect
reflect
reflect changes
changes
changes in
ininthe
the izquierdo
son dethermodynamic
una clase diferente
thermodynamic
thermodynamic state
state
state de
of los
ofofthe
the de
thesystem la derecha.
system
system as
asasreflected Los by
reflected
reflected términos
by byits de la izquierda
itsitsthermodynamic
thermodynamic
thermodynamic reflejan among
properties,
properties,
properties, cambios
amongwhich
among en el estado
which
which
termodinámico
are
are del sistema.
aretemperature,
temperature,
temperature, Dichoand
pressure,
pressure,
pressure, estado
anddensity.
and se refleja
density.
density. ForFormediante
For aaahomogeneous
homogeneous
homogeneous sus propiedades
pure
puresubstance
pure termodinámicas
substance
substance we
we weknow knowfrom
know como
fromla tem-
from
peratura, la presión y la densidad. Se sabe por experiencia que para una sustancia pura homogénea,its
experience
experience
experience that
that
that fixing
fixing
fixing two
two
two of
of ofthese
these
these properties
properties
properties also
also
also fixes
fixes
fixes allall
all thethe
the others,
others,
others, andand
and thus
thus
thus determines
determines
determines alitsfijar dos
its
de sus propiedades termodinámicas, automáticamente se establecen las demás y así se determina su estado
thermodynamic
thermodynamic
thermodynamic state.
state.
state. ForFor
For example,
example,
example, nitrogen
nitrogen
nitrogen gas
gasgas at
at at a
a atemperature
temperature
temperature of
of of 300
300300 K
K K and
andand aa a
pressure
pressure
pressure
55 5kPa energy.105 kPa
termodinámico.
of
ofof10
1010 kPa Por
kPa (1 ejemplo,
(1(1bar)
bar)has
bar) hasel
has aaanitrógeno
fixed
fixedspecific
fixed en forma
specific
specific volume
volume
volume de or gas adensity
orordensityuna temperatura
density and
andaaafixed
and fixed
fixed de 300 internal
molar
molar
molar K y una presión
internal
internal energy.
energy.
(1 bar) tiene volumen específico o densidad fijos y una energía interna molar fija. En efecto, tiene un
Indeed,
Indeed,
Indeed, it
it it
hashas
has aa a
complete
complete
complete set
setset of
ofofintensive
intensive
intensive thermodynamic
thermodynamic
thermodynamic properties.
properties.
properties. If
IfIfthis
this
this gas
gasgas is
isisheated
heated
heated ororconjun-
or
to completo de propiedades termodinámicas intensivas. Si este gas se calienta o enfría, se comprimeits
cooled,
cooled,
cooled, compressed
compressed
compressed or
ororexpanded,
expanded,
expanded, and
andand then
then
then returned
returned
returned to
totoits
itsits
initial
initial
initial temperature
temperature
temperature and
andand pressure,
pressure,
pressure, its
its o expan-
de, y aintensive
intensiveproperties
continuación
intensive properties
regresa
properties areare
area restored
surestored to
temperatura
restored tototheir
their
their yinitial
initialvalues.
presión
initial values.
iniciales,
values. They
They
They do
sus
do do notnotdepend
propiedades
not dependon
depend onthe thepast
intensivas
on the pastrecuperarán
past history
history
history sus
valoresof
ofofthethesubstance
iniciales.
the substance nor
noron
Tales propiedades
substance nor ononthe themeans
the means
no
means by
dependen
by bywhich
which
which de itla
ititreaches
reachesaaanterior
historia
reaches agiven
givenstate.
given destate.
state. They
Theydepend
la sustancia
They depend
depend ni deonly onlymedios
los
only on
onon por
present
los cualespresent conditions,
alcanzan
present conditions,
conditions,un estado however
however reached.
determinado,
however reached.
reached. Such
sóloSuch
Such dequantities
quantities
las condiciones
quantities are
areknown
are known
actuales
known as
asasstate
state functions.
functions.
sin importar
state functions. When
cómo When
When two
éstas
twotwo se hayan
ofofthem
them areare held
held at atfixed
fixed values
values for for a a
homogeneous
homogeneous pure
pure substance,
substance, 33 3thethe thermodynamic
thermodynamic state
state
alcanzado. Dichas cantidades son conocidas como funciones de estado. Cuando dos de ellas se mantienen en
of them are held at fixed values for a homogeneous pure substance, the thermodynamic state
valoresof
ofofthe
thesubstance
fijos
the substance
para
substance is
isisfully
una sustancia fullydetermined.
fully determined.
pura homogénea,
determined. ThisThismeans
This 3 se determina
means
means that
thataaastate
that state
state function,
function,such
totalmente
function, such
el
such as
asasspecific
estado specific
specific internal
internal de la
termodinámico
internal
sustancia. Esto significa que una función de estado, tal como la energía interna específica, es una as
energy,
energy,
energy, is
is isa
a a
property
property
property that
that
that always
always
always hashas
has aa a
value;
value;
value; it
it it
maymay
may therefore
therefore
therefore be
be be expressed
expressed
expressed mathematically
mathematically
mathematically as as
propiedad
a a
function
function of of such
such coordinates
coordinates asas temperature
temperature andand pressure,
pressure,
que siempre tiene un valor; por lo tanto, se puede expresar matemáticamente como una función de coordena-
a function of such coordinates as temperature and pressure, or
oror temperature
temperature
temperature and
and
and density,
density,
density, and
and
and its
itsits
values
das tales values
como
values maymay
may be
bebeidentified
la temperaturaidentified
identified ywith
withpoints
presión,
with points
points on onaaagraph.
o temperatura
on graph.y densidad, mientras que sus valores se pueden iden-
graph.
On On thethe other
tificar como puntos en una gráfica.
On the other
other hand,
hand,
hand, thethe
the terms
terms
terms on
onon the
thethe right
rightsides
right sidesof
sides ofofEqs.
Eqs.(2.3)
Eqs. (2.3)through
(2.3) through(2.6),
through (2.6),representing
(2.6), representing
representing
heat
heat and
and work
work quantities,
quantities, areare not
not properties;
properties; they
they
Por otra parte, los términos en el lado derecho de las ecuaciones (2.3) a la (2.6) representan
heat and work quantities, are not properties; they account
account
account for
for
for thethe
the energy
energy
energy changes
changes
changes that
thatoccur
that occur
occur cantidades
ininthe
the surroundings.
surroundings. They
They depend
depend on on thethe nature
nature of of the
de calor y trabajo, que no son propiedades; consideran los cambios de energía que ocurren en los alrededores.
in the surroundings. They depend on the nature of the
the process,
process,
process, andand
and maymay
may bebe
be associated
associated
associated with
with
with
Dependenareas
areas
areas derather
rather than
la naturaleza
rather thanpoints
than points
pointsdel on onaaagraph,
proceso
on graph,
y pueden
graph, as
asassuggested
suggested by
estar asociados
suggested bybyFig. Fig.1.3.
Fig. 1.3.Although
con
1.3. Although
áreas
Although antestime time
queis
time con
is isnotnot
not aaathermo-
puntos thermo-
thermo-en la gráfica
dynamic
dynamic coordinate,
coordinate, the
the passage
passage of of time
time is is
inevitable
inevitable
como lo sugiere la figura 1.3. Aunque el tiempo no es una coordenada termodinámica, el transcurso
dynamic coordinate, the passage of time is inevitable whenever
whenever
whenever heatheat
heat is
isis
transferred
transferred
transferred or
ororwork
workis
work is tiem-
isdel
accomplished.
accomplished.
po es inevitable cada vez que se transfiere calor o se realiza un trabajo.
accomplished.
TheThedifferential
La diferencial
The differential
de una función
differential of
ofofaaastate
state
statedefunction
function
estado
function represents
represents
representa
represents un an
anan infinitesimal
infinitesimal
cambio change
infinitesimal
infinitesimal change
change in
ininsu
en its
itsits
value.
value.
valor.
value. LaInte-
Inte-
integración
Inte-
gration
gration ofof such
such a a
differential
differential results
results in ina a
finite
finite difference
difference
de esta diferencial da como resultado una diferencia finita entre dos de sus valores, por ejemplo:
gration of such a differential results in a finite difference between
between
between two
twotwo of
ofofitsits
its values,
values,
values, e.g.:
e.g.:
e.g.:
��PP2P2 ��VV2V2
22 22
dddPPP= ==PP2P 2 −
2− − P
P P
11 =
1= = �P
�P�P and
andy
and dddVVV= ==VV2V2 2− −−VV1V1 1===�V �V�V
PP11P11 VV11V11
Las diferenciales
The
The de calor
Thedifferentials
differentials
differentials ofofyheat
of trabajo
heat andno
heatand
and sonare
work
work
work cambios
arenot
are not sino cantidades
notchanges,
changes,
changes, but
butbutare infinitesimales.
areinfinitesimal
are infinitesimal
infinitesimal Cuando
amounts.
amounts.
amounts. se integran,
When
When
When inte- estas
inte-
inte-
diferenciales
grated,
grated,no
grated, presentan
these
these
these cambios
differentials
differentials
differentials give
givefinitos,
give not sinochanges,
notfinite
not finite
finite cantidades
changes,but
changes, but
but finitas.
finite Así,
finiteamounts.
finite amounts.Thus,
amounts. Thus,
Thus,
��
QQ=
dddQ ==QQQ y
and
and
and dWW=
ddW ==W WW
Para un For
Forsistema
For aaaclosed
closedcerrado
closed system
system sometido
system undergoing
undergoing al mismo
undergoing the
thesame
the cambio
same
same change de in
change
change estado
ininstate por
state
state by
by medio
severalde
byseveral
several diferentes
processes,
processes,
processes, procesos, los
experi-
experi-
experi-
experimentos
ment
ment
ment shows muestran
shows
shows that
that queamounts
the
that thethe las cantidades
amounts
amounts of heatde
of of
heat
heat andcalor
and
and work y trabajo
work
work requiredrequeridas
required
required differ
differfor
fordifieren para
different
different
differ for different los distintos
processes,
processes,
processes, but
but that
but procesos,
that
that
pero que
thelasum
the
the
sumsuma
sum QQ+Q+ +
QW W+W
W isis es la
the
is thethe
samemisma
same
same for
for para
all
for allallprocesses.
processes.
processes. This isÉste
todo proceso.
This
This isis
the
the es el fundamento
basis
basis
the basis for
for para of
identification
identification
for identification la internal
of ofidentificación
internal
internal en- de la
en-
en-
energíaergy
interna
ergy
ergy asasaaacomo
as state
state función
statefunction.
function.
function. de
The
Theestado.
The sameEl
same
same mismo
value
value
value of
ofof�U
�U
�U tt is
valor isde ΔUby
t isgiven
given
given t by
byestá
Eq. dado
Eq.
Eq. (2.3) por
(2.3)
(2.3) la ecuación
regardless
regardless
regardless of (2.3)
ofofthe
the
the independien-
process,
process,
process,
tementeprovided
del proceso,
provided
provided only
only siempre
that
that
only that the
the que el cambio
change
change
the change inin
thethe en el sistema
system
system
in the system isis
between ocurra
between
is between theentre
the
the samelos
same
same mismos
initial
initial
initial and
and estados
final
final
and final inicial y final.
states.
states.
states.
33For
3 For
systems
systems
more
more
complex
complex
than
than
aa simple
asimple
simple
homogeneous
homogeneous
pure
pure
substance,
substance,
thethe
number
number
of
For systems more complex than homogeneous pure substance, the number ofof
state
state
state functions
functions
functions that
that
that must
must
must be
bebe
arbitrarily
arbitrarilyspecified
arbitrarily specifiedin
specified ininorder
orderto
order totodefine
definethe
define thestate
the stateof
state ofofthethesystem
the systemmay
system maybe
may bebedifferent
differentfrom
different fromtwo.
from two.The
two. Themethod
The methodof
method ofofdetermining
determining
determining
3 this
Para this
losnumber
this number
sistemas
number isisis
thethe
más
the subject
subject of
complejos
subject ofof
Sec.
Sec.
que2.7.
Sec. 2.7.simple sustancia pura homogénea, el número de funciones de estado que deben especifi-
una
2.7.
carse en forma arbitraria con la finalidad de definir el estado del sistema puede ser distinto de dos. El método para determinar este número
es el tema de la sección 2.7.

2.5. Thermodynamic State and State Functions 27
2.5. Estado termodinámico y funciones de estado 27

Example 2.2
A gas is confined in a cylinder by a piston. The initial pressure of the gas is 7 bar,
Ejemplo
and the2.2
volume is 0.10 m3 . The piston is held in place by latches in the cylinder wall.
Un gasThe
estáwhole apparatus
confinado is placed
en un cilindro porinuna pistón.
total vacuum. What
La presión is the
inicial del energy
gas es dechange
7 bar, of the
y el volumen
3
es 0.10 m . El pistón se mantiene en su lugar mediante seguros en las paredes del cilindro.toTodo el
apparatus if the restraining latches are removed so that the gas suddenly expands
aparatodouble its initialenvolume,
se encuentra un vacíothe piston
total. striking
¿Cuál es el other
cambiolatches at the end
en la energía del of the process?
aparato si se eliminan los
seguros restrictivos, permitiendo así que el gas se expanda de manera repentina al doble de su volu-
men original, y al final 2.2
Solution del proceso el pistón choca con otros seguros?
SoluciónBecause
2.2 the question concerns the entire apparatus, the system is taken as the
gas, piston, and cylinder. No work is done during the process, because no force
Dado que la pregunta
external to thetiene quemoves,
system ver conand
todonoelheat
aparato se tomaráthrough
is transferred como sistema el gas,sur-
the vacuum el pistón y
el cilindro. Durante el proceso no se realiza trabajo, ya que no se aplica
rounding the apparatus. Hence Q and W are zero, and the total energy of the una fuerza externa al
sistema,system
ni se transfiere
does not change. Without further information we can say nothing abouty W son
calor del vacío hacia los alrededores del aparato. Por lo tanto, Q
cero y lathe
energía total del
distribution ofsistema
energy no cambia.
among Sin mayor
the parts of theinformación
system. Thisnomay es posible
well bedecir nada más
differ-
acerca de la distribución de la energía
ent than the initial distribution. entre las partes del sistema. Esto puede ser diferente de la
distribución inicial.
Example 2.3
Ejemplo 2.3 described in Ex. 2.2 is repeated, not in a vacuum but in air at atmo-
If the process
spheric pressure of 101.3 kPa, what is the energy change of the apparatus? Assume
Si se repite el proceso
the rate of heatdescrito en elbetween
exchange ejemplo 2.2,
the no en el vacío
apparatus andsino
theensurrounding
el aire a unaair
presión atmosfé-
is slow
rica de compared
101.3 kPa,with
¿cuál
theesrate
el cambio enthe
at which la energía
processdel aparato? Suponga que la rapidez de intercam-
occurs.
bio de calor entre el aparato y el aire de los alrededores es lenta en comparación con la rapidez con la
que ocurre el proceso.
Solution 2.3
SoluciónThe
2.3system is chosen as before, but here work is done by the system in pushing
Se eligeback the atmosphere.
el mismo It is evaluated
sistema que antes, pero ahoraaselthe product
trabajo of the force
es realizado ofsistema
por el atmospheric
al empujar el
pressure on the back side of the piston F = P A and the displacement
pistón de regreso a la atmósfera. Este trabajo se evalúa como el producto de la fuerza ejercida
atm of the por la
�l =en�V t /A. Here, A is the area of the piston and �V t is the volume
presión piston
atmosférica el lado opuesto del pistón F = Patm A y el desplazamiento del mismo, Δ l =
ΔV t / A. change
Aquí, A of
es the gas.del
el área This
pistón y ΔV tdone
is work es el by the system
cambio on thedelsurroundings,
de volumen gas. Esto es eland is a realiza-
trabajo
negative quantity; thus,
do por el sistema sobre los alrededores, y es una cantidad negativa; en estos términos,
kN
W = −F �l = −Patm �V t = −(101.3)(0.2 − 0.1) kPa m3 = −10.13 2 m3
m
or W = −10.13 kN m = −10.13 kJ
o W = –10.13 kN m = –10.13 kJ
Heat transfer between the system and surroundings is also possible in this case,
En este but
casothetambién
problem esisposible
workedlafortransferencia de calor
the instant after entre el has
the process sistema y susand
occurred alrededores,
before pero
el problema está planeado
appreciable para elhas
heat transfer instante después
had time to takedeplace.
que elThus
proceso
Q is ha ocurrido
assumed y antes
to be zero de que
se tengainelEq.
tiempo
(2.2),suficiente
giving para que se presente una transferencia de calor apreciable. Así, su-
poniendo que Q es cero en la ecuación (2.2), obtenemos
�(Energy of the system) = Q + W = 0 − 10.13 = −10.13 kJ
Δ(Energía del sistema) = Q + W = 0 – 10.13 = –10.13 kJ
The total energy of the system has decreased by an amount equal to the work done
La energía total
on the del sistema ha disminuido en una cantidad igual al trabajo realizado sobre los
surroundings.
alrededores.

Ejemplo 2.4
En la figura 2.1, cuando se lleva un sistema del estado a al b a lo largo de la trayectoria acb, fluyen
100 J de calor hacia el sistema y éste realiza 40 J de trabajo.
a) ¿Cuánto calor fluye hacia el sistema a lo largo de la trayectoria aeb, si el trabajo hecho por el
sistema es de 20 J?
b) El sistema regresa de b a a siguiendo la trayectoria bda. Si el trabajo hecho sobre el sistema es

de 30 J, ¿el sistema absorbe o libera calor? ¿Cuánto?
b
c
d
Figura 2.1: Diagrama para el ejemplo 2.4. P
Solución 2.4
Supóngase que el sistema se modifica sólo en su energía interna y que se puede aplicar la ecua-
ción (2.3). Para la trayectoria acb, y desde luego para cualquier trayectoria que conduzca de a
hacia b,
t = Q
ΔUba acb + Wacb = 100 – 40 = 60 J
a) Para la trayectoria aeb,
t = 60 = Q
ΔUba aeb + Waeb = Q aeb – 20 de donde Q aeb = 80 J
b) Para la trayectoria bda,

t = – ΔU t = – 60 = Q
ΔUba ba bda + W bda = Q bda + 30
y Q bda = –60 – 30 = –90 J
En consecuencia, se transfiere calor desde el sistema hacia los alrededores.

2.6. Equilibrio 29
2.6 EQUILIBRIO
Equilibrio es una palabra que denota una condición estática, es decir, la ausencia de un cambio. En termodi-
námica significa no sólo la ausencia de un cambio sino de cualquier tendencia hacia el cambio en una escala
macroscópica. De esta manera existe un sistema en equilibrio bajo la condición de que no puede ocurrir en él
ningún cambio de estado. Puesto que cualquier tendencia hacia el cambio es causada por una fuerza impulso-
ra de uno u otro tipo, la ausencia de estas tendencias también indica la carencia de cualquier fuerza impulsora.
Por tanto, en un sistema en equilibrio todas las fuerzas están en un balance exacto. Si en realidad ocurre un
cambio en un sistema que no está en equilibrio, éste depende tanto de la resistencia como de la fuerza impul-
sora. Muchos sistemas experimentan cambios no mensurables aun bajo la influencia de grandes fuerzas im-
pulsoras, porque su resistencia al cambio es muy grande.
Las diferentes clases de fuerzas impulsoras tienden a producir distintos tipos de cambios. Por ejemplo,
las fuerzas mecánicas no equilibradas como la presión en un pistón llegan a ocasionar transferencia de energía
en forma de trabajo; las diferencias de temperatura suelen producir flujo de calor; los gradientes en el poten-
cial químico tienden a originar que las sustancias sean transferidas de una fase a otra. En equilibrio, tales
fuerzas están balanceadas.
En muchas aplicaciones de la termodinámica no interesan las reacciones químicas. Por ejemplo, una
mezcla de hidrógeno y oxígeno en condiciones ordinarias no está en equilibrio químico, debido a la gran
fuerza impulsora para la formación de agua. Sin embargo, si la reacción química no se ha iniciado, el sistema
puede estar en equilibrio térmico y mecánico a largo plazo, y sólo se analizarán los procesos puramente físi-
cos sin considerar las posibles reacciones químicas.
2.7 REGLA DE LAS FASES
Como se ha indicado con anterioridad, el estado de un fluido homogéneo puro se determina cada vez que se
dan valores definidos a dos propiedades termodinámicas intensivas. En contraste, cuando dos fases están en
equilibrio, el estado del sistema se establece al especificar sólo una propiedad. Por ejemplo, una mezcla de
vapor y agua líquida en equilibrio a 101.33 kPa sólo puede existir a 100 °C. Es imposible cambiar la tempe-
ratura sin modificar también la presión, si se quiere que el vapor y el agua líquida continúen existiendo en
equilibrio.
Para sistemas de fases múltiples en equilibrio, el número de variables independientes que deben fijarse
en forma arbitraria a fin de establecer su estado intensivo se proporciona por la célebre regla de las fases de J.
Willard Gibbs,4 quien la dedujo por medio de un razonamiento teórico en 1875. Aquí se presenta sin compro-
bación, en la forma que se aplica para sistemas que no tienen reacciones químicas:5
F=2–p +N (2.7)
donde p es el número de fases, N es el número de especies químicas y F representa los grados de libertad del
sistema.
4Josiah Willard Gibbs (1839-1903), físico matemático estadounidense.

5La justificación de la regla de las fases para un sistema que no contiene reacciones químicas está dada en la sección 10.2, mientras
que la regla de las fases para sistemas con reacciones químicas se considera en la sección 13.8.

El estado intensivo de un sistema en equilibrio se establece cuando su temperatura, presión y composi-

ciones de todas las fases se encuentran fijas. Debido a eso, éstas son variables de la regla de las fases, pero no
todas son independientes. La regla de las fases proporciona el número de variables de este conjunto, las cuales
deben especificarse de manera arbitraria para fijar todas las demás variables restantes de la regla de las fases,
y con ello el estado intensivo del sistema.
Una fase es una región homogénea de materia. Un gas o mezcla de gases, un líquido o una solución lí-
quida y un sólido cristalino son ejemplos de fases. Una fase no necesita ser continua; son ejemplos de fases
discontinuas un gas disperso como burbujas en un líquido, un líquido disperso como gotas en otro líquido con
el cual no es miscible, y cristales de un sólido dispersos ya sea en un gas o en un líquido. En cada caso, una
fase dispersa está distribuida en todas las partes de una fase continua. Siempre ocurre un cambio repentino de
las propiedades en las fronteras entre las fases. Pueden coexistir varias fases, pero deben estar en equilibrio
para aplicar la regla de las fases. Un ejemplo de un sistema de tres fases en equilibrio es una solución salina
acuosa que está saturada en su punto de ebullición con un exceso de cristales de sal. Las tres fases (π = 3) son
la sal cristalina, la solución acuosa saturada y el vapor generado en el punto de ebullición. Las dos especies
químicas (N = 2) son agua y sal. Para este sistema, F = 1.
Las variables de la regla de las fases son propiedades intensivas, las cuales son independientes de la
extensión del sistema y de las fases individuales. De este modo, la regla de las fases proporciona la misma
información tanto para sistemas grandes como para sistemas pequeños y para cantidades diferentes de fa-
ses presentes. Además, sólo las composiciones de fases individuales son variables de las reglas de las fases.
Las composiciones totales o globales no son variables de la regla de las fases cuando ésta presenta más de
una fase.
El número mínimo de grados de libertad para cualquier sistema es cero. Cuando F = 0 el sistema es
invariante; la ecuación (2.7) se transforma en p = 2 + N. Este valor de p es el número máximo de fases que
pueden coexistir en equilibrio para un sistema que contiene N especies químicas. Cuando N = 1, este número
es 3, característico de un punto triple (véase la sección 3.1). Por ejemplo, el punto triple del agua, donde el
líquido, el vapor y la forma común de hielo existen juntos en equilibrio, se presenta a 0.01 °C y 0.0061 bar.
Cualquier cambio de estas condiciones provoca la desaparición de al menos una de estas fases.
Ejemplo 2.5
¿Cuántos grados de libertad tienen cada uno de los siguientes sistemas?
a) Agua líquida en equilibrio con su vapor.
b) Agua líquida en equilibrio con una mezcla de vapor de agua y nitrógeno.
c) Una solución líquida de alcohol en agua en equilibrio con su vapor.
Solución 2.5
a) El sistema contiene una sola especie química que existe en dos fases (una líquida y otra gaseo-
sa). Así,
F = 2 – π+ N = 2 – 2 + 1 = 1

2.8. El proceso reversible 31
Este resultado está de acuerdo con el hecho de que para una presión de agua dada sólo se tiene un
punto de ebullición. Es posible especificar la temperatura o la presión, no ambas, para un sistema
que contiene agua en equilibrio con su vapor.
b) En este caso están presentes dos especies químicas. Hay otra vez dos fases.
Ahora, F = 2 – π+ N = 2 – 2 + 2 = 2
La adición de un gas inerte a un sistema de agua en equilibrio con su vapor cambia las caracterís-
ticas del sistema. Ahora la temperatura y la presión pueden variar en forma independiente, pero
una vez que se fijan el sistema descrito puede existir en equilibrio sólo para una composición
particular de la fase vapor. (Si se considera que la solubilidad del nitrógeno en agua es desprecia-
ble, la fase líquida es agua pura.)
c) Aquí N = 2, y π = 2, y
F = 2 – π+ N = 2 – 2 + 2 = 2
Las variables de la regla de las fases son la temperatura, la presión y las composiciones de la
fase. Las variables de la composición son las fracciones de masa o de moles de las especies en
una fase, y deben sumar la unidad para cada fase. De esa forma, si se fija la fracción molar de
agua en la fase líquida, la fracción molar de alcohol se fija automáticamente. Estas dos composi-
ciones no se especifican en forma arbitraria.
2.8 EL PROCESO REVERSIBLE
El desarrollo de la termodinámica se facilita por la introducción de una clase especial de proceso en sistemas
cerrados que se caracteriza como reversible:
Un proceso es reversible cuando la dirección puede ser invertida en cualquier punto por
un cambio infinitesimal en las condiciones externas.
Expansión reversible de un gas
La naturaleza de los procesos reversibles se ilustra con el ejemplo de una expansión simple de gas en una
combinación pistón/cilindro. El aparato que se muestra en la figura 2.2 se supone que está en un espacio va-
cío. Se elige como sistema el gas retenido en el interior del cilindro; todo lo demás son los alrededores. Los
procesos de expansión ocurren cuando se retira masa del pistón. Con la finalidad de simplificarlo, se supone
que el pistón se desliza dentro del cilindro sin presentar fricción, y que ni el pistón ni el cilindro absorben o
transmiten calor. Además, ya que la densidad del gas en el cilindro es baja y que la masa del gas es pequeña,
se ignoran los efectos de la gravedad sobre el contenido del cilindro. Esto significa que los gradientes de pre-
sión inducidos por la gravedad en el gas son muy pequeños en comparación con su presión, y que los cambios
en la energía potencial del gas son despreciables en comparación con los cambios de la energía potencial del
montaje del pistón.

Figura 2.2: Expansión de un gas.

Δl
El pistón de la figura 2.2 confina el gas a una presión suficiente para equilibrar el peso del pistón y todo
lo que éste soporta. Tal condición de equilibrio para el sistema no debe tender al cambio. Se debe eliminar
masa del pistón para que se eleve. Primero suponga que una masa m se desliza repentinamente del pistón a
una repisa (al mismo nivel). El pistón se acelera hacia arriba y alcanza su velocidad máxima en el punto en
que la fuerza ascendente sobre el pistón se equilibra con su peso. A continuación el momentum del pistón lo
lleva a su nivel máximo donde invierte la dirección. Si el pistón se mantuviera en esta posición de elevación
máxima, su energía potencial aumentaría a un valor muy cercano al trabajo realizado por el gas durante el
recorrido inicial. Sin embargo, cuando no existe restricción, el pistón oscila con la disminución de la ampli-
tud, hasta alcanzar finalmente una nueva posición de equilibrio a un nivel arriba de su posición inicial.
Las oscilaciones del pistón se amortiguan, ya que la naturaleza viscosa del gas de manera gradual con-
vierte el movimiento ordenado global de las moléculas en un movimiento molecular caótico. Este proceso
disipativo transforma parte del trabajo hecho inicialmente por el gas para elevar el pistón, de nuevo en energía
interna del gas. Una vez que se inicia el proceso, ningún cambio infinitesimal en las condiciones externas
puede invertir su dirección; el proceso es irreversible.
Todos los procesos que se llevan a cabo en un tiempo finito con sustancias reales se acompañan en
cierto grado por efectos disipativos de una u otra clase y, por lo tanto, todos son irreversibles. No obstante, se
pueden imaginar procesos que están libres de efectos disipativos. Para el proceso de expansión de la figura
2.2, tales efectos tienen su origen en el retiro repentino de una masa finita del pistón. El desequilibrio resul-
tante de fuerzas que actúan en el pistón causa su aceleración y conduce a su subsecuente oscilación. El retiro
repentino de pequeñas cantidades de masa reduce pero no elimina este efecto disipativo. Incluso el retiro de
una masa infinitesimal lleva a que el pistón oscile con una amplitud infinitesimal y, por lo tanto, a un efecto
disipativo. Sin embargo, es posible imaginar un proceso en donde se retiran pequeñas cantidades de masa una
tras otra con una rapidez tal que la elevación del pistón es continua, con pequeñas oscilaciones sólo al final
del proceso.

El caso límite del retiro de una sucesión de masas infinitesimales del pistón se aproxima cuando las
masas m de la figura 2.2 son sustituidas por una pila de polvo, soplando en una línea de corriente muy fina
desde el pistón. Durante este proceso, el pistón se eleva con una rapidez uniforme pero muy lenta, y el polvo
se almacena siempre a niveles más altos. El sistema nunca se desplaza más que de manera diferencial, ya sea
desde su equilibrio interno o del equilibrio con sus alrededores. Si se detiene el traslado de polvo desde el
pistón y se invierte la dirección de la transferencia del polvo, el proceso invierte su dirección y continúa a la
inversa a lo largo de su trayectoria original. Al final, tanto el sistema como sus alrededores regresan virtual-
mente a sus condiciones iniciales. El proceso original se aproxima a la reversibilidad.
Sin la suposición de un pistón sin fricción no podemos suponer un proceso reversible. Si el pistón se
pega debido a la fricción, se debe eliminar una masa finita antes de que se libere el pistón. De esta forma, no
se mantiene la condición de equilibrio que es necesaria para la reversibilidad. Por otro lado, la fricción entre
las dos partes deslizantes es un mecanismo para la disipación de la energía mecánica en energía interna.
Este análisis se ha centrado en un simple proceso de sistema cerrado, la expansión de un gas en un ci-
lindro. El proceso opuesto, la compresión de un gas en un cilindro, se describe de la misma manera. De cual-
quier modo, hay muchos procesos que son manejados por el desequilibrio de fuerzas distintas de las
mecánicas. Por ejemplo, ocurre flujo de calor cuando existe una diferencia de temperatura, la electricidad
fluye bajo la influencia de una fuerza electromotriz, y las reacciones químicas suceden porque existe un po-
tencial químico. En general, un proceso es reversible cuando la fuerza impulsora neta sólo es de tamaño dife-
rencial. Así, el calor se transfiere en forma reversible cuando fluye desde un objeto finito a temperatura T
hacia otro objeto a la temperatura T – dT.
Reacción química reversible
El concepto de una reacción química reversible se ilustra con la descomposición del carbonato de calcio que,
al ser calentado, forma óxido de calcio y dióxido de carbono gaseoso. En equilibrio, para una temperatura
dada el sistema ejerce una presión de descomposición específica de CO2. Cuando la presión cae por abajo de
este valor, se descompone el CaCO3. Supongamos que a un cilindro se le adapta un pistón sin fricción que
contiene CaCO3, CaO y CO2 en equilibrio. Se le sumerge en un baño a temperatura constante, como se mues-
tra en la figura 2.3, y el equilibrio térmico asegura la igualdad de la temperatura del sistema con la del baño.
La temperatura se ajusta a un valor tal que la presión de descomposición es suficiente para equilibrar el peso
sobre el pistón, una condición de equilibrio mecánico. La reacción química se mantiene balanceada (en equi-
librio) por la presión del CO2. Cualquier cambio de las condiciones, incluso de manera ligera, altera el equili-
brio y provoca que la reacción avance en una u otra dirección.
Si el peso se aumenta en forma diferencial, la presión del CO2 se incrementa de manera diferencial, y
el CO2 se combina con el CaO para formar CaCO3, permitiendo que la pesa baje lentamente. El calor gene-
rado por esta reacción incrementa la temperatura en el cilindro, y el calor fluye hacia el baño. La disminución
diferencial del peso sobre el pistón provoca una cadena opuesta de eventos. Se obtienen los mismos resulta-
dos si la temperatura del baño aumenta o disminuye. Si la temperatura del baño aumenta en forma diferencial,
fluye calor hacia el interior del cilindro y se descompone el carbonato de calcio. El CO2 generado ocasiona
que la presión aumente en forma diferencial, lo cual origina que se eleven el pistón y el peso. Esto continúa
hasta que se descompone totalmente el CaCO3. El proceso es reversible, ya que el sistema nunca se desplaza
del equilibrio más que de forma diferencial, y sólo una disminución diferencial de la temperatura del baño
hace que el sistema regrese a su estado inicial.

34 34 CAPÍTULO
CHAPTER 2. The 2. LaLaw
First primera ley y otros
and Other Basicconceptos
Concepts básicos
w
w
T CO2
CO2
Figura 2.3: Reversibilidad de una reacción química. T
Figure 2.3: Reversibility of a chemical reaction.
CaCO3 �CaCO
CaO 3  CaO
Termostato
Thermostat
Some chemical reactions can be carried out in an electrolytic cell, and in this case they
Algunas
may bereacciones químicas
held in balance seapplied
by an realizanpotential
en una celda electrolítica,
difference. If suchy en esteconsists
a cell caso pueden mantenerse
of two elec- en
equilibrio al aplicar una diferencia de potencial. Si esta celda se compone de dos electrodos, uno
trodes, one of zinc and the other of platinum, immersed in an aqueous solution of hydrochloric de zinc y otro
de platino,
acid,sumergidos enthat
the reaction unaoccurs
solución
is: acuosa de ácido clorhídrico, la reacción que ocurre es:
Zn + 2HCl � H2 + ZnCl2
La celdaThe
se mantiene
cell is heldbajo condiciones
under fijas deof
fixed conditions temperatura
temperature y presión, y los electrodos
and pressure, están conectados
and the electrodes are con- exter-
namentenected
a un potenciómetro. Si la fuerza electromotriz
externally to a potentiometer. producida
If the electromotive porproduced
force la celda se
byequilibra
the cell isenexactly
forma exacta
por la diferencia
balanced byde potencial del difference
the potential potenciómetro,
of thelapotentiometer,
reacción se mantiene en equilibrio.
the reaction is held inEs posible hacer que
equilibrium.
la reacción
The proceda
reaction enmaysentido directo
be made disminuyendo
to proceed un pocodirection
in the forward la diferencia de potencial
by a slight opuesta,
decrease y se puede
in the op-
revertir posing
mediante un aumento
potential correspondiente
difference, and it may be enreversed
la diferencia de potencial deincrease
by a corresponding la fem de
in la
thecelda.
potential
difference above the emf of the cell.
Resumen de lasRemarks
Summary observaciones en los procesos
on Reversible Processesreversibles
A reversible
Un proceso process:
reversible:
• Es sin• fricción.
Is frictionless.
• Nunca
• se
Is sale
neverdel equilibrio
more más que de una
than differentially manera
removed diferencial.
from equilibrium.
• Recorre una sucesión

• Traverses de estados
a succession ofde equilibrio.states.
equilibrium
• Está controlado
• Is drivenpor fuerzaswhose
by forces cuyo desequilibrio tiene magnitud
imbalance is differential diferencial.
in magnitude.
• Se puede invertir
• Can en cualquier
be reversed at any punto mediante
point by un cambio
a differential diferencial
change en conditions.
in external las condiciones externas.
• Cuando se invierte, vuelve a trazar su trayectoria y restaura el estado inicial del sistema y de sus alre-
• When reversed, retraces its forward path, and restores the initial state of system and
dedores.
surroundings.
Una ecuación deducida

An equation en lainsección
derived 1.7gives
Sec. 1.7 proporciona
the work el of
trabajo de compresión
compression o expansión
or expansion de un gas
of a gas
que es causado porthe
caused by el differential
desplazamiento diferencial
displacement of de un pistón
a piston in a en un cilindro:
cylinder:
ddW = –−P
W = Vt
P ddV (1.2) (1.2)

2.8.
2.8. The
The Reversible
Reversible Process
Process 35
35
The
The work
work done
done on
on the
the system
system is is given
given byby this
this equation
equation only only when
when certain
certain characteristics
characteristics ofof
El trabajo
the hecho sobre el sistema se da por esta ecuación sólo cuando
the reversible process are realized. The first requirement is that the system be
reversible process are realized. The first requirement is thatse efectúan
the system ciertas
no características
be no more
more than
than del
procesoinfinitesimally
reversible. El primer
displacedrequisito
from a es que
state el
of sistema
internal se desplace
equilibrium, sólo en forma
characterized
infinitesimally displaced from a state of internal equilibrium, characterized by uniformity of infinitesimal
by uniformity de un
of estado
de equilibrio internoand
temperature
temperature caracterizado
and pressure.
pressure. The
Theporsystem
la uniformidad
system then
then always
alwaysde lahas temperatura
has an y la presión.
an identifiable
identifiable set
set of El sistemainclud-
of properties,
properties, siempre tiene
includ-
un conjunto
ing identificable
pressure P. de
The propiedades,
second incluyendo
requirement is la
that presión
the P.
system El segundo
be
ing pressure P. The second requirement is that the system be no more than infinitesimallyno more requisito
than es que el sistema no
infinitesimally
se desplace más
displaced que en forma infinitesimal del equilibrio mecánico con sus
displaced from mechanical equilibrium with its surroundings. In this event, the internal pres-
from mechanical equilibrium with its surroundings. In thisalrededores.
event, the En este
internal caso, la pre-
pres-
sión interna
sure P is never more than minutely out of balance with the external force, and we may make la sus-
sure P
P nunca
is neverestá más
more que
than un poco
minutely fuera
out ofde equilibrio
balance with con
the la fuerza
external externa,
force, andy se
we puede
may hacer
make
tituciónthe
F=
the PA, que transforma
substitution
substitution F =
F = P PA la ecuación
A that
that transforms
transforms (1.1)
Eq.en(1.1)
Eq. la (1.2).
(1.1) into Los(1.2).
into Eq.
Eq. procesos
(1.2). para los
Processes
Processes forque
for se reúnen
which
which these estos
these
requisitos se conocen
requirements como
are met mecánicamente
are said to be reversibles
mechanically y se puede
reversible, integrar
and Eq.
requirements are met are said to be mechanically reversible, and Eq. (1.2) may be integrated:la ecuación
(1.2) may (1.2):
be integrated:
�� V tt
V22
t
= −
W =− t P
W Vt
P dd V (1.3)
(1.3) (1.3)
V
V11t
The reversible
The reversible process
reversible esprocess is ideal in
in that itit produces the
the best possible result. It
It represents aa
El proceso ideal is
enideal thatde
el sentido produces
que produce best
el possible
mejor result.posible.
resultado represents
Representa un
limit
limit to
to the
the performance
performance of
of actual
actual processes,
processes, but
but is
is never
never fully
fully realized.
realized. An
An initial
initial calculation
calculation
límite en el desempeño de los procesos reales, ya que nunca se puede realizar por completo. Con frecuencia
of work is
is often made for aa reversible process, because the
the choice
choice is
islabetween such
such aa calculation
se hace of
unwork
cálculo often made
inicial del for
trabajoreversible
para unprocess,
procesobecause
reversible, porque between
opción estriba calculation
entre realizar o no
and
and no
no calculation
calculation at
at all.
all. The
The reversible
reversible work
work as
as the
the limiting
limiting value
value may
may be
be combined
combined with an
withapropiadas
an
estos cálculos. El trabajo reversible con el valor limitante puede combinarse con las eficiencias
appropriate
appropriate efficiency
efficiency to
to yield
yield aa reasonable
reasonable approximation
approximation to
to the
the work
work of
of an
an actual
actual process.
process.
para producir aproximaciones razonables del trabajo de los procesos reales.
Example 2.6
Ejemplo
A 2.6 piston/cylinder
A horizontal
horizontal piston/cylinder arrangement
arrangement is
is placed
placed in
in aa constant-temperature
constant-temperature bath.
bath.
The
The piston slides
slides in
pistonhorizontal
Una combinación in the
the cylinder
cylinder with
with negligible
de pistón/cilindro negligible
se coloca en friction,
friction,
un bañoand
anda an
an external
external force
temperatura force holds
holds El
constante. itit pistón
in place against an initial gas pressure of 14 bar. The initial gas volume is 0.03 m 33. The
in place against an initial gas pressure of 14 bar. The initial gas volume is
se desliza en el cilindro con una fricción insignificante, y una fuerza externa lo mantiene en su lugar en 0.03 m . The
contra external
external
de force on
on the
forceinicial
la presión delpiston
the piston
gas que is
is reduced
es de 14gradually,
reduced gradually, and
and the
bar. El volumen the gas expands
gas del
inicial gas esisothermally
expands 0.03 m3. La fuerza
isothermally
as
as its
its volume
volume
externa sobre el pistón doubles.
doubles. If
If the
the volume
volume of
of the
the gas
gas is
is related
related to
to its
its
se reduce de manera gradual y el gas se expande de forma isotérmica pressure
pressure so
so that
that the
theal doble
product
product PV
PV
tt is constant, what is the work done by the gas in moving the external
de su volumen. Si el volumen del gas está relacionado con su presión, de modo que el producto PV t es
is constant, what is the work done by the gas in moving the external
force?
force?
constante, ¿cuál es el trabajo hecho por el gas al cambiar la fuerza externa?
¿Cuánto How
How much
much
trabajo sework
work would
would
hubiera be
be done
realizado si laififfuerza
done the
the external
externaforce
external force were suddenly
suddenly reduced
were repentinamente
se reduce reduceda la to
to
mitad de
half
half its
its initial
initial value
value instead
instead of
of being
being gradually
gradually
su valor inicial en vez de hacer la reducción de manera gradual? reduced?
reduced?
Solución 2.6
Solution 2.6
El proceso
Therealizado,
The process, como se
process, carried
carried outdescribió
out as
as first en un principio,
first described,
described, is es mecánicamente
is mechanically
mechanically reversible,reversible
reversible, and
and Eq. y se puede
Eq. (1.3)
(1.3)
aplicar la ecuación (1.3). Si ttPV t = k, entonces P =tt k / V t y
is applicable. If P V = k, then P = k/V
is applicable. If P V = k, then P = k/V , and , and
�� V t �� V t t t
V22t V22t V t = −k ln V
dd V V22t
W=
W =−
− Pd V tt
P dV =
= −k
−k = −k ln t
V t
V11t V t
V11t V tt
V V1t
V
1
t 3 t 3
With
With V11t =
V = 0.03
0.03 m m3 V22t =
V = 0.06
0.06 m
m3
Con t
V 1 = 0.03 m 3 V 2 = 0.06 m 3
t
kk = t t 5
and
and =P V =
PV t =P V11 =
P11V t (14 ×
= (14 × 10 )(0.03) =
105)(0.03) = 42,000
42,000 JJ
y t = (14 × 10 5 )(0.03) = 42 000 J
k = PV t =WP 1=V −42,000
1
W = −42,000 ln ln 22 =
= −29,112
−29,112 JJ
W = –42 000 ln 2 = –29 112 J

36 CHAPTER 2. The First Law and Other Basic Concepts
La presiónThefinalfinal
es pressure is
k 42,000
P2 = t = = 700,000 Pa o or 7 bar7 bar
V2 0.06
En el segundo
In thecaso, después
second case,de haber reducido
reduction a la mitad
of the initial forcelabyfuerza
half isinicial,
followedel gas
by experimenta
sudden
una súbitaexpansion
expansiónofcontra
the gasunaagainst
fuerzaaconstante que equivale
constant force equivalenta una
to apresión
pressurede of
7 bar. Con el
7 bar.
tiempo, la Eventually,
transferencia de transfer
heat calor regresa
returnsal the
sistema a una
system condición
to the same finalde equilibrio
equilibriumidéntica al esta-
state as
t es el mismo que antes, pero el
do final alcanzado en el proceso
in the reversible reversible.
process. Thus �V Det is
esta same asΔV
themanera, before, but the work accom-
trabajo realizado
plishedno estágiven
is not dado byporEq.
la ecuación (1.3).the
(1.3). Rather, Enwork
su lugar,
doneelagainst
trabajotherealizado
externalenforce
contra de
la fuerza externa
equals thees igual a la presión
equivalent externalexterna
pressureequivalente
times thepor el cambio
volume change:de volumen:
5)(0.06
W ==–(7
W −(7××
1010 5 – 0.03)
)(0.06 = –21
− 0.03) 000 J J
= −21,000
Este proceso
Thisesprocess
claramente irreversible,
is clearly y comparado
irreversible, con el proceso
and compared with thereversible
reversibleseprocess
dice que
is tiene
una eficiencia
said de:
to have an efficiency of:
000/29 112 = =
2121,000/29,112 0.721
0.721 o or 72.1%
72.1%
Example
Ejemplo 2.7 2.7
The piston/cylinder arrangement shown in Fig. 2.4 contains nitrogen gas trapped be-
La combinación
low thepistón/cilindro que se muestra
piston at a pressure en laThe
of 7 bar. figura 2.4 contiene
piston gas
is held in nitrógeno
place atrapado
by latches. debajo
The
del pistónspace
a una above
presiónthe de piston
7 bar. El pistón se mantiene en su lugar mediante unos seguros.
is evacuated. A pan is attached to the piston rod and a mass El espacio
sobre el pistón es kg
m of 45 evacuado. Se une
is fastened un plato
to the pan. alThe
vástago delpiston
piston, pistón,rod,
y una masa
and de 45 kg have
panmtogether se sujeta
a al
plato. El mass
pistón,ofel23
vástago y el plato juntos tienen una masa de 23 kg. Los seguros
kg. The latches holding the piston are released, allowing the piston to que sostienen
Masa
Mass
mm
Plato
Pan
Evacuated
Espacio
space
evacuado
0.5m
0.5 m Cylinder
Cilindro
Figura 2.4: Diagrama para
Figure 2.4: el ejemplo
Diagram 2.7.2.7.
for Ex.
Piston
Pistón
Latch
Seguro
Gas under
Gas bajo
pressure
presión
rise rapidly until it strikes the top of the cylinder. The distance moved by the piston is
−2 . Discuss the energy changes that
al pistón se
0.5liberan
m. Thepermitiendo que ésteofsuba
local acceleration conisrapidez
gravity 9.8 m shasta golpear la parte superior del cilindro.
El pistón occur
recorrebecause
una distancia
of thisde 0.5 m. La aceleración local de la gravedad es 9.8 m s–2. Analice los
process.
cambios de energía que ocurren debido a este proceso.

2.9. Procesos con V y P constantes 37
Solución 2.7
Este ejemplo sirve para ilustrar algunas de las dificultades encontradas al analizar los procesos
irreversibles donde no hay flujo. Considere el gas sólo como sistema. De acuerdo con la defini-
ción básica, el trabajo hecho por el gas en los alrededores es igual a ∫ P ′ dV ′, donde P ′ es la
presión ejercida por el gas sobre la cara del pistón. Ya que la expansión es muy rápida, existen
gradientes de la presión en el gas, y no es posible evaluar P ′ ni la integral. Sin embargo, al regre-
sar a la ecuación (2.1) se evita el cálculo del trabajo. El cambio en la energía total del sistema (el
t
gas) es igual al cambio en la energía interna, ΔU sistema . Para Q = 0, los cambios de energía en los
alrededores consisten en los cambios en la energía potencial del pistón, del vástago, del plato y de
la masa m, así como de los cambios en la energía interna del pistón, del vástago y del cilindro. Por
lo tanto, la ecuación (2.1) se escribe como:
t
ΔU sistema t
+ (ΔU alrededores + ΔE P alrededores) = 0
donde ΔE P alrededores = (45 + 23)(9.8)(0.5) = 333.2 N m
Por lo tanto t
ΔU sistema t
+ ΔU alrededores = –333.2 N m = –333.2 J
Los valores para ΔU tsistema y ΔU talrededores no pueden ser determinados.
2.9 PROCESOS CON V y P CONSTANTES
Para n moles de un fluido homogéneo contenido en un sistema cerrado el balance de energía es:
d(nU) = dQ + dW (2.6)
donde Q y W representan siempre el calor y el trabajo total para cualquier valor de n. El trabajo de un proceso
mecánicamente reversible en un sistema cerrado está dado por la ecuación (1.2), que se escribe a continuación:
dW = –P d(nV)
estas dos ecuaciones se combinan:
d(nU) = dQ – P d(nV) (2.8)
Este balance de energía es general para n moles de fluido homogéneo en un sistema cerrado que experimenta
un proceso mecánicamente reversible.
Proceso a volumen constante
Si el proceso ocurre a un volumen total constante, el trabajo es cero. Por otra parte, para sistemas cerrados el
último término de la ecuación (2.8) también es cero, porque tanto n como V son constantes. De este modo,
dQ = d(nU)(V constante) (2.9)
Integrando se obtiene: Q = n ΔU (V constante) (2.10)
De esta manera, el calor transferido en un proceso mecánicamente reversible para un sistema cerrado a volu-
men constante, es igual al cambio en la energía interna del sistema.

Proceso a presión constante
Resolviendo para dQ, de la ecuación (2.8) se obtiene que:
dQ = d(nU) + P d(nV)
Para un cambio de estado a presión constante:
dQ = d(nU) + d(n PV) = d[n(U + PV)]
La aparición del grupo U + PV, tanto aquí como en otras aplicaciones, sugiere la definición conveniente de
una nueva propiedad termodinámica. De esta forma, la definición matemática (y única) de la entalpía6 es:
H ≡ U + PV (2.11)
donde H, U y V son valores molares o por unidad de masa. La ecuación anterior ahora se puede escribir
como:
dQ = d(nH) (P constante) (2.12)
La integración produce: Q = n ΔH (P constante) (2.13)
De este modo, el calor transferido en un proceso mecánicamente reversible de un sistema cerrado a presión
constante, es igual al cambio en la entalpía del sistema. Al comparar las ecuaciones (2.12) y (2.13) con las
ecuaciones (2.9) y (2.10) se muestra que en los procesos a presión constante la entalpía desempeña un papel
semejante a la energía interna en los procesos a volumen constante.
2.10 ENTALPÍA
La utilidad de la entalpía se sugiere por las ecuaciones (2.12) y (2.13). También aparece en los balances ener-
géticos para los procesos con flujo en relación con los intercambiadores de calor, evaporadores, columnas de
destilación, bombas, compresores, turbinas, máquinas, etc., para el cálculo del calor y del trabajo.
La tabulación de los valores de Q y de W para la combinación infinita de los posibles procesos es
imposible. Sin embargo, las funciones de estado intensivas, tales como el volumen, la energía interna y la
entalpía específicos, son propiedades intrínsecas de la materia. Una vez que son determinadas para una sus-
tancia particular, sus valores para fases líquida y vapor se pueden tabular como funciones de T y P para su
uso futuro en el cálculo de Q y de W para cualquier proceso que involucre dicha sustancia. La determinación
de los valores numéricos para estas funciones de estado, así como su correlación y uso se tratarán en los
últimos capítulos.
Todos los términos de la ecuación (2.11) deben expresarse en las mismas unidades. El producto PV
tiene unidades de energía por mol o por unidad de masa, al igual que U; por lo tanto, H también tiene unidades
de energía por mol o por unidad de masa. En el sistema SI la unidad básica de la presión es el pascal o el
6 Una palabra propuesta por el físico holandés H. Kamerlingh Onnes, quien fue el primero en licuar el helio en 1908. Descubrió
la superconductividad en 1911 y ganó el premio Nobel de Física en 1913. (Véase: Comunications from the Physical Laboratory of the
University of Leiden, núm. 109, p. 3, pie de página 2, 1909.)

2.10. Entalpía 39
N m–2 y, para el volumen molar, m3 mol–1. El producto PV tiene por consiguiente las unidades N m mol–1 o
J mol–1. En el sistema inglés de ingeniería una unidad común para el producto PV es el (pie lbf)(lbm)–1, que
surge cuando la presión se encuentra en (lbf)(pie)–2 y con el volumen en (pie)3(lbm)–1. Este resultado general-
mente se convierte a (Btu)(lbm)–1 mediante la división entre 778.16 y haciendo uso de la ecuación (2.11),
porque la unidad inglesa de ingeniería común para U y H es el (Btu)(lbm)–1.
Dado que U, P y V son funciones de estado, la H definida por la ecuación (2.11) también es una fun-
ción de estado. Como U y V, H es una propiedad intensiva del sistema. La forma diferencial de la ecuación
(2.11) es:
dH = dU + d(PV) (2.14)
Esta ecuación se aplica siempre que ocurre un cambio diferencial en el sistema. Al efectuar la integración se
convierte en una ecuación para un cambio finito en el sistema:
ΔH = ΔU + Δ(PV) (2.15)
Las ecuaciones (2.11), (2.14) y (2.15) se aplican a la unidad de masa de una sustancia o a un mol.
Ejemplo 2.8
Calcule ΔU y ΔH para 1 kg de agua cuando se evapora a la temperatura constante de 100 °C y a una
presión constante de 101.33 kPa. Los volúmenes específicos del agua líquida y de su vapor en estas
condiciones son 0.00104 y 1.673 m3 kg–1. Para este cambio se agrega al agua una cantidad de calor
de 2 256.9 kJ.
Solución 2.8
Se toma 1 kg de agua como el sistema, ya que es lo que nos interesa. Imaginemos que se encuen-
tra contenido en los cilindros mediante un pistón sin fricción que ejerce una presión constante de
101.33 kPa. A medida que se agrega calor, el agua se evapora y se expande desde su volumen
inicial hasta su volumen final. La ecuación (2.13) escrita para el sistema de 1 kg se tiene a conti-
nuación:
ΔH = Q = 2 256.9 kJ
Por la ecuación (2.15), ΔU = ΔH – Δ(PV) = ΔH – P ΔV
Evaluando el término final:
P ΔV = 101.33 kPa × (1.673 – 0.001) m3

= 169.4 kPa m3 = 169.4 kN m–2 m3 = 169.4 kJ
Entonces ΔU = 2 256.9 – 169.4 = 2 087.5 kJ

40
40 CHAPTER 2.
CHAPTER 2. The
The First
First Law
Law and
and Other
Other Basic
Basic Concepts
Concepts
2.11 CAPACIDAD CALORÍFICA
2.11 HEAT
2.11 HEATCAPACITY
CAPACITY
2.11
El punto de vistaHEAT CAPACITY
moderno con respecto al calor como energía en tránsito fue precedido por la idea de que un
cuerpo tiene una capacidad para el calor. Entre más pequeño fuera el cambio de temperatura en un cuerpo
The modern view of heat as energy in transit was preceded by the idea that a body has a
provocado
The por
The la transferencia
modern
modern view
view of of heatdeas
heat una
as cantidad
energy
energy in dada de
in transit
transit was
was calor, mayorby
preceded
preceded bysería
the su
the ideacapacidad.
idea that En has
that aa body
body realidad,
has aa una
capacity for heat. The smaller the temperature change in a body caused by the transfer of a
capacidad calorífica
capacity
capacity for puede
for heat.
heat. Thedefinirse
The smallercomo
smaller the C ≡ dQ/dT. change
the temperature
temperature La dificultad
change in con esta
in aa body
body expresión
caused
caused by thees
by the que hace
transfer
transfer of aque
of a C, al
given quantity of heat, the greater its capacity. Indeed, a heat capacity might be defined as
igual que Q, sean
given
given cantidades
quantity
quantity of heat,más
of heat, thedependientes
the greater
greater its del proceso
its capacity.
capacity. que de
Indeed,
Indeed, una
heatfunción
aa heat capacitydemight
capacity estado.
might beNo
be obstante,
defined
defined as sugie-
as
C ≡ d Q/dT . The difficulty with this is that it makes C, like Q, a process-dependent quantity
re la definición
CC ≡ de dos
≡ ddQ/dT
Q/dT cantidades
.. The
The difficultycon
difficulty witheste
with nombre
this
this thatanticuado,
isis that itit makes
makes C,C,quelikedeQ,
like hecho
Q, son funciones dequantity
aa process-dependent
process-dependent estado relacio-
quantity
rather than a state function. However, it does suggest the definition of two quantities with this
nadas sin ambigüedad
rather
rather than
than aa statecon
state otras funciones
function.
function. However,
However, deititestado.
does
does suggest
suggest the
the definition
definition ofof two
two quantities
quantities with
with this
this
outmoded name that are in fact state functions, unambiguously related to other state functions.
outmoded name that are in fact state functions, unambiguously related
outmoded name that are in fact state functions, unambiguously related to other state functions.to other state functions.
Capacidad caloríficaataConstant
Heat Capacity
Heat volumen constante
Constant Volume
Heat Capacity
Capacity at
at Constant Volume
Volume
The constant-volume heat capacity of a substance is defined as:
La capacidad
The calorífica a volumen
The constant-volume
constant-volume heat constante
heat capacity
capacity of ade
of una sustancia
a substance
substance is definedse define
as: como:
as:
� is � defined
�� ∂U��
C ≡ ∂U ∂U (2.16) (2.16)
CCVVV≡≡ ∂T V (2.16)
(2.16)
∂∂TT VV
Esta definición se acomoda
This definition a ambas capacidades,
accommodates both the molar tantoheata capacity
la capacidad and thecalorífica
specificmolar como a la
heat capacity capacidad
(usu-
This
calorífica
This definition
específica
definition accommodates
(usualmente
accommodates both
llamada the
themolar
bothcalor heat
heatcapacity
específico),
molar and
dependiendo
capacity andthe specific
theen todo
specific heat
caso capacity
heatde que U
capacity (usu-
sea la energía
(usu-
ally called specific heat), depending on whether U is the molar or specific internal energy.
internaally
molar
ally called
o
called specific
específica. heat),
heat), depending
specific Aunque esta on
on whether
definición
depending no
whetherhace U isis the
the molar
Ureferencia a
molar or
or specific
cualquier
Although this definition makes no reference to any process, it relates in an especially simple
internal
proceso,
specific se
internal energy.
relaciona
energy. de una
maneraAlthough
especialmente
Although
way
this
this definition
definition
to a constant-volume
makes
simple con un
makes no
process
no reference
proceso
in aaclosed
to
volumen
reference to any process,
process,deititun
constante
any
system,
relates
sistema
relates
for which Eq.
in
in an
(2.16)
especially
especially simple
cerrado,
an
may bepara el que la ecua-
simple
written:
way
way to
ción (2.16) to aescribe
se a constant-volume
como:
constant-volume process
process inin aa closed
closed system,
system, for for which
which Eq.Eq. (2.16)
(2.16) may
may bebe written:
written:
dU = C V dT (const V ) (2.17)
dU =
dU
dU =C
= CCVVdT
dT (const
(const VV))
V dT (V constante)
(2.17)
(2.17) (2.17)
�
�� T T2
Integration yields: �U = T22 C V dT (const V ) (2.18)
Integrando:
Integration
Integration yields:
yields: �U =
�U = T1 CCVV dT dT (V constante)
(const
(const VV)) (2.18) (2.18)
(2.18)
TT11
La combinación dewith
This result este Eq.
resultado
(2.10) con
for alamechanically
ecuación (2.10) para unconstant-volume
reversible, proceso mecánicamente
process777reversible,
gives: a volu-
This
This result
result
7 with
with Eq.
Eq. (2.10)
(2.10) for
for aa mechanically
mechanically reversible,
reversible, constant-volume
process gives:
gives:
men constante, nos da: �
�� T T2
Q = n �U = n T22 C V dT (const V ) (2.19)
QQ= �U =
= nn �U = nn T1 CCVV dT dT (V(const
constante)
(const VV)) (2.19) (2.19)
(2.19)
TT11
Si el volumen varía durante
If the volume
IfIf the
varieselduring
proceso,the pero
processal final de éste at
but returns regresa a su
the end ofvalor inicial, to
the process noits esinitial
correcto que
the volume
volume varies
varies during
during the the process
process but but returns
returns atat the
the end
end ofof the
the process
process to to its
its initial
initial
el proceso se
value, llame
the volumen
process constante,
cannot rightly aunque
be called V =
one
2 Vof
1 y ΔV =
constant 0. De
volume,cualquier
even modo,
though V los
2 cambios
= V1 and en las
value,
value, thethe process
process cannot
cannot rightly
rightly be be called
called oneone ofof constant
constant volume,
volume, even though VV22 =
even though = VV11 and
and
funciones�Vde = estado son independientes
0. However, changes indestate la trayectoria
functions y, arepor lo tanto, pueden
independent of path, calcularse
and may mediante
therefore ecuacio-
�V =
�V = 0. 0. However,
However, changes
changes in in state
state functions
functions are are independent
independent of of path,
path, andand maymay therefore
therefore
nes para
be un
be proceso
calculated a volumen
by equationsconstante real
for a truly con las mismas
constant-volume
� condiciones
process withinicialthe same y final. La
initial ecuación
and final (2.18)
be calculated
calculated by by equations
equations for for aa truly
truly constant-volume
constant-volume
�� C V dT process
process with
with thethe same
same initial
initial and
and final
final
da entonces ΔU = ∫ CEquation
conditions. V dT, porque(2.18)U,then ygives
CV givesT son�U todas=funciones de estado oU, propiedades.
, because , C V , and T Por are otra parte, Q y
all state
conditions.
conditions. Equation
Equation (2.18)
(2.18) then
then gives �U �U = = CCVV dT dT,, because
because U U , CCVV,, andand TT areare allall state
state
W dependen de
functions.
functions. la trayectoria,
On the other y la ecuación
hand, Q and (2.19) es
W depend una expresión
on path, and válida
Eq. para
(2.19) Q, isy aWvalid
en general
expressiones cero sólo
functions. On On thethe other
other hand,
hand, Q Q and
and W W depend
depend on on path,
path, and
and Eq.Eq. (2.19)
(2.19) isis aa valid
valid expression
expression
para unfor
proceso
for Q, and a volumen
W is inconstante.
general zero, Ésta es
only la razón
for para la distinción
a constant-volume entre
process. las funciones
This is the de estado,
reason for Q y W.
for Q,
Q, andand W W isis in
in general
general zero,
zero, onlyonly forfor aa constant-volume
constant-volume process. process. This This isis the
the reason
reason for for
El principio de que las between
the distinction
the funcionesstatede estado
functionsson independientes
and Q and W . del Theproceso
principlees unthatconcepto importante
state functions are y útil.
the distinction
distinction between
between state
state functions
functions and and Q Q and
and W W.. The
The principle
principle thatthat state
state functions
functions are are
independent of the process is an important and useful concept.
independent
independent
Para el cálculo
of
of the process
the los
de process isis an
cambios an important
important
en
and
and useful
las propiedades, useful concept.
concept.
un proceso real se puede sustituir por
For
otro cualquiera the calculation
que consiga elof property
mismo cambio changes,
en el an actual process may be
estado.
For
For the the calculation
calculation of of property
property changes,changes, an an actual
actual process
process may may be be
replaced by any other process which accomplishes the same change
replaced
replaced by
by any
any other
other process
process which
which accomplishes
accomplishes the
the same
same change
change
De este modo,in puede
state. seleccionarse un proceso alternativo, por ejemplo, debido a su simplicidad.
inin state.
state.
Such an alternative process may be selected, for example, because of its simplicity.
Such
Such anan alternative
alternative process
process may may be be selected,
selected, for for example,
example, because
because of of its
its simplicity.
simplicity.
7 Estas restricciones sirven para excluir el trabajo de agitación, que es intrínsecamente irreversible.
7 These restrictions serve to rule out work of stirring, which is inherently irreversible.
77These
Theserestrictions
restrictionsserve
serveto
torule
ruleout
outwork
workof
ofstirring,
stirring,which
whichisisinherently
inherentlyirreversible.
irreversible.

2.11. Heat Capacity
2.11. Capacidad 41 41
2.11. Heat calorífica
Capacity 41
2.11. Heat Capacity 41
HeatCapacity
Capacidad
Heat Capacity
caloríficaataConstant
at Constant Pressure
presión constante
Pressure
Heat Capacity at Constant Pressure
The constant-pressure
La capacidad heat capacity se
calorífica a presión is defined as:
define como:
The constant-pressure heat constante
capacity is defined as:
The constant-pressure heat capacity is defined � as: �
� ∂ H�
C P ≡� ∂ H � (2.20) (2.20)
C P ≡ ∂ ∂HT P (2.20)
CP ≡ ∂ T P (2.20)
De nuevo, T P
∂caloríficas
Again, the definition accommodates both molar and specific heat capacities, depending de
la definición se acomoda a las capacidades molar y específica, dependiendo on si H es
Again,
la entalpía theodefinition
molar específica. accommodates
Esta capacidad both molarseand
calorífica specific
relaciona de heat
una capacities,
manera depending simple
especialmente on para
whether
Again, theHdefinition
is the molar or specific enthalpy. Thisandheatspecific
capacityheat
relates in an especially simple
whether
un proceso a H is
presión the molaraccommodates
constante or
en specific
un sistema both
enthalpy.molar
cerrado,This
paraheat
el capacity
que la ecuacióncapacities,
relates (2.20) de depending
in an especially
igual simple
manera onestá bien
way to aHconstant-pressure, closed-system process, for capacity
which Eq. (2.20) isan equally well written:
escrita:whether is the molar or specific
way to a constant-pressure, enthalpy.
closed-system This heat
process, for which Eq.relates
(2.20) in especially
is equally simple
well written:
way to a constant-pressure, closed-system process, for which Eq. (2.20) is equally well written:
d H ==CC PdTdT (P constante)
(const P) (2.21)
ddH
H = CPP dT (const P) (2.21) (2.21)
d H =�C P dT (const P) (2.21)
� T2T2
whence �H = C dT (const P) (2.22)
de dondewhence �H = � TT12 C PPdT (P(const constante)
P) (2.22) (2.22)
whence �H = T1 C P dT (const P) (2.22)
For a mechanically reversible, constant-P T1 process, this result may be combined with Eq. (2.13):
Para unFor
proceso mecánicamente
a mechanically reversible
reversible, a presión
constant-P constante,
process, estemay
this result resultado puede combinarse
be combined con la ecua-
with Eq. (2.13):
For a mechanically reversible, constant-P process,
ción (2.13): � T2 this result may be combined with Eq. (2.13):
� T
Q = n �H = n 2 C dT (const P) (2.23)
Q = n �H = n � TT12 C PPdT (const P) (2.23)
Q = n �H = n 1 C P dTT (P(const
constante)
P) (2.23) (2.23)
T1
Because H , C , and T are state functions, Eq. (2.22) applies to any process for which P = P
Because H , C PP, and T are state functions, Eq. (2.22) applies to any process for which P2 2= P1 1
Dado quewhether Hor Tnot
y,not , it is Tactually carried out at constant pressure. However, only for thePmechan-
H, CPor
Because
whether C Pson
it istodas
and funciones
are
actuallystate deout
estado,
functions,
carried at Eq. la ecuación
(2.22)
constant (2.22)
applies
pressure. seprocess
toHowever,
any aplica afor
only cualquier
which
for proceso
2 = P1 para el
the mechan-
ically
cual P2whether
= P , reversible,
se esté o no constant-pressure
realizando
�
or not it constant-pressure
is actually process
realmente a can
presión
carried out at constant heat and
constante.work
Sin be calculated
embargo, sólo by the
para equations
un proceso mecá-
ically1 reversible, � C P dT , and process can heatpressure.
and workHowever, only by
be calculated forthe
theequations
mechan-
nicamenteQ =
ically n �H
reversible , Qa = n
presión constante W
se = −Pn
puede �V
calcular. el calor y el trabajo por medio de las ecuaciones
Q = nreversible,
�H , Q =constant-pressure
n � C P dT , and Wprocess
= −Pn can�V heat
. and work be calculated by the equations
Q = n ΔH, Q = n∫C dT y W = –Pn ΔV.
Q = n �H , PQ = n C P dT , and W = −Pn �V .
Example2.9
Example 2.9
Ejemplo
Example 2.9 2.9
Air at 1 bar and 298.15 K (25◦ ◦ C) is compressed to 5 bar and 298.15 K by two different
Air at 1 bar and 298.15 K (25 C) is compressed to 5 bar and 298.15 K by two different
mechanically
Se comprime
Air at 1 aire a1
bar andreversible
bar
298.15 processes:
y 298.15
(25K◦ C)
(25is°C),
Kprocesses: hasta 5 bar
compressed to 5y bar
298.15
andK298.15
mediante
K bydos
twoprocesos
differentmecáni-
mechanically reversible
camente reversibles diferentes:
mechanically reversible processes:
(a) Cooling at constant pressure followed by heating at constant volume.
a) Enfriamiento a presión constante seguido de un calentamiento a volumen constante.
(b) Heating at constant
b) Calentamiento volumeseguido
followeddebyuncooling at constant pressure.
(b) Heatingaatvolumen
constant constante
volume followed enfriamiento
by cooling a presión
at constant constante.
pressure.
(b) Heating at constant volume followed by cooling at constant pressure.
CalculeCalculate
los requerimientos
the heat and de calor
work yrequirements
de trabajo, yandΔU y�U ΔHand
del aire
�H para
of thecada unaeach
air for de las trayecto-
path.
Calculate
rias. Las the heat
siguientes and workcaloríficas
capacidades requirements para and
el �U se
aire and �H ofque
supone the son
air for each path. de la
independientes
The following
Calculate heatand
the heat capacities for air may be assumed
work requirements independent of temperature:
The following
temperatura: capacities for air may beand �U and
assumed �H of theofair
independent for each path.
temperature:
The following heat capacities for air may be assumed independent of temperature:
C = 20.78 and C = 29.10 J mol−1 −1 K−1
C VV= 20.78 C PPC=P 29.10 –1KK−1
–1
CV = 20.78 and y J mol
= 29.10 J mol
C V = 20.78 and C P = 29.10 J mol−1 K−1
Assume also for air that P V /T is a constant, regardless of the changes it undergoes.
Assume
Supóngase also for
también para airelthat
aire P
que is aesconstant,
PV/T
V /T regardless
una constante, of the
sin considerarchanges
3 mol it undergoes.
los cambios
−1 que experimen-
At 298.15
Assume K and 1 bar the molar avolume of air is 0.02479 m −1 .
K yalso forelair thatthe /T isdel constant,deregardless mof the–1changes it undergoes.
At 298.15 P Vmolar 3m 3 mol
ta. A 298.15 1Kbar
and 1volumen
bar molar volume of air
aire es is 0.02479
0.02479 mol . .
At 298.15 K and 1 bar the molar volume of air is 0.02479 m3 mol−1 .

42 CHAPTER 2. The First
First Law
Law and
and Other
Other Basic
Basic Concepts
Concepts
42 CHAPTER 2. The
42 42 CAPÍTULO
Conceptsbásicos
Solution 2.9
Solution 2.9
Solution
Solución 2.9
In2.9
Solution 2.9
each case take the system as 1 mol of air contained in an imaginary pis-
In each case take the system as 1 mol of air contained in an imaginary pis-
En cadaIn
Incaso considere
each al sistema
case arrangement.
ton/cylinder take como
the system
as1 1mol
as 1 mol
Because deprocesses
the aireair
of aircontenido enin
contained una
in
considered combinación
anare
imaginary imaginaria
pis-
mechanically
Solution 2.9arrangement.
each case
ton/cylinder take the system
Because mol of
the processes contained
consideredanare
imaginary pis-
mechanically
de pistón/cilindro.
reversible, Debido
ton/cylinder
ton/cylinder the a que
arrangement.
piston
arrangement. is estos
imagined procesos
Because
Because to the
move seprocesses
consideran
processes mecánicamente
considered
in the cylinder without reversibles,
are mechanically
friction. The supon-
reversible, the piston is imagined to the
move considered
in the cylinder withoutare mechanically
friction. The
ga que elInpistón
reversible,
each
final volume
reversible, se
casemueve
the take
is: en
piston theel cilindro
issystem
imagined assin 1fricción.
to moveofinEl
mol air volumen
the
theis:piston is imagined to move in the cylinder without friction. The
cylinder
contained finalin es:
without friction. The
an imaginary pis-
final volume
final volume is:
ton/cylinder arrangement. Because the processes � � considered are mechanically
final volume is: P1 � 1�
reversible, the piston V2 = is Vimagined
P = to
0.02479 move � 1in �the = cylinder
0.004958 m33
without friction. The
V = V 1 P1 = 0.02479 � 1 � = 0.004958 m
1
1 PP
final volume is: V2 = V1 P12 = 0.02479 5 = 0.004958 m33
2 2 15
V2 = V1 P2 = 0.02479 � 5 � = 0.004958 m
(a) During the first step thePPair 2 is cooled at the
1 is cooled at the
51 constant pressure of 1 bar until the
(a) During
a) Durante la primera the etapa,
firstVstep=
el the
aire
V air
se
3 =enfría
0.02479 a presión constant
= 0.004958
constante pressure 3 of 1 bar until the
deof1mthe
barof hasta que sethe
alcanza el
(a)
finalDuring
volume the first
offirst step
2
0.004958 the
1 air
mPair
32 is is cooled
isisreached. at the
The 5 constant
temperature pressure air1 at
bartheuntil
end of
(a)
finalDuring
volume theof step
0.004958 3 them cooled
reached. at
Thethe constant
temperature pressure
of the ofair1 at
barthe until
endthe
of
volumenfinal
final de
volume
this cooling 0.004958
of
step m
0.004958
is: . La m temperatura
3 is reached.del The aire al final
temperature de esta
of theetapa
air de
at enfriamiento
the end of es:
final volumestep
this cooling of 0.004958
is: m3 is reached. The temperature of the air at the end of
this coolingthe
(a) During step is: step the air is cooled�at the constant
first � pressure of 1 bar until the
this cooling step is: V 3 is reached. � 0.004958 �
final volume of 0.004958 T� = T V m 2
V2 = 298.15� � 0.004958 � = 59.63
The temperature of the K air at the end of
T �� = T11V 2 = 298.15 0.004958 � = 59.63 K
this cooling step is: V
T = T V211 = 298.15 0.004958 0.02479
T � = T11 V 0.02479 = 59.63 K
1 = 298.15 � 0.02479 � = 59.63 K
Whence, VV12 0.02479
0.004958
De donde,
Whence, T � = T1 = 298.15 = 59.63 K
Whence, V 0.02479
Whence,
Q = �H = C P1�T = (29.10)(59.63 − 298.15) = −6,941 J
Q = �H = C P �T = (29.10)(59.63 − 298.15) = −6,941 J
Whence,�U Q = = �H �H = −C C P �T = (29.10)(59.63
�H − P �V − − 298.15) = −6,941 J
�U = �H =
Q �(P V)= 298.15) = −6,941 J
= �H − �(P P �T V) = (29.10)(59.63
�H − P �V
�U = = �H�H
−6,941 − �(P
− (1V× V ) = �H
5 − P �V −− = −4,958
�U Q= = �H −6,941 −
= �(P C− (1�T × )= 10�H
=
10 − P �V−
)(0.004958
5(29.10)(59.63
)(0.004958
0.02479)
298.15)=
0.02479) −6,941JJJ
=−4,958
= −6,941 −P(1 × 1055 )(0.004958 − 0.02479) = −4,958 J
= −6,941
=second
�H −step − (1V×) 10 = �H )(0.004958 − 0.02479) = −4,958 J
During �Uthe �(P the volume is−held
P �V constant at V while the air is heated
During the second step the volume is held constant at V22 while the air is heated
During
to its final the second
state. By Eq. step the
(2.19), volume 5 is held constant at V while the air is heated
Durante
to its lafinal
During the=second
segunda
state. −6,941
etapa,
By Eq. − (1 ×
el(2.19),
step volumen
the 10se)(0.004958
volume mantiene
is held constant − 0.02479)
constante V=2 mientras
at Va22 while −4,958
the airJ que se calienta a
is heated
to its final state. By Eq. (2.19),
su estado
to final.
its final Porstate.
la ecuación (2.19),
By Eq. (2.19),
During�U �U = Q = C V the
the second �T = (20.78)(298.15 − 59.63) = 4,958 J is heated
= Q =step C �Tvolume is held constant
= (20.78)(298.15 at V2 while
− 59.63) = 4,958 the Jair
to its final �U �U =ByQEq.
state. = C VV �T = (20.78)(298.15 − 59.63) = 4,958 J
= Q = C(2.19), V �T = (20.78)(298.15 − 59.63) = 4,958 J
The complete process represents the sum of its steps. Hence,
The complete process represents the sum of its steps. Hence,
The complete process
= Q = represents
C =the sum of its steps. − Hence,= 4,958 J
El proceso
Thecompleto �U
completerepresenta
process represents V �T
la suma de the(20.78)(298.15
sus
sumetapas.
of its Por steps.lo 59.63)
tanto,
Hence,
Q = −6,941 + 4,958 = −1,983 J
Q = −6,941 + 4,958 = −1,983 J
The complete process represents Q = −6,941 the sum + 4,958 of its = −1,983 J
QQ==−6,941 –6 941 ++ 44,958
958 ==steps.
–1 983Hence,
−1,983 JJ
and �U = −4,958 + 4,958 = 0
and �U = −4,958 + 4,958 = 0
and Q �U �U
= −6,941 = −4,958 + 4,958 + 4,958 =0 J
= −1,983
and
Because the first law applies to=the −4,958
entire + 4,958
process, =
�U 0 = Q + W , and therefore,
y Because the first law appliesΔU to the= –4 958
entire + 4
process,958 =
�U 0 = = Q + W , and therefore,
Because the first law applies to the entire process, �U Q + W , and therefore,
Because
and the first law applies �U to = the−4,958 +
entire process, 4,958 =
�U 0 = Q + W , and therefore,
0 = −1,983 + W whence W = 1,983 J
Debido a que la primera 0 =ley
0 = −1,983 se aplica
−1,983
+ Wa todo el whence
+ to W the entire proceso, ΔU = W
whence Q +=
W =W, y porJ lo tanto,
1,983
1,983
Because the first 0 =law applies
−1,983 +W process, �UW= =
whence + W , JJand therefore,
Q 1,983
Equation (2.15), �H = �U + �(P V ), also applies to the entire process. But
Equation (2.15), 0 = –1�H �H
983P= =
+VW �U + �(P V ), also appliesWto=the entire process. But
T1 = Equation
T , and(2.15),
therefore,
0 = −1,983 +�U�U
1W =+ P �(P V de Vdonde
), also
. whence
Hence �(P applies
V ) =to to0,
=the
1and
the 983
entireJ process. But
T1 = T22, and (2.15),
Equation therefore, �HP =
1
1V
1 =+ P22�(P V22. Hence
V ), also �(P V) W
applies = 0, 1,983
and entire J process. But
T1 = T2 , and therefore, P1 V1 = P2 V2 . Hence �(P V ) = 0, and
T1 = T2 , (2.15),
La ecuación and therefore,
ΔH �H = ΔU = P2 V2también
P1 V+1 Δ(PV), . Hence se �(P V ) = 0, andel proceso. Pero T = T , y
Equation (2.15), = �U �H �H
+ �(P =V �U = 0aplica
), also appliesa to todothe entire process. But1 2
= �U = 0
por lo tanto,
T1 =PT12V, 1and 2V2. Así, Δ(PV)
= Ptherefore, P1 V1 = = �H0,
P yV2= . �U =�(P
Hence 0 V ) = 0, and
�H = �U = 0
2
(b) Two different steps are used in this case to reach the same final state of the air.
(b) Two different steps are used inΔH this=case ΔU to
== reach the same final state of the air.
0reach
(b) Two
In the different
first steps
step the air is are used
heated in
at�H athis case
constant
=case�Uto tovolume0 the the same
equal final
to final statevalue
its initial of theuntil
air.
(b) Two
In the different
first step thesteps air isare used at
heated in athisconstant reach
volume same
equal to its statevalue
initial of theuntil
air.
In the
the final first step
pressure the air is
ofair5 is heated
barheated
is reached. at a constant
The air volumevolume
temperature equal to
attotheits initial
end value
of this until
step is:
In
thethe
b) En este first step theof at a constant equalat itsendinitial value until
(b)caso
Twose emplean dos etapas diferentes The para alcanzar
reach theelsame mismo estado final
thedelis:aire. En
final pressure 5 bar is reached. air temperature the of this step is:
the final pressure
different of 5 bar
steps are isused
reached. in thisThe caseair
� totemperature
� at thefinal
end of this
state of step air.
the etapa
la primera final pressure seofcalienta
5 bar is areached. The air � 5temperature at the end ofinicial,
this step is: que se
In the firstelstep airethe air
T � is heated
= T
Pun volumen
P22 at = a298.15
constant �constante
�
� = 1,490.75
5volume
igual
equalatoK suitsvalor
initial value hastauntil
alcanza the
la presión final deof5T5bar. �
= La
� bar
1 temperatura
P 2 = 298.15
Tis1 reached. �
del 5 �
aire = al final
1,490.75 de esta
K etapa es:
final pressure T =T P P The air
= 298.15 51 = 1,490.75 K1temperature at the end of this step is:
T � = T11 P P211 = 298.15 � 1 � = 1,490.75 K
1
PP1 15
2
T � = T1 = 298.15 = 1,490.75 K
P1 1

2.11. Capacidad
2.11. Heatcalorífica
2.11. Heat Capacity
Capacity 43
43 43
Para esta etapa

For
For thisel
this volumen
step
step the es constante,
the volume
volume y and
isis constant,
constant, and
Q=
Q �U =
= �U �T =
= CCVVV �T (20.78)(1,490.75 −
= (20.78)(1,490.75 298.15) =
− 298.15) = 24,788
24,788 JJ
En la segunda
In
In the etapa elstep
the second
second airethe
step se air
the enfría a una presión
air isis cooled
cooled at PP =
at = 5P = 5to
5 bar
bar bar
to itspara
its finalsustate:
final estado final:
state:
Q=
Q �H =
= �H �T =
= CCPPP �T (29.10)(298.15 −
= (29.10)(298.15 1,490.75) =
− 1,490.75) = −34,703
−34,703 JJ
�U =
�U �H −
= �H �(PVV)) =
− �(P �H −
= �H − PP �V
�V
55
=
= −34,703
−34,703 − (5 ×
− (5 × 10 )(0.004958 −
105)(0.004958 0.02479) =
− 0.02479) = −24,788
−24,788 JJ
Para lasFor
dosthe
For etapas
the twocombinadas,
two steps
steps combined,
combined,
Q=
Q 24,788 −
= 24,788 34,703 =
− 34,703 = −9,915
−9,915 JJ
�U =
�U 24,788 −
= 24,788 24,788 =
− 24,788 = 00
W=
W �U −
= �U −QQ== 00 − (−9,915) =
− (−9,915) = 9,915
9,915 JJ
y como and
antes
and as
as before
before ΔH=
�H
�H = ΔU
�U ==
= �U =000
Los cambios
The en las propiedades
The property
property changes
changes �U �UΔUand
and ΔH
y �H
�Hque son calculados
calculated
calculated for
for the para change
the given
given el cambio
change in dado
in state en el esta-
state are
are
do son iguales
the same
the samepara
forambas
for both trayectorias.
paths.
both paths. On thePor
On the otrahand
other
other parte,
hand thelas
the respuestas
answers
answers to a los(a)
parts
to parts incisos
(a) and (b)
and (b) yshow
b) demues-
a) show
tran quethat
Q yQ
that dependen
QWand
and WW dependde laon
depend trayectoria.
on the
the path.
path.
Example
Example 2.10
2.10
Ejemplo 2.10
Calculate the internal-energy and enthalpy changes that occur when air is changed
Calculate
Calculate the
the internal-energy
internal-energy and
and enthalpy
enthalpy changes
changes that
that occur
occur when
when air
air is
is changed
changed
Calculefrom
los cambios ◦◦◦F)laand 333(lb de un
from an initialque
an initial ocurren
state
state of
of 40(
40(en F) andenergía interna
10(atm),
10(atm), y en its
where
where la
its entalpía
molar cuandois
molar volume
volume isel36.49(ft)
aire cambia
36.49(ft) (lb
estado mole) −1
inicial−1de 40(°F)
,, to aa finaly 10(atm),
state donde ◦
◦◦F)su volumen molar es 36.49(pie) 3 (lbPPmol) –1 ,isaconstant
un estado final
mole) −1 to final state of
of 140(
140( F) and
and 1(atm).
1(atm). Assume
Assume for
for air
air that
that /T is
VV/T constant
de 140(°F) y 1C (atm). Suponga para el aire −1
que ◦◦◦F)−1
−1((PV/T −1.es
and
and that
that C VV=
V = 55 and
and CCPPP== 7(Btu)(lb
7(Btu)(lb mole)
mole) −1
F)−1 . constante y que CV = 5 y CP = 7 (Btu)
–1
(lb mol) (°F) . –1
Solution 2.10
Solution
Solución 2.10 2.10
Because
Because property
property changes
changes are are independent of of the process that brings them about,
Ya que los cambios en la propiedad sonindependent
independientes thedelprocess
procesothat quebrings themlos
los causa, about,
cálculos se
calculations may be based on aa two-step, mechanically reversible process in which
pueden basar en un proceso de dos etapas y mecánicamente reversible, en el cual 1(lbwhich
calculations may be based on two-step, mechanically reversible process in mol) de aire
1(lb
1(lb mole)
mole) of
of air
air isis (a)
(a) cooled
cooled at constant volume to the
the final
final pressure, and (b)
es: a) enfriado a volumen constante paraatlaconstant
presión volume
final, y b) to calentado pressure,
a presión and (b) para
constante
heated
heated at
at constant
constant pressure
pressure to
to the
the final
final temperature.
temperature. The
The absolute
absolute temperatures
temperatures
la temperatura final. Las temperaturas absolutas están dadas en la escala Rankine:
here
here areare on
on the
the Rankine
Rankine scale:scale:
T1 = 40 + 459.67 = 499.67(R) T2 = 140 + 459.67 = 599.67(R)
TT111 = 40 +
= 40 459.67 =
+ 459.67 = 499.67(R)
499.67(R) TT222 = 140 +
= 140 459.67 =
+ 459.67 = 599.67(R)
599.67(R)
Dado que PV = kT, la relación T/P ratioes constanteispara la etapa a). Por lo tanto, la temperatura inter-
Because PPVV =
Because = kTkT,, thethe ratio TT/P /P is constant
constant for for step
step (a).
(a). The
The intermediate
intermediate
media entre los dos pasos
temperature between es:the two steps is therefore:
temperature between the two steps is therefore:
TTT�� ′== (499.67)(1/10) ==49.97(R)
(499.67)(1/10) = 49.97(R)
= (499.67)(1/10) 49.97(R)
y los cambios
and thede
and the temperatura
temperature
temperature para lasfor
changes
changes dos
for theetapas
the two son: are:
two steps
steps are:
ΔT
�T
�Taaaa== 49.97
= 49.97–−
49.97 −499.67
499.67==
499.67 =–449.70(R)
−449.70(R)
−449.70(R)
�T
�Tb =
ΔTbbb = 599.67
= 599.67 − 49.97
599.67–−49.97 = 549.70(R)
49.97==549.70(R)
549.70(R)

44
44
44 CHAPTER2.
CHAPTER
CHAPTER 2. The
2. TheFirst
The FirstLaw
First Lawand
Law andOther
and OtherBasic
Other BasicConcepts
Basic Concepts
Concepts
For
Forstep
For step(a),
(a),by
byEqs.
Eqs.(2.18)
(2.18)and
and(2.15),
(2.15),
Para la etapa a),step
por(a),
las by Eqs. (2.18)
ecuaciones and
(2.18) y(2.15),
(2.15)
�Uaa =
�U �T =
= CC �T (5)(−449.70) =
= (5)(−449.70) = −2,248.5(Btu)
−2,248.5(Btu)
�U a = CVVV �Taaa = (5)(−449.70) = −2,248.5(Btu)
�Haa =
�H �U +
= �U +VV �P�P
�H a = �Uaaa + V �Paaa
== −2,248.5
−2,248.5 ++ (36.49)(1−
= −2,248.5 + (36.49)(1
(36.49)(1 − 10)(2.7195) =
−10)(2.7195)
10)(2.7195) = −3,141.6(Btu)
= −3,141.6(Btu)
−3,141.6(Btu)
El factor
The2.7195
The factorconvierte
factor 2.7195 el producto
2.7195 converts
converts the PPPPV
the de (atm)(pie)
VVV product
product from 3(atm)(ft)
, el cual333,,,es
from (atm)(ft) una is
which
which unidad
is an de energía a
an energy
energy
The factor 2.7195 converts the product from (atm)(ft) which is an energy
(Btu). unit,
unit, into
into (Btu).
(Btu).
unit, into (Btu).
Para la For
etapa
Forstep
For step
step el volumen
b),(b),
(b),
(b), the
the finalfinal
thefinal
final volumedelof
volume
volume aire
of
of thees:
the
the air
airis:
air is:
is:
��
�10 �
� ��
PPP11TTT22 10� �599.67
10 599.67�
599.67 333 3
VVV22 =
= VV 1 2 =
= 36.49
36.49 =
= 437.93(ft)
437.93(ft) (pies)
2 = V111PP22TT11 = 36.49 11 499.67
499.67 = 437.93(ft)
P2 T1 1 499.67
Por las By
ecuaciones
ByEqs.
By Eqs. (2.22)
Eqs.(2.22)
(2.22)
(2.22) andy(2.15),
and
and (2.15),
(2.15),
(2.15),
�Hbb =
�H = CC �T�T = (7)(549.70) =
= (7)(549.70) = 3,847.9(Btu)
3,847.9(Btu)
�H b = CPPP �Tbbb = (7)(549.70) = 3,847.9(Btu)
�U
�U =
= �H
�H −
− P
P �V
�V
�Ubb = �Hbb − P �Vbb
b b b
=
= 3,847.9−
= 3,847.9
3,847.9 − (1)(437.93−
−(1)(437.93
(1)(437.93 − 36.49)(2.7195) =
−36.49)(2.7195)
36.49)(2.7195) = 2,756.2(Btu)
= 2,756.2(Btu)
2,756.2(Btu)
Para lasFor
dosthe
For
For
etapas
the
the two
two
juntas,
twosteps
stepstogether,
steps together,
together,
ΔU=
�U
�U = −2,248.5
= –2 248.5 ++
−2,248.5 +22,756.2
756.2 ==
2,756.2 507.7
= (Btu)
507.7(Btu)
507.7(Btu)
�U = −2,248.5 + 2,756.2 = 507.7(Btu)
ΔH
�H =
�H = –3 141.6
= −3,141.6
−3,141.6++ 3 847.9 =
3,847.9 =
+3,847.9 706.3 (Btu)
= 706.3(Btu)
706.3(Btu)
�H = −3,141.6 + 3,847.9 = 706.3(Btu)
2.12 BALANCES DE MASA Y ENERGÍA PARA SISTEMAS ABIERTOS

2.12
2.12 MASS
2.12 MASS AND
MASS AND ENERGY
AND ENERGY BALANCES
ENERGY BALANCES FOR
BALANCES FOR OPEN
FOR OPEN SYSTEMS
OPEN SYSTEMS
SYSTEMS
Aunque en las secciones anteriores nos hemos concentrado en sistemas cerrados, los conceptos mencionados
Although
tienen un uso másthe
Although
Although the
the focus
focus of
extenso.
focus of the
Las
of the preceding
preceding
leyes
the sections
sections has
de conservación
preceding sections de been
has
has been on
masa
been on
y de
on closed
closed systems,
energía
closed systems, the
the concepts
se aplican
systems, the aconcepts
todos los
concepts pre-
pre-
procesos,
pre-
sented
sented
ya seansented
sistemasfind
find far
farmore
findabiertosmore
far more extensive
extensive
o cerrados.
extensiveDe application.
application. The
The
hecho, el sistema
application. laws
laws of
of
The lawsabiertomass
mass
of mass and
and
incluye energy
energy conservation
conservation
el sistema
and energy apply
apply
cerrado como
conservation to
to espe-
applycaso
to
all
all
cial. Por processes,
processes,
allloprocesses,
tanto, el toto
toopen
open
resto
open as
as well
well
deaseste as
as to
wellcapítulotoclosed
closed systems.
systems.
se dedica
as to closed systems. Indeed,
Indeed,
al tratamientothe
the
Indeed, the de open
open
open system
system
sistemas includes
includes
system abiertos the
includes ythethe closed
closed
al closed
desarrollo de
system
system
ecuaciones
systemde asasaaaspecial
aplicación
as special case.
specialmás
case.
case. The
Theremainder
extensa.
The remainderof
remainder ofthis
of thischapter
this chapteris
chapter istherefore
is thereforedevoted
therefore devotedto
devoted tothe
to thetreatment
the treatmentof
treatment of
of
open
open systems
systems and
and thus
thus to
to the
the development
development of
of equations
equations of
of
open systems and thus to the development of equations of wide applicability. wide
wide applicability.
applicability.
Medidas de flujo
Measures
Measures of
of Flow
Flow
Measures of Flow
Los sistemas
Open
Open abiertos
Opensystems
systemsare
systems se
arecaracterizan
are characterizedpor
characterized
characterized bycorrientes
by
by flowing
flowing que circulan;
flowingstreams;
streams;
streams; there
there existen
thereare
are
are fourcuatro
four
four common
common
common medidas de flujo
measures
measures
measures of comunes:
offlow:
of flow:
flow:
... ...
• Rapidez
•••Mass
de flujo
Mass
Mass flowrate,
flowrate,
flowrate, m ṁ ••••Rapidez
de masa,
m
m Molar
Molar de flujo molar,
Molarflowrate,
flowrate,
flowrate, nnn ṅ••• •Volumetric
Rapidez deflowrate,
Volumetric
Volumetric flujo volumétrico,
flowrate,
flowrate, qqq q • Velocidad,
••• Velocity,
Velocity,
Velocity, uuu u
Las medidas
The
The de flujo of
Themeasures
measures
measures están
offlow
of correlacionadas:
flow
flow are
areinterrelated:
are interrelated:
interrelated:
... ... ·
m
m
m ṁ
=
=M
= =MnMn
M nn y
and
and
and qqqq==
uAuuuAAA
=
=
donde where
M es laM
where
where Mmasa
M is
is molar.
ismolar
molar
molar En Importantly,
mass.
mass.
mass. forma importante,
Importantly,
Importantly, mass
mass la rapidez
massand
and
and molar
molar de flujo relate
molarflowrates
flowrates
flowrates de masa
relate
relate to y molar se relaciona con la
tovelocity:
to velocity:
velocity:
velocidad:

2.12.
2.12.Mass andandEnergy Balances forforOpen Systems 4545
2.12. Balances
2.12. de masa
Mass
Mass and y energía
Energy
Energy para sistemas
Balances
Balances Open
for Open abiertos
Systems
Systems 45 45
2.12.
2.12. Mass
Massand andEnergy
EnergyBalancesBalancesfor forOpen
OpenSystems
Systems 45
45
. . . .
mm .ṁ===uuArAρ (2.24a)
(2.24a)
n .n= = u Aρ
= uuAr
(2.24b)
(2.24b)
m.. = u Aρ u Aρ a
(2.24a)
(2.24a) n.ṅ. = uAρAρ b
(2.24b)
(2.24b)
mm = = uuAρ Aρ (2.24a) nn =
(2.24a) = uuAρ Aρ (2.24b)
(2.24b)
The area forforflow A is isthethecross-sectional areaareaofde ofa aun
aconduit, and ρ is isspecific orormolar
El
density.AThe
área Theparaarea
area
Althoughel for
flujo flow
es elAAárea
flow
velocity isis theade cross-sectional
sección transversal
cross-sectional
vector quantity, area
its of
scalar
conduit,
conducto,
conduit,
magnitude
and
and yuρrρisis specific
esused
la densidad
specific
here
molar
específica
orasmolar
thethe o
molar.average
Aunque The
density.
The area
area
laAlthough
density.speed for
Althoughfor
velocidad flow
velocity
flow
es
velocity A
A
una isis the
is the
cantidad
is aa cross-sectional
vector
vector quantity,
cross-sectional
vectorial,
quantity, su area
area its of
magnitud
its a
scalar
of
scalara conduit,
magnitude
conduit,
escalar
magnitudeand
and
u .
se ρ
uu
ρ .is
is specific
utiliza
is used
specific
used en here
este
here or
or molar
as
molar
caso
as the como la
ofofa astream . .
density. Although
average speed
density. speed
Although streaminen
a velocity
velocity isisthe
in athedirection
a vector
direction
vector
normal
quantity,
normal
quantity,
toto
its A.A.Flowrates
scalar
itsrespecto
scalar magnitude
Flowrates
magnitude
m,m,.uun,isis
.n,and
used q here
represent
andflujo
qqhere deas
asṁ,the
represent
rapidezmeasures
promedio
average of de una
of corriente
quantity stream
per unit in of dirección
thetime. normal
direction normal
Velocity ucon is to
quite a A. Lainrapidez
A. different
Flowrates m,
.. n,
nature, .. used
de
and
as it represent
does not
the
ṅ, y q re-
presentaaverage
measures
average
medidas
measures speed
of
speed
de
of laof
of a
quantitya stream
cantidad
quantity per
stream
per por
unitin
unitin the
of
the
unidad
of direction
time.
time. de normal
Velocity
direction normal
tiempo.
Velocity La
u u is
is to
to A.
quite
quiteA.
velocidad Flowrates
different
Flowrates
u es
different de in
in m,
m,
una n,
nature,
nature,n, and
andasq
naturaleza
as qit
it represent
does
represent
muy
does not
not diferente
suggest
measuresthethe
magnitude ofofflow. Nevertheless, it itis isan important design parameter.
suggest
measures
porque suggest
no theof
sugiere of quantity
quantity per
magnitude
lamagnitude
magnitud per
of unit
flow.
unit
delflow.
flujo. of
of time.
time.
Sin Velocity
Nevertheless,Velocity
embargo,
Nevertheless, it esis uan uanisis
un quite
quite different
important
importante
important design
different in
in
parámetro
design nature,
parameter.
nature,
parameter. as
as itit does
de diseño. does not not
suggest
suggestthe
themagnitude
magnitudeof offlow.
flow. Nevertheless,
Nevertheless,ititisisan animportant
importantdesigndesignparameter.
parameter.
Example
Example 2.11
2.11
Ejemplo
Example
Example2.11
n-hexane
Example
2.11
2.11
2.11
. . −1 in a pipe with inside diameter
Liquid
Liquid flows
n-hexane atata arate
flows rate . ==0.75
ofofmm 0.75kgkgsss−1
−1 in a pipe with inside diameter
Liquid n-hexane flows at a rate of m =
. .and 0.75 kg . · =would .
in a pipe with inside diameter
D==
El n-hexano=55líquido
DLiquid
Liquid 5cm. circula
cm.What
n-hexane
n-hexane
What are aq,una
flows
are
flows q,at
at arelación
n,.n, u?u?
rate
and
aand
rateu?of
of mm. m=
de
What
What 0.75 kg
0.75
would
= would
these
0.75 kg
kg ss–1
s−1en
these in una
−1quantities tubería
aa pipe
quantities
in−3 pipe
be
befor
with
with con
the diámetro
inside
for the
inside
same ..if if
interno
mm
diameter
same
diameter de
D = 5D
D
cm.= 2 cm?cm.
¿Cuáles
What
son
Assume are
los
q,
valores
for n,
.
liquid
. n-hexane
de q, ·
n
What
y u? =
¿Cuáles
that ρ these
659serían
kg quantities
m estas
.
−3
be for
cantidades
the same
para la .. if m· si
m
misma
=
DD ==2525cm?
cm.
cm? What
What are
Assume
cm. Assume are q,
for
for n, and
n,
liquid
q,liquid n-hexane
and u? What
u?
n-hexane What would
that =these
ρρ =
would
that 659kg
these kgquantities
m−3 .
quantities be
be for
for the
the same
same mm ifif
D
D = 2 cm?
659 –3 m−3 .
DD ==Suponga
22 cm? que parafor
cm? Assume
Assume elliquid
for n-hexano
liquid líquidothat
n-hexane
n-hexane r =ρρ659
that = kg
659mkg
= 659 kg.m m−3..
Solution 2.11
Solution 2.11
Solución 2.11 2.11
Solution . .−1 . . . . −1
Solution
Solution
We have 2.11
2.11 q q==mρ and n .n=
We have q = mρ
. −1
mρ −1 and n= =mm .MM−1 −1
· r –1 n· =n.n.m=
· Mm.–1
We have ..= −1 and M −1
Tenemos
Weque
Wehave
have qq = q
= mρmρ m
−1 y
−1 and
and = mmM
.
M −1
0.75
0.75 kgkgs s−1 −1 3 −1
whence
whence q q== 0.75 kg −3 s−1==0.00114 0.00114mm3s3 s−1 −1
whence q =659 0.75
0.75
659 kgkg
kgmm
kg −3 = 0.00114 m3 s−1
−1
ss−3
de donde whence
whence qq =
= 659 kg m−3 == 0.00114
0.00114m m ss−1
3
659 −1
659 kg
kg mm 3−3 −1
. . (0.75
n .n= (0.75kg kgs ss−1
)(10
−1 )(103g3 ggkg kg−1 ))
−1
)==8.703 −1
n.. == (0.75
(0.75
kg
86.177
kg s −1
−1g
)(10
mol
)(10 3−1
3 g−1
kg
kg −1
−1) = 8.703mol
8.703 mols ss−1
mol
−1
kg s )(10
(0.7586.177 g mol g kg )
−1 −1
. . nn = = 86.177 g mol−1 == 8.703
8.703mol molss−1
Given
Givenm,m,
. thesethesequantities
quantities 86.177
are
86.177
are mol−1 ofofD.D. The
ggmol
independent
independent The velocity,
velocity,however,
however,de-de-
Givenonm,
pends these quantities
..diameter through u are= independent
q A −1 , where,offor
−1
D.a circular
The velocity, however,
cross-section, A Ade-
==
· Given
pends
Given
Dada m(π/4)D
,pends m,
on
2m,
these
diameter quantities
these son
estas cantidades
on diameter through
quantities are
u
independientes=independent
q A−1
uare= independent ,
de, D. where, of D.
for
Noofobstante, aThe velocity,
circular
D.a circular however,
cross-section,
Thela velocity,
velocidad however, de-
de-
dependeAdel
= diáme-
. 2For DD==5through
5cm, uu =
q A−1 where,
qqAA−1,transversal
for cross-section,
pends
pendsuon
(π/4)D
tro mediante
(π/4)D on .diameter
=22 .qAFor
–1,D
diameter
For = through
donde cm, una
5through
para
cm, =
sección , where,
where, for aa circular
forcircular,
circular (p/4)D2. ParaAAD=
A =cross-section,
cross-section, == 5 cm,
(π/4)D 2.. For
(π/4)D For DD = = 55cm,cm,π π� � −2
�2� 2
A A== π 5� × × 1010−2 −2 mm�2= 2 0.00196 m 2
=0.00196
A =4ππ 4 ��55× 10−2 m ��22 = 0.00196m m2
2
AA == 4 5 × 10 −2
5 × 10 m = 0.00196 m2
m = 0.00196 m
44
0.00114 3 −1
whence 0.00114mm
u u== 0.00114 m3s3 ss−1−1
==0.582 −1
de donde whence
whence u = 0.00114
0.00196 mm 3 2
3 s −1
2−1 = 0.582mm
0.582 ms ss−1
−1
0.00114
0.00196 m m 2s −1
whence
whence for D = 2 cm,
Similarly,
uu == 0.00196 m22 = = 0.582
0.582m mss−1
De manera similar,for
Similarly, para
for D =
D= 2 2 cm,
cm, 0.00196
0.00196 mm
Similarly, D= 2 cm,
Similarly,
Similarly,for for DD = = 22cm,cm, 0.00114
===0.000314 22 0.00114= 3.63 m s−1−1
AA A 0.000314
0.000314 mmm 2
2 yand
and u u== 0.00114 = 3.63 m s−1
A = 0.000314 m2 and u =0.000314
0.00114 = 3.63 m s−1
0.00114
0.000314
AA == 0.000314
0.000314m m2 and
and uu == 0.000314 = = 3.63
3.63m mss−1
0.000314
0.000314
Balance de masa para sistemas abiertos

Mass
MassBalance
Balancefor forOpen
OpenSystems Systems
Mass Balance for Open Systems
Mass
Mass
La región
The del Balance
Balance
espacio que es for
for Open
identificada Systems
Open Systems
para el análisis de systems
sistemas abiertos se llama volumen de control; se
Theregion
encuentra regionofofspace
Theseparada
region of spaceidentified
despace identifiedforforanalysis
sussurroundings
alrededores analysisofofopen
mediante
identified for una open systemsis iscalled
superficie calleda acontrol
de control. controlvolume;
El afluido volume;it itis is
dentro del volumen de
separated
The from its bybyanalysis
a acontrolofsurface.
open systems
The is called
fluid within control volume;
thethecontrol volumeit is
elregion
separated
The region
control separated
es sistemaof
from
from space
its identified
its surroundings
surroundings
oftermodinámico
space identified for
for
para analysis
byel se of
control
analysis
aque
control open
open systems
surface.
ofsurface.
escriben The
systems
losThe is
is called
fluid
balances
fluidcalled
de aa control
within
masa
within control
y de
the volume;
control
volume;
energía.
control itit is
volume
El
volume is
volumen
separated
separated from
from itsits surroundings
surroundings by by aa control
control surface.
surface. The
The fluid
fluid within
within thethe control
control volume
volume

46 CHAPTER 2. 2.
TheThe
First Law andand
First Other Basic Concepts
46 46 CHAPTER
CHAPTER 2. The First LawLaw Other
and Other Basic
Basic Concepts
Concepts
46 46 CAPÍTULO
Conceptsbásicos
ṁ1 ṁ 3
ṁ1 ṁ1 ṁ 3 ṁ 3
ṁ1 ṁ 3
ṁ1 ṁ 3
ṁ1 ṁ 3
Control
Controlvolume
volume
Control volume
Figure 2.5: Schematic representation of a Control
dmcvdmvolume
/dt /dt
Figure
Figure 2.5:2.5: Schematic
Schematic representation
representation of aof a dmVolumen
/dtcv
de control
control
Figure volume.
2.5: Schematic dmcv
Control cvvolume
/dt
Figura 2.5: control
control volume.
Representación
volume. esquemática de unofvolumen
representation a dmcv /dt
control
Figure volume.
2.5: Schematic representation of a dmcv /dt
de control.
control volume.
Control surface
Control surface
ṁ 2 Control surface
ṁ 2 ṁ 2 Control surface
ṁ 2 Superficie de control
ṁ 2 Control surface
ṁ 2
is theis thethermodynamic
thermodynamic systemsystem for which mass and energy balances are written. The control
is the thermodynamic system for for which which mass mass andand energy energy balances
balances are are written.
written. TheThe control
control
de control
volume
is theque
volume se muestra
shown
thermodynamic
shown en
schematicallyforma
system
schematically esquemática
in
for Fig.
in which
Fig.2.5 isen
mass
2.5 is la
separated
andfigura
separated energy 2.5
from from está
its
balancesseparado
surroundings
its are
surroundings de
written.sus
by an
by alrededores
The controlpor una
extensible
an extensible
volume shown schematically in Fig. 2.5 is separated . . from . . its surroundings
· ym · están by an extensible
superficie de control
control
volume
is the
control surface.
shown
thermodynamicextensiva.
surface. Two streams
schematically Dos
system corrientes
with
inforFig. flow
which 2.5conrates relaciones
is rates
mass m
separated1 and
.and de
m. flujo
from
energy are m
itsshown directed
surroundings
balances 1 are written.
2 directed dirigidas
into
by the
anThe hacia
control
extensible el volu-
control surface. TwoTwo streams
streams with withflowflow. rates. m· . 1 mand1 and m. 22mare 2 are
shownshown directed intointothe the control
control
men de volume,
control,
control
volume
volume, y
and una
surface.
shown onecorriente
stream
Two con
with
streams
schematically relación
flow
with
in rate
Fig. de
flow m
2.5. flujois
rates
is m
directed
m
separated está
and
is .3directed dirigida
out.
m
from Because
areits hacia
shown afuera.
mass is
directed
surroundings Dado
conserved,
byintoanque
the la
the masa
extensible rate
control se con-
volume, andand oneone streamstream with with
flowflow raterate m. 33m is3directed 1
out. . out.
2 Because
Because mass mass is conserved,
is conserved, the theraterate
serva, laof rapidez
change
volume,
control
of change de
andof
surface.cambio
mass
one stream
Two
of mass de
within la masa
with
streams
within the flow
withdentro
control rate
flow del
volume,
m volumen
is
rates dm
directed
m and de/dt,control,
out.
m equals
Because
are dm
shownthemass
cvthe/ dt,
net es
rate
is
directed igual
of
conserved,
into a
flow la
the rapidez
of
the of mass de
mass
rate
control neta
of change of mass within the the controlcontrol . volume,
3
volume, dm 1 dm cv cv /dt,
cv /dt,
2
equalsequalsthe net netraterate of flow
of flow of mass
flujo deinto
ofmasa the
change
volume, en el
control
andof interior
mass
one volume. del
within
stream volumen
The
withthe convention
control
flow de
rate control.
is
volume,
m isthat La flow
dm
directed convención
is
/dt,positive
out. equalses
Because que
when
themassel
net flujo
directed
rate
is es
of positivo
into
conserved,flowthe of
the cuando
rate está
control
mass
intointo the the control
control volume.
volume. TheThe convention
convention 3 is that flow
is that flowcvis positive is positive when when directed
directed intointothe the control
control
dirigidovolume
ofhacia
into the
change
volume el volumen
and negative
control
of de
volume.
mass control,
when
within The the y
directed negativo
convention
control out. cuando
The
is
volume, mass
that se
flow
dm dirige
balance
is
/dt, hacia
positiveis
equals afuera.
expressed
when
the El
directed
net balance
mathematically
rate into
of de
flowthe masa
of by:
control
massse expresa
volume andand negative
negative when when directed
directed out.out. TheThe mass mass cv balance is expressed mathematically by:
balance is expressed mathematically by:
en forma matemática
volume
into the and control por:
negative
volume. when The directed
convention out. The is that mass flow balance
is positive is expressed
when directed mathematically
into the control by:
volume and negative when directed out. dm cvThe mass. balance . = 0 is expressed mathematically (2.25) by:
dmdm cv + cv �(m)
+ �(. fs m) = 0 (2.25) (2.25)
dm dtcv + �(m) . fs = 0 fs (2.25)
dmdt dt+ �(m)fs = 0 (2.25)
dtcv .
+ �(m)fs = 0 (2.25)
donde elwheresegundo thethe término
second para
term el for
for volumen
thethe control devolume
control
dt ofque Fig.se 2.5muestrais: en la figura 2.5 es:
where the second term for the control volume of Fig.Fig.
where second term control volume of 2.52.5 is: is:
where the second term for the control .volume. of Fig. . 2.5 is:
.
�( m)
. .=m . . m
− . . m
− .is:2m. 2
where the second term for the control �(m) �( m)
fs
.volume = fs m=.
3
ofm− Fig.
3 −
m .
1 m
2.5
− 1 m−.
�(m)fsfs = m33 − m11 − m22
El operador dedifference
The difference diferencia operator“Δ” en “�”este here caso representa
.
signifies
m)fs =
. la diferencia
the difference . . entreexit
between los flujos
and entrancede salida flowsyflows
entrada,
and y el
TheThe difference operator
operator “�”“�” herehere �(signifies
signifies themthe 3 −difference
differencem1 − m 2 between
between exitexitandand entrance
entrance flows andand
subíndice The“fs”
the indica
subscript
difference que
“fs” el
operator término
indicates “�” se
that
here aplica
the term
signifiesa todas
applies
the las to corrientes
all
difference flowing que
between circulan.
streams.
exit and entrance flows and
the the subscript
subscript “fs”“fs” indicates
indicates thatthat .the.theterm termappliesapplies to all to flowing
all flowing streams.
streams.
Cuando
the
Thesubscript laWhen
When
differencerelación
the
“fs”massde flujo
flowrate
indicates
operator “�” dethatmasa
m
here. is
the está
given
term
signifies dada
by
applies
theEq.por to la
(2.24a),
all
difference ecuación Eq.
flowingbetween (2.24a),
(2.25)
streams. la
becomes:
exit andecuación
entrance (2.25)
flows seand convierte
When the the mass mass flowrate
flowrate m. ismgiven is given by Eq. by Eq. (2.24a),
(2.24a), Eq.Eq. (2.25)
(2.25) becomes:
becomes:
en: When the
the subscript “fs”mass flowrate
indicates thatmthe is given
term appliesby Eq. to (2.24a),
all flowing Eq. (2.25)streams. becomes:
. dmdm cv cv
When the mass flowrate m isdm givencv + by�(ρu+Eq. (2.24a),
A) = Eq. 0 (2.25) becomes: (2.26)
dm dtcvdt+ �(ρu �(ρu A)fsfsA)=fs 0= 0 (2.26)
(2.26) (2.26)
dt + �(ρu A)fs = 0 (2.26)
dm dtcv
De estaInIn this
forma, form
la formthe mass-balance
ecuación del balance equation
deequation
masa +
is often �(ρu called A) fsthe= 0continuity equation. (2.26)
In this
this form the the mass-balance
mass-balance equation dtasisse isllama
often oftencalledecuación
called the the decontinuity
continuidad.
continuity equation.
equation.
thisThe
ElInproceso formTheflow
de the
flujo
flowprocess
mass-balance characterized
caracterizado
process equation
como
characterized is as
un steady
often
estado
steady state
called is an
the
estacionario
state is important
continuity
an es un
importantcaso special
equation. especial
special case e
casefor which
importante,
for whichen el
The flow process characterized as steady state is an important special case for which
conditions
In thisThe
cual lasconditions
condiciones formflow
conditions within
the
dentro
within thedel
process control
mass-balance
the volumen
control volume
characterized
equation
de
volume do
control not
asisdosteady
often
no change
not statewith
called
cambian
change iscon
the an
with time.
continuity
el TheThe
important
tiempo.
time. control
special
equation.
Por lo
control volume
case
tanto el
volume then
for
volumen
thencon-
which de con-
con-
within the control volume do not change with time. The control volume then con-
tains
trol contiene auna
conditions
tains constant
The a within
flow
masa
constant massthe
process
constante
massof fluid,
control
of de andand
volume
characterized
fluido
fluid, the
y first
do
el
the or accumulation
not
asprimer
steady
first change
or statewith
término
accumulation isdean term
time. of Eq.
The
important
acumulación
term of (2.25)
control
special
Eq.de la
(2.25)is
volumezero,
case
ecuación
is reducing
then
for
zero, con-es cero,
which
(2.25)
reducing
tains a constant mass of fluid, and the first or accumulation term of Eq. (2.25) is zero, reducing
Eq.
con lo quetains (2.26)
aecuación
conditions
la to:
constantwithin massthe of fluid, volume
control and the first do not or accumulation
change with time. term The of Eq. (2.25)volume
control is zero,then reducingcon-
Eq.Eq. (2.26) (2.26)to: to:(2.26) se reduce a:
Eq.
tains(2.26)
a constant to: mass of fluid, and the first �(ρu or
�(ρu A)fsA)=fs 0= 0 term of Eq. (2.25) is zero, reducing
accumulation
�(ρu A)fs = 0
Eq. (2.26) to: �(ρu A)fs = 0
The term “steady state” does not necessarily imply thatthat flowrates are constant, merely that thethe
TheThe term term “steady
“steady state”state”does does
notnot necessarily
necessarily �(ρu A)imply
imply fsof =
that 0 flowratesflowrates are are constant,
constant, merelymerely thatthat the
inflow
The
Elinflow term
término
inflow of mass
“steady
“estado
of mass is exactly
state”
estacionario”
is exactly matched
does not
matched noby by the
necessarily
implica
by the outflow imply
necesariamente
outflow mass.
that flowrates
of mass. are constant,
que las relaciones de flujo sean merely thatconstantes,
the
of mass is exactly matched the outflow of mass. . .
inflow
The
sino sólo queWhen When
term of mass there
“steady
el flujo is is but
exactly
state”
dethere
masa a
does
is hacia single
matchednot
a dentro entrance
by the
necessarily and
outflow
es exactamente a
imply single
of mass.
that
igual exit stream,
flowrates the
are mass
constant, flowrate
merely m.
thatis the
When there is but but
a single single entrance
entrance andand a single
a single exital exitderrame
stream,
stream, thedethemasa.
mass mass flowrate
flowrate m. ismthe is the
same
inflow
Cuando same for
When
of
sóloboth
mass
for hay
bothstreams;
thereisuna butthen,
is corriente
exactly
streams; amatched
single
then, que entrance
by
entra and
theyoutflow
una acorriente
single
of mass. exit
que stream,
sale, la the mass flowrate
relación de flujo mdeismasa the es la
same for both streams; then, .
misma parasameambas for
When both streams;
there
corrientes; then,
is butpor a single
esto, entrance ρ u A and − ρa singleu A = exit0 stream, the mass flowrate m is the
ρ22uρ222Au222 A −2ρ−11uρ111Au111 A =1 0= 0
same for both streams; then, ρ 2 u 2 A 2 − ρ1 u 1 A 1 = 0
ρ 2 u 2 A 2 − ρ1 u 1 A 1 = 0

2.12.
2.12.Mass
2.12. Balances Massand
andEnergy
de masa Balances
yEnergy Balances
energía for
forOpen
para sistemasOpenSystems
Systems
abiertos 4747 47
2.12.
2.12.2.12.
2.12.
Mass Mass
Mass and
Mass
and and
and
Energy Energy
Energy
Energy Balances
Balances
Balances
Balances for Open for
forfor
OpenOpen
Open Systems
Systems
SystemsSystems 47
47 4747
..
o oror . . .m .m==const
const==ρρ 2u2u 2 2AA 2 2==ρρ 1u1u 1 1AA
11
or or or
or m m=
m = const=const
m ==const
ρ2= =2ρ
u 2=ρA
const 2=
2uρ2u =
u2ρ22A1A
2A 2u21==1ρ
ρA 1uρ u111AA1 1
1A
11u
Dado Because
queBecause specific
specific
el volumen volume
volumeis
específico esisthe
elthereciprocal
reciprocal
recíproco deofof density,
density,
ladensity,
densidad,
Because
Because
Because
Because specific
specific
specific
specific volume volume
volume
volume isis
thethe
is theisreciprocal
the reciprocal
reciprocal
reciprocalofof ofdensity,
density,
of density,
. . uu1 1AA1 1 uu2 2AA2 2 uuAA
. .u 1.m
A.m1u 1= 1 2u=
=uAu 1uAA1 A 2=
uAu222uAAA ==
22 u AuuAA (2.27)(2.27)
(2.27)
m = m m= m= ==11V2V 1=1=== VV 2=2== VV (2.27)
(2.27)
(2.27) (2.27)
V1 V1VV 1V1 2 V2VV 2V2 V VV
Esta forma
This de la
form ecuación
of the de continuidad
continuity equation es de uso
finds frecuente.
frequent
This form of the continuity equation finds frequent use. use.
This
This This form
This
form form
ofform ofofthe
the
theofcontinuity
the continuity
continuity equation
equation
continuity
equation findsfinds
equation finds
finds
frequent frequent
frequent
use. use.
frequent use.
use.
The
TheGeneral
El balance Energy
General Energy
energético Balance
Balance
general
The The
The
The General
General
General
General Energy
Energy
Energy
Energy Balance
Balance
Balance
Balance
Because
Becauseenergy, energy,like likemass,mass,isisconserved,
conserved,the theraterateofofchangechangeofofenergy energywithin withinthe thecontrol
controlvolume volume
Ya que
Because la
Because
Because energía
Because
energy,
equals
equals energy,
energy,
thelike
the senet
energy,
net conserva,
like
mass,rate like
like
rate mass,
of mass,
ismass,
of alis
is
conserved,
energy
energy igual
isconserved,
conserved, que
conserved,
the rate
transfer
transfer lathe
into masa,
the
intothe
rate
of rate
rate of
change
thethe lacontrol
of rapidez
of
change
control change
change
of energyofde
volume.
volume.ofofcambio
energyenergy
energy
within
Streams de
within
the
Streams energía
within
within thethe
control
flowing the
control
flowing dentro
control
control
volume
into
into del
volume
volume
volume
and
and volumen
out
out ofof de
control
equalsequals es
equals
equals
the
the igual
the
net the
the
thecontrol net
rate a
net la
net
rate
of
controlvolume rapidez
rate
rate of
energy
volumehave of of
energy neta
energy
energy
transfer de transferencia
transfer
transfer
transfer
haveassociated into into
the
associatedwith into
into the
control the
the
withthem de energía
control
control
control
volume.
themenergy volume.volume.
volume. en
Streams el volumen
StreamsStreams
Streams
energyininitsitsinternal, flowing de
flowing
into control.
flowing
flowing
internal,potential, into
and into
into
potential,and and
out Las
and
andofout corrientes
out
out of
andkinetic ofof
kinetic que
circulan
the the
thethe
control hacia
control
control
forms,
forms,volumedentro
control volume
and
and volume
have
all
allycontribute
volume hacia
have have
have fuera
associated
contribute associated del
associated
associated
toto with
the volumen
the with with
with
them
energy
energy themdethem
them
energy
changecontrol
changeenergy energy
energy
in se
ofofits in
thetheasocian
insystem.
inits itsits
internal,
system. con
internal,
internal,
internal, energía
potential,
Each
Each en
potential,
potential,
potential,
unitand
unit mass sus
and
mass andformas
and
kinetic
ofof akinetic interna, po-
akinetic
kineticstream
stream
tencial
forms, ycarries
forms,
forms,
and cinética,
forms, and
all and
and
carrieswith all y
all
contributetodas
all
contribute
contribute
withitita atotal contribuyen
contribute
to the
totalenergy to
energytoto
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energythethe al
energycambio
energy
1 1 2 change
energy
change
UU++12 uu ++zg, 2 de
change
change
of energía
theof
zg,where of of
the del
the
the
system.
whereuuisisthesystem. sistema.
system.
system.Each
theaverage Each Cada
Each
Each
unit
averagevelocity unidad
unit unit
unit
mass mass mass
mass
of
velocityofofthe a deof masa
ofof
a
stream stream,z ziscorrien-
a de
stream
a
thestream, streamuna
stream is
1+12 u 2 + zg,
te lleva
carries
carries consigo
carries
carries
with with
it with
with
a
itsitselevation una
it
total a
it
elevationabove it
a energía
a
total total
total
energy energy
abovea adatum total
energy
U +
energy
datum U1 +
U
u 2+
U
2 level, + u u
zg,
2 2 2and
level,
2 where
+ + zg,
andggisisthezg, donde
where where
where
u is u
the
thelocal u
localu
is u es
is is
the the
average lathe
acceleration
accelerationvelocidad
average
average
average
velocity promedio
velocity
velocity
velocity
of the
ofofgravity.
gravity.of of of
the
stream,
Thus, de
the
the
Thus, la corriente,
stream,
stream,
stream,
z
eachis
each z zisis z es su
zstream
is
stream
elevación sobre un nivel a de referencia yis es . .acceleration
its its
itsits
elevation elevation
elevation
elevation
above
transports
transports above above
aabove
datum
energy
energy aataat
datum datum
datumthelevel,
level,
the and
rate level,
level,
rate (U and
g(U g+and
and +the u1laglocal
g1gis
12 2 2u.��
aceleración
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the
2is
+the
+the local
zg) local
local
acceleration
.zg).m.
.m.The
local
acceleration
acceleration
The net deenergy
of
net laofgravedad.
gravity.
energy ofofgravity.
gravity.
gravity.
Thus,
transported Así,
Thus,
transported Thus,
Thus,
each cada
each
into each
stream
into corriente
eachstream
the
the stream
stream
system
system transpor-
ta energía
transports en proporción
transports
transports
transports energy energy energy
energy
at theatrate de
atthe
atthe the
rate
(U +(U2(U
rate
rate 1 ++
u(U 2 1
++ u1 2u
zg) +
u +
m. +
zg)��
Por
zg)zg)
m.
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m.
The
net tanto,
The
The net
energynet la
net �energy
energy� � �transported
energía
energy
transported neta transportada
transported
transported
into into
the into
into the
system hacia
the
the system adentro
system
system del
. .
−�� m � , wherethe
2�� zg
�� UU++112 �u1 u2 .2+ �+ . �.m
�zg
bybythe 2 2−�
theflowing
flowingstreams streamsisistherefore therefore . fsfs, where theeffect
effectofofthe theminus
minus
sistema
by byby
the bypor
the
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the las
flowing corrientes
flowing
flowing
streams streams streams
streams que
is is
is therefore circulan
is −�
therefore
therefore
therefore es−�
−� U−� + UU 1
u+ 2
U+ +1 12
+u2zg2u+
2
u+ 2 +zg
mzg zg mm
,mwhere , ,,where
,fswhere donde
where
the thethe
effect el
the efecto
effect
effect
of del
theofminus
effect of ofthe
the signo
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signwith with“�” “�”isistotomake makethe theterm termread read2inin−− 2 out.
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The fsrate ratefsof offsenergy
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accumulation
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withinthe the
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with hacer
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controlwith
control que
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isvolume
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make is to
istoincludes
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term
read read
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quantity − in
read inin
out. inin −
−addition
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the rate de
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heat acumulación
of
heatof
energy energy
energy
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transfer
transfer . de
accumulation
rate
rate .Q.Qlaand
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and thedentro
within
work within
within
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volume volume incluye
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and
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rate:
d(mU �� ..
d(mU)cv )cv�� 1� 1 2 2+ � � � � �m �..m �. +
d(mU )cv dtd(mU d(mU
d(mU ) ) )
cv cvcv
= = −�−� U U + + u
222 .
1 u + zg zg
. . fsfs. + .Q.Q++work workrate rate
1 2 1 1 2
= dt −� ==−� =−� U−� + U2 U u+ U+ +2
+u2zg u+
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fs +mm Qfs+
fs +fs+ +Q+
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work Q+ razón
+
work work
work
rate de
rate trabajo
rate
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dt dtdtdt
Q̇Q̇ u 2u 2 u 2u 2
Q̇ Q̇
Q̇ Q̇Q̇ u2 u 2u 2uuu222 u 2u 2uu22
Actual
Actual
Actual Actual
Perfil
Actual
Actual de
velocity
velocity
velocity velocity
velocity
velocidad
velocity
profile
profile
Control
Control profile
Volumen profile
profile real
profile
Control Control
Control
Control
volume
volume
de
volume
volume control
volume
volume
PP
P V,V,U,U,HH u1u1 ẆẆ
P P PP V,U,
U,HHH ss
V, U, H V,
V, V,
U, HU, u1 u1 u1uu11 Ẇ
ẆsẆẆ
Ẇs s ss
Figure
Figure2.6:
2.6:Control
Controlvolume
volumewith
withone
oneentrance
entranceand
andoneoneexit.
exit.
Figure Figura
Figure
Figure
Figure
2.6: 2.6:
2.6:2.6:
2.6:
Control Volumen
Control
Control
Control
volume de control
volume
volume
volume
with with
one con
with
one
with one
one una entrada
entrance
entrance
entrance and
entrance
and oneand y one
and
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exit. onesalida.
exit.
exit.
exit.
The
Thework
workrate
ratemay
mayinclude
includework workofofseveral
severalforms.
forms.First,
First,work
workisisassociated
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include
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entrances
entrances of
ofandseveral
several
several
forms.
andexits.
exits.forms.
forms.
forms.
First,
The
The First,
First,
work
fluid
fluidwork
First, is
atatwork
work is is
associated
any
any associated
associated
is associated
entrance
entrancewith
ororwithwith
moving
exit
exithas moving
moving
with moving
hasa aset
setofof con el
theLa
the
the
the flowing rapidez
flowing
flowing
flowing
averagestreamsdel trabajo
streams
streams
streams
through
properties,
puede
through
through
through
entrances
P, V , U
incluir
entrances
entrances
entrances
, Hand,
el
and
etc.
trabajo
and
and
exits. exits.defluid
exits.
exits.
The
Imagine
varias
The The
The
thatfluid
at
a
formas.
fluid
fluid
anyat
unit atat
any Primero,
any
any
entrance
mass entrance
entrance
entrance
of
average properties, P, V , U , H , etc. Imagine that a unit mass of fluid with these properties or el
or
exit
fluid
trabajo
oror
exit
has
with exit
exit
a está
hashas
has
set
these a
ofaasociado
a
set set
of
set ofof
properties
movimiento
average
average
average average deproperties,
las corrientes
properties,
properties,
properties, P, VP, ,UP,P, que
HV
V, ,VU,,,U circulan
UH, ,H
,etc. ,H
etc.
ImagineaImagine
, ,etc.
etc.través
thatde
Imagine
Imagine las
athat
that
unitaentradas
thata aunit
unit
mass unit
massymass
ofmasslas salidas.
ofof
fluid of
fluidfluid
fluid
with El
with fluido
with
with
these these
these
these enproperties
cualquier entrada
properties
properties
properties

48 CHAPTER 2. 2. TheThe First First Law and and Other Basic Basic Concepts
Concepts
48 48
48
CHAPTER CAPÍTULO 2. LaLaw
CHAPTER 2. The First Law and Other Basic Concepts
primeraOther ley y otros conceptos básicos
exists at an entrance or exit, as shown in Fig. 2.6 (at the entrance). This unit mass of fluid is
o salidaexists
tiene at
exists
acted un
at an
upon conjunto
an entrance
entrance
by deor
additional propiedades
or exit, as
exit,fluid,
as shown
shown
here promedio,in Fig.
in
replaced
Fig.P,2.62.6
by
(at H,
V, a(at
U, theetc.
the
piston Suponga
entrance).
entrance).
which This
exerts quethe
This una
unit
unit masa
mass of
mass
constant unitaria
of fluid
fluid is
pressure de fluido
is
con estas exists
acted at an by
upon
propiedades
acted upon entrance
by additional
existe
additional or una
en exit,
fluid,
fluid, as here
entradashown
hereoreplaced
unain Fig.
replacedsalida, 2.6
bycomo
by aa(at the
piston
pistonse entrance).
which exerts
muestra
which exerts
en This
la unit
the
figura
the mass
constant
2.6
constant (en ofpressure
fluid
pressure
la entrada).is Esta
P. Theupon
acted workbydone by this fluid,
additional pistonhere in movingreplaced theby unit aque mass through
piston which the entrance
exerts the is P V ,pressure
constant and the
unidad P. P. masa
de The work
The work
del done
fluido
done .by
by this
actúa thissobrepiston
piston in
el in moving
fluido
moving the unit
adicional,
the unit mass
mass aquí through
es sustituido
through the entrance
the entrance
por unis ispistón
PPVquantities,
V,, and
and the
que the pre-
ejerce
work
P. The rateworkis (P doneV ) m..
. by Because
this piston “�” denotes
indenotes
moving thethe difference
unit massbetween between
through exit
the andand
entrance entrance isa P V , and the
work
sión constante
work rate
rateP. is (P
El
is (P
trabajo
VV))m.m. Because
Because “�”
“�”este denotes
pistón en the
the difference
movimiento,
difference between
. the system when all entrance and exit sections are taken into accountlais entrada
hecho por de la exit
unidad
exit and
de entrance
masa
entrance quantities,
través
quantities,de
the
work netrate
work is (Pdone V ) m.on Because ·
“�” denotes the difference between exit and entrance quantities,
the
es PV, ythe net work
la net
rapidezwork .dedone
done
trabajo on the the(PV)m
es system whenque
. Dado all entrance
entrance
“Δ” denota andlaexit
exit sectionsentre
diferencia are taken
taken
las into account
cantidades account is y de
de salida
−�[(P
the net V V )m]
work .. fsdone . on on the system
system when
when cuando
all
all entrance
and
and exit sections
sections are
are taken.into
into
account
is
is
−�[(P
entrada,−�[(P
el trabajo V))m]m]
neto fs . . realizado en el sistema
. fs form of work is the shaft work indicated in Fig. 2.6 by rate W se consideran todas las secciones . s . In addition de sali-
de entrada y
−�[(P Another
·V ) m] . .
da es –Δ[(PV)m Another form of
]fs.be fsassociated of work
work is is the
the shaft
shaft workwork indicated
indicated in in Fig.
Fig. 2.6 2.6 by by rate rate W W.ss.. In In addition
addition
work Another
may
Another
form
form es of el with isexpansion
work thepor shaft or
work contraction
indicated ofinthe Fig. control
2.6laby volume
rate WẆ and there . may
work
Otra
work may
forma
may betrabajo
de
be associated
associated with
señalado
with expansion
expansion la or
flecha
or contraction
en
contraction la of the
figura
of the
2.6 control
por
control volume
rapidez
volume s .. Además,
and
and In
thereaddition
there mayel trabajo
be stirring work. These forms of work are all included in a rate term represented s by W .. . may
The
se puede work
be
be asociarmaycon
stirring
stirring be la
work.
work. associated
These forms
expansión
These with
formso la expansion
of
of work are
contracción
work orall
are contraction
all
del included
volumen
included inof
inde aathe
ratecontrol
control
rate term
term y volume
represented
ahí se
represented andby
considera bythere
WWtrabajo
. . may
. The
The de agi-
preceding
be stirring equation
work. may now
These forms beofwritten:
work are all included in a rate
preceding
tación. preceding
Todas estas equation
formas
equation may now be
de trabajo
may now beestán
written:
written: incluidas en un término determ represented
la rapidez representadoby W . The por Ẇ. La
preceding equation may now ��
be written: � �
ecuación anterior ahora d(mU se puede
)cv escribir �� como: 1 2 . .
� �� + Q. − �[(P V )m] + W. . .
d(mU))cv
d(mU cv = −� �� U + 21 u 2 + zg� m .. �fs + Q . − �[(P V )m] .. fs .
d(mU dt )cv = = −� −� ��U U+ + 12uu2 + + zg zg �m m . fsfs + Q. − �[(P V )m] . fsfs ++W W .
dt
dt 1 2
2
= −� U + 2 u + zg m fs + Q − �[(P V )m]fs + W
Combination of terms dt in accord with the definition of enthalpy, H = U + P V , leads to:
Combination of
Combination of terms
terms in in accord
accord with with the the definition
definition of of enthalpy,
enthalpy, H H= =U U+ + PPVV,, leads leads to: to:
La combinación
Combination de términos
of termsd(mU dein acuerdo
accord
)cv with con the la��definición
definitionde of entalpía,
� � HH=.=
enthalpy, UU + .PV,
+ Pnos lleva a:
V , leads to:
�� 1 2 .
� �� + Q. + W.
d(mU))cv
d(mU cv = −� �� H + 21 u 2 + zg� m .
. � +Q+W
fs . .
d(mU dt )cv = = −� −� ��H H+ + 12uu2 + + zg zg �m m . fs + Q. + W.
dt
dt = −� H + 212 u 2 + zg m fsfs + Q + W
which is usually written: dt
lo que porwhich
which lo regular
is usually
is usually se escribe
written:como:
written:
which is usually written: ��
d(mU )cv
d(mU ) + � ��H + 1 u 2 + zg�� m. �� = Q.. + W..
�� (2.28) (2.28)
d(mU dt ))cv
cv
+ � ��H H+ + 1212uu22 + + zg � m .. �fs = Q . +W . (2.28)
d(mU dt cv + � 21 2 zg m. fs fs = Q. + W. (2.28)
dt + � H + 2 u + zg m fs = Q + W (2.28)
La velocidad u en los términos dt de energía cinética de los balances de energía es la magnitud media de
The velocity u in the kinetic-energy terms · /rA. of energy balances is the bulk-mean velocity
la velocidad, como
The velocity
The sethe
velocity define uu in por
in the
the lakinetic-energy
ecuación, . u=m
kinetic-energy terms
terms Los
of
of fluidos
energy
energy que circulan
balances the en
is the tuberíasprofile,
bulk-mean exhiben
velocity un per-
as defined The by
velocity equation,
u in the u = m/ρ
..
kinetic-energy A. Fluids
terms flowing
of energy in balances
pipes
balances
is
exhibit
is the abulk-mean
velocity
bulk-mean
velocity as
fil de velocidad,
as
as defined
defined
shown in comoby
by the
Fig.
the se equation,
2.6, muestra
equation,
which enu la
u
rises
= figura
=from m/ρ
m/ρ. zero A.2.6,
A. elthe
Fluids
Fluids
at cual se incrementa
flowing
flowing
wall (the
in pipes desde
pipes
inno-slip exhibit
exhibit
condition) elavalor
a velocity
velocity
to cero
a envelocity
las paredes
profile,
profile,
maximum
as
as
at (la
condición as defined
de
shown
shown noin
in by
Fig.
Fig. the
deslizamiento)2.6,
2.6, equation,
which
which hasta
rises
rises u =
llegarm/ρ
from
from a A.
un
zero
zero Fluids
máximo
at
at the
the flowing
wall
wall en el
(the
(the in
centro pipes
no-slip
no-slip de exhibit
la tubería.
condition)
condition) a velocity
La
to
to aenergía
a profile,
maximum
maximum cinéticaas
at de un
at
the
shown center of the
in Fig. 2.6, pipe.which Therises kineticfrom energy
zero atofthe a fluid
wall in(thea pipe
no-slip depends
condition) on itstovelocity a maximum profile.
fluido en the
the
For una tubería
center
center
the case
of the
of ofdepende
the pipe.
pipe.
laminar de
The
The sukinetic
flow, perfil
kinetic
the de velocidad.
energy
energy
profile of
is
of aa fluidParain
fluid
parabolic,
ineland
aacasopipe
pipe del flujo
depends
depends
integration laminar,
on its
on
across el
its velocity
velocity
the perfil
pipe es deattipo pa-
profile.
profile.
shows
rabólico, the
For center
the
y the caseof
la integración the
of pipe.
laminar
a través Theflow, kinetic
the
dethe energy
profile
la tubería is of a fluid
parabolic,
muestra in a
and pipe depends
integration on
across its velocity
the pipe profile.
shows
For
that
For the case
case
of laminar
kinetic-energy
ofun laminar termflow,should
flow,
profile
properly
the completamente
profile
is
is be be u 22. que
parabolic,
parabolic, In fullyel término
and integration
developed
anddeveloped
integration
de energía
across cinética
turbulent
across
theflow,
the
pipe
pipethedebería
more ser en
shows
that
sentidothat
estricto
the u 2. En
the kinetic-energy
kinetic-energy flujo term
turbulento
term should
should properly
properly be uu2 ..desarrollado,
In fully
In fully developedque es turbulent
el
turbulentcaso flow,
más
flow, theshows
común
the more
moreen la prác-
common
that the case in practice,
kinetic-energy term the velocity
should properly across be the
u 2 . major
In fully portion
developed of the pipe isflow,
turbulent not the far morefrom
common
tica, la common
velocidad case
a
case través in
in practice,
de
practice,la parte the
the 2 velocity
principal
velocity deacross
la
across the
tubería
the major
no
major se portion
aleja
portion muchoof
of the
the de pipe
lo
pipe is
uniforme,
is not
not far
far y from
la
from expresión
uniform,
common and
casethe the expression
inexpression
practice, u 2/2,
the as used
velocity in thethe
across energy major equations,
portion is more
of the pipe nearly is not correct.
far from
u2/2, comouniform,
uniform, and
seAlthough
emplea
and theen expression
Eq.las ecuaciones
(2.28) isu 2an
u2 /2,
u /2,de asenergía,
as
energy
used
used ines
in
balance
themucho
the energy
energy más
of reasonable
equations,
correcta.
equations, is more
is more
generality,
nearly
nearly correct.
correct.
it has correct.limitations.
uniform,
Aunque la and
Although
AlthoughecuacióntheEq. expression
Eq. (2.28)es
(2.28)
(2.28) isun
is an
an/2, as usedbalance
energy
balance
energy deinenergía
balance the energyof reasonable
of en equations,
reasonable
general is more tiene
generality,
razonable,
generality, nearly
it has
hassus
itcontrol limitations.
limitaciones.
limitations. En
In particular,
Although it reflects
Eq. (2.28) the tacit
is an assumption
energy balance that the
of center
reasonable of mass of
generality, the it has volume
limitations. is
In
particular,
In particular,
refleja
particular, la it
it reflects
suposición
reflects the
tácita
the tacit
de
tacit assumption
que el
assumption centro that
de
that the
masa
the center
del
center of
volumen
of mass
mass de of
of the
control
the control
es
control volume is
estacionario.
volume isDe este
stationary.
In se
particular, Thus no terms
ittérminos
reflects for
thefor kinetic-
tacit assumption and potential-energy
that the center changes
ofymass ofofthe thedelfluid
control in the control
volume is
modo, no stationary.
incluyen
stationary. Thus
Thus no terms
no terms para for kinetic-
elkinetic-
cambio and
de las
and potential-energy
energías
potential-energy cinética changes
changes potencialof the
of the fluid
fluid fluidoin the
in the control
encontrol
el volumen de
volume
stationary. are included.
Thus no For
terms virtually
for kinetic- all applications
and potential-energyof interest to
changeschemical of the engineers,
fluid in Eq.
the (2.28)
control
volume
control.volume
En are
realidad, included.
paramany
are included. todas For
For lasvirtually
aplicaciones
virtually all applications
de interéskinetic-
allapplications,
applications of
ofpara interest
losand
interest to chemical
ingenieros
topotential-energy
chemical engineers,
químicos,
engineers, Eq.
la ecuación (2.28)
Eq. (2.28) (2.28) es
is adequate.
volume For
are included. (but not all) changes in the
adecuada. is adequate.
Para muchas For(aunquemanyFor (butvirtually
no not all)
todas all)
lasall applicationskinetic-
applications,
aplicaciones), oflos
kinetic-interest andtopotential-energy
chemical
potential-energy engineers, changes Eq.yin (2.28)
inpotencial
the
is
is
adequate.
flowing
adequate. streams For
For
many
are
many also(but not
negligible,
(but not all)
applications,
and Eq. (2.28)kinetic-
applications, thencambios and
simplifies
and
ento: las energías
potential-energy
cinética
changes
changes in
the
the
en
flowing
las corrientes streams
flowingdestreams flujo también are also
are alsoson negligible,
despreciables,
negligible, and Eq.
and Eq.y (2.28) (2.28)
por esto then
then simplifies
la ecuación
simplifies(2.28) to:
to: se simplifica a:
flowing streams are also negligible, d(mUand )cv Eq. (2.28) . then simplifies. . to:
d(mU))cv
d(mU cv + �(H m) . fs = Q .. +W .. (2.29)
dt )cv + + �(H�(Hm) .
m) fs ==Q Q. + +W W. (2.29) (2.29)
d(mU dt . fs (2.29)
dt + �(H m)fs = Q + W (2.29)
dt
Example
Example 2.12
2.12
Ejemplo 2.12
Example
Example
Show that
2.12
Eq. 2.12
(2.29) reduces to Eq. (2.3) for the case of a closed system.
Show that Eq. (2.29) reduces to Eq. (2.3) for the case of a closed system.
Show that Eq. (2.29) reduces to Eq. (2.3) for the case of a closed system.
Demuestre
Show que la Eq.
that ecuación
(2.29)(2.29) se reduce
reduces a la ecuación
to Eq. (2.3) (2.3)ofena el
for the case caso system.
closed de un sistema cerrado.

2.12.
2.12. Mass
Mass and
and Energy
Energy Balances
Balances for
for Open
Open Systems
Systems 49
49
2.12. Balances de masa y energía para sistemas abiertos 49
Solution
Solución 2.12 2.12
Solution 2.12
El segundo
The término
The second de laof
second term
term ecuación
of Eq. (2.29)
Eq. (2.29)
(2.29) is se omitein
is omitted
omitted inenthe
la absence
the ausenciaof
absence deflowing
of corrientes
flowing de flujo,
streams,
streams, andy por lo
and
tanto la the
ecuación se
equation multiplica
is then por dt:
multiplied by dt:
the equation is then multiplied by dt:
.. ..
d(mU
d(mU))cv = Q dt + W dt
cv = Q dt + W dt
Integration
Integrando a travésover
Integration time
time gives:
del tiempo
over dado:
gives:
�� tt22 �� tt22
.. ..
�(mU
�(mU))cv =
cv =
Q dt
Q dt ++ W
W dt
dt
tt11 tt11
or �U tt = Q + W
o or ΔU t =
�U = QQ+ +WW
The
The Q and W terms are defined by the integrals of
Q and W terms are defined by the integrals of the
the preceding
preceding equation.
equation.
Los términos Q y W se definen mediante integrales de la ecuación anterior.
Equation
Equation (2.29)
(2.29) may
may be
be applied
applied to
to aa variety
variety of
of processes
processes of
of aa transient
transient nature,
nature, as
as illus-
illus-
La ecuación
trated (2.29) se puede aplicar a una variedad de procesos de naturaleza transiente (fenómeno
trated in
in the
the following
following examples.
examples.
momentáneo que sucede en un sistema previo a lograr una condición de estado estacionario), como se mues-
tra en los siguientes ejemplos.
Example 2.13
An
An evacuated
Ejemplo 2.13 tank
evacuated tank is
is filled
filled with
with gas
gas from
from aa constant-pressure
constant-pressure line.
line. What
What is
is the
the relation
relation
between the enthalpy of the gas in the entrance line and the internal energy of the gas
between the enthalpy of the gas in the entrance line and the internal energy of the gas
Se llenaincon
in the gas unNeglect
the tank?
tank? tanque heat
Neglect vacío desde una
heat transfer
transfer línea the
between
between a presión
the gas constante.
gas and
and the tank.¿Cuál es la relación entre la
the tank.
entalpía del gas en la línea de entrada y la energía interna del gas en el tanque? Ignore la transferencia
de calor entre el gas y el tanque.
Solution
Solution 2.13
2.13
The
The tank
tank with
with its
its single
single entrance
entrance serves
serves as
as the
..the control
control volume.
volume. Because
Because there
there is
is
Soluciónno
2.13
no expansion
expansion work,
work, stirring
stirring work,
work, or
or shaft
shaft work, W=
work, W = 0.
0. If
If kinetic-
kinetic- and
and potential-
potential-
energy
energy changes
changes are
are negligible,
negligible, Eq.
Eq. (2.29)
(2.29) becomes:
becomes:
El tanque con una sola entrada sirve como volumen de control. Debido a que no hay trabajo de
·
expansión, de agitación o en la flecha, W
d(mU = )
d(mU )tank 0. Si los cambios
.. �� en las energías cinética y potencial
tank − H ��m = 00
son despreciables, la ecuación (2.29) será: dt − H m =
dt
d (mU ) tanque
where
where the
the prime
prime (�)
(�) identifies
identifies the
the entrance
entrance −H ′ m ′ = and
stream
stream 0 the
and the minus
minus sign
sign is
is required
required
because it is an entrance stream. dt mass balance is:
The
because it is an entrance stream. The mass balance is:
donde la prima (′) identifica la corriente de entrada dm y se requiere el signo menos porque se tiene
.. � dmtank
una corriente de entrada. El balance de masa m� =
m es: tank
= dt
dt
dmtanque
Combining
Combining these
these two
two balance m ′ = yields:
balance equations
equations yields:
dt
Al combinar los resultados de las dos d(mU
d(mU )
ecuaciones
)tank − Hde
tank � dm
dmbalance:
tank
tank
dt − H � dt = = 00
dt dt
d (mU ) tanque dmtanque
− H′ =0
dt dt

50 50 CHAPTER CAPÍTULO 2. The First Law and ley
Other Basic Conceptsbásicos
50 CHAPTER 2. The2. LaLaw
First primeraand Other y otros
Basicconceptos
Concepts
5050 CHAPTER2.2.The
CHAPTER TheFirst FirstLaw
Lawand andOther
OtherBasic
BasicConcepts
Concepts
Multiplicando por dtby
Multiplying e integrando a través over
dt and integrating del tiempo
time (noting (observe H � H′
thatque es constante)
is constant) se obtiene:
gives:
Multiplying by dt and integrating over time (noting that H� �� is constant) gives:
Multiplying
Multiplyingbybydtdtand andintegrating
integratingover overtime time(noting(notingthat thatHH isisconstant)
constant)gives:
gives:
Multiplying by dt and integrating Δ(mU)
�(mUtanque over−
)tank –timeH � �m
H′Δm (notingtank =
tanque =00 H � is constant) gives:
that
�(mU )tank − H� ��m tank =0
�(mU
�(mU)tank )tank−−HH��m �mtank tank==00
� (m −
Whence 2 U2 −)m
m�(mU 1 U−
tank 1 = HH �m � 2 =m01 )
tank
De donde m 22UU22−– m 11U11 ==HH′� (m –−mm1)1)))
mmm
Whence � (m22−
Whence
Whence 2U2U 2 2−−mm 1U1U 1 1==HH(m 2 2 −mm 11
where subscripts 1 and 2mdenote − initial and
= � (m conditions
final in the tank.
Whence
where subscripts 1 and 2 U
denote
2 2 initialm U H
1 1and final conditions 2 − m1) in the tank.
donde los
wheresubíndices
where subscripts
Because 1 ymass
subscripts
the 121and
denotan
andin
22denotecondiciones
denote
the tankinitial
initial
initially and inicial
and isfinal
final
zero, yconditions
final
m 1 =en0;elthen,
conditions intanque.
inthe Debido a que la masa
thetank.
tank.
en el tanque
where Because
essubscriptsthe mass
inicialmente 1 and in2the
cero, m tank
denote = 0;initially
entonces,
initial and isfinal m 1 = 0; then,
zero,conditions in the tank.
Because
Becausethe themass
massininthe thetank
1tankinitially
initiallyisiszero, zero,mm1 1==0;0;then, then,
� m 1 = 0; then,
Because the mass in the tank initially U2 =isHzero, �
U = H
UUU2222===HH′ H� � �
a result showing that in the absence of U2heat =H transfer the energy of the gas contained
a result
un resultado que showing
muestra that
que, inenthe absencede
ausencia of heat transfer de thecalor,
energy of the gas contained
awithin
aresult
resultshowing
theshowing
tank atthat
that
theininthe
endtheabsence
ofabsence ofoftransferencia
the process heat
heat istransfer
transfer
equal tothe
theenergy
energylaof
enthalpy energía
ofthe
thegas
of en
gas
the el added.
gas contenido
contained
contained
gas
within
en el tanque
awithin the
althe
result finaltank
showing at
delatat the
proceso
that end esof the
igual process
a laofentalpía is equal to
deltotogasthe enthalpy
agregado. of the gas added.
within the tank
tank thethein
end the
end absence
ofofthetheprocess
process heat transfer
isisequal
equal the
the
the energy
enthalpy
enthalpyofofthe gasgas
ofthe
the contained
gasadded.
added.
within the tank at the end of the process is equal to the enthalpy of the gas added.
Example 2.14
Example 2.14
Example
Example 2.14
2.14 heated tank for hot water contains 190 kg of liquid water at
Ejemplo 2.14 electrically
An insulated,
Example
An◦insulated,
electrically
2.14 heated tank for hot water contains 190 kg of liquid water at
An
Aninsulated,
60 Cinsulated,
when aelectrically
electrically
power heated
heated
outage tank
tankfor
occurs. Ifforhot
hotwater
water watercontains
containsfrom
is withdrawn 190
190kg
kgoftank
the ofliquid
liquid
at water
awateratat
steady
Un tanque
60◦ C when
An . a power outage occurs. If water is withdrawn from the tank at a steady
aislado .
◦insulated, electrically heated tankitIffor hot water contains 190 kg tank
of liquid water °Catcuando
6060◦C
rate Cof m. = que
when
when a0.2 calienta
apower
power
kg −1
s−1outageagua
outage
, how eléctricamente
occurs.
occurs.
long will Ifwater
water
take forcontiene
isthe
iswithdrawn190 kg
withdrawn
temperature deofagua
from
from the
the líquida
tank
water inaaa
atat 60
steady
thesteady
tank
rate
60
ocurre rate
una
◦ Cofwhenm
. . =
interrupción
0.2
a kg
power
del
s , how
outage
suministro
long will
occurs.
eléctrico.
it take
If waterfor
Siwater
el
the
is
agua
temperature
withdrawn
se retira from of
del tanque
the
the water
tank
aC,una at in athe tank
steady
rate
to of
drop ofmm ==0.2
from
.–1 60
0.2 kg
kg −1
toss35−1 ◦
, ,how
howAssume
C? long
long will
willcold
itittake
take forforthethetemperature
enterstemperature
the tank of
ofthe
at 10 ◦
the
◦water andproporción
water inin the tankestable
thetank
negligible
−1◦◦,◦C?
de m· = to
to drop
0.2
rate kg sm
from
oflosses = 0.260kg
, ¿cuánto
tos35tiempo howAssume
longliquid
debe
cold
willcold
itwater
transcurrir
water
take for
para
enters
the the
temperature
que la
tank at
temperatura of 10
the ◦C,
del
andinen
water
agua
negligible
the
el tank
tanque
todrop
heat drop from
from 6060toto
from 35
the35tank.
C? C?Assume
Assume
For cold water
water
let enters
C V =
enters Cthe
the=tank
tank
C, atat1010◦ C,
independent C, and
andofnegligible
negligible
T and P. dis-
heat
todedrop
losses
afrom
from
60 to the tank. For el
◦ C? Assume
35tank. liquid water
cold let
water V = el
Centers C PPtanque
=tank
C, independent ◦ C, and of Tlasand P.
minuyaheatheat 60
losses
losses 35from
°C?
from Suponga
the
the que
tank.ForForliquid agua
liquid waterfría
water entra
let
letCC ==CCPthe
V Ven P==C, aat1010°C,
C,independent
independent ofofnegligible
y que TTandandpérdidas
P.P. de
heat losses
calor desde el tanque fromson the tank. For liquid
despreciables. Parawater el agua V = C Pse
let Clíquida = supone
C, independent
que C V =ofCTP = andC son
P. inde-
Solution
de T y P . 2.14
pendientesSolution
2.14
Solution
Solution . 2.14.
2.14
Here, .Q.. =
Solution W. = 0. Additionally, assume perfect mixing of the contents of the
2.14
.. =
Here, Q = W 0. Additionally, assume perfect mixing of the contents of the
Solución 2.14
Here,
Here,Q
tank; Q. =implies
this = WW . ==that
implies 0. 0.Additionally,
that Additionally,
the propertiesassume assume
of the perfect perfect
water mixing
mixing
leaving theofoftank
the
thecontents
contents
are thoseofof ofthethe
the
Here,
tank;
tank; Q· the
tank; this
this
this ·W
=implies
implies =that
0. the
that
the propertiesassume
Additionally,
theproperties
properties of
of the water
of thethe perfect
water
water
leaving
mixing
leaving
leaving
theoftank
the
the tankthe
tank
are
are
are
those of
contents
those
those
of the
of
of
the
thethe
En este water
caso, Q
water
in =the
in Wtank.= 0. Además,
tank. With
Withthe
the se supone
mass
theproperties
mass
flowrate
flowrate unainto mezcla
into the perfecta
tank
theleaving
tank
equal
equal detolos
to thecontenidos
theare
mass
mass del tanque;
flowrate
flowrate
tank;
water
water this
in inthe implies
the tank. that
tank.With
With the
the of theinto water theandtank those of and
the
esto implica
out,
out, que
m
m cv las
is
is propiedades
constant;
constant; delmass
moreover,
moreover,
mass
agua flowrate
the
the
flowrate
que deja into
differences
differences
the
thetank
el tanque
between
between
tank
sonequal
equal
inlet
inlet
to
las mismas
and
tothe
themass
outlet
outlet
mass
que flowrate
las flowrate
kinetic
kinetic delandagua en el
water in
cv the tank. With the mass flowrate into the tank equal to the mass flowrate
tanque.out,
out,mmcvla
Como
potential
potential cvis isconstant;
constant;
relación
energies
energies de moreover,
can
can
moreover,
flujo
be de masathe
be neglected. thedifferences
neglected.
differences
hacia
Equation
Equation
between
el interior between
(2.29)
(2.29) delis inlet
inletand
istanque
therefore
therefore
and outlet
outlet
es igual akinetic
written:
written:
kinetic
la and
relaciónandde flujo
out, m is constant; moreover, the differences between inlet and written:
outlet kinetic and
de masapotential
potential
hacia cv energies
afuera,energies
mcv can
escan bebeneglected.
neglected.
constante; Equation
por otra Equation
parte, (2.29)
se(2.29)
pueden isistherefore
therefore
despreciar written:
las diferencias entre las
potential energies can be neglected. dU Equation . (2.29) is therefore written:
energías cinética y potencial de entrada m dU y de+salida.
.
m(H −PorHlo) tanto,= 0 la ecuación (2.29) se escribe:
mdU dt + m(H
dU . . − H11) = 0
mmdU dt ++m(H m(H
. −−HH 1 )1 )==00
where unsubscripted quantities m dtdtrefer+ m(H to the −H 1 ) = 0 of the tank and H is the
contents
where unsubscripted quantities dt refer to the contents of the tank and H11 is the
where
whereunsubscripted
specific
donde las
unsubscripted
cantidadesenthalpy queof
quantities
quantities
ofcarecen
the water refer
refertoto
entering
de entering
subíndices thethethe contents
tank.
se
contents
With C
refieren
ofofthe = P =and
theCtank
tank andHH
C, 1 1isisthethe
specific
where enthalpy the water thethe tank. With al CofVVcontenido
= Ctank = del
C, tanque y H1 es la
specificunsubscripted
specific enthalpy
enthalpyofofthe quantities
the water refer the
waterentering
entering to thetank. contents
tank. With
WithCC =the
=CCPPP==C, C, H1 is the
and
entalpíaspecific
específica deldU
enthalpy agua quedT entra entering
en el tanque. DadoWith que C CV ==CCP ==
V V C,C,
dU of=the C
water
dT and
the tank.
H − H = V
C(T P
− T )
dUdt ==
dU CdT dT
dt and H − H1 = C(T − T11)
1
dt
dU = C C dt
dT andy
and H H − − H H
11 = = C(T
C(T − − T T
1 1)
)
dtdt = C dtdt and H − H 1 = C(T − T 1)
The energy balance dt thendtbecomes, on rearrangement,
El balance
Theenergético
The
energy balance
Theenergy
energybalance será en
balancethen ese
then caso,
becomes,
thenbecomes, después de
on rearrangement,
becomes,ononrearrangement, una
rearrangement, reordenación,
The energy balance then becomes, on rearrangement, m dT
dt = −mm . dT
dt = − m . TdT
m dTT
−
dtdt==−− m . . T dT− T11
dt = − mm T−−TT
. Tarbitrary 11
Integration
Integrando desde t =from from t = 0 (where
0 (donde = T0) en T = unT Ttiempo
0) m to − T1 time
arbitrario time t sett yields:
yields:
obtiene:
Integration t = 0 T(where T = 0 ) to T
arbitrary
Integration
Integrationfrom fromt t==00(where (whereTT==TT 0 )0 )toto�arbitrary
arbitrarytime �timet tyields:yields:
Integration from t = 0 (where T = T m0 ) to � T − T1��
arbitrary �time t yields:
t =− m m . ln � � T − T 1
t = −mm . ln �TTT−− −TT T
1 1�
t t==−−m . .lnln T00 − − TT111
t = − mm . ln TT 0 0−−TT 11
m T0 − T1

2.12.Mass
2.12.
2.12. Massand
Mass andEnergy
and EnergyBalances
Energy Balancesfor
Balances forOpen
for OpenSystems
Open Systems
Systems 51
51
51
2.12.
2.12. Balances
Mass and
de masa
Energy Balances
y energía
for
para sistemas
Open Systems 51
51
2.12. Mass and Energy Balances for Openabiertos
Systems 51
Substitution
Substitution of
of numerical
numerical values
values into
into this
this equation
equation gives,
gives, for
for the
the conditions
conditions
Substitution of numerical values into this equation gives, for the conditions of this of
of this
this
Sustituyendo los valores
problem,
problem,
Substitution
problem, numéricos
of numerical en esta
values intoecuación
�this se��
� equation obtiene,
gives, para
for thelasconditions
condiciones of de
thiseste pro-
Substitution of numerical values 190
190 into� this
35−
35 − 10� gives, for the conditions of this
equation
−10
10
blema, problem, ==− 190
−−190 ln 35
lnln� 35 − 10 � = ==658.5
problem, tt t= 0.2 �60
0.2 60−
60 −−10
658.5s s
10� 658.5 s
t = − 190 0.2 ln 35 − 10
10 = 658.5 s
Thus,ititittakes
takesabout
about11
11 = − 0.2for
t minutes
minutes lnthe
for 60
the − 10temperature
water = 658.5 in
temperature s the
Thus,
Thus, takes
◦ ◦
about 11 minutes 0.2for the water
− 10
water
60 temperature ininthe
thetank
tankto
tank totodrop
dropfrom
drop from
from
60
60
60 to
Thus,to35
it
to 35 35◦ C.C.
takes about 11 minutes for the water temperature in the tank
C. about 11 minutes for the water temperature in the tank to drop from to drop from
Así, le tomatocerca
Thus,
60 35 C.de 11 minutos a la temperatura del agua en el tanque disminuir de 60 a 35 °C.
it ◦takes
60 to 35 C. ◦
BalancesEnergy
Energy
Energy Balancespara
Balances
energéticos
Balances forSteady-State
for
for Steady-State
Steady-State
los procesosFlow Flow
Flow Processes
Processes
de flujo en estado estacionario
Processes
Energy Balances for Steady-State Flow Processes
Energy
Flow
Flow
Los procesos Balances
Flowprocesses
processes
processes
de flujo
forwhich
for
for
para
which
which for
the
the
los cuales Steady-State
theaccumulation
accumulationterm
accumulation
el
term Flow
termof
ofofEq.
Eq.
término de acumulación Processes
Eq.(2.28),
(2.28),d(mU
(2.28), d(mU))cv
d(mU
de la ecuación
) /dt,
/dt,
cvcv
isiszero
/dt,is
(2.28),
zeroare
zero
d(mU)
aresaid
are saidtoto
said
/dt estocero, se cv
occurprocesses
occur
Flow atatsteady
steadystate.
steady state.
state.
for which AsAsdiscussed
discussed
discussed
the accumulation withrespect
with respect
respect
term to oftothe
to themass
the
Eq. massbalance,
mass
(2.28), balance,
balance,
d(mU )this this
this
cv means
means
/dt, is zero that
that the
are the mass
mass
said to
dice queoccur
ocurren
Flow at en estado
processes for As
estacionario.
which the Alwith
accumulation igual que term conof el
Eq. análisis
(2.28), del
d(mU balance) cv
means
/dt,de ismasa,that
zero the
esto
are mass
significa
said to que
ofof the
the
occur system
system
at steady within
within
state. the
the
As control
control
discussed volume
volumewith isis constant;
constant;
respect to theit it also
also
mass means
means
balance, that
that thisnono changes
changes
means that occur
occur
the with
with
mass
la masaof delthe
occur system
sistema within
dentro delthe control
volumen volume
de control is constant;
es constante; it also means
también that
significa no changes
que no occur
ocurre with
ningún cam-
time
time
of inat
thein in steady
theproperties
the
system state.the
properties
properties
within As discussed
ofofthe
thefluid
the
control fluid
fluid with respect
within
within
volume the
the
is control
constant; to the
control mass
itvolume
volume
also means balance,
norat
nor itsitsthis
atatthat means
entrances
entrances
no changes that
and
and the
exits.
exits.
occur mass
No
withNo
bio contime
el
of tiempo the
theinsystem en laswithin of
propiedades
the control del within
fluido the
dentro control
del volume
volumen de norcontrol its nientrances
en sus and
entradas exits.ni No
salidas. No
expansion
expansion
time
expansion theof ofofthe
thethecontrol
properties control
control volume
of the
volume fluidvolume
volume ispossible
possible
iswithin
is possible is
theconstant;
underthese
under
control
under
it also
these
these
volume means
nor at that
circumstances.
circumstances.
circumstances.
noThe
its entrances
The
changes
The only
only
only and occur
work
work
workexits. of
with
ofof the
the
No
the
hay expansión
time del
in the volumen
properties de ofcontrol
the fluidbajo estas circunstancias. El único trabajo del proceso es el de la flecha
process
process
expansion
process isisshaft
is shaft
shaft
of work,
work,
thework, control and
and
and the
the
volume
the generaliswithin
general energy
possible the under
energy control
balance,
balance, volume
these Eq.Eq. nor atbecomes:
(2.28),
(2.28),
circumstances. its entrances
becomes: The onlyand workexits. No
of the
y el balance energético
expansion of the general,
control de la general
volume ecuación
is energy
possible(2.28), balance,
será:these
under Eq. (2.28),
circumstances. becomes: The only work of the
process is shaft work, and the general energy balance, Eq. (2.28), becomes:
process is shaft work, and the ��
general energy balance, �� Eq. (2.28),
� . . . . becomes:
��H HH+ ++112u12u2u2 2+
++zg zgzg� m m..m�. ==Q.Q++W .W (2.30)(2.30)
(2.30)
�
�� 21 2 � . �fsfsfs= Q. + W. ss s (2.30)
� H + 21 u 2 + zg m. fs = Q. + W. s (2.30)
� H + 2 u + zg m fs = Q + Ws (2.30)
Although
Although
AunqueAlthough
el “estado“steady “steady
“steady
estacionario” state”
state”
state” does does
does
no implica not
not necessarily
necessarily
necesariamente
not necessarily imply
imply
imply“flujo “steady
“steady
“steady flow,”
flow,”
estable”,
flow,” la thethe usual
usual
theaplicación application
application
usual de esta
usual application ofof ecua-
of
this
this
ción es Although equation
equation
Although
para procesos is
“steady is to to
en8 8estadosteady-state,
steady-state,
state” does
estacionarionot steady-flow
steady-flow
necessarily
y de flujoimply processes,
processes,
imply
estable, because
because
“steady
ya queflow,”flow,” such
such the
tales procesos processes
processes
usual represent
represent
application the
the
of
this equation
industrial
industrial
this8 equation norm.
norm.
is
“steady
is
to
to
steady-state,
state” does not
steady-state,
steady-flow
necessarily
steady-flow
processes,
processes,
because
“steady
because
such
such the usualrepresentan
processes
processes
represent
application
represent
elof
the
the
modelo
industrial.
industrial
this equation norm. 8
is 8specialization
tospecialization
steady-state,results steady-flow processes, because such processes represent the
Un AAfurther
industrial
resultado further
further
norm.
másspecialization
8especializadoresults
results whenwhen thethecontrol
control
control volume
volume hasbut
has butbut oneentrance
one entrance
entrance and
and one y una
one
A
industrial norm. .se
. . obtiene when cuando
the el volumen volume dehas control tiene
one sólo una and entrada
one
exit.
exit. The
The
A
salida. Por lo Atanto same
same
furtherse aplicamass
mass flowrate
flowrate
specialization m m
la misma. relación then
then
results applies
applies
when de the to
the to
flujo both
both
control streams,
streams,
de masa volume andand
a ambas has Eq.
Eq. but (2.30)
(2.30)
one
corrientes, reduces
reduces
entrance to:to:
and
y la ecuación one
exit.
exit.
The same
Thefurther
same mass
mass flowrate
specialization m
flowrate m.results
then
then
applies
when to both
control streams,volume and Eq.
has
Eq.but
(2.30) reduces
one reduces
entrance to:and one (2.30)
se reduce a: �� applies to both
� �� streams,
. . . and
. . (2.30) to:
exit. The same mass flowrate m then applies tozgzg
both .
.mstreams, and
.W Eq. (2.30) reduces to: (2.31)
�� HH+ + +112u12u2u2 2+
++ zg � m m ==Q.Q++W (2.31)
�
�
H 21 2 � . = Q. + W. ss s (2.31)
� H + 21 u 2 + zg m. = Q. + W. s (2.31) (2.31)
wheresubscript
where subscript“fs”
subscript “fs”has
“fs” hasbeen
has been
been �omitted H + 2inuinthis
omitted + zg
this simple
simple m =case Q +and
case Ws “�”
and “�”denotes denotesthe
denotes thechange
the change
change (2.31)
from
from
where . omitted
. en esteincaso this simple case and “�” from
donde elwhere
subíndice
entrance
entrance toto
subscript“fs”
exit.
exit. ha sido
Division
Division
“fs” has omitido
by
beenby m.m gives:
gives:
omitted in this simple
simple y “Δ”
case denota
and “�” el cambio
denotes de
the la entrada
change a la salida.
from
entrance to· exit. Division by m. omittedgives: in this simple case and “�” denotes the change from
Dividiendo
where entre m
subscript se obtiene:
“fs”
entrance to exit. Division by m. gives:has been
.. ..W.
entrance to exit. Division by ��m gives: �� Q Q..Q W W ss
��H
� HH+ 1 1
++12u2u2u +2 2
++zg zgzg� = ==Q.. .+ ++ ..s. = ==Q QQ+ ++W WW ss s
� 21 2 � m .m W m.ms
� H + 21 u 2 + zg = m Q. + W m. s = Q + Ws
� H + 2 u + zg = m. + m. = Q + Ws
m m
�u
�u
�u 22 2
o or
oror �H �H
�H + �u + + 2 + +
+ g �z = QQ+
g g�z�z = = Q ++W WW ss s
(2.32a)
(2.32a)
(2.32a) (2.32a)
or �H + �u 2222 + g �z = Q + Ws (2.32a)
or �H + 2 + g �z = Q + Ws (2.32a)
Esta ecuación
This es la expresión
equation is the matemática
mathematical 2
deexpression
la primera
expression ley
of para
the un law
first proceso
law for ena estado estacionario
steady-state, steady-flow y flujo esta-
This equation is the mathematical of
This equation is the mathematical expression of the first law for a steady-state, steady-flow the first for a steady-state, steady-flow
ble entreThis
unaequation
process
process entradabetween
between yisuna one
the salida.
one entrance Todos
entrance
mathematical andandlos onetérminos
one exit.
exit.
expression All representan
Allof terms
terms the represent
first energía
represent
law por
energy
energy
for a unidad
per
per unit
steady-state, demass
unit masa
mass ofdel
of
steady-flow fluido.
fluid.
fluid.
process between one entrance and one exit. All of terms represent energy per unit mass of fluid.
Enprocess
todas
This In las
equation
In allecuaciones
between
all ofof isthe
the the
one de balance
mathematical
energy-balance
entrance
energy-balance and energético
expression
equations
one
equationsexit. so
All
so escritas
farfar
terms the
written, hasta
firstthe
written,
represent ahora
law
the for
energy
energy sea supone
energy steady-state,
unit
unit perisis que lasteady-flow
presumed
unit mass
presumed unidad
of
toto be
fluid.
be detheenergía
the
In between
all of theone energy-balance equations so farterms
written, the energy unitper is unit
presumed to be the
es el joule,
joule,deIn
process
joule, inacuerdo
in accord
accord
all of the con with
with elentrance
thesistema
the SI
energy-balance SI and
system
system deequations
unidades
one
ofof exit.
units.
units. SI.
All
so Para
For
For
far thethe
written,el sistema
represent
English
English the inglés
energy
engineering
engineering
energy unit deisunidades
system
system
presumedmassof de
of of ingeniería,
fluid.
units,
units,
to be the los
the
joule, In in accord of thewith the SI system of units.soFor far the English the engineering unit issystem of units,
to be the
joule, in all accord energy-balance
with the SI system equations
of units. For written,
the English energy
engineering presumed
system of units, the
the
joule,
88
in accord with the SI system of units. For the English engineering system of units, the
Anexample
An
8 An exampleof
example ofofaa asteady-state
steady-stateprocess
steady-state processthat
process thatis
that isisnot
notsteady
not steadyflow
steady flowis
flow isisaa awater
waterheater
water heaterin
heater ininwhich
whichvariations
which variationsin
variations ininflow
flowrate
flow rateare
rate are
are
8 exactly compensated bychanges
changes inthe
therate
rate ofheat
Un ejemplo
exactly
exactly de un proceso
8 An compensated
example
compensatedof a bybyde estado
changes
steady-stateestacionario
inprocess
in the ratethat
of isheat
ofque
heat transfer
notransfer
tiene
transfer
not steadyflujo
so sothat
flow
so that
estable
that atemperatures
es unheater
temperatures
istemperatures
water throughout
calentador de agua
throughout
in which
throughout remain
en el
remain constant.
cual
constant.
variations
remain las variaciones
in flow
constant. rate are en el
8 An example of a steady-state process that is not steady flow is a water heater in which variations in flow rate are
caudal sonexactly
compensadas exactamente
compensated by changescon los cambios
in the rate ofenheat
la rapidez
transferdesotransferencia
that temperaturesde calor, de modo remain
throughout que las constant.
temperaturas permanezcan
constantesexactly
en todas partes.
compensated by changes in the rate of heat transfer so that temperatures throughout remain constant.

52
52 CHAPTER 2.
CHAPTER 2. The
The First
First Law
Law and
and Other
Other Basic
Basic Concepts
Concepts
kinetic-
kinetic- and
and potential-energy
potential-energy terms,
terms, wherever
wherever they
they appear,
appear, require
require division
division by
by the
the dimensional
dimensional
términosconstant
de las energías
gc cinética
(Secs. 1.4 andy1.8).
potencial,
In thisdondequiera
event Eq. que aparezcan,
(2.32a), for requieren
example, is la división entre la cons-
written:
constant gc (Secs. 1.4 and 1.8). In this event Eq. (2.32a), for example, is written:
tante dimensional gc (secciones 1.4 y 1.8). En este caso, por ejemplo, la ecuación (2.32a) se escribe:
2
�H + �u 2 + gg �z = Q + Ws
�u
(2.32b)
�H + 2gc + gc �z = Q + Ws (2.32b)(2.32b)
2gc gc
Aquí, laHere,
Here, the
unidad usual
usual unit
thehabitualunit forΔH
for
para �Hy Q
�H and
andesQQelis the
the (Btu);
is(Btu);(Btu); kinetic
la energía
kinetic energy,
energy,lapotential
cinética, energía energy,
potential−1 –1
energy, and
potencial y work
and work are
el trabajo
are se ex-
usually expressed
presan generalmente como as (ft
(pie lb
lbf ).
). Therefore
Por lo the
tanto, factor
el 778.16(ft
factor 778.16(pie
usually expressed as (ft lbff). Therefore the factor 778.16(ft lbf )(Btu) lbf )(Btu)
lb f)(Btu)−1 must be used with the
must be used with the los tér-
se debe utilizar con
appropriate
minos apropiados terms
para to
poner put
a them
todos all
en in consistent
unidades units of
convenientes either
en (ft
(pie lb
lb
appropriate terms to put them all in consistent units of either (ft lbff ) or (Btu).)
f ) oor
en(Btu).
(Btu).
En muchas
In aplicaciones
many se
applications, omiten
kinetic-
In many applications, kinetic- and los términos
and de las energías
potential-energy cinética y potencial
potential-energy terms are omitted, because
terms are omitted, porque
because theyson
they aredespre-
are
9 En9 For such cases, Eqs. (2.32a) and (2.32b) reduce to:
ciables negligible
en comparación con
compared otros
with términos.
other terms. 9 estos casos las ecuaciones (2.32a)
negligible compared with other terms. For such cases, Eqs. (2.32a) and (2.32b) reduce to: y (2.32b) se reducen a:
�H =
�H =QQ+
+WWss (2.33) (2.33)
(2.33)
Esta expresión
This de la primera ley para un proceso en estado estacionarioprocess
y flujo estable es análoga a la ecuación
This expression
expression of
of the
the first
first law
law for
for aa steady-state,
steady-state, steady-flow
steady-flow process is
is analogous
analogous toto Eq.
Eq. (2.3)
(2.3)
(2.3) para
for un
a proceso sin
nonflow flujo. Sin
process. embargo,
However, más que
enthalpy la energía
rather than interna,energy
internal la entalpía
is theesthermodynamic
una propiedad termo-
for a nonflow process. However, enthalpy rather than internal energy is the thermodynamic
dinámica de gran importancia.
property
property ofof importance.
importance.
A
A Flow
Calorímetro Calorimeter
Flow de flujo parafor
Calorimeter Enthalpy
mediciones
for Measurements
Enthalpy de la entalpía
Measurements
The
The application
application of
of Eqs. (2.32)
(2.32)yand
Eqs. (2.32) and (2.33)
(2.33) to the solution of
of practical problems requires en-
La aplicación
thalpy de las ecuaciones
values. Because H is a (2.33)
state paratolaits
function,
the solution
solución
values depend
practicalprácticos
de problemas
only on
problems
point
requires
requiere
conditions;de en-
valores de
once
thalpy values.
entalpía.determined,
Porque H es Because
una H
función is a
de state function,
estado, sus its
valores values depend
dependen only
sólo deon point conditions;
condiciones once
puntuales; una vez
determined, they
they may
may be
be tabulated
tabulated for
for subsequent
subsequent use
use for the
forvez same
the que
same sets
sets of conditions.
of el
conditions. To
To this
thisde con-
determinados
end, pueden
Eq. (2.33) ser
maytabulados
be para el uso consecutivo cada se tenga mismo conjunto
end,
diciones. ConEq. (2.33)
este may
fin, la be applied
applied
ecuación
to
(2.33)
laboratory
to se
laboratory processes
processes
puede aplicar
designed for
a losdesigned
procesosfor
enthalpy measurements.
de enthalpy
laboratoriomeasurements.
diseñados específica-
mente para medir la entalpía.
Section 1
Section 1 T2
T2 P2
P2
Sección 1Heater T2
Heater P2 Valve
Valve
Calentador Discharge
Válvula Discharge
Constant Descarga
Constant
temperature
temperature
Baño a
bath
bath
temperatura
Section 2
constante Section 2
Applied Sección 2
Applied
emf
emf
fem
Supply aplicada
Supply
Suministro
Figure
Figure 2.7:
2.7: Flow
Flow calorimeter.
calorimeter.
Figura 2.7: Calorímetro de flujo.
AA simple
simple flow
flow calorimeter
calorimeter is
is illustrated
illustrated schematically
schematically in
in Fig.
Fig. 2.7.
2.7. Its
Its essential
essential feature
feature
is
is an
an electric
electric resistance
resistance heater
heater immersed
immersed in
in a
a flowing
flowing fluid.
fluid. The
The design
design provides
provides for
for minimal
minimal
Un calorímetro de flujo simple se ilustra en forma esquemática en la figura 2.7. Su característica esen-
cial es un calentador de resistencia eléctrica sumergido en un líquido que circula. El diseño proporciona para
9 Exceptions are applications to nozzles, metering devices, wind tunnels, and hydroelectric power stations.
9 Exceptions are applications to nozzles, metering devices, wind tunnels, and hydroelectric power stations.
9 Las excepciones son las aplicaciones a las toberas, a los aparatos de medición, a los túneles de viento y a las estaciones hidroeléctricas.

velocidad y cambios de elevación mínimos de la sección 1 a la sección 2, haciendo despreciables los cambios en
las energías cinética y potencial del fluido. Además, como no se hace trabajo en la flecha del sistema, la ecuación
(2.33) se reduce a ΔH = H2 – H1 = Q. La rapidez de transferencia de calor al fluido se determina por la resisten-
cia del calentador y por la corriente que pasa a través de éste. En la práctica se necesita poner atención a un gran
número de detalles, pero en principio la operación del calorímetro de flujo es simple. Las medidas del rendi-
miento térmico y la relación de flujo permiten el cálculo del cambio ΔH entre las secciones 1 y 2.
Como ejemplo, se determinan fácilmente las entalpías del H2O como líquido y como vapor. El baño a
temperatura constante se llena de una mezcla de hielo molido y agua para mantener una temperatura de 0 °C.
Se suministra agua líquida al aparato y el serpentín que lleva el agua a través del baño a temperatura constan-
te es lo suficientemente extenso, de modo que el líquido emerge a la temperatura del baño que es esencial-
mente de 0 °C. La temperatura y la presión en la sección 2 se miden con instrumentos adecuados. Los valores
de la entalpía del H2O para diversas condiciones en la sección 2 están dados por:
H2 = H1 + Q
donde Q es el calor agregado por unidad de masa del flujo de agua.
La presión varía en cada una de las experimentaciones, pero en el intervalo aquí encontrado tiene un
efecto despreciable sobre la entalpía del agua que entra, y para propósitos prácticos H1 es constante. Los va-
lores absolutos de la entalpía, al igual que los valores absolutos de la energía interna son desconocidos. Por lo
tanto, se le puede asignar a H1 un valor arbitrario como base para los demás valores de la entalpía. Estable-
ciendo H1 = 0 para el agua líquida a 0 °C obtenemos:
H2 = H1 + Q = 0 + Q = Q
Los valores de la entalpía se pueden tabular para las temperaturas y presiones que existen en la sección
2, para una gran cantidad de mediciones. Además, las mediciones del volumen específico realizadas para
estas mismas condiciones se pueden agregar a la tabla, junto con los valores correspondientes de la energía
interna calculados por medio de la ecuación (2.11), U = H – PV. De esta manera, las tablas de propiedades
termodinámicas se compilan sobre toda la gama útil de condiciones. El uso más extenso posible para esta
tabulación es para el H2O y se conoce como las tablas de vapor.10
La entalpía se puede tomar igual a cero para algunos otros estados del líquido a 0 °C. La elección es
arbitraria. Las ecuaciones termodinámicas, tales como las ecuaciones (2.32) y (2.33) se aplican a los cambios
de estado, para los cuales las diferencias de entalpía son independientes de la localización del punto cero. Sin
embargo, una vez que se elige un punto cero arbitrario para la entalpía, no se puede hacer una elección arbi-
traria para la energía interna, debido a que los valores de la energía interna pueden calcularse a partir de los
de la entalpía mediante la ecuación (2.11).
Ejemplo 2.15
Para el calorímetro de flujo recién analizado se toman los siguientes datos con el agua como líquido de
prueba:
Relación de flujo = 4.15 g s –1 t1 = 0 °C t 2 = 300 °C P2 = 3 bar
10 Las tablas de vapor se dan en el apéndice F. Las tablas para otras sustancias se encuentran en la literatura. Un análisis de compila-
ciones de las propiedades termodinámicas aparece en el capítulo 6.

54 CHAPTER 2.
2. The First Law
Law and Other Basic Concepts
54
54
54 CHAPTER
CHAPTER 2. The
CAPÍTULO
First
The2. La Law
First and
and Other
primera ley
Basic
y otros
Other Concepts
Basicconceptos
Conceptsbásicos
Rate of heat addition from resistance heater = 12,740 W

Rapidez Rate of
of heat
de adición
Rate deaddition
heat from
fromelresistance
calor desde
addition calentadorheater
resistance =
= 12,740
12,740=W
de resistencia
heater 12 740 W
W
The
The water
water is
is completely
completely vaporized
vaporized in
in the
the process.
process. Calculate
Calculate the
the enthalpy
enthalpy of
of steam
steam at
at
The
El agua300 water is
se ◦evapora completely
3totalmente
based en vaporized in liquid
el proceso. the process.
Calcule atCalculate
la entalpía the enthalpy
0◦◦C. del vapor a 300 °Cofysteam
3 bar, at
conside-
300◦◦CC and
and bar
andel33agua
bar
bar based
on
on HH= = 0 for
= 00 for
for liquid
water
liquid water
water at
at 00◦C.
= 0C
rando H300 para based
líquidaon
a 0H°C. C.
Solution
Solución 2.15 2.15
Solution 2.15
Solution 2.15
Si Δz y Δu
If 2 son
�z �u 222 are
anddespreciables,
negligible
y si W and
y Hif1 Wsons and
cero,H1entonces
are zero, Hthen H
2 = Q, 2y = Q, and
If �z and
If �z �u are
and �u are negligible
negligible Sand
and if
if W Wss and
and H H11 are
are zero,
zero, then
then H22 =
H = Q,
Q, and
and
12,740 J s−1
−1
12,740 J ss−1 = 3,070 J g−1
H 2 = 12,740 J −1 −1
H22 =
H = 4.15
4.15 gg ss−1
−1
=
= 3,070
3,070 JJ gg−1
4.15 g s
Example
Example 2.16
2.16
Ejemplo
Example2.16 2.16
Air at 1 bar and 25◦◦C enters a compressor at low velocity, discharges at 3 bar, and
Air
Air at
at 11 bar
bar and
and 25
25◦C
C enters
enters aa compressor
compressor at
at low
low velocity,
velocity, discharges
discharges
−1
at
at 33 bar,
bar, and
and
Se introduce
enters
enters aire
a a 1 barin
aa nozzle
nozzle in ywhich
25 °C it
which ititaexpands
un compresor
expands to
to a a baja
aa final
final velocidad,
velocity
velocity of
of 600sem descarga
ss−1 at a 3initial
the bar ycondi-
entra en una
enters
tobera en la
tions cual
of nozzle
se
inand
expande
pressure which
a una
expands
velocidad
temperature. tothe
If final
final de
workvelocity
600
of m s
of a600
–1 600
las
compression
m
m at
at the
s−1240
condiciones
is the
kJ
initial
initial
iniciales
per
condi-
condi-
de presión
kilogram
tions
tions of
of pressure
pressure and
and temperature.
temperature. IfIf the work
work of
theduring of compression
compression is is 240
240 kJ
kJ per
per kilogram
kilogram
y temperatura.
of
of air, howSi el trabajo
much heatde compresión
must be es
removed de 240 kJ por kg de
compression? aire, ¿cuánto calor debe eliminarse
of air,
air, how
how much
much heatheat must
must be be removed
removed duringduring compression?
compression?
durante la compresión?
Solution 2.16
Solution
Solución 2.16 2.16
Solution 2.16
Because
Because the air returns to its initial conditions of T and P, the overall process
Dado que el aire the
Because air
air returns
regresa
the to
to its
its initial
a sus condiciones
returns conditions
iniciales
initial conditions de Tof TT el
ofy P, and
and P,
P, the
proceso overall
thetotal process
no produce
overall process ningún
produces
produces no
no change
change in
in enthalpy
enthalpy of
of the
the air.
air. Moreover,
Moreover, the
the potential-energy
potential-energy change
cambio en la entalpía
produces no del aire.
change in Por otra parte,
enthalpy of the elair.
cambio en la energía
Moreover, the potencial del change
potential-energy aire se supone
change
of
of the air is presumed negligible. Neglecting also the initial kinetic energy of the
of the
air,the
we
air
que es insignificante.
air is
is presumed
write
Ignorando
presumed
Eq. (2.32a)
negligible.
también Neglecting
negligible.
as:
la
Neglecting also
also the
energía cinética initial
theinicial kinetic
initial del aire,energy
kinetic of
of the
escribimos
energy thela ecua-
air,
air, we
ción (2.32a) write
write Eq.
como:
we Eq. (2.32a)
(2.32a) as: as: 2
uu222
Q = u2 − W
=
Q = 222 −
Q s
−W Wss
The kinetic-energy term is 2
The kinetic-energy term is evaluated
evaluated as
as follows:
follows:
El término
Thede energía cinética
kinetic-energy term seisevalúa de laassiguiente
evaluated follows:forma:
11 2 11 �
�� m �
� 2 m 2
2
m �2 =
m m
2
1uu222 =
= 1 600600 = 180,000
180,000 m22
22 u22 = 22 600 ss = 180,000 ss22
2 2 s 2 kg
m s
m 2 kg −1 = 180 kJ kg−1
=
= 180,000 2 · =
m kg = 180,000 N180,000 m kg −1 = 180 kJ kg−1
180,000 ss222 ·· kg
= 180,000 kg = 180,000 N
N m
m kg
kg −1 = 180 kJ kg−1
s kg
==180 −1
Then
En tal caso
Then
Then
Q
QQ=
Q = 180 180−
180 − 240 =
240
−– 240
240 =
=
−60
= –60
−60kJ
−60 kJ
kJkg
kJ kg
kg–1−1
kg−1
Heat
Heat in
in the amount of 60 kJ must be removed per kilogram of air compressed.
Se deben in the
eliminar
Heat the60 amount
kJ de of
amount of 60
calor kJ
kJ must
60 por be
be removed
kilogramo
must de aireper
removed kilogram
kilogram of
comprimido.
per of air
air compressed.
compressed.
Example
Example 2.17
2.17
Ejemplo 2.17
Example 2.17
Water at 200( ◦F) is pumped from a storage tank at the rate of 50(gal)(min)−1
◦
Water at 200( ◦F) is pumped from a storage tank at the rate of 50(gal)(min) −1. The
Water at 200( F) °F)
is pumped from aatstorage tank
−1.
atlathe rate The
of 50(gal)(min) . –1The
Se bombea
motor
motoragua
for
for a 200(0
the
the pump
pump de un tanque
supplies
supplies work
work deat almacenaje
the
the rate
rate of
of en
2(hp).
2(hp).proporción
The
The de 50(gal)(min)
water
water goes
goes through
through . El
aa motor
a
motor
de la bomba
heat for the
suministra
exchanger, pump
givingsupplies
trabajo con
up un
heat work
valor
at theat
de the
rate rate
2(hp).
of Elof 2(hp).
agua pasa
40,000(Btu)(min) The
a −1water
través
−1 , and de goes
is un through
intercambiador
delivered to a de
heat
heat exchanger,
exchanger, giving
giving up heat
heat at
at the
upproporción the rate
rate of
of 40,000(Btu)(min)
40,000(Btu)(min) −1,, and
and is
is adelivered
delivered to
to aatanque
calor, proporcionando
second storage calor
tank aatuna
an elevation de
50(ft) 40 000(Btu)(min)
above the first –1, y se
tank. entrega
What is the un segundo
temperature
second
second storage
storage tank
tank at
attoan
an elevation
elevation 50(ft)
50(ft) above
above the first
first tank.
thetanque.tank. What
What is the temperature
de almacenaje
of
of the
the a
water
wateruna elevación
delivered
delivered to de
the
the50(pies)
second
second sobre
tank?
tank? el primer ¿Cuál esislathe temperature
temperatura del agua
of the water delivered
entregada al segundo tanque? to the second tank?

2.12.
2.12.Mass
Massand
andEnergy
EnergyBalances
Balancesfor
forOpen
OpenSystems
Systems 5555
Solución 2.17 2.17

Solution
Solution 2.17
Éste esThis
un proceso en estado estacionario yprocess
flujo establewhich
para el que(2.32b)
se aplica la ecuación (2.32b).
Thisisisa asteady-state,
steady-state,steady-flow
steady-flow processfor for whichEq. Eq. (2.32b)applies.
applies. The The
Las velocidades
initial and inicial
final y final delofagua
velocities watereninlosthetanques
storagedetanks
almacenaje
are son insignificantes,
negligible, and the y se
initial and final velocities
2/2g . Losof water in the storage tanks are negligible, and the
puede omitir
term �uel 2término
/2g
2 Δu
may be c
omitted. términos
The restantes
remaining se expresan
terms are en unidades
expressed in de
units(Btu)(lb
of m )–1
term �u /2g c c may be omitted. The remaining terms are expressed in units of
mediante el uso
(Btu)(lb ) de
−1 factoresuse
−1through de conversión apropiados. A 200(°F) la densidad
◦ ◦ F)the del agua es
(Btu)(lb–3, )y 1(pie)
mm through useofofappropriate
appropriateconversion
3 es equivalente conversionfactors.
factors.AtAt200(
200(F) theden-
den-
60.1 (lbsity
m )(pie)
of water is 60.1(lb )(ft) −3
−3, and a 7.48(gal);
1(ft) así, la
3 3is equivalent rapidez
to de flujo
7.48(gal); de
thus masa
the masses:
sity of water is 60.1(lb mm )(ft) , and 1(ft) is equivalent to 7.48(gal); thus the mass
flowrate is:
flowrate is:
(50)(60.1/7.48) = 402(lbm)(min)−1 –1
(50)(60.1/7.48)==402(lb
(50)(60.1/7.48) 402(lb
mm )(min)−1
)(min)
De donde QQ= = –40 000/402 = –99.50(Btu)(lbm))–1
Q −40,000/402 −1
Whence
Whence = −40,000/402==−99.50(Btu)(lb
−99.50(Btu)(lb mm )−1
−1 , the shaft work is:
Dado que 1 (hp)1(hp)
Because
Because es equivalente
1(hp) a 42.41
isisequivalent
equivalent (Btu)(min)–1, el−1
toto42.41(Btu)(min)
42.41(Btu)(min) trabajo en lawork
, the shaft flecha
is:es:
= =(2)(42.41)/(402) −1
)–1
sW
WW s s= (2)(42.41)/(402) =
(2)(42.41)/(402) ==0.21(Btu)(lbmm
0.21(Btu)(lb )−1
Si el valor local devalue

g seoftoma –2−2
IfIfthe
thelocal
local value ofg gisiscomo
taken elasthe
takenas valor estándar,
thestandard 32.174(pie)(s)
value,
standard 32.174(ft)(s)
value, , el
32.174(ft)(s) −2 término
, the de la energía
, thepotential-
potential-
potencial se convierte
energy
energy term en:
termbecomes:
becomes:
−2
ggg 32 .174(pie)(s)−2
32.174(ft)(s) −2 50 (pie)
50(ft)
Δ
�zz
�z =
==
32.174(ft)(s)
−1 −2 −2 ⋅· ·
50(ft)
−1
ggcgc
c
32.32.174(lb
174(lbmm)()(ft)(lb
32.174(lb pie )( lb) )
−1−1(s
(s)
f f ) (s)
)(ft)(lb ) −2 778778.16(ftlblb
. 16(
778.16(ftpie f))(Btu)
( Btu−1
f )(Btu)
lb )−1
m f f
==0.06(Btu)(lb
0.06(Btu)(lb
mm)−1
)−1
Equation
Equation (2.32b)
(2.32b)now yields �H: :
�H
yieldsΔH:
La ecuación (2.32b) ahoranow
produce
gg
�H==QQ++WW
�H s s−− �z = −99.50 + 0.21 − 0.06 = −99.35(Btu)(lbm )−1−1
gcgc �z = −99.50 + 0.21 − 0.06 = −99.35(Btu)(lbm )
◦ ◦ is:
El valorThe
en steam-table
Thelasteam-table value
tabla de vapor
valuefor
forthe
para la enthalpy
theentalpía ofofagua
del
enthalpy liquid water
waterat
líquida
liquid 200(
200(F)
aat200(°F) es:is:
F)
1 11==
HH
H =168.09(Btu)(lb
168.09 )−1
(Btu)(lbmmm
168.09(Btu)(lb ))–1
−1
Thus,
Thus, �H==HH
�H 2 2−−HH
1 1==HH2 2−−168.09
168.09==−99.35
−99.35
De esta forma, ΔH = H2 – H1 = H2 – 168.09 = –99.35
and
and 2 2==168.09
HH 168.09−−99.35
99.35==68.74(Btu)(lb
68.74(Btu)(lb
mm)−1
)−1
y –1
The
Thetemperature H2 = having
temperatureofofwater
water168.09 –this
99.35
havingthis = 68.74
enthalpy
enthalpy (Btu)(lb
isisfound
foundfromm) the
from thesteam
steamtables:
tables:
La temperatura que el agua tiene a esta entalpía se encuentra
t t==100.74( ◦◦ en las tablas de vapor:
100.74(F) F)
t = 100.74(°F)
InInthis
thisexample
exampleWW s sand
and(g/g c )�z
(g/g are small compared with Q, and for practical
c )�z are small compared with Q, and for practical
purposes they could be neglected.
En este purposes
ejemplo W theyy could
s
be neglected.
(g/gc)Δz son pequeños en comparación con Q, y para fines prácticos se
pueden despreciar.

PROBLEMAS
2.1. Un recipiente no conductor lleno con 25 kg de agua a 20 °C tiene un agitador, el cual se mueve
debido a la acción de la gravedad sobre una pesa con masa de 35 kg. La pesa cae lentamente a una
distancia de 5 m accionando el agitador. Suponiendo que todo el trabajo hecho en la pesa se trans-
fiere al agua y que la aceleración local de la gravedad es 9.8 m s–2, determine:
a) La cantidad de trabajo realizado en el agua.

b) El cambio en la energía interna del agua.
c) La temperatura final del agua, para la cual CP = 4.18 kJ kg–1 °C–1.
d) La cantidad de calor que debe extraerse del agua para que regrese a su temperatura inicial.
e) El cambio en la energía total del universo debido a: 1) el proceso de bajar el peso, 2) el proceso
de enfriamiento del agua para que regrese a su temperatura inicial, y 3) ambos procesos juntos.
2.2. Trabaje de nuevo con el problema 2.1 para un recipiente aislado que cambia de temperatura junto con
el agua, y que tiene una capacidad térmica equivalente a 5 kg de agua. Trabaje el problema con:
a) El agua y el recipiente como el sistema; b) considere sólo al agua como el sistema.
2.3. Un huevo, inicialmente en reposo, se deja caer sobre una superficie de concreto y se rompe. Si se
considera al huevo como el sistema,
a) ¿Cuál es el signo de W?
b) ¿Cuál es el signo de ΔEP?
c) ¿A qué es igual ΔEK?
d) ¿A qué es igual ΔU t?
e) ¿Cuál es el signo de Q?
Al configurar este proceso, suponga que pasa el tiempo suficiente para que el huevo roto regrese a
su temperatura inicial. ¿Cuál es el origen de la transferencia de calor del inciso e)?
2.4. Un motor eléctrico bajo carga fija toma 9.7 amper a 110 volts, liberando 1.25(hp) de energía mecá-
nica. ¿Cuál es la intensidad de transferencia de calor desde el motor en kW?
2.5. Un mol de gas en un sistema cerrado se somete a un ciclo termodinámico de cuatro etapas. Use la
información que se proporciona en la tabla siguiente para determinar los valores numéricos de las
cantidades faltantes, es decir, “complete los espacios en blanco”.
Paso ΔU t/J Q/J W/J

12 –200 ? –6 000
23 ? –3 800 ?
34 ? –800 300
41 4 700 ? ?
12 341 ? ? –1 400

Problemas 57
2.6. Explique la factibilidad de enfriar su cocina durante el verano abriendo la puerta de un refrigerador
accionado eléctricamente.
2.7. Un laboratorio de renombre reporta coordenadas del punto cuádruple de 10.2 Mbar y 24.1 ºC para
el equilibrio en las cuatro fases de las formas alotrópicas sólidas del exótico producto químico b-
miasmone. Evalúe la afirmación.
2.8. Un sistema cerrado sin reacción química contiene a las especies 1 y 2 en equilibrio vapor/líquido.
La especie 2 es un gas muy ligero, esencialmente insoluble en la fase líquida. La fase vapor contie-
ne ambas especies. Se agregan algunas moles adicionales de la especie 2 al sistema, el cual regresa
a su T y P iniciales. Como resultado del proceso, ¿el número total de moles del líquido se incremen-
ta, disminuye o no cambia?
2.9. Un sistema compuesto por cloroformo, 1,4-dioxano y etanol existe como un sistema de dos fases
vapor/líquido a 50 °C y 55 kPa. Se encuentra que después de agregar cierta cantidad de etanol puro,
el sistema regresa al equilibrio de dos fases a su T y P iniciales. ¿En qué aspecto el sistema cambia?
¿En qué aspecto no cambia?
2.10. Para el sistema descrito en el problema 2.9:
a) ¿Cuántas variables de la regla de la fase, además de T y P, se deben seleccionar para fijar las
composiciones de ambas fases?
b) Si la temperatura y la presión siguen siendo las mismas, ¿puede la composición global del sis-
tema cambiar (por la adición o eliminación de materia) sin afectar las composiciones de las fa-
ses líquida y vapor?
2.11. Un tanque que contiene 20 kg de agua a 20 °C cuenta con un agitador que proporciona trabajo al
agua a la intensidad de 0.25 kW. ¿Cuánto tiempo transcurre para incrementar la temperatura del
agua a 30 °C si no hay pérdida de calor desde el agua? Para el agua, CP = 4.18 kJ kg–1 °C–1.
2.12. Se agrega a un sistema cerrado 7.5 kJ de calor a medida que su energía interna disminuye 12 kJ.
¿Cuánta energía se transfiere como trabajo? Para un proceso que ocasiona el mismo cambio de es-
tado pero cuyo trabajo es cero, ¿cuánto calor se transfiere?
2.13. Un bloque de acero fundido de 2 kg tiene una temperatura inicial de 500 °C. En un tanque de 5 kg
de acero perfectamente aislado se tienen 40 kg de agua a 25 °C. Se sumerge el bloque en el agua y
se permite al sistema llegar al equilibrio. ¿Cuál es la temperatura final? Ignore cualquier efecto de
expansión o contracción y suponga constantes el calor específico del agua que es de 4.18 kJ kg–1
K–1 y del acero 0.50 kJ kg–1 K–1.
2.14. Un fluido incompresible (r = constante) está contenido en un cilindro aislado con un pistón sin
fricción hecho a la medida. ¿Puede transferirse energía al fluido en forma de trabajo? ¿Cuál es el
cambio en la energía interna del fluido cuando la presión aumenta de P1 a P2?
2.15. Un kg de agua líquida a 25 °C:
a) Experimenta un aumento en la temperatura de 1 K. ¿Cuánto es ΔU t, en kJ?

b) Experimenta un cambio en la elevación Δz. El cambio en la energía potencial ΔEP es igual a la

que presenta ΔU t para el inciso a). ¿Cuánto es Δz en metros?
c) Se acelera desde el reposo hasta la velocidad final u. El cambio en la energía cinética ΔEK es
igual al que presenta ΔU t en el inciso a). ¿Cuánto es u, en m s–1?
Compare y analice los resultados de estos tres incisos.
2.16. Un motor eléctrico funciona “caliente” en servicio, debido a sus irreversibilidades internas. Se su-
giere que la pérdida de energía asociada sea minimizada por el aislamiento térmico del armazón del
motor. Realice un comentario crítico con respecto a esta sugerencia.
2.17. Una hidroturbina funciona con una carga de 50 m de agua. Los conductos de entrada y salida tienen
2 m de diámetro. Estime la potencia mecánica desarrollada por la turbina para una velocidad de
salida de 5 m s–1.
2.18. El agua líquida a 180 °C y 1 002.7 kPa tiene una energía interna (en una escala arbitraria) de 762.0
kJ kg–1 y un volumen específico de 1.128 cm3 g–1.
a) ¿Cuál es su entalpía?
b) El agua se hace llegar al estado de vapor a 300 °C y 1 500 kPa, donde su energía interna es
2 784.4 kJ kg–1 y su volumen específico es 169.7 cm3 g–1. Calcule ΔU y ΔH para el proceso.
2.19. Un cuerpo sólido con temperatura inicial T0 se sumerge en. un baño de agua a la temperatura inicial
Tw0. Se transfiere calor del sólido al agua en proporción Q = K · (Tw – T), donde K es una constan-
te Tw y T son los valores instantáneos de las temperaturas del agua y del sólido. Desarrolle una ex-
presión para T en función del tiempo t. Compruebe su resultado para los casos límites, t = 0 y t =
∞. Ignore los efectos de la expansión o contracción y suponga constante el calor específico tanto
para el agua como para el sólido.
2.20. Observe una lista de operaciones unitarias comunes:
a) Intercambiador de calor de una sola tubería; b) intercambiador de calor de doble tubería; c) bom-
ba; d) compresor de gas; e) turbina de gas; f) válvula reguladora, y g) tobera.
Desarrolle una forma simplificada del balance energético general en estado estacionario más apropia-
do para cada operación. Indique y justifique de manera cuidadosa cualquier suposición que haga.
2.21. El número de Reynolds, Re, es un grupo adimensional que caracteriza la intensidad de un flujo. Para
Re grandes, un flujo es turbulento; para Re pequeños, es laminar. Para el flujo en la tubería, Re ≡
urD/m, donde D es el diámetro de la tubería y m es la viscosidad dinámica.
.
a) Si D y m están fijos, ¿cuál es el efecto al aumentar la relación de flujo de masa m en Re?
.
b) Si m y m están fijos, ¿cuál es el efecto sobre Re al aumentar D?
2.22. Un líquido incompresible (r = constante) fluye de manera estable a través de un conducto de sec-
ción transversal circular con diámetro en aumento. En el punto 1, el diámetro es de 2.5 cm y la ve-
locidad es 2 m s–1; en el punto 2, el diámetro es de 5 cm.

Problems 59
Problemas
Problems 59 59
a) (a)¿Cuál
Whatesislathe
(a) Whatvelocidad
velocityen
at el
is the velocity punto
location 2?
at location
2?
2?
−1 ) of the fluid between locations 1 and 2?
–1
b) (b)¿Cuál
What is the kinetic-energy change (J kg(J kg
(b) es el
What cambio en la energía
is the kinetic-energy cinética
change −1 ) delfluid
) of the fluido entre locations
between los puntos11and
y 2?
2?
2.23.
2.23.SeAproduce
stream una
2.23. A stream corriente
of warm
of warmde
water isagua
water iscaliente
in–1en
produced
produced un
in aproceso de
steady-flow
a steady-flow mezcla
mixing
mixingde process
process flujo
byestable al combinar 1.0
by combining
combining
s–1kg1.0
kg1.0 kg s−1
des−1
agua fría
ofacool
25 °C con 25◦kg
at0.8 s de kg s−1
0.8agua caliente
of hotawater 75◦ C. During
at 75 C. During mixing, se pierde
75 °C.
water ◦ C with −1 at Durante
◦ la mezcla
mixing,
of cool water at 25 C with 0.8 kg s of –1 hot water
calor hacia los alrededores en proporción
at thederate
30 kJ s . s−1 . What
¿Cuál es la temperatura de la
thecorriente de
heat is lost to the surroundings of 30 kJ
−1 is the temperature of the
heat is lost to the surroundings at the rate of 30 kJ s . What is the temperature of −1 −1 . –1
agua caliente? Suponga
warm-water que
stream? el calor
Assume específico
the specificdel agua
heat es constante
of water constant e igual a
at 4.18 4.18
kJ
−1 kgkJ
−1 K–1
kg K .
warm-water stream? Assume the specific heat of water constant at 4.18 kJ kg K .
2.24. 2.24. Gas

queisestá
bled from a tank. deNeglecting heat transfer between the gas and the el
tank,
gasshow
2.24.Imagine
Gas is bled fromsaliendo
a tank. gas un tanque.
Neglecting Ignore
heat transfer la transferencia
between the gasde calor
and the entre
tank, show y el tanque
y that that mass
demuestre que and
los energy balances
balances produce
energéticos y de the differential
masa producen equation:
la ecuación diferencial:
mass and energy balances produce the differential equation:
dU dm
dU dm=
�
H −U= m
H� − U m
Here, U and m refer to the gas remaining in the tank; � is the specific enthalpy of the
� is H
Here,
En estegasU and
caso, m refer
U y mthe to the
setank.
refierengas remaining
al gas in
restante the tank;
en el can H
tanque;
one H ′ esspecific
the � enthalpy
la entalpía of the del gas que
específica
leaving Under what conditions assume � =HH ?= H ?
abandona el tanque. ¿Bajo qué condiciones se supone que H ′ = H?
gas leaving the tank. Under what conditions can one assume H
2.25. Water at ◦ C flows in a straight horizontal pipe in which there is no exchange of
2.25. Water at 28 ◦ C28 flows in atubería
straight horizontal pipeeninlawhich there is no −1exchange calor
of o de tra-
2.25. Fluye agua
eithera heat
28 °Corenwork una with thehorizontal recta,
surroundings. cual no
Its velocity ishay
14intercambio
m s in ade
−1 pipe with
either
bajo con heat or work with the surroundings. Its velocity
–1 is 14 m s in a pipe with
anlos alrededores.
internal diameterSu ofvelocidad
2.5 cm es de 14
until m s into
it flows en una tubería where
a section con diámetro
the pipe interno de 2.5 cm
diameter
an internal
hasta que fluyediameter of 2.5 cm
aincreases.
una sección dondeuntil it flows into
el diámetro de laachange
section aumenta
tubería where the pipe diameter ¿Cuál es el
repentinamente.
abruptly What is the temperature of the water if the downstream
abruptly
cambio increases.
en la temperatura What isagua the si
temperature change of abajo
the water deif3.8
thecm?
downstream
diameter is 3.8 cm?del If it is 7.5elcm]?
diámetro
Whatcorriente
is the maximum estemperature ¿Si el diámetro
change for an es de
diameter is
7.5 cm?enlargement3.8 cm?
¿Cuál es el in If it
máximo is 7.5 cm]? What is the maximum temperature
cambio de temperatura para un alargamiento de la tubería? change for an
the pipe?
enlargement in the pipe?
2.26. Se comprimen
2.26. Fifty (50) cincuenta(50)
kmol per hour kmol porishora
of air de aire defrom
compressed P1 = P1.2
1 = bar
1.2aP 2 =to6.0
bar P2bar= en
6.0unbar
compresor
in
2.26.con
Fifty (50)
flujo kmol La
estable. perpotencia
hour of mecánica
air is compressed from
transmitida = 1.2
P1 98.8
es de barLas P2 = 6.0
to temperaturas baryinlas velocida-
a steady-flow compressor. Delivered mechanical powerkW.is 98.8 kW. Temperatures and
a steady-flow
des son: compressor. Delivered mechanical power is 98.8 kW. Temperatures and
velocities are:
velocities are:
T1 T=1300 K K
= 300 T2T2= =520 KK
520
T1 = 300 K –1 T2 = 520 K
u1 u=110=m10s−1m s −1 uu2 2= =
3.53.5
mm s–1s−1
u 1 = 10 ms u 2 = 3.5 m s−1
CalculeEstimate
la rapidez thederate
transferencia de calor
of heat transfer delthe
from compresor.
compressor. Suponga
Assume paraforelair
airethat
queCC = = 7 R,
R y que
Estimate the rate of heat transfer from the compressor. Assume for air that C P = P72 PR 2
la entalpía
and esthatindependiente de la presión.
enthalpy is independent of pressure.
and that enthalpy is independent of pressure.
2.27. Circula nitrógeno
2.27. Nitrogen en estado
flows estacionario
at steady a través
state through de una tubería
a horizontal, horizontal,
insulated pipe withaislada
insidecon un diámetro
diameter
2.27. Nitrogen flows at steady state through a horizontal, insulated pipe with inside diameter
interiorofde1.5(in).
1.5 (pulg.). Debido drop
A pressure al flujo por una
results fromválvula parcialmente
flow through abierta
a partially se produce
opened valve.unJust
descenso
of 1.5(in). A pressure drop results from flow through a partially opened valve. Just ◦ F), and
en la presión.
upstreamAntes
fromdethe
la válvula
valve thela presión
pressureesisde100(psia),
100(psia),the
la temperatura
temperatureesisde
◦ 120(°F)
120( y la velo-
upstream from the valve the pressure is 100(psia), the temperature is 120( F), and
–1. Si la−1
cidad promedio
the averagees de 20(pie)(s)
velocity is 20(ft)(s) presión
. If thea la salida de
pressure justla downstream
válvula es defrom
20(psia), ¿cuál es la
the valve
the average velocity is 20(ft)(s)−1 . If the pressure just downstream from the valve
temperatura? Suponga
is 20(psia), whatque paratemperature?
is the el nitrógeno PV/T
Assume es constante,
for nitrogen = (5/2)R
CVthat P V /Ty C = (7/2)R. (Los
isPconstant,
is 20(psia), what is the temperature? Assume for nitrogen that P V /T is constant,
valoresCde = están
V R dados
(5/2)R, anden C el
P =apéndice
(7/2)R.A.) (Values for R are given in App. A.)
C V = (5/2)R, and C P = (7/2)R. (Values for R are given in App. A.)
2.28.
2.28.Circula
Water agua
flowsathrough
2.28. Water través
flows de
through unaserpentín
horizontalhorizontal
a horizontal
coil heated
coil heated from que esoutside
from
the calentado
the outsidedesde el exterior mediante
by high-temperature
by high-temperature flue
flue gases
degases.
combustión
gases. Asde alta through
it
As it◦ passes temperatura.
passes through
the coilMientras
the coil pasachanges
the
the water a travésstate
water del serpentín
changes state from
from liquidel agua
liquid
at−1 cambia
200
at
kPa del –1
200 kPaestado
◦ C. Its
líquido
and 80a◦ 200
and
C to kPa
80 C to
vapory 80
vapor °C akPa
at 100
at vapor
100 kPa
and a 125
100◦ C.
and kPaIts
125 y 125 °C. La
entering
entering velocidad
velocity
velocity is 3 mdesentrada
is 3 m s
−1 and itses de
and
exit3 m s y su
its exit
velocidad mdes−1 –1. Determine
velocity is 200 m s . Determine the heat transferred through the coil per unit mass of de agua a
de salida es 200 m s
velocity is 200 −1 . Determine the heat el calor transferido
transferred through por unidad
the coil per de
unitmasa
mass of
través
water.delEnthalpies
serpentín.ofLas
water. Enthalpies
theentalpías
inlet andde
of the inlet las corrientes
and
outlet
outlet de entrada y salida son:
streams
streams are:
are:
Inlet: 334.9 kJ kg −1 ; Outlet: 2,726.5 kJ kg−1
−1 −1
Entrada: 334.9kJ
Inlet: 334.9 kJkgkg–1; Outlet:
salida: 22,726.5
726.5 kJ kg–1
kJ kg

2.29. Steam flows at steady state through a converging, insulated nozzle, 25 cm long and
2.29. Circula
with anvapor
inleten estado estacionario
diameter of 5 cm. At athetravés de entrance
nozzle una tobera convergente
(state aislada, de and
1), the temperature 25 cm de largo
y pressure
un diámetroare 325◦ C and 700 kPa, and the velocity–1is 30 m s−1 . At the nozzle exit (statey la presión
de entrada de 5 cm. En la entrada de la tobera (estado 1), la temperatura
son 325 °C y 700
2), the steam kPa, y la velocidad
temperature es de
and pressure are30 m◦ C
240 s and
. En350
la salida de la tobera
kPa. Property (estado
values are: 2), la tempe-
ratura y la presión del−1 vapor son 240 °C y 3503kPa. Los valores de sus propiedades son:
H1 = 3,112.5 kJ kg V1 = 388.61 cm g−1
H1H=2 =3 112.5 kg–1
kJ kJ
2,945.7 kg−1 V2 = V 1 = 388.61
667.75 −13 –1
cm3 gcm g
HWhat is the kJ
= 2 945.7
2
velocity
kg–1 of the steam at
V the nozzle cm
= 667.75
2
exit,
3 gand
–1 what is the exit diameter?
2.30.¿Cuál
In theesfollowing
la velocidad
takedel = 20.8
C Vvapor en and C P =de29.1
la salida J mol−1y ◦¿cuál
la tobera?, C−1 for
es el diámetro
nitrogen de salida?
gas:
2.30. Considere
(a) Threea moles of nitrogen
CV = 20.8 at 30J◦ mol
y CP = 29.1 –1 °C–1 para
C, contained in aelrigid is heated to 250◦ C.
vessel,gaseoso:
nitrógeno
How much heat is required if the vessel has a negligible heat capacity? If the
vessel weighs 100 kg and has a heat capacity of 0.5 kJ kg−1 ◦ C−1 , how much heat
a) Tres moles de nitrógeno a 30 °C, contenidas en un recipiente rígido, se calientan a 250 °C.
is required?
¿Cuánto calor se requiere si el recipiente tiene una capacidad calorífica insignificante? Si el
◦ is contained in a piston/cylinder arrangement.
(b)recipiente
Four moles
pesaof100
nitrogen at 200
kg y tiene unaC capacidad calorífica de 0.5 kJ kg–1 °C–1, ¿cuánto calor se
How
requiere?much heat must be extracted from this system, which is kept at constant
pressure, to cool it to 40 ◦ C if the heat capacity of the piston and cylinder is ne-
b) Cuatro moles de nitrógeno a 200 °C están contenidas en una combinación de pistón/cilindro.
glected?
¿Cuánto calor debe extraerse de este sistema, que se mantiene a presión constante, para enfriar-
lo a 40 °C si la capacidad calorífica del pistón y del cilindro se desprecia?
2.31. In the following take C V = 5 and C P = 7(Btu)(lb mole)−1 (◦ F)−1 for nitrogen gas:
2.31. Considere a CV = 5 y CP = 7(Btu)(lb mol)–1◦(°F)–1 para el nitrógeno gaseoso:
(a) Three pound moles of nitrogen at 70( F), contained in a rigid vessel, is heated to
350(◦ F). How much heat is required if the vessel has a negligible heat capacity? If
a) Tres libras mol de nitrógeno a 70(°F), contenidas en un recipiente rígido, se calientan a 350(°F).
it weighs 200(lbm ) and has a heat capacity of 0.12(Btu)(lbm )−1 (◦ F)−1 , how much
¿Cuánto calor se requiere si el recipiente tiene una capacidad calorífica insignificante? Si el
heat is required?
recipiente pesa 200(lbm) y tiene una capacidad calorífica de 0.12(Btu)(lbm)–1(°F)–1, ¿cuánto
◦ F) is contained in a piston/cylinder arrange-
(b)calor
Foursepound moles
necesita? of nitrogen at 400(
ment.libras
b) Cuatro How mol
muchdeheat must be
nitrógeno extracted
a 400(°F) from
están this system,
contenidas which
en una is kept at con-
combinación de pistón/cilin-
stant pressure, to cool it to 150( ◦ F) if the heat capacity of the piston and cylinder
dro. ¿Cuánto calor debe extraerse de este sistema, que se mantiene a presión constante, para
is neglected?
enfriarlo a 150(°F) si se desprecia la capacidad calorífica del pistón y del cilindro?
2.32.
2.32.Encuentre la ecuación
Find the equation for para el trabajo
the work de una compresión
of a reversible, isothermalisotérmica
compressionreversible
of 1 moldeof1gas
mol de gas en
una
in combinación de pistón/cilindro
a piston/cylinder assembly if thesimolar
el volumen
volumemolar
of thedel
gasgas
is está
givendado
by por
RT
V = +b
P
whereb by and
donde R constantes
R son are positivepositivas.
constants.
2.33.
2.33.Vapor
Steam a 200(psia) y 600(°F)
at 200(psia) and 600( ◦ F) [state
[estado 1] entra en unaaturbina
1] enters turbinea through
través deauna tubería de 3 pulgadas de
3-inch-diameter
diámetro
pipe with con una velocidad
a velocity of 10(ft)(s) −1 . The–1exhaust
de 10(pie)(s) . La descarga desde
from the la turbina
turbine se efectúa
is carried a través
through a de una
tubería de 10 pulgadas
10-inch-diameter pipe de
anddiámetro y está
is at 5(psia) anda200( ◦ F) y
5(psia) 200(°F)
[state [estado
2]. What 2].power
is the ¿Cuáloutput
es la potencia de
salida
of thedeturbine?
la turbina?
H1 = 1,322.6(Btu)(lbm )−1 V1 = 3.058(ft)3 (lbm )−1
H1 = 1 322.6(Btu)(lbm)–1 −1 V = 3.058(pie)3(lb )–1
H2 = 1,148.6(Btu)(lbm ) V21= 78.14(ft)3 (lbmm)−1
H2 = 1 148.6(Btu)(lbm)–1 V2 = 78.14(pie)3(lbm)–1

Problems 61
Problemas 61
Problems
2.34. Carbon dioxide gas enters a water-cooled compressor at conditions P11 = 15(psia) and 61
2.34. Dióxido de carbono entra a un compresor que se enfría con agua en las condiciones P 1 = 15(psia) y
T1 = 50(◦◦F), and is discharged at conditions P22 = 520(psia) and T22 = 200(◦◦F).
T1 =1 50(°F), y descarga en las condiciones P2 = 520(psia) y T2 = 200(°F). El CO2 que−1 −1entra, circula
The entering
2.34.a Carbon COgas 22 flows through a 4-inch-diameter pipeat with a velocity 1 =
of15(psia)
20(ft)(s) ,
través dedioxideuna tubería enters
de 4 apulgadas
water-cooled de compressor
diámetro con una conditions
velocidad Pde 20(pie)(s) –1and
, y se descarga
and
1 = de
is 50(
discharged
◦ F), and through a 1-inch-diameter pipe. =The shaft work T supplied
2 =
to◦the
aTtravés una tuberíaisdedischarged
1 pulgada −1
−1
at
de conditions
diámetro. ElP2trabajo 520(psia)
de flechaand que se 200(
proporciona F). al compre-
compressor
The entering isCO 5,360(Btu)(mol)
flows through
–1 a. What is the
4-inch-diameter heat-transfer
pipe with rate
a from
velocity the
of compressor
20(ft)(s) −1 ,
sor es de 5 360(Btu)(mol)
−1
−1?
2 . ¿Cuál es la rapidez de transferencia de calor desde el compresor en
in (Btu)(hr)
and is discharged
–1? through a 1-inch-diameter pipe. The shaft work supplied to the
(Btu)(hr) −1
H11 = 307(Btu)(lb
compressor m)
−1
is 5,360(Btu)(mol)
m V11−1=. What
9.25(ft)is 33the
(lbm )−1
−1
heat-transfer
m rate from the compressor
in (Btu)(hr) −1 ? −1 −1
H1H=22 =
307(Btu)(lb –1 3 3 –1
m) m V22 =V0.28(ft)
1 = 9.25(pie)
330(Btu)(lb −1 3(lbm )(lb −1 )
m) m m
H1 = 307(Btu)(lb–1 −1 V1 = 9.25(ft)3 (lbm3)−1 –1
m)
2 = 330(Btu)(lb
2.35.HShow m)Q for = 0.28(pie)
V2mechanically (lb m)
H2 = that W and
330(Btu)(lb m)
−1 an arbitrary
V2 = 0.28(ft) 3 (lb )−1
m
reversible nonflow process are given
by:
2.35. Demuestre que W y Q�para un proceso arbitrario sin flujo, mecánicamente � reversible, están dados
2.35.por:
Show that W and W = Q forVandarbitrary
P − �(Pmechanically
V) reversible
Q = �H nonflow − V dprocess P are given
by: � �
2.36. One kilogram W of = air isVheatedd P −reversibly
�(P V ) at constant Q =pressure
�H − from V danP initial state of
300 K and 1 bar until its volume triples. Calculate W , Q, �U , and �H for the
2.36.
2.36.Un kilogramo
process.
One Assume
kilogram deofaire forseisair
air calienta enV forma
/T = reversible
that Preversibly
heated 83.14
at constantbaracm presión
pressure
−1
−1 K−1
33 molconstante −1 de un
from anand C PPestado
initial = 29of
state inicial
J de 300
K300
y1K
mol −1
−1barK −1
hasta
−1 . el triple
and 1 bar until its volume de su volumen. Calcule W, Q,
triples. Calculate W–1, Q, ΔU y ΔH para el proceso.
�U , and �H for the Suponga para el
aire que PV/T = 83.14 bar cm 3 mol–1 K–1 y C = 29 J mol K –1
−1 . −1
process. Assume for air that P V /T = 83.14 bar cm mol K ◦ and C P = 29 J P 3
2.37. mol
The−1 conditions
K−1 . of a gas change in a steady-flow process from 20 ◦C and 1,000 kPa
◦
2.37. Lasto condiciones
◦
60 C and 100 dekPa.
un gas cambian
Devise en un proceso
a reversible nonflow deprocess
flujo estable de 20 °Cofysteps)
(any number 1 000 for kPa a 60 °C y
2.37.100
The kPa.
accomplishingDiseñe this
conditions un
of proceso
achange
gas changereversible
of state, a sin
in and flujo (cualquier
calculate
steady-flow �Uprocessandnúmero
from for
�H 20de◦the
Cetapas)
process
and paraonlograr
1,000 the este cam-
kPa
bio de
60◦estado
basis
to of
C 1andmol y,100con
of kPa.baseAssume
gas. en 1 mol
Devise afor dethegas,
reversiblegascalcule
that
nonflow PΔUV /T y ΔH para
(anyelnumber
is constant,
process proceso.
C VV = of Asuma para
steps) and
(5/2)R, for el gas que
PV/T
C PP =es (7/2)R.
constante,
accomplishing this = (5/2)R
CVchange y CP =and
of state, (7/2)R.
calculate �U and �H for the process on the
basis of 1 mol of gas. Assume for the gas that P V /T is constant, C V = (5/2)R, and
2.38. (a)Un=
2.38.a)C
P
Anfluido incompresible
incompressible
(7/2)R. fluid(con(ρ r==constant)
constante)flows circula a través
through de una
a pipe of tubería
constantcon un área de sec-
cross-
ción transversal constante. Si el flujo es estable, demuestre que la velocidad u y la relación
sectional area. If the flow is steady, show that velocity u and volumetric flowrate
2.38. (a)deAn qflujo
are volumétrico qfluid
constant.
incompressible son constantes.
(ρ = constant) flows through a pipe of constant cross-
b)(b)Una A corriente
chemically
sectional dereactive
area. gas
If the gas is
químicamente
flow stream
steady, flows
reactivo
show steadily
fluye through
de
that velocity manerau aand
pipe
estable of aconstant
volumetric cross-
travésflowrate
de una tubería con
qsectional
área de sección
are constant.area.transversal
Temperature fija. La andtemperatura
pressure vary y.lawith
presión
.
pipevarían
length. con Which
la of the
longitud de la tubería.
Afollowing
(b)¿Cuál de las quantities
chemically siguientes
reactive are necessarily
cantidades
gas streamson constant:
necesariamente
flows steadily m,through u? a pipe ofm·constant
n, q,constantes: , n·, q, u? cross-
sectional area. Temperature and pressure vary with pipe length. Which of the
2.39.ElThe mechanical-energy balance provides a basis . .estimating pressure drop owing
for
2.39. balance
following de laquantities
energía mecánica proporciona
are necessarily constant: un fundamento
m, n, q, u? para calcular la caída de presión que
resulta de la fricción en el flujo del fluido. Para un flujo establefluid
to friction in fluid flow. For steady flow of an incompressible de unin afluido
horizontal pipe
incompresible en una
of constant
2.39.tubería cross-sectional
horizontal de área balance
The mechanical-energy area,
de sección it may be written,
transversal
provides a basis fija,forpuede establecerse
estimating pressure que: drop owing
to friction in fluid flow. For steady �Pflow of 2 an incompressible fluid in a horizontal pipe
of constant cross-sectional area, it may f FF ρu 22 = 0
+ be written,
�L D
�P 2 11 011 proporciona
2 11
donde
wherefF fes el the
F is
F factor de fricción
Fanning frictiondefactor.
Fanning. fChurchill
+ Churchill
F ρu = gives the following la siguiente
expression expresión
for para fF
quef Fcorresponde
for turbulentalflow: flujo con turbulencia: �L D
F
where f F is the Fanning friction factor.� � Churchill11
� gives the
�0.9 ��
following
−2
−2 expression for
� 7 0.9
f F for turbulent flow:f = 0.3305 ln 0.27 +
F
F
� � D Re
� �0.9 ��−2
� 7
f F = 0.3305 ln 0.27 +
11
11AIChE
AIChE J.,
J., vol.
vol. 19,
19, pp.
pp. 375–376,
375–376, 1973
1973
D Re
11 AIChE J., vol. 19, pp. 375-376, 1973.
11 AIChE J., vol. 19, pp. 375–376, 1973

Aquí, Re es el número de Reynolds (véase el problema 2.21) y /D es la aspereza adimensional de

Here, Re is the Reynolds number (see Pb. 2.21), and �/D is the dimensionless pipe
la tubería. Se obtiene flujo turbulento para Re > 3 000.
roughness. Turbulent flow obtains for Re > 3,000.
Consider the flow of liquid water at 25◦ C. For one of the sets of conditions given
Considere el flujo del agua en estado líquido a 25 °C. Para cada uno de los conjuntos de condiciones
. · (en kg s
below, determine m (in kg s−1 ) and
dados a continuación, determine m �P/�L (in kPa m−1 ). Assume
–1), y ∆P/∆L (en kPa m –1). Suponga que /D = 0.0001.
�/D = 0.0001.
◦ −3
–3
For liquid water at 25 C, ρ = 996 kg m , y m = 9.0 × 10 –4
and µ = 9.0 × 10 −4 –1 sm–1−1 s−1 . Verify
Para el agua líquida a 25 °C, r = 996 kg m kg mkg . Verifique si el flujo tiene
turbulencia.
that the flow is turbulent.
(a) D = 2 cm, u = 1 m s−1
a) D = 2 cm, u = 1 m s–1 −1
(b) D = 5 cm, u = 1 m s
b) D = 5 cm, u = 1 m s–1 −1
D = 2 cm, u = 5–1
c) (c)D = 2 cm, u = 5 m s m s
= = −1
d) D = 5 cm, u = 5 m s m s
(d) D 5 cm, u 5 –1
2.40.Un sistema de propano y n-butano existe en un equilibrio de dos fases vapor/líquido a 10 bar y 323
2.40. A system of propane and n-butane exists in two-phase vapor/liquid equilibrium at
10 bar and 323 K. The mole fraction of propane is about 0.67 in the vapor phase
K. La fracción molar del propano es aproximadamente 0.67 en la fase vapor y alrededor de 0.40 en
and about 0.40 in the liquid phase. Additional pure propane is added to the system,
la fase líquida. Se agrega propano puro adicional al sistema, que de nuevo lleva al equilibrio a las
which is brought again to equilibrium at the same T and P, with both liquid and vapor
mismas T y P con ambas fases, líquida y de vapor aún presentes. ¿Cuál es el efecto de agregar el
phases still present. What is the effect of the addition of propane on the mole fractions
propano sobre las fracciones molares de propano en las fases líquida y de vapor?
of propane in the vapor and liquid phases?
2.41. Seis especies químicas se encuentran presentes en cantidades significativas en un sistema de frac-
2.41.cionamiento de petróleo: metano, etano, propano, isobutano, n-butano y n-pentano. Una mezcla de
Six chemical species are present in significant amounts in a light-ends petroleum frac-
tionation system: methane, ethane, propane, isobutane, n-butane, and n-pentane. A
estas especies existe en equilibrio vapor/líquido en un recipiente cerrado. ¿De cuántas variables
mixture of these species exists in vapor/liquid equilibrium in a closed vessel. On how
de la regla de fase dependen las composiciones de las fases además de T y P?
many phase-rule variables in addition to T and P do the compositions of the phases
Si T y P permanecen iguales, ¿existe alguna manera de que la composición del contenido total del
depend?
recipiente pueda modificarse (agregando o eliminando material) sin afectar las composiciones de
If T and P are to remain the same, is there any way the composition of the total con-
las fases?
tents of the vessel can be changed (by adding or removing material) without affecting
the compositions of the phases?
2.42. Se introduce etileno a una turbina a 10 bar y 450 K, y se vacía a 1 (atm) y 325 K. Para m · = 4.5 kg s–1,
determine el costo C de la turbina. Establezca las suposiciones que considere necesarias.
2.42. Ethylene enters a turbine at 10 bar and 450 K, and exhausts at 1(atm) and 325 K. For
.
m = 4.5 kg s−1 , determine the cost C of the–1turbine. State any assumptions
· you make.
Datos: H1 = 761.1 H2 = 536.9 kJ kg−1 C/$ = (15 200)(|W.|/kW)0.573
Data: H1 = 761.1 H2 = 536.9 kJ kg C/$ = (15, 200)(|W |/ kW)0.573
2.43. Para incrementar la temperatura de una casa, la calefacción debe modelarse como un sistema abier-
2.43.to, ya que la expansión del aire doméstico a presión constante produce una fuga de aire hacia los
The heating of a home to increase its temperaature must be modeled as an open system,
because expansion of the household air at constant pressure results in leakage of air
exteriores. Suponiendo que las propiedades molares del aire que abandona la casa sean las mismas
to the outdoors. Assuming that the molar properties of air leaving the home are the
que las que corresponden al aire en el hogar, demuestre que los balances molar y de energía produ-
same as those of the air in the home, show that eneregy and mole balances yield the
cen la siguiente ecuación diferencial:
following differential equation:
. dn dU
Q = −P V +n
dt dt
.
Here, ·Q is the rate of heat transfer to the air in the home, and t is time. Quantities P,
Aquí, Q
V , n, and es la rapidez de transferencia de calor para el aire en la casa, y t es el tiempo. Las cantidades
U refer to the air in the home.
P, V, n y U se refieren al aire dentro de la casa.
.
2.44. (a) Water flows through the nozzle of a garden hose. Find an expression for m in terms
2.44. a) E
lof agua fluye a través de la boquilla de una manguera de jardín. Encuentre una expresión para
line pressure P1 , ambient pressure P2 , inside hose diameter D1 , and nozzle
m· en términos de la presión de la línea P1, la presión ambiental P2, el diámetro interno de la

Problemas 63
manguera D1 y el diámetro de la boquilla de salida D2. Suponga que se tiene un flujo estable,
así como operación isotérmica y adiabática. Para el agua líquida modelada como un fluido in-
compresible, H2 – H1 = (P2 – P1)/r para una temperatura constante.
b) De hecho, el flujo no puede ser realmente isotérmico: esperamos que T2 > T1, obedeciendo a la
fricción del fluido. Por lo tanto, H2 – H1 = C(T2 – T1) + (P2 – P1)/r, donde C es el calor especí-
fico del agua. De modo direccional, ¿de qué forma la incorporación del cambio de temperatura
podría afectar el valor de m· como fue calculado en el inciso a)?

Capítulo 3
Propiedades volumétricas
de fluidos puros
Las cantidades de trabajo y calor que se necesitan para llevar a cabo procesos industriales se calculan a partir
del conocimiento de propiedades termodinámicas, tales como la energía interna y la entalpía. Para los fluidos,
esas propiedades con frecuencia son evaluadas a partir de medidas del volumen molar como una función de
la temperatura y la presión, y proporcionan relaciones de presión/volumen/temperatura (PVT), las cuales se
expresan en forma matemática como ecuaciones de estado. La ecuación menos compleja, PV = RT, propor-
ciona el modelo realista más simple del comportamiento de un fluido. Además las ecuaciones de estado sirven
para la medición de los fluidos y la dimensión de recipientes y tuberías.
En este capítulo se describe, en primer lugar, la naturaleza general del comportamiento PVT de fluidos
puros; de ahí, se continúa con un tratamiento detallado del gas ideal; a continuación, la atención se enfoca en
ecuaciones de estado más realistas, que proporcionan los fundamentos para la descripción cuantitativa del
comportamiento de los fluidos reales; por último, se presentan las correlaciones generalizadas que permiten
la predicción del comportamiento PVT de fluidos, de los cuales no se tiene información experimental.
3.1 COMPORTAMIENTO PVT DE SUSTANCIAS PURAS

Las líneas 1-2 y 2-C de la figura 3.1 representan las condiciones de presión y temperatura de una sustancia
pura en donde existen las fases líquida y sólida en equilibrio con una fase de vapor. Estas líneas de presión de
vapor en función de temperatura caracterizan las relaciones de equilibrio sólido/vapor (línea 1-2) y líquido/
vapor (línea 2-C). La relación de equilibrio sólido/líquido está representada en la línea 2-3. Las tres líneas
despliegan las condiciones de P y T, en las cuales es posible coexistir en dos fases y separa en el diagrama las
regiones de una sola fase. Así, la línea 1-2, la curva de sublimación, separa las regiones de sólido y de gas; la
línea 2-3, la curva de fusión, separa las regiones de sólido y líquido; la línea 2-C, la curva de vaporización,
separa las regiones de líquido y de gas. El punto C se conoce como el punto crítico; sus coordenadas Pc y Tc
corresponden a la presión y temperatura más altas a las cuales se observa que una especie química pura exis-
te en equilibrio vapor/líquido. Las tres líneas se encuentran en el punto triple, donde las tres fases coexisten
en equilibrio. De acuerdo con la regla de la fase, ecuación (2.7), el punto triple es invariante (F = 0). Si el
sistema existe a lo largo de cualquiera de las líneas de dos fases de la figura 3.1, éste es univariante (F = 1),
mientras que en las regiones de una sola fase es divariante (F = 2).
64

3.1. Comportamiento pvt de sustancias puras 65
Es posible representar los cambios de estado mediante líneas en el diagrama PT: un cambio isotérmico
por una línea vertical y un cambio isobárico por una línea horizontal. Cuando una línea así cruza una frontera
de fase, se presenta un cambio súbito en las propiedades del fluido a T y P constantes; por ejemplo, la vapo-
rización para la transición de líquido a vapor.
3 A Región de fluido
Pc C
Curva de fusión Región líquida
Presión
Curva de
vaporización
Figura 3.1: Diagrama PT
B
Región sólida para una sustancia pura.
Región gaseosa
Punto Región
2 triple de vapor
1 Curva de
sublimación
Tc
Temperatura
Es evidente que el agua en un matraz abierto es un líquido que está en contacto con el aire a través de
un menisco. Si el matraz se encuentra sellado y el aire se extrae, el agua se vaporiza para reemplazar el aire,
y el H2O llena el matraz. Aunque la presión en el matraz se reduce, todo parece igual. El agua líquida reside
en la parte inferior del matraz porque su densidad es mucho mayor que la del vapor de agua, y las dos fases
están en equilibrio en las condiciones representadas por un punto de la curva 2-C de la figura 3.1. Las propie-
dades del líquido y del vapor son muy diferentes. No obstante, si la temperatura aumenta de tal forma que el
estado de equilibrio avanza de manera ascendente a lo largo de la curva 2-C, las propiedades de las dos fases
se hacen cada vez más parecidas; así, en el punto C se hacen idénticas y el menisco desaparece. Una conse-
cuencia es que las transiciones de líquido a vapor es posible que sucedan a lo largo de trayectorias que no
cruzan la curva de vaporización 2-C, es decir, de A hasta B. Por lo tanto, la transición de líquido a gas es gra-
dual y no incluye etapa de vaporización.
La región que existe a temperaturas y presiones mayores que Tc y Pc se marca por las líneas disconti-
nuas en la figura 3.1; éstas no representan fronteras de fase, sino más bien los límites establecidos por los
significados concedidos con las palabras líquido y gas. En general, se considera una fase líquida si se produ-
ce vaporización a partir de la reducción de presión a temperatura constante. Se considera gas una fase si se
produce una condensación a partir de la reducción de la temperatura a presión constante. Debido a que nin-
guno de estos procesos puede iniciarse más allá de la región de las líneas punteadas, se le llama región de
fluido.
La región gaseosa algunas veces está dividida en dos partes, como se indica mediante la línea vertical
discontinua de la figura 3.1. A un gas a la izquierda de esta línea, que puede ser condensado por compresión
a temperatura constante o por enfriamiento a presión constante, se le llama vapor. Un fluido que existe a una
temperatura mayor que Tc se conoce como supercrítico. Un ejemplo es el aire atmosférico.

66 CAPÍTULO 3. Propiedades volumétricas de fluidos puros
Diagrama PV
La figura 3.1 no proporciona información alguna acerca del volumen, tan sólo despliega las fronteras de fase
en un diagrama PT. En un diagrama PV [figura 3.2a)] estas fronteras, a su vez, serán regiones donde dos fases
(sólido/líquido, sólido/vapor y líquido/vapor) coexisten en equilibrio. Estas regiones están separadas por
curvas limítrofes que representan fases únicas, cuyas cantidades relativas determinan los volúmenes molares
(o específicos) en puntos intermedios. Aquí, el punto triple de la figura 3.1 es una línea horizontal, donde
coexisten las tres fases a una sola temperatura y presión.
Sólido/líquido
Tc
Fluido
C C
Líquido
Pc Pc Pc
Q
Sólido
Líquido
P Gas P
Va
por T  Tc
Líquido/vapor
Vapor Tc Tc
J K
Líquido/vapor T1  Tc
Sólido/vapor B T2  Tc
D
Vc Vc
V V
a) b)
Figura 3.2: Diagramas PV para una sustancia pura. a) Se muestran las regiones sólida, líquida y gaseosa. b) Se muestran
las regiones de líquido, de líquido/vapor y de vapor con isotermas.
La figura 3.2b) muestra las regiones de líquido, de líquido/vapor y de vapor en un diagrama PV, con
cuatro isotermas sobrepuestas. Las isotermas en la figura 3.1 son líneas verticales, y a temperaturas mayores
que Tc no cruzan una frontera de fase. En la figura 3.2b) la isoterma marcada con T > Tc es, por lo tanto,
uniforme.
Las líneas señaladas con T1 y T2 corresponden a temperaturas subcríticas y se componen de tres seg-
mentos. El segmento horizontal de cada isoterma representa todas las posibles combinaciones de líquido y de
vapor en equilibrio, variando desde 100% líquido en el extremo izquierdo hasta 100% vapor en el derecho. El
lugar de estos puntos extremos es la curva en forma de domo marcada con BCD, donde la mitad izquierda (de
B a C) representa líquidos de una sola fase en sus temperaturas de vaporización (ebullición) y la mitad derecha
(de C a D), vapores de una sola fase a sus temperaturas de condensación. Los líquidos y vapores representados
por BCD se conocen como saturados, y las fases coexistentes se conectan mediante el segmento horizontal de
la isoterma a la presión de saturación específica para ésta. También conocida como la presión de vapor, está
dada por un punto en la figura 3.1, donde una isoterma (línea vertical) cruza la curva de vaporización.
La región de dos fases líquido/vapor se encuentra debajo del domo BCD, la región de líquido subenfria-
do se localiza a la izquierda de la curva de líquido saturado BC y la región de vapor sobrecalentado está si-

3.1. Comportamiento pvt de sustancias puras 67
tuada a la derecha de la curva de vapor saturado CD. El líquido subenfriado existe para temperaturas por
abajo y, el vapor sobrecalentado en temperaturas por arriba del punto de ebullición para una presión deter-
minada. Las isotermas en la región de líquido subenfriado son de pendiente muy pronunciada, porque el vo-
lumen de los líquidos cambia muy poco con grandes variaciones en la presión.
Los segmentos horizontales de las isotermas en la región de dos fases se vuelven progresivamente más
cortos a temperaturas altas, y al final se reducen a un punto en C. Por esto, la isoterma crítica, marcada como
Tc, exhibe una inflexión horizontal en el punto crítico C en la parte superior del domo, donde las fases líquida
y de vapor no pueden distinguirse entre sí.
Comportamiento crítico
Se obtiene cierta idea acerca de la naturaleza del punto crítico a partir de una descripción de los cambios que
ocurren cuando se calienta una sustancia pura en un tubo recto, sellado y de volumen constante. Estos proce-
sos se indican en la figura 3.2b) mediante las líneas discontinuas verticales. También es posible trazar en el
diagrama PT de la figura 3.3, donde la curva de vaporización (figura 3.1) aparece como una línea continua, y
las líneas discontinuas son trayectorias a volumen constante en las regiones de una sola fase. Si el tubo se
llena, ya sea con líquido o vapor, el proceso de calentamiento produce cambios que se sitúan a lo largo de las
líneas discontinuas, por ejemplo, el cambio de E a F (líquido subenfriado) y el de G a H (vapor sobrecalenta-
do). Las líneas verticales correspondientes de la figura 3.2b) no se muestran, pero se encuentran a la izquierda
y a la derecha de BCD, respectivamente.
V2l Vc
Líquido
C
V2v
l
V1 Q
Figura 3.3: Diagrama PT para un fluido puro donde se
P F N muestra la curva de presión de vapor y las líneas a volumen
(J, K) V1v
constante en las regiones de una sola fase.
H
G
E
Vapor
Si el tubo se llena sólo de manera parcial con líquido (el resto es vapor en equilibrio con el líquido), el
calentamiento provoca, al principio, los cambios descritos por la curva de la presión de vapor (línea continua)
de la figura 3.3. Para el proceso indicado con la línea JQ de la figura 3.2b), de manera inicial, el menisco está
cerca de la parte superior del tubo (punto J), y el líquido se expande lo suficiente debido al calentamiento
hasta que llena completamente el tubo (punto Q). En la figura 3.3 el proceso describe una trayectoria que va
de (J, K) hasta Q, y con calentamiento adicional se desvía de la curva de presión de vapor siguiendo la línea
del volumen molar constante V 2l .
El proceso indicado por la línea KN de la figura 3.2b) comienza con un nivel inferior del menisco en el
tubo (punto K), y el calentamiento origina que el líquido se vaporice hasta el punto en que el menisco retro-

68 68 CAPÍTULO
CHAPTER 3.3. Volumetric
3. Propiedades
Volumetric volumétricas
Properties
Properties of deFluids
of Pure
Pure fluidos puros
68 68
68 CHAPTER
CHAPTER
VolumetricProperties
PropertiesofofFluids
Pure
PureFluids
Fluids
cede hacia el fondo del tubo (punto N). En la figura 3.3 el proceso se indica mediante una trayectoria que va
bottom of
of the
bottombottom theoftube
tube the(point
(point N
N).). OnOnNN).Fig.
Fig. 3.3
3.3 the
the process
process traces atraces
a path
tracestraces pathaafrom
from (J,
(J, K ))(J,
K(J, to
to KNK)..)to
N With
With
de (J, K) a N. bottom
Con calentamiento
of the tube
tube(point
adicional,
(point ).elOn
On Fig.
proceso
Fig. 3.3 the
theprocess
continúa
3.3 a lo largo
process de lapath
líneafrom
path del
vv. volumen
from NN. . With
molar
to cons-
With
vfurther heating
furtherfurther
heating the
the
heating path
path
the continues
continues
path along
along
continues the
the
along line
line
theof
of constant
constant
line of molar
molar
constant volume
volume
molar V
V
volume . V vv.
tante V 2. further heating the path continues along the line of constant molar volume 22 V22 .
For aa unique filling of
of the tube, thewith
tube,aawith
particular intermediate meniscus level,
level, the heating
Para un For
llenado unique
For
Forúnico fillingfilling
aauniquedel tubo,
unique theof
filling contube,
ofthe
una with
tube,
altura particular
intermedia
with intermediate
aaparticular intermediate
particular
particular meniscus
del
intermediate meniscus
menisco,
meniscus the
level,
el proceso heating
level, the
deheating
the calenta-
heating
process
process follows
follows
process a
a vertical
followsvertical
a line
line
vertical on
on Fig.
Fig.
line on 3.2(b)
3.2(b)
Fig. that
that
3.2(b) passes
passes
that through
through
passes the
the
through critical
critical
the point
point
critical C.
C.
point Physically,
Physically,
C. Physically,
miento describe una línea
process followsvertical en la line
a vertical figura on 3.2b) que pasa
Fig. 3.2(b) that por el punto
passes through crítico C. Físicamente,
the critical el proceso
point C. Physically,
heating does
does not
heatingheating not produce
produce much
much changechange in
in the
theinlevel
leveltheof
of the meniscus.
theof
meniscus. As
As thetheAs critical
critical point is
point point
ispointisis
no produce unheating does
gran cambiodoes notenproduce
not el nivel much
produce del
much change
menisco.
change the
Ainmedida level
levelqueofelthe
the meniscus.
proceso
meniscus.se acerca
As the alcritical
the punto
critical crítico, el
approached,
approached,
approached,the
the meniscus
meniscus
the meniscusbecomes
becomes indistinct,
indistinct,
becomes then
then
indistinct, hazy,
hazy,
then and
and
hazy, finally
finally
and disappears.
disappears.
finally disappears. On
On Fig.
Fig.On 3.3
3.3
Fig.
Fig.3.3
menisco se torna indistinguible,
approached, despuésbecomes
the meniscus es nebuloso y al final
indistinct, thendesaparece.
hazy, and finallyEn la figura
disappears. 3.3, laOn trayectoria3.3
the
the path
path first
pathfollows
first follows the
the vapor-pressure
vapor-pressure curve, proceeding
curve, curve,
proceeding from
from point
point (J,
(J, K ))(J,
K(J, to
toKthethe))tocritical
critical
primero siguethe the path
la curva first
de
first follows
presión
follows dethe vapor-pressure
vapor,
the procediendocurve,
vapor-pressure del puntoproceeding
(J, K) alfrom
proceeding puntopoint
from crítico
point C,Kdonde to the
se critical
the introdu-
critical
point C,
point point
C, where
where
C, it
it
whereenters
entersit the
the
enters single-phase
single-phase
the fluid
single-phasefluid region,
region,
fluid and
and
region, follows
follows
and V
V
follows
c ,, the
the
V line
line
, the of
of constant
lineconstant
ofof constant
ce a la región fluida
point C, de unawhere solait fase
enters y sigue a Vc, la líneafluid
the single-phase de volumen
region, and molar constante
c
follows Vcc , igual
the line al volumenconstantcrí-
molar
molar volume
volume equal to
equal equalto the
theto critical
critical volume
volume of
of the
theoffluid.
fluid.
tico del fluido.molar
molarvolume
volume equal tothethecritical
critical volume
volume ofthe
thefluid.
fluid.
Single-Phase Region
Single-Phase Region
Regiones Single-Phase Region
de una sola fase
For
For the
theForregions
regions
For the of
of the
theregions theof
regions diagram
diagram
of the
thediagram where
diagram aa single
wherewhere
wheresingle phase
phasephase
aasingle
single exists,
exists,
phaseexists,Fig.
Fig. 3.2(b)
exists, 3.2(b)
Fig. implies
implies
Fig.3.2(b)
3.2(b) aa relation
relation
implies
implies con-
con- con-
aarelation
relation con-
necting
Para lasnecting
regiones P,
P,del
necting V
V ,
, and
diagrama
and T
T .
. Expressed
donde
Expressed sólo analytically,
existe una
analytically, as
fase,
as f
fla (P,
(P, V,
figura
V, T
T
necting P, V , and T . Expressed analytically, as f (P, V, T ) = 0, such a relation isknown
P, V , and T . Expressed analytically, as f (P, )
) =
=
3.2b)
V, T0,
0,) such
implica
such
= 0, a
a relation
una relación
relation
such a is
is known
que
known
relation is as
conecta
as aas
known P,
as
V y T, laaacual
PVT
PVTse aaequation
expresa
equation
PVT of
de
of
equation state.
manera
state.of It
It
state. relates
analítica
relates
It pressure,
mediante
pressure,
relates molar
f (P,
molar
pressure, V, or
T)
or
molar specific
= 0;
specific
or
PVT equation of state. It relates pressure, molar or specific volume, and temperature for auna volume,
relación
volume,
specific and
así
and
volume, temperature
se conoce
temperature
and como
temperature for
for a
ecuación
a for a
de estadopure
pure
PVT.homogeneous
Relaciona
homogeneous
pure
pure homogeneous lafluid
homogeneous in
presión,
fluid in equilibrium
fluid elin
volumen
equilibrium
fluid inequilibriumstates.
states.
equilibrium The
molarstates.
The
states. ideal-gas
o específico
ideal-gas
The y equation
Theideal-gas la temperatura
equation
ideal-gas of
of state,
equation
equation para
state,
of P VV=
un
Pstate,
ofstate, = PPRT
fluido
RT
VV = ,,homogéneo
=has
has
RT
RT, ,hashas
approximate
puro en approximate
estados de
approximatevalidity
equilibrio.
validity for
La
for the
the low-pressure
ecuación de
low-pressure estado gas
gasde region
gas
region of
ideal,
of Fig.
Fig.
PV
approximate validity for the low-pressure gas region of Fig. 3.2(b), and is discussed indetail
validity for the low-pressure gas region of 3.2(b),
=
3.2(b),
RT,
Fig. and
tiene
and
3.2(b), is
una
is discussed
validez
discussed
and is in
in
discussed detail
aproximada
detailin para
detail
la regiónin Sec.
indel
Sec.gas 3.3.
de baja
3.3.
ininSec.
Sec. 3.3.presión de la figura 3.2b), y se discutirá con detalle en la sección 3.3.
3.3.
Una ecuaciónAn
An equationde
Anestado
equation
An of
of state
equation
equation puede
stateofofmay statebe
resolverse
may
state be
maysolved
maysolved
bepara
be for
for
solved
solved any
cualquiera
any
for
for one
one
any
any of
deofonethe
las
one three
thetres
ofthree
of the
the quantities
cantidades,
quantities
three P,P,
threequantities V oVVT,
P,
quantities ,,P,
or
or
P, VTT
como V, ,asuna
or TTfun-
as
or as
as
a function
ción de alasfunction
otras of
dos.
of
aa function the
Por
the other
ejemplo,
other
of the two.
two.
other si seFor
For
two. example,
considera
example,
For a Vif
if
example, V
como
V is
is
if considered
una función
considered
V is
function of the other two. For example, if V is considered a function of T and P, then considereda
de
a function
T y P,
function
a of
of
function T
entoncesT and
ofV
and T =P,
P,V(T,
and then
thenP),
P, y
then
VV= =V VVV(T,
(T,
==V P),
P),
V(T, and
andP),
P),and ��
(T, and � � � � � � �
∂∂VV �∂∂VV � ∂∂V V �∂∂VV �
ddVV= =ddVV == dT dT + +dT dd PP d P (3.1)
(3.1) (3.1)(3.1)
∂∂TT PP∂∂TT dT ∂∂+P+ TT∂∂PP T d P
P (3.1)
PP T
The
The partial
partial
The derivatives
derivatives
partial in
derivativesin this
this inequation
equation
this have
have
equation definite
definite
have physical
physical
definite meanings,
meanings,
physical and
meanings,and yare
are
and related
related
are to
to two
related twotototwo
Las derivadas parciales en esta ecuación tienen significados físicos bien definidos
The partial derivatives in this equation have definite physical meanings, están
and relacionadas
are related con
two
properties,
properties, commonly
commonly
properties, commonly tabulated
tabulated for
for
tabulated liquids,
liquids,
for and
and
liquids, defined
defined
and as
as
defined follows:
follows:
as follows:
dos propiedades que comúnmente se tabulan para los líquidos, y que se definen como:
properties, commonly tabulated for liquids, and defined as follows:
��
11 ∂∂V 1V1 ∂∂VV
• Volume
• Volume
• Coeficiente ••Volume
de expansivity:
expansivity:
expansión
Volume expansivity:
expansivity: β
volumétrica:β ≡ Vββ≡≡∂ T ≡ (3.2)
(3.2) (3.2)(3.2)
(3.2)
V ∂VTV PP∂∂TT P
P
��
11 ∂∂V 1V1 ∂∂VV
•• Isothermal
Isothermal
• Isothermal
• Isothermal compressibility:
compressibility:
compressibility:
compressibility: κ
κ ≡
≡ −
− ≡ − (3.3)
(3.3) (3.3)
• Compresibilidad isotérmica: κκVV≡ − ∂∂V PPV TT∂∂PP T (3.3)
(3.3)
T
In
In combination
combination
La combinación
In de Equations
Equations
las ecuaciones
Incombination
combination (3.1)
(3.1)through
(3.1)
Equations
Equations through
a(3.1)
(3.3)
(3.1) (3.3)
(3.3) yield:
yield:
produce
through
through la ecuación:
(3.3)
(3.3) yield:
yield:
ddVV ddVV
== ββ dT ==−
dT −
ββdTκκdT P−κ κddPP
dd −
P (3.4) (3.4)
(3.4) (3.4)
(3.4)
VV VV
Las isotermas
The para la fase
The isotherms forlíquida
for the liquidde laphase
partephase
izquierda
on the left deside
la figura 3.2b) son are
de
arependiente muy pronun-
isotherms
The
The isotherms
isotherms theforliquid
for the phase
the liquid
liquid on
phasetheon left
on the
thesideleftof
left of Fig.
sideFig.
side of3.2(b)
of 3.2(b)
Fig.
Fig. 3.2(b)
3.2(b) very
veryaresteep
are steep
very and
and
very steepsteep and
and
ciada y closely
muy cercanas
closely spaced.
spaced.
closely entre
Thus
Thus sí. De
both
both esta
(∂
(∂ VVmanera,
/∂
/∂ TT )
) (∂V/∂T)
and
and (∂
(∂ VVP y
/∂
/∂ P)(∂V/∂P)
P) and
and T y,
hence
hence por tanto,
both
both ββb y
and
and k son
κ
κ are
are pequeños.
small.
small. Este
closely spaced.
spaced. Thus Thus bothboth (∂ (∂VVP/∂
P /∂TT))PP andand (∂ (∂VVT/∂
T /∂P) P)TT and and hence
hence both both ββ and and κκ are are small.
small.
comportamiento
This característico
This characteristic
characteristic
This debehavior
behavior
behavior losof
oflíquidos
liquids
liquids (lejos
(outsidede
(outside la
the
theregión
critical
criticaldelregion)
puntoregion)
region) crítico)
suggests
suggests sugiere
an una
an idealization,
idealization,idealización,
This characteristic
characteristic behavior of
of liquids
liquids (outside
(outside the
the critical
critical region) suggests
suggests anan idealization,
idealization,
comúnmente
commonly
commonlyutilizada
commonly en
employed
employed mecánica
in
in fluid
fluid de fluidos,
mechanics
mechanics que
and
and se conoce
known
known as
as como
the
the el fluido
incompressible
incompressible incompresible,
fluid,
fluid, for
for para
which
which el
bothqueboth
both b yk
commonlyemployedemployedininfluid fluidmechanics
mechanicsand andknown
knownas asthetheincompressible
incompressiblefluid, fluid,for forwhich
which both
son cero.
ββ Deandhecho,
and κκ
ββandare
are ningún
zero.
zero. No
No fluido
real
real real
fluid
fluid es
is
is incompresible,
truly
truly incompressible,
incompressible,pero la idealización
but
but the
the es
idealization
idealization muy isútil
is porque
useful,
useful, con
because
because frecuen-
andκκ are arezero.
zero. No Noreal
realfluid
fluidisistruly
trulyincompressible,
incompressible,but butthe theidealization
idealizationisisuseful, useful,because
because
cia proporciona
itit provides
provides unaamodelo
ititprovides bastante
sufficiently
sufficiently
aasufficiently realista
realistic
realistic delmodel
model
model
realistic comportamiento
of
of liquid
liquid
of behavior
behavior del forlíquido
for many
many para finespurposes.
practical
practical prácticos.
purposes. No existe
No
No
provides sufficiently realistic model ofliquid
liquid behavior
behavior for
formanymanypractical
practical purposes.
purposes. No
No
ningunaequation
ecuación
equation ofde
of
equation estado
state
state exists
existspara
for
forunan
anfluido incompresible,
incompressible
incompressible fluid,
fluid, porque
because
because V VVes isindependiente
is independent
independent de
of
of TT
T y
and
andP. P.
P.
equationof ofstate
stateexists
existsfor foran anincompressible
incompressiblefluid, fluid,because
becauseVV isis independent
independent ofof TT andand P.
P.
Para líquidos,
For
For liquidsb casi
liquids
For ββ siempre
is
is almost
almost esalways
positiva
always (es positive
positive
positive una(liquid
excepción
(liquid waterelwater
water agua líquida
between
between 00◦◦C entre
C and00◦◦C4C
and 0C
Cyis
4◦◦and is444an
°C) isisyan
◦CCexcep-
◦an excep- k es nece-
Forliquids
liquids ββisisalmost
almost always
always positive (liquid
(liquid waterbetweenbetween and anexcep-
excep-
sariamente
tion),
tion),positiva.
and
and
tion), κκ En
is
is condiciones
necessarily
necessarily no cercanas
positive.
positive. At
At al punto
conditions
conditions crítico
not
not b
close
close y k
to
to son
the
the funciones
critical
critical débiles
point,
point, ββ de
and
and laκ
κ temperatu-
are
are
tion),andandκκ isisnecessarily
necessarilypositive.positive. At Atconditions
conditionsnot notclose
closetotothe thecritical
criticalpoint,
point,ββ and andκκ are
are

3.1.
3.1.PVTPVT Behavior
Behavior of of
Pure Substances
Pure Substances 6969
69
3.1. PVT
3.1. PVT Behavior
Behavior of of Pure
Pure Substances
Substances 69
69
3.1. PVT Behavior of Pure Substances 69
3.1. PVT Behavior
3.1. Comportamiento of Pure Substances puras Thus for small changes in T and P little error is69 69
weak
weak
3.1.
weak functions
functions
PVT
functions ofpvt
Behavior of
of
de sustancias
temperature
temperature
temperature andandpressure.
and
of Pure Substances pressure. Thus
pressure. Thus for for small
small changes
changes in in TT and
and PP little
little error
error69 is
is
weak
weak
introducedfunctions
functions
if they of
of temperature
temperature
areareassumed and
and
constant. pressure.
pressure. Thus
Thus
Integration for
for small
small changes
changes in
in TT and
and PP little
little error
error is
is
introduced
weak functions
introduced
introduced
if they
if they
ifeste of
they
are
are
assumed
temperature
assumed
assumed
constant.
and
constant.
constant.pressure. Thusof
Integration
Integration
Integration forEq.
of
of
of Eq.(3.4)
Eq.
small
Eq.
(3.4) then
changes
(3.4)
(3.4) thenyields:
then yields:
in T and P little error is
yields:
then yields:
yields:
ra y la introduced
presión.
weak De
functions
if they
of
are
modo, assumed
para
temperature
introduced if they are assumedVconstant.
constant.
cambios
and
Integration
pequeños
pressure. Thus
Integration de of
for
ofT Eq.
y
small
Eq. P(3.4)
se
changes
(3.4)
then
introduce
then in T un
andpequeño
yields: error is
P little error si se les
weak functions 2V
V 222 pressure. Thus for small changes in T and P little error is
considera constantes.
introduced Laofintegración
if they temperature
are assumed de
ln ln
ln
and
V
V=
la
constant.ecuación
β(T
= β(T − T
−(3.4)
)
T
Integration−) produce:
−κ(Pκ(P
of −
Eq.
22 = β(T222 − T111) − κ(P222 − P111)
2 1 2 −P )
P
(3.4)
1 ) then yields: (3.5)
(3.5)
(3.5)
introduced if they are assumed lnVconstant.
ln 1V
V 1121 == β(T
β(T − TT11)) −
22 −
Integration − of
κ(P
κ(P Eq. −(3.4)
22 − PP11))then yields: (3.5)
(3.5)
ln VV
V1 21 = β(T 2 − T 1 ) − κ(P 2 − P 1 ) (3.5)
This
This
Thisis is
a less
is a lessrestrictive
restrictive approximation V21 =than
approximation
ln V than
β(T the
2−
assumption
the ) − κ(P2of−of
T1assumption anP1anincompressible

) incompressible fluid.
fluid. (3.5) (3.5)
This is aaa less
This is less restrictive
less restrictive approximation
restrictive approximation
approximation
ln V1 = β(T
than
than
than 2−
the assumption
theTassumption
the 1assumption
) − κ(P2 −of
of an
ofPan
1an
incompressible fluid.
incompressible fluid.
) incompressible fluid. (3.5)
This is a less restrictive approximation V1 than the assumption of an incompressible fluid.
Ésta es una
Thisaproximación
is a less restrictive menosapproximation
restrictiva quethan la suposición
the assumption de unof fluido incompresible.fluid.
an incompressible
This is a less restrictive approximation than the assumption of an incompressible fluid.
Example
Example 3.1
3.1
Example 3.1
Example 3.1 ◦ ◦◦
Example
For liquid
For
For acetone
liquid
liquid 3.1
acetone
acetoneat at
2020
at 20C◦ Cand
C and
and1 bar,
1 bar,
Example
For liquid
For 3.1
liquid acetone
acetone 20◦◦◦C
at 20
at and 111 bar,
C and bar,
bar,
Ejemplo
Example
ββ3.1
For liquid
= =1.487 3.1
acetone
× 10
× at
−3 20
◦
−3
−3
−3 C◦
◦
◦ C
−1
C and
−1
−1
−1 1κ bar,
=
κκ = ××
6262 −6−6
1010 −6
bar
−6 −1−1
−1
−1 VV == 1.287 cmcm 3 333−1−1
g33 g −1
−1
For liquid
1.487 10
β = 1.487 × 10−3
=acetone −3 ◦◦C−1
◦ −1 × 10 at = 62 ×
20◦ C −6 bar
10−6 bar−1
−1
and 1 bar, = × V =
=
1.287
1.287 cm gg−1
−1
ββ = 1.487 ×
1.487 10−3 C κκ = 62
62 × 10
10 bar
bar VV = 1.287
1.287 cm
cm g
Para For
la For
acetona
liquid
acetone,β líquida
= acetone
1.487
find: a×20 at
10 20 y◦C
°C C 1−1 bar, 1 bar,
and κ = 62 × 10 −6 bar−1 V = 1.287 cm 3
g −1
For
For acetone,
acetone, find:
find: −3 ◦ C−1 −6 bar−1 −1
For β = 1.487
For acetone,
acetone, find:
find: × 10−3 ◦ C−1
κ = 62 × 10−6 −1
V = 1.287 cm33 g−1
For β
acetone,
(a)(a)The =
The 1.487
value find:
value ×
of of 10
(∂ (∂ P/∂ T )TV ) at 2020 κ ◦ =◦
◦
C◦ C 62
and × 10
1 bar. bar V = 1.287 cm g
(a) The value of P/∂ V at at 20 C and
and 1 bar.
(a) The
For (a) The value
acetone, value
find: of of (∂(∂ P/∂
P/∂TTT)))VVVV at
(∂P/∂ at 20 20◦◦◦C C andand 111 bar. bar.
bar.
Para la For
acetona,
(a)
(b)(b)The The
acetone, encuentre:
value
find:
pressure of (∂ P/∂
generated T ) at
V byby 20 C
heating and 1
at at bar.
constant VV from 2020 ◦ C◦◦◦ and 1 bar to
(b) The
The pressure
pressure generated
generated by heating
heating at constant
constant from
from 20 C
C and 1 bar to
(a)
(b)
(b) The
The
◦ ◦◦◦C.value
pressure
pressure of (∂ P/∂
generated
generated T ) V at 20
by
by
◦ C and
heating
heating 1 bar.
at
at constant
constant V
V
V from
from 20
20 ◦◦C C and
◦ C and
and 111 bar bar to
bar to
to
(b)3030
a) El valor
(a) deC.
30
The
30 ◦ (∂P/∂T)
◦C.value
pressure Vofa(∂ 20 P/∂°CTy)1
generated V bar.at by 20◦heating
C and 1at bar.
constant V from 20 and 1 bar to
30◦C. C. ◦ C and 1 bar to
b) La(c)
presión
(b) 30
The
The generada
C.
change
pressure
in in por
volume calentamiento
generated
forfor a by
by heating
change a V from constante ◦ C◦◦◦desde
at constant
20 and 1V20
V from
bar °Cto yto 1
◦ C◦bar
20
020 ◦◦◦Candhasta1010 30 °C.
(c)
(b)
(c) The
The ◦ change
pressure
change in volume
generated
volume for a
a change
heating
change from
fromat 20
constant
20 ◦ ◦ C
C and
and 11 bar
from
bar to 0
0 ◦10◦C
C and
and 1bar.
10 bar.
bar
bar. to
c) El cambio
(c) The
(c) 30
Thede C.
◦ C. volumen
change
change inin para
volume
volume una modificación
for
for aa change
change de
from
from 20 20
20 °C ◦ Cy
C 1
and
andbar 1 1 a 0
bar
bar °Cto
to y
00 ◦ CC bar.
and
and 10
10 bar.
bar.
30
(c) The change in volume for a change from 20 C and 1 bar to 0 C and 10 bar.
(c) The change in volume for a change from 20◦◦ C and 1 bar to 0◦◦ C and 10 bar.
Solución (c)
Solution3.1
SolutionThe change 3.1 3.1 in volume for a change from 20 C and 1 bar to 0 C and 10 bar.
Solution
Solution
a) LaSolution
derivada (∂P/∂T) 3.1
3.1
(a) The
(a)
(a) The
The derivative 3.1 V(∂se(∂
derivative
derivative
determina
P/∂ P/∂
P/∂ T )T V )is V is
con la aplicación
determined
determined byby de la ecuación
application
application of of Eq.Eq.(3.4)
(3.4) para
(3.4) to to elthe
the caso
case caseen el que
(∂ TTTd)))V is determined by application of Eq. (3.4) to the case
V
V es constante
(a)
Solution
for(a)
for
Theyderivative
The
which
which V dV
derivative
3.1
Vis = 0:
constant
is
(∂
constant
P/∂
(∂P/∂ and and V
V
V is = is determined
determined by
0: by application
application of of Eq.Eq. (3.4)
(3.4) to to the
the case
case
(a)
for
Solution The
which
for which
for which derivative
V
3.1
V is
V isis constant (∂ P/∂and
constant
constant and
andT )VddddV V
is
V
V=
= 0:
determined
== 0:
0:
0: by application of Eq. (3.4) to the case
(a) The derivative (∂ P/∂ T ) is determined by(V application of Eq. (3.4) to the case
for
(a)
which V is constant β dT and
β )V−
dT
Vd V
− = 0:
dκκPdd P
κ determined == 0 00 by (const constante)
(const V )V )) of Eq. (3.4) to the case
for The
which derivative
V is�constant (∂ P/∂
��
ββTdT
and
β dT
dT d is
−
V
− − =
κκ d0:
d P
PP ==
= 0 0
application
(const
(const
(const V
VV ))
for which V is constant �
� � andβ d V− 1.487 = 0: =×
∂��P∂∂ PP �� β dT β κ 1.487 dP ×
1.487 10
×
0 10 −3−3
10
−3(const V )
−3
o or or
or �∂∂P P �= β= =dTβββ =−= = κ 1.487 P =×
d1.487 × 0−6 10
10 −3
−3 = 2424
(const
=
= 24bar
Vbar
bar)◦ C◦◦◦◦◦−1
CC
−1
−1
−1
−1
or
or ∂�T∂∂ TP
T V�V β
V ==κ
dT β
κκ− == κ d
62 P
1.487
62
62× = 10
×
× ×0 10
10
−6
10
−6
−6
−6
−3
−6 (const== 24
24 V )
bar
bar ◦ CC−1−1
or ∂∂ T
T V = κκ = 62 62 ×× 10
10 −3 = 24 bar C
� ∂∂ TP �VV βκ = 1.487 1.487
62 ×× ×1010 −6−3
orIf β and κ are assumed ∂P V = β 10 = 24 bar ◦◦ C−1
◦ C◦◦◦ temperature
−1
b) Si se supone
(b)(b)
or
(b) If
If β
β queand
and bκ
κ y are
arek son
∂assumed
T
assumedconstantes
V = constant
constant
κ =
constant en in
62elinintervalo
the
in× the
the10 10−610
10 ◦ ◦C
Cde
= temperatura
temperature
24 bar
temperature C de 10 °C,
interval,
interval,
interval, then por
then
then lo tanto la
thethe
the
(b) If
(b) If ββderived
andand κκ in are
are assumed
∂assumed
Tmay κconstant
constant 62 in
in × the
the10 −610◦C
10 C temperature
temperature interval, interval, then then the the
ecuación deducida
equation
equation
(b) If β and en
derivedκ area) se
(a)
in puede
(a) may
V escribir
be bewritten
writtencomo (V (V= (V =
const):
= constante):
const):
equation
equation
equation derived
derived
derived in assumed
in
in (a)
(a) may
(a) may
may be be
be constant
writtenin
written
written (Vthe
(V
(V 10 C temperature interval, then the
=== const):
const):
const):
(b) If β and
equation derivedκ are in assumed
(a) may βbe constant
β written in(Vthe = 10◦◦ C temperature interval, then the
const):
(b) If β and κ are assumed == β
constant == in the 10=C temperature interval, then the
equation derived in (a) �P �P
�P may = be�Tββwritten
�T
�T =(24)(10)
(24)(10)
(V
(24)(10) = const): =
=240 240
240barbar
bar
equation derived in (a)�P �P may= =κbe κβ
κ �T =
�T
written = (V (24)(10)
(24)(10) = const): == 240 240 bar
bar
�P = κβκ �T = (24)(10) = 240 bar
y and and
and P2P P = 222 =
= P1= P
P +1 κ+ �P
+ �P === = +
1(24)(10)
1+ + 240 240== =
=241 241barbar
and
and �P
22 =
PP�P == PP1111β +
κ
�T
+�T �P
�P=
�P = 111 +
=(24)(10) 240
+ 240
240= ==240 241
240
241bar
241 bar
bar
bar
bar
and P2 = P1 κ+ �P = 1 + 240 = 241 bar
c) La (c)
sustitución
Direct
and
(c)
(c) Direct
Direct directa
substitution
substitution
substitution en la Pecuación
into 2 =
into
into Eq.Eq. P(3.5)
Eq. 1+ (3.5)
(3.5)
(3.5) gives:
�P da:
= 1 + 240 = 241 bar
gives:
gives:
(c) Direct
(c)
and Direct substitution
substitutionPinto 2 = Eq.
into P1 +
Eq. (3.5)
(3.5)
�Pgives: = 1 + 240 = 241 bar
gives:
(c) Direct V substitution
2V
V 222
into Eq. −3−3
(3.5) gives: −6−6
ln ln V2= (1.487 ×× 10 −3
)(−20) −− (62(62 ×× 1010 −6
)(9) == −0.0303
(c) Direct ln V 2 =
substitution = (1.487
(1.487 into × Eq.10
10 −3
(3.5)
−3
−3 )(−20)
)(−20) gives: − (62 × 10 −6
−6)(9)
)(9) = −0.0303
−0.0303
(c) Directln V1V
ln 1121 =
substitution
V = (1.487
(1.487 into× ×Eq. 10−3
10 (3.5))(−20)
)(−20) gives: − − (62 (62 × × 1010−6 −6
)(9) =
)(9) = −0.0303
−0.0303
ln V V121 = (1.487 × 10 )(−20) − (62 × 10 )(9) = −0.0303
V
V2V V V −3
222ln V21 = (1.487 × 10−3 )(−20) − (62 × 10−6 )(9) = −0.0303
−6
3 333−1−1 −1
V2=
V 2ln=
=0.9702
V0.9702
1 = (1.487and
0.9702 and × 10 V2)(−20)
and V
V =222 =
= − (62 × 10 =
(0.9702)(1.287)
(0.9702)(1.287)
(0.9702)(1.287) =
=
)(9)1.249 1.249 cmcm
= −0.0303
1.249 cm g33 gg−1 −1
−1
V1V V =
1121 V1= 0.9702
0.9702 and
and y V
V 22 == (0.9702)(1.287)
(0.9702)(1.287) == 1.249
1.249 cm
cm 3 gg−1
V
V 1 1 = 0.9702 and
V2 �V = V − V = 1.249 − 1.287 = −0.038 cm3 g333−1−1 V 2 = (0.9702)(1.287) = 1.249 cm
−1 3 −1
g
Then,
Then, V �V = 2V 2− 1V 1= V2 =−
1.249 1.287 = −0.038 =cm −1
gg−1
Then, V
Then, 21 = �V 0.9702
�V
�V = ==V V
V2222 − −
−andand
VV1111 = =
= 1.2491.249 −
−
−
(0.9702)(1.287)
1.287 = =
= −0.038
−0.038
−0.038 cm 1.249
33 g −1cm g
Then, V1 = 0.9702 V 1.249
V = 1.287
1.287
(0.9702)(1.287)
2 − 1.287 = −0.038 cm3 g−1 = cm
cm 1.249 g cm3 g−1
En tal caso,
Then, V1 �V = V2 − V1 = 1.249
Then, �V = V2 − V1 = 1.249 − 1.287 = −0.038 cm3 g−1
Then, �V = V2 − V1 = 1.249 − 1.287 = −0.038 cm3 g−1

70 70 CAPÍTULO
Properties deFluids
of Pure fluidos puros
70 CHAPTER 3. Volumetric Properties of Pure Fluids
3.2 ECUACIONES DE ESTADO
3.2 VIRIAL EQUATIONS VIRIALES
OF STATE
3.2 VIRIAL EQUATIONS OF STATE
Las isotermas para gases y vapores, que se localizan arriba y a la derecha de CD en la figura 3.2b), son curvas
Isotherms for gases and vapors, lying above and to the right of C D in Fig. 3.2(b), are rela-
relativamente simples para las que V disminuye a medida que P se incrementa. Aquí, el producto PV para una
Isotherms
tively simple forcurves
gases for andwhich
vapors,V lying aboveasand
decreases to the right
P increases. of Cthe
Here, D product
in Fig. 3.2(b),
P V forare rela-
a given
T determinada es mucho más constante que cualquiera de sus integrantes, y por tanto más fácil de representar
Ttively simple
should be muchcurvesmore for which
nearlyVconstant
decreases as P
than increases.
either Here, the product
of its members, P Vmore
and hence for a easily
given
de manera analítica como una función de P. Esto sugiere expresar a PV para una isoterma, por medio de
T should beanalytically
represented much moreasnearly constant
a function of P.than
Thiseither of its
suggests members,Pand
expressing V forhence more easily
an isotherm by a
un desarrollo en serie de potencias de P:
represented
power seriesanalytically
in P: as a function of P. This suggests expressing P V for an isotherm by a
power series in P: P V = a + b P + c P 22 + · · ·
2
Si b ≡ aB ′,
If b ≡ B ��, c etc.,
c ≡a aC ′, ≡ aCen��, tal then, P V = a + b P + c P + · · ·
etc.,caso,
If b ≡ a B � , c ≡ aC � , etc., then,
P V = a(1 + B �� P + C �� P 22 + D �� P 33 + · · ·) (3.6) (3.6)
� � 2 � 3
P V = a(1 + B P + C P + D P + · · ·) (3.6)
donde a,where
B ′, C ′,
a, Betc.,
��, Cson constantes
��, etc., para una
are constants for atemperatura y especie
given temperature química
and a givendeterminadas.
chemical species.
Enwhere
principio,B � ,elClado
Ina,principle, derecho
� , etc.,
the are
right de
sidela of
constants ecuación
for
Eq.a(3.6) (3.6)
given es infinite
una serie
istemperature
an infinita.
and a given
series. Dechemical
However,cualquier modo,
species.
in practice en la prácti-
a finite
ca se emplea
number un
In ofnúmero
principle,
terms is finito
the de In
right
used. términos.
side VDe
fact,ofPEq. hecho,
T(3.6) la información
dataisshow
an infinite low PVT
that atseries. muestra
However,
pressures inque a presiones
practice
truncation twobajas el
a finite
after
truncamiento
number
terms después
of terms
often de is
provides dosused.
términos con
In fact,
satisfactory Pfrecuencia proporciona
V T data show
results. that at resultados
low pressures satisfactorios.
truncation after two
terms often provides satisfactory results.
Ideal-Gasde
Temperaturas Temperatures; Universal
gases ideales; Gas
constante Constant
universal de los gases
Ideal-Gas�� Temperatures;
�� Universal Gas Constant
Parameters B , C , etc., in Eq. (3.6) are species dependent and functions of temperature, but
Los parámetros B ′,a BC ′,
Parameters
parameter Cetc.,
is� , found en
byla
� , etc., in ecuación
Eq. (3.6)(3.6),
experiment are son
the funciones
species
to be dependent
same de and
function laof
temperatura
functions
temperature y dependen
of temperature, de la
for all chemical butespecie,
pero, enspecies.
forma experimental,
parameter a isisfound
This shown seby
by demuestra
experiment que elof
to be
measurements parámetro
the a es
same function
volume as la misma offunción
of temperature
a function de la
for
P for variousalltemperatura
gases at para
chemical
todas lasconstant
especiestemperature.
species. químicas.
This is shown Esto bysemeasurements
Figure muestra
3.4, fora través
of de
example, mediciones
volume as a of
is a plot del
P Vvolumen
function como
vs.ofPPfor
forfour una
various función
gases gases atde P pa-
at the
ra diferentes gases
constant atemperature
temperatura
temperature.
triple-point ofconstante.
Figure 3.4,The
water. Porlimiting
for ejemplo,
example, islaafigura
value V3.4as
plotP of
of Pes
VPuna→ gráfica
vs. P forthe
0 is desame
four PV en
forfunción
gases at of de P,
allthe
para cuatro
the gases en
triple-point
gases. la temperatura
Intemperature
this del punto
of water.
limit (denoted thetriple
by The del agua.
limiting
asterisk), value Todos Vlos as gases
of Pbecomes:
Eq. (3.6) P →tienen el mismo
0 is the same for valor límite de
all of
PV conforme P →In0.this
the gases. En limit
este límite (denotado
(denoted por∗el asterisco),
by the asterisk), Eq. (3.6)labecomes:
ecuación 3.6 será:
(P V )∗ = a = f (T )
(P V )∗ = a = f (T )
H22
H H2
H2
�1 �1
PV/cm3 bar mol1
N22
N
molmol
N2
Air
Air
Figure 3.4: (P V )∗∗, the
Figura 3.4: (PV)*, el valor límite N 2 Aire
3 bar
Air
de PV conforme
limiting P
value
Figure 3.4: ofVes)P∗V
→(P0, as
, the O22
O
(PV)*t*t � cm33 bar
3 bar
�1
(PV) 22,711.8
� 22,711.8 bar mol
mol3�1
independiente
P → 0, delisgas.
independent
of P V asof the (PV)*  cm
22 711.8 cm bar mol1 O2
PV/cm
limiting value t
O2
(PV)*t � 22,711.8 cm3 bar mol�1
P → 0, is independent of the
gas.
PV/cm
gas.
273.16 K
� 273.16
TT � K� triple point
� triple point of
of water
water
T  273.16 K  punto triple del agua
T � 273.16 K � triple point of water
0 0 P P
0 P
Esta propiedad de losof

This property gases
gasesesiselthe
fundamento para establecer
basis for establishing una escala
an absolute de temperatura
temperature absoluta.
scale. All that Todo
lo que seis requiere
This es
required is la
theasignación
property of gases
arbitrary arbitraria deoffor
is the basis
assignment lathe
relación funcional
establishing
functional an f (T) y temperature
absolute
relationship laf (T
asignación
) and the de
scale.unAll
valor
thatespecí-
assignment
fico a unof
issolo puntoisde
required
a specific thelaarbitrary
value escala. Elassignment
to a single procedimiento
point onofthethemás simple,
functional
scale. adoptado
The relationshipa nivel
f (T )internacional
simplest procedure, andthe
theone para definir la
assignment
adopted
escala Kelvin (sección
of a specific
internationally 1.5),
value
to toes:a the
define single pointscale
Kelvin on the
(Sec.scale.
1.5): The simplest procedure, the one adopted
internationally to define the Kelvin scale (Sec. 1.5):

3.2. Virial
3.2. VirialEquationsEquationsofofState State 71
71
3.2. 3.2. Virial
3.2.
Ecuaciones Equations
Virial estadoofviriales
deEquations State
of State 71 71 71
3.2. Virial Equations of State 71
•• MakesMakes(P (PVV)∗)∗∗∗directly
directlyproportional
proportionaltotoTT, ,with withRRasasthe theproportionality
proportionalityconstant: constant:
• Makes
• Establecer• Makes (P V(P)∗de
(PV)* )manera
Vdirectly directly queproportional
sea directamente
proportional to Tto, with proporcional
T , with R asRthe as the aproportionality
T, con R como
proportionality la constante de propor-
constant:
constant:
• Makes (P V )∗ directly proportional to T , with
cionalidad: ∗ R as the proportionality constant:
(P(PVV)∗)∗∗ ==aa≡≡RT RT (3.7)
(3.7)
(P V(P)∗V= ) a=≡a RT ≡ RT (3.7)(3.7)
∗
(P V ) = a ≡ RT (3.7) (3.7)
•• Assigns
Assignsthe thevalue value273.16 273.16KKtotothe thetemperature
temperatureofofthe thetriple
triplepointpointofofwater water(denoted
(denotedby by
• Assigns
• Assigns the thevalue value 273.16 273.16 K toKthe to thetemperature
temperature of theof the tripletriplepoint pointof water
of water (denoted
(denoted by by
• Asignar
• subscript
Assigns el valor
subscript
subscript the de t):273.16
t): K a la temperatura del punto triple delpoint
agua of (denotado por el subíndice t):
subscript t): value
t): 273.16 K to the temperature ∗
of the triple water (denoted by
∗
(PVV)t)∗t ==RR××273.16
∗ 273.16KK (3.8)
subscript t): (P (3.8)
(P V(P)∗tV= )t R=×R273.16 × 273.16 K K (3.8)(3.8) (3.8)
∗ t
(P V )t = R × 273.16 K (3.8)
DivisionofofEq.
Division Eq.(3.7)
(3.7)by byEq. Eq.(3.8)
(3.8)gives:
gives:
El resultado
Division
Division de
of la Eq.ofdivisión
(3.7)
Eq. bydeEq.
(3.7) by la Eq.
ecuación
(3.8) gives:
(3.8) (3.7) por la (3.8) nos da:
gives:
Division of Eq. (3.7) by Eq. (3.8) gives:
(P(PVV)∗)∗∗ TT/K /K
(P V(P)∗V )∗∗∗ ==T /K T /K
(P V (P
V (P∗VV= )t)∗t∗t =T273.16273.16
/K K K K
(P (P))∗tV = )t 273.16 273.16 K
(P V )t ∗ 273.16 K
(P(PVV)∗)∗∗
o oror TT/K /K==273.16 273.16(P V(P)∗V )∗∗∗ (3.9) (3.9)
(3.9)
or or T /K T /K= 273.16
= 273.16 (P (P
V (P)∗VV))∗t
∗ ∗
t
t
(3.9)(3.9)
or T /K = 273.16 (P V(P)t∗V )t (3.9)
(P V )t
La ecuación
Equation
Equation (3.9)(3.9) establece
(3.9) establishes la escala
establishes the
the Kelvin
Kelvin
Kelvin de temperaturascale
temperature
temperature en todo
scale el intervalo
throughout
throughout de temperatura
thetemperature
the temperature para
range
range el que se
for
for
Equation
Equation (3.9) (3.9)establishes
establishes ∗)∗∗the Kelvin
the Kelvin temperature
temperature scale scalethroughout
throughout the thetemperature
temperature range rangefor for
tieneEquation
acceso experimental
which
which values
values
(3.9)
of
of (P(P
establishes a los
∗V V ) ∗ valores
are
are
the de temperature
experimentally
experimentally
Kelvin (PV)*. accessible.
accessible.
scale throughout the temperature range for
which
whichvalues values of (P of V(P) Vare ) are experimentally
experimentally accessible.
accessible.
El estado
which The
The
values deof un
state
state(Pgasofof)en
V lagas
∗aaare
gas condición
atatthe límite,accessible.
thelimiting
experimentally limiting donde
condition
condition P →where 0 merece
where PP → →cierto análisis.discussion.
00deserves
deserves A medida que
discussion. The
The disminu-
ye la presiónThe
molecules state
The
sobre unof
state a
of
gas,
making gas a
las
up gas at the
at
moléculas
a gas limiting
the
become limiting
del condition
mismo
more condition
andse where
separan
more where P
cada
widely →P vez →0
separateddeserves
más0 deserves
y el
as discussion.
volumen
pressure discussion.
de
is las The The
moléculas se
decreased,
molecules
The makingstate making
of upa gas up a gas become more and more widely →separated as pressure is decreased,
molecules
conviertemolecules
enthe una making
fracción aup gas aatgasthebecome
become limiting
more morecondition
andand more morewhere
widely widelyPseparated 0 deserves
separated assmaller
pressure
as discussion.
porpressure is decreased, The
is decreased,
acada vez másthemselves
pequeña del volumen total ocupado elfraction
gas. Además, las fuerzas
and
and the volume
volume ofofthe the molecules
molecules themselves becomes
becomes aasmaller
smaller and
and smaller fraction ofofthethetotal
total
molecules
and the
and volume
the making
volume of up
the
of the gas
molecules become
molecules more
themselves
themselves and becomesmore
becomes widely
a smaller
a separated
smaller and as
smaller
and pressure
smaller fraction is of
fraction decreased,
the
of total
the total
de atracción
volume
volume
andvolume entre
the volume occupiedlas
occupied moléculas
ofby by
thethe
by the
molecules
the se
gas. vuelven
gas. Furthermore,
themselves más
Furthermore, pequeñas
becomes
the
the forcesdebido
forces ofof
aofsmaller a que
attraction
attraction la
andbetween distancia
between
between
smaller entre
fraction ellas
molecules
moleculesof the estotal vez más
cada
become
become
volume
everoccupied occupied by gas.
the ofgas.Furthermore,
Furthermore, the forces
the forces attraction
of attraction between molecules
molecules become
become
grande (sección
ever
volume
smaller
smaller
occupied 16.1). En
because
because
by the el límite,
of the
the conforme
increasing
increasing P →
distances 0,
distances las moléculas
between
between están
them
them separadas
(Sec.
(Sec. 16.1).
16.1). porInIndistancias
thethe limit,indetermi-
limit, asas
ever smaller
ever smaller becausebecause of gas. the
of Furthermore,
increasing
the increasing the
distances
distances forcesbetweenof attraction
between them them between
(Sec. 16.1).
(Sec. molecules
16.1). Inbecome
the
In become
limit,
the as as
limit,
nadas. Sus
ever
P →→volúmenes
P smaller 0,
0, the the se vuelven
molecules
molecules
because ofare theare
are despreciables
separated
separateddistances
increasing
by en comparación
infinite
by infinite distances.
distances.
between themconTheir el volumen
Their
(Sec.
volumes
volumes
16.1). total
become
In thedellimit,
gas, yaslas fuerzas
negligible
negligible
P → →
0, the
Pcompared 0, the molecules
molecules separated
are separated bytheinfinite
by infinite distances.
distances. Their Their volumes
volumes become become negligible
negligible
intermoleculares
P →compared
0, the tienden
with
with
molecules
the
the a cero.
totalvolume
total Estas
volume
are volume
separated condiciones
ofofthe
by
gas,
gas,
infinite definen
and
and the
the un estado
intermolecular
intermolecular
distances. de
Their forces gas ideal,
forces
forces
volumes y la
approach
approach
become ecuaciónzero.
zero.
negligible (3.9)
Theseestable-
These
compared
compared with the
with total
the volume
total of the
of gas,
the and
gas, the
and intermolecular
the intermolecular forcesapproach
approach zero. These
zero. These
ce lacompared
escala
conditions dewith
conditions temperatura
define
define
theantotal
an del
an ideal-gas
volume gas ideal.
ideal-gas state,
ofstate,
theand La and
gas, constante
and Eq.
Eq.the
and
(3.9)
(3.9) deestablishes
proporcionalidad
establishes
intermolecular
the
the ideal-gas
ideal-gas
forces de latemperature
Rapproach ecuación
temperature
zero. These (3.7) se conoce
scale.
scale.
conditions
conditions define define ideal-gas
an ideal-gas state, state, Eq.
and (3.9)
Eq. establishes
(3.9) establishes the the ideal-gas
ideal-gas temperature
temperature scale.scale.
como constante
The
The
conditions universal
proportionality
proportionality
define anconstant de los
constant
constant
ideal-gas gases. R R Su
inin Eq.valor
Eq. (3.7)numérico
(3.7) isis called
called se determina
the
the universal
universal mediante
gas
gas la
constant.
constant. ecuación Its
Its scale. partir de
(3.8)
numerical
numerical a
The proportionality
The proportionality constant Rstate,
inREq. inand (3.7)
Eq. Eq. is(3.9)
(3.7) called establishes
is called the theuniversal the ideal-gas
universal Pgas constant.
VTTgas
temperature
constant. Its numerical
Its numerical
información
value
value
Thevalue PVT
is
proportionality experimental:
isdetermined
determined by
constant
bymeans means
RofinEq.
of
of
Eq.
Eq.
Eq. (3.8)
(3.8)
(3.7) from
is from
from
called
experimental
experimental
the universal P V data:
data:
value is determined
is determined by means
by means of (3.8)
Eq. from
(3.8) experimental
experimental P VPTgas T constant.
Vdata: data: Its numerical
value is determined by means of Eq. (3.8) from experimental ∗ ∗ P V T data:
(P(PVV))∗t
RR== (P V(P)∗tV )t∗tt
R =R =(P273.16 273.16
V )∗tK K K
R = 273.16 273.16 K
Because PPVVTTPVT dataen cannot ininfact
fact betaken
taken 273.16 atat K pressure,
zero pressure, datatakentaken atat finite
Ya que Because
la
Because información
Because P VPTVdata
data
Ttodatacannot
cannot
cannot realidad
in factin factbe
be
no taken
es
be posible
takenat zero
zero
attomarse
pressure,
zero a unadata
pressure,
data
presión
datataken cero,
takenat finite
finite
atsefinite
toma apressures
pressures
pressures presiones
pressures
are
are
arefinitas y
arevalue
después extrapolated
extrapolated
se extrapola to the
the
althe
estado zero-pressure
zero-pressure
dein3presión state.
state.
cero. Determined
Determined
Determinado asas indicated
indicated
como se by
by Fig.
Fig. 3.4,
3.4, the
the accepted
accepted value
Because
extrapolated
extrapolatedP V∗∗to T thedata
to cannot
zero-pressure
zero-pressure
cm333mol
fact bestate.
state. −1
taken at zero as
Determined
−1 Determined pressure,
indicated
asfollowing
indicated byindica
data taken
Fig.
by Fig.3.4,en3.4,
at la 1figura
finite
the
111
accepted
the 3.4,value
pressures
accepted elare
valor
value acepta-
do de ofof(P
(PV) *(P
extrapolated
t
V)22
∗Vis
es t t to
is22,711.8
)∗∗t is711.822,711.8
the cm 3 bar
zero-pressure 3cm
bar
bar ,mol
–1mol
−1 lo
state.
−1 , ,leading
cual
−1
leading
nos
Determined totoas
lleva the
the
al following
siguiente
indicated by
value
value
valor
Fig. deofofR:
3.4, 1R:
R:
the accepted value
of (P V ) 22,711.8 cm bar mol ,
of (PtV )t is 22,711.8 cm bar mol , leading to the following value of R: leading to the following value of R:
of (P V )∗t is 22,711.8 cm3 bar mol−1 , 3leading to−1the following value of R:1
22,711.83cm
22,711.8 cm333 barbarmol mol−1 −1
−1 −1 = 83.1447 cm 3 −1 K −1
== 22,711.8
RR22,711.8 cm cm bar bar molmol = 83.1447 3cm333 bar barmol mol−1
−1 K
−1
−1−1 K−1 −1
R = =
R 22,711.8 cm 273.16
3
273.16 bar K K
mol −1 = 83.1447
= 83.1447 cm cm bar bar molmol K−1
R= 273.16273.16 K K = 83.1447 cm3 bar mol−1 K−1
Through the use of conversion
Through the use of conversion factors, R may be 273.16 K
factors, R may beexpressed
expressedininvarious variousunits. units.CommonlyCommonlyused used
Through
Through
values theare use
the of conversion
use
given of
in conversion
Table A.2factors,
offactors,
App. R mayA.R may be expressed
be expressed in various
in various units. units. Commonly
Commonly usedused
Mediantevalues
elare usoarede given
factoresin Table
deA.2 A.2factors,
conversión, of App. A.
se puede expresar en in diversas unidades. En general, usedse usan los
Through
values
values the
given
are use
given ofTable
in conversion
in Table of App.
A.2 of App. A.RR A. may be expressed various units. Commonly
valores dados
values areen given la tabla A.2 del
in Table A.2apéndice
of App. A. A.
1 http://physics.nist.gov/constants.
11http://physics.nist.gov/constants.
http://physics.nist.gov/constants.
http://physics.nist.gov/constants.

72 72
72 CAPÍTULO
CHAPTER 3.
CHAPTER Propiedades
Properties
Properties deFluids
of Pure
Fluids
CHAPTER
Dos formas
Two de laof
Two Forms
Forms ecuación
of Virialvirial
the Virial
the Equation
Equation
Se define
A una propiedad
A useful
useful auxiliarytermodinámica
auxiliary thermodynamicauxiliar
thermodynamic property
propertyútilis
ismediante la the
defined by
defined by ecuación:
the equation:
equation:
PV
Z≡
Z ≡ PV (3.10) (3.10)
(3.10)
RT
RT
RT
Esta relación
This adimensional ratio
This dimensionless
dimensionless se llama
ratio factorthe
is called
is called de compressibility
the compressibility Con esta
compresibilidad.factor.
factor. definición
With
With y con aand
this definition
this definition = RT
and [ecuación
with
with
(3.7)], la
a ecuación
= RT (3.6)
[Eq. será:
(3.7)], Eq. (3.6) becomes:
a = RT [Eq. (3.7)], Eq. (3.6) becomes:
Z=
Z = 11 +
+BB�� P
P+ C �� P
+C P2222 +
+DD�� P
P3333 +
+ ·· ·· ·· (3.11) (3.11)
(3.11)
An alternative expression for Z is also in common use: 2 2

An alternative
alternative
Una expresión
An expression
alternativa for
deZZuso
tambiénfor
expression is also
is also
comúnin common
in common 22
use:
para Z es:use:
B
B+ CC
C + D DD + ···
Z== 11 +
+ B (3.12) (3.12)
Z V + V 222 + V 3 + ··· (3.12)
V V2 V 333
Ambas Both
ecuaciones
Both of theseseequations
these
of these conocen are
equations
equations como
are expansiones
known
known as virial
as virial viriales,
expansions,
virial expansions,
expansions,y los
and
and parámetros
the B ′, C ′,
parameters
the parameters
parameters B � C ��, etc.,
B��,,,D ′, D
C�� ,, D
� etc.,y B,and
D��,,, etc.,
etc., C, D, etc.,
and
Both of are known as and the B C and
se llaman
B,
B, coeficientes
C,
C, D,
D, etc.,
etc., viriales.
are
are called
called Los parámetros
virial
virial coefficients.
coefficients. y B son los B
B ′ Parameters
Parameters segundos
B
�
�� and
and BB coeficientes
are
are second
second virial
virialviriales; C ′ y C son los
coefficients;
coefficients;
B,� C, D, etc., are called virial coefficients. Parameters B and B are second virial coefficients;
Ccoeficientes
tercerosC
C
�� and
and C
and
C are
C are viriales,
third
are third
third etc.
virial
virial
virial
Para ciertoetc.
coefficients;
coefficients;
coefficients;
gasFor
etc.
etc.
los aacoeficientes
For
For
given gas
given gas
a given gas the viriales
the
the virial son funciones
coefficients
virial coefficients
virial coefficients areúnicamente
are
are functions de la
functions
functions
temperatura.
of
of temperature
temperature only.
only.
of temperature only.
Los dosThe conjuntos setsdeof
two sets ofcoeficientes
coefficientsen in las ecuaciones
Eqs. (3.11) andand(3.11)
(3.12)yare(3.12)
are estánasrelacionados
related follows: de la manera si-
The two coefficients in Eqs. (3.11) (3.12) related as follows:
guiente:
B C−−BB2222 D−− 3BC

3BC + + 2B 2B3333
= B
B�� = (3.13a) C �� =
= C (3.13b) D�
�� = D
D� = (3.13c)
B RT
RT a)
(3.13a) C (RT ))2222
(RT
b)
(3.13b) (RT ))3333
(RT
c)
(3.13c)
RT
To derive
To derive these
these relations,
relations, we
we setset ZZ= =P P V /RT
/RT in in Eq.
Eq. (3.12), and and solve
solve for
for P.P. This
This allows
allows elim-
elim-
Para deducir estas relaciones, establecemos ZV= PV/RT en la(3.12),
ecuación (3.12) y resolvemos para P. Esto per-
ination of P on the
inationPofdePlaonderecha right
the right of Eq. (3.11). The resulting equation reduces to a power series in 1/V
mite eliminar
which may be compared
deofterm
laEq. (3.11).(3.11).
ecuación
by term
The resulting
with
La ecuación
Eq. (3.12)
equation
to yield
reduces
resultante
the
setoreduce
given
a powera una
relations.
series
They
in de
serie 1/Vpotencias
hold
which
en 1/V que es may
posiblebe compared
compararse term by term
término a with Eq.
término con(3.12)
la to yield(3.12)
ecuación the given
para relations.
lograr las They hold
relaciones que se
exactly
exactlySe only
only for the
for the two virial
theprecisamente
two virial expansions
virial expansions
expansions as
as infinite
infinite series, but
series, but are acceptable
but viriales
are acceptable
acceptable approximations
approximations
proporcionan.
exactly
for the cumplen
only for
truncated
two
forms used in sólo
practice.para aslas dos
infiniteexpansiones
series, are como series infinitas,
approximations pero son
for the
the truncated
aproximaciones
for truncated
aceptables forms used
paraused
forms in practice.
las formas
in practice.
truncadas que se emplean en la práctica.
Many other
other equations
equations of state state have
have been
been proposed
proposed for for gases,
gases, but
but the virial
virial equations
equations are are
Se han Many
propuesto muchas otrasofecuaciones de estado para los gases, perothelas ecuaciones viriales son las
the only ones firmly based on statistical mechanics, which provides physical significance to
únicas que tienenones
the only unafirmly
base teórica
based on firme en la mecánica
statistical mechanics, estadística, que proporciona
which provides physical un significado
significance to físico a
the virial coefficients. Thus, for the expansion in 1/V , the term B/V arises on account of
the virialviriales.
los coeficientes coefficients.
De esta Thus,
manera,for the
paraexpansion
el desarrolloin 1/V , theel2term
en 1/V, términoB/VB/V arises
surge ona account
causa de oflas inter
interactions between
between pairs
pairs ofof molecules
molecules (Sec.(Sec. 16.2);
16.2); the C/V term, on
C/V 222 term, on account of of three-body
three-body
accionesinteractions
entre pares de moléculas (sección 16.2); el términothe C/V 2, con motivoaccount
de las interacciónes entre un
interactions;
interactions; etc. Because two-body interactions are many times more common than three-
conjunto de tres, etc.etc. Because
Ya que two-body interactions
las interacciones entre conjuntos are many
de dostimes more common
son mucho más comunes than que
three-entre tres,
body interactions,
interactions, andand three-body
three-body interactions
interactions are are many
many times
times more
more numerous
numerous than than four-body
y éstas body
a su vez son más numerosas que las correspondientes entre conjuntos de cuatro, etc.,four-body
las contribucio-
interactions, etc., the contributions to Z of the successively higher-ordered terms decrease
nes a Z interactions, etc., de
de estos términos theorden
contributions to Z of the con
superior disminuyen successively
mucha rapidez. higher-ordered terms decrease
rapidly.
rapidly.
2Proposed by H. Kamerlingh Onnes, “Expression of the Equation of State of Gases and Liquids by Means of
222Proposed
Propuesto por H. Kamerlingh
Proposed by H.
by Onnes, “Expression
H. Kamerlingh
Kamerlingh of the Equation
Onnes, “Expression
Onnes, “Expression of the
of of State ofof
the Equation
Equation Gases
of Stateand
State of Liquids
of by Means
Gases and
Gases and Liquidsofby
Liquids Series”,
by MeansCommunica-
Means of
of
Proposed
Series,” by H. Kamerlingh
Communications from the Onnes, “Expression
Physical Laboratory of
of the
the Equation ofof State
University of no.
Leiden, Gases
71, and Liquids by Means of
1901.
Series,”
tions fromSeries,”
Series,” Communications
the Physical
Communications
Communications from
Laboratoryfrom the
of thethe
from Physical Laboratory
University
the Physical
Physical Laboratory
of
Laboratory of the
Leiden, núm.
of
of the
the University
71, 1901. of
University
University of Leiden,
of Leiden, no.
Leiden, no. 71,
no. 71, 1901.
71, 1901.
1901.

3.3. The
3.3. The Ideal
Ideal Gas
Gas 73
73
3.3. El3.3.
gas ideal
3.3. The
The Ideal
Ideal Gas
Gas 73
73 73
3.3 GAS
3.3 EL THE IDEAL GAS
3.3 THEIDEAL
IDEAL GAS
Ya que Because
los términos
Because the terms
the B/V, C/V
terms B/V
B/V C/Vde22,,laetc.,
2, ,,etc.,
C/V expansión
etc., of the
of virialexpansion
the virial
virial [ecuación [Eq.
expansion (3.l2)]
[Eq. surgen
(3.12)]
(3.12)] a causa
arise
arise de las interaccio-
on account
on account of
of
Because the terms B/V , C/V 22, etc., of the virial expansion [Eq. (3.12)] arise on account of
nes moleculares, los coeficientes viriales B, C, etc., serían cero donde no existen estas interacciones. of
Because
molecular
molecular the terms
interactions,
interactions, B/V ,
the
the C/Vvirial
virial , etc., of
coefficients
coefficients the virial
B,
B, C,
C, expansion
etc.,
etc., would
would [Eq.
be
be (3.12)]
zero
zero were
were ariseno
no onsuch
suchaccount
interac-
interac- Con esto,
molecular
la expansión
molecular
tions
tions virial
to
to interactions,
seandreduce
interactions,
exist,
exist, and a:
the virial
the the
the virial
virial virial
expansion
expansion coefficients
coefficients B,
would reduce
would B, C,
C, etc.,
reduce to: would
etc.,
to: would be be zero
zero were
were no no such
such interac-
interac-
tions
tions to to exist,
exist, and and the the virial
virial expansion
expansion would would reduce
reduce to: to:
ZZ
Z= = 11
= 1 o PPPV
or
or VV = = RT
= RT
RT
ZZ = = 11 or
or PPV V= = RT RT
De hecho, las interacciones
Molecular
Molecular interactions
interactions moleculares
do in
do in fact existen
fact exist,
exist, and
and y influence
ejercen
influence influencia
the observed
the observedsobrebehavior
el comportamiento
behavior of real
of real gases.
gases.observa-
do de gases reales.
As pressure
As MolecularConforme
Molecular
pressure is interactionsdisminuye
interactions
is reduced
reduced at constant
at do inla presión
fact exist,
do intemperature,
constant a temperatura
and influence
fact exist, andVVinfluence
temperature, increasesthe
increases constante,
the
and
and observed
observed V aumenta
behavior
behavior of
the contributions
the contributions y las
of contribuciones de
real
of real gases.
gases.
the terms,
the terms,
los términos 2, D/V 33,3, ,... → 0, Zunity,
As
As
B/V
B/V ,,B/V,
C/VC/V
pressure
pressure
C/V 22is
is reduced
reduced
,, D/V
D/V ...etc.,
at
atinin en la
constant
constant
Eq.
Eq. ecuación
temperature,
temperature,
(3.12),
(3.12), (3.12)V
decrease.
decrease. disminuyen.
increases
VFor
increases
For PP → → 0, andZZPara
0,and theP
the contributions
contributions
approaches
approaches se aproxima
unity, of
of
not
notthe
the a uno, pero
terms,
terms,
because
because
no por ofalgún
B/V
B/V
of , cambio
C/V
any, C/V
any change
change en
22, D/V
, D/V los 33,coeficientes
...
the,virial
in the
in in
... in Eq.
virial Eq. viriales
(3.12),
(3.12), decrease.
coefficients,
coefficients, sino
decrease. porque
but because
but becauseFor
For V PP V →
→ tiende
V becomes 0, Z a infinito.
approaches
0, Z approaches
becomes infinite. Thus
infinite. Por lo
unity,
unity,
Thus in tanto,
not
in not
the limitelas
en
because
the because
limit aslímite, a
medidaof que
of
PP→ any
→ P
any0, → 0,
change
0,change la
the equation
the ecuación
in the
in the virial
equation virial de
of state
of estado se
coefficients,
coefficients,
state reduces to
reduces reduce
but
tobut a la
because
the because
the misma
same simple
same V forma
becomes
V becomes
simple form as
form simple que
infinite.
asinfinite.
for the
for para
Thus el
in caso
the
Thus in the limit
the hypothetical
hypothetical hipotético
limit
case of
case as don-
as
of
de B = C PP=
BB =→
→C
= · · ·0,
C0,== 0;
the
=the es decir,
equation
·· ·· ··equation
= 0;
= of state reduces to the same simple form
i.e.,of state reduces to the same simple form as for the hypothetical case of
0; i.e., as for the hypothetical case of
BB= =C C= = ·· ·· ·· = = 0;0; i.e.,
i.e., ZZZ→ → 11 or PPVV → → RT
→ RT
ZZ → → 1 or o PV RT
→ 11 or
or PPV V→ → RT RT
We know
We know from from the the phasephase rule rule that
that thethe internal
internal energy
energy of of aa real
real gas
gas is is aa function
function of of
De la reglaWe dewell
know la fase sabemos querule la energía interna de un gas real aaesreal
unafrom
función tanto de la
ofpresión
pressure
pressure Weas know
as well fromfrom
as of
as of the
the phase
phase
temperature.
temperature. rule that
that the
This
This the internal
internal
pressure
pressure energy
energy
dependency
dependency of
ofresults
real
results gas
gas
from is aa function
isforces
forces function
between
between of
como depressure
la temperatura.
pressure
the molecules.as well
as wellIf Esta
as
Ifas suchof dependencia
temperature.
of forces
temperature.
forces did de
did not la
not Thispresión
This
exist,pressureaparece
pressure
no energy
energy como
dependency
dependency
would be resultado
results
results
be required de las
from
requiredfrom fuerzas
forces
to alterforces
alter entre
averagemolécu
between
the between las
the molecules. such exist, no would to the average
las. Si estas
the fuerzas
molecules.
the molecules. distance,
intermolecular no existieran,
If such
If such forces
distance, forcesno se
didnecesitaría
not
did not no
and therefore
therefore exist,
exist, energía
no energyno
no energy
energy alguna
energy would
would would para
be requiredbe
requiredalterar
required
be required la distancia
to alter
bringtoabout
to bring intermolecular
the
alter volume
about average
the average
volume and pro-
intermolecular and would be to and
medio y, en consecuencia,
intermolecular
intermolecular
pressure changes distance,
distance,no
in aa gas se
gasand andrequeriría
therefore
therefore
at constant
constant energía
no para
energy
no energy would
temperature. originar
would be
We conclude cambios
required
be required
conclude that inde
to
in volumen
bring
tothe
bring
the about
aboutof
absence y presión
volume
ofvolume
molecularenandun gas a
and
pressure changes in at temperature. We that absence molecular
temperatura
pressure constante.
pressure changes
interactions, changes Concluimos
in a gas
in a gas energy
the internal
internal at
at que
constanten
constant
energy ausencia
temperature.
of aatemperature. de interacciones
dependsWe
gas depends We conclude
on conclude
temperature moleculares,
that in
thatonly. the la energía
absence
in theThese
only. absence
These of interna
molecular
of molecular
considerations del gas de-
interactions, the of gas on temperature considerations
pende exclusivamente
interactions,
interactions,
of the behavior
behavior the de
theof la
internal
ofinternaltemperatura.
energy
energy of of Estas
a
gasa ingas consideraciones
depends
gaswhich
depends on acerca
temperature
on temperatureforces del comportamiento
only. These
only. exist
These de un
considerations
considerations gas
gas hipoté
of the aa hypothetical
hypothetical gas in which no intermolecular
no intermolecular forces exist and
and of aa real
of real gas
tico en ofel que
the
of the
in no existen
behavior
behavior
the limit
limit as of fuerzas
a hypothetical
of a hypothetical
as pressure
pressure moleculares,
approaches gas in
gaszero y de
which
in which
zero un
lead to gas
no
no real en
intermolecular
intermolecular
to the
the el límite
definition of conforme
forces
offorces exist
existgas
an ideal
ideal la
and
gasandaspresión
of
asofonea real
a real
one tiende
whosegas a cero,
gas
in approaches lead definition an whose
conducen in a
thela definición
limit
in the limit as
macroscopic as de
pressure
pressure
behavior un gas ideal
approaches
is approaches
characterizedcomo zero
zeroby:lead to the definition of an ideal gas as one whose por:
aquel
lead cuyo
to comportamiento
the definition of macroscópico
an ideal gas as seonecaracteriza
whose
macroscopic behavior is characterized by:
macroscopic behavior
macroscopic behavior is characterized by: is characterized by:
• La ecuación de estado
•• The
The equation
equation of state:
of state:
•• The
The equation
equation of
of state:
state:
PPVV = = RTRT (ideal (gas ideal)
(ideal gas)
gas) (3.14) (3.14)
(3.14)
PPV V= = RT RT (ideal
(ideal gas)gas) (3.14)
(3.14)
• Una •energía
• An
An internal internaenergy
internal que esthat
energy unaisfunción
that is a function
a function sóloofdetemperature
of la temperatura:
temperature only:
only:
•• An
An internal
internal energy energy that that is is aa function
function of of temperature
temperature only: only:
U=
U =U (T )) (ideal
U(T (gas ideal)
(ideal gas)
gas) (3.15) (3.15)
(3.15)
U=
U =U U(T
(T )) (ideal
(ideal gas)gas) (3.15)
(3.15)
Implied Property Relations for an Ideal Gas

Relaciones
Impliedde una propiedad
Property implícitas
Relations paraGas
for an Ideal un gas ideal
The definition
The definition of of heat
heat capacity
capacity at at constant
constant volume,
volume, Eq. Eq. (2.16),
(2.16), leads
leads for
for an
an ideal
ideal gas
gas to
to the
the
The definition
La definición
The de capacidad
definition
conclusion
conclusion that of
of
C heat
heat
that C VV isis a capacity
térmica
capacity
function
a function at
at
ofconstant
a volumenconstant
temperature
of temperature volume,
constante,
volume,
only:
only: Eq.
Eq. (2.16),
(2.16), leads
leads for
for an
an ideal
ecuación (2.16), para un gas ideal conduce
ideal gas
gas to
to the
thea la con-
conclusion
conclusion that
that C
C V is
is a
a function
clusión de que CV es una Vfunción exclusiva�
function of
of temperature
�de la� only:
�temperatura:
temperature only:
�� ∂U �
∂U � = dU(T
dU (T ))
C ≡
C VV ≡ ∂U ∂U = dUdU (T )) =
(T =C CVV (T
(T )) (3.16)
(3.16)
CVV ≡
C ∂ T
≡ ∂ T VV = = dT =dT =C (T ))
CVV (T (3.16) (3.16)
(3.16)
∂∂TT VV dT
dT
The defining
The defining equation
equation forfor enthalpy,
enthalpy, Eq.Eq. (2.11),
(2.11), applied
applied to to an
an ideal
ideal gas,
gas, leads
leads to
to the
the conclusion
conclusion
The
La ecuación
The H
that
that defining
Hque
defining
also
also isequation
define
is equation
aa function
function forofenthalpy,
a la entalpía,
forof ecuación
enthalpy,
temperature
temperature Eq. (2.11),
Eq.(2.11),
(2.11),
only: applied
applied to
only: aplicada an
atoun ideal
angas gas,
ideal,
ideal leads
leads to
gas,conduce to athe
la conclusion
the conclusión de que
conclusion
that
H también H
thates also
Huna is
is aa function
alsofunción sólo de
function of
oflatemperature
temperatura:
temperature only:
only:
H≡
H ≡UU+ + PPVV = =UU(T + RT
(T )) + RT = =H H(T
(T )) (3.17)
(3.17)
H≡
H ≡UU+ +P PVV= =UU(T(T )) +
+ RTRT = =H (T ))
H(T (3.17) (3.17)
(3.17)

74 74
74 CAPÍTULO
CHAPTER 3. Propiedades
Properties
Properties of deFluids
of Pure
Pure fluidos puros
Fluids
The heat
La capacidad capacity
calorífica at constant
a presión pressure
constante CP, C P , defined
definida por labyecuación
Eq. (2.20), likecomo
(2.20) CV , C isVa, es
function of sólo
una función
The
The heat
heat
temperature capacity
capacity
only: at
at constant
constant pressure
pressure CC PP,, defined
defined by
by Eq.
Eq. (2.20),
(2.20), like
like C
C VV,, is
is aa function
function of
of
de la temperatura: � �
temperature
temperature only:
only: � ∂ H � d H (T )
C P ≡ �∂∂H H
� =
ddHH(T(T)) = C P (T ) (3.18)
CCPP ≡≡ ∂T P = = dT = =C CPP(T(T)) (3.18) (3.18)
(3.18)
∂∂TT PP dT
dT
A useful relation between C P and C V for an ideal gas comes from differentiation of Eq. (3.17):
Una útilAArelación
useful entre Cbetween
useful relation
relation y CV para
Pbetween CPPun
C and
andgas
CCVVideal
for proviene
for an
an ideal
ideal gas
gasdecomes
la derivada
comes from de la ecuación of
from differentiation
differentiation (3.17):
of Eq.
Eq. (3.17):
(3.17):
dH dU
C P = ddH H = dU dU + R = C V + R (3.19)
CPP =
C = dT = = dT + + RR = =C CVV ++ RR (3.19) (3.19)
(3.19)
dT
dT dT
dT
This equation does not imply that C P and C V are themselves con-
Esta ecuación
This
stant no implica
This equation
equation
for an ideal que
does
does C P ybut
not
not
gas, C V sean
imply
imply only enthat
that
that síCCmismas
and constantes
CVV are
C
andvary
PPthey para un gas
withthemselves
are themselves
temperature ideal,
in sino
con-
con-
que varían
stant únicamente
for
stant afor
such wayan
anthat con
ideal
ideal la temperatura
gas,
gas,
their but only
but onlyisthat
difference de tal
that
equal manera
they
they que
vary
to Rvary
. su
with diferencia
with temperature in
temperature es igualina R.
such a way that their difference
such a way that their difference is equal to R . is equal to R .
Para cualquier
For anycambio
change deof estado
state ofenanun gasgas
ideal ideal las(3.16)
Eqs. ecuaciones (3.16)lead
and (3.18) y (3.18)
to: nos conducen a:
For
For any
any change
change of of state
state of
of an
an ideal
ideal gas
gas Eqs.
Eqs. (3.16)
(3.16) and
and (3.18)
(3.18) lead
lead to:
to:
�
dU = C V dT (3.20a) a) �U = �� C V dT (3.20b) b)
dU =
dU =C CVV dT
dT (3.20a)
(3.20a) �U �U = = C CVV dT
dT (3.20b)
(3.20b)
�
d H = C P dT (3.21a) a) �H = �� C P dT (3.21b) b)
ddH H= =C CPP dT
dT (3.21a)
(3.21a) �H �H = = C CPP dT
dT (3.21b)
(3.21b)
Ya que Because both the

tanto la energía internal
interna comoenergy
CV deand unCgas V of an son
ideal idealfunciones
gas are functions
sólo de laof temperatureDU para
temperatura,
only, Because
Because
�U for both
anboth
idealthe
the internal
internal
gas is energy
energy
always givenand
and C
C
by of
of
VVEq. an
an ideal
ideal
(3.20b), gas
gas are
are
regardless functions
functions
of the of
of
kind temperature
temperature
of process
un gas ideal siempre se da por la ecuación (3.20b), sin considerar la clase de proceso que ocasione el cambio.
only,
only,
causing �U
�U thefor
for an
an
change.ideal
ideal
This gas
gasis is
is always
always
demonstratedgiven
given in by
by
Fig. Eq.
Eq. (3.20b),
(3.20b),
3.5, which regardless
regardless
shows a of
of
graph the
theof kind
kind of
internalof process
process
energy
Esto se prueba en la figura 3.5, la cual exhibe una gráfica de la energía interna como una función del volumen
causing
causing the
the change.
change. This
This is
is demonstrated
demonstrated in
in Fig.
Fig. as3.5,
3.5, which
which shows
shows a graph of
of internal energy
as
molar con alafunction of molar
temperatura como volume with temperature
parámetro (cantidad que parameter.
es constante bajoacierto
Because graph internal
U is independent
conjunto deenergy
of V,
condiciones,
as
aas aa function
plotfunction
of U of
of
vs. molar
Vmolar
at volume
volume
constant with
with temperature
temperature
temperature is a as
as parameter.
parameter.
horizontal line. Because
Because
For U
U is
is
different independent
independent
temperatures, of
of VV
U,, de U
pero es posible que sea diferente bajo otras condiciones). Ya que U es independiente de V, una gráfica
aa plot
hasplot of
of UU vs.
different vs. VV at
at constant
values, constant
with a temperature
temperature
separate line is
is aaeach
for horizontal
horizontal line.
line. For
temperature. For
Two different
different
such linestemperatures,
temperatures,
are shown UU
in
en función de V a temperatura constante es una línea horizontal. A diferentes temperaturas, U tiene valores
has
has different
different values,
values, withwith aa separate
separate line
line for
for each
each temperature.
temperature. Two Two such
such lines
lines areare shown
shown in in
distintos, con una línea separada para cada temperatura. En la figura 3.5 se muestran dos de estas líneas, una
b c d
U2 bb cc dd T2
U
U22 TT2
b c 2 d
U2 T2
Figure 3.5: Internal energy changes for an ideal U
Figure
Figure 3.5:
gas. 3.5: Internal
Internal energy
energy changes
changes for
for an
an ideal
ideal U U1
U a
T1
Figura 3.5:
gas. Cambios en la energía interna de un gas U
U11 TT1
gas. U aa 1
ideal. U1 T1
a
V
VV
V
Fig. 3.5, one for temperature T1 and one for a higher temperature T2 . The dashed line connect-
Fig. 3.5,
3.5, one
Fig.points
ing onea andfor
for temperature
b representsTTa11 constant-volume
temperature and
and oneone for for aa higher
higher temperature
temperature
process for which TT22..the
The dashed
dashed line
Thetemperature connect-
lineincreases
connect-
ing
ing points
points a
a and
and bb represents
represents
from T1 to T2 and the internal energy changes a
a constant-volume
process for
for which
which the
the temperature
temperature
by �U = U2 − U1 . This change in internal increases
increases
para la temperatura y la the
otra para unaenergy temperatura � superior . La
from
from TT1is
energy 1 to
to TTT221 and
given and
by Eq. internal
the(3.20b)
internal �U =changes
asenergy changes
�� C V dT by �UTdashed
�U
by. The 2=
= U2línea
U 2− −U
linesUdiscontinua
11.connecting
. This
This change que une
changepoints in a los puntos a
in internal
internal
a and c
y b representa
energy un
is proceso
is given a volumen constante = para el que la temperatura aumenta de T 1 a T y laccenergía
aa2and
energy
and points a andby
given byd Eq.
Eq. (3.20b)
(3.20b)other
represent as
as �U�U = C
processes dT
CVVnot .. The
The dashed
dToccurring dashed lines
lines connecting
at constant connecting
volume but points
points
which and
also
interna cambia
and
and pointspor DU
aa and = U – U
2represent
and dd represent 1 . Este cambio
other en la energía interna es conocido por la ecuación (3.20b)
also como
lead points
from an initial temperature T1 processes
other processes
to not
not occurring
a final temperatureoccurring T2at constant
.atThe graphvolume
constant volume
shows thatbut
but which
which
the also
change
DU = ∫ lead
C dT.
V from Las an líneas
an initial discontinuas
temperature que unen a los puntos a y c, así como a los puntos a y d, representan
lead
in U from
for these initial
processes is the T
temperature T11 to
same to aaasfinal
for temperature
final temperature
the TT22.. The
� constant-volume
The graph
graph
process, shows
showsandthatit isthe
that the change
change
therefore
otros procesos
in
in U
U forque
for no ocurren
these
these processes
processes a volumen
is
is the
the constante,
same
same as
as for
for pero
the
the que también conducen
constant-volume
constant-volume process,
process, de una
and
and temperatura
it
it is
is therefore
therefore inicial T1
given by the same equation, namely, �U = �� C V dT . However, �U is not equal to Q for
a la temperatura
given
given by final
by thethe same T . La gráfica
2 equation,
same muestra
equation, namely,namely, �U que�U = el cambio
= C CVV dTen U para
dT.. However, estos
However, �U procesos
�U is is notes el
not equal mismo
equal to to Q que
for para el
Q for

3.3. El gas ideal 75
3.3. The Ideal Gas 75
3.3. The Ideal Gas 75
proceso a volumen constante, y esto es consecuencia de la misma ecuación, a saber, DU = ∫ CV dT. No obs-
tante, DU es igual a Q
no processes,
these para estos
because procesos,
Q depends notya queonQTdepende
only 1 and T2 no
butsólo
alsode 1 y path
onTthe T2, sino también
of the process.de la tra-
these processes, because Q depends not only on T11 and T22 but also on the path of the process.
yectoriaAndelentirely
proceso. A la entalpía
analogous H de un
discussion gas ideal
applies seenthalpy
to the le aplicaHunofanálisis
an idealcompletamente
gas. (See Sec. análogo.
2.11.) (Véase
An entirely analogous discussion applies to the enthalpy H of an ideal gas. (See Sec. 2.11.)
la sección 2.11.)
The ideal gas is a model fluid described by simple property relations, which are fre-
The ideal
Elquently
gas ideal ungas is a model
es approximations
modelo fluid described
de fluido by simple property
de relations, whichsimple,
are fre-
good when descrito
applied tomediante relaciones
actual gases. In processunacalculations,
propiedad gases atque con
quently
frecuencia good
son una approximations when applied to actual gases. In process calculations, gases at
pressures upbuena aproximación
to a few cuando
bars may often se aplican aideal,
be considered los gases reales. equations
and simple En los cálculos de los procesos,
then apply.
pressures up to a few bars may often be considered ideal, and simple equations then apply.
los gases con presión hasta de unos pocos bar con frecuencia se consideran ideales, y en tal caso se les aplican
ecuaciones sencillas.
Equations for Process Calculations for Ideal Gases
Equations for Process Calculations for Ideal Gases
Ecuaciones para cálculos
Process calculations de procesos:
provide work gases
and heat quantities. Theideales
work of a mechanically reversible
Process calculations provide work and heat quantities. The work of a mechanically reversible
closed-system process is given by Eq. (1.2), here written for a unit mass or a mole:
closed-system
Los cálculos process
de procesos is given bycantidades
proporcionan Eq. (1.2), de
here written
trabajo for a unit
y calor. mass orpara
El trabajo a mole:
un proceso mecánica-
mente reversible en un sistema cerrado se conoce por la ecuación
d W = −P d V (1.2), y en este caso se escribe para un mol
o una unidad de masa: d W = −P d V
For an ideal gas in any closed-system process, the first law as given by Eq. (2.6) written for a
For an ideal gas in any closed-system process,
unit mass or a mole, may be combined with = –PdV
dWEq. the first law as given by Eq. (2.6) written for a
(3.20a) to give:
unit mass or a mole, may be combined with Eq. (3.20a) to give:
Para un gas ideal en cualquier proceso de sistema cerrado, la primera ley se conoce por la ecuación (2.6),
Q + d Wcombinarla
escrita para una masa unitaria o un mol, y esddposible = C V dT
Q + d W = C VV dT con la ecuación (3.20a) para dar:
Substitution for d W and solution fordQ d Q+ dW = Can
yields V dT
equation valid for an ideal gas in any
Substitution for d W and solution for d Q yields an equation valid for an ideal gas in any
mechanically reversible closed-system process:
mechanically
La sustitución reversible
para dW closed-system
y la solución para dQ process:
conducen a una ecuación que es válida para un gas ideal en
cualquier proceso mecánicamente reversible dQ de=sistema
C V dTcerrado:
+ P dV
d Q = C VV dT + P d V
dQ = CV dT + PdV
This equation contains the variables P, V , and T , only two of which are independent.
This equation contains the variables P, V , and T , only two of which are independent.
Esta ecuación
Working contiene
equations forlas
d Qvariables V y T,on
and d WP,depend pero sólopair
which dos of
sonthese
independientes.
variables is Las ecuaciones
selected as de
Working equations for d Q and d W depend on which pair of these variables is selected as
trabajo independent;
para dQ y dWi.e.,
dependen de cuál
upon which par de
variable estas variables
is eliminated se (3.14).
by Eq. seleccione
Withcomo
P = independiente;
RT /V , es decir,
independent; i.e., upon which variable is eliminated by Eq. (3.14). With P = RT /V ,
de qué variable se elimine mediante la ecuación (3.14). Con P = RT/V,
dV dV
d Q = C VV dT + RT d V (3.22) d W = −RT d V (3.23)
d Q = C V dT + RT V (3.22) d W = −RT V (3.23)
V V
With V = RT /P and with C VV given by Eq. (3.19), the equations for d Q and d W become;
Con V =With V y=con
RT/P, V determinada
RTC/P and with C Vpor la ecuación
given (3.19),the
by Eq. (3.19), lasequations
ecuaciones
forpara dQ yd dW
d Q and se convierten en:
W become;
dP dP
d Q = C PP dT − RT d P (3.24) d W = −R dT + RT d P (3.25)
d Q = C P dT − RT P (3.24) d W = −R dT + RT P (3.25)
P P
Con T =With = P V /R,es

T el thesimplemente
work is simply
dW dd=W = −Py dcon
V , and withvez
C V given again
porby
la Eq. (3.19),(3.19),
With T = trabajo
PV/R, P V /R, the work is simply W–P=dV,
−P d V , C V otra
and with C Vsegiven
conoce
again
V by ecuación
Eq. (3.19),
CV CP
d Q = C VV V d P + C PP P d V (3.26) (3.26)
d Q = R V d P + R P dV (3.26)
R R
Es posible aplicar estas ecuaciones para gases ideales a diversas clases de procesos, como los descritos
These
a continuación. equations may
Las suposiciones be applied
implícitas fordeducción
en su ideal gases
sonto various kindsesofcerrado
processes,
y queasel de-
These equations may be applied for ideal gases toque el sistema
various kinds of processes, as proceso es
de-
scribed
mecánicamente in what follows.
reversible. The assumptions implicit in their derivation are that the system is
scribed in what follows. The assumptions implicit in their derivation are that the system is
closed and the process is mechanically reversible.
closed and the process is mechanically reversible.

76 76 CAPÍTULO
3. 3.
Properties of Pure de fluidos puros
Fluids
767676
76 CHAPTER3.3.Volumetric
CHAPTER
CHAPTER
CHAPTER Volumetric
3.
3. Volumetric
Volumetric
Volumetric
VolumetricProperties
Properties
Properties ofof
Properties
Properties Pure
of
of ofPure
Pure PureFluids
Fluids
Fluids
Pure Fluids
Fluids
76 76
76 76 76
76
76
CHAPTER
3.
CHAPTER
CHAPTER 3. 3.
CHAPTER
CHAPTER
CHAPTER
CHAPTER
3. Volumetric
Volumetric Properties
Properties
Properties
3. Volumetric
Volumetric of Pure
of Pure
Properties
Properties of of Pure
Fluids
Fluids
of Pure
Pure Fluids
Fluids
Fluids
Proceso isotérmico
Isothermal Process
Isothermal
Isothermal
Isothermal
Isothermal
Isothermal
Isothermal
Isothermal Process
Process
Process
Process
Process
Process Process
Isothermal
Isothermal Process
Process
ByIsothermal
De las ecuaciones
Process
(3.20b) y (3.21b), DU = �H = DH ==00=
0=0000= 0
Eqs. (3.20b) and (3.21b), �U
By
By By
Eqs.
Eqs. Eqs.(3.20b)
(3.20b)(3.20b)
and
and and(3.21b),
(3.21b), (3.21b), �U�U ==
�U �H
=
= =�H
�H �H ==
ByBy
By By
Eqs.
By Eqs.
Eqs.
Eqs.
By By
Eqs. (3.20b)
(3.20b)
Eqs.
(3.20b)(3.20b)
(3.20b)
By Eqs.
Eqs. (3.20b) andand
and
(3.20b)
and
(3.20b) and(3.21b),
and (3.21b),
(3.21b),
and (3.21b),
(3.21b),
(3.21b),
and (3.21b),
(3.21b), �U�U �U=
�U
�U =
�UV=
�U �H �U=
�H
= �H
�H =
�H=
�H0�H= 0==
= 000 P
=
V 2V P2P2P
By Eqs. (3.22) and (3.24), Q = RT ln V 2 2V
VV= = 2 −RT
V−RT ln 2PP 2
De ByBy
las
By By
Eqs.Eqs.
ecuaciones
Eqs. (3.22)
(3.22) (3.22)
and
(3.22)
and and(3.24),
y
(3.24), (3.24),
(3.24), Q Q = =
Q RT =
RT RT
ln VVln
ln 2V ln 2222=−RT =2−RT−RT ln PP
ln 2Pln 222 P2
PP2ln
By
ByBy
Eqs.
By Eqs.
Eqs.
Eqs.By
(3.22)
Eqs.
(3.22)(3.22)
(3.22)
Eqs. and
(3.22)
and and
and
(3.22)
(3.24),
and
(3.24),(3.24),
(3.24),
and
(3.24), (3.24),
QQ ==Q =
QQRT =
=
RT Q RT
RT
ln
RT=
ln ln
VRT
ln
2
V =
1V
=
VVln
2 2 =
−RT=
−RT= −RT
−RT= lnln−RTln
Pln
ln
2 1P
P P 22
By
By Eqs.
Eqs. (3.22)
(3.22) and
and (3.24),
(3.24), Q=
Q = RT RTVln ln 1 1V 1 1= = −RT−RTPln ln1 1P111 1 P1
V11 V VV11111 V1
V
V P11PP PP111
P
V V 2 V P P 2P
By Eqs. (3.23) and (3.25), W =
== −RT
−RT
=−RT−RT lnVV2V 2 2
VV=V = 2
222=RTV=RT ln
PP2P 2 PP
2 2
222 P2
By
By By
ByBy
Eqs.
Eqs. Eqs.
Eqs.
Eqs.
By (3.23)
(3.23) (3.23)
(3.23)
(3.23)
Eqs. and
andandand
and
(3.23) (3.25),
(3.25), (3.25),
(3.25),
(3.25),
and (3.25),WW= =W
W
W −RT
=
−RT W −RT= ln
ln−RT ln
ln 2ln= 1VV2V
ln =
= RT
2 ln
RT
RT RT
= ln ln
lnRT ln
2 1P PP2ln
De By
las
Byecuaciones
Eqs.
By
Eqs.
By (3.23)
Eqs.
(3.23)
By Eqs.
Eqs. (3.23) (3.23)
and
(3.23)
and and
(3.23) and y
(3.25),
(3.25), (3.25),
(3.25),
and (3.25),
(3.25), W
W =
W
WW= =
−RT −RT
= −RT lnln
−RTVln Vln
lnV1V 1 = 22RT
VV1111 =
1 =
RT
=1RT ln
RT
ln
RTPln P ln P P 22
ln1 P111 1 P1
1
Note that Q = −W , a result that also follows V1from
1V V11 Eq. V P11 P
(2.3). PPP111
Therefore,
Note
Note Note
that
that that
QQ = =
Q−W
==−W
=−W
−W−W
,
= a, a ,result
a
result
−W result
that
that that
also
also alsofollows
follows follows from
from from Eq.
Eq. Eq.(2.3).
(2.3). (2.3). Therefore,
Therefore, Therefore,
NoteNote
Note
NoteNote
that
ObserveNote
that
that
Note
that Q
that
que that
Note Q Q =
=Q
that
Q
=Q
Q −W
that=
−W
–QW,
= Q ,
−W ,
comoaa ,
,, a
a
result
a
resultresult
result
, a
result
−W,, aaresultado
= −W that
result
that
that
result
that also
that
result thatalso
that
also
also
that
also
dealso
follows
follows
also
followsfollows
follows
la ecuación
also follows follows
from
from
follows from
from
from
fromEq.
Eq.
(2.3).Eq.
from
Eq.
Eq.
from(2.3).
Eq.
(2.3).(2.3).
Debido
Eq.
(2.3).
Eq.
(2.3).
(2.3). (2.3).
Therefore,Therefore,
Therefore,
Therefore,
(2.3).aTherefore, Therefore,
Therefore,
eso,
Therefore,
V 2V P
Q = −W = RT lnVV 2V 2V2= 2V −RT ln P2P2P2PP 2 (const T ) (3.27)
Q QQ = =
Q=−W −W
= −W
= = =
RTRT RT
ln VV
ln ln V=222=−RT −RT
= 2 −RT ln lnPP ln 222 P(const
PP2ln 2(const
(constT ) T)) ) T )
T(const (3.27)
(3.27)
)))TT (3.27)
2V VV 2P
2 1P
QQ== QQ −W=
=
−W Q−W
−W
−W=
= =
=
−W
RT
= RT
RT
ln
RT = ln
ln
RT
ln
2
V =
1
=Vln
2 2 =
−RT==
−RT −RT
−RT
−RT =ln −RTln
ln
ln P P22 (const
1P1 1
(const
(const
(T TT
constante)
(const (3.27)
(3.27)
(3.27) (3.27)
(3.27)
QQ= = −W
−W = RT
= RT ln
RTVlnV ln
1V 1V 1 1= =
V −RT
−RT ln P
ln
ln1
PP11 P P P (const
(const
(const TTT))) (3.27)
(3.27)
(3.27)
(3.27)
V11 V VV11111 1 PP11111 1
Isobaric
Isobaric
Isobaric
Isobaric Process
Process
Process
Process
Isobaric
Isobaric
Proceso
Isobaric Process
Process
isobárico
Isobaric
Isobaric ProcessProcess
Process
Isobaric
Isobaric Process
Process
By Eqs. (3.20b) and (3.21b),
ByBy By
Eqs.
Eqs.
By
By Eqs.
Eqs.
Eqs. (3.20b)
(3.20b)(3.20b)
(3.20b)
(3.20b) and
and and (3.21b),
(3.21b),
and (3.21b),
(3.21b),
By Eqs.
By By
Byecuaciones
De las Eqs.
By
By Eqs. Eqs.
(3.20b)
Eqs.
(3.20b)
Eqs. (3.20b) andand
(3.20b)
and
(3.20b)
(3.20b)
(3.20b)
(3.21b),
and
(3.21b),
and
and
(3.21b),
and
y (3.21b),
(3.21b),
(3.21b),
(3.21b),
(3.21b), ��
�U =�� C V�dT and �H =�� C P�dT
�U �U �U ==�U
�U =
= =CC CVdT
VdT
C VdTdTdT andand andand
and �H�H �H==
�H =
= =CCPCC PdT CPdT PdT dT
=CCV=
VC
�U�U == VVV dT andand == =CCP= PPP dT
C �H C
�U �U
�U
�U =
= VC
dT
C
dT
C dT
VV dT
dTV and and
and
andy �H
�H �H
�H
�H �H=
= PC
dT
CdT
C PP dTdTP dT
dT
and
and by by
and Eqs. (3.24) and (3.25),
and bybyby Eqs.
Eqs. Eqs.(3.24)
(3.24)(3.24)
and and and (3.25),
(3.25), (3.25),
lasand
y deand
and and
and
and
and
by
and
ecuaciones
by
byEqs.
by
Eqs.
by
Eqs.
Eqs.
by
(3.24)
Eqs.
by Eqs.
Eqs.
(3.24)
(3.24)
Eqs.
(3.24)
and
(3.24)
(3.24) and
(3.24)
(3.24)
and
(3.24)and
yand
and(3.25),
(3.25),
and
(3.25),
(3.25),
and
(3.25), �� (3.25),
(3.25),
(3.25),
(3.25),
� �
Q =�� C P�dT and WW = −R(T 2−− TT−1 ))T )
QQ =
Q =
Q= = =CC PdT
C CPdT
PdTdT and and and
and WWW
y and ==
W = −R(T
=−R(T
−R(T −R(T
−R(T 2− 2T−1))T
1T1−
TT11111))))) T1 )
= 1
CCP= −22222T2T−
== PC =222−−R(T
QQ Q
QQQ= ==Q dT
PCCC PPP dT
dT CdTP dTand
dT
PP dT and and
and
and
and WW= =
WW−R(T
W =
=W
−R(T
= −R(T
−R(T
−R(T −
1 )2T
1−
−
Note that Q == �H
= ,, aa ,result also given by Eq. (2.13). Therefore,
ObserveNote
Note
Note
Note
que
Note
Note that
that Q that
that
that
Note
that Q Q== =
Q
Q∆H
QthatQ=
�H
�H= es
�H
Q�H
�H
, un
�H
,=
a aresult
,�H aaresult
,resultaresult
resultado
result result
result
, a also
also also
also
also
result
also given
given
también
given given
given
given
also by
by
byby
by
given
Eq.
by
Eq.
conocido
Eq. Eq.
Eq.
Eq.
by(2.13).
(2.13).(2.13).
Eq.
(2.13). por Therefore,
Therefore,
laTherefore,
ecuación
Therefore,
(2.13).
(2.13). Therefore,
(2.13).
Therefore, Therefore,(2.13). Por lo tanto,
Note Note
Notethat that
Note that Q
that Q=Q
Q= =
�H �H
= �H , a ,
�H,, aa result a result
also also
result also given given
also given by
given � by
Eq.
by
by Eq.Eq. (2.13).
(2.13).
Eq. (2.13). Therefore,
Therefore,
(2.13). Therefore,
Therefore,
� �
Q = �H =�� C P�dT (const P) (3.28)
Q
Q=Q = =
Q �H
=
= =
�H �H
= =
= �H=
= =CC =PC CPdT
PdT PdTdTdT (const
(P
(const
(const
P) P) P) P)
constante) (3.28)
(3.28)(3.28) (3.28)
QQ Q
=
QQ�H
Q= =
�H Q �H
�H
�H
= �H ==
�H = = CC
= PCCP dT
P C
dT
C P
dTP dT
C
dT
dTP (const
(const(const
(const
(const
(constP)
(const P)
P)
P)
(const
P) P)
P)
(3.28)
(3.28)
(3.28) (3.28)
(3.28)
(3.28)
(3.28)
(3.28)
PP
Isochoric (Constant-V ))Process

Process
Proceso isocórico
Isochoric
Isochoric
Isochoric
Isochoric
Isochoric
Isochoric
Isochoric
Isochoric (V constante)
(Constant-V
(Constant-V
(Constant-V
(Constant-V
(Constant-V
(Constant-V
(Constant-V
(Constant-V )))Process
)Process
)))Process Process
Process
Process) Process
Isochoric
Isochoric (Constant-V
(Constant-V ) Process
Process
Equations (3.20b) and (3.21b) again apply:
Equations
Equations
Equations
Equations (3.20b)
(3.20b)(3.20b)
(3.20b)andand andand (3.21b)
(3.21b) (3.21b)
(3.21b) again
again again
again apply:
apply: apply:
Equations
Se aplican Equations
de
Equations nuevo
Equations
Equations
Equations
Equations
(3.20b)
(3.20b) (3.20b)
las
and
(3.20b)
(3.20b)
(3.20b) and
(3.20b)
and
ecuaciones
(3.21b)
and
and
(3.21b)
(3.21b)
and and
(3.21b)
(3.21b)
(3.21b)again
�
againagain
(3.21b)
(3.20b)apply:
again yapply:
apply:
again
apply:apply: apply:
(3.21b): ��
� ��again
again
� � apply:apply:
�U =�� C V dT and �H �� C P�dT
=
�U �U ==�U
�U = =CC CVdT
VdT dTdT and
and andand�H�H ==
�H = =CCPCC CPdT
PdT dT
C V y
�U = VdT and �H = PdT
=CCV=
VC
�U�U == VVV dT andand == =CCP= PPP dT
C �H C
�U �U
�U
�U == VC
dT
CdT
C dT
VV dT
dT and and
and
and �H
�H �H
�H
�H �H
=
= PC
dT
CCdTPP dT dTP dT
dT
By
By Eq.
By
Eq. (3.22)
Eq.
(3.22)
(3.22)and
and the basic equation for work,
De By
laBy
ecuación
Eq. (3.22)(3.22)
and yand
thethe
la thebasic
ecuación
basic basic equation
equation
fundamental
equation forfor for
work,
work, work,
delwork,
trabajo,
ByBy
By
Eq.
By
Eq.
By
Eq.
Eq.
By
(3.22)
Eq.
By Eq.
Eq.
(3.22)
(3.22)
Eq. and
(3.22)
(3.22)
(3.22) and
(3.22)
and
and
thethe
(3.22)
the
and
and
and
the
and
basic
the
basic
the
the
basic
basic
the
basic
basic
basic
equation
equation
basic
equation
equation
��equation
equation
equation forfor
equation
for for
work,
for
work,
for
for
work,
work,
for
work,
work,
work, �
� ��
Q= � � �
��C dTdT and = �
− � ��P d V = 0
�P
QQ =Q =
Q= = = C C VdT
CVCVdTdT andand andandWW
y
and WW=W
W ==−=−
=− −− PdPPdVPdV dVVP=
= V0d=0= 000
Vddd=
VdT
= VV00=
VC
== = − −Pd−
= =V000= 0
QQ Q = Q
C dT C dT
and and W = =W − P dV =
QQ
Q= =C V C
V C
CVV
dT dT
dT andand
VV dT
V
V and
and W W W−
W ==− PPP d= V =
Observe que
Note
Note that
Note
that Q=
Qthat
Q
=∆U
=
=
QthatQ= es,�U
�U
= también
,, aa ,result unalsoresultado
given byconocido
Eq. porTherefore,
(2.10). la ecuación
Therefore, (2.10). Por lo tanto,
Note
Note
Note
that
Note
Note
Note that
that
Note
that
that Q
that
Q =Q
Q
=Q �U=
�U
�U
=
�UQ �U
�U
,
�U,=
a aresult
a �U
, aaresult
a
aresult
result
,,result result
result
, a
result
also
also
result
also
also
also
also
also given
given
given
also
given
given
given
also
given by
given
bybyby
by
given
by Eq.
by
Eq.
by
Eq.
Eq. Eq.
Eq.
Eq.
by
Eq.
(2.10).
(2.10).(2.10).
(2.10).
(2.10).
Eq.
(2.10).
Therefore,
Therefore,
Therefore,
Therefore,
(2.10).
Therefore,
(2.10).
(2.10). Therefore,
Therefore,
Therefore,
Note
Note that
that Q Q= = �U�U,, aa result result also also given
given by by
�� Eq.
Eq. (2.10).
(2.10). Therefore,
Therefore,
Q = �U �� C V�dT
= (V constante)
(const V ))V ) (3.29) (3.29)
QQ = =
Q=�U
= =
�U ==�U
�U
= =
= =CC =
VC CVdT
VdT VdTdTdT (const
(const(const
V V)V (3.29)
(3.29)(3.29)
QQ ==
QQ
Q
QQ=�U=
�U Q�U
= �U
�U
�U==
�U = = CC C
dT
C
= V CCV dT
V V
dTV dT
C
dT
dTV (const
(const
(const V
(const
(const
(constV )
(const VV))
V
(const
) V )
)) V ) (3.29)
(3.29)
(3.29) (3.29)
(3.29)
(3.29)
(3.29)
(3.29)
VV

3.3.
3.3. The
The Ideal
Ideal Gas
Gas 77
7777
3.3. The
3.3.
3.3.
3.3.
3.3.TheIdeal
The
TheIdealGas
Ideal
The Gas
Ideal
Gas
Ideal Gas
Gas 7777
7777
3.3.
3.3. El3.3.
gas The
ideal
3.3.The Ideal
TheIdeal Gas
IdealGas
Gas 77
7777 77
Adiabatic Process; Constant Heat Capacities
Adiabatic
Adiabatic
Adiabatic
Adiabatic
Adiabatic Process;
Process;
Process;
Process;
Process; Constant
Constant
Constant
Constant
Constant Heat Heat
Heat
Heat
Heat Capacities
Capacities
Capacities
Capacities
Capacities
Proceso adiabático:
Adiabatic
Adiabatic
Adiabatic
An
Process;
Process; capacidades
Process; Constant
Constant
Constant caloríficas
Heat
Heat
Heat constantes
Capacities
Capacities
Capacities
An adiabatic
AnAnadiabatic process
An An process is
adiabatic is one
adiabatic one for
adiabatic for which
which there
process there is
process is no
process no heat
heat transfer
is isone transfer between
isisone
one
isonefor between the
onefor the system
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for and its
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there there is is
there no
isisnoisheat
no heat transfer
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andits itsitsits
AnAn adiabatic
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adiabatic
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i.e.,
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for
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(3.22),
there isisnononono
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(3.24),
heat
heat
heat and
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transfer
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(3.26)
transfer
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between
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may
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system
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and its
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An surroundings;
An adiabatic
adiabatic i.e.,
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process = Qis =one
is 0.0.
one Each
for
for whichofof
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there is (3.24),
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heat and
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transfer may
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thethesystembebe
system set
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Un proceso
surroundings;
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to adiabático
surroundings;
surroundings;
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i.e.,
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Q d
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(3.22),
Eqs.
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Eqs. transferencia
(3.22),
(3.22), (3.24),
(3.22),
(3.22),then
(3.24),
(3.24),
(3.24),and
(3.24),
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(3.24),
and de
(3.26)
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(3.26)may
(3.26)
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may
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Q = = C
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0.
V and
Each
Each Cof P
of
P constant
Eqs.
Eqs. (3.22),
(3.22),then yields
(3.24),
(3.24), andsimple
and (3.26) relations
(3.26) maymay among
therefore
therefore the
bebe variables
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TT
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andIntegration
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and
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and
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then de
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adiabatic
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simple
simple relations
simple relations
compression
simple (3.22),
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and
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with
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then
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sencillas
adiabatic
adiabatic
adiabatic
adiabatic simple
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compression relations
compression relations
las
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y variables
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and
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for
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forfor (3.22)
mechanically
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mechanically
mechanically becomes:
becomes: reversible
reversible
reversible adiabatic
adiabatic
adiabaticde compression
compression
compression ororexpansion
or expansion
expansion ofofideal
of ideal
ideal
compresión
gases.
gases.
gases.
gases.
gases.
For oFor
For expansión
example,
For
For
Forexample,
example,
example,
example,
Eq. adiabática,
Eq.(3.22)
Eq. Eq.
Eq.
Eq.
(3.22)
(3.22) (3.22)
(3.22)
(3.22) mecánicamente
becomes:
becomes:
becomes:
becomes:
becomes:
becomes: reversible gases ideales Por ejemplo, la ecuación
gases.
(3.22) será: gases. For
For example,
example, Eq.
Eq. (3.22)
(3.22) becomes:
becomes: dT
dT R
R dd V
V
dTdT dT dT= −
R RR dRVdRdV VdVV
== −−
dTdT RR ddVVV
dT =TT
dT =− =−= −−C CR VV d
T TTT ==C T = −
− −VCCC V C
VVV
V VVdVV V
TTT CCCV V VV
Integration
Integration with
with C VV constant gives: V V
Integration
De la Integration
Integration
Integration
integración
Integration with with
with
con C
with
with CC
V CVCconstantconstant
constant
constant
CVconstant
VVconstante
C Vconstant gives:se
gives:
gives:
gives:
gives:
obtiene:
gives:
Integration with C V constant gives: � �
��
Integration
Integrationwith withCCV Vconstant constantgives: gives: R/C
TT22� � �� 1�
1�
VVR/C �R/C
R/C
R/CVV
R/C
T2 TT22TT 2=
= V ��
1V
2 = V11 R/CV
� 1V
1 V �
�1�
VR/C
R/C V
V
VV V V
TT
=TT2T11=
2 == VVVV 2
R/C VV
T1 TT11TT 2 = V2VV2V 1 2
V1
TTT11 = 1=
V2V22 2
V
Similarly,
Similarly, Eqs.
Eqs. (3.24)
(3.24) and
and (3.26)
(3.26) lead
lead to:
to:1 1 2 2
De manera
Similarly,
Similarly,
Similarly,
Similarly,
Similarly, similar,
Similarly, Eqs. Eqs.
Eqs.
Eqs. las(3.24)
(3.24)
Eqs.
Eqs. ecuaciones
(3.24) andand
(3.24)
(3.24)
(3.24)
and(3.26)
and
and
and(3.26)(3.24)
(3.26) lead
(3.26)
(3.26)
(3.26)
lead
lead ylead
to:
lead
lead (3.26)
to:
to:to:
to:
to: conducen a:
� � R/C � �
��
Similarly,
Similarly,Eqs. Eqs.(3.24) (3.24)and and(3.26) (3.26)
R/Clead
PPleadto: to: C
CPP/C
TT22� � �� PPR/C
2� � �
R/C
R/C R/C PP22� � ��VVC1��
/C
CCPC
/CVV
C/C
/C
/C PVV/C
T2 TT22T2 2= T =P��2�PP2P 2
P
2 2�2�� PR/CP
R/C P
PPP P
and
and P 2 PP2P
2 P 2=V
= �
�
1 V
�V V
1
1
P�
1V
� 1�
PV
C PP/C
P VVV
TT
=TTT2 ==
112= =
= PPP PP 2112
R/CR/C P P and and
and yand
and PP
=
PPP2
1
2
=
= == VV
VVV1
2
1 CC P /C
P /C V
VV
T1 TT11TT 2
1= 1=P1PP1P 2 P and P1PP1P 2 P=
12 V2VV2V 1 2
V1
TTmay
T1 1 also P1P11 1
P
and
and
PP1P11 =1=
VV2V22 2
These
These equations
equations 1
may also 1 1
be
bebe expressed
expressed as:
as: 1 1 2 2
Estas ecuaciones
These
These
TheseThese
These
equations
These equations también
equations
equations
equations
equations
may may
may may
may esalso
also
may posible
be
also also
also
also
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be expresarlas
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be expressed
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beexpressed
expressed
expressed
as:as: as: como:
as:
as:
as:
These
Theseequations equationsmay mayalso alsobebeexpressedexpressedas: as:
T V γγ−1
−1 = const. (3.30a) T P (1−γ
(1−γ )/γ
)/γ = const. (3.30b) P VVγγγγγ γ= const. (3.30c)
T VTTγT T TV
VV−1V −1
γγV
γ
−1
γ=γ −1
−1
−1 ===
constante
const.
= = const.
const.
const. const.
const. (3.30a)(3.30a)
(3.30a)
(3.30a)
(3.30a)
(3.30a)
(3.30a)
TPTP
T PTT(1−γ
T P (1−γ
P
(1−γ)/γ
(1−γ
P(1−γ
(1−γ
)/γ
)/γ=)/γ
)/γ ==
)/γ
= =
const.
=
const.
constante
const.
const. const.
const. (3.30b)(3.30b)
(3.30b)
(3.30b)
(3.30b)
(3.30b)
(3.30b) P VPPγP
VVP=
P VγγV===
const.= const.
const.
=const. constante
const.
const. (3.30c)(3.30c)
(3.30c) (3.30c)
(3.30c)
(3.30c)
(3.30c)
T V γ −1
γ
TTVV ==const. −1 = const.
const. (3.30a) (3.30a)
(3.30a) TTPP T P (1−γ
(1−γ )/γ)/γ = const.
==const.const. (3.30b) (3.30b) P V
(3.30b) PPVV ==const. γ = const.
const. (3.30c)(3.30c)
(3.30c)
C PP
Where by definition, 33 γγC≡ PCCC PPC (3.31)
γ≡
Donde por definición,
Where byby 3 33 3
definition, C PP (3.31)
Where
Where
Where by
Where
Where definition,
by
by definition,
by 33
definition,
definition,
definition, γ ≡ γγ γ≡ ≡ ≡ ≡C
CC
C CPPC
VVP (3.31) (3.31)(3.31)
(3.31)
(3.31)
(3.31)
Where
Where by definition,
Wherebybydefinition, 33
definition, γ ≡
C
γ γ≡≡C VVV C
C C
VV V (3.31)
(3.31)
(3.31)
CCV V
Equations
Las ecuaciones
Equations (3.30)(3.30)
(3.30) are
restringen
are restricted
su aplicación
restricted in
inin application
a gases ideales
application to
toto ideal
ideal congases capacidades
gases with
with con-
caloríficas
con-
Equations
Equations
Equations
Equations
Equations (3.30)(3.30)
(3.30)
(3.30) are
(3.30) are
are restricted
are
are restricted
restricted
restricted
restricted in in application
in application
application
inapplication
application toto ideal
to ideal
toideal gases
ideal
ideal gases
gases gases
gases with with
with con-
con-
with
with con-con-
con-
constantesstant
Equations
stant
Equationsque
Equations heat
heat son capacities
sometidos
(3.30)
capacities
(3.30)
(3.30) are
are
are undergoing
a expansión
restricted
undergoing
restricted
restricted in
inin mechanically
o compresión
application
mechanically
application
application to
toto reversible
adiabática
ideal
ideal gases
reversible
ideal gases
gases adiabatic
mecánicamente
with
with
with con-
adiabatic
con-
con- re-
stant
stant
stant
stantheat
stant heat
heat
heat capacities
heat capacities
capacities
capacities
capacities undergoing
undergoing
undergoing
undergoing
undergoing mechanically
mechanically
mechanically
mechanically
reversible
reversible
reversible
adiabatic
adiabatic
adiabatic
adiabatic
versible. expansion
stant
expansion
stant
stant heat
heat
heat or
or compression.
capacities
compression.
capacities
capacities undergoing
undergoing
undergoing mechanically
mechanically
reversible
adiabatic
adiabatic
expansion
expansion
expansion
expansion
expansion oror compression.
or ororcompression.
compression.
compression.
compression.
expansion
expansion
expansionor or compression.
orcompression.
compression.
Para gases ideales, el trabajo de cualquier proceso adiabático en sistema cerrado se conoce por:
For
For ideal
ideal gases,
gases, the
the work
work of any adiabatic closed-system process is given by:
ForForideal
For ideal
For
Forideal gases,
ideal
ideal gases,
gases, thethe
gases,
gases, work
the the work
the
work of of
work
work ofof
any ofany
adiabatic
any
ofany any
any
adiabatic
adiabatic
adiabatic
adiabatic
adiabatic
closed-system
closed-system
closed-system
closed-system
closed-system
closed-system process process
process
process
process
process isis
is given
is isgiven
given
isgivengiven
given
by:
by:by:
by:by:
by:
For
For ideal
Forideal gases,
idealgases, gases,the the work
thework of
workofofany any
any dW
adiabatic
adiabatic =
adiabatic dU = C
closed-system
V
closed-system dI
closed-system process
process
process is
is isgiven
given
given by:
by:
by:
ddW = dU =C VV dT
d WddW dW=dWWW ===
dU =dU=
dU dU
=dU
dU ==
=
C =VC =
CdTCC dT
VV VdT
C
dT
dT
VdT
dd dWW W == = dU
dU dU =
= = CC CV dT
dTdT
Para CVFor
constante,
constant C VV ,, W = �U = C V V�T (3.32) (3.32)
For
ForFor
For For
For
constant
constant
constant
constant
constant C VC
constant C,C
VVC
C ,V, V, , WW W=W W= W ==
�U =�U=�U
�U �U=�U ===
C =VCC=�TCVC
C
V�T
VV V�TV
�T
�T�T (3.32)(3.32)
(3.32)
(3.32)
(3.32)
(3.32)
For constant C , W = �U = C �T (3.32)
For
Forconstant
Se obtienen constant
Alternative
formas C V
CV V, , of
forms
alternativas Eq. (3.32)
de la result
ecuación WW ifif= C=V�U
(3.32) �Uis ==CCV V�T
eliminated V �Telimina
in favor Cof the heat-capacity (3.32)
(3.32)
ratio γγ :: capaci-
Alternative
Alternative
Alternative forms
Alternative
Alternative
Alternative
forms
forms
forms of of
forms
forms ofof
Eq. of
ofEq.
Eq.
(3.32)
Eq.
Eq. Eq. (3.32)
(3.32) result
(3.32)
(3.32)
(3.32)
result
result
result if CififVifC
result
result
C
is
CifVVC
C V is
is iscuando
iseliminated
Veliminated eliminated
eliminated
iseliminated
Vis eliminated se
in inin
favor
in infavor
favor
infavor of of
favor
favor the
ofof
Vthe
of en
the
the
of the favor
heat-capacity de la ratio
heat-capacity
heat-capacity
the relación
heat-capacity
heat-capacity
heat-capacity
ratio
ratio
ratio
ratio:γγde
γratio :γ: γ: :
Alternative
dades caloríficas
Alternative
Alternative forms
: formsofofEq.
γ forms of Eq.
Eq. (3.32)
(3.32)
(3.32) result
result
result if
if ifC
C C eliminated
V isiseliminated
eliminated in
in in favor
favor
favor of
of of the
thethe heat-capacity
heat-capacity
heat-capacity ratio
ratio
ratio γγ γ:: :
CC PP CC VV ++ R
R V V RR R
R
γγC≡ PCCCPPC C=VC C+VVC V++
R +R+RRR= 1+ R RRRR or C VV = =R RRRR
γ≡ PP
== CC 1== 111++1+ oror CC
C V
+ RR= RR R
γ ≡ γγ γ≡ ≡ ≡≡C C= VVP= ==C CVVCC += +
= 1= ++C or or oror C VC =
VVCV= = ==γγ R −R 11
CPPC C+ γ−
γ ≡ C = V VV R = 1 + C
R VV or CC V=
γ γ≡≡ C C
V CC VV V == V C
V C C VV
V C V = = 1 C
+
1 + C
V CC VVVC V or o
or C CV γ
= = −
γγ γ−1−−11−11
C
CC V C
CC V C
CC V V V −
γ γ−−111
γ
VV VV VV
33If C and C are constant, γ is necessarily constant. For an ideal gas, the assumption of constant γ is equivalent
3 If 33CIf If3 CVV and CPP are constant, γ is necessarily constant. For an ideal gas, the assumption of constant γ is equivalent
If3VIf
CCand
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C C
and
and CCare
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are γ isγγnecessarily
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/C VV ≡
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que constant
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and
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V
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andandthe
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difference
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Except
Except
Except Except
constant.
constant.
for
Except
Ésta
to es the
for
for
la
temperature for
This
the
for
única
the
This
monotonic
the is isthe
monotonic
monotonic
the the
monotonic
manera
than only
the only
en way
gases, gases,
way
both
gases,
gases,
gases,
que
heat lathat
that
C the
both
both
both
relación
capacities P the
CC C
P C
ratio
and ratio
C
and
and
C P and/
V
themselves.
P P
and
CCCC
C PC
Vγ
V/C
P C/C
actually ≡
actually
actually
≡
V VV ≡
actually
laγ γdiferencia
actually
V y
increase
and the difference C P − C Vbut=the
with temperature, R ratio
can both γ is be lessconstant.
sensitiveExcept
to temperature
for the monotonicthan the heat capacities
gases, both Cthemselves.
P P C
and VV actually
and
increaseand
increase
C – C increase
the
Rincrease
=increase
thedifference
with
seanwith withdifference
temperature,
with
with CC
temperature, P−
but
temperature,
temperature,
temperature,
constantes.
−Cbut
PExcepto C
the
but =
Vbut
the
Vbut =
ratio
the
para
Rratio
thethe Rcan
ratioγ can
isγγboth
ratio
ratio
los gases
both
less
isγis
γis be
is
less beconstant.
less
less constant.
sensitive
less sensitive
sensitive
sensitive
monotónicos, toExcept
Except
to temperature
sensitive to to
en
forforthan
temperature
totemperature the
temperature
temperature
realidad
themonotonic
than
Cthan
monotonic
the than
ythan
C
heat
the
the gases,
heat
the
heat
the heat
aumentan
gases,
capacities both
capacities
heat boththemselves.
capacities
capacities Cthemselves.
C
themselves. PandandCC
Pthemselves.
con la themselves.
capacities temperatura, V Vactually
actually
pero la relación γ
P V
increase with temperature, but the ratio γ is less sensitive to temperatureP thanVthe heat capacities themselves.
increase
increasewith
withtemperature,
temperature,but
butthe
theratio
ratioγ γisisless
lesssensitive
sensitivetototemperature
temperaturethan
thanthe
theheat
heatcapacities
capacitiesthemselves.
themselves.
es menos sensible a la temperatura que a las mismas capacidades caloríficas.

78
78 CHAPTER 3.
CHAPTER 3. Volumetric
Properties of
of Pure
Pure Fluids
Fluids
78 78
78 CAPÍTULO
CHAPTER
CHAPTER 3. Volumetric Properties
Properties
Propiedades of Pure
of Pure
volumétricas Fluids
deFluids
fluidos puros
RR �T
�T
Whence
Whence WW= =C CVV �T�T = = γR R �T�T
Whence
De donde,
Whence W=
W =C CVVV �T�T = = γ− − 11
γγ − − 11
Como RT Because
1 = P1VRT
Because RT
1 y11 RT
=
= 2PP= 1V VP112and
V
and RT
2, esta
== PP22VV22,, this
RT22expresión expression
es posible
this expression may
may be
escribirla como:
be written:
written:
Because
Because RT
RT 111 ==P P1111VV111 and
and RT222 =
RT =P P222VV222,, this
this expression
expression may may be be written:
written:
RT − RT P
RT22 − RT11 = P22 V22 − P11 V11 V − P V
W=
W = RT RT2 − − RT RT11 = P P2V V2 − −P P11VV11 (3.33)
(3.33) (3.33)
WW= = γγ22 − − 11 1 = = 22 γγ22 − − 111 1 (3.33)
(3.33)
γγ − − 11 γγ − − 11
Equations
Las ecuaciones
Equations (3.32)
(3.32)
(3.32) and
and (3.33)
y (3.33) are
are general
son generales
(3.33) general paraforunadiabatic
for proceso de
adiabatic compression
compresiónand
compression expansion
y expansión
and pro-
expansionadiabático
pro- en
cesses Equations
Equations
in a closed (3.32)
(3.32)
system, and whether
and (3.33)
(3.33) are
are general
general
reversible for
for
or adiabatic
adiabatic
not, because compression
compression
P, V , and and
andT expansion
expansion
are state pro-
pro-
func-
un sistema cerrado,
cesses in a
cessesindependent sea
closed
in aa closed o no
closed system, reversible,
system,
system,
whether
whetherya que P,
reversible
reversible V y T son
or funciones
not,
or2 not,
not,
because de
becauseunknown. estado,
P,
P, V
V , independientes
and
V ,, and
T
and TT are
are state
are state
state of de
func-
func-la trayec-
cesses
tions, in of whether reversible or because P, func-
toria. De cualquier
tions, modo, por
independent of path. However,
lo general
path. However,T2 y VTT 222no
and
andse VV are usually
conocen.
2 are usually unknown. deElimination
La eliminación of VV22 (3.33)
V2 de la ecuación
Elimination
tions,
tions,
from independent
independent
Eq. of
of path.
path. However,
However, T
T 2 and
and VV 2 are
are usually
usually unknown.
unknown. Elimination
Elimination of
of VV2
mediante from Eq. (3.33)
la ecuación(3.33) by
by Eq.
(3.30c), Eq.que (3.30c), valid
es válida
(3.30c), validsólo only 2
only2para for
for mechanically
2
procesos
2
reversible processes,
mecánicamente reversibles,
processes, leads
nosto
leads to the
the22
conduce a la
from
from Eq.
Eq.
expression: (3.33)
(3.33) by
by Eq.
Eq. (3.30c),
(3.30c), valid
valid only
only for
for mechanically
reversible processes,
processes, leads
leads to
to the
the
expresión:
expression:
expression:
expression: � � � �
��P � �(γ � �� P � �(γ �
PP11VV11 � �� P22 � (γ−1)/γ
�(γ −1)/γ �
� RT 1 ��
� � 2 �
� (γ−1)/γ
−1)/γ �
�
−1)/γ − 1 = RT P −1)/γ − 1 (3.34) (3.34)
W = (γ−1)/γ
(γ −1)/γ 1 2 (γ(γ−1)/γ
(γ −1)/γ (3.34)
W = γP P111VV111 P222
P − 1 = RT111
RT PP222 − 1
WW= = γ− − 11 PP11 − 11 =
− = γγ − − 11 PP11 − 11
− (3.34)
(3.34)
γγ − − 11 P111
P γγ − − 11 PP111
The
Theelsame
Se obtiene mismo
same result
result is
is obtained
resultado obtained ��when
cuando when the
the relation
la relación relation entrebetween PP and
P y V conocida
between and VVpor given by
by Eq.
la ecuación
given Eq. (3.30c)
(3.30c)is
(3.30c) isseused
usa para la
used
Thethe
The same
same result is
result is W obtained
obtained
= − � when
when the
the relation(3.34)
relation between
between P and
P and VV forgiven
given bygases
by Eq. (3.30c)
Eq. (3.30c) is used
is used
for
integración
for the integration,
de integration,
la expresiónW W= = –−∫ P P
� P
dV.d V . Equation
d VLa. Equation
ecuación (3.34) (3.34) is is
sólovalid only
es válida
valid only for ideal
para gases
ideal with
ideales
gases constant
with con capacidades
constant
for the
for
heat the integration,adiabatic,
integration,
capacities WW= =− − P P ddV V .. Equation
Equation (3.34) is
(3.34) is valid
valid only
only for for ideal
ideal gases
gases with
with constant
constant
caloríficas capacities in
heatconstantes, yinen procesosmechanically
adiabatic, reversible,
reversible, closed-system
adiabáticos mecánicamente
mechanically reversiblesprocesses.
closed-system de sistema cerrado.
processes.
heat capacities
heat capacities in
in adiabatic,
adiabatic, mechanically
reversible, closed-system
closed-system processes.
processes.
CuandoWhen se aplican
When applied
applieda gases to
to real gases,
reales,
real gases, lasEqs. (3.30)
(3.30) through
ecuaciones
Eqs. (3.30) a (3.34)
through (3.34) often
(3.34) con yield
yield satisfactory
oftenfrecuencia proporcionan
satisfactory approx-
approx- aproxima-
imations,When
When appliedthe
applied
provided to real
to real gases, Eqs.
gases,
deviations Eqs. (3.30)
from (3.30)
ideality through
through
are (3.34) often
(3.34)
relatively often
small. yield
yield For satisfactory
satisfactory
monatomic approx-
approx-
gases,
ciones satisfactorias,
imations, provided siempre they deviations
cuando lasfrom desviaciones
ideality are de lorelatively
ideal sean relativamente
small. pequeñas.
For monatomic Para gases
gases,
imations,
γimations, provided the
provided the deviations
deviations from1.4
from ideality
ideality are relatively
are relatively small. For
small. For simple
monatomic
monatomic gases,
gases,
γ= = 1.67;
monoatómicos, 1.67;γ =approximate
1.67; los valores
approximate values of
of γγ are
valuesaproximados are 1.4de for
forγdiatomic
para gases
diatomic gases and
and 1.3
diatómicos
gases 1.3sonfor
for de polyatomic
1.4 para
simple gases diatómi-
polyatomic
γ
γ =
= 1.67;
1.67; approximate
approximate values
values of
of γ
γ are
are 1.4
1.4 for
for diatomic
diatomic gases
gases and
and 1.3
1.3 for
for simple
simple polyatomic
polyatomic
cos y degases such
1.3 para
gases as
suchgasesas COCO 2 ,, SO
SO22,, NH
poliatómicos NH33,simples,
, and
and CH CH4tales.. como CO2, SO2, NH3 y CH4.
gases such
gases such as as CO CO2222,, SOSO222,, NH NH333,, and
and CH CH4444..
Polytropic
Polytropic Process
Process
Polytropic
Proceso Process
politrópico
Because polytropic means “turning many ways,” polytropic process suggests a model of some
Because polytropic means “turning many ways,” polytropic process suggests a model of some
Because polytropic
Because polytropic means “turning
means “turning many ways,”
many ways,” polytropic
polytropic processbysuggests
process suggests aa model
model of of some
some
Debidoversatility. With
With δδ asignifica
a que politrópico
versatility. a constant, itit is
is defined
“cambios
constant, as
as aa process
de muchas
defined maneras”,
process represented by the
los procesos
represented empirical
empirical equation:
thepolitrópicos sugieren un mo-
equation:
versatility. With
versatility. With δδ aa constant,
constant, itit is
is defined
defined as as aa process
process represented
represented by by the
the empirical
empirical equation:
equation:
delo con algo de versatilidad. Con d como una constante, éste se define como un proceso representado por la
ecuación empírica: PPVV δδδ == constant
constant (3.35a)
(3.35a)
PPVV δδ = = constant
constant (3.35a)
(3.35a)
d
PV =(3.30a)
constante (3.30b) are readily derived: (3.35a)
For
For an
an ideal
ideal gas
gas equations
equations analogous
analogous to to Eqs.
Eqs. (3.30a) and and (3.30b) are readily derived:
For an
For an ideal
ideal gas
gas equations
equations analogous
analogous to to Eqs.
Eqs. (3.30a)
(3.30a) and and (3.30b)
(3.30b) are
are readily
readily derived:
derived:
Es fácil deducir las ecuaciones análogas a las ecuaciones (3.30a) y (3.30b) para un gas ideal:
TT VV δ−1
δ−1 =
δ−1 = constant
constant (3.35b)
(3.35b) TT PP(1−δ)/δ
(1−δ)/δ =
(1−δ)/δ = constant
constant (3.35c)
(3.35c)
δ−1
δ−1 = = constant (1−δ)/δ
P(1−δ)/δ = constant
TT V TP(1–d)/d = =
Vd–1 constant (3.35b) TT P
(3.35b) constant (3.35c)
TV = constante (3.35b) constante (3.35c)(3.35c)
��
When
When the relation between P and V is given by Eq. (3.35a), evaluation of
the relation between P and V is given by Eq. (3.35a), evaluation of �� PP ddVV yields
yields
Cuando
Eq. la relación
When
When the entre between
the relation
relation P y Vδ:está
between P dada
P and V
and Vpor la ecuación
is given
is given Eq.(3.35a),
by Eq.
by (3.35a), la
(3.35a), evaluación
evaluation
evaluation of deP
of P∫ddPV
V dV produce la
yields
yields
Eq. (3.34)
(3.34) with
with γγ replaced
replaced by
by δ:
ecuaciónEq.
Eq.(3.34)
(3.34)
(3.34)con
with
withγ reemplazada
replaced by
γγ replaced por
by δ:d:
δ: � �
�� P � �(δ−1)/δ �
RT
RT1 1 �� 2 �
� (δ−1)/δ
P2 (δ−1)/δ ��
W = (δ−1)/δ − 1
(δ−1)/δ (3.36)
W = δRT RT111 P222
P − 1 (3.36)
W=
W = δ− − 11 PP11 −− 11 (3.36) (3.36)
(3.36)
δ−1
δ − 1 P
P111
Moreover,
Moreover, forfor constant
constant heat
heat capacities,
capacities, the the first
first law
law solved
solved for for Q Q yields:
yields:
Además, para capacidades
Moreover,
Moreover, for constant
for caloríficas
constant heat constantes,
heat capacities,
capacities, thela
the primera
first
first law solved
law
� ley resuelta
solved for Q
for para
Q yields:
yields:
� Q produce:
��
� (δ−1)/δ �
(δ −
(δ )RT11 �
− γγ )RT �� PP22 ��(δ−1)/δ ��
(δ−1)/δ − 1
Q=
Q = (δ(δ −
− γγ )RT
(δ − )RT111
−
P222 (δ−1)/δ
P (δ−1)/δ −1 (3.37)
(3.37)
Q=
Q 1)(γ
= (δ − 1)(γ − 1) 1) PP11 − 11
− (3.37) (3.37)
(3.37)
(δ −
(δ − 1)(γ
1)(γ − − 1) 1) P111
P

3.3. El gas ideal 79
Los procesos descritos en esta sección corresponden a las cuatro trayectorias que se muestran en la figura 3.6
para valores específicos de d:
• Proceso isobárico: mediante la ecuación (3.35a), d = 0.
• Proceso isotérmico: por la ecuación (3.35b), d = 1.
• Proceso adiabático: d = γ.
• Proceso isocórico: mediante la ecuación (3.35a), dV/dP = V/Pd; para V constante, d = ±∞.
0
Figura 3.6: Trayectorias de procesos

P 1
politrópicos caracterizados por valores

específicos de d.

Proceso irreversible
Todas las ecuaciones desarrolladas en esta sección fueron deducidas para procesos mecánicamente reversi-
bles en sistemas cerrados para gases ideales. Sin embargo, las ecuaciones que proporcionan cambios de pro-
piedad (dU, dH, ∆U y ∆H) son válidas para gases ideales sin considerar el proceso. se aplican de igual modo
a procesos reversibles e irreversibles tanto en sistemas cerrados como abiertos, ya que los cambios en las
propiedades dependen sólo de los estados inicial y final del sistema. Por otra parte, una ecuación para Q o W,
a menos que sea igual al cambio en una propiedad, se somete a las restricciones en su deducción.
El trabajo de un proceso irreversible se calcula con un procedimiento de dos pasos. Primero, se deter-
mina W para un proceso mecánicamente reversible que alcanza el mismo cambio de estado que el proceso
irreversible real. Segundo, este resultado se multiplica o se divide por una eficiencia para obtener el trabajo
real. Si el proceso produce trabajo, el valor absoluto para el proceso reversible es muy grande y debe multi-
plicarse por una eficiencia. Si el proceso requiere trabajo, el valor para el proceso reversible es muy pequeño
y debe dividirse entre la eficiencia.
Las aplicaciones de los conceptos y de las ecuaciones de esta sección se ilustran en los siguientes ejem-
plos. En particular, el trabajo de los procesos irreversibles se trata en el ejemplo 3.4.
Véase el problema 3.13.

Ejemplo 3.2
Se comprime aire a partir de la condición inicial de 1 bar y 25 °C hasta alcanzar un estado final de 5
bar y 25 °C mediante tres procesos diferentes y mecánicamente reversibles en un sistema cerrado:
a) Calentamiento a volumen constante seguido por un enfriamiento a presión constante.
b) Compresión isotérmica.
c) Compresión adiabática seguida por enfriamiento a volumen constante.
Suponga que el aire es un gas ideal con capacidades caloríficas constantes, CV = (5/2)R y C P = (7/2)R.
Calcule el trabajo requerido, el calor transferido y los cambios en la energía interna y la entalpía del
aire para cada proceso.
10
8
c
6
P/bar
Figura 3.7: Diagrama para el ejemplo 3.2. 2
4 a
b
2
1
0 5 10 15 20 25
V  103/m3
Solución 3.2
Elija como sistema 1 mol de aire. Para R = 8.314 J mol–1 K–1,
CV = 20.785 CP = 29.099 J mol–1 K–1
Los estados inicial y final del aire son idénticos a los del ejemplo 2.9, donde:
V1 = 0.02479 V2 = 0.004958 m3
Ya que T es la misma al principio y al final del proceso, para todos los casos:
DU = DH = 0
a) El proceso en este caso es exactamente el del ejemplo 2.9b), para el cual:
Q = –9 915 J y W = 9 915 J

3.3. El 3.3.
gas ideal
The Ideal Gas 81 81
3.3.
3.3. The
3.3. The Ideal
The Ideal Gas
Ideal Gas
Gas 81
81
81
b) Aplicamos la ecuación
(b) Equation (3.27)(3.27)
for thepara la compresión
isothermal isotérmica
compression of ande idealun gas gas ideal:
applies:
(b) Equation
(b) Equation
(b) Equation (3.27) (3.27) for
(3.27) for
for thethe isothermal
the isothermal compression
isothermal compression
compression of of an
of an ideal
ideal gas
an ideal gas applies:
gas applies:
applies:
P1 1
Q = −W = RT ln P PP111 = (8.314)(298.15) ln 111 = −3,990 J
Q=
Q
Q == −W
−W =
−W == RT RT ln
RT ln P
ln P 2 = == (8.314)(298.15)ln
(8.314)(298.15)
(8.314)(298.15) ln 55 =
ln == −3,990
−3,990 JJJ
−3,990
PP222 55
(c) The
c) La etapa initial
inicial step of adiabaticadiabáticacompression takes the air it to its final
un volume
volumenof
(c)
(c) The
(c) The
The
0.004958 3de
initial
initial
initial
m .
la compresión
step
step
step
By
of
of
Eq.
adiabatic
of (3.30a),
adiabaticthe
adiabatic compression
compression
compression
temperature
tomatakesel aire
takes
takes
at
the y lo
air
thepoint
the
this air
air it lleva
ititis:to
toto its
its afinal
its final
final volume
volume
volume offinal de
of
of
0.004958 m 3 . Usando 3 la ecuación (3.30a), la temperatura en este punto es:
0.004958
0.004958 m
0.004958 m 33.
m .. ByBy Eq.
By Eq. (3.30a),
Eq. (3.30a),
(3.30a), the the temperature
the temperature
temperature at at this
at this point
this point
point is: is:
is:
� �γ −1 � �0.4
�
�V ��γγγ−1 �� 0.02479 ��0.4
T �� = T1 � VV1111� −1 = (298.15) �
−1 0.02479
0.02479 0.4
� 0.4 = 567.57 K
T �� = T1 V = 0.02479 =
TT = = TT11 V2 V = (298.15)
= (298.15) 0.004958
(298.15) 0.004958 = = 567.57
567.57 K
567.57 K
K
VV222 0.004958
0.004958
For this step, Q = 0, and by Eq. (3.32), the work of compression is:
En esta For
For this
etapa
For this
this Q step,
= 0 y,Q
step,
step, Q =
Qpor
= 0,
= la
0, and
and by
0, ecuación
and byby Eq.
Eq.
Eq. (3.32),
(3.32),
(3.32),
(3.32), el the
the
the work
workdeof
trabajo
work of compression
ofcompresión
compression
compression es:is:
is:
is:
W = C V �T = (20.785)(567.57 − 298.15) = 5,600 J
W
WW= ==CCCVVV �T �T =
�T = (20.785)(567.57 −
= (20.785)(567.57
(20.785)(567.57 − 298.15) =
− 298.15)
298.15) == 5,600 5,600 JJJ
5,600
For the constant-volume step, no work is done; the heat transfer is:
For
For the
Para la etapa
For the
the constant-volume
a volumen constante
constant-volume
constant-volume step,
no se
step,
step, no
no work
work is
noefectúa
work is done;
done; the
istrabajo;
done; la heat
the
the heat transfer
transfer is:
transferencia
heat transfer de calor es:
is:
is:
�
Q = �U = C V (T2 − T � ) = −5,600 J
Q=
Q
Q = �U
= �U =
�U ==C C (T222 −
CVVV(T
(T −−TTT��))) =
== −5,600
−5,600 JJJ
−5,600
Thus for process (c),
De esta Thus
manera,
Thus
Thus for para
for
for process
process
process el proceso
(c),
(c),
(c), c),
WW == 5,600
5 600 J J and y QQ == –5−5,600
600 J J
W
WW= == 5,600
5,600 JJJ
5,600 and
and
and Q
QQ= = −5,600
= −5,600 JJJ
−5,600
Aunque Although
los cambios theenproperty
la propiedad
changes ∆U y�U ∆H and son cero
�H para cada for
are zero proceso,
each Q y W dependen
process, Q de
Although the
theQproperty changes �U and �H are zero for each process, Q
la trayectoria, W pero
Although
and Although aquí
the = –W. Lachanges
property
property
are path-dependent, figura
changes
but here3.7 Q muestra
�U
�U and
=and
−W .cada
�H
�H areproceso
are
Figure zero
zero
3.7foren each
for un
each
shows diagrama
process,
process,
each Q Ya que
PV.
Q
process
and W are path-dependent, but here Q = −W
−W..of
=each
= −W . Figure 3.7
3.7 shows each process
el trabajoand
and
on para
aWWPVcada
are uno de estos
arediagram.
path-dependent,
path-dependent, procesos
Because but
but
the here
here
� work mecánicamente
Qfor
Q reversibles
Figure
Figure 3.7 es conocido
shows
shows
these mechanically each
each por W = –∫ P
process
process
reversible
on a P V diagram. Because the work for each of these mechanically reversible
dV, el trabajo
on aa PPde
on
processes VVcada proceso
diagram.
diagram.
is given es proporcional
Because
byBecause
W = −the d V ,al
�� Pwork
the work forárea
for
the eachtotal
each
work of
of debajo
for these
these de las trayectorias
mechanically
eachmechanically
process en el diagra-
reversible
reversible
is proportional
ma PV que
processes
vatotal
processes
processes
to the
is
de 1isis given
a given
2. Los
given
area
by
by
by
below
W
WW=
tamaños
the =
= −
−− on
paths
P
relativos
dddV
PP the ,,, the
VVde the
Pthe
V
work
estas
work
work
diagram
for
áreas
each
each1process
corresponden
forfrom
for each process
process
to 2. The
is
ais
proportional
islos valores
proportional
relative numéricos
proportional
sizes
to
to the
the total area below
below the paths on
on the
the P PPV diagram from 1 toto 2.
2. The
The relative
relative sizes
de W. to of the
these total
total area
area
areas below
correspond theto
the paths
paths
the on the
numerical VV values
diagram
diagram from
W . 11 to
offrom 2. The relative sizes
sizes
of
of these
of these areas
these areas correspond
areas correspond to
correspond to the
to the numerical
the numerical values
numerical values of
values of W
of W...
W
Ejemplo
Example3.3 3.3
Example
Example
Example 3.3
3.3la siguiente secuencia de procesos mecánicamente reversibles en un siste-
3.3
Un gas ideal experimenta
An ideal gas undergoes the following sequence of mechanically reversible processes
An
Anaideal
ma cerrado:
An ideal
ideal gas
gas
gas undergoes
undergoes the
undergoes the following
the following sequence
following sequence of
sequence of mechanically
of mechanically reversible
mechanically reversible processes
reversible processes
processes
in closed system:
in
in a
in aa closed
closed system:
closed system:
system:
a) Desde un estado inicial de 70 °C y◦ 1 bar, se comprime adiabáticamente hasta la temperatura de
(a) From an initial state of 70◦ C and 1 bar, it is compressed adiabatically to 150◦◦ C.
150 (a)
°C. From
(a) From
(a) an
From an initial
an initial state
initial state of
state of 70
of 70 ◦
◦
70 C C and
C and 1 bar,
and 11 bar, it is
bar, itit is compressed
is compressed adiabatically
compressed adiabatically to
adiabatically to 150
to 150 ◦
◦
150 C.C.
C.
(b) It is then ◦
b) A continuación secooled
(b) It is then cooled
from
enfría de
from
150
150 to °C
a 70
150
70 C at constant
to 70◦◦a◦Cpresión
pressure.
constante.
at constant pressure.
(b) ItIt is
(b) is then
then cooled
cooled fromfrom 150
150 to to 70
70 C C at
at constant
constant pressure.
pressure.
c) Por (c)
último, se expande
Finally, it is expanded isotérmicamente
isothermally hasta su original
to its estado original.
state.
(c)
(c) Finally,
(c) Finally, it
Finally, itit is
is expanded
is expanded isothermally
expanded isothermally to
isothermally to its
to its original
its original state.
original state.
state.
W, Q, ∆UW
CalculeCalculate y ,∆H Q, para
�U , cada and �Huno for
de each
los tres
of procesos
the three yprocesses
para el ciclo
andcompleto.
for the entire CV = (3/2)R
Tomecycle.
Calculate
Calculate
Calculate W ,,, Q,
W(3/2)RQ, �U ,,, and
and
and �H for
for each
for each of
each of the
of the three
the three processes
three processes and
processes and for
and for the
for the entire
the entire cycle.
entire cycle.
cycle.
y C P = Take C V =W
(5/2)R. Q, �U
�U and C P�H�H
= (5/2)R.
Take
Take C
Take CVVV =
C = (3/2)R and
= (3/2)R
(3/2)R and C
and CCPPP =
= (5/2)R.
= (5/2)R.
(5/2)R.

82
82 CHAPTER 3.
Properties of
of Pure
Pure Fluids
Fluids
3
3 b 22
70°C 3 b 150°C
70°C b 2 150°C
70°C 150°C
3 b 2
70°C 3 150°C
b 23 b 2
70°C 150°C 150 °C
70 °C
PP a
a
Figure c
Figure 3.8:
3.8: Diagram
Diagram for
for Ex.
Ex. 3.3.
3.3. P c
c
a
Figure 3.8: Diagram for Ex. 3.3.
P a
Figure 3.8: Diagram for Ex. 3.3. c
FiguraFigure
3.8: Diagrama para el
3.8: Diagram forejemplo
Ex. 3.3.3.3.
P P c
a a 70°C
c 70°C
1 70°C
1
1
70°C
VV 1 70°C
V 70 °C
1 1
V
V V
Solution 3.3
Solution 3.3
Solución 3.3
Solution 3.3
−1 −1
R =For
Para SolutionR=
R
8 314
For 3.3–1 JJKmol
=J 8.314
mol
8.314 –1, −1 K −1,
mol −1 K−1 ,
For R = 8.314
Solution 3.3 J mol K ,
−1 K−1 , −1 −1
For R = 8.314 CV J=
C mol
= 12.471
12.471 CCP == 20.785
20.785 JJ mol
mol−1 K K−1
For R = 8.314 C VVJ =
mol −1 K−1 ,
12.471 C PP = 20.785 J mol−1 K−1
−1 K 11−1
El cicloThe
estácycle is
is C
representado V = en
shown on
on aa P
12.471 PV V diagram PVin enFig. = 20.785
3.8.
C Pfigura Take as aa basis
J mol mol
baseof
1 gas.
onuna diagrama la 3.8. Tome como mol
gas. de gas.
The cycle shown diagram in Fig. 3.8. Take as basis
−1 mol of gas.
The cycle isCshown
V = 12.471 P V diagram in Fig.
C P 3.8. Take
= 20.785 as a basis
J mol K1−1 mol of
a) Para (a)
un gas
(a) For
For ideal
an que
an ideal
ideal se
gas somete
gas undergoing
undergoing a una compresión
adiabatic
adiabatic adiabática,
compression,
compression, Q
Qa=
Q =
= 0;0, de
0; whence
whence donde
The cycle
(a) For an isideal
showngas on a P V diagram
undergoing in Fig.
adiabatic 3.8. Take asQ
compression, =basis 1 mol of gas.
0; whence
The cycle is shown on a P V diagram in Fig. 3.8. Take as a basis 1 mol of gas.
(a) For an ideal�U �Ugas= WW= =C
=undergoing CV �T�T =
= (12.471)(150
adiabatic compression,
(12.471)(150 − Q ==
− 70)
70) =0;998 JJ
whence
998
(a) For an ideal�U gas= W = C VV �T
undergoing = (12.471)(150
adiabatic compression, − 70)
Q ==0;998 whenceJ
�U �H = =W
�H = CPP �T C = C
�T =
�T = (12.471)(150
(20.785)(150 − −
70)
V = (20.785)(150 − 70) = 1,663 J =
70) =
1,663998 J J
�U �H == W C=P C �TV �T = (12.471)(150
= (20.785)(150 − 70)
− 70) = 998J J
= 1,663
Pressure
La presión P2 se P
Pressure P22 is
puedeis found
found
�H from
encontrar
=
fromC aEq.
Eq.
�T (3.30b):
partir
= de
(3.30b): la ecuación
(20.785)(150 (3.30b):
− 70) = 1,663 J
Pressure P2 is found from PEq. (3.30b):
�H � = C �T = (20.785)(150 − 70) = 1,663 J
Pressure P2 is found � 2� P
�γγ/(γ �
(3.30b): �150 + 273.15 �2.5
Eq.−1)
−1)
�
P = P � TTfrom /(γ 2.5
2 �γ /(γ −1) = (1) � 150 + 273.15 �2.5 = 1.689 bar
Pressure PP22 is=found
2 P1 TTfrom
1 2 = (1) 150
Eq. (3.30b): + 273.15 = 1.689 bar
P2 = P1 � T11 �γ /(γ −1) = (1) � 70 70 ++ 273.15
273.15 �2.5 = 1.689 bar
T 70
150 ++ 273.15
273.15
= P1 � T2 �γ /(γ −1) = (1) � 150 + 273.15 �2.5 = 1.689 bar
21
(b) P2constant-pressure
(b) For
For this
this
P = P T
constant-pressure
1
process,
(1) 70 + 273.15
process,
= = 1.689 bar
(b) For this2 constant-pressure
1
T1 constante: process, 70 + 273.15
b) Para este proceso a presión
Q=
Q = �H�H =
(b) For this constant-pressure =C CP �T = (20.785)(70 −
= (20.785)(70
process,
�T 150) =
− 150) = −1,663
−1,663 JJ
Q = �H = C PP �T
(b) For this constant-pressure = (20.785)(70 − 150) = −1,663 J
process,
Q =�U �H= ==C CVC P �T==
�T (20.785)(70
(12.471)(70 −− 150)==−998
150) −1,663J J
�U V �T = (12.471)(70 − 150) = −998 J
Q =�U �H==CC V P�T�T==(12.471)(70
(20.785)(70−−150) 150)==−998−1,663 J J
�U WW= =
= C�U�UV �T
−−Q Q=== −998 − (−1,663)
− 150) =
−998 − (−1,663)
(12.471)(70 = 665
= −998 J
665 J J
�U W= =C�U − Q = −998 − (−1,663) = 665 J
V �T = (12.471)(70 − 150) = −998 J
(c)
(c) For
For ideal
ideal gases
gases W undergoing
= �U − Qan
undergoing = isothermal
an −998
isothermal process,
process,=�U
− (−1,663) 665 and
�U and �H
Jand �H areare zero;
zero;
(c) (3.27)
Eq. For ideal gases
yields: W undergoing
= �U − Q an
= isothermal
−998 − process,=
(−1,663) �U
665 J �H are zero;
Eq. (3.27) yields:
Eq. For
(c) (3.27) yields:
ideal gases undergoing an isothermal process, �U and �H are zero;
c) Para (c)
gases
For ideales
Eq.Q(3.27) ideal que seundergoing
gases
yields: someten
P
P3 a an
un isothermal
proceso
PP2 process, ∆U
isotérmico, �U y1.689∆H �H
and
1.689 son cero; la ecuación
are zero;
(3.27) produce:
Q =
= −W −W == RTRT ln ln P P33 == RTRT lnln PP22 = (8.314)(343.15) ln
= (8.314)(343.15) ln 1.689 =
= 1,495
1,495 JJ
Eq. Q
(3.27) yields:
= −W = RT ln P11 = RT ln P11 = (8.314)(343.15) ln 11 = 1,495 J
P31 P21 1
1.689
Q = −W = RT ln P3 = RT ln P2 = (8.314)(343.15) ln 1.689 = 1,495 J
Q = −W = RT ln P1 = RT ln P1 = (8.314)(343.15) ln 1 = 1,495 J
P1 P1 1

3.3. The
3.3.
3.3. The Ideal
The Ideal Gas
Ideal Gas
Gas 83
83
83
3.3. El3.3.
gas ideal
3.3. The
The Ideal
Ideal Gas
Gas 83
83 83
For the
For
Para todo the entire cycle,
entire cycle,
Forelthe
ciclo,
For
For the entire
entire cycle,
the entire cycle,
cycle,
Q
QQ= = 000 −
= − 1,663
− 1,663 +
1,663 + 1,495
+ 1,495 =
1,495 == −168
−168 JJJ
−168
QQ= = 00 − 1,663 +
− 1,663 1,495 =
+ 1,495 = −168
−168 JJ
W =
W
W = 998
= 998 + 665
998 +
+ 665 −
665 − 1,495
− 1,495 =
1,495 = 168
= 168 JJJ
168
W =
W 998 +
= 998 665 −
+ 665 1,495 =
− 1,495 = 168
168 JJ
�U =
�U
�U = 998 −
998
= 998 − 998 +
998
− 998 + 0 =
+ 000 = 0
= 000
�U =
�U 998 −
= 998 998 +
− 998 + 0= =0
�H
�H
�H = =
= 1,663
1,663
= 1,663 − −
− 1,663
1,663
− 1,663 + +
+
+ 000 =
== 000
�H = 1,663
�H 1,663 + 00 =
1,663 − 1,663 = 00
The property
The
The property changes
property changes �U
changes �U and
�U and �H
and �H both are
�H both
both are zero
are zero for
zero for the
for the entire
the entire cycle,
entire cycle, because
cycle, because the
because the
the
Los cambios
The
The
initial
initial en
and
andla final
property
property propiedad
changes
changes
final states
states ∆U
�U
�U
are
are ∆H�H
yidentical.
and
and son cero
�H
identical.
both
both
Note
Note para
are
are
also
also elthat
zero
zerociclo
that
for
for
Q
Q completo,
the
the
==
entire
entire
−W
−W yathe
quebecause
cycle,
cycle,
for
for the los estados
because
cycle.
cycle. the inicial
the
This
This
initial
y final son and final
idénticos.final states are
Observe are identical.
también Note
que==Q also thatelQ
Q= = −W −W for the cycle.
cycle. This
0.= – also
W parathat Qciclo. Estefor
resultado surge de la pri-
initial
initial and
and final states
states are identical.
identical. Note
Note also that = −W for the
the cycle. This
This
follows
follows
follows from
from
from the
the
the first law
first
first law
law with
with
with �U
�U
�U = 0.
0.
con ∆Ufrom
mera leyfollows
follows = 0.the first law with �U = 0.
from the first law with �U = 0.
Example
Example 3.4
3.4
Example
Ejemplo
If
If the 3.4 3.4
processes of Ex.
Ex. 3.3
3.3 are
are carried
carried out irreversibly but
out irreversibly but so
so as
as to
to accomplish
accomplish exactly
exactly
If the processes of
the processes of Ex. 3.3 are carried out irreversibly but so as to accomplish exactly
IfIf the
the processes
processes of
changes
changes of of Ex.
Ex. 3.3
state—3.3 are
are carried out irreversibly
carried out irreversibly but
but so
so as
as to
to accomplish
accomplish exactly
exactly
the same
the samedel
Si los procesos ejemploof
changes of state—
state—
3.3 the same
the same changes
son irreversibles, changes in P,
in
pero de modo P, TTT ,,,, U
se,,,, and
U and H H—— then
then different
differentlos mis-
P, que consigan
— exactamente
the
the same
same changes of state— the
the same changes in P, U and H — then different
the same
values
values of
of changes
Q
Q and
and W
W of state—
result.
result. the same
sameQ
Calculate
Calculate Q
changes
changes
and
and W
W
in
in
ifif
P,
each
each
TT ,stepU
U
step , and
and
is
is H—
H then
carried
carriedthen
out
out
different
different
with an
with an
mos cambios
valuesdeofestado
and(los
W mismos
result. cambios enQ U yW
WH),ifif por lo tantostep se is producen diferentes
anvalores
Calculate and
QP, and each carried out
out with an
Q T,
values of Q and
values Q
of of
efficiency
efficiency and W
Q 80%.
of 80%. W result.
result. Calculate
Calculate and W if each each step
step is is carried
carried out with
with an
de Q y efficiency
W. Calculeof
efficiency y W si cada etapa se lleva a cabo con una eficiencia de 80%.
ofQ80%.
80%.
efficiency of 80%.
Solución 3.4
Solution
Solution
Solution 3.4
3.4
3.4
Solution 3.4
If the
If the same
Si se realizan same changes
changes
los mismos of state
of
cambios statede asestado
as in Ex.
in Ex.que
3.3 en
3.3 are carried
are carried out3.3
out by irreversible
by irreversible processes,
medio deprocesses,
areelcarried
ejemplo bypor procesos irrever-
If
If the
the same
same changes
changes of
of state
state as
as in
in Ex. 3.3 are carried out by irreversible processes,
If
the
thethe same
property
property changes
changes
changes offor
state
for the
the in Ex.
assteps
steps Ex.
are
are
3.3
3.3 are carried
identical
identical with
with
out
out by
those
those
irreversible
irreversible
of
of Ex.
Ex. 3.3.
3.3.
processes,
processes,
However,
However,
sibles, los
the
the
the cambios
property
property
property en la
changespropiedad
changes for for the
the para
steps
the steps las
steps are etapas
are son
identical
are identical idénticos
with
identical with a
those
with those los
those of
ofdel
Ex.
of Ex. ejemplo
3.3.
Ex. 3.3. 3.3. No obstan-
However,
3.3. However,
the values
the values
te, los valores
the de
values Qofychanges
of
of Q
Q
QW and
and
se
and W
WWforchange.
change.
modifican.
change.
However,
the
the values
values of of Q Q and
and W W change.
change.
(a)
(a)
a) Para (a)
una For
For mechanically
mechanically
compresión
(a) For
For mechanically reversible,
reversible,
adiabática, adiabatic compression,
adiabatic
mecánicamente
reversible, adiabatic compression,
reversible, W
compression, W==
W
W =
=998998
998
998 J. J.J. If
Si
J. If
If the
elthe process
process
proceso
the tiene 80%
process
(a) For mechanically
reversible, adiabatic
adiabatic compression,
compression, W
W =
= 998
998 J.
J. If
If the
the process
process
is
is 80%
80%
de eficiencia efficient
efficient
80%enefficient
is 80% comparación
efficient compared
compared
compared con with
with
esto,
with this,
this,
W
this,= WW =
=
998/0.80
W 998/0.80
998/0.80
= 998/0.80=
998/0.80 1 248==
= J.1,248
1,248
En
1,248 J.
J.
este This
This
J. Thiscaso
This step
step
no
step cannot
cannot
es posible
cannot que
is
is 80% efficient compared with this, W = = 1,248 J.
this, W = 998/0.80 = 1,248 J. This step cannot step cannot
here
here
esta etapa
hereseabe
be adiabatic.compared
beadiabática.
adiabatic.
adiabatic. By
By
Por
By the
the
la
the
with
first
first
primera
first law,
law,
law, ley,
here be adiabatic. By the
here be adiabatic. By the first law, first law,
Q=
Q
Q = �U
= �U −
�U −W
− W=
W = 998
= 998 −
998 − 1,248
− 1,248 =
1,248 = −250
= −250 JJJ
−250
Q=
Q = �U�U − −W W= 998 −
= 998 1,248 =
− 1,248 = −250
−250 JJ
b) El trabajo
(b) The
(b)
(b)
(b)
The
The
Thepara el proceso
work
work
work
work
for the
for
for
for
thede
the
the enfriamientoreversible
mechanically
mechanically
mechanically
mechanically mecánicamente
reversible
reversible
reversible
coolingreversible
cooling
cooling
cooling
process is
process
process
process
ises665
is
is de 665
665
665
665 J.
J. J. Para
J. For
J. For
For
For
the el pro-
the
the
the
(b) The
ceso irreversible,
irreversible work for
= 665/0.80
process, the W mechanically
=
=
= 831 reversible
=
=
J, y = 831
665/0.80 831 J, cooling
and process is 665 J. For the
irreversibleWprocess,
irreversible process,
process, WW= = 665/0.80
665/0.80 831 J,
831 J, andand
and
irreversible
irreversible process, W 665/0.80 =
W = 665/0.80 = 831 J, J, and
Q=
Q
Q = �U
= �U −
�U −W
− WW= == −998
−998 −
−998 −− 831
831 =
831 = −1,829
= −1,829 JJJ
−1,829
Q=
Q = �U�U − −W W= = −998
−998 − 831 =
− 831 = −1,829
−1,829 JJ
c) A medida
(c) As
(c)
(c) As
Asque el trabajo
work
work
work is done
is
is done
done es by
realizado
by
by the system
the
the systempor elin
system insistema
in this step,
this
this step,en the
step, esta
the etapa, el trabajo
the irreversible
irreversible
irreversible workirreversible
work
work absoluteen valor
in absolute
in
in absolute
(c)
(c) As
As work
work is
is done
done by
by the
the system
system in
in this
this step, the
step,J:J:the irreversible
irreversible work work in in absolute
absolute
absolutovalue
es
value menor
value is is
is less
lessque
than
than
is less than el trabajo
the
the reversible
reversible
reversible
than the reversible work
work
reversible work of deof
of –1 495
−1,495
−1,495
of −1,495 J: J:
J:
value
value is less
less than the the reversible work work of −1,495
−1,495 J:
WW=
W == (0.80)(−1,495)
(0.80)(−1,495) =
(0.80)(−1,495) == −1,196
−1,196 JJJ
−1,196
WW= (0.80)(−1,495) =
= (0.80)(−1,495) = −1,196
−1,196 JJ
Q
QQ= = �U
= �U −
�U −W
− WW= = 000 +
= ++ 1,196
1,196 =
1,196 = 1,196
= 1,196 JJJ
1,196
QQ= = �U�U − −W W= = 00 + 1,196 =
+ 1,196 = 1,196
1,196 JJ
For the
For
For the entire
the entire cycle,
entire cycle, �U
cycle, �U and
�U and �H
and �H are
�H are zero,
are zero, with
zero, with
with
Para el For
ciclo
For the completo,
the entire ∆ U �U
entire cycle,
cycle, y�U∆H and
andson�H
�H cero,arecon
are zero,
zero, with
with
Q=
Q
Q = −250
= −250 −
−250 − 1,829
− 1,829 +
1,829 ++ 1,196
1,196 =
1,196 = −883
= −883 JJJ
−883
Q=
Q = −250
−250 − 1,829 +
− 1,829 1,196 =
+ 1,196 = −883
−883 JJ
W
WW= == 1,248
1,248 +
1,248 + 831
+ 831 −
831 − 1,196
− 1,196 =
1,196 = 883
= 883 JJJ
883
WW= 1,248 +
= 1,248 831 −
+ 831 1,196 =
− 1,196 = 883
883 JJ
A summary
A
A summary of
summary of these
of these results
these results and
results and those
and those for
those for Ex.
for Ex. 3.3
Ex. 3.3 is
3.3 is given
is given in
given in the
in the following
the following table;
following table;
table;
A
A summary
En la siguiente
summary tabla of
of sethese
these results
proporciona
results and
un
and those
resumen
those for
for Ex.
de
Ex. 3.3
estos
3.3 is given
resultados
is given in
in the
y los
the following table;
correspondientes
following table; para
values
values
values areare in
are in joules.
in joules.
joules.
values
el ejemplo 3.3,are
values in
in joules.
donde
are los valores se proporcionan en joules.
joules.

Mecánicamente reversible, ejemplo 3.3 Irreversible, ejemplo 3.4

∆U ∆H Q W ∆U ∆H Q W
a) 998 1 663 0 998 998 1 663 –250 1 248
b) –998 –1 663 –1 663 665 –998 –1 663 –1 829 831
c) 0 0 1 495 –1 495 0 0 1 196 –1 196
Suma 0 0 –168 168 0 0 –883 883
Es un ciclo que requiere trabajo y produce una cantidad igual de calor. La característica más
sorprendente de la comparación mostrada en la tabla es que el trabajo total requerido cuando el
ciclo se compone de tres etapas irreversibles es más de cinco veces el trabajo total requerido
cuando las etapas son mecánicamente reversibles, aun cuando cada etapa irreversible se supone
con 80% de eficiencia.
Ejemplo 3.5
Se confina una cantidad de gas nitrógeno en un cilindro vertical mediante un pistón sin fricción. La
parte superior del pistón está abierta hacia la atmósfera. El peso del pistón hace que la presión del
nitrógeno sea 0.35 bar mayor que la de la atmósfera de los alrededores, que es de 1 bar y 27 °C. De
este modo, el nitrógeno se encuentra inicialmente a una presión de 1.35 bar y se encuentra en equili-
brio mecánico y térmico con respecto a sus alrededores. El pistón es empujado dentro del cilindro, de
modo que comprime el nitrógeno hasta una presión de 2.7 bar. A esta presión, se permite que el nitró-
geno llegue al equilibrio térmico con la atmósfera circundante a 27 °C. En este punto, el pistón se fija
en su sitio mediante seguros.
Los seguros se retiran liberando al pistón de su restricción, y con el tiempo el aparato regresa al
equilibrio mecánico y térmico con sus alrededores. Discuta la aplicación de la termodinámica a este
proceso. Suponga que el nitrógeno en estas condiciones es un gas ideal.
Solución 3.5
Cuando los seguros que sostienen el pistón sin fricción son removidos, dicho pistón se mueve
rápidamente hacia arriba, y debido a su inercia al ir más allá de su posición de equilibrio. Esta
expansión inicial se aproxima a un proceso adiabático reversible, ya que se produce poca turbu-
lencia de un solo recorrido del pistón y porque la transferencia de calor es relativamente lenta. Sin
embargo, la oscilación consecutiva del pistón introduce la irreversibilidad como resultado de la
agitación y la turbulencia tanto del gas como de la atmósfera. Este proceso sigue durante un tiem-
po considerable, durante el cual se presenta transferencia de calor en una cantidad suficiente para
regresar el nitrógeno a su temperatura inicial de 27 °C a una presión de 1.35 bar.
No es posible especificar la trayectoria de un proceso irreversible, y esto hace imposible el
cálculo tanto de Q como de W. A diferencia del calor y el trabajo, es posible calcular los cambios
de la propiedad del sistema, ya que dependen únicamente del estado inicial y final, y éstos son
conocidos. Tanto ∆U como ∆H para el proceso de expansión son cero, porque las temperaturas

3.3. 3.3.
El gas ideal
The
3.3. Ideal Gas Gas
The Ideal 85 85 85
inicial
arey zero,
final son 27
because
are zero, °C.
theLa
because primera
initial
the and ley
initial andsefinal
final aplica tanto para
temperatures are 27
temperatures procesos
27◦ C.irreversibles
◦ C. The
are first
The law lawcomo
firstapplies reversi-
applies
bles, to
y nos lleva a
irreversible que:
as well
to irreversible as to as
as well reversible processes,
to reversible and itand
processes, becomes:
it becomes:
�U DU
= ==
�UQ Q
+Q+WW
+==W00 =
de donde
whence
0 whence Q =QQ==
−W–W−W
Aunque no
Althoughes posible
neither
Although calcular
Q
neithernorQ W nor ni
Qcan W,
W be sus
be valores
cancalculated, absolutos
their
calculated, sonvalues
absolute
their los values
absolute mismos.
are the Eltheresultado
aresame. same. del
proceso es la elevación
The process results
The process del pistón
in elevation
results y la atmósfera,
of theofpiston
in elevation así como
and the
the piston una disminución
andatmosphere,
the atmosphere, en
and aand la compensación
compen-
a compen-
en la sating
energía interna
decrease
sating dethe
in
decrease lainatmósfera
internal circundante.
energy
the internal of theofsurrounding
energy atmosphere.
the surrounding atmosphere.
Ejemplo 3.6
Example
Example3.63.6
En una
Air tubería
flows athorizontal
a atsteady que
ratecontiene
through unaa válvula
horizontalparcialmente
pipe pipe
to a tocerrada,
partly circulavalve.
closed aire conTheuna rapidez
Air flows a steady rate through a horizontal a partly closed valve. The
uniforme. La
pipe pipe tubería
leaving que
the valve deja la válvula
is enough es
largerlo suficientemente
thanthan
the entrance larga con
pipe piperespecto
that that a la tubería
the kinetic-energy de entra-
leaving the valve is enough larger the entrance the kinetic-energy
da, de modo que el cambio de energía cinética del aire a medida que fluye a través
changechangeof theofair
theasairit as
flows through
it flows the valve
through is negligible.
the valve is negligible.The The
valvevalve
and and connecting es
de la
connecting válvula
despreciable. Tanto la válvula como las tuberías de conexión se encuentran bien aisladas. ◦ CLas
pipespipes
are well insulated.
are well insulated. The The
conditions of the
conditions of air
theupstream
air upstream fromfrom
the valve are 20
the valve are 20◦ Ccondi-
ciones del
and and aire
6 bar, corriente
and and arriba
the downstream de la válvula
pressure son de 20
is 3 bar. °C y 6 bar,
If airIfisairy la presión
regarded as ancorriente abajo es de 3
6 bar, the downstream pressure is 3 bar. is regarded asideal gas, gas,
an ideal
bar. what
Si el aire se considera
is theistemperature como
of the un gas ideal, ¿cuál es la temperatura del aire a cierta distancia co-
what the temperature ofair
thesome distance
air some downstream
distance downstream fromfrom
the valve?
the valve?
rriente abajo de la válvula?
Solución 3.6 3.6 3.6

Solution
Solution
El flujo a través de una válvula parcialmente cerrada se conoce como un proceso de estrangula-
FlowFlow
through a partly
through closed
a partly valvevalve
closed is known as a throttling
is known process.
as a throttling The system
process. is is
The system
ción. El sistema se aísla, lo cual hace que se ignore a Q; además, son despreciables los cambios
insulated, making
insulated, Q negligible;
making moreover,
Q negligible; the potential-energy
moreover, and kinetic-energy
the potential-energy and kinetic-energy
de energías potencial y cinética. Ya que no hay trabajo de flecha, Ws = 0. Por tanto, la ecuación
changes are negligible.
changes Because
are negligible. no shaft
Because workwork
no shaft is accomplished, Ws =W0.
is accomplished, s =
Hence,
0. Hence,
(2.32) se reduce a ∆H = 0. Así, para un gas ideal,
Eq. (2.32) reduces
Eq. (2.32) to: �H
reduces = 0. =
to: �H Thus, for anfor
0. Thus, ideal gas, gas,
an ideal
� T2 � T2
= = C P dT
�H �H
C P=dT0 = de donde
whence T2 =TT21= T1
0 whence
T1 T1
The result that �H

The result that �H=0= is general for a for
0 is general throttling process,
a throttling because
process, the assump-
because the assump-
El resultado de que ∆H = 0 es general para un proceso de estrangulación, ya que son válidas las
tionstions
of negligible heat transfer
of negligible and potential-
heat transfer and kinetic-energy
and potential- changes
and kinetic-energy are usu-
changes are usu-
suposiciones de que la transferencia de calor y los cambios en las energías potencial y cinética son
ally valid. If theIffluid
ally valid. is an is
the fluid ideal gas, no
an ideal temperature
gas, change
no temperature occurs.
change The throttling
occurs. The throttling
despreciables. Si el fluido es un gas ideal, no ocurre cambio en la temperatura. El proceso de es-
process is inherently
process irreversible,
is inherently but this
irreversible, butisthis
immaterial to thetocalculation,
is immaterial because
the calculation, because
trangulación es inherentemente irreversible, pero esto no tiene importancia en el cálculo, ya que
Eq. (3.21b) is valid
Eq. (3.21b) for anfor
is valid ideal gas whatever
an ideal the process.
gas whatever the process.
la ecuación (3.21b) es válida para un gas ideal sin importar el proceso.
Ejemplo 3.7 3.73.7

Example
Example
−1 −1
Si enIfel
inejemplo
Ex.
If in 3.6 the
Ex.3.6
3.6laflow
the rate rate
flow
rapidez of
detheofair
flujotheisair
del 1 mol 1 smol
is es
aire and if, both
s s–1and
1 mol upstream
if both
y si la and un
upstream
tubería tiene downstream
and downstream
diámetro interno de
pipes have
pipes an
have inner
an diameter
inner of
diameter 5 cm,
of 5 what
cm, is
what theiskinetic-energy
the change
kinetic-energy
5 cm, tanto en la entrada como en la salida de la válvula, ¿cuál es el cambio en−1la energía of
change theofair
theand
air and del
cinética
what is
what its temperature
is its temperaturechange?
change?For air,
For Cair,=C =
(7/2)R(7/2)Rand and
M = M29=g mol
29 g .
mol −1 .
aire y cuál es su cambio en la temperatura? ParaP el aire, P C P = (7/2)R y M = 29 g mol . –1

86
86
86 CHAPTER 3.
CHAPTER
3. Volumetric Properties
Volumetric Properties of
Properties of Pure
of Pure Fluids
Pure Fluids
Fluids
86
86
86 CHAPTER 3. Volumetric Properties of Pure
CHAPTER
CHAPTER 3.
3. Volumetric
Properties of
of Pure Fluids
Pure Fluids
Fluids
86 86 CAPÍTULO
Properties deFluids
Solución 3.7
Solution
Solution 3.7
3.7
Solution
Solution
Solution 3.7
3.7
Solution 3.73.7 .
nn..
..
nV.
Por laSolution
ecuación 3.7
(2.24b), nV
3.7 uu = =
By Eq.
By Eq. (2.24b),
Eq. (2.24b),
(2.24b), = n..
. = nV
...
Solution
By u = Aρ n
Aρn
n. = = nV nV
nV AA
By
By Eq.
Eq. (2.24b),
(2.24b),
By Eq. (2.24b), u u = =
u = Aρ Aρ == nV .A
�� π ��u = Aρ Aρn . .
AA
A
By Eq. (2.24b), π
π D 22 = � π �u(5=×Aρ n = 2nV
By
where Eq. (2.24b), A = π �� π �
� 10 −2
−2 = ) 2 A= 1.964 ×
= 1.964 × 10
−3
−3 m m22
2
donde where
where A
A = π4π = D
D 2 =
= � π π
4 � (5
(5 ×× 10
Aρ
10 −2 )
) 2 A= 1.964 × 10−3
10 m
π D22 = 2
= � 4π −2 2 −3 m222
where
where A=
AA =
=π 44 D 4 � (5 (5 × × 10 10−2 −2))22 = = 1.964
1.964 × × 10 10−3 −3 m
where 4π44 D2 = �π 4π 44 � (5 × 10−2 )2 = 1.964 × 10−3 m2
where
The
The upstream
upstream A = volume
molar
molar D 2 = as
volume as4 givengiven (5 ×by by 10thethe 2 = 1.964
−2))ideal-gas
ideal-gas × 10 −3is:
equation
equation is:m2
El volumenwhere
The molar
upstream corrienteA = 4arriba,
molar D =que
volume as se(5
given conoce ×by 10the la=ecuación
porideal-gas 1.964 × del
equation 10 gas is: mideal es:
The
The upstream
upstream molar
molar 4volume
volume
The upstream molar volume as given by the ideal-gas equation is: as
as 4 given
given by
by the
the ideal-gas
ideal-gas equation
equation is:
is:
The upstream RT molar (83.14)(293.15)
volume as given by the ideal-gas equation
RT (83.14)(293.15) −3is:
11 −6 −3 3 −1

The upstreamV
VV11 = = RT
=
RT
RT Pmolar1 =
1 = volume
=
(83.14)(293.15)
(83.14)(293.15)
(83.14)(293.15) as given by
6
×
× the
×
10
10−6
10
−6 =
= 4.062
ideal-gas
=
×
× 10
4.062equation
4.062 × 10−3
10
m
m33 mol
is:
m mol−1
mol
−1
1
VV111 = = RT P 1 1
= (83.14)(293.15) 6 × −6
−6 = × −3
−3 3
33 mol−1 −1
V = RT P1 =
1 1
= (83.14)(293.15) 6 × × 1010
10 −6 =
= 4.062
4.062
4.062 × × 10
1010 −3 mm
m mol
mol −1
P P
P 111 1 6
66 −6 −3 3 −1
V1 = RT 1 = (83.14)(293.15) × −3 10 −6 = 4.062 × 10 −3 m 3 mol −1
V1 = P1 = (1)(4.062
6
(1)(4.062 ×× 10 × −3
10 −310)) = 4.062 ×−1 10 m mol
Then,
Then, P1 uu11 = = (1)(4.0626 ×
×
10 −3−3 )= = 2.069
2.069 m
m ss−1
−1
Then, u = (1)(4.062
(1)(4.062
1.964 ×
1.964
(1)(4.062 ×× × 10 10
10
1010
−3
−3 −3 )) = 2.069 m s
En tal caso,
Then,
Then, uuu1111 = = × −3−3 ) = = 2.0692.069 m m ss−1 −1
−1
Then, = (1)(4.062
1.964
1.964
1.964 ××
10
×10
10 10 −3
−3
−3 −3 ) = 2.069 m s−1
Then,
If the u 1 = 1.964
(1)(4.062 × × 10 10 ) = 2.069 m s
If
If the downstream
Then,
the downstream temperature
downstream u 1 = 1.964
temperature
temperature
is
is little
is × 10−3
little
little
changed
changed
changed
−3
= 2.069from
from the
from m s−1
the
the
upstream
upstream temperature,
upstream temperature,
temperature,
Si la temperatura
then
If
If
then the
the to
to a corriente
good
downstream
downstream
a good abajo
approximation:
temperature
temperature
approximation: cambia 1.964 is is un ×
little
little 10
poco changed
changed de la correspondiente
from
from the
the upstream
upstream a la temperature,
corriente
temperature, arriba, por
If the downstream
then to a good approximation: temperature is little changed from the upstream temperature,
lo tantothen
Ifpara
then
thenthe una
to
to aa buena
good
good
downstream aproximación:
approximation:
approximation:
temperature is little changed from the upstream temperature,
If thetodownstream
a good approximation: temperatureand is little changed from 4.138 the upstream −1 temperature,
then to a goodV 22 = = 2V
Vapproximation: 2V11 and uu22 = = 2u 2u11 = 4.138 m
= 4.138 m sss−1 −1
then to a goodV = 2V
approximation:
2 1 and u2 = 2u 1 = m −1
−1
VV V222 = =
= 2V 2V111 and
2V and
and y uuu222 = == 2u 2u111 =
2u = 4.138
= 4.138
4.138 m m
m sss−1
The
The rate rate
rate of of change
of change V
change = in 2V kinetic
in2Vkinetic
kinetic energy
energy and is therefore:
is therefore:
therefore:u = 2u = 4.138 m s−1
The V22 =in 1
1 energy and is u22 = 2u11 = 4.138 m s−1
Debido The
aThe
The esto,rate
rate
rate laof
of rapidez
changedein
change incambio
in kinetic
kinetic deenergy
energy la energía is
is cinética es:
therefore:
is therefore:
..of change
11 22
kinetic
.. energy
11 22
therefore:
The ratem of
.
m.of �(
change u
21 u 2 ) = ) =
in n
kinetic
. M �( energy u ) is therefore:
The ratem �(
.. �( 1221 u22) =
change nn...M
in kinetic M �(
�(energy21 u 2 )
1221 u22) is therefore:
mm
m. �( �(2212uuu 2))) =
�( =
= nnn. M M �(2212uuu 2))) −3 (4.138
�(
M �( 2 2
(4.13822 − − 2.069
2.06922))) = 0.186 J s−1
m. �( 121u 22) = = (1 (1
n .
(1 × M× �(
× 29 29
2921×
1×210 −3) (4.138
u
× 210 )
10−3 ))(4.138 22 −
−
2.069 2 2 = 0.186 J s−1 −1
m �( 2 u ) = =
== (1 nM
(1 ×
× �( 29
29 ×
2× u 10 ) −3
10 −3
−3 )) (4.1382 −
(4.138 2.069
2.0692))) =
22 2.069
− = 0.186 J s−1
= 0.186
0.186 JJ s
s −1
−1
= (1 × 29 × 10 ) (4.138 2 − 2
−3
2
2 22 2.069 2) = 0.186 J s−1
2
In = (1 × 29 × 10 ) (4.138 − 2.069 ) = 0.186 J s
In the
In the absence
the absence of
absence of heat
of heat
heat = transfer
(1 × 29and
transfer
transfer and
× 10
and
work,
work,
work,
−3 ) the the energy
the energy
energy 2 balance,
balance,=Eq.
balance, Eq.
0.186
Eq.
(2.31),
(2.31),
(2.31),J s−1becomes:
becomes:
becomes:
In
In the
the absence
absence
In thedeabsence of
of heat
heat
of heatde transfer
transfer
transfer and
and work,
work, the
the energy
energy 2 balance,
balance, Eq.
Eq. (2.31),
(2.31), becomes:
becomes:
En ausencia transferencia calor
+
y11and
u
de m
work,
22 trabajo,
..
= m
the
.. elenergybalance
+ m
.. balance,
de11energía,
u 22
Eq. (2.31),
= 0
ecuación becomes:
(2.31), será:
In the absence of heat�(H transfer
�(H + 1 and
u 2 ))work,
m . = the
m . �H
�H energy + m . �(
balance,
�( 1 u 2 )
) Eq.
= 0(2.31), becomes:
In the absence of heat�(H transfer + 122211and u222)m ... = m
work, ... �H
the energy �( 122211u222) Eq.
+ m...balance, = 0(2.31), becomes:
.. C C PP �T �(H +
�(H
�(H ..+
+ 222uuu11 )))m m=
22m .)) =
=
=m m
m... �H �H +
�H ++m m
m. �(.. 222uuu1 )))22=
�(
�( =
= 000
mm .. C C P �T �(H ++ mm.+ �(
�( 1 212u
u u) m
2 . = nC
.
nC
m . �HP �T
�T + +
+
m . m.
m
�( �(
�(1 2112u
u u
) 2=)) = =0 000
m.. C CMMPPP �T�T�(H + m..+�(
. 12211u
21 u 2 ) = nC .m . P
P �T + m.
.. �( 21 u1221 u)22=
2 )=
m m M �T ++ mm �(
�( uu)222m) ) == nC
nC . �H �T
�T + +
+m m�(
m �(
�( 1 uu 2) ) ==0 00
m. C M �T + m �(22 u ) = nC 2
. .PP �T + m. �(2122 u2 ) = 0
P 2
m CMMPP �T + m.. �( 121u 22) = nC + m =
Whence .
�T + m �(22 u ) = =−
. m . P �T �T 1 2
2 = . �(
−0.186 21 u 2 ) = 00
u )
Whence
Whence
mM (1)(7/2)(8.314)�T
(1)(7/2)(8.314)�T
(1)(7/2)(8.314)�T =
= −
−
nC
m �( 2112 uuu+
m... P�(
�( 2))) m
= �(
= −0.186
−0.186 2
M = − 1
. �(121uu22)) = 2
Whence
Whence
Whence (1)(7/2)(8.314)�T
(1)(7/2)(8.314)�T
(1)(7/2)(8.314)�T == −−m m
m. �( �(2K 22 u ) = −0.186
= −0.186
−0.186
and �T = −0.0064
==−0.0064
−0.0064
and
Whence
and (1)(7/2)(8.314)�T �T =
�T −m. �( 12K K 2
1u 2) = −0.186
De donde and
and
and
Whence (1)(7/2)(8.314)�T �T =
�T
�T ==
= −m �(K
−0.0064
−0.0064
−0.0064 K
K2 u ) = −0.186
andClearly,
Clearly, the the assumption
assumption of �T = −0.0064
of negligible
negligible temperature
temperature K change
change across across the the valve
valve is is
andClearly, the assumption of �T = −0.0064
negligible temperature K change across the valve is
justified.
Clearly,
Clearly,
justified.
Clearly, Eventhe
the
Even
the for for
assumption
assumption
for
assumption an
an upstream
upstream of
of pressure
negligible
negligible
of negligible pressure of
temperature
of 10
temperature
10
temperature bar
bar and
andchange
change
change a
a downstream
across
across
downstream the
the
across thepressure pressure
valve
valve is
valve
pressure is
is
y justified.
of 1
justified.bar and Even
Evenfor the
for
an
ansame upstream
flow
upstream DT pressure
rate,
pressure= the
–0.0064 of 10
temperature
of 10K barbar
andchange
and
a downstream
a is
downstream only −0.076
pressureK.
justified.
of 1 Clearly,
bar
justified. Even
and the
Evenfor for
assumption
the
for an
an same upstream of
flow
upstream pressure
negligible
rate,
pressure the of
temperature10
of 10 bar and bar andchange a downstream
across
is
a downstream only the pressure
valve
−0.076
pressure is
K.
of 1 bar
Clearly, and for
the the
assumption same flow of rate,
negligible the temperature
temperature change
change = is
acrossonly −0.076
the valve K.is
We
of
of 111conclude
justified.
Weof bar
bar
bar and
conclude and
Even
and that,
for
for
forfor
that, except
the
theexcept
the an same
same
same for
upstream
for flow
flow
flowvery
very rate,
rate, unusual
pressure
rate,unusual the
the
the conditions,
temperature
temperature
of 10 bar and
conditions,
temperature �H
change
change
�H
change is000 only
is
is
a downstream is
only
=despreciable
only −0.076
−0.076
is aaa satisfactory
pressure
−0.076
satisfactory K.
K.
K. de la
Es evidente,
We conclude
justified. se justifica
Even that, for except la
an suposición
for
upstream very del
unusual
pressure cambio de
conditions,
of 10 temperatura
bar and�H a =
downstream
=
is a través
satisfactory
pressure
energy
We
We
of
energy barbalance
conclude
1conclude and that,
balance for for
that,
forthe aexcept
except throttling
samefor forflow very process.
very rate, unusual
unusual the temperature conditions,
conditions, �H
�H
change ==is 00 only
is
is −0.076 K.
is aaa satisfactory
satisfactory
We
válvula.energy
Aun
of 1conclude
para
barbalance unafor
and that,
presión
for theaaexcept
throttling
throttling
same for
corriente
flow process.
very
process.arriba
rate, unusual the conditions,
detemperature
10 bar y unachange �H presión is0corriente
only satisfactory
abajoK.de 1 bar
−0.076
energy
energy
Weenergy balance
balance
conclude
balancethat, that,for
for
for a a
except throttling
throttling
a throttling for very process.
process.
process. unusual conditions, �H = 0 is a satisfactory
para la misma
We conclude relación de exceptflujo, elfor cambio very en la temperatura
unusual conditions,es�H de sólo = 0 –0.076 K. Concluimos
is a satisfactory
energy balance for a throttling process.
que, excepto
energy parabalancemuy pocas for a throttlingcondiciones process. inusitadas, ∆H = 0 es un balance de energía satisfacto-
rio para un proceso de estrangulación.

3.4. Aplicación
3.4. de las ecuaciones
3.4. Application
Application of
of the viriales
the Virial
Virial
Equations
Equations 87
87 87
3.4. Application of the Virial Equations 87
3.4 APLICACIÓN
3.4
3.4 DE LAS
APPLICATION OFECUACIONES
THE VIRIAL VIRIALES
EQUATIONS
3.4 APPLICATION
APPLICATION OF
OF THE
THE VIRIAL
VIRIAL EQUATIONS
EQUATIONS
Las dos formas de la expansión virial conocidas en las ecuaciones (3.11) y (3.12) son series infinitas. Para
The
The twotwo forms
forms of of the
the virial
virial expansion
expansion givengiven by
by Eqs.
Eqs. (3.11)
(3.11) and
and (3.12)
(3.12) are
are infinite
infinite series.
series. For
For
propósitos
Thetécnicos,
two forms su of
usothees virial
práctico sólo cuando
expansion givenlaby
convergencia
Eqs. (3.11) esandmuy
(3.12)rápida, esto es,series.
are infinite cuandoFor
dos o tres
engineering
engineering purposes
purposes their
their use
use isis practical
practical only
only where
where convergence
convergence isis very
very rapid,
rapid, that
that is,
is, where
where
términos son suficientes
engineering
two para
purposes una
theiraproximación
use is practicalrazonable
only a
wherelos valores de
convergence las
is series.
very Esto
rapid, ocurre
that is, para
where gases y
two oror three
three terms
terms suffice
suffice for
for reasonably
reasonably close
close approximations
approximations to to the
the values
values of
of the
the series.
series. This
This
vaporesistwo
de presiones
or three bajas
terms a moderadas.
suffice for reasonably close approximations to the values of the series. This
is realized
realized for
for gases
gases andand vapors
vapors atat low
low to
to moderate
moderate pressures.
pressures.
is realized for gases and vapors at low to moderate pressures.
400(F)
440000((��FF))
1.00 250(F) 00(�F)
1.00
1.00 2254
500((��FF))
1.00 250(�F)
100(F)
110000((��FF))
100(�F)
0.75 F)
0 ( F))
Z  PV/RT
0.75
0.75 00((��FF)
PV/RT
PV/RT
0.75 0 (�
PV/RT
150 F) Figura 3.9: Gráfica del factor de compresibilidad

�150 0 ( )
(�FF)
�150 5 5500((��F)
Figure
Figure 3.9:
3.9: Compressibility-factor
Compressibility-factor
�
(F) para el metano.

Z�
�150
(�F) � Figure 3.9: Compressibility-factor
(�F)
Z Z�
� 50 graph
0.50 (�F) ) � graph for
for methane.
methane.
0.50
0.50 ( F )) graph for methane.
0.50 10
0
0 ((�FF )
�
 00
1 ( 0 � F
��1 00
1
�
0.25
0 0.25
0.2501 000 2 000 3 000
0.25 0 1000
1000 2000
2000 3000
3000
0 1000
P(psia) 2000 3000
P(psia)
P(psia)
P(psia)
La figura 3.9 muestra

Figure una gráfica del factor de compresibilidad para el metano. Los valores del factor
Figure 3.9
3.9 shows
shows aa compressibility-factor
compressibility-factor graph graph for for methane.
methane. Values
Values of of the
the compressibil-
compressibil-
de compresibilidad Figure Z (como
3.9 shows se calculan
a a partir
compressibility-factor de la información
graph for PVT
methane. del metano
Values ofmediante
the la ecuación
compressibil- que
ity
ity factor
factor ZZ (as
(as calculated
calculated fromfrom PPVVTT data data for
for methane
methane by by thethe defining equation ZZ =
defining equation = PPVV/RT
/RT))
la define
areZ
ity = PV/RT)
factor Z (asestán graficados
calculated from en
P Vfunción
T data de
for la presión
methane by para
the varias
defining temperaturas
equation Z constantes.
= P V /RT Las
) iso-
are plotted
plotted vs.
vs. pressure
pressure for for various
various constant
constant temperatures.
temperatures. The The resulting
resulting isotherms
isotherms show show graph-
graph-
termas ically
resultantes
are plotted vs. muestran
pressure deformanera gráfica
various constantlo que se intenta
temperatures. representar
The resulting en isotherms
formaisotherms
analítica con la expan-
show graph-
ically what
what the
the virial
virial expansion
expansion in in PP isis intended
intended to to represent
represent analytically.
analytically. All All isotherms origi-origi-
sión virial en
ically P. Todas
what the las isotermas
virial expansion se originan
in P is en
intendedel valor to Z = 1
represent para P = 0, y
analytically. a bajas
All presiones
isotherms las isotermas
origi-
nate
nate atat the value ZZ =
the value for PP =
= 11 for = 0,
0, and
and the
the isotherms
isotherms are are nearly
nearly straight
straight lines
lines atat low
low pressures.
pressures.
son líneas
nate casi
at rectas.
the value Así,
Z =la1 tangente
for P = a
0, una
and isoterma
the isothermsen P =
are 0 es una
nearly buena
straight aproximación
lines at low de la
pressures. isoterma
Thus
Thus the the tangent
tangent toto an
an isotherm
isotherm at at PP = = 00 isis aa good
good approximation
approximation of of the
the isotherm
isotherm from from PP → → 00
desde Pto →
Thus 0 para
the alguna
tangent presión
to an finita.
isotherm atAlP derivar
= 0 is ala ecuación
good (3.11)
approximation para ofcierta
the temperatura
isotherm from se
P obtiene:
→ 0
to some
some finite
finite pressure.
pressure. Differentiation
Differentiation of of Eq.
Eq. (3.11)
(3.11) for for aa given
given temperature
temperature gives: gives:
to some finite pressure. Differentiation
�� of Eq. (3.11) for a given temperature gives:
�∂∂ZZ � � � � 2
∂Z == BB � + + 2C 2C �PP + + 3D3D �PP 2 + + ······
∂∂PP TT = B � + 2C � P + 3D � P 2 + · · ·
∂P T � � � �
�∂∂ZZ � �
from which,
from which, ∂ Z == BB ��
a partir from
de la which,
cual, ∂∂PP TT;P=0 = B
∂ P T ;P=0 ;P=00
�
Así, la Thus
Thus the
ecuación equation
the de la rectaof
equation the
the tangent
tangente
of es: Z =line
tangent 1 +isis
line ZZ =
B ′P, =
que + BB ��P,
+
11también P,esaa un
result also
also given
resultado
result que seby
given by truncating
obtiene al truncar la
truncating
Thus
Eq. the
(3.11) equation
to two of
terms. the tangent line is Z = 1 + B P, a result also given by truncating
ecuación (3.11)
Eq. a
(3.11)
Eq. (3.11) dos términos.
to two terms.
to two terms.form of this equation results from substitution for B �� by Eq. (3.13a):
A
A more
Una forma máscommon
común deform expresar
of thisesta ecuación es sustituyendo B ′ porfor
la B
ecuación
B � by Eq.(3.13a):
more common equation results from substitution by Eq. (3.13a):
A more common form of this equation results from substitution for (3.13a):
PPVV BBPP
ZZ =
= PV = = 11 +
+ BP (3.38) (3.38)
(3.38)
Z = RT RT = 1 + RT RT (3.38)
RT RT
This
This equation
Esta ecuación expresaexpresses aa direct
direct proportionality
una proporcionalidad directa entre between ZZ and
y P, y con and P,P, and
andseisisaplica
often
often applied
vaporesto
Z frecuencia is oftena applied
equation expresses proportionality Z
between applied toa tempe-
This equation expresses a direct proportionality between and P, At andhigher to
raturas vapors
vapors at
at subcritical
subcríticas hasta sus
subcritical temperatures
presiones
temperaturesde up
up to
to their
saturación. theirAsaturation
temperaturas
saturation pressures.
altas
pressures. se
vapors at subcritical temperatures up to their saturation pressures. At higher temperatures
higher temperatures
proporciona
At una aproximación
temperatures

88 88 CHAPTER 3.3. Volumetric
CAPÍTULO Properties
Propiedades of Pure
volumétricas deFluids
fluidos puros
razonable para los gases

it provides hasta unaapproximation
a reasonable presión de varios bar, incrementando
for gases el intervalo
up to a pressure de bars,
of several presión a medida
with the que
aumentapressure
la temperatura.
range increasing as the temperature increases.
La ecuación (3.12)
Equation también
(3.12) es posible
as well may betruncarse
truncatedatodos
twotérminos para
terms for su aplicación
application at lowa bajas presiones:
pressures:
PV B
Z=
=1+ (3.39) (3.38)
RT V
De cualquier
However,modo,Eq.la(3.38)
ecuación (3.38)
is more es más conveniente
convenient in applicationy suand
aplicación es tan
is normally exacta
at least as como la (3.39).
accurate as De
este modo, cuando Thus
Eq. (3.39). la ecuación
when thevirial se trunca
virial equation a dos términos to
is truncated setwo
prefiere
terms,la Eq.
ecuación
(3.38)(3.38).
is preferred.
El segundoThe coeficiente
second virial virial B depende
coefficient B isdesubstance
la sustancia y de una and
dependent función de la temperatura.
a function Los valores
of temperature.
experimentales están disponibles para varios Además, es posible
5
Experimental values are available forgases.
a number calcularestimation
of gases.5 Moreover, el segundoof coeficiente
second virial
cuando virial
no hay información
coefficients disponible,
is possible wherecomo no se analiza
data en la sección
are available, 3.6.
as discussed in Sec. 3.6.
Para presiones que están
For pressures abovearriba del intervalo
the range de aplicabilidad
of applicability de labut
of Eq. (3.38) ecuación
below (3.38), peropres-
the critical abajo de la
presiónsure,
crítica,
thelavirial
ecuación virialtruncated
equation truncadatoa three
tres términos con provides
terms often frecuencia proporciona
excellent excelentes
results. resultados.
In this case
En este Eq.
caso, en la the
(3.12), ecuación (3.12)inla1/V
expansion expansión en 1/V estomuy
, is far superior Eq. superior que en
(3.11). Thus la ecuación
when the virial(3.11). Así, cuan-
equation
do la ecuación virialtosethree
is truncated trunca a tres
terms, thetérminos,
appropriatela forma
form apropiada
is: es:
PV B C
Z= =1+ + 2 (3.40) (3.40)
RT V V2
Esta ecuación se puedecan

This equation resolver directamente
be solved parapressure,
directly for la presión,
butpero es cúbica
is cubic en el volumen.
in volume. SolutionLa
forsolución
V is para
V se obtiene fácilmente
readily usando
accomplished byun
an esquema iterativo as
iterative scheme, deillustrated
cálculo, como
in Ex.se3.8.
ilustra en el ejemplo 3.8.
100 100 4,000 4 000

C
C C 2,000 2 000
0 0 0 0
B
�2
B
�1
C/cm6 mol2
B/cm3 mol1
mol�2
B
mol�1
�2,000 2 000
C/cm66mol
B/cm33mol
Figura 3.10: Coeficientes

3.10: Virialviriales B y �100 100 �4,000 4 000
C/cm
B/cm
Figure
C de la progresión
coefficientsenBlaand
densidad
C para
el nitrógeno.
for nitrogen.
�200 200
�300 300
0 0 100 100200 200300 300400 400
T/K T/K
Values of C, like those of B, depend on the gas and on temperature. However, much less
Los valoresabout
is known de C,third
al igual que
virial los de B, dependen
coefficients than aboutdel gas yvirial
second de lacoefficients,
temperatura.though
Sin embargo,
data forse sabe
mucho amenos
numbersobre los terceros
of gases coeficientes
are found virialesBecause
in the literature. que acerca de coefficients
virial los segundos coeficientes
beyond viriales,
the third are aun
cuando rarely
es posible
known encontrar en la literatura
and because the virial alguna información
expansion with morepara
thanvarios
threegases.
terms Ya que rara
becomes vez se conocen
unwieldy,
los coeficientes
its use isviriales más allá de los terceros, y ya que la expansión virial es muy difícil de manejar debido
uncommon.
a que tiene más de tres términos, su uso no es muy común.
55 J. H. Dymond and E. B. Smith, The Virial Coefficients of Pure Gases and Mixtures, Clarendon Press, Oxford,

1980.
J. H. Dymond y E. B. Smith, The Virial Coefficients of Pure Gases and Mixtures, Clarendon Press, Oxford, 1980.

3.4. Application of the Virial Equations 89
3.4. Aplicación de las ecuaciones
3.4. Application viriales
of the Virial
Equations 89 89
Figure 3.10 illustrates the effect of temperature on the virial coefficients B and C for
La figura 3.10 3.10
Figure ilustra el efecto the de laeffect
temperatura sobre losoncoeficientes viriales B y BC and
para el for
nitrógeno;
nitrogen; althoughillustrates
numerical values areofdifferent
temperature for otherthe virialthe
gases, coefficients
trends are similar.C The
aunque nitrogen;
los valores
curve of Fig. numéricos
although son diferentes
numericalthat
3.10 suggests values para otros
are different
B increases gases, las tendencias
for other gases,
monotonically with Tthe son similares.
trends are
; however, similar. Thede la fi-
La curva
at temperatures
gura 3.10 sugiere
curve
much of que
Fig. than
higher B aumenta
3.10 shown
suggests en forma
B that monotónica
B increases
reaches a maximum con T;
monotonically no obstante,
and then slowly a temperaturas
with Tdecreases.
; however,The mucho mayores que
at temperatures
temperature
las mostradas
much B alcanza
higherofthan
dependence un máximo
C isshown y en
B reaches
more difficult seguida disminuye
a maximum
to establish lentamente.
and then slowly
experimentally, La dependencia
decreases.
but its de la temperatura
The temperature
main features are clear: C de
C es más difícil
dependence de
is negative atoflow establecer de manera
C istemperatures,
more difficultpasses experimental,
to establish
through pero sus
experimentally,
a maximum atbutcaracterísticas principales
its main features
a temperature nearare son
theclear:claras:
C
critical, C es
negativais
anda bajas
negative temperaturas,
thereafter at low pasa
temperatures,
decreases por un máximo
passes
slowly with a una temperatura
through aT maximum
increasing . cercana a la crítica, y después
at a temperature near the critical, disminu-
ye de forma lenta
and thereafter
A class conforme
decreases
of T aumenta.
equations slowly withby
inspired increasing
Eq. (3.12), T .known as extended virial equations, is illus-
Hay unaA
trated byclase
class de ecuacionesinspired
of equations
the Benedict/Webb/Rubin inspiradasby en la
Eq.
equation: (3.12),
(3.12),
6 que se
known asconoce
extended como ecuaciones
virial equations,viriales
is illus-extendi-
das. Éstas se ilustran mediante la ecuación de Benedict/Webb/Rubin:
6
6
trated by the Benedict/Webb/Rubin equation:
RT B0 RT − A0 − C0 /T 2 b RT − a
P = RT + B00 RT − A002 − C00/T 22 + b RT 3− a
P= V + V + V
V V 22 � � V 33
aα c γ −γ
+ aα6 + 3c 2 � 1 + γ 2 � exp −γ2
+ V 66 + V 33 T 22 1 + V 22 exp V 22
V V T V V
where A0 , B0 , C0 , a, b, c, α, and γ are all constant for a given fluid. This equation and its
donde Awhere
0, B0, C A000,,a,Bb,
modifications, 00, c,
C0a0, y
a,γ b,
despite son c,constantes
their α, and γ are
complexity, all
unconstant
paraare fluido
used forpetroleum
a given Esta
indeterminado.
the fluid. This equation
andecuación and its
y susindustries
natural-gas modificaciones,
modifications,
a pesar de
forsu complejidad,
light despite
hydrocarbons their
se utilizan complexity,
and a few en las are
industrias
other commonlyused in the
del petróleo petroleum
y delgases.
encountered and natural-gas industries
gas natural para hidrocarburos ligeros
forotros
y algunos light gases
hydrocarbons
comúnmente and aencontrados.
few other commonly encountered gases.
Example 3.8
Example
Ejemplo 3.8for the virial coefficients of isopropanol vapor at 200◦ C are:
3.8values
Reported
Reported values for the virial coefficients of isopropanol vapor at 200◦◦C are:
Los valores reportadosBpara los coeficientes
= −388 cm3 mol−1 viriales del
C vapor de isopropanol
= −26,000 cm6 mol−2a 200 °C son:
B = −388 cm33 mol −1
−1 C = −26,000 cm 66 −2
−2
B = –388 cm 3 mol–1 C = –26 000 cm 6 molmol
–2
◦
Calculate V and Z for isopropanol vapor at 200 C and 10 bar by:
Calculate V and Z for isopropanol vapor at 200◦◦C and 10 bar by:
Calcule V y(a)
Z para
Theelideal-gas
vapor deequation;
isopropanol
(b)a Equation
200 °C y 10 bar mediante:
(3.38); (c) Equation (3.40).
(a) The ideal-gas equation; (b) Equation (3.38); (c) Equation (3.40).
a) La ecuación del gas ideal; b) La ecuación (3.38); c) La ecuación (3.40).
Solution
Solución 3.8 3.8
Solution 3.8
La temperatura absoluta
The absolute es T = 473.15
temperature is T K, y el valor
= 473.15 K, apropiado de la constante
and the appropriate valuede
oflos
thegases
gas es R =
83.14 cm 3 bar
The is –1
mol
absolute
constant RK=–183.14
.
temperaturecm3isbar
T mol −1 K−1
= 473.15 K,. and the appropriate value of the gas
constant is R = 83.14 cm33 bar mol−1 −1 K−1
−1.
a) Para (a)
un gas
For ideal, Z =gas,
an ideal 1, yZ = 1, and
(a) For an ideal gas, Z = 1, and
RT (83.14)(473.15)
V = RT = (83.14)(473.15) = 3,934 cm3 mol−1
V = P = 10 = 3,934 cm33 mol−1−1
P 10
(b) Solving Eq. (3.38) for V gives:
b) Resolviendo paraEq.
(b) Solving V de la ecuación
(3.38) (3.38) se obtiene:
for V gives:
RT
V = RT + B = 3,934 − 388 = 3,546 cm3 mol−1
V = P + B = 3,934 − 388 = 3,546 cm33 mol−1 −1
P
6 M. Benedict, G. B. Webb, L. C. Rubin, J. Chem. Phys., vol. 8, pp. 334–345, 1940; vol. 10, pp. 747–758, 1942.
66M. Benedict, G. B. Webb, L. C. Rubin, J. Chem. Phys., vol. 8, pp. 334–345, 1940; vol. 10, pp. 747–758, 1942.
M. Benedict, G. B. Webb y L. C. Rubin, J. Chem. Phys., vol. 8, pp. 334-345, 1940; vol. 10, pp. 747-758, 1942.

90 90 CAPÍTULO
CHAPTER 3. 3.3. Volumetric
Properties of Pure
PuredeFluids
fluidos puros
90
90 CHAPTER 3. Volumetric
CHAPTER Volumetric Properties
Properties of of Pure Fluids
Fluids
PV
P V V
V 3,546
De donde,
Whence, Z= = PV = = V = = 3,546
3,546 = 0.9014 0.9014
Whence,
Whence, ZZ = PRT RTV
V = RT
= V
RTV/P /P = 3,934 =
3,546
3,934 = 0.9014
Whence, Z = PRT RT /P = 3,546 3,934 = 0.9014
Whence, Z = RT = RT /P = 3,934 = 0.9014
c) Para facilitar
(c) To el proceso
To facilitate
facilitate de
iteration, RT Eq.
iteración,
write laRT
ecuación
(3.40) 3,934 se escribe como:
/P as:(3.40)
(c) iteration,
(c) To facilitate iteration, write
write Eq.Eq. (3.40)
(3.40) as:as:
(c) To facilitate iteration, write Eq. (3.40) � as:
� �
�
(c) To facilitate iteration, write Eq. (3.40) � as: B �
RT
RT � B C�
C
V = RT
= P �11 + 1 + B + C
V i+1
i+1 = RT
Vi+1 P +V Bi + +V C222 �
Vi+1 = RT P 1+ V VBii + V Ci
V
Vi+1 = P 1 + Vi + Viii22
P Vi Vthe
i first iteration, i = 0, and
where subscript iii denotes
denotes the iteration
iteration number. For
donde elwhere
subíndice
where i denota
subscript
subscript el número
denotes the de iteración.
the iteration number.
number. ParaFor
Forla primera
the
the first iteration, iii =
iteración,
first iteration, == 0,
0, yand
0, and
where subscript i denotes the iteration� �number. For the �
� first iteration, i = 0, and
where subscript i denotes the iteration�number. For the
RT � B C� � first iteration, i = 0, and
V11 =
V = RT RT �11 + + B B + + C C�
V = RT P 1+ V VB +V C22
V11 = RT P
P 1 + VB00 + VC02
V1 = P 1 + V00 + VV00022
P V0 V0
where V
where = 3,934,
V00 = 3,934, the the ideal-gas
ideal-gas value.value. Numerically,
Numerically,
donde Vwhere=
where
0 3 934,
V 0 =
el valor
3,934, del
the gas ideal.
ideal-gas En forma
value. numérica,
Numerically,
V = 3,934, the ideal-gas � value. Numerically, � �
where V00 = 3,934, the ideal-gas �� value. 388Numerically,
26,000 �
V11 == 3,934 �11 − � − 388
388 − 26,000
26,000 � = 3,539
3,539
V = 3,934
V 3,934 1 − 3,934 388 − 26,000222 � =
− (3,934) = 3,539
V11 = 3,934 1 − 3,934 388 − (3,934)
3,934 26,0002 = 3,539
(3,934)
V1 = 3,934 1 − 3,934 − (3,934) 2 = 3,539
The second
second iteration
iteration depends
depends on this this3,934
result: (3,934)
The
The second iteration depends on on this result:
result:
The second
La segunda iteration
� depends on�this result:
The iteración depende
�
second iteration de
depends este resultado:
on� this result: ��
RT �
RT
� B
B C�
C
� � 388
388 26,000 ��
26,000
=
V22 = RT �1 + B + 2� =
C = 3,934 �11 +� + 388 − 26,000 � = 3,495
3,495
V
V = RT P 11 + +V B + +V C22 = 3,934 3,934 1 + 3,539 388 − 26,000222 � =
− (3,539) = 3,495
V22 = RT PP 1+ V VB111 + V C112 = 3,934 1 + 3,539
V 388 − (3,539)
3,539 26,0002 = 3,495
(3,539)
V2 = P 1 + V1 + V112 = 3,934 1 + 3,539 − (3,539) 2 = 3,495
P V 3,539 (3,539)
Iteration
Iteration continues until until1 theVdifference
difference
1 Vi+1
i+1 − −V Vii is
is insignificant,
insignificant, and and leads
leads after
after
Iteration continues
continues until the the difference
7
VV i+1 − V i is insignificant, and leads after
five
five iterations
Iteration to
continues the final
until value,
the difference
7 V − V is insignificant, and leads after
five iterations
La iteración iterations
continúa
to
to the
hasta
final
theuntil
finalthe value,
value, 7 i+1
1–− Vii isinsignificante,
the que
finallavalue,diferencia Vi sea
Iteration continues difference
7 Vi V+i+1 insignificant, yand después
leads de cinco ite-
after
five iterations to 7
racionesfive
se obtiene
iterationsel to
valor final value,
the final, V= = 3,488 cm 3
cm3 mol−1 −1
V
V = 3,4883,488 cm3 mol mol−1 −1
V = 3,488 cm33 mol–1 −1
from which
which Z = = 0.8866. In == 33,488
InVVcomparison488 cm cmwith mol
molthis result, the ideal-gas value is
from
from which Z Z = 0.8866.0.8866. In comparisoncomparison with with this
this result,
result, thethe ideal-gas
ideal-gas value
value is is
13%
from
13%
a partir from too
which
too
del cual high
high Z =
and
and
Z =Z0.8866. Eq.
0.8866.
Eq. (3.38)
(3.38)
En Ingives
gives
comparación a
comparison
a value
value 1.7%
with
1.7%
con1.7% too
this
too
este this high.
result,
high.
resultado, the ideal-gas value
idealis
13% too high
which = Eq.
and 0.8866.(3.38) Ingives a value
comparison with too result, el
high. thevalor del gas
ideal-gas value is es 13%
mayor y13% too high(3.38)
la ecuación
13%
and Eq.
too high and Eq.
(3.38) gives
proporciona
(3.38) gives unaavalor
value1.7%1.7% too high.
value 1.7%mayor. too high.
3.5 ECUACIONES
3.5 CUBIC CÚBICAS DE
CUBIC EQUATIONS OF ESTADO
STATE
3.5
3.5 CUBIC EQUATIONS
EQUATIONS OF OF STATE
STATE
3.5 CUBIC
Si una ecuación
EQUATIONS OF STATE
3.5 CUBIC EQUATIONS OF STATEPVT para líquidos y vapores, debe abarcar un amplio
de estado representa el comportamiento
intervalo
If de
If antemperaturas
If an
equation of
an equation y presiones.
of state
equation of state
state
is to
is Aun así,the
to represent
is to represent
represent no P
the
the debe
PV V T ser
PVT tan compleja
behavior
T behavior
behavior of bothcomo
of both
of both liquids paraand
liquids
liquids presentar
and
and
vapors,grandes
vapors,
vapors, it it mustdificul-
it must
must
tades numéricas
encompass
If an o analíticas
equation
encompass a wide
of
aa wide para
range
state is
range su
of
to aplicación.
temperatures
represent the Las
and
P Vecuaciones
Tpressures.
behavior polinomiales
Yet
of it
bothmust que
not
liquids son
be
and socúbicas
complex
vapors, en
it asel to
must volumen
to
encompass
If an equation wide
of state is of
range to temperatures
of the and
temperatures
represent P V Tpressures.
and behaviorYet
pressures. Yet it
it must
of bothmust not
not be
liquids andso
be complex
sovapors,
complex as
as to
it must
molar ofrecen
present
encompass
present un compromiso
excessive
a
present excessive
wide range entre
numericalof la
or generalidad
analytical
temperatures and y la simplicidad
difficulties in
pressures. Yet adecuadas
application.
it must para
Polynomial
not be somuchos
equations
complex propósitos.
asthat
to De
encompass a widenumerical
excessive numerical or
or analytical
analytical difficulties
range of temperatures difficulties
and pressures. in
in application.
Yet it mustPolynomial
application. Polynomial equations
equationsasthat
not be so complex that
to
hecho, las
are ecuaciones
cubic
present
are
are cubic
in
excessive
in cúbicas
molar
in molar son
volume
numerical
volume las
offer
volume offer
or más
a sencillas,
compromise
analytical pero
difficulties
aa compromise betweencapaces
between in de representar
generality and
application. el comportamiento
simplicity
Polynomial that is
equations suitable
that tanto de
cubic
present molarnumerical
excessive offer compromise
or analytical between
difficulties ingenerality
generality and simplicity
simplicity that
andPolynomial
application. that is
is suitable
equationssuitable
that
líquido are
como
to
to many de
cubic
to many vapor.
purposes.
in molar Cubic
volume equations
offer a are in
compromise fact the
between simplest equations
generality and capable
simplicity of representing
that is suitable
are cubicpurposes.
many purposes. Cubic equations
Cubic offer
in molar volume equations are
are in
in fact
a compromise the
the simplest
factbetweensimplest equations
equations
generality capable
capable of
and simplicity of representing
representing
that is suitable
both
to
both liquid
many and vapor
purposes.
liquid and vapor behavior.
Cubic equations are in fact the simplest equations capable of representing
behavior.
both
to liquid
many and vapor
purposes. behavior.
Cubic equations are in fact the simplest equations capable of representing
both liquid and vapor behavior.
Losboth liquid and vapor behavior.
esquemas de iteración, incorporados en los paquetes de software, llevan a cabo esta iteración de manera inadvertida y ru-
777Iteration
Iteration schemes,
schemes, incorporated in
in software packages,
packages, accomplish this
this iteration routinely
routinely and unobserved.
unobserved.
tinaria. Iteration schemes, incorporated
incorporated in software
software packages, accomplish
accomplish this iteration
iteration routinely and
and unobserved.
7 Iteration schemes, incorporated in software packages, accomplish this iteration routinely and unobserved.
7 Iteration schemes, incorporated in software packages, accomplish this iteration routinely and unobserved.

3.5. Ecuaciones cúbicas de estado 91
3.5. Cubic Equations of State 91
La ecuación de estado de van der Waals
The van der Waals Equation of State
La primera ecuación de estado cúbica que se considera práctica fue propuesta por J.8 D. van der Waals en
1873: The first practical cubic equation of state was proposed by J. D. van der Waals in 1873:
RT a
P= − 2 (3.41) (3.41)
V −b V
En este Here,
caso, aa yand b son
b are constantes positivas; when
positive constants; cuando sonare
they cero, se the
zero, recupera
ideal-gas la ecuación
equationdel gas ideal.
is recovered.
Conocidos Given losvalues
valoresofde a y bb para
a and for a un fluido particular,
particular fluid, one can es posible
calculate calcular como una
P as aPfunction of función
V for de V
para valores
variousdiferentes
values of deTT.. La figura
Figure 3.11isesa un
3.11 diagrama
schematic PV esquemático,
PVdiagram showing quethree
muestrasuchtres isotermas. Está
isotherms.
sobrepuesto el “domo”isque
Superimposed therepresenta los estados states
“dome” representing de líquido y de vapor
of saturated liquidsaturados. Para lavapor.
and saturated isoterma ForT1 > Tc,
la presión
the es una función
isotherm T1 > T que
c , decrece
pressure monótonamente
is a monotonically conforme
decreasing aumenta
function el volumen
with molar.
increasing La
molar isoterma
crítica (marcada
volume. The como Tc) contiene
critical isothermuna inflexión
(labeled horizontal
Tc ) contains the en C, característica
horizontal inflection delat Cpunto crítico. Para la
characteristic
isotermaofTthe
2 < critical
Tc, la presión
point. decrece en forma Trápida
For the isotherm en la región de líquido subenfriado conforme V aumenta;
2 < Tc , the pressure decreases rapidly in the subcooled-
después,liquid
cruzaregion
la línea de increasing
with líquido saturado,V ; afterllega a un mínimo,
crossing se eleva a un
the saturated-liquid máximo
line, it goesythrough
a continuación
a mini- decre-
ce, cruza la línea
mum, risesdetovapor saturadoand
a maximum, y continúa
then decreases, hacia abajo dentro
crossing the de la región de vapor
saturated-vapor line andsobrecalentado.
continuing
Las isotermasinto
downward experimentales
the superheated-vaporno exhibenregion. esta transición uniforme de líquido saturado a vapor saturado;
más bien, contienen un segmento
Experimental isotherms horizontal
do notdentro exhibit dethis
la región
smooth de transition
dos fases donde el líquidoliquid
from saturated y el vapor
to satu-
rados coexisten
saturateden diferentes
vapor; rather,proporciones
they containaalahorizontal presión de saturación
segment withino dethevapor. Este comportamiento,
two-phase region where que
se muestra mediante
saturated la línea
liquid discontinua
and saturated vapor de la figurain3.11,
coexist no esproportions
varying analítico, yatesthe aceptado como
saturation or una
vaporconducta
inevitable no realista
pressure. Thisdebehavior,
las ecuacionesshown de by estado
the dashed en laline
región de dos
in Fig. fases.
3.11, is nonanalytic, and we accept
Enasrealidad,
inevitableelthe comportamiento
unrealistic behavior PV predicho en esta
of equations región,
of state mediante
in the two-phase ecuaciones
region. de estado cúbicas
apropiadas, noActually,
es del todo ficticio. Cuando la presión disminuye en
the P V behavior predicted in this region by proper cubic equations un líquido saturado sin que hayaissitios de
of state
formación de núcleos de vapor en un experimento controlado de manera
not wholly fictitious. If pressure is decreased on a saturated liquid devoid of vapor-nucleation cuidadosa, la vaporización no ocurre
y la fasesites
líquida persiste sólo a presiones que razonablemente están por
in a carefully controlled experiment, vaporization does not occur, and liquid persists alone debajo de la presión de vapor. De
manera to similar, el aumento en la presión en un vapor saturado en un
pressures well below its vapor pressure. Similarly, raising the pressure on a saturated vapor experimento apropiado no ocasiona
condensación y el vapor
in a suitable persistedoes
experiment a presiones
not cause que, de manera razonable,
condensation, and vapor están persistsporalone
arribatode la presión
pressures de vapor.
well
Estos estados
above the de no equilibrio
vapor pressure. o metaestables
These nonequilibrium para el líquido sobrecalentado
or metastable states ofysuperheated
para el vapor subenfriado
liquid and se
aproximan por aquellas
subcooled vapor partes de la isoterma
are approximated by PV thosequeportions
se encuentran
of the PenVlaisotherm
región de dos fases
which lie inadyacentes
the two- a los
estados phase
de líquido
region y de vapor to
adjacent saturados.
the states of saturated liquid and saturated vapor.
Las ecuaciones cúbicas
Cubic equations of state de estadohave tienenthreetres raícesroots,
volume para el of volumen,
which twodemay las be
cuales es posible
complex. Phys-que dos
sean complejas.
ically meaningful values of V are always real, positive, and greater than constant b. For an que la
Los valores de V físicamente significativos siempre son reales, positivos y mayores
constante b. Para at
isotherm unaT isoterma a T > Tc,tolaFig.
> Tc , reference figura 3.113.11 muestra
shows that que la solución
solution for V at para de cualquier
anyV positive valuevalor
of posi-
tivo de PP da
yields only one such root. For the critical isotherm (T = Tc ), this is also true, except at a la
sólo una de estas raíces. Para la isoterma crítica (T = T c), esto también es cierto, excepto
presión the
crítica donde
critical existenwhere
pressure, tres raíces
thereiguales
are three a Vroots,
c. Paraall lasequal
isotermas
to Vc .a For T < isotherms
Tc, la ecuaciónat T puede
< Tc , exhibir
una o tres raíces reales, dependiendo de la presión. Aunque estas raíces
the equation may exhibit one or three real roots, depending on the pressure. Although these son reales y positivas, no hay estados
físicos estables para la parte
roots are real and positive, de una isoterma
they are not que está entre líquido y vapor saturados
physically stable states for the portion of an isotherm (debajo del “domo”).
Sólo laslying
raícesbetween P saturadoliquid
para P =saturated , es decir, V saturado(líquido) y V saturado(vapor), son estados estables, conecta-
and saturated vapor (under the “dome”). Only for the vapor or
dos porsaturation
la parte horizontal
pressure P desatlaare
isoterma
the roots, real. Para
V sat (liq)otras
and presiones
V sat (vap),(questablesestates,
indican lyingmediante las líneas
at the ends of ho
rizontales de la figura 3.11 arriba y abajo de P saturado), la raíz más pequeña es un volumen líquido o
the horizontal portion of the true isotherm. For other pressures (as indicated by the horizontal
“semejante
linesa shown
un líquido”,
on Fig. y la3.11
másabovegrande and es below
un volumenP sat ),de
thevapor o “semejante
smallest root is a al vapor”.
liquid La tercera raíz, que
or “liquid-like”
está entre los otros valores, no es importante.
volume, and the largest is a vapor or “vapor-like” volume. The third root, lying between the
other values, is of no significance.
Johannes Diderik van der Waals (1837-1923). Físico holandés ganador del premio Nobel de Física en 1910.
8 Johannes Diderik van der Waals (1837–1923), Dutch physicist who won the 1910 Nobel Prize for physics.

92
92 3. Volumetric
CHAPTER 3.
Properties of
of Pure
Pure Fluids
Fluids
C
C
T1  Tc
P
Figura 3.11: Isotermas T �T
T11 � Tcc
proporcionadas por
3.11:una
Figure 3.11: ecuaciónas
Isotherms PP Tc
Figure Isotherms as Psaturado
cúbica degiven
estado.
by a cubic equation of
of
given by a cubic equation T
Tcc
state. sat
state. PPsat
T2  Tc
T �T
T22 � Tcc
Vsat urado(líquido) Vsat urado(vapor)

sat (liq) sat (vap)
VVsat (liq) VVsat (vap)
V
VV
Una ecuación
GenericdeCubic
A Generic estado
Cubic cúbica of
Equation genérica
State
A Equation of State
Desde laSince
introducción de la ecuación
the introduction
introduction of the de van
the van
van derder Waals
Waals se han propuesto
equation, varias cubic
several hundred
hundred ecuaciones de estado
equations cúbicas.
of state
state
Since the of der Waals equation, several cubic equations of
Todas son casos
have beenespeciales
proposed99de la ecuación:
have been proposed .. All
All are special
are special cases
cases of
of the
the equation:
equation:
RT θθ(V
(V − − η)
η)
P=
P = RT − − 2 + κ V + λ)
V − b (V − b)(V 2
V − b (V − b)(V + κ V + λ)
Here, b,
Here, b, θθ,, κ,
κ, λ, and ηη are
λ, and are parameters
parameters which
which inin general
general depend
depend on on temperature
temperature and and (for
(for mix-
mix-
Aquí, b,tures) l y h son parámetros
q, k, composition. Although que enequation
this general dependen
appears tode la temperatura
possess great y de la composición
flexibility, it has inherent (para las
tures) composition. Although this equation appears to possess great flexibility, it has inherent
mezclas). Aunque esta
limitations because ecuación
because of
of its parece
its cubic tener
cubic form. 10 gran
form.10 It flexibilidad,
It reduces
reduces to
to the posee
the van
van der limitaciones
der Waals
Waals equation inherentes
equation when
when ηη =debido
b, a su
= b,
limitations
10 Ésta se reduce
forma cúbica.
= a,
a, and
and κκ = = λλ =
= 0.
0. a la ecuación de van der Waals cuando h = b, q = a y k = l = 0.
θθ =
Una claseAn importante
important de ecuaciones
class of cubic cúbicas results
cubic equations
equations resultafrom
de lathe
ecuación
precedinganterior haciendo
equation lasas-
with the
the designa-
An important class of
ciones: signments: results from the preceding equation with as-
signments:
= bb
ηη = = a(T
θθ = a(T )) = (�
κκ = + σσ )b
(� + )b λλ = �σ bb22
= �σ
It is
It is thus
thus transformed
transformed into
into an
an expression
expression general
general enough
enough to
to serve
serve as
as aa generic
generic cubic
cubic equation
equation of
of

Para una revisión, véase J. O. Valderrama, Ind. Eng. Chem. Res., vol. 42, pp. 1603-1618, 2003.
10
M. M. 9Abbott, AIChe J., vol. 19, pp. 596-601, 1973; Adv. in Chem. Series 182, K. C. Chao y R. L. Robinson, Jr., eds., pp. 47-70,
For aWashington,
9 For
Am. Chem. Soc., a review,
review, see
see D.
J. O.
J. O. Valderrama,
C.,Valderrama,
1979. Ind. Eng.
Ind. Eng. Chem.
Chem. Res.,
Res., vol.
vol. 42,
42, pp.
pp. 1603–1618,
1603–1618, 2003.
2003.
10 M. M. Abbott, AIChE J., vol. 19, pp. 596–601, 1973; Adv. in Chem. Series 182, K. C. Chao and R. L. Robinson,
10 M. M. Abbott, AIChE J., vol. 19, pp. 596–601, 1973; Adv. in Chem. Series 182, K. C. Chao and R. L. Robinson,
Jr., eds.,
Jr., eds., pp.
pp. 47–70,
47–70, Am.
Am. Chem.
Chem. Soc.,
Soc., Washington,
Washington, D.C.,
D.C., 1979.
1979.

3.5.
3.5. Cubic
3.5. Ecuaciones
3.5.
3.5. Cubic
Cubic Equations
cúbicas
Equations
Equationsof
ofState
de estado
of
State
State 93
93
93 93
3.5. Cubic
Cubic Equations
Equations of
of State
State 93
93
Así, ésta se transforma

state,
state,
state, which
whichreduces
which en una
reduces
reduces toexpresión
to
to all
allothers
all othersof
others general
ofinterest
of bastante
interest
interesthere
here útil assignment
hereupon
upon
upon como una ecuación
assignment
assignment of de estado
ofappropriate
of appropriate
appropriate cúbica genérica,
parameters:
parameters:
parameters:
state, which reduces to all others of interest here upon assignment of appropriate parameters:
la cual se reduce
state, whicha todas las otras
reduces to all ecuaciones de interés,
others of interest here pero
uponbajo la designación
assignment de parámetros
of appropriate parameters:apropiados:
RT
RT
RT − a(T
a(T)))
a(T
PP =
P
P = V RT
=
= RT
− b −
−(V + �b)(V
−
a(T
a(T )) + σ b) (3.42)
(3.42)
(3.42)
(3.42)
P=V −
VV −−bbb − (V
(V +
(V ++�b)(V
�b)(V
�b)(V + ++σσσb)b)
b) (3.42) (3.42)
V − b (V + �b)(V + σ b)
For
Foraaaagiven
For
For givenequation,
given
given equation,��and
equation,
equation, andσσσ are
and arepure
are purenumbers,
pure numbers,the
numbers, thesame
the samefor
same forall
for allsubstances,
all substances,whereas
substances, whereasparam-
whereas param-
param-
Para unaForecuación
eters a given
a(T conocida,
equation,
and b are � and
and
substance
are
y s σσson
are
pure
números
pure
dependent.
numbers,
puros,
numbers,
The
the
the
same
iguales
same
temperature
for
para
for
all
all
substances,
todas las of
substances,
dependence a(T
whereas
sustancias,
whereas
param-
mientras
param- que los
eters a(T
etersa(T
eters ) and
andbbbare
a(T)))and are substance
aresubstance dependent.
substancedependent.
dependent. TheThe temperature
Thetemperature dependence
temperaturedependence
dependenceof of a(T))))is
a(T
ofa(T isisspecific
is specificto
specific
specific to
to
to
parámetros
eters a(T)
a(T y
) b
anddependen
b are de
substancela sustancia.
dependent. La dependencia
The temperature de la temperatura
dependence of de
a(Ta(T)
) is se especifica
specific to para
each
eachequation
each
each equationof
equation
equation ofstate.
of
of state. For
state.
state. Forthe
For
For thevan
the
the vander
van
van derWaals
der
der Waalsequation,
Waals
Waals equation,a(T
equation,
equation, a(T)))) =
a(T
a(T = aaaa is
=
= isisaaaasubstance-dependent
is substance-dependent
substance-dependent
substance-dependent
cada ecuación
each de estado.
equation of Para
state. la ecuación
For the van de van
der der
Waals Waals, a(T)
equation, =
a(T a,
) es
= una
a is constante
a que depende
substance-dependent del tipo
constant,
constant,and
constant, and��=
and ==σσσ ===0.0.
0.
constant,
de sustancia,
constant, = s ��= =
y  and
and =0. σσ =
= 0.
0.
Determination
Determinationof
Determination ofEquation-of-State
of Equation-of-StateParameters
Equation-of-State Parameters
Parameters
Determination
Determinación
Determination of
de los Equation-of-State
ofparámetros Parameters
de la ecuación
Equation-of-State de estado
Parameters
The
Theconstants
The
The constantsin
constants
constants ininan
in anequation
an
an equationof
equation
equation ofstate
of
of statefor
state
state foraaaparticular
for particularsubstance
particular substancemay
substance maybe
may beevaluated
be evaluatedby
evaluated byaaaafit
by fitto
fit to
to
Las constantes
The
available enPuna
constants
V Tecuación
in an
data. de estado
equation
For of
cubic para for
state unaaasustancia
for
equations
particular
particular
of state,
substance
particular
substance
however, es may
may
suitable
be
posible
be
evaluated
evaluarlas
evaluated
estimates
by
by
are a
fit
mediante
fit
usually
to
toun ajus-
available
available P
available PPVVVT
TT data.
data.
data. For For cubic
For cubic equations
cubic equations
equations of of state,
of state, however,
state, however, suitable
however, suitable estimates
suitable estimates are
estimates are usually
are usually
usually
te de lafound
información
available PV TPVTdata. disponible.
Forcritical
cubicNoequations
obstante, of para
state,lasc .however,
ecuacionesthe de estado
suitable cúbicas,
estimates are lasusually
estimaciones
foundfrom
found
found fromvalues
from
from valuesfor
values
values for
for forthe thecritical
the
the criticalconstants
critical constantsTT
constants
constants TTccccand
andP
and
and PPccc...Because
P Because
Becausethe
Because thecritical
the criticalisotherm
critical
critical isothermexhibits
isotherm
isotherm exhibitsaaaa
exhibits
exhibits
adecuadas usualmente
found se
frominflection
horizontal encuentran
values foratthe a partir
critical de los
constants valores
c
Tmay andimpose para
c las
Pc . Because constantes críticas T
the critical isotherm
c y P . Ya que la
cexhibits a isoter-
horizontalinflection
horizontal
horizontal inflectionat
inflection atatthe
thecritical
the
the criticalpoint,
critical
critical point,we
point,
point, wemay
we
we may
cmay impose
impose
impose the
themathematical
the
the mathematicalconditions:
mathematical
mathematical conditions:
conditions:
conditions:
ma crítica exhibe una inflexión horizontal en el punto crítico, podemos
horizontal inflection at the critical point, we may impose the mathematical conditions: imponer las condiciones matemáticas:
� �� 2 � ��
��∂ P �
� ��
� ∂∂∂∂2222P
�
�
� ∂∂PP�
∂ P = P
P P =
P
∂∂∂∂∂V =0000
=
= (3.43)
(3.43)
(3.43)
(3.43) ∂∂∂∂∂V
2 P2 =0000
=
= (3.44)
(3.44)
(3.44)
(3.44)
VV TTTT;cr
V ;cr
;cr
;cr
=0 (3.43) VVV22222 T ;cr = 0 (3.44)
∂ V TT ;cr ∂ V TT ;cr TT;cr
;cr
;cr ;cr T ;cr
donde el subíndice
where
where
where
where the
the
the “cr” denota
thesubscript
subscript
subscript
subscript “cr”el
“cr”
“cr”
“cr” denotespunto the
denotes
denotes
denotes crítico.
the
thethecritical
critical
critical
critical Derivando
point.
point.
point. la ecuación (3.42)
point.Differentiation
Differentiation
Differentiation
Differentiation of
ofEq.
of
of Eq.
Eq.
Eq. produce
(3.42)
(3.42)
(3.42) expresiones
(3.42)yieldsyieldsexpres-
yields
yields expres-
expres-
expres- para am-
where
bas derivadas, the
las subscript
cuales se “cr”
pueden denotes igualar the a critical
cero point.
para = Differentiation
, = = of Eq. (3.42)
= yields expres-
=
sions
sions
sions
sions
for
for
for
for
both
both
both
both
derivatives,
derivatives,
derivatives,
derivatives,
which
which
which
which
may
may
may
may
be
be
bebe equated
equated
equated
equated P to
to
totoPzero
zero
zero
c
zero T for
for
for
for T cP = Pccc,c T = Tccc, and V = Vccc.... puede
P
P y
P V
=
= = P
PV
P
c ,,,.
T TTLa ==ecuación
T
TTc ,
, ,and
and
and Vde
V
V estado
=
= V
VVc
sions
escribirse
The paraforlas
both
equation derivatives,
condiciones
of state maycríticas.which
itself may
Estas
be writtenbe
tres equated
ecuaciones
for the tocritical
zero for
contienen P =cinco
conditions. Pcc , T = Tcthree
constantes:
These V, V=, VTcc,. a(T ) y
, andequations
The
The equation
equation of
of state
state may
may itself
itself be be
The equation of state may itself be written for the critical conditions. written
written for
for the
the critical
critical conditions.
conditions. Thesecthree
These
These threePequations
three equations
c c c
equations c
The equation
b. Entrecontain five of state may itself be written for the critical conditions. These three equations
contain
contain fiveconstants:
las diferentes
contain five
five manerasP
constants:
constants:
constants: P ccc,,,,V
PPdec VVcccc,,,,TT
tratar
V TTcccc,,estas
,,a(T
a(T c),),and
a(Tcccecuaciones,
a(T ),
), andb.
and
and b. Of
b.
b. Oflathe
Of
Of themás
the
the several
adecuada
several
several
several ways
wayses
ways
ways totolatreat
to
to treat
treat
treat these
theseequations,
eliminación
these
these de Vc para ob-
equations,
equations,
equations,
contain
the five constants: Pcc ,a(T Vcc ,) Tyof cc , a(Tcc ), and b. Of the several ways to treat these equations,
themost
the mostsuitable
tener expresiones
the most
most que
suitable
suitable
suitable is
isiselimination
relacionen
is elimination
elimination
elimination c of of bV
of aV
VVcP to
to
to
cc cto yyield c. Laexpressions
Tyield
yield
yield razón es que
expressions
expressions
expressions relating
Pc y Tca(T
relating
relating
relating a(T
a(T
a(T )and
andbbbbto
soncccc)))conocidas
and to P
to PPccc and
con másTT
and
and .
TTcprecisión
cc...
the most suitable is elimination of Vccc tomore yieldaccurately
expressions relating a(T cc ) and to P and
and b to Pccc and Tccc .
que Vc.The
The
The reason
reason
reason is
isisthat
that
that P
PPc and
and
and T T Tc are
are
are usually
usually
usually
The reason is that Pcccc and Tcccc are usually more accurately known than Vcccc. more
more accurately
accurately known
known
known than
than
than V
VV c .
. .
The reason
An is thatequivalente
Pc but
and Tc are usually more accurately known than Vc .for
Un Anequivalent,
procedimiento
An
An equivalent,
equivalent,
equivalent, butmore
but
but more
more
more pero straightforward,
más directo
straightforward,
straightforward,
straightforward, seprocedure
ilustra para
procedure
procedure
procedure is
is illustrated
isisla ecuación
illustrated
illustrated
illustrated de
for
for the
thevan
forvan
the
the der
van
van der
derWaals
vanWaals.
der
der Puesto que
Waals
Waals
Waals
V = Vc equation.
para An
cada equivalent,
Because
una de las V but
=
tres
= V more
raíces for straightforward,
each
en el ofpuntothe three
crítico, procedure
roots at the is illustrated
critical point, for the van der Waals
equation.
equation. Because
Because VV = V Vc for
for each
each of
equation. Because V = Vcccc for each of the three roots at the critical point,of the
the three
three roots
roots at
at the
the critical
critical point,
point,
equation. Because V = Vc for each of the three roots at the critical point,
3
(V(V −
(V
(V −
−−V VVVccc))))3333==
==0000
(V − Vccc )3 = 0
3 2 2 − V 333= 0
o or
or
or
or V
VVV3333− −
− −3V 3VcccV
3V
3V VV2222+
V +
++3V 3V
3V3Vc2222V VVV − −−V =
VVc33 ==000 (A)
(A) (A)
(A)
(A)
or V 3 − 3Vccc V 2 + 3Vcccc2c V − Vcccc3c = 0 (A)
Equation
Equation
Equation (3.41),
(3.41),
(3.41), written
written
written for
for
for=(T (T
(T (T = == T , P
TTccc=c,,,PPP)= =
==P P
P ) and
Pcccc)))and
and expanded
andexpandedexpanded
expanded in
in polynomial
in polynomial
polynomial form,
form,
form, becomes:
becomes:
becomes:
La ecuación (3.41),
Equation (3.41),escrita
writtenpara for (T (TTc= = , PT
� P c =y � desarrollada en forma in polinomial,
in polynomial es: becomes:
form,
Equation (3.41), written for ��Tcc , PRT
� ��cc ) and expanded
P
�
polynomial form, becomes:
3 � RTcccc� V 2222+ aaaa V − ab
RT
RT ab
ab = 0
ab
VVV33333− −−− bbbb+ ++ + RT cc V VV22 + ++ Pa V VV − −
− ab =
==000 (B)
(B)
(B) (B)
PPcccc = 0
V P P (B)
V − b+ P PPccc V + P
c PPcccV − P
c (B)
Pcc Pcc Pc c
where
where
where
where parameters
parameters
parameters
parameters aaaaand
andbdependientes
and
and bbbare aresubstance
are
are substance
substance
substance dependent,
dependent,
dependent,
dependent, but
but
but
but independent
independent
independent
independent of
oftemperature.
of
of temperature.
temperature.
temperature.
donde los parámetros
whereTerm-by-term
parameters a y b
a son
and b
comparison are substance
of Eqs. de la sustancia,
dependent,
(A) and (B) but pero independientes
independent
provides three of de la temperatura.
temperature.
equations:
Term-by-term
Al compararTerm-by-term
Term-by-term
término acomparison
comparison
comparison
término las of
ofof Eqs.
Eqs.
Eqs.
ecuaciones (A)
(A)
(A) and
and
and
(A) (B)
(B)
(B)
y (B) provides
provides
provides
se obtienen three
three
three equations:
equations:
equations:
tres ecuaciones:
Term-by-term comparison of Eqs. (A) and (B) provides three equations:
RTRTcccc (C) 3V 222= aaaa
RT
RT 333= abab
ab
ab
3V
3V
3Vccc=
=
= bbbb+
+ + RT cc (C)
(C) 3V
3V 22 = =
= a (D)
(D)
(D) V
VV 3 == ab (E)
(E)
(E)
3V c =
3Vc = b + P
c + P
PPccc
c
(C) 3V
(C) 3Vc = P
c
c
c
c2c P
PPccc
c
(D)
(D) Vc = P
V c
c
c
c33c = P
PPcccc
(E)
(E)
Pcc Pcc Pcc
Solving
Al resolver
Solving
Solving Eq.
Eq.(D)
la ecuación
Eq. (D)
(D)for
(d)
for a,
a,combining
forpara
a, a, combinarthe
combining
combining el result
the
the resultwith
resultado
result with
with Eq.
con la(E),
Eq.
Eq. (E),and
(E), andsolving
ecuación
and (e)
solving
solving forforbbbgives:
y resolver
for para b se encuentra que:
gives:
gives:
Solving
Solving Eq.
Eq. (D)
(D) for
for a,a, combining
combining the the result
result with with Eq.Eq. (E),
(E), and
and solving
solving for for bb gives:
gives:
2 111
aaaa==3P
=
= 3PccccV
3P
3P VVccc2222c2
V bbbb=
= 311 V
=
= VVccc
V
a = 3Pc Vcc
c b = 333Vccc
3

94
94 CHAPTER 3.
Properties of of Pure
Pure Fluids
Fluids
Substitution
Substitution for for
for bb inb in Eq.
in Eq.
Eq. (C) (C) allows
(C) allows solution
allows solution
solution for for V
for Vc , whichwhich can can thenthen be be eliminated
eliminated from from the the
Substitution
equations for a and b: Vcc,, which can then be eliminated from the
equations
Substitution
equations forfor
for a and
andb inb:b:Eq. (C) allows solution for Vc, which can then be eliminated from the
Sustituyendo a b en laa ecuación (c) se puede encontrar a V2c, la que después se elimina de las ecuaciones para
a y b: equations for a V and b:33 RT RTcc 27 R
27 R22 TTc222 1 RTRTcc
V c= = 3 RTc a=
a = 27 R Tcc b=
b = 11 RT
c
Vc = 838 RT Pcc
P a = 64 64 P 2PTcc c2
b = 818 RT Pccc
P
8 P c 27 RP
64 8 Pcc
V c = c a = c b =
Although
Although these these equations
these equations 8
equations cmay P may
may not not yield
not yield
yield the the
the best best
64 possible
P
best possible
possible
c
results,
results, they they provide
8
they provide
provide P reasonable val-
reasonable
c reasonable
val-
Although
ues which can almost always be determined, because results,
critical temperatures and pressures val-
(inrazona-
Aunqueues conwhich
ues
Although estasthese
which ecuaciones
can almost
can almost
equations no
always
alwaysse
may obtienen
be los the
determined,
notdetermined,
be yield mejores best resultados
because
possible
because critical posibles,
results,
critical theysíprovide
temperatures
temperatures proporcionan
and
and valores
pressures
reasonable
pressures (in
val-
(in
contrast
bles quecontrast
casiwhich to
siempre extensive P V T data) are often known, or can be reliably estimated.
contrast
ues to canse
to extensive
extensive pueden
almost PV V Tdeterminar,
always data) are
beare ya que
often
determined, lasbecause
known, temperaturas
or cancan ytemperatures
be reliably
critical presiones
reliably estimated.críticas (en contraste
and pressures (in con la
gran cantidad Substitution
de información
Substitution forPV
for VccTin
PVT) indata)
the equation
con
the
often
equation
frecuencia
known,
for
for sonthe
or
theconocidas
critical
critical
be
compressibility
o se calculan
compressibility
estimated.
defactor
manera
factor reduces
fiable.
reduces it im-
it im-
contrast to extensive
Substitution P V T data) are often known, or can be reliably estimated.
Lamediately
sustitución to:de V for Vc in the equation for the critical compressibility factor reduces it im-
mediately
mediately to:
Substitution
to: c en
forlaVcecuación para el factor
in the equation for Pthe de critical
compresibilidad compressibility crítico la reduce
factor inmediatamente
reduces it im- a:
PccV Vcc
V 33
mediately to: Z c
Zc ≡ ≡
≡ RT P c c = = 3
Z c RT
P c = 8 8
RTc Vccc 83
A single
A single
single valuevalue
value for for
for Z Z , applicable
Z cc,, applicable
applicable alike alike
alike toZtoc ≡
to allall substances,
all substances,
substances, = results whenever
results whenever the the parameters
parameters of of aa
ResultaA un solo valor
two-parameter para
equationZcc, el of cual es apropiado
state are found deRT
by igual
c manera
imposition
8 results
of para
the todas las
whenever
critical sustancias,
the parameters
constraints. cadaofvez
Different a que se
two-parameter equation of state
state are are found bysubstances,
impositionresults of the
the critical
critical constraints.
constraints. Different
encuentran
A los
single
two-parameter
values are parámetros
value
are found
found forfor
equationZdec , una
for different of ecuación
applicable
different equations de
alike
equations of estado
foundto allby
of state, de
state, as dos
imposition parámetros
as indicated
indicated in of mediante
in Tablewhenever
Table 3.1, 3.1, p. la
theimposición
p. 98. Unfortunately,a restric-
parameters
98. Unfortunately, de of
Different las
values
ciones críticas.
two-parameter
values
the values Se
are
values so encuentran
found equation
so obtained for
obtained do valores
different of
do not state
not in diferentes
are
equations
in general found
of
general agree paraby
state,
agree with lasas distintas
imposition
indicated
with those ecuaciones
of
those calculated the
in critical
Table
calculated from de
3.1, estado,
constraints.
p. 98.
from experimental como se
Unfortunately,
experimental indica en la
Different
values
the values
tabla 3.1.
the Por
values
values
of TTcc,, P desgracia,
are found
so
Pcc,, and
and V obtained los
for
Vcc;; each valores
different
do
each chemical not así
in
chemical species obtenidos
equations
general
species in of
agree
in factpor
state, with
fact has lo
as general
indicated
has itsthose
its own no
in están
Table
calculated
own valuevalue of de
3.1,
from acuerdo
p. 98.
of ZZcc.. Moreover, con los calculados
Unfortunately,
experimental
Moreover, the values
the values
values a
of values
partir deoflos
the T c
given invalores
values
, P c , so
and
in Table experimentales
Table B.1 obtained
V c ;
B.1 ofeach do
of App. not
chemical
App. B de inT
B for , P
general
species
c various
for c y V in;
agree de
fact hecho,
with
has cada
those
its own especie
calculated
value química
of
c substances are almost all smaller than any of the from
Z c . tiene
Moreover, su
experimental propio
the valor
values de Z c.
given various substances are almost allZsmaller
smaller than any
any of the
the
Además, of casi
T
given c , todos
P
in c
equation values, and
Table los V
values given valores
B.1
c ; each
of
given in proporcionados
chemical
App.
in Table B
Table 3.1. for
3.1.species
various enin la
fact tabla
substances has B.1
its del
own
are apéndice
value
almost of
all B c para
. diferentes
Moreover,than the sustancias
values
of son
equation
más pequeños
given An
equation inque Tablecualquiera
values
analogous B.1
given of inde
App.
procedure los B
Table valores
for
3.1.
applied obtenidos
variousto thethe a partircubic,
substances
generic de las
are ecuaciones
almost
Eq. all smaller
(3.42), en lathan
yields tabla 3.1.of the
any
expressions for
An values
analogous procedure applied to generic cubic, Eq. Eq. (3.42), yields expressions for
Un procedimiento
equation
parametersAn analogous
a(T c ) análogo
given
and in
procedure
b. Forque
Table these
3.1.puede
applied
former, aplicar
to the a
generic la cúbica
cubic, genérica, (3.42),ecuación
yields (3.42), produce
expressions for expre-
parameters a(Tc)) and andprocedure
b. ForFor the theapplied
former,to the generic cubic, Eq. (3.42), yields expressions for
siones para los
parametersAnparámetros
analogous
a(T c a(T b. c) y b. Para la
former, anterior,
parameters a(Tc ) and b. For the former, RR222TTc222
a(T
a(T c)) == �� R Tcc
a(Tcc) = � RP P
2T c2
a(T c ) = � Pcc c
Este resultado
This result
This se puede
result is extended
is extender
extended to a temperaturas
to temperatures
temperatures other
otherdiferentes
than the
than thePde c la crítica
critical
critical mediante laof
by introduction
by introduction ofintroducción
a dimensionless
dimensionless de una fun-
This resultα(T is extended to temperatures other than the critical by introduction of aa dimensionless
ción adimensional
function
function α(T a(T ) ), que
that
rr ) rthat es igualunity
becomes
becomes a uno
unity at
at en
the
the lacritical
temperatura
critical temperature.
temperature. crítica. Thus Así
Thus
This result
function α(T isrextended
) that becomes to temperatures
unity at the other thantemperature.
critical the critical byThus introduction of a dimensionless
function α(Tr ) that becomes unity at the critical temperature. Thus
α(Trr )R
α(T )R222TTc222
a(T )) =
a(T =� � α(T r )R Tcc (3.45) (3.45)
(3.45)
a(T ) = � α(TrP Pcc 2 2
)R T (3.45)
a(T ) = � Pc c (3.45)
La función a(Tr)α(T
Function es una
α(T rr ) isexpresión
) is an empirical empírica,
expression, específicaspecific para P
tocuna ecuaciónequation
a particular
particular de estado
equation particular
of state
state (Table
(Table (tabla
3.1).3.1). El
Function
Function α(T an empirical
is an empirical
)given expression, specific to a
expression, specific to a particular equation of state (Table 3.1). of 3.1).
parámetro b se conoce
Parameter
Parameter b r
is por: by: by:
Function α(T
Parameter bb is
isr )given
given
is an by: empirical expression, specific to a particular equation of state (Table 3.1).
Parameter b is given by: RTcc
RT
b=
b =� � RT (3.46)
(3.46)
b = � RT Pccc
P (3.46) (3.46)
b = � Pc
c
(3.46)
In these
In these equations
equations � � andand � � areare pure
pure numbers,
numbers, independent Pc
independent of substance
of substance and and determined
determined for for aa
In these equations �ofand � fromare pure numbers, independent of σsubstance
.sustancia,and determined for a
En estasparticular
ecuaciones
particular W y Ψofson
equation
equation state
state números
from the
thepuros
values
values e independientes
assigned
assigned to �� and
to de la
and σ . que se determinan para una
In these
particular equations
equation �of and
state � are
from pure
the numbers,
values assigned independentto � and ofσ substance
. and determined for a
ecuación de estado The modern
The particular
modern a partir deof
development
development oflos valores
cubic
cubic equations
equations asignados of state
of a  was
state y s.initiated
was initiated in in 1949
1949 by by publication
publication
particularThe equation
modern of state
development from ofthe values
cubic 11 assigned
equations of to
state� and
was σ .
initiated in 1949 by publication
Elof
ofdesarrollo
the Redlich/Kwong
the moderno de
Redlich/Kwong (RK)
(RK) las equation:
ecuaciones
equation:11 11 de estado cúbicas se inició en 1949 con la publicación de la
of the The modern development
Redlich/Kwong (RK)
11 of cubic equations of state was initiated in 1949 by publication
equation:
ecuación Redlich/Kwong (RK): 11 RT a(T ))
of the Redlich/Kwong (RK) equation: P= = RT RT − a(T a(T (3.47)
P − ) (3.47)
P = V VRT −
− bb − VV (V
(V
a(T +) b)
+ b) (3.47)
P = V − b − V−1/2 (V + b) (3.47) (3.47)
where
where a(T
a(T )) is
is given
given by
by Eq.
Eq. (3.45)
(3.45) with
with V
α(T
α(T − b) = TV
r ) = Trr−1/2 (V .+
−1/2 . b)
where a(T ) is given by Eq. (3.45) with α(Tr ) = Tr r .
−1/2
–1/2 .
where
donde a(T) a(T ) is given by Eq.
11 se conoce por la ecuación (3.45) con a(T ) = T
(3.45) with
r pp. 233–244,
r
α(T r ) = T r .
Otto Redlich
11 Otto Redlich and
and J.
J. N.
N. S.
S. Kwong,
Kwong, Chem.
Chem. Rev.,
Rev., vol.
vol. 44,
44, 1949.
pp. 233–244, 1949.
11 Otto Redlich and J. N. S. Kwong, Chem. Rev., vol. 44, pp. 233–244, 1949.
11 Otto Redlich and J. N. S. Kwong, Chem. Rev., vol. 44, pp. 233–244, 1949.
Otto Redlich and J. N. S. Kwong, Chem. Rev., vol. 44, pp. 233–244, 1949.
11 Otto Redlich y J. N. S. Wong, Chem. Rev., vol. 44, pp. 233-244, 1949.

3.5. Ecuaciones cúbicas de estado 95
3.5.3.5.
3.5.Cubic
3.5. Cubic
Equations
Cubic Equations
Equations
Cubic ofofState
Equations of State
State
of State 959595
95
Teorema de estados correspondientes; factor acéntrico

Theorem
Theorem
Theoremofofof
Theorem of
Corresponding
Corresponding
Corresponding States;
Corresponding States;
States;Acentric
States; Acentric
AcentricFactor
Acentric Factor
Factor
Factor
Las observaciones
Experimental
Experimental experimentales
observation
observationshowsmuestran
shows
that thatque los factores
compressibility
compressibility
factorsde Z
compresibilidad
factors para
Zfluids diferentes fluidos
Experimental
Experimental observation
observation shows
shows thatthatcompressibility
compressibility factors
factorsZfor
Z for
different
Zforfor different
different
differentfluids
fluids exhibit
fluids exhibit
exhibit simi-
exhibit simi-
simi-
simi-
exhiben una
larlarlar conducta
behavior
lar behavior
when similar
when cuando
correlated
correlated
asasaas
asse correlacionan con una función de temperatura reducida T r y una
behavior
behavior when
when correlated
correlated afunction
afunction
function
afunction ofofreduced
of
of reduced
reduced temperature
reduced temperature
temperature
temperature TrTrand
TTand
r and
reduced
reduced
reduced pressure
pressure
pressure
r and reduced pressure rPr ;
PrP; P
; r;
presión reducida
bybyby
definition,
by Pr; por
definition, definición,
definition,
definition,
TT TT PP PP
TrTr≡ ≡ and yand
PrPr≡ ≡
TTr≡
r≡
TcTcTTc and
and PP≡
r
r≡
PcPcPPc
c c
Estas Thesecoordenadas
These
These
These termodinámicas
dimensionless
dimensionless
dimensionless
dimensionless thermodynamic
thermodynamic adimensionales
thermodynamic
thermodynamic coordinatesproporcionan
coordinates
coordinates
coordinatesprovide
provide
provide the
provide thelas
the
the bases
basisbasis
basis for
basisfor para
the
for
forthe lasimplest
the forma
simplest
the simplest
simplest más
form form
form
form simple
del teorema
ofoftheof
ofthe de
the estados
theorem
theorem
thetheorem of correspondientes:
corresponding
of corresponding
theoremofofcorresponding states:
correspondingstates: states:
states:
TodosAll All
All
losfluids,
fluids,
fluids,
fluidos,
All when
fluids, when
when
cuando
when compared
compared
compared
se atatthe
les compara
compared at
atthethe
same
the same
same
consame reduced
reduced
reduced
la misma temperature
reduced temperature
temperature
temperatura and and
and
y presión
temperature andre-
re-re-
reducidas,
re-
duced
duced
duced pressure,
pressure,
ducedpressure,
tienen aproximadamente have
pressure,el have
have approximately
approximately
approximately
mismo
have the
thethe
samesame
thesame compressibility
compressibility
samecompressibility
factor de compresibilidad
approximately factor,
factor,
factor,
y todos se desvían
compressibility del com-
factor,
andand
and
portamientoall
alldeviate
all
del deviate
deviate
gas fromfrom
from
ideal ideal-gas
casi ideal-gas
ideal-gas
al mismo behavior
behavior
behavior
grado. totoabout
to about
aboutthe
thethe
and all deviate from ideal-gas behavior to about the same degree. same
same
samedegree.
degree.
degree.
Corresponding-states
Corresponding-states correlations
correlations
correlations
correlations ofofZof
ofZbased
ZZ
based based ononon this
on
this this
theoremtheorem
theorem areare are
called called
called two-parameter
two-parameter
two-parameter corre-corre-
corre-
Las correlaciones
lations,
lations, because de estados
because they they correspondientes
requirerequire use use
of the
of debased
the
two Ztwo están
reducing reducing
this
basadas theorem
parameters en este
parameters
are
T
called
teorema
T
and andP
two-parameter
.yPAlthough
se. conocen
Although these
corre-
como
thesecorre-
lations,
lations, because
because they they require
require use of
use of thethe two two reducing
reducing parameters
parameters T
c and
c P
c . c Although
cTc and cPc . Although these these
laciones de
correlationsdos
correlations parámetros,
are are
very very porque
nearly nearly requieren
exact exactfor the
for del
the
simple usosimple de
fluidslos dos
fluids
(argon, parámetros
(argon, krypton,
krypton, reducidos
and and
xenon) T c
xenon), y P systematic estas
c
systematic. Aunque
correlations
correlations areare very
very nearly
nearly exact
exact for for the the simple
simple fluids
fluids (argon,
(argon, krypton,
krypton, and and xenon)
xenon) systematic
systematic
correlaciones
deviations están
deviations are cerca
observed
are de
observed ser
for exactas
more
for more para
complex fluidos
complex fluids. simples
fluids. Appreciable (argón,
Appreciable kriptón
improvement
improvementy xenón) results se observan
resultsfrom from
intro- desviacio-
intro-
deviations
deviations areare observed
observed forfor more
more complex
complex fluids.
fluids. Appreciable
Appreciable improvement
improvement results
results fromfrom intro-
intro-
nes sistemáticas
ductionduction para
ofofaof of fluidos más complejos. Los resultados mejoran de manera apreciable a partir de la
ofintro-
duction
duction athird
a third
third
athird corresponding-states
corresponding-states
corresponding-states parameter parameter
parameter
parameter (in addition
(in
(in(in addition
addition
addition totoTto to TTcand
cTcand and
c andPcP),cPP ),ccharacteristic
c),), characteristic
characteristic
characteristic ofofof
ducción de
molecular un
molecular tercer
structure; parámetro
structure; the the
most de
most estados
popularpopular suchcorrespondientes
such parameterparameter isisthe (además de T c , y P c ), característico byde la
estructura
molecular
molecular
molecular;
structure;
structure;
el más
thethe
popular
most
most
12 de
12
popular
popular
estos
suchsuch
parámetros
parameter
parameteres el isis
factor
the the
acentric
the acentric
acentric
acentric
acéntrico
factor factor
factor
factor
w,
ω,ω,ω, introduced
introducido
ω, introduced
introduced
introducedpor
bybyby
K. S. Pitzer
K.K.S. K.
K. S.Pitzer
S.
S. Pitzer
Pitzer andand
12 and
Pitzer and
coworkers.
coworkers.12
coworkers.
coworkers.
12
y colaboradores. The Theacentric
acentric factor factorfor for
a apure a pure
purechemicalchemical species species isisdefined
El factor
The
The acentric
acentric
acéntrico
factor
para factor
una
for for
especie apure chemical
chemical
química pura
species
species
estáofdefinido isis defined
defined
defined with
with
confluid
with
withreference
respecto
reference
reference
reference totoits to
to
a su presión
vapor
its
itsits vapor
vapor
vapor
de vapor.
pressure.
pressure.
pressure.
pressure. Because
Because
Because
Because thethe the
logarithm
logarithm
logarithm
thepresión
logarithm ofof the
ofthe the
vapor
vapor
of thedevapor vapor pressure pressure
pressure
pressure of a ofpure
a a
purepure
fluid
fluid
ofesa aproximadamente is isapproximately
is approximately
approximately
pure fluid is approximately linear linear
linear
linear con
Puestoinque el logaritmo de la de vapor un fluido puro lineal en relación
inthe
in
inthe the
reciprocal
the reciprocal
reciprocal ofofabsolute
of absolute
absolute temperature,
temperature,
temperature,
el recíproco de reciprocal
la temperatura of absolute
absoluta, temperature,
d log dlog log satsat
PsaturadoP sat
d dlog dlog PrrP rPrrsat
= S= S
d(1/T d(1/T ) )==S S
dd(1/T
1 / rTrr ))rr)
(d(1/T
dondewhere saturado PrPsat
es satthe
Pisla presión de vapor reducida, TTrrTes
Pwhere
where isis the
reducedreduced vapor vapor pressure,
pressure, TTrisla
ris rthe temperatura
isis the
reduced reduced reducida,
temperature,
temperature, yandSand es Sla
and SisSSpendiente
the
isis the
slope de
ofofuna
slope of grá-
sat
rwhere rPrrsatissatthethe reduced
sat reduced
vapor
vapor pressure,
pressure, thethe reduced
reduced temperature,
temperature, and is thethe slope
slope of
fica dea log P saturado en función de 1/T . Observe que “log” denota un logaritmo de base 10.
aplot
a
plotplot
a plotof oflog
of
r of loglog log
P P P
satvs.
vs.
sat
r rP r vs. 1/T1/T
vs. 1/Tr1/T
. Note
. .
Note
r Note
that
r that
that “log”
“log”“log” denotes denotes
denotes a
r r . Note that “log” denotes a logarithm to the base 10. alogarithm
a logarithm
logarithm to tothe
tothe the
base
base base
10.10. 10.
r
Si el teorema
IfIfthe
IfIf
the the
the detwo-parameter
estados correspondientes
two-parameter
two-parameter
two-parameter theoremtheorem
theorem
theorem of con
ofofcorresponding
ofcorresponding dos parámetros
corresponding
corresponding states
statesstates
states enwere
were
were general
were generally fuera
generally
generally
generally valid,válido,
valid,
valid,
valid, thethe la
the
slope
the pendiente
slope
slope
slope S
sería laSSmisma
S
would would
would para
be be todos
the
bethe the
same los
samesame fluidos
forfor for
all all puros.
pure
all
pure pure Sin
fluids. fluids.
fluids. embargo,
This ThisThis
S would be the same for all pure fluids. This is observed not to be true; each fluid has its is is no
observed
is se
observed
observed ha observado
not
not not
to to be
tobe que
true;
betrue; esto
true;eacheach sea
eachfluid cierto;
fluidfluid
hashas cada
has
itsitsitsfluido
tiene su
own propio
own own
own valor característico
characteristic
characteristic
characteristic
characteristic value
valuevalue
value ofofS,ofofdeS,
S, S,which que
S,which
which which coulden
could
could principio
could ininprinciple
inin puede
principle
principle
principle serve servir
serveserve
serveasasaascomo
asathird elcorresponding-states
a third
third
athird tercer parámetro de estados
correspondientes.
parameter.
parameter.
parameter. No obstante,
However,
However,
However, PitzerPitzer
Pitzer
Pitzer notedobservó
noted
noted
parameter. However, Pitzer noted that all vapor-pressure that
that que
that
all
all todos
vapor-pressure
all los
vapor-pressure
vapor-pressure datos de
data
datapresión
data
forfor for
the de
the thevapor
simple simple
simple
data for the simple fluids para
fluids los
fluids
fluids (Ar,fluidos
(Ar, (Ar,
Kr,
(Ar, Kr, simples
Kr,
Kr,
(Ar, Kr,
Xe) Xe)Xe)
lie seonencuentran
lie the
on the
same sobre
same line la
line
when misma
when plottedlínea
plotted ascuando
log
as log
P satsat
se P sat vs.
grafica
vs. 1/T log
1/TandP saturado
and
that thaten
the función
the
line line
passesde 1/T
passes ,
through y que
through la línea
Xe) lie on the same line when
Xe)satliesaton the same line when plotted as log rPr vs. 1/T plotted as log P
r sat
r vs. 1/T r and
r that the line
r r rand that the line passes through passes through
r
pasa por log saturado
= −1.0
= −1.0 = =
log log rPrr = −1.0 at rTr = 0.7. This is illustrated in Fig. 3.12. Data for other fluids definedefine
log
P P P = –1.0
at T en
at TT =
0.7. 0.7.
0.7. Esto
This This se
is ilustra
illustrated
is en
illustrated la
in figura
Fig.
in Fig. 3.12.
3.12. 3.12. Información
Data Datafor for
other para
other otros
fluids fluids fluidos
define define
log P satsat = −1.0 at T = 0.7. This is illustrated in Fig. 3.12. Data for other fluids define
r r r rr
otras líneas
other other
other
other cuyas
lines lines
lines
lines posiciones
whose whose
whose
whose locations se fijan
locations
locations
locations cancan con
can
can respecto
bebefixed
be
befixedfixed
fixed inarelation
ininrelation
in la línea
relation
relation totopara
the
to
tothe the
the fluidos
linelineline
for
line for simples
the
for
for the the
simple
the (FS)
simple
simple
simple fluids mediante
fluids
fluids
fluids(SF)(SF) byla
(SF)
(SF) diferencia:
the
bybybythethe
the
difference:
difference:
difference:
difference:
loglog saturado saturado
P PrPsat sat(SF) –logloglog P
sat satsat sat
log rlog
log
sat
P(SF)
rP r(SF)
(SF)
(SF) −− − −
log PrP
log rPsat
rP r
r r
The
El factor The
acentric
acentric
acéntrico
The acentric
The factor
factor
sefactor
acentric isisdefined
define
factor is
comodefined
defined
is laasdiferencia
defined asthis
as this
this
as difference
this difference
evaluated
evaluada
difference evaluated
en Tr =at0.7:
evaluated
difference evaluated rTr=
atTat
at TTr===
r0.7:0.7:
0.7:
0.7:
ωω≡ satsat sat )
≡−1.0
ωω ≡
≡ −1.0
−−log(P
−1.0
−1.0 −
− log(P
log(Pr r )rsat
log(P T)rT=0.7Tr =0.7
)r T=0.7
=0.7
(3.48)(3.48)
(3.48)
(3.48)
(3.48)
r r
Por loTherefore
tanto, w seωωpuede
Therefore
Therefore
Therefore can
ωω
cancan
can determinar
bebedetermined
be
bedetermined para
determined
determinedfor
forcualquier
any
for
any
for any
fluid
any fluido
fluid
fluid from
fluid TcTa,cTT
from
from
from ,partir
P cP, and
P ,de
, candand ,aPsingle
a aTsingle c, vapor-pressure
csingle yvapor-pressure
devapor-pressure
una sola medición
measure- de la pre-
measure-
measure-
c , cPc , and a single vapor-pressure measure-
sión de vapor
ment ment
ment hecha
mademadeat TaatT=
T =
madeatatTrTr==0.7.
mentmade r r r 0.7.
=
0.7. Los
0.7.
Valuesvalores
Values
0.7.Values of ωof para
andω
Valuesofofωωand and
thew
andthe y
thelas
criticalconstantes
critical
thecritical constants
constants
criticalconstants críticas
T
constantsTcT,cP
c , T
P c
c ,
, TP ,
and
c ,
, cP,cand
c Pand
V
c y V
for
c
, andVcVcfor
c para
a
for varios
number
a number
fora anumber offluidos
numberofofof se
encuentran
fluids
fluidsen
fluids
areel
are
fluidsare apéndice
listed
listed
arelistedin B.
App.
in App.
listedininApp. B.
App.B.B.B.
12 La descripción completa seinS.
encuentra en K. S. Pitzer, Thermodynamics, 3a. ed., apéndice 3, McGraw-Hill,
1212 12 Fully
Fully described
Fully
12 described
described ininK.K.K.K.
S.Pitzer,
S. Pitzer,
Thermodynamics,
Pitzer, Thermodynamics,
Thermodynamics, 3d3ded.,
3d App.
ed.,ed.,
App.App.
3,3,McGraw-Hill,
3, McGraw-Hill,
McGraw-Hill, New
NewNew
York,
York,
1995.
York, 1995. Nueva York.
1995.
Fully described in S. Pitzer, Thermodynamics, 3d ed., App. 3, McGraw-Hill, New York, 1995.

96 96 CAPÍTULO
Properties deFluids
1/Tr 1/Tr
1.0 1.0
1.2 1.2
1.4 1.4
1.6 1.6
1.8 1.8
2.0 2.0
0 0
log Prsaturado
Figura 3.12:
FigureDependencia
3.12: Approximate 1
�1
log Prsat
aproximada con respecto
temperature a la
dependence of Pendiente  2.3
temperatura Slope � �2.3
the reduced vaporde vapor
de la presión
(Ar, Kr, Xe)
(Ar, Kr, Xe)
reducida.pressure.
�2 2
1 1 Slope �Pendiente
�3.2  3.2
1 1   1.43
� �T 1.430.7 (n-Octane) (n-octano)
Tr 0.7 r
La definición de w hace que su valor sea cero para el argón, kriptón y xenón, y la información experi-
mental produceThefactores
definition
de of ω makes its value
compresibilidad parazero
los for
tresargon, krypton,
fluidos and correlacionados
que están xenon, and experimental
por las mismas
data yield
curvas cuando Z secompressibility
representa como factors for all three
una función de Tr fluids that es
y Pr. Ésta arelacorrelated by thedel
premisa básica same curvesteorema
siguiente
when
de estados Z is representedcon
correspondientes as tres
a function of Tr and Pr . This is the basic premise of the following
parámetros:
three-parameter theorem of corresponding states:
Todos los fluidos que tienen el mismo valor w, cuando se les compara con la misma Tr y Pr
Allmismo
tienen el fluidsvalor
having
de Z,the same se
y todos value of ω ,del
desvían when compared atdethe
comportamiento gassame
idealTelr mismo
grado. and P r , have about the same value of Z , and all deviate from ideal-
gas behavior to about the same degree.
VaporVapor
y las &
raíces de la ecuación
Vapor-Like Roots ofde
theestado cúbica
Generic Cubicgenérica
Equation of State
AunqueAlthough
es posibleoneresolver en forma
may solve explícita
explicitly for para sus tres
its three raíces,
roots, la ecuación
the generic cubicdeequation
estado cúbica genérica,
of state,
ecuaciónEq.(3.42), enislainpráctica
(3.42), practiceusualmente se resuelvesolved
far more commonly mediante procedimientos
by iterative iterativos.
procedures. 13 Los problemas
13 Convergence
de convergencia
problems se areevitan
most más
likelyfácil cuando
avoided whenla ecuación se reacomoda
the equation en una
is rearranged to a forma adecuada
form suited para
to the encontrar
solu-
una raíztion
en particular. Para la
for a particular raízFor
root. másthegrande,
largestesroot,
decir, unavolumen
i.e., vapor orde vapor o de
vapor-like algo parecido,
volume, la is
Eq. (3.42) ecuación
(3.42) se multiplicathrough
multiplied por (V by– b)/RT. Ésta entonces
(V − b)/RT . It can se puede
then escribir como:
be written:
RT a(T ) V −b
V = +b− (3.49) (3.49)
P P (V + �b)(V + σ b)
La solución para for

Solution V seVpuede
may be encontrar
by trial,mediante
iteration,ensayo,
or withiteración
the solveoroutine
con unaofrutina de un paquete
a software package.deAn software.
Una estimación inicial for
initial estimate paraVVisesthe
el valor del gas
ideal-gas ideal
value RTRT/P.
/P. ForParaiteration,
la iteración,
this este
valuevalor se sustituye
is substituted onde V en
el lado derecho
the rightde la ecuación
side (3.49).The
of Eq. (3.49). El valor resultante
resulting value ofdeVV on
en el
thelado
leftizquierdo se regresa
is then returned después
to the right al lado
derechoside,
y el and
proceso continúacontinues
the process hasta queuntil
el cambio en Vin
the change esVadecuadamente
is suitably small. pequeño.
Una ecuación para Z,forequivalente
An equation Z equivalenta lato(3.49) se obtiene
Eq. (3.49) a través
is obtained byde la sustitución
substituting V =VZ=RT ZRT/P.
/P. In Además,
la definición de dos
addition, the cantidades
definition of adimensionales
two dimensionlessconduce a la simplificación.
quantities Así,
leads to simplification. Thus,
13 Estos13
procedimientos se encuentran
Such procedures integrados
are built into computerdentro de los
software paquetesfor
packages detechnical
software calculations.
de las computadoras parapackages
With these cálculos técnicos.
one Con
estos paquetes es posible
can solve calcular
routinely for V Vinmediante
equationsuna
suchrutina en ecuaciones
as (3.42) with little como la as
thought (3.42) conitmuy
to how pocaHowever,
is done. labor mental de thought
careful cómo fue hecho.
should
Sin embargo, be tenerse
debe given toespecial
the question of whether
cuidado the answers
con la pregunta de siare
lasreasonable.
respuestas en realidad son razonables.

3.5. Cubic
3.5. Ecuaciones
3.5. Cubic
3.5. Equations
Cubiccúbicas of State
de estado
Equations
Equations of State
of State 97
97
97 97
3.5.
3.5. Cubic
Cubic Equations
Equations of
of State
State 97
97
≡ bbbPP
P (3.50) ≡
a(T
a(T)))
a(T
ββ
β≡ ≡ bRT bPP (3.50) qqq ≡
(3.50) ≡ a(Ta(T )) (3.51)
(3.51)
(3.51)
ββ ≡ ≡ RT RT (3.50) qq ≡
(3.50) ≡ bbbRTRT
RT (3.51)
(3.51)
RTRT bbRT
RT
MedianteWith
estas
With
With these
these
these substitutions
sustituciones,
substitutions
substitutions Eq.
enEq.
Eq. (3.49)
la ecuación becomes:
(3.49) se obtiene:
(3.49) becomes:
(3.49) becomes:
With
With these
these substitutions
substitutions Eq.Eq. (3.49)
(3.49) becomes:
becomes:
ZZ
Z− −
− βββ
ZZ
Z= = +
= 111 +
+ βββ− − qβ
− qβ
qβ (Z + �β)(Z ZZ − − ββ+ σβ) (3.52)
(3.52) (3.52)
(3.52)
ZZ = = 11 ++ ββ − − qβ
qβ(Z(Z + + �β)(Z
�β)(Z + + σβ) σβ) (3.52)
(3.52)
(Z +
(Z �β)(Z +
+ �β)(Z + σβ) σβ)
Equations
Con lasEquations
ecuaciones
Equations (3.50)
(3.50)
(3.50)
(3.50) and
and
and (3.51)
y (3.51)
(3.51)en
(3.51) in combination
combinación
in combination
in combination with with
con las
with Eqs.
Eqs.
Eqs. (3.45)
ecuaciones
(3.45) and
(3.45) and (3.46)
and(3.45) yield:
(3.46)yyield:
(3.46) (3.46) se obtiene:
yield:
Equations
Equations (3.50)
(3.50) and
and (3.51)
(3.51) in in combination
combination with with Eqs.
Eqs. (3.45)
(3.45) and and (3.46)
(3.46) yield:
yield:
= PP
Prrr (3.53) =
qq = �� α(Trrr)))
α(T
� α(T (3.54)
ββ
β= =� �
�P Prr (3.53)
(3.53) q = �� α(Trr))
α(T (3.54)
(3.54)
ββ =
=� �TT Trrr (3.53) qq =
(3.53) = � � TT
� Trrr (3.54)
(3.54)
TTrr �TTrr
�
La solución iterativa
Iterative
Iterative
Iterative de la
solution
solution
solution ofecuación
of
of Eq.
Eq. (3.52)
Eq. (3.52)
(3.52)(3.52)
startsinicia
starts
starts withcon
with
with the
the el valor
value
the value
value Z de
ZZ = =substituted
1 sustituido
= 1Z11 substituted
= substituted on en
on
on theelright
the
the ladoside.
right
right derecho. El
side.
side.
valor calculado
The Iterative
Iterative
de
calculated Z sesolution
solution
regresa
value of of
of
al
Z Eq.
isEq.
lado (3.52)
(3.52)
returnedderechostarts
tostarts
y
the with
elwith the
the value
proceso
right side value
continúa
and the =
=hasta
ZZ process
11 substituted
substituted
la on
on the
the
convergencia.
continues to right
right
El side.
side.final de
valor
convergence.
The calculated value of Z is returned to the right side and the process
The calculated value of Z is returned to the right side and the process continues to convergence. continues to convergence.
The
The calculated
Z produce calculateddel value
value of
of ZZmediante
is returned
isthereturned to the
the right
toZRT/P. right side
side and
and the
theRT process
process continues
continues to
to convergence.
convergence.
Theelfinal
The valor
final
final value
value
value volumen
of
of ZZ
of yields
Z yields
yields the volume
the V=
volume
volume root through
through VV
root through
root V= =
= ZZZ RT
RT/P. /P.
/P.
The
The final
final value
value ofof ZZ yields
yields the the volume
volume root through VV =
root through = ZZRT RT/P.
/P.
Liquid
Liquid
Liquid & Liquid-Like
&raíces
Liquid-Like Roots of
Roots of the
of the
the Generic Cubic
Genericcúbica Equation
Cubicgenérica of
Equation of State
of State
State
Líquido y las&
Liquid
Liquid &
Liquid-Like
& Liquid-Like
Liquid-Like
Roots
de la ecuación
Roots
Roots of de
of the
Generic
theestado
Generic
Cubic
Generic Cubic
Equation
Cubic Equation
Equation of
of State
State
Equation
Equation (3.49)
Equation (3.49)
(3.49) may may
may be be solved
be solved
solved for for the
the VV
for the V inin the
in the numerator
the numerator
numerator of of
of thethe final
the final fraction
final fraction
fraction to to give:
to give:
give:
Equation
Equation(3.49)
Con la ecuación (3.49)
(3.49)es may
may be
be solved
posible solved for
for the
resolver paraVVVin
the inentheelnumerator
the numerator
numerador
� of
ofdethe
thela final
final
fracción fraction
fraction
� final to
to give:
give:
obteniendo:
�� RT + b P − V P ��
= + + + �� +
RT + b P − V P
RT b P − V P �
�
VV
V= = bbb ++ (V(V
(V + �b)(V
+ �b)(V
�b)(V + + σσσb)b)
b) RT RT + +a(TbbPP − − VV PP (3.55)
(3.55)
(3.55)
VV = = bb ++ (V(V + �b)(V +
+ �b)(V + σσb) b) a(T)))
a(T (3.55) (3.55)
(3.55)
a(T
a(T))
This equation
This equation
This equation with with
with aaa starting
starting
starting value value
value of of
of VVV = =
= bbb on on the
on the right
the right
right side side converges
side converges
converges upon upon iteration
upon iteration
iteration to to
to aaa
Esta ecuación
This
This equation
liquid con
equation
or un valor
with inicial
with aaroot.
liquid-like starting
starting de value
V = b of
value en
of V el
V lado
= bb derecho,
= on
on the
the right converge
right side por iteración
side converges
converges upon
upon a una raíz de
iteration
iteration to líquido
to aa o
liquid or
liquid or liquid-like
liquid-like root. root.
de algoliquid
parecido.
liquid or
Anor liquid-like
liquid-like
equation forroot.
root.
An equation
An equation for for ZZ equivalent
Z equivalent
equivalent to to Eq.
to Eq. (3.55)
Eq. (3.55)
(3.55) is is obtained
is obtained
obtained when when
when Eq. Eq. (3.52)
Eq. (3.52)
(3.52) is is solved
is solved
solved for for
for thethe
the
UnaZ inecuación
An
Annumerator
the para Zfor
equation
equation quethe
for
of ZZequivale
equivalent
equivalent
final a lato
fraction: to(3.55)
Eq. se obtiene
Eq. (3.55)
(3.55) is cuandowhen
is obtained
obtained la ecuación
when Eq.
Eq. (3.52) (3.52)
(3.52) is se resuelve
is solved
solved for
for the para Z en
the
ZZ in in the
the numerator
numerator of of thethe final
final fraction:
fraction:
el numerador
ZZ in in thedenumerator
the la fracciónof
numerator offinal:
the
the final
final fraction:
fraction: ��
�1 + β − Z� ��
Z = β + (Z + �β)(Z + σβ) ��11 + + ββ − − ZZ � � (3.56)
Z = β + (Z +
Z = β + (Z + �β)(Z + σβ) �β)(Z + σβ) 1
1 +
+ β
β
qβ −
− Z
Z (3.56)
(3.56)
ZZ == ββ + + (Z(Z + �β)(Z +
+ �β)(Z + σβ)
σβ) qβ
qβ (3.56) (3.56)
(3.56)
qβ
qβ
For iteration
iteration aaa starting
For iteration starting
starting value value
value of of
of ZZZ= =
= ββ is substituted
is substituted
β is substituted on on
on thethe right
the right side.
right side.
side. Once Once
Once ZZ Z isis known,
is known,
known, the the
the
Para la For
iteración,
For
For iteration
volume iteration
root unisaavalor
starting
Vstarting
= inicial
Z RTvalue
valuede of
/P. of=ZZb=
Z =seββsustituye
is
is substituteden el on
substituted lado
on thederecho.
the right
right side. UnaOnce
side. vez que
Once ZZ is se conoce,
isZknown,
known, the la raíz
the
volume root
volume root is is VV = = ZZ RT RT/P. /P.
del volumen
volume
volume es V
root =
root is
Equations ZRT/P.
is VVof==state
ZZRT RT /P.
/P. express Z as a function of Tr and Pr are said to be generalized,
which
Equations of
Equations of state
state whichwhich express
express ZZ as as aa function
function of of TTrr and and PPrr are are said
said to to be
be generalized,
generalized,
Las
becauseecuaciones
Equations
Equations
of their deof
ofestado
state
general que
state which
which expresan
expressato
express
applicability ZZZall
asenaagases
as función
function
function
and de
of
of TTTrrryand
liquids. and se
PPrrdice
Pr Any are
are que to
said
said
equation deben
to be ser generalizadas,
be generalized,
of generalized,
state can be
because of
because of their
their general
general applicability
applicability to to all
all gases
gases and and liquids.
liquids. Any
Any equation of
equation of state
state can
can be be
debido because
aput su
because campo
into of
this de
of their
their
form aplicación
general
general
to provide general
applicability
applicability
a para
generalized totodos
to all los
gases
allcorrelationgases
gases and andfor y los
liquids.
liquids.
the líquidos.
Any
Any equation
properties Es
equation
of posibleof
fluids. presentar
of state
state
This can
can be
allows cualquier
be
put into
put into this
this form
form to to provide
provide aa generalized
generalized correlation
correlation for for the the properties
properties of of fluids.
fluids. This This allows
allows
ecuaciónput
the de
put into estado
into this
estimation en
this form
formesta
of to forma
to provide
provide
property para proporcionar
aa generalized
generalized
values from very una correlación
correlation
correlation
limited for
for the generalizada
the properties
information. properties
Equations of para
of fluids. las
fluids.
of propiedades
This
state, allows
Thissuchallows as de los
the estimation
the estimation of of property
property values values fromfrom very very limited
limited information.
information. Equations Equations of of state,
state, such
such as as
fluidos.the
Esto permite
the estimation
estimation
van der el
of
Waals cálculo
of property
property
and de valores
values
values from
Redlich/Kwong de la
from very propiedad
very limited a partir
limitedwhich
equations, information.de
information. información
express Equations
Equations muy of limitada.
of state,
state, such
such Las as
asecuacio-
the van
the van der der Waals
Waals and and Redlich/Kwong
Redlich/Kwong equations, equations, which which express express ZZ Z as as functions
as functions
functions of of
of TT
Trr andand
and
nes de estado,
the
the
P r vancomo
van
only, der
der
yield la two-parameter
Waals
Waals de van andder
and Waals
Redlich/Kwong
Redlich/Kwong y la de Redlich/Kwong,
corresponding equations,
equations,
states whichque
which
correlations. expresan
express
express ZZ as
The a Zfunctions
as sólo como
functions
Soave/Redlich/Kwong of TTrrr and
offuncionesand de Tr
only, yield
PPrr only, yield two-parameter
two-parameter corresponding corresponding states states correlations.
correlations. The The Soave/Redlich/Kwong
Soave/Redlich/Kwong
y Pr, producen
PPrr only,
(SRK) only, correlaciones
yield
equation 14
yield two-parameter
two-parameter
14 and
14 de
the estado correspondientes
corresponding
corresponding
Peng/Robinson (PR) states
statesdecorrelations.
dos15 parámetros.
15
correlations.
equation, 15 in which The
The La
the ecuaciónfactor
Soave/Redlich/Kwong
Soave/Redlich/Kwong
acentric de Soave/Redlich/
enters
(SRK)
(SRK) equation
equation
14 14 and
and
14 and the
the Peng/Robinson
Peng/Robinson 15 en (PR)
(PR) equation,
equation, 15
15 inin
in which
which the
the acentric factor
acentric factor enters
enters
Kwong(SRK)(SRK)
(SRK)
through
through function y
equationla
equation
function de
function α(T Peng/Robinson
andr the
α(T
α(Trr;; ω) ;the
ω) (PR),
Peng/Robinson
Peng/Robinson
ω) as as an
as an additional
an additional las
(PR)
(PR)
additional parameter, que el
equation,
equation,
parameter, factor
parameter, yield yield acéntrico
in which
which the se
the
three-parameter
yield three-parameter introduce
acentric
acentric a través
factor
factor
corresponding-
three-parameter corresponding-corresponding-
enters
enters de la fun-
through
ción a(Tstates
r ;
through
throughw) como un
function
function
correlations.
states correlations. parámetro
correlations. The
α(T
α(TThe rr ;; ω)
ω) adicional,
as
as
numerical
The numerical
an
an produce
additional
additional
assignments
numerical assignments
assignments for correlaciones
parameter,
parameter,
for yield
yield
parameters
for parameters
parameters �, de estados
three-parameter
�, σ ,
�, σσ,, �,�, correspondientes
three-parameter
�, andand
and �, �, corresponding-
corresponding-
both
both for
�, both for con
these
for these
these tres pará-
states
metros.states
Las
states
equations asignaciones
equations and
correlations.
correlations.
and
and forfor
for the numéricas
The
theThevan
the van
numerical
numerical
van der der para
Waals
der Waals los parámetros
assignments
assignments
Waals and and for
Redlich/Kwong
and Redlich/Kwong s,
for parameters
parameters
,
Redlich/Kwong equations, W y Ψ,
�, σσpara
�,
equations, ,, �,
equations, are
�,areambas
and
and �,ecuaciones
�,
given
are given
given in
both
both
in for
Table
in Table 3.1.para las
for these y
these
Table 3.1.3.1.
equations
ecuaciones
equationsde
equations
Expressions van
Expressions are
Expressions der
and
andare Waals
for
for
also
are also
the
also giveny
thegiven de
van
van
given for Redlich/Kwong,
der Waals
derα(T
for Waals ;
α(Trr;; ω)
for α(T r ω)and
and
ω) forfor se proporcionan
Redlich/Kwong
Redlich/Kwong
the
for the SRK
the SRK
SRK and and
and PR PR en la
equations,
equations, tabla
equations.
PR equations.
equations. 3.1.
are
are También
given
given in se
in Table
Table dan 3.1.expresio-
3.1.
nes para a(Tr; w) para las ecuaciones SRKrr y PR.
Expressions
Expressions are
are also
also given
given for
for α(T
α(T ;
; ω)
ω) for
for the
the SRK
SRK and
and PR
PR equations.
equations.
14
14 G. Soave, Chem. Eng. Sci., vol. 27, pp. 1197–1203, 1972.
14 G. Soave,
G. Soave, Chem.
Chem. Eng.
Eng. Sci.,
Sci., vol.
vol. 27,
27, pp.
pp. 1197–1203,
1197–1203, 1972.
1972.
14
14G.
G. Soave,
Soave, Chem.
Chem. Eng.
Eng. Sci.,
Sci., vol.
vol. 27,
27, pp.
pp. 1197–1203,
1197–1203, 1972.
1972.
14 G. Soave,
15 Chem. Eng. Sci., vol. 27, pp. 1197-1203, 1972.
15 D.-Y.
15 D.-Y. Peng
Peng and
and D.
D. B.
B. Robinson,
Robinson, Ind.
Ind. Eng.
Eng. Chem.
Chem. Fundam.,
Fundam., vol. 15,
vol. 15, pp.
15, pp. 59–64,
pp. 59–64, 1976.
59–64, 1976.
1976.
15 D. Y.15 D.-Y. Peng and D. B. Robinson, Ind. Eng. Chem. Fundam., vol.
Peng
15D.-Y.y D.
D.-Y. B. and
Peng
Peng Robinson,
and D.
D. B. Ind. Eng. Chem.
B. Robinson,
Robinson, Ind.
Ind. Eng.
Eng. Chem. vol.
Fundam.,
Chem. 15, pp.vol.
Fundam.,
Fundam., 59-64,
vol. 15, 1976.
15, pp.
pp. 59–64,
59–64, 1976.
1976.

98 98 CHAPTER 3. Volumetric
Properties
Properties
of Pure
of Pure
Fluids
Fluids
98
CHAPTER 3. Volumetric Properties of Pure Fluids
Table Table3.1:3.1: Parameter
Parameter Assignments
Assignments for for Equations
Equations of State
of State
TablaTable Table 3.1: Parameter
3.1: Asignación Assignments
de parámetros para forlas Equations
ecuaciones of State
de estado
3.1:
Table 3.1:For Parameter
Parameter Assignments
Assignments for
for Equations
Equations of State
For
use usewithwith Eqs. Eqs.
(3.49)
(3.49)
throughthrough (3.56)(3.56) of State
ParaFor Forsu useusowith
use con las
with
Eqs.ecuaciones
Eqs. (3.49) through
(3.49) through (3.49)(3.56)
through a (3.56)
(3.56)
For use with Eqs. (3.49) (3.56)
Eq.Eq.
Ecuación of de
State
ofestado
State α(T a(T α(T
r )r) r ) sσ σ σ � � � �Ω � � Ψ � Z c Z cZc
Eq. of State α(T r) � � Z
Eq.
Eq. of
of State
State α(T
α(T r )
) σ
σ ��
� Zccc
Z
vdWvdW(1873)
vdW(1873)(1873) 11 1 r 00 0 00 0 1/81/8 27/64
1/8 27/64
27/64 3/8 3/83/8
vdW (1873) −1/2 1−1/2 0 0 1/8 27/64 3/8
RK vdW
RK (1949)RK (1873)
(1949)(1949) T T –1/2
T1 10
1 0 1 00
0 0 0 0.086641/8
0.08664
0.08664 27/64
0.42748
0.42748 3/8
1/3 1/31/3
vdW
RK (1949)(1873) 1
r r −1/2
Tr−1/2 r
1 0 1/8
0.08664 0.42748 27/64 3/8
1/3
−1/2 † †
SRKSRKRK SRK
(1972)(1949)
(1972)(1972)α aαSRK (Trr r ;(T
T ω) r;; ω) 11√ 1
11 1√ 00√ 0
00 0√ 0.08664 0.08664
0.086640.42748 0.42748
0.42748 1/3 1/3
1/3
RK
SRK (1949)
(1972) SRK αSRK T
SRK (T(T r ;rω)
†
√ √
0.08664
0.08664
0.08664 0.42748 0.42748
0.42748 1/3 1/3
1/3
PR SRKPR
(1976)(1972) αα
(1976) αPR α(T
SRK (T ;†
(T ω)
r ;
; ;‡ω)
ω) †† ‡ 1 +11 1
+ 2 2 1 − 1 0
− 2 2 0.08664
0.07780
0.07780 0.42748
0.45724
0.45724 1/3
0.30740
0.30740
SRK
PR (1976)(1972) w)
PR (T
r
PR (Trr; ω)‡
αSRK r ω) ‡ 1 +√ √2 1 − √ 0 √2 0.07780 0.45724 0.30740
0.08664 0.42748 1/3
PR (1976)
(1976) αPR
�α (Trr ;; ω)
PR�(T ω)‡‡ + 22 11 −
11+ + − 22 �0.07780 0.07780
� 0.45724
��0.45724 0.30740
PR
PR †(1976) 1 √ 2 1 – √ 2 2�� 0.30740
a (T ; w) 2 )ω0.07780 0.45724 0.30740
� r 2
† α (T ;(Tω); = PR
= + + + + − − 21� − −
1/2 1/2 �� 2
α†SRK SRK r r ω) 1�
� 1 (0.480 (0.480 1.574 1.574
ω ω 0.176 0.176ω 2 ��
) 1 T T
1/2
r r �� 2 ��
αSRK (Tr ; ω) = 1 + (0.480 + 1.574 ω −20.176 ω12/ 2) 12 − Tr1/2
) (1 − Tω ω2 )))11 −
†α 1/2 2
† a †α
SRK (T
SRK
‡ α ‡SRK
w)rr ;;=ω)
(T
r; (T
ω) =
1�= + (0.480
+�(0�11.480
+ (0.480
+ 1.574 ++ω1.574
1.574
− 0.176ω−
ω − 0.176
ω 0.176 r  2
−�TTr �
2�r
��2��2
1/2 1/2��
α
(T ;
(T ω) ; =ω) =1� + 1 +
(0.37464 (0.37464 + +
1.54226
1.54226
‡ α (T ; ω) = � 1 + (0.37464 + 1.54226 ω − 0.26992 ω2 ) � 1 − T r ��
PR PRr r ω − ω −
0.26992
0.26992 ω )ω 1�) − 1T −
r T
1/2 ��2
1/2 22
) (1 − Trω ω2))) 11 −
‡ PR r 2 2 r
‡ a ‡ (T
PR α αPR
PR w)rr ;;=ω)
(T
r; (T ω)1= = + (0.37464
+ (011.37464
+ (0.37464+ 1.5422 +ω
+ − 0.26992
1.54226
1.54226 ω−
ω −ω0.26992
2
0.26992 1 / 2

− TTr
r
1/2
Example
Example
Ejemplo 3.9 3.9
Example 3.9
3.9
Example
Example
Given
Given
thatthat 3.9
3.9
thethe
vapor
vapor
pressure of n-butane
pressure of n-butane
at 350
at 350
K isK 9.4573
is 9.4573
bar,bar,
findfind
thethe
molar
molar
Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find the molar
Teniendo en cuenta que la presión de vapor para el n-butano a 350 K es 9.4573 bar, encuentre los
Given
volumes that
volumes ofthe
of (a) (a)vapor pressureand
saturated-vapor
saturated-vapor n-butane
ofand
(b) (b) at 350
350 KK n-butane
saturated-liquid
saturated-liquid n-butane
is 9.4573
9.4573atbar,
thesefindconditions
at these the molar
conditions
Given
volúmenes
volumes that
of the
molares vapor pressure
de saturated-vapor
(a) a) vapor ofy n-butane
saturadoand b)(b)
líquido at
saturado is
de
saturated-liquid n-butanobar,
n-butane find
enthese
at estas the molar
condiciones,
conditions me-
volumes
asvolumes
given
as given ofthe
byofby(a)
(a) saturated-vapor
the
Redlich/Kwong
Redlich/Kwong
saturated-vapor and (b)
equation.
equation. saturated-liquid n-butane at these conditions
and (b) saturated-liquid n-butane at these conditions
diante la
asecuación
given byde theRedlich/Kwong.
Redlich/Kwong equation.
as given
as given by
by the
the Redlich/Kwong
equation.
Solución 3.9 3.9
Solution
Solution
Solution 3.9
3.9
Solution
Solution
A partir deValues
Values
3.9
Tof3.9
losofvaloresand de
Tc and cPcy for
PcTfor Pc para
n-butane
n-butaneelfrom
n-butano
from
App. del
App. apéndice
yield: B, se obtiene:
B yield:
B
Values of cTc and Pc for n-butane from App. B yield:
Values of T
Values of Tc and c and P c for n-butane from App.
Pc for n-butane from App. B yield: 9.4573 B yield:
350350 9.4573
Tr = Tr = 350 350 = 0.8233= 0.8233 andyand Pr = 9.4573= 0.2491
Pr =9.4573 = 0.2491
Tr =425.1 425.1
350 = 0.8233 and Pr = 37.9637.96=
9.4573 = 0.2491
T = 425.1
Trr = 425.1 = 0.8233 = 0.8233 and
and P = 37.96
Prr = 37.96 = 0.2491 0.2491
425.1 37.96
Parameter
El parámetroParameter q is q
q se qconoce
Parameter
given
is given
is given
by
por Eq.
by Eq.
(3.54)
bylaEq.
(3.54)
ecuación with
(3.54) with
with
�,
(3.54) �,
�,
�, con
and
�,
�, andW, α(T
and
α(T Ψr yr )a
α(T
) for
r (Tr) para laequation
) for
the the
RK RK
equation from
ecuación
for the RK equation
from
fromRK de la
Parameter
Table
tabla 3.1: Table
3.1:
Parameter 3.1:qq is
is given
given by
by Eq.
Eq. (3.54)
(3.54) with
with �,
�, �,
�, and
and α(T
α(T r )
) for
for the
the RK
RK equation
equation from
from
Table 3.1: r
Table 3.1:
Table 3.1: −1/2−1/2
�Tr�T −1/2
r � �−3/2−3/2 0.42748 0.42748 −3/2−3/2
q =q =�T �Tr−1/2−1/2= =� Tr T −3/2 0.42748
r = =0.42748 (0.8233)
(0.8233) −3/2= 6.6048
= 6.6048
q = �T
�T rr�Tr = � �
� T
� =
−3/2 0.08664
r−3/2 0.08664
0.42748 (0.8233)−3/2 = 6.6048
q = �T
q = �Tr = � Tr
r = � T r = 0.08664 (0.8233)
= 0.08664 (0.8233) −3/2 = 6.6048
= 6.6048
Parameter
Parameter β isβfoundis �T
found rr from
from Eq. �Eq. (3.53):0.08664
(3.53):
Parameter
El parámetro b se β β is found afrom
determina partir Eq. (3.53):
de(3.53):
la ecuación (3.53):
Parameter
Parameter β is found
is found from from Eq. (3.53):
Pr Eq. Pr (0.08664)(0.2491)
(0.08664)(0.2491)
β =β�= � P (0.08664)(0.2491)
β = �TrP Prrr= =
=(0.08664)(0.2491)= 0.026214
Tr= (0.08664)(0.2491)
0.82330.8233
= 0.026214
= 0.026214
β =
β =�T = � T r 0.8233 = 0.026214
= 0.026214
Trrwrite 0.8233
0.8233
(a) (a)
ForForthe the
saturated
saturated vapor,
vapor, writethe the
RK RK
formform
of Eq.
of Eq.
(3.52)(3.52)
which
which
results
results
uponupon
(a) For the saturated vapor, write the RK form of Eq. (3.52) which results upon
(a)
a) Para (a)
el For
vapor the saturated
saturado, vapor,
escribiendo write
la formathe RK form
RKform of Eq. (3.52) which results upon
σdefrom
laofecuación (3.52) lo que resulta por susti-
substitution
substitution
For the of appropriate
of
saturatedappropriate values values
vapor,values
write for for
�
the �RKand
� and
σ from
σ from
Table
Eq.Table3.1:
(3.52)3.1:
which results upon
substitution of appropriate for and Table 3.1:
tución desubstitution of appropriate
valores apropiados
substitution of appropriate values
para values
y s deforfor and 3.1:
la ��tabla
and from Table
σ from
σ Table 3.1:
3.1:
(Z −(Zβ) − β)
Z =Z 1=+1β+−βqβ − qβ(Z(Z − β)
Z = 1 + β − qβZ (Z +− β)
+ β)
(Z−+β)
= 11 + +β qβ Z(Z
− qβ Z (Z β)
ZZ = β−
Z (Z +
β)
β)
Z (Z + β)

3.6.
3.6. Generalized
Generalized Correlations
Correlations for
for Gases
Gases 99
99
3.6. Correlaciones generalizadas
3.6. Generalized para
Correlations forgases
Gases 99 99
Iteration
Iteration with
with an
an initial
initial value
value Z= = 11 converges on Z=
Z = 0.8305. Thus,
La iteración con with
Iteration un valor Z = 1ZZconverge
inicialvalue
an initial
converges
en Z =on
= 1 converges
on
0.8305. 0.8305.
Así,
Z = 0.8305.
Thus,
Thus,
v Z
Z RT
RT = (0.8305)(83.14)(350)
(0.8305)(83.14)(350) = 2,555 cm33 mol −1
VV vv == Z RT = (0.8305)(83.14)(350) = 2,555 cm mol−1
V = P = P 9.4573
9.4573 = 2,555 cm3 mol−1
P 9.4573
An 3 −1
An experimental
experimental value value isis 2,482
2,482 cmcm33 mol
mol−1−1..
An experimental value
Un valor experimental es 2 482 cm mol . is 2,482
3 cm
–1 mol .
(b) For
For the
(b)líquidothe saturated
saturated liquid,
liquid, apply
apply Eq.
Eq. (3.56)
(3.56) in its
in en RK
RK form:
its su form:
b) Para (b)
el For thesaturado
saturatedseliquid,
aplicaapply
la ecuación (3.56)
Eq. (3.56) in its RKforma
form:RK:
�
�1 + β − Z � �
Z = β + Z (Z + β) � 1 + β − Z�
Z = β + Z (Z + β) 1 + β
qβ − Z
Z = β + Z (Z + β) qβ
qβ
o (1.026214 −
(1.026214 −Z Z ))
or
or Z=
Z 0.026214 +
= 0.026214 +Z (Z +
Z (Z + 0.026214) (1.026214 − Z )
0.026214) (6.6048)(0.026214)
or Z = 0.026214 + Z (Z + 0.026214) (6.6048)(0.026214)
(6.6048)(0.026214)
La etapaThe
The initial
inicial es step
initial is
is substitution
la sustitución
step de Z of
substitution = bZ
of =
=β
Z en el on
β the
lado
on right
right side
thederecho deof
side this
esta
of equation.
thisecuación. Iteration
equation.La iteración con-
Iteration
The
leads
duce a laleads initial
to step is
convergence
convergencia substitution
on
en el valor the of
value Z Z=
= 0.04331.=β on the
0.04331. right
De donde, side
Whence, of this equation. Iteration
to convergence on theZvalue Z = 0.04331. Whence,
leads to convergence on the value Z = 0.04331. Whence,
l Z
Z RT
RT = (0.04331)(83.14)(350)
(0.04331)(83.14)(350) = 133.3 cm33 mol−1
Vll =
V = Z RT = (0.04331)(83.14)(350) = 133.3 cm mol−1
V = P P = 9.4573
9.4573 = 133.3 cm3 mol−1
P 9.4573
3 –1 3 −1
Un valor experimental es 115.0 cm mol .33 mol
An
An experimental
experimental value
value is
is 115.0
115.0 cm
cm mol−1..
An experimental value is 115.0 cm mol−1 .
For v l
For comparison,
comparison, values
values ofof VV vv and
and VVll calculated
calculated for
for the
the conditions
conditions of of Ex.
Ex. 3.9
3.9 by
by all
all four
four
of the For
cubiccomparison,
equations values
of state of V
v and
consideredl V calculated
here are for the conditions
summarized as follows:of Ex. 3.9 by all four
Por
of comparación, los valores
the cubic equations of statede considered
V y V calculados
here are con las condiciones
summarized del ejemplo 3.9 para las cuatro
as follows:
of the cubic equations vof state considered here are summarized as follows:
ecuaciones de estado cúbicasV se resumen
3 −1de la siguiente forma: V ll /cm 33 mol −1
V vv/cm
/cm33 mol
mol−1−1 V /cm mol−1
V /cm mol V l /cm3 mol−1
Exp.
Exp. vdW V v/cm3RK
vdW mol–1 SRK
RK SRK PR PR Exp.
Exp. vdW vdWV /cm
l RK 3
RK molSRK
–1
SRK PR PR
Exp. vdW RK SRK PR Exp. vdW RK SRK PR
Exp.2,482vdW
2,482 2,667 RK
2,667 2,555 SRK
2,555 2,520
2,520 2,486PR
2,486 Exp. 191.0
115.0
115.0 vdW 133.3
191.0 RK 127.8
133.3 SRK 112.6
127.8 PR
112.6
2,482 2,667 2,555 2,520 2,486 115.0 191.0 133.3 127.8 112.6
The 2 482 2 667 2 555 2the 520 2 486 115.0 191.0 133.3 127.8 112.6
The Soave/Redlich/Kwong
Soave/Redlich/Kwong and and the Peng/Robinson
Peng/Robinson equations
equations were
were developed
developed specifically
specifically forfor
The Soave/Redlich/Kwong
vapor/liquid equilibrium and the Peng/Robinson
calculations (Sec. 14.2). equations were developed specifically for
vapor/liquid equilibrium calculations (Sec. 14.2).
Las ecuaciones de Soave/Redlich/Kwong
vapor/liquid
Roots
Roots
equilibrium
of
of equations
equations of state yare
calculations
of state de
are Peng/Robinson
(Sec.
most 14.2). found
most easily fueron
easily found withdesarrolladas
with software en
aa software forma such
package
package específica
such as para
as
cálculosMathcad
de �
equilibrio
Roots
�R
R or Maple �
ofvapor/líquido
equations
�R
R , in (sección
ofwhich are14.2).
state iteration
mostis easily
an foundpart
integral with of a software
the package such
equation-solving routine.as
Mathcad� or Maple�
R or R ,, in
in which iteration is an integral part of the equation-solving routine.
Las raícesvalues
Mathcad
Starting
Starting de lasMaple
values ecuaciones
or
or bounds
bounds de estado
which
may
may be se encuentran
iteration
be required,
required,
isand
mustenbe
and must beforma
an integral part ofmás
the fácil
appropriate
appropriate to conparticular
to the
the un paquete
equation-solving
particular root
rootdeof
routine. software
of
como Mathcad®
Starting
interest. A o Maple®,
values
Mathcad �
R
�Ren
or bounds que
may
program la iteración
be
for es
required,
solving una parte
and3.9
Ex. must
is integral de
be appropriate
given in App.la rutina de
to the
D.2. solución
particular de la
root ecuación.
of
interest. A Mathcad� program for solving Ex. 3.9 is given in App. D.2.
R program
Se puede requerir
interest. A de los valores
Mathcad inicialesforosolving
de frontera másisapropiados
Ex. 3.9 given in App. paraD.2.
la raíz que nos interese. Un pro-
grama Mathcad® para solucionar el ejemplo 3.9 está dado en el apéndice D.2.
3.6
3.6 GENERALIZED
GENERALIZED CORRELATIONS
CORRELATIONS FOR FOR GASES
GASES
3.6 GENERALIZED CORRELATIONS FOR GASES
3.6 CORRELACIONES GENERALIZADAS PARA GASES
Generalized correlations find widespread use. Most popular are correlations of the kind de-
Generalized
Generalized correlations
correlations find
find widespread
widespread use.
use. Most
Most popular
popular are
are correlations
correlations of
of the
the kind
kind de-
de-
Generalized
veloped by correlations
Pitzer and find widespread
coworkers for the use. Most popular
compressibility are Z
factor correlations
and for of second
the the kindvirial
de-
veloped bygeneralizadas
Las correlaciones Pitzer and coworkers
tienen un for
usothe
muycompressibility
extendido. Lasfactor
más Z and for son
populares the las
second virial
desarrolladas por
veloped by B.
coefficient Pitzer
16
16 and coworkers for the compressibility factor Z and for the second virial
coefficient
Pitzer ycoefficient B.16
colaboradores para el factor de compresibilidad Z y para el segundo coeficiente virial B.16
B.
16
16See
See Pitzer,
16 See Pitzer, op.
op. cit.
cit.
16 Pitzer, op. cit.
Véase Pitzer, op. cit.

100 100 CAPÍTULO 3. Volumetric
CHAPTER 3. Propiedades volumétricas
Properties de Fluids
1.2
1.2
4.0
4.0
1.0
1.0
Tr  0.7 Gases
Tr � 0.7 Gases 1.5
0.8 1.5
0.8 0.9
0.9 1.2
1.2
Z 0 0.6
Z 0 0.6 1.0
Región de 1.0
Two-phase
dos fases 0.7
region 0.7
0.4
0.4
C
C
0.9
0.2 0.9
0.2
Líquidos comprimidos
Compressed
(Tr  1.0) liquids
(Tr � 1.0)
0
0 0.05 0.1 0.2 0.5 1.0 2.0 5.0 10.0
0.05 0.1 0.2 0.5
Pr 1.0 2.0 5.0 10.0
Pr
Figura 3.13: La correlación de Lee/Kesler para Z 0 = F 0 (Tr, Pr).

Figure 3.13: The Lee/Kesler correlation for Z 0 = F 0 (Tr , Pr ).
Correlaciones de Pitzer para el factor de compresibilidad

Pitzer Correlations for the Compressibility Factor
La correlación para Z toma
The correlation for la forma:
Z is: Z = Z 0 + ωZ 1 (3.57) (3.57)
0 y Z 1 son
donde Z where Z 0 and Z 1 arede
funciones functions
Tr y de P ofr. both
CuandoTr and Whenesωel=caso
w =P0,r . como 0, asdeislos
thefluidos
case for the simple
simples, el segundo
fluids, the second 0 term disappears, and Z 0 becomes identical with Z . Thus a generalized corre-
término desaparece, y Z es idéntico a Z. Así, una correlación generalizada para Z como función de Tr y Pr,
que estálation
basada forenZinformación
as a functionpara
of Treland
argón,Pr based on data
el kriptón y elforxenón,
just argon, krypton,laand
proporciona xenonZ
relación 0 = F 0(T , P ).
provides r r
the relationship Z 0 = F 0 (T , P ). By itself, this represents a two-parameter corresponding-
Por sí misma, ésta representa una correlación r r de estados correspondientes con dos parámetros para Z. Ya que
el segundostates correlation
término for Z . Because
de la ecuación (3.57) the second
es una term of relativamente
corrección Eq. (3.57) is apequeña
relativelyparasmall correction
esta correlación, su
0 0
to this correlation, its omission does not introduce large errors, and
omisión no introduce grandes errores y es posible usar una correlación para Z y así obtenermay a correlation for Z be
estimaciones
used alone for quick but less accurate estimates of Z than are obtained from
rápidas de Z, pero menos precisas que las que se consiguen a partir de una correlación de tres parámetros. a three-parameter
Lacorrelation.
ecuación (3.57) es una relación lineal simple entre Z y w para valores conocidos de Tr y de Pr. La
Equation (3.57)
información experimental paraisZ,
a simple
de fluidos linear
querelation
no son between
simples, Z queand for given values
sonω graficados of Tr de
en función andw a Tr y
P
Pr constantes,
r . Experimental data for Z for nonsimple fluids plotted vs.
producen líneas aproximadamente rectas y sus pendientes proporcionan valores ω at constant T r and P
para Z 1 a par-
r do
1 = F 1provide 1
tir de losindeed
cualesyield approximately
es posible construir lastraight
función lines, and their Z
generalizada slopes (Tr, Pr).values for Z from which
1
Z = del 1 constructed.por Lee y Kesler17 es la más favorecida.
Dethelasgeneralized
correlaciones function
disponibles F (T r, P
tipo r ) canla
Pitzer, bedesarrollada
Of the Pitzer-type correlations available, the onededeveloped by deLee and Kesler 17 has
Aunque su desarrollo se fundamenta en una forma modificada la ecuación estado de Benedict/Webb/
17 17 B. I. Lee and M. G. Kesler, AIChE J., vol. 21, pp. 510–527, 1975.
B. I. Lee y M. G. Kesler, AIChE J., vol. 21, pp. 510-527, 1975.

3.6. Generalized
3.6. Generalized Correlations
Correlations for for Gases
Gases 101
101
3.6.
3.6. Generalized
3.6. Correlaciones
generalizadas
Correlations para for Gases
forgases
Gases 101
101 101
3.6. Generalized Correlations for Gases 101
found
found greatest
greatest favor.
favor. Although
Although its
its development
development is
islos based
based on
on a modified
0
aamodified
modified 1 form
form of
of the
the Bene-
Bene-
Rubin,found
ésta adquiere
greatestlafavor.
greatest formaAlthough de las tablas its que presentanis
itsitdevelopment valores ade Z y Z form comoof funciones de T y de
found
dict/Webb/Rubin
dict/Webb/Rubin
favor.
equation
equation
Although
of state,
of state, it
development
takes the
takes the formformisbased ofbased
of tables
tables
ononwhich
which
modified
presentform
present values
values
ofthe
theZBene-
of
of Z and r
0Bene-
000and
and
Pr, quedict/Webb/Rubin
se proporcionan en el
equation apéndice
of state,E de
it las
takes tablas
the E.1
form a E.4.
of El
tables uso
which de estas
presenttablas con
values frecuencia
of Z requie-
Zdict/Webb/Rubin
Z
found
111as
as
greatest favor.
1 as functions
functions ofequation
of Tr and
T Pof
Although
and P
state,
r .. These
Theseitsitdevelopment
takes
are
are given
given
the form is of
in App.
in App. tables
based
E as
E
which
asonTables
a modified
Tables present
E.1
E.1 through
through
values
form E.4.of
of
E.4.
ZBene-
theUse
Use
and
of
of
re de interpolación,
Z functions
Z astablesfunctions la cual
of T se
r trata
and P al
r . inicio
These del
are apéndice
given in F.
App. La naturaleza
E as Tables de la
E.1 correlación
through E.4.se indica
Use 0 of of la fi-
en
dict/Webb/Rubin
these
these tables often of
often
Tr r andinterpolation,
equation
requires
requires
P
r r .state,
of These
0 en función which
interpolation,
are
it takes given
which theisform
is
in App.
treated
treated
of at
at
Ethe
tablesas beginning
the
Tables
which present
beginning
E.1ofthrough
of App.
App. F.E.4.
values
F.
of Z
The
The
Useand
nature
nature
gura 3.13,
these1 que es
tables una
often gráfica
requires de Z
interpolation, de
which P para
is seis
treated isotermas.
at the beginning of App. F. The nature
these
Z the
of
of the
tables
ascorrelation
functions
correlation
oftenof isrequires
is
Tr andinterpolation,
indicated
indicated
Prby . These
by Fig. 3.13,
Fig. 3.13, a rplot
arewhich
givenplot isintreated
of App.
Z0000vs.
vs.at
EP the
asr forbeginning
Tables E.1 of
six isotherms. App. F.E.4.
through
isotherms. TheUse nature of
La
ofof correlación
the correlation
theThe
these correlation
tables de Lee/Kesler
often is isindicated
indicated
requires proporciona
byby Fig.
interpolation,Fig. 3.13,
3.13, aaaplot
resultados
which plotis of
ofof ZZconfiables
treated Z vs.
vs.
at P
P P
the for
rrrfor para
for six
six
six
beginning gases que
isotherms.
isotherms.
of sonF.noThe
App. polares
nature o ligera-
The Lee/Kesler correlation
Lee/Kesler correlation provides provides reliablereliable resultsresults for gases
for gases which which are are nonpolar
nonpolar or or only
only
mente polares;
of theThe para éstos,
Lee/Kesler los errores
correlation indicados no son mayores 0 de 2 o 3%. Cuando se aplica a gases muy
slightly
slightly
correlation
Thepolar;
polar;
Lee/Kesler is indicated
for these,
for these, errorsby
correlation
errors ofprovides
of
Fig.
provides
no
no
3.13,reliable
more
more
a plot
reliable
than
than 2 or
2
results
ofresults
or 3
for
3Z percent
vs.
percentforPgases
are
are
which
for indicated.
rgases six
indicated.
are
arenonpolar
isotherms.
which nonpolar
When
When
ororonly
applied
applied
only
to
to
polaresslightly
o asociados,
slightly polar;
The polar; se
for pueden
forthese,
Lee/Kesler these, esperar
errors
errors errores
ofofno nomore más
morethan grandes.
than 22oror 33percent
percent areare indicated.
which areWhen
indicated. When applied
applied toto
highly
highly polar
polar gases
gases or
or tocorrelation
to gases
gases that
that
provides
associate,
associate,
reliable
larger
larger
results
errors for be
can gases expected. nonpolar or only
Los
highly gases
highly
slightly polarcuánticos
polar
polar; gases
gases
for or(por
or to
these, to ejemplo,
gases
gases
errors that
that
of hidrógeno,
associate,
associate,
no more thanhelio
larger
larger2 yerrors
or neón)
errors
errors
3 can
cannobe
can
percent be
se
be expected.
areajustan
expected.
expected. al mismo
indicated. When comportamiento
applied de
The quantum
quantum gases gases (e.g.,
(e.g., hydrogen,
hydrogen, helium, helium, and and neon)
neon) do do not not conform
conform to to the
the same sameto
estados highly
correspondientes
The
The polar
The quantum
gases or
quantum como
gases los
(e.g.,
to gases
gases fluidos
(e.g., that normales.
hydrogen,
associate,
hydrogen, helium,Algunas
largerTheir
helium, and
errors veces
neon)
can
andtreatment
neon) su
bedo análisis
not
expected.
do not mediante
conform
conform las
totothethesamecorrelaciones
same
corresponding-states behavior as do normal fluids.
fluids. by the usual correlations
correlations is
acostumbradas se adapta
The quantum a través
behavior
behavior del
behavior
gases (e.g., uso
as
asas do
do denormal
do parámetros
normal
normal
hydrogen, fluids.
fluids.
helium,críticos
Their
Their
Theirand eficaces
treatment
treatment
treatment
neon) que
do by
byby son
the
the
not the dependientes
usual
usual
usual
conform correlations
correlations
to the desame
18 lais
istempera-
is
18 sometimes accommodated by use of temperature-dependent effective critical parameters. 18 For
Para
tura. sometimes el
sometimes hidrógeno,
accommodated
accommodated el gas cuántico
by use of más encontrado
temperature-dependent en los procesos
effective químicos,
critical las ecuaciones
parameters. 18 18 For recomen-
sometimes
hydrogen, accommodated
the quantumbehavior gasby by use
most asof
use oftemperature-dependent
do temperature-dependent
normal fluids.
commonly found in Their
in effective
effective
treatment
chemical critical
bycritical
processing, parameters.
the usualparameters.
the correlations
recommended For
Foris
dadas son:
hydrogen,
hydrogen,
hydrogen,
sometimes the
the
the quantum
quantum
quantum
accommodated gas
gas
gas most
most
bymost use commonly
commonly
commonly
of found
found
found
temperature-dependent in in chemical
chemical
chemical processing,
processing,
processing,
effective critical the
the
therecommended
recommended
recommended
parameters. 18 For
equations are:
equations are:
equations
hydrogen,are:
equations are:
the quantum gas most commonly 43.6found in chemical processing, the recommended
equations are: Tc /K
T /K = = 43.6
43.6
43.6 (para
(for H
(for Hel2H ) 2) (3.58) (3.58)
c /K== 1 + 43.6
TTcc/K 21.8
21.8 (for
(for HH222))) (3.58)
(3.58)
(3.58)
++ 2.016 21.8
21.8
Tc /K =111+ 2.016 T
T (for H2 ) (3.58)
2.016 21.8TT
2.016
1+
2.016 T
20.5
Pc /bar
/bar = = 20.5
20.5 (for H H ) ) (3.59) (3.59)
P 44.2 (para
20.5 (for el2H
c
c /bar== 1 + 20.5
PPc /bar 44.2
44.2 (forHH222)))2
(for (3.59)
(3.59)
(3.59)
++ 2.016 44.2
Pc /bar =111+ 2.016 T (for H ) (3.59)
2.016 44.2TTT
2.016
2
1+
2.016 51.5T
/cm3333mol
Vc /cm mol−1 −1 =
−1 = 51.5
51.5
51.5 (for H H2 )) (3.60)
V
VVcc/cm mol−1== 1 − 9.91 9.91 (para (for elH22H) )2) (3.60)
(3.60) (3.60)
c /cm mol 9.91
51.5
(for
(forH 2 (3.60)
3 −1 1 − 9.91
Vc /cm mol = 1 −2.016 T 1 − 2.016 T (for H2 ) (3.60)
2.0169.91TT
2.016
where T is absolute temperature in kelvins. 1Use− of these effective critical parameters for hy-
where
whereTTrequires
where Tisisisabsolute
temperature ininkelvins.
in kelvins. Use of of
2.016 these effective
T effective critical parameters for hy-
drogen absolute
the further temperature
further specification that Use
kelvins. ωUse = 0.
=
ofthese
0. these effectivecritical criticalparameters
parametersfor forhy- hy-
donde drogen
es la requires
Tdrogen
drogen
where temperatura
requires
Trequires the
the
is absolute absoluta
thefurther
further en kelvins.
specification
specification
temperaturespecification El
in kelvins.that
that
thatusoω
ωω de
=
Use =0.estos
0. these
of parámetros
effective críticos critical eficaces
parameters paraforelhy- hidrógeno
requieredrogen
la especificación
requires theadicional de que w = 0.
further specification that ω = 0.
Pitzer Correlations
Pitzer Correlations for for the
the Second
Second Virial
Virial Coefficient
Coefficient
Pitzer
PitzerCorrelations
Correlationsfor forthe
theSecond
SecondVirial
VirialCoefficient
Coefficient
Correlaciones
Pitzer
The
The tabular de Pitzer
Correlations
tabular nature
nature of the
of para el compressibility-factor
for the
the generalized
generalized segundo
Second Virialcoeficiente
Coefficient
compressibility-factor virial
correlation
correlation is aa disadvantage,
is disadvantage, but
but
The
the tabular
tabularnature
Thecomplexity nature ofofthe
of the
the thegeneralized
generalized
functions compressibility-factor
Z0000 and
andcompressibility-factor
Z1111 precludes
precludes their correlation
correlation
their accurate
accurate isisaadisadvantage,
disadvantage,
representation by simple
simplebut
but
the
the
the
The complexity
complexity
complexity
tabular of
ofof
nature the
the
of functions
functions
functions
the Z
ZZ
generalized and
and Z
Z Z precludes
precludes
compressibility-factor their
their accurate
accurate representation
representation
representation
correlation is a by
byby
disadvantage,simple
simple
La naturaleza
equations.
equations. tabular de la correlación
However,
However, we can
we can givegeneralizada
give approximate
approximate delanalytical
factor deexpression
analytical compresibilidad
expression to these
to es functions
these una desventaja,
functions forbut
for a pero la
equations.
equations.
the
complejidad
limitedcomplexity
derange However,
However,
of
las funciones
range of thewewe
pressures. can
0cangive
give
1
functions
Z y The Z 0approximate
approximate
Z impide
The basisandforZ 1 precludes
su this analytical
analytical
representación
this is Eq. theirexpression
(3.38), expression
accurate
exacta
the to
to these
these
representation
medianteform
simplest functions
functions
ecuaciones
form of by
the foraaa
for
simple
sencillas.
virial Sin
limited
limited
limited range
equations. range of pressures.
ofofpressures.
However, we canThe
pressures. The
givebasis
basis
basis for
for
for
approximatethis is
thisisis Eq.
Eq.
Eq.de
analytical (3.38),
(3.38),
(3.38), the
the simplest
thesimplest
simplest
expression topara form
form
these of the
ofofthe virial
thevirial
virial
embargo, es posible
equation:
equation: dar una expresión analítica aproximada estas funciones unfunctions
intervalo for a
limitado de
equation:
equation:
limited range ofesto
pressures. The basis for Bla
this is Eq. (3.38), the simplest form of the virial
presiones. La base para es la ecuación (3.38), B Pforma
P más P
Psimple
r de la ecuación virial:
equation: Z= = 11 +
+ BBPP = =1+ + B̂
B̂ PPrr (3.61)
ZZZ= =11++ RT RT ==111+ +B̂B̂TTr r (3.61)
(3.61)
(3.61)
B
RTRTP P
TTrr
Z =1+ = 1 + B̂ r r (3.61) (3.61)
RT Tr
where B̂
where B̂ isis a reduced
reduced second
second virial
virial coefficient,
coefficient, given
given by: by:
donde where
B̂where isisaaareduced
es unB̂B̂segundo coeficiente
reduced secondvirial
second virialreducido,
virial coefficient,
coefficient, conocido
given
givenby: por:
by:
where B̂ is a reduced second virial coefficient, B given
B P c
PPcc by:
B̂ =
B̂ = BBP (3.62)
(3.62)
B̂== RT
B̂ RTcc (3.62) (3.62)
(3.62)
B
RT
RT P c c
B̂ = c c (3.62)
RTc
18 J. M. Prausnitz, R. N. Lichtenthaler, and E. G. de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilib-
18 J.
18 M. Prausnitz,
Prausnitz, R.
R. N.
N. Lichtenthaler,
Lichtenthaler, and
and E.
E. G.
G. de Azevedo,
Azevedo, Molecular
Molecular Thermodynamics
Thermodynamics of Fluid-Phase Equilib-
Equilib-
18J.
18 ria, 3dJ.M.
M. Prausnitz,
ed., R. N.
pp. 172–173,
172–173, Lichtenthaler,
Prentice Hall PTR,
PTR, E. G.de
andUpper de Azevedo,
Saddle 1999. ThermodynamicsofofFluid-Phase
River, Molecular
NJ, 1999. Fluid-Phase Equilib-
J. ria,
M. Prausnitz,
ria, 3d
3d ed.,
ed., pp.
pp. R. N. Lichtenthaler
172–173, Prentice
Prentice y E.PTR,
Hall
Hall G. deUpper
Azevedo,
Upper Molecular
Saddle
Saddle River,
River, Thermodynamics
NJ,
NJ, 1999. of Fluid-Phase Equilibria, 3a. edición, pp.
ria,
183d ed., pp. 172–173,
J. M. Prausnitz, Prentice Hall PTR,
R. N. Lichtenthaler, Upper Saddle River, NJ, 1999.
and E. G. de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilib-
172-173, Prentice-Hall PTR, Upper Saddle River, 1999.
ria, 3d ed., pp. 172–173, Prentice Hall PTR, Upper Saddle River, NJ, 1999.

102 102
102 3. Volumetric
CHAPTER 3.
CHAPTER
CAPÍTULO Volumetric Properties
Properties of Pure
of Pure Fluids
deFluids
102 CHAPTER 3.3. Volumetric
Properties of Pure fluidos puros
Fluids
Así, Pitzer y colaboradores

Thus,
Thus, Pitzer and
Pitzer recomiendan
and coworkers
coworkers unaaasegunda
proposed
proposed correlación,
second correlation,
second la cualyields
correlation, which
which produce
yields valores
values
values para B̂:
for B̂:
for B̂:
Thus, Pitzer and coworkers proposed a second correlation, which yields values for B̂:
= BB000 +
B̂B̂ = ωB111
+ ωB
B̂ = B 0 + ωB 1
(3.63) (3.63)
(3.63)
(3.63)
Equations
Al unir Equations (3.61)
(3.61)
las ecuaciones and (3.63)
and
(3.61) (3.63) together
together
y (3.63) become:
become:
se obtiene:
Equations (3.61) and (3.63) together become:
PPr PPr
= 11 +
ZZ = + BB000 Prrr +
+ ωB ωB111 Prrr
Z = 1 + B 0 TTrrr + ωB 1 TTrrr
Tr Tr
Al comparar esta ecuación
Comparison
Comparison of this
of con la (3.57)
this equation
equation withse
with obtienen
Eq.
Eq. las identificaciones
(3.57) provides
(3.57) provides the following
the followingsiguientes:
identifications:
identifications:
Comparison of this equation with Eq. (3.57) provides the following identifications:
PPr
ZZ0000 =
= 11 ++ BB000 Prrr (3.64) (3.64)
(3.64)
Z = 1 + B 0 TTrrr (3.64)
Tr
PPr
and
and = BB1111 Prrr
ZZ1111 =
y and Z = B TTrrr
Tr
Second virial
Second virial coefficients
coefficients are
are functions
functions of
of temperature
temperature only, only, and similarly BB0000 and
and similarly and BB1111 are
are func-
func-
Second
Los segundos
tions of
tions
virial coefficients
ofcoeficientes
reduced temperature
reduced
are
temperature functions
viriales sononly.
only.
of
funciones
They are
They
temperature
sólo only,
de la temperatura,
are reasonably
reasonably and similarly B
y de manera
well represented
well represented andthe
by
by
B following
similar
the B0 y B1 son
are func-
following
tions
funciones of
sólo de19
equations:
equations: la temperatura reducida. Se representan bien mediante las ecuaciones siguientes:19
reduced
19
19 temperature only. They are reasonably well represented by the following
equations:19
0.422
0.422 0.172
0.172
BB0000 =
= 0.083 − 0.422
0.083 − (3.65)
(3.65) BB1111 =
= 0.139 − 0.172
0.139 − (3.66)
(3.66)
B = 0.083 − TTrr1.6 1.6
1.6 (3.65) B = 0.139 − TTrr4.2 4.2
4.2 (3.66)
Trr1.6 Trr4.2
The simplest
The simplest form form of of the
the virial
virial equation
equation has has validity
validity onlyonly at at low
low to to moderate
moderate pressures
pressures
La forma más simple form de la of ecuación virial tiene validez sólo aonly presiones
at lowdetobajas a moderadas, donde Z
whereThe
where issimplest
ZZ is linear in
linear in pressure.
pressure. theThevirial equation
generalized
The generalized
has validity
virial-coefficient
virial-coefficient correlation
correlation
moderate
is therefore
is thereforepressures
useful
useful
es una función
where Zlineal
is de
linear
0
0 lain presión.
pressure.
11 Por
Thelo tanto,
generalizedla correlación generalizada
virial-coefficient del
correlation coeficiente
is thereforevirial es
useful útil sólo
only
only
0 y Z where
where
1 son al ZZ 00 and
and ZZ 11 are are at
at least
least approximately
approximately linear linear functions
functions of of reduced
reduced pressure.
pressure. Fig-
Fig-
donde Z only where Z menos
and Zaproximadamente
are at least funciones
approximately
00 lineales
linear de la
functions presión
of reducida.
reduced En la
pressure. figura
Fig- 3.14 se
ure 3.14
ure 3.14 compares
compares the the linear
linear relation of
relation
0 en función of ZZ 00 to
to PPrrr as
as given
given byby Eqs.
Eqs. (3.64)
(3.64) andand (3.65)
(3.65) with
with values
values
comparaure la 3.14
relación
00 lineal
compares de
the Z linear relation de
of P
Z r como
to P r se
as conocen
given by por
Eqs. las ecuaciones
(3.64) and (3.64)
(3.65) with y (3.65)
values con los
of ZZ 000from
of from the the Lee/Kesler
Lee/Kesler compressibility-factor
compressibility-factor correlation, correlation, TablesTables E.1 E.1 and
and E.3.
E.3. The
The two
two cor-
cor-
valores ofde ZZ from
de la the
correlación delcompressibility-factor
factor de compresibilidad de Lee/Kesler, tablas E.1 y E.3. Las dos
cor-correla-
relations
relations differ Lee/Kesler
differ by less
by less than
than 2%2% in in the
the region
region above
above correlation,
the dashed
the dashed Tables
line of
line
E.1
of the
the
and E.3.
figure.
figure.
The
For two
For reduced
reduced
ciones difieren
relations endiffer
menos by de
less2%than en la
2% región
in the que está above
region arriba the de ladashed
línea punteada
line of thedefigure.
la figura.
For Para temperatu-
reduced
temperatures greater
temperatures greater thanthan TTrrr ≈ ≈ 3,3, there
there appears
appears to to be
be no
no limitation
limitation on on the
the pressure.
pressure. ForFor lower
lower
ras reducidas mayoresgreater
temperatures que Trthan ≈ 3,Tparece
r ≈ 3, ser
there queappears
no haytolímite be noenlimitation
la presión. on Para
the valores menores
pressure. For lower que Tr, el
values of
values the allowable
of TTrrr the allowable pressure
pressure range range decreases
decreases with with decreasing
decreasing temperature.
temperature. A A point
point is is
intervalo de presión
values of Tr permisible
the allowable disminuye
pressure conforme
range se reduce
decreases with ladecreasing
temperatura. Sin embargo,
temperature. A se alcanza
point is
20
20 un
reached, however,
reached, however, at ≈ 0.7
at TTrrr ≈ 0.7 where
where the the pressure
pressure range range isis limited
limited by by the
the saturation
saturation pressure.
pressure.
20 Esto 20
20
Tr ≈ 0.7,
punto enreached, donde el
however, at intervalo
T r ≈ 0.7 de presión
where the está limitado
pressure range por
is la presión
limited by de saturation
the saturación.pressure. 11 se indica
This is
This is indicated
indicated by by the
the left-most
left-most segment
segment of of the
the dashed
dashed line.
line. TheThe minor
minor contributions
contributions of of ZZ 11 to
to
por el segmento que estáby
Thiscorrelations
is indicated entheel extremo
left-most izquierdo
segment de the
of la línea.
dashed Seline.
ignoranThe las
minorcontribuciones
contributions másof Zpequeñas
to de
the
the correlations are
are here
here neglected.
neglected. In
In view
view of
of the
the uncertainty
uncertainty associated
associated with
with any
any generalized
generalized
Z 1 a lasthe
correlaciones.
correlations En
are vista
here de la incertidumbre
neglected. In view asociada
of the
00 con
uncertaintycualquier correlación
associated with generalizada,
any generalized las des-
correlation,
correlation, deviations of
deviations of no
no more
more thanthan 2% 2% in in ZZ 0 are
are not
not significant.
significant.
viaciones en Z 0 no mayores
correlation, deviationsdeof2% noson
more irrelevantes.
than 2% in Z 0 are not significant.
The relative
The relative simplicity
simplicity of of the
the generalized
generalized second-virial-coefficient
second-virial-coefficient correlation correlation doesdoes much
much
La simplicidad
The relative relativa de la correlación generalizada del coeficiente virial la hace muy recomendable.
to recommend
to recommend it. simplicity
it. Moreover,oftemperatures
Moreover,
the generalized
temperatures and
and
second-virial-coefficient
pressures of
pressures of many correlation
many chemical-processing
chemical-processing does muchop-
op-
Por otratoparte, las temperaturas
recommend it. y presiones
Moreover, de operación
temperatures and de varios procesos
pressures of many químicos se encuentranop-
chemical-processing dentro de
erations lie
erations lie within
within the the region
region where
where itit doesdoes not not deviate
deviate by by aa significant
significant amount
amount fromfrom the the
la regiónerations
donde no lie sewithin
desvían the enregion
una cantidad
where significativa
it does not de la correlación
deviate by a del factor
significant de compresibilidad.
amount from the Al
compressibility-factor correlation.
compressibility-factor correlation. Like Like the the parent
parent correlation,
correlation, itit is is most
most accurate
accurate for for nonpolar
nonpolar
igual que la correlación generadora,
compressibility-factor ésta esLike
correlation. másthe exacta
parent para especies no
correlation, it polares,
is most y menosfor
accurate para moléculas al-
nonpolar
species and
species and least
least accurate
accurate for for highly
highly polar
polar and and associating
associating molecules.
molecules.
tamentespecies
polaresand y asociadas.
least accurate for highly polar and associating molecules.
1919
19These
These correlations first appeared in 1975 in the third edition of this book, attributed as
Thesecorrelations
19 These correlationsfirst
firstappeared
appearedin in1975
1975in
inthe
thethird
thirdedition
editionofofthis
thisbook,
book,attributed asaaapersonal
attributedas personal communication
personalcommunication
communication
to correlations first appeared in 1975 in the third edition of this book, attributed as a personal communication
to M.
to
19 Estas M.
M. M.
M. Abbott,
M.Abbott,
correlaciones
who
who developed
whodeveloped
Abbott,aparecieron
developedpor
them.
them.
them.
vez primera en 1975 en la tercera edición de este libro, como una comunicación personal de
to M. M. Abbott, who developed them.
M. M. Abbott,20
20 quien
20Although
Althoughlas desarrolló.
the Lee/Kesler tables of Appendix
Althoughthe
20 Although theLee/Kesler
Lee/Keslertables
tablesof AppendixEEElist
ofAppendix list values
listvalues for
valuesfor superheated
forsuperheated vapor
superheatedvapor
vaporandand subcooled
andsubcooled liquid,
subcooledliquid, they
liquid,they do
theydo not
donot
not
20 Aunque lasvalues
tablasthe
de Lee/Kesler
Lee/Kesler del apéndice
tables E exhiben
of Appendix E listvalores
values para el vapor sobrecalentado
for superheated y el líquido
vapor and subcooled subenfriado,
liquid, no propor-
they do not
provide
provide
provide values
values at
at saturation
atsaturation
saturation conditions.
conditions.
conditions.
provide
cionan valores en values at saturation
condiciones conditions.
de saturación.

3.6. Correlaciones generalizadas
3.6. Generalized
Generalized para
Correlations forgases
Gases 103 103
3.6. Correlations for Gases 103
4.0
4.0
4.0
4.0
1.0
1.0
1.0
1.0 2.4
2.4
2.4
2.4
1.8
0.9 1.8
1.8
1.8
0.9
0.9
0.9
Z0
ZZ000
Z
T  0.8
� 0.8
TTrr � 0.8 0.9
T rr � 0.8
0.9
0.9
0.9 1.0 1.1 1.5
0.8 1.0 1.1
1.1
1.1 1.5
1.5
1.5
0.8 1.0
1.0
0.8
0.8
1.3
1.3
1.3
1.3
0.7
0.7
0.70.0
0.7 0.5 1.0 1.5 2.0 2.5
0.0
0.0
0.0 0.5
0.5
0.5 1.0
1.0
1.0 1.5
1.5
1.5 2.0
2.0
2.0 2.5
2.5
2.5
Pr
P
Prrr
P
Figura 3.14:
Figure Comparación
3.14: de correlaciones
Comparison of correlations Z 0.ZLa
para for 0 correlación del coeficiente virial is
se represented
representa por medio de lí-
Figure 3.14:
Figure 3.14: Comparison
Comparison of of correlations
correlations for
for ZZ00... The
The virial-coefficient
The virial-coefficient correlation
virial-coefficient correlation
correlation is
is represented
represented byby the
by the
the
neas rectas; la correlación
straight lines; the de Lee/Kesler
Lee/Kesler mediante
correlation, by los
the puntos.
points. En
In la región
the region por encima
above the de la
dashed líneathe
line discontinua,
two las dos
straight lines;
straight lines; the
the Lee/Kesler correlation,
correlation, by
by the
the points.
points. In
In the
the region
region above
above the
the dashed
dashed line
line the
the two
two
correlaciones
correlations por Lee/Kesler
difierendiffer menos
by less de 2%.
than 2%.
correlations differ
correlations differ by
by less
less than
than 2%.
2%.
Correlaciones parafor
Correlations
Correlations elthe
for tercer
the coeficiente
Third
Third virial
Virial Coefficient
Virial Coefficient
Accurate precisa
La información
Accurate data for
data forpara
third
third virial
losvirial coefficients
terceros are viriales
coeficientes
coefficients are far less
far less es
common than
bastantethan
common for
másfor second
escasa virial
quevirial
second coef-
para los segundos
coef-
ficients.
coeficientes Nevertheless,
viriales.
ficients. No obstante,
Nevertheless, generalized correlations
aparecencorrelations
generalized for
en la literatura third virial
for correlacionescoefficients do
generalizadas
third virial coefficients appear in the
para losinterceros
do appear the co-
literature.
eficientes viriales.
literature.
Equation
La ecuación (3.40)
(3.40)
Equation puede
(3.40) may
may be written:
written:
escribirse:
be
Z=
Z = 11 +
+ Bρ
Bρ + Cρ 222
+ Cρ (3.67) (3.67)
(3.67)
where
donde rwhere
= 1/Vρ =la1/V
ρes= 1/V is molar
molar
densidad
is density.
molar. Rewritten
Al volverse
density. in reduced
reduced
a escribir
Rewritten in form, reducida,
en forma
form, this equation
this equation becomes:
esta becomes:
ecuación se convierte en:
�
� �
Pr
P Pr �222
P
Z = 1 + B̂ rr + Ĉ
Z = 1 + B̂ T Z + Ĉ T Z
rr (3.68) (3.68)
(3.68)
Trrr Z Trrr Z
donde el segundo
where coeficiente
the reduced
reduced virialvirial
second reducido está definido
coefficient B̂ is por la by
is defined
defined ecuación (3.62)and
Eq. (3.62),
(3.62), y elthe
tercer coeficiente
reduced third virial
where
reducido se the
define como: second virial coefficient B̂ by Eq. and the reduced third
virial coefficient
virial coefficient is
is defined
defined as:
as:
CP
C Pc222
Ĉ ≡
Ĉ ≡ R 222Tcc222
R Tc cc
Una correlación
A tipo correlation
A Pitzer-type
Pitzer-type Pitzer para Ĉ
correlation forseĈ
for Ĉescribe:
is written:
is written:
=C
Ĉ =
Ĉ C 000 +
+ω C 111
ωC (3.69) (3.69)
(3.69)

104 CAPÍTULO 3. Propiedades volumétricas de21fluidos puros
An expression for C0
as a function of reduced temperature is given by Orbey and Vera:
An expression for C as a function of reduced temperature is given by Orbey and21Vera:21
0
Una expresión para C 0 como una función de temperatura reducida
0.02432 la dan Orbey y Vera:
0.00313
C 0 = 0.01407 + − (3.70)
0 Tr
0.02432 Tr10.5
0.00313
C = 0.01407 + − (3.70) (3.70)
1
Tr Tr10.5
The expression for C given by Orbey and Vera is replaced here by one that is algebraically
Aquí, la expresión para C 1 conocida por Orbey y Vera se reemplaza por una que en términos algebraicos es
simpler, but essentially
The expression for C 1 equivalent
given numerically:
by Orbey and Vera is replaced here by one that is algebraically
más simple, pero numéricamente es equivalente:
simpler, but essentially equivalent numerically:
0.05539 0.00242
C 1 = −0.02676 + − (3.71) (3.71)
1 Tr2.7
0.05539 Tr10.5
0.00242
C = −0.02676 + − (3.71)
La ecuación (3.68) es cúbica en Z, y no es posibleTexpresarla
2.7 Ten10.5
la forma de la ecuación (3.57). Al es-
Equation (3.68) is cubic in Z , and cannot ber expressedr in the form of Eq. (3.57). With
pecificarse Tr y Pr, la solución para Z es por iteración. Una aproximación inicial de Z = 1 en el lado derecho
Tr andEquation
Pr specified, solution
(3.68) is cubicfor ZZ is by iteration.
beAn initial guess Z =of1 Eq.
in theofform on the rightWith
side
de la ecuación (3.68) por lo general nosinlleva
, and cannot
a una expressed
convergencia rápida. (3.57).
of
Tr Eq.
and(3.68) usually solution
Pr specified, leads to rapid
for Z convergence.
is by iteration. An initial guess of Z = 1 on the right side
of Eq. (3.68) usually leads to rapid convergence.
Condiciones
Conditions de validez aproximada
of Approximate de laofecuación
Validity del gas
the Ideal-Gas ideal
Equation
Conditions
The of arises
question often Approximate Validity
as to when the ideal-gasof the Ideal-Gas
equation may be used Equation
as a reasonable ap-
Con frecuencia surge la pregunta acerca de cuándo la ecuación del gas ideal puede utilizarse como una aproxi-
maciónproximation
razonable
The question tooften
a la reality.
realidad.Figure to3.15
Laasfigura
arises canthe
3.15
when serve
puede as a guide.
servir
ideal-gas como unamay
equation guía.
be used as a reasonable ap-
proximation to reality. Figure 3.15 can serve as a guide.
10
10
10
Z 0 � 1.02
1 Z 0  1.02
Z 0 � 1.02
1 1
Z 0 � 0.98
Figure 3.15: Region where Z 0 lies Pr 0.1
Z 0 � 0.98
Z 0  0.98
between 0.98 Region
Figure 3.15: and 1.02, and the
where Z 0 lies Pr 0.1
Pr 0.1
Figura 3.15: Región
ideal-gas dondeisZ a0 reasonable
equation reside
between 0.98 and 1.02, and the
entre 0.98 y 1.02, y la ecuación del gas
approximation.
ideal-gas equation is a reasonable
ideal es una aproximación razonable.
approximation.
0.01
0.01
0.01
0.001
0 1 2 3 4
0.001 Tr
0
0.001 1 2 3 4
0 1 Tr 2 3 4
Tr
21 H. Orbey and J. H. Vera, AIChE J., vol. 29, pp. 107–113, 1983.
21 H. Orbey and J. H. Vera, AIChE J., vol. 29, pp. 107–113, 1983.
21 H. Orbey y J. H. Vera, AIChE J., vol. 29, 107-113, 1983.

3.6. Generalized
Correlations for
for Gases
Gases 105
105
3.6.
3.6. Generalized
Generalized
3.6. Correlaciones Correlations
parafor
Correlations
generalizadas for Gases
Gases
gases 105
105 105
Example 3.10
Example 3.10
Ejemplo 3.10
Example
Example
Determine the
3.10
3.10
the molar
molar volume
volume of n-butane at
of n-butane at 510
510 K
K and
and 25
25 bar
bar by
by each
each of
of the
the following:
following:
Determine the molar volume of n-butane at 510 K and 25 bar by each of the following:
Determine
Determine
Determine the molar volume of n-butane at 510 K and 25 bar by each of the following:
Determine the molar
el volumen molar de
volume of n-butane
n-butano a 510 K at 510
y 25 K mediante:
bar and 25 bar by each of the following:
(a) The
(a) The ideal-gas
ideal-gas equation.
equation.
(a)
(a) The
The ideal-gas
a) La ecuación ideal-gas
del equation.
equation.
gas ideal.
(b) The
(b) The generalized
generalized compressibility-factor
correlation.
b) La correlación
(b)
(b) The generalizada
The generalized
generalized del factor de compresibilidad.
compressibility-factor
correlation.
(c) Equation
(c) Equation (3.61),
(3.61), with
with the
the generalized
generalized correlation
correlation for
for B̂.
B̂.
c) La ecuación
(c) (3.61)(3.61),
(c) Equation
Equation con lawith
(3.61), correlación
with the generalizada
the generalized
generalized para B̂.for
correlation
correlation for B̂.
B̂.
(d) Equation
(d) Equation (3.68),
(3.68), with
with the
the generalized
generalized correlations
correlations for
for B̂ and Ĉ.
B̂ and Ĉ.
d) La ecuación
(d) (3.68)(3.68),
(d) Equation
Equation con laswith
(3.68), correlaciones
with the generalizadas
the generalized
generalized parafor
correlations
correlations B̂ yB̂
for B̂Ĉ.
and
and Ĉ.
Ĉ.
Solution
Solución 3.10
3.10 3.10
Solution
Solution
Solution 3.10
3.10
a) Por la(a)
ecuación
(a) By the
By del gas ideal,
the ideal-gas
ideal-gas equation,
equation,
(a)
(a) ByBy thethe ideal-gas
ideal-gas equation, equation,
RT (83.14)(510)
V=
V = RT RT
RT = (83.14)(510)
= (83.14)(510)
(83.14)(510) == 1,696.1
1,696.1 cm cm33 mol
mol−1 −1
P 25 33 −1
VV = = P = = 25 == 1,696.1
1,696.1 cm cm mol mol−1
PP 25
25
b) De los(b)valores
(b) From the
From the values
de Tvalues
c y Pc of
of TTcc and
conocidos and P Pen given
la tabla
cc given
in Table
in Table
B.1 del B.1
B.1 of App.
apéndice
of App.B, B,
B,
(b)
(b) From
From the the values
values of of TTcc and and PPcc given
given in in Table
Table B.1 B.1 of of App.
App. B, B,
510
510 25
25
TTrr = = 510 510 = = 1.200
1.200 Pr =
P = 25 25 = = 0.659
0.659
TTrr = 425.1
= 425.1 =
= 1.200
1.200 PPrrr = 37.96
= 37.96 == 0.659
0.659
425.1
425.1 37.96
37.96
Interpolation in Tables E.1 and E.2 then provides:
La interpolación
Interpolation
Interpolation
Interpolation en las in tablas
in
TablesE.1
in Tables
Tables E.1
E.1yand
E.1 and E.2E.2
and E.2proporciona:
E.2
then provides:
then
then provides:
provides:
Z 00 =0 0.865 Z 1
11 = = 0.038
0.038
=
ZZ00Z= = 0.865 ZZ ZZ= 11 0.038
Z 0.865
= 0.865
0.865 =
= 0.038
0.038
Thus,
Así, mediante
Thus, by by Eq.
la ecuación (3.57)
Eq. (3.57)(3.57) with
with ωcon ω =
=w 0.200,
= 0.200,
0.200,
Thus,
Thus, by by Eq.
Eq. (3.57)
(3.57) with with ω ω= = 0.200,
0.200,
0 1
ZZ = = ZZ 0 + + ωZ ωZ 1 = = 0.865
0.865 + + (0.200)(0.038)
(0.200)(0.038) = = 0.873
0.873
ZZ = = ZZ00 + + ωZ ωZ11 = 0.865 +
= 0.865 (0.200)(0.038) =
+ (0.200)(0.038) = 0.873
0.873
Z RT
Z RT (0.873)(83.14)(510)
(0.873)(83.14)(510) −1
and
and VV= = ZZ RT RT = = (0.873)(83.14)(510)
(0.873)(83.14)(510) = 1,480.7
= 1,480.7 cm cm33 mol
mol−1
P 25 33 −1
−1
y and
and VV == P =
= 25 =
= 1,480.7
1,480.7 cm
cm mol
mol
PP 25
25
If ZZ 11,, the
If the secondary
secondary term, term, is is neglected,
neglected, ZZ = = ZZ 00 = = 0.865.
0.865. ThisThis two-parameter
two-parameter
If ZZ11,, the
Si se desprecia
If el
the término
secondary
secondary
corresponding-states secundario,
term,
term, is
correlation Z 1, Z = Z 0Z
is neglected,
neglected,
yields V = = ZZ00 Así,
=
Z=1,467.1
0.865. =cm 3 con
= 0.865.
0.865.
3 mol −1
la correlación
This
−1This
, dethan
two-parameter
whichtwo-parameter
is less
less estados co-
than
corresponding-states correlation yields V = 1,467.1 cm 3cm 33 mol −1,,, which
−1
–1, que
is
rrespondientes de dos
1% lower than parámetros
the correlation
correlation
value se
given obtiene
by yieldsV
yields
the
1% lower than the value given by the three-parameter correlation. =VV1==467.1
1,467.1
1,467.1
three-parameter cm cmmol mol
mol
correlation. es 1%
which
which menor
is
is less que
less than
than el valor
conocido 1%
1% por la correlación
lower
lower than
than the the de
value
value tresgiven
givenparámetros.
by
by the
the three-parameter
three-parameter correlation.
correlation.
(c) Values
(c) Values of of B B00 andand B B11 are are given
given by by Eqs.
Eqs. (3.65)
(3.65) and and (3.66):
(3.66):
00 and
(c)
(c) Values
Values of
of0
c) Los valores de B y B se conocen
BB 1
and B11 are
B are given por by
given las ecuaciones
by Eqs.
Eqs. (3.65)
(3.65) and (3.65)
and (3.66):y (3.66):
(3.66):
B 00 = −0.232 B 11 = 0.059
B 00 =0 −0.232 B
1B= 11 = 0.059
BB B = ==−0.232
–0.232 B B
−0.232 =
0.059
= 0.059
0.059
Equations (3.63)
Equations (3.63) and and (3.61)
(3.61) then then yield:
yield:
De las ecuaciones
Equations
Equations (3.63) (3.63) and yand(3.61)
(3.61)
(3.61) sethen
obtiene:
then yield:
yield:
B̂ = B 00 + ωB11 = −0.232 + (0.200)(0.059) = −0.220
B̂ = B 00 + ωB 11 = −0.232 + (0.200)(0.059) = −0.220
B̂B̂ = = BB + + ωB ωB = = −0.232
−0.232 + (0.200)(0.059) =
+ (0.200)(0.059) = −0.220
−0.220
0.659
0.659
ZZ = = 11 + + (−0.220)
(−0.220) 0.659 0.659 = = 0.879
0.879
ZZ = = 11 + + (−0.220)
(−0.220)1.200 1.200 == 0.879
0.879
3 mol−1 −1 , a value 1.200
1.200
from which V = 1,489.1
from which V = 1,489.1 cm33 mol−1 cm 3 less than 1% higher
higher than
than that
that given
given
from
from which
which VV == 1,489.1
1,489.1 cm
cm mol
mol −1,,, a value less than 1%
aa value
value less
less than
than 1%
1% higher
higher than
than that
that given
given por la
by
de la cual the compressibility-factor 3 –1
correlation.
by se
theobtiene V = 1 489.1 cmcorrelation.
compressibility-factor mol , un valor que es 1% mayor que el conocido
by
by the
the compressibility-factor
correlation.
correlación del factor de compresibilidad.

106
106 3.
CHAPTER 3.
Volumetric Properties of
of Pure
Pure Fluids
Fluids
106
106 CHAPTER 3.
CHAPTER 3.Volumetric
Properties of
of Pure
Pure Fluids
Fluids
106 106 CAPÍTULO 3. Propiedades volumétricas de Fluids
CHAPTER 3.Volumetric Properties of Pure fluidos puros
(d) Values
(d) Values of of C C000 and
and C C111 are
are given
given by by Eqs.
Eqs. (3.70)
(3.70) and and (3.71):
(3.71):
(d) Values of
0 C 0 and
1 C are
are given
C11 dados by Eqs. (3.70)
(3.70) and (3.71):
d) Los valores
(d) Values
(d) de C
Values of yC
of CC and
0 andestán
C are por by
given
given lasEqs.
by ecuaciones
Eqs. (3.70) (3.70)
and
and y (3.71):
(3.71):
(3.71):
C 000 = 0.0339 C 111 = 0.0067
C 0=0==0.0339
= C1 11 = 0.0067
CCC
C0 =
0.0339
0.0339 C C
0.0339
0.0339 CC= = == 0.0067
0.0067
0.0067
0.0067
Equation
Equation (3.69)
(3.69) then
then yields:
yields:
Por lo tanto,
Equationla ecuación
Equation
Equation
(3.69)
(3.69) then
(3.69) (3.69)
then
then nos da:
yields:
yields:
yields:
Ĉ = C 00 + ω C111 = 0.0339 + (0.200)(0.0067) = 0.0352
0
ĈĈ =
Ĉ = =C
C 00 +
C + +ω
ωC
ωC C11 =
= 0.0339
0.0339+
= 0.0339
+ (0.200)(0.0067)
(0.200)(0.0067) =
+(0.200)(0.0067)
= 0.0352
= 0.0352
0.0352
Ĉ = C + ω C = 0.0339 + (0.200)(0.0067) = 0.0352
With
Con esteWith this
valorthis value
de value of
Ĉ y elofvalor Ĉ and
Ĉ and de thethe
B̂ delvalue
inciso
value of
of B̂B̂ from part
la ecuación
c),from (c),
part (c), Eq.
(3.68) (3.68) becomes,
se convierte
Eq. (3.68) becomes, en,
With
With thisthis value
value of of ĈĈ and
and the the value
value of of B̂
B̂ from
from part part (c),(c), Eq.
Eq. (3.68)
(3.68) becomes,
becomes,
With this value of Ĉ and the value
� of B̂ from� part (c), Eq.
� (3.68) becomes,
�
� 0.659 �
�� 0.659 �� 0.659 �
�� 0.659 ��222
Z = 1 + (−0.220) � 0.659 � + (0.0352) � 0.659 �
ZZZ =
= 11 ++ (−0.220)
(−0.220) 0.659 +
0.659
1.200Z + (0.0352)
(0.0352) 0.659 22
0.659
1.200Z
= 1 + (−0.220) 1.200Z
Z = 1 + (−0.220) 1.200Z + (0.0352) 1.200Z + (0.0352) 1.200Z
1.200Z
1.200Z 1.200Z
1.200Z
0.121 0.0106
or Z = 11 − − 0.121
0.121 + 0.0106
0.0106
o
or
or
or ZZ =
Z =
= 11− − Z +
0.121
0.121
Z ++
0.0106
0.0106
Z22
or Z =1− Z + Z ZZ222
ZZ Z
Whence, Z = 0.876 and V = 1,485.8 cm333 mol
mol−1−1
Whence,
Whence, ZZZ = ==
0.876
0.876 and
and VV =
V ==
1,485.8
1,485.8 cm
cm 3 mol
−1
−1
De donde, Whence,
Whence,
ZZ 0.876
==0.8760.876 and andy VV ==1 1,485.8 1,485.8
485.8 cm cm
cm 3
3 molmol
mol-1−1
The value
The value of of V V differs from from that
that of of part
part (c)
(c) by by about
about 0.2%.
0.2%. An An experimental
experimental
The value of VV differs
differs 3from −1that of part (c) by about 0.2%. An experimental
El valor
value
value de
The
Thefor
forV difiere
value
V
value
V is of del
1,480.7
of V que
differs
cm
differs corresponde
3 from
mol
from −1 that
.
that of al inciso
part
Significantly,
of part (c)
(c) c)
by
bytheen aproximadamente
about 0.2%.
results
about 0.2%.of An
parts
An (b), 0.2%.
experimental
(c), and
experimental andUn valor
value for VV is
isis 1,480.7
1,480.7 cm
cm 3 mol
33mol
−1 .. Significantly,
−1
−1–1 Significantly, the
the results
results of
of parts
parts (b),
(b), (c),
(c), and
experimental
value
(d)
value
(d) are
are para
for
in
for
in V es
excellent
V is
excellent 1 480.7
1,480.7
1,480.7 cm
cm
agreement.
cm
agreement.
3 mol
mol
mol Mutual
Mutual.
.. De manera
Significantly,
agreement
Significantly,
agreement at significativa,
the
at
the results
these los
of resultados
parts
conditions
results of
these conditionsparts (b),
is de
(c),
suggested
(b),
is (c), los
and
and incisos
(d) are in excellent agreement. Mutual
Mutual agreement atat these conditions isissuggested
suggested
b), c) y d)
(d)seFig.
by
(d)
by encuentran
are
are
Fig.
in excellent
3.14.
in excellent
3.14. en excelente
agreement.
agreement. concordancia.
Mutual agreementLa
agreement mutuaat correlación
these
these conditions
conditions de estas
is condiciones
suggested
suggested se
by Fig. 3.14.
sugiere enbyla
by figura
Fig.
Fig. 3.14.3.14.
3.14.
Example 3.11
Example 3.11
Example
Ejemplo 3.11 3.11
What pressure is generated when
when 1(lb mol)
mol) of methane
methane is stored
stored in aa volume 2(ft)33
volume of 2(ft)
What
What pressure
pressure is
is generated
generated when 1(lb
1(lb mol) of
of methane is
is stored in
in a volume of
of 2(ft)3
What
at 122(
What ◦◦ F)? Base
pressure
pressure is generated
is generated when
calculations 1(lb mol)
on each
when 1(lb mol)
of offollowing:
theof methane is
methane is stored
stored in
in aa volume
volume of 2(ft)33
of 2(ft)
at 122(se
¿Qué presión ◦ F)? Base
genera calculations on each of the de metano en un volumen de 2(pie) 3 a 122(°F)?
following:
at
at 122(
at 122(◦◦F)?
122( F)?
F)? Basecuando
Base
Base
se almacena
calculations
calculations
calculations
on
on
1(lb
on each
each
each ofmol)
of
of
the
the following:
the following:
following:
Apoye sus cálculos
(a) The en lo siguiente:
ideal-gas equation.
(a)
(a) The
The ideal-gas
ideal-gas equation.
equation.
(a) The
(a) The del
a) La ecuación ideal-gas
ideal-gas equation.
equation.
gas ideal.
(b) The Redlich/Kwong equation.
(b)
(b) The
b) La ecuación Redlich/Kwong
The de equation.
Redlich/Kwong.
(c) A generalized correlation.
c) Una(c)
(c)
(c)
A
AA generalized
correlación
generalized
generalized
correlation.
generalizada.
correlation.
correlation.
(c) A generalized correlation.
Solution
Solución 3.11
3.11 3.11
Solution
Solution 3.11
Solution 3.11
Solution 3.11
a) Por la(a)
ecuación
By the del gas ideal,
the ideal-gas
ideal-gas equation,
(a)
(a) By
By the ideal-gas equation,
equation,
(a) By the ideal-gas equation,
RT (0.7302)(122 + + 459.67)
459.67)
P = RT
RT = (0.7302)(122
(0.7302)(122 +
+459.67) = 212.4(atm)
212.4(atm)
PP =
P ==
RT
RT
VV =
=
=
(0.7302)(122
(0.7302)(122 2
2
+ 459.67) =
459.67) == 212.4(atm)
212.4(atm)
P= V = 22 = 212.4(atm)
VV 2
(b) The
b) La presión
(b) The pressure
sepressure as given
conoce por
as given by the
the Redlich/Kwong
la ecuación
by Redlich/Kwong
de Redlich/Kwong equation is:
que es:is:
equation
(b)
(b) The
The pressure
pressure as
as given
given by
by the
the Redlich/Kwong
Redlich/Kwong equation
equation is:
is:
(b) The pressure as given by the Redlich/Kwong
RT equation
a(T )) is:
P=
P = RT RT
RT − a(T
− a(T
a(T)) (3.47)
(3.47)
PP ==V VRT− bb −−V
a(T+) b)
V (V
(V (3.47)
P= VV −
− b − V
− bb VV(V (V +
+
+ b)
(V +
b)
b)
b)
(3.47)
(3.47) (3.47)
V−

3.6. Generalized
3.6. Correlaciones generalizadasCorrelations parafor gasesGases 107 107
3.6. Generalized
3.6. Generalized Correlations Correlations for for Gases Gases 107
107
3.6.
3.6. Generalized
Correlations for
for Gases
Gases 107
–1/2
Tr r) =inTr 107 107
−1/2
Los valores
Values de of a(T) a(T y )b and se desarrollan
b come from de Eqs.las ecuaciones
(3.45) and (3.45) (3.46),ywhere (3.46),α(T donde r ) = a(T en
la ecuación
Eq. (3.45). Con
Values of of a(T
Withlos
a(T )) and
values
and bb come valores of Tde
come from c and T
fromc Eqs. y PP del
from
Eqs.c (3.45)
c apéndice
(3.45) and
Table B.1
and (3.46), B convertidos
converted
(3.46), where where α(T
to a
(R)
α(Tr )) = (R) and y
= TTr−1/2(atm),
(atm),
−1/2
−1/2 in
Values
Values of rrrr)))= TTTrr−1/2
−1/2in in
Values
Values
Eq. (3.45).ofa(T
of a(T
a(TWith
)))and
and
andvalues
bbbcome
come
come
of T
from
from
from
and
Eqs.
c andTPc fromEqs.
Eqs.
P
(3.45)
(3.45)
from(3.45)
581.67
and
Tableand
and (3.46),
(3.46),
B.1(3.46),
converted
where
where
where α(T
α(T
α(T
to (R) ==
and (atm),
rr in
in
Eq.
Eq. (3.45). With values of T Table B.1 converted to (R) and (atm),
Eq.(3.45).
Eq. (3.45).With
(3.45). Withvalues
With valuesof
values ofTTTcccrcand
of andPPPcccc=
=
and from
fromTable
from Table
Table =B.1 1.695
B.1
B.1 converted
convertedto
converted toto(R)
(R)and
(R) and(atm),
and (atm),
(atm),
Tc
T 343.1
581.67
Tr =
T = TTTT = 581.67
= 581.67
581.67
581.67 = 1.695
= 1.695
TTTrr = =
= TTTccc(0.7302) 343.1 = =1.695
(1.695) rr = −1/2 == 343.1
343.1 =
2 (343.1) 1.695
1.695
2
6
a = 0.42748 TTcc 343.1
343.1 = 453.94(atm)(ft) (pie)6
(1.695)−1/2 −1/2 45.4
(0.7302)22 (343.1)
−1/2 (0.7302)
2 (343.1)22 2
a= = 0.42748
0.42748(1.695) (1.695) −1/2(0.7302) 22(343.1) 453.94(atm)(ft)666
= 453.94(atm)(ft)
aaaa= 0.42748 (1.695)−1/2
(1.695) (0.7302)
(0.7302)
(0.7302)(343.1)
45.4 (343.1)22 =
(343.1) = 453.94(atm)(ft) 66
== 0.42748
0.42748 b = 0.08664 45.4 45.4 == 453.94(atm)(ft)
= 0.4781(ft) 33
453.94(atm)(ft)
(pie)
45.4
45.4 45.4
(0.7302)(343.1)
(0.7302)(343.1) 3
Substitution of numerical b= = 0.08664
0.08664 values (0.7302)(343.1)
(0.7302)(343.1)
(0.7302)(343.1)
into 45.4
the Redlich/Kwong == 0.4781(ft)
0.4781(ft) 3333
equation now yields:
bbbb= = 0.08664
= 0.08664
0.08664 === 0.4781(ft)
0.4781(ft)
0.4781(ft)
45.4
45.4
Sustituyendo los valores numéricos en la ecuación 45.4
45.4 de Redlich/Kwong, se obtiene:
Substitution of
Substitution of numerical
numerical
(0.7302)(581.67) values into
values into thethe Redlich/Kwong
Redlich/Kwong
453.94 equation now
equation now yields: yields:
Substitution
SubstitutionPof
Substitution of=numerical
of numericalvalues
numerical valuesinto
values into−the
into theRedlich/Kwong
the Redlich/Kwong
Redlich/Kwong =equation
187.49(atm)
equation
equation nownowyields:
now yields:
yields:
2 − 0.4781
(0.7302)(581.67) (2)(2453.94 + 0.4781)
P= (0.7302)(581.67)
= (0.7302)(581.67) − 453.94
453.94 = 187.49(atm)
187.49(atm)
P = (0.7302)(581.67)
(0.7302)(581.67)
− 0.4781 −− 453.94
453.940.4781) =
+ 0.4781) =
(c) BecausePPPthe = = pressure 2−
2222−
0.4781
here is high,
0.4781 − (2)(2
−(2)(2 the generalized
(2)(2 ++ 0.4781) ==187.49(atm)
187.49(atm)
187.49(atm) cor-
relation is the proper − − 0.4781
0.4781
choice. In the absence (2)(2 +
(2)(2 +of0.4781)
0.4781)
a known value for Pr , an iterative
(c) Because
Because the the pressurepressure here here is is high,
high, the the generalized
compressibility-factor cor- cor-
c) Ya que (c)en
(c)
(c)
procedure
(c) este caso
Because
Because
Because isthe
based
the
the lapressure
presión
pressure
pressureon thees here
here alta,
following
here isisla
is elección
high,
high,
high, the
equation:
the apropiada es
thegeneralized
generalized
generalized la correlación del factor
compressibility-factor cor-de com-
cor-
cor-
relation is the proper choice. In the absence of a known value for P r , an iterative
presibilidad.
relation
relation
relation En
relation is
isausencia
is the proper
the
is isthe
thebased
proper
proper
proper de un
choice.
choice.valor Inconocido
In the absence
the absence para of
P
of ,
aael procedimiento
known
known
ofr aa known
value
value for
for iterativo
P
P r
for PPrrr,, an
,
, an
an iterative en la
se
iterative
iterativeapoya
procedure onchoice.
choice.
theZ RT followingIn
In the the absence
absence of
equation:
Z (0.7302)(581.67) known value value for an iterative
siguiente ecuación:
procedure
procedure
procedure
procedure is
is based
is based on
basedPon
is based
on
on=the
the
the following
following
the following
following=
equation:
equation:
equation:
equation: = 212.4 Z
Z V
RT Z (0.7302)(581.67) 2
P= = ZZZZRT RT = ZZ(0.7302)(581.67)
RTRT = =
(0.7302)(581.67) = 212.4 Z
ZZ(0.7302)(581.67)
(0.7302)(581.67) = 212.4
Because P = Pc P P
PPr = =
= 45.4P
= V r=,=this equation 2 becomes: ==
212.4 ZZ
= 212.4
212.4 ZZ
V
VVV 2222
Because P
Because P= =P Pc P Pr = = 45.4P
45.4P 45.4P , this
r rrr,, this
this equation
equation becomes: becomes: Z
Ya que Because
P = PcPr PP
Because
Because =P = 45.4
== PP PccccPPP
Z =Prrr,r =esta
=45.4P
= ecuación
45.4P
45.4P = thisserá:
rr,,0.2138
this equation
Pr
equation
equation becomes:
or
becomes:
becomes: Pr =
212.4
45.4Pr 0.2138Z
Z= = 45.4P 45.4P rrrr = = 0.2138
0.2138 P Pr or Pr = = ZZZZ
Z
Z = 45.4P
45.4P = 0.2138 P or
or PP =
One now assumes ZZ = = 212.4 212.4
a starting
212.4 == 0.2138 value for
0.2138 r
PPrrr Z , say orZ = 1.
o
or r
PPrrrThis
= gives Pr = 4.68, and
0.2138
= 0.2138
0.2138
allows a new value 212.4 212.4
of Z to be calculated by Eq. (3.57) from 0.2138
0.2138values interpolated
One now
One now assumesassumes aa starting starting value value for for ZZ,, say say ZZ = = 1.1. This This gives
gives P Pr = = 4.68,
4.68, and and
One
in Tables
One
One now
now
nowE.3 assumes
and
assumes
assumes E.4 aaa starting
at the
starting
starting value
reduced
value
value for
for
for ZZ Z ,
temperature,,say
say
say ZZZ ==of
= 1.
1. T
1. This
r =
This
This gives
1.695.
gives
gives r = 4.68,
PPPrWith == this and
4.68,
4.68, new
and
and
allows
Se puede a
suponernew value
un valor of Z
of Zinicial to be paracalculated
Z, digamos by Eq.
Z =the (3.57)
1. Ésta from
da Pvaluesvalues
=continues
4.68, interpolated
y permite
until nocalcular
rr
allows
allows
value aaaanew
of new
Znew value
, a value
new of
value Z oftoto P be
be calculated
calculated by and
by Eq.
Eq. (3.57)
(3.57) from
from rvalues interpolated
interpolated
allows
allows new value
value of
of Z
Z to
to ber is
be calculated,
calculated
calculated by
by Eq.
Eq. procedure
(3.57)
(3.57) from
from values
values interpolated
interpolated
in
con la ecuaciónTables
Tables(3.57) E.3 and
un valor E.4 at the
atnuevo reduced
de Z asteptemperature
partir de los of
valores T = 1.695.
interpolados With this new
in
ininTables
significant E.3
E.3 change and
and
andE.4
E.4
occurs at the
the from reduced
reducedone temperature
temperature
to the next. ofThe
of r
TTTTrr = =
final1.695.
1.695.
valueWith of Zenthis
With solasfound
this tablas E.3 y
new
new
in
value
E.4 a lavalue Tables
Tables
of ZZE.3
temperatura E.3 and
, aareducida
new E.4
E.4
value deat
atof
Tthe
the =Prreduced
reduced
is calculated,
1.695. temperature
temperature
calculated,
Con este and
valor theof
of rr =
procedure
nuevo =de 1.695.
1.695.
Z secontinuesWith
calculaWith this
unthis
until new
new
no recien-
valor
value
is 0.890of
of ZZat ,
,,,aaP new
new
rnew = value value
4.14. of of r
This P
PPPrr isis
may calculated,
be confirmed and
and the
the procedure
byprocedure
substitution continues
continues
into Eq. until
until no
no
(3.57)
value
value
significant
te de Prsignificant
,ofy el of
of Z
procedimiento a
change new value
value
occurs
continúaof
of from is
is
one calculated,
calculated,
step to the and
andnext.the
the procedure
procedure
The final valuecontinues
continuesof Z sountil
until
found no
noun paso
significant
values change
change
for Z 0 and occurs
occurs Z 1 fromfromhastarr
one
one
Tables queE.3
step
step no
to the
to ocurra
the
and E.4ningún
next.
next. The final
The
interpolated cambio
final value
value atsignificativo
of
Pof r = ZZZZ so
so
4.14 found
foundde
and
significant
significant
is
al siguiente. 0.890 at change
change
P = occurs
occurs
4.14. from
from
This one
one
may step
step
be to
to
confirmedthe
the next.
next. by The
The final
final
substitution value
value intoof
of Eq.so
so found
found
(3.57)
is =El1.695.
isTr0.890
0.890 valor
at P
at rfinal
r
PWith =
= de=Z0.012,
4.14.
4.14.
ω que This
This se may encuentra
may be es de 0.890
be confirmed
confirmed by para
by Pr = 4.14.
substitution
substitution into
into Éste Eq.
Eq. se(3.57)
puede confir-
(3.57)
0=
is
isla0.890
of 0.890
values atforPPrrZ
at rZ0en0=and 4.14.
4.14. Z111 from
This
This (3.57)
from may
may be
Tables be confirmed
E.3confirmed
and E.4 by by substitution
substitution
interpolated 0 y Z at 1 deinto
Pinto =Eq.
Eq.4.14 (3.57)
(3.57)
and
mar porofof sustitución
values
values for
for ZZZ00 and and la ecuación
Z
ZZZ11 from Tables
Tables deE.3
E.3 los and
and valores
E.4
E.4 para
interpolated
interpolated Z at
at P r las
PPPr =
r = tablas
4.14
4.14 E.3 y E.4,
and
and
of
Tof
interpolados values
values
= 1.695.
en P for
for= With
4.14 and
and
ω
y =
T 0 from
0.012,
= from
1.695. 1 Tables
Tables
Con w E.3
E.3
= and
and
0.012, E.4
E.4 interpolated
interpolated at
at r r =
= 4.14
4.14 and
and
T r
TTTr = = 1.695. r With Z = ω =
Zr +
0.012, ωZ = 0.887 + (0.012)(0.258) = 0.890
r
=1.695.
= 1.695.With
1.695.
rr Withωωω===0.012,
With 0.012,
0.012,
0 1
ZZ ==ZZZRT + ωZ
00 + 11 = = 0.887
0.887 +
ωZ(0.890)(0.7302)(581.67) + (0.012)(0.258)
(0.012)(0.258) = = 0.890
0.890
PZZZ==== ZZZ00+++ωZ=ωZ11=
ωZ = 0.887+
=0.887
0.887 ++(0.012)(0.258)
(0.012)(0.258)
(0.012)(0.258) =
==0.890
= 189.0(atm)
0.890
0.890
Z V
RT (0.890)(0.7302)(581.67)2
PP= = ZZZZRT
RT = (0.890)(0.7302)(581.67)
RT
RT factor
(0.890)(0.7302)(581.67) = 189.0(atm)
= (0.890)(0.7302)(581.67)
(0.890)(0.7302)(581.67) = 189.0(atm)
189.0(atm) compressibil-
Because the acentric is small, the 2 two- and three-parameter
PPP = =
= V V
V
=
== =
=
= 189.0(atm)
189.0(atm)
2222 Both the Redlich/Kwong
ity-factor correlations V
V are little different. equation and
Because
Because the
the acentric
acentric factor
factor is small,
is small,
small, the two-
the two- and
two- and
and three-parameter
three-parameter compressibil-
compressibil-
theBecause
Porque factor
Because
Because the
generalized
el acentric
acéntrico
the
the acentric
acentric esfactor
pequeño,
factor
factor is las the
correlation
correlaciones three-parameter
give
del answers
factor declose compressibil-
to the exper-con dos
compresibilidad
ity-factor
ity-factor correlations
correlations are
are littleis
little
isdifferent.
small,
small, the
different.
theBoth
two-
two-the
Both
and
andRedlich/Kwong
the
three-parameter
three-parameter compressibil-
Redlich/Kwong
compressibil-
equation
equation and
and
ity-factor
imental
y tres parámetros
ity-factor
ity-factor correlations
value of
difieren
correlations
correlations are
185(atm).
un little
poco.
are The
are little different.
Tanto ideal-gas
la
little different.
different. Both
ecuación
Both the
equation
de
Both the
the Redlich/Kwong
yields a result
Redlich/Kwong
Redlich/Kwong
that
como is high
equation
equation la and
by
correlación
and
and
the
the generalized
compressibility-factor correlation give
correlation respuestas answers
give answers
answers close
close to the
to the exper-
the exper-
exper-
the generalized
14.6%.
generalizada del factor compressibility-factor
de compresibilidad correlation
proporcionan give muyclose to
próximas al valor
the
the generalized
generalized
imental
imental value of
value ofcompressibility-factor
185(atm). The
185(atm). The ideal-gas
ideal-gascorrelation
correlation
equation
equation
give
give answers
answers
yields
yields
close
close
aa result
result
result that
that
to
tois
the
thehigh
exper-
is high
high by expe-
exper-
by
rimentalimental
de
imental value
185(atm).
imental value
14.6%.
of
value ofLa 185(atm).
ecuación
of 185(atm).
185(atm). The The
del ideal-gas
gas ideal
The ideal-gas equation
produce
ideal-gas equation un yields a
resultado
equation yields que
yields aa result that
es
result that is
mayor
that is en
is high by
high by14.6%.
by
14.6%.
14.6%.
14.6%.
14.6%.

108 108 CAPÍTULO
Properties deFluids
Ejemplo
Example
Example3.12 3.12 3.12
Example
A mass
mass of g500
5003.12
g of
of gaseous
gaseous ammonia is contained
contained in aarecipiente
30,000-cm 3 vessel immersed
3 sumergido en
Una masa
A de 500
of de g
amoniaco gaseoso está
ammonia contenida
is en in
un 30,000-cm de33 30 000 cm
vessel immersed
Example
A
in mass
a of 5003.12
g of gaseous
constant-temperature ammonia
bath at 65◦
◦ is
C. contained
Calculate in
the a 30,000-cm
pressure
un baño a temperatura constante de 65 °C. Calcule la presión del gas mediante: of thevessel
in a constant-temperature bath at 65◦ C. Calculate the pressure of the gas by:gas immersed
by:
in mass
A a constant-temperature
of 500 g of gaseousbath at 65 C.is Calculate
ammonia containedthe
in apressure of the
30,000-cm gas by:
3 vessel immersed
a) in (a)
(a) The
Laaecuación ideal-gas
The ideal-gas equation;
del gas ideal;
constant-temperature b) (b)
unaat(b)
equation;
bath ◦A generalized
correlación correlation.
generalizada.
65 AC.generalized
Calculate correlation.
the pressure of the gas by:
(a) The ideal-gas equation; (b) A generalized correlation.
(a) The ideal-gas equation; (b) A generalized correlation.
Solución 3.12 3.12
Solution
Solution 3.12
Solution
El volumen molar 3.12
del amoniaco en el recipiente es: is:
The molar
molar volume
volume of ammonia
ammonia in thethe vessel
vessel
Solution
The 3.12
The molar volume oft ammonia
of in
in the vessel
is:
is:
V V t 30,000
t t −1
The molar volume
VV ==V Voft ammonia
=
V
= V t in ==the30,000 vessel is:= 1,021.2 cm33 mol−1
30,000
= 1,021.2 cm3 mol−1
V = nt = m/M n m/M 500/17.02
= 500/17.02 = 1,021.2 cm mol
Vn Vt
m/M 30,000
500/17.02
a) Por la(a)ecuación
(a) By the del
the ideal-gas= ideal,
V gas
ideal-gas =
equation, = = 1,021.2 cm3 mol−1
By nequation, m/M 500/17.02
RT
RT (83.14)(65 + + 273.15)
273.15)

(a) By the ideal-gas
PP = = equation,
RT = (83.14)(65
= (83.14)(65 + 273.15) = 27.53
= 27.53 barbar
P = VV = 1,021.2
1,021.2 = 27.53 bar
RT
V (83.14)(65 + 273.15)
1,021.2
(b) Because
Because the the P =
reduced =
pressure is low
low (P(Pr ≈ = 27.53 bar
≈ 27.53/112.8
27.53/112.8
b) Ya que(b) la presión reduced
reducida esV pressure
menor (P r ≈
is 27.53/112.8
1,021.2 r = 0.244), == 00.244),
0.244), the
la correlación
the gener-
1the
gener-
generalizada del
(b)
alizedBecause
alized the reduced
virial-coefficient
virial-coefficient pressure
correlation
correlation is low
should
shouldde (P r ≈
suffice.27.53/112.8
Values
0 y BValues
suffice. of
1 se conocen
=
B 00.244),
of B 0 porand B
and las 1 aregener-
given
B 1ecuaciones
are given
coeficiente
alized virial debe ser
virial-coefficient suficiente. Los
correlation valores
=should B = 0.834: (3.65)
by Eqs.
(b) Eqs.
Because(3.65) and
theand (3.66),
reduced with TTr is
pressure (Psuffice.
338.15/405.7
low
r = 338.15/405.7
Values
r ≈ 27.53/112.8
= of B
0.834: and B the
= 0.244), aregener-
given
y (3.66),by
byconEqs.Tr (3.65)
= 338.15/405.7
(3.65)
(3.66),
and (3.66), = with
0.834:
with Tr =should 338.15/405.7 = 0.834: 0 and B 1 are given
alized virial-coefficient correlation
0
suffice. Values of B
BB00 B==
0= −0.482
Tr = 338.15/405.7 B11 == −0.232
by Eqs. (3.65) and (3.66), with
−0.482
–0.482 BB1 1= = 0.834:
−0.232
–0.232
B = −0.482 B = −0.232
Substitution
Sustituyendo w = 0.253
Substitution intoen
into Eq.la(3.63)
Eq. (3.63)
0 with(3.63)
= −0.482
Becuaciónwith ωω == 0.253
0.253 yields:
B 1 = −0.232
se obtiene:
yields:
Substitution into Eq. (3.63) with ω = 0.253 yields:
Substitution into Eq. == −0.482
B̂B̂ (3.63)−0.482
with+ + (0.253)(−0.232)
= 0.253 yields: =
ω (0.253)(−0.232) = −0.541
−0.541
B̂ = −0.482 + (0.253)(−0.232) = −0.541
B̂RTRT B̂cc = −0.482−(0.541)(83.14)(405.7)
+ (0.253)(−0.232) = −0.541 3
BB = = B̂ = −(0.541)(83.14)(405.7) = = −161.8
−161.8 cm cm3 molmol−1−1
B̂ RT
P c c = −(0.541)(83.14)(405.7)112.8 3 −1
B = Pc = 112.8 = −161.8 cm mol
B̂ RT c c P: −(0.541)(83.14)(405.7)
Pfor 112.8
Solve Eq.
Solve Eq.B(3.38)(3.38)
= for P: = = −161.8 cm3 mol−1
Solve Eq. (3.38)Pfor c P: 112.8
Resolviendo RT(3.38):(83.14)(338.15)
(83.14)(338.15)
Solvepara P de lafor
Eq. (3.38) ecuación
= RT
P: = (83.14)(338.15) = = 23.76 bar
PP = RT =
− BB = 1,021.2 161.8 = 23.76
+ 161.8
bar
P = VV − 1,021.2 + 23.76 bar
VRT −B 1,021.2 + 161.8
(83.14)(338.15)
An iterative
iterative solution
solutionP =is not necessary, = because BB is is=independent
23.76 bar of pressure. The
An is Vnot−necessary,
B 1,021.2 because
+ 161.8 independent of pressure. The
An iterative
calculated P solution
corresponds is not necessary,
to a
calculated P corresponds to a reduced pressure of Pr =reduced because
pressure B is
of P r = 23.76/112.8
independent
23.76/112.8 = 0.211.
of pressure.
= The
0.211.
calculated
AnReference
No es necesarioiterative P
to
Referenceencontrar corresponds
Fig.
solution
to Fig. 3.14 3.14 is not
unaconfirmsto
confirms a reduced
the
necessary,
solucióntheiterativa, pressure
suitability
because
suitability of
porqueB of
the
is P = 23.76/112.8
generalized
independent
r of
es independiente
of theBgeneralized =
pressure. 0.211.
virial-coefficient
The
de la presión. El
virial-coefficient
Reference
correlation.
calculated
valor calculado
correlation. detoPP Fig. 3.14 confirms
corresponds
corresponde to the
a reduced
a una presiónsuitability
pressure
reducidaof of
thedePgeneralized
r r=
P virial-coefficient
23.76/112.8
= 23.76/112.8 ==0.211.
0.211.
La figura
correlation.
Experimental
Reference
3.14 confirma to Fig.
que el uso de data
3.14 indicate
confirms
la indicate
correlación that
the the pressure
suitability of is
the 23.82 bar
generalized at the given condi-
virial-coefficient
Experimental data thatgeneralizada
the pressuredel coeficiente
is 23.82 bar atvirial es apropiado.
the given condi-
Experimental
tions.
correlation.
Información
tions. Thus
Thusexperimental
the data indica
the ideal-gas
ideal-gas indicate
equation
que
equation that the
yields
layields pressure
presión an es
an deis23.82
answer
answer 23.82
highbar
high barpara
by
by at the
about
about given
15%,
las15%, condi- conoci-
whereas
condiciones
whereas
tions.
das. Dethethe Thus the
virial-coefficient
Experimental
estevirial-coefficient ideal-gas
modo, la ecuación data equation
correlation
indicate gives
that
del gas gives
correlation yields
ideal anthean an
answer
pressure
produce answer
answeruna in
is high
23.82 by
substantial
bar
respuesta que
in substantial about
at the15%,
agreementgiven
es mayor
agreement whereas
with ex-
condi-
withenex-
casi 15%,
the virial-coefficient
periment,
tions.
mientrasperiment, Thus even
the
que la correlación though
ideal-gas
even though correlation
ammonia
equation
delammonia
coeficiente gives
is a
yields
is avirialan
polaranswer
an in
molecule.
answer
polarproporciona substantial
high by agreement
about 15%,
molecule. una respuesta de conformidad con- with ex-
whereas
siderableperiment,
the con even though
virial-coefficient
el experimento, ammonia
correlation
aun cuando is el
gives a polar
amoniacomolecule.
an answer inuna
es substantial
molécula agreement
polar. with ex-
periment, even though ammonia is a polar molecule.

3.7. Generalized
Correlations for
for Liquids
Liquids 109
109
3.7. Generalized
3.7. Generalized
3.7. Correlaciones Correlations
Correlations
generalizadas for Liquids
para for Liquids
líquidos 109 109
109
3.7
3.7 GENERALIZED
3.7 CORRELACIONES CORRELATIONS
GENERALIZADAS
GENERALIZED FOR
FORLIQUIDS
CORRELATIONSPARA LÍQUIDOS
LIQUIDS
Although
AunqueAlthough
los volúmenesthe molar
the molar volumes
volumes
molares oflíquidos
de losof liquids can
liquids can
son be
be calculated
calculated
posibles by means
by meanspor
de calcularse of medio
of generalized
generalized cubic equa-
cubic
de ecuacionesequa-
cúbicas de
Although
Although the molar
the molar volumes
volumes of
of liquids
liquids can
can be
be calculated
calculated by means
by means of
of generalized
generalized cubic equa-
cubic equa-
tions
tions
estado, con of
of state,
state,
frecuencia the
the results
results are
are often
often not
not of
of high
high accuracy.
accuracy. However,
However, the
the Lee/Kesler
Lee/Kesler correlation
correlation
tions
tions of state, los
of state, the resultados
the results areno
results are sonnot
often
often muy
not ofexactos.
of De cualquier
high accuracy.
high accuracy. However,
However, modo, the la
the correlación
Lee/Kesler
Lee/Kesler de Lee/Kesler
correlation
correlation
includes
incluyeincludes
información data para
data for subcooled
for subcooledsubenfriados,
liquids, and
liquids, and Fig.
Fig.la3.13
3.13 illustrates
illustrates curves
curves for both
for both liquids
liquidslíquidos
and gases.
and gases.
includes
includes data
data forlíquidos
for subcooled
subcooled liquids, andyFig.
liquids, and Fig.figura
3.13 3.13 ilustra
3.13 illustrates
illustrates curvas
curves
curves fortanto
for bothpara
both liquids
liquids como para
and gases.
and gases.
Values
Values for
for both
both phases
phases are
are provided
provided in
in Tables
Tables E.1
E.1 through
through E.4.
E.4. Recall,
Recall, however,
however, that
that thisque esta
gases. Los valores
Values
Values forde
for ambas
both
both fases
phases
phases areseprovided
are proporcionan
provided en lasE.1
in Tables
in Tables tablas
E.1 E.1 aE.4.
through
through E.4. Recall,
E.4. No obstante,
Recall, however,
however, thatthis
recuerde
that this
this
correlation
correlation
correlación es la más is most
is most suitable
suitable for
parafor nonpolar
nonpolar and slightly
and slightly polar fluids.
polar fluids.
correlation
correlation isadecuada
is most suitable
most suitable fluidos
for
for no polares
nonpolar
nonpolar y ligeramente
and slightly
and slightly polares.
polar fluids.
polar fluids.
Además, Inestán
In addition,
addition, generalized
generalized
disponibles equations
equations
ecuaciones are available
are available
generalizadas paraforlathe
for the estimation
estimation of molar
of molar volumes
volumes ofde líqui-
of
In
In addition,
addition, generalized
generalized equations
equations are available
are available forestimación
for the22estimation
the estimationde volúmenes
of molar
of molares
molar volumes
volumes of
of
saturated
saturated liquids.
Laliquids. The simplest equation, proposed by Rackett, 22 is
22 es un ejemplo: an example:
dos saturados.
saturated
saturated liquids.The
ecuación
liquids. más
The
The simplest
simple,equation,
simplest
simplest propuesta
equation,
equation, proposed
proposed
proposed byby
por Rackett, Rackett,
by Rackett,22
Rackett, is is
22 anan
is example:
an example:
example:
sat 2/7
(1−Trr ))2/72/7
V sat =V
= V Z Z (1−T (1−Trr))2/7 (3.72)
V saturado
V sat
V sat
V == ccV VccccZZc(1−T
c (3.72)
(3.72)(3.72)
(3.72)
An
An alternative
alternative form
form of
ofof this
this equation
equation is sometimes
is is
sometimes useful:
useful:
En ocasionesAn
An alternative
alternative
es útil unaform form
forma of this
this
alternativa equation
equation de is sometimes
sometimes
esta ecuación:useful: useful:
P
= PrP
sat rP [1+(1−T 2/7 ]
Z sat
Z = Zrr cc[1+(1−T
Z
)2/7 ] ]]
rr ) ))2/7
2/7 (3.73)
(3.73)
Z saturadosat
ZZsat =T
= Trr ZZ [1+(1−T
[1+(1−T
cc
rr
(3.73)(3.73)
(3.73)
TTrr
La únicaThe
The only
información
only data
data required
que
required are
se requiere
are the
the critical
son
critical constants,
las constantes
constants, given
críticas,
given in
inin Table
conocidas
Table B.1.
B.1. Results
en la tabla
Results are
are usually
B.1. Por lo
usually accu-
accu-regular los
The
The only
only data
data required
required are
are the
the critical
critical constants,
constants, given
given in Table
Table B.1.
B.1. Results
Results are
are usually
usually accu-
accu-
rate
resultadosrate to
tienen1 or 2%.
rate to
rate to 11una
to1 or 2%.
or 2%.
or exactitud de 1 o 2%.
2%. 23 developed a two-parameter corresponding-states
Lydersen, Lydersen,
Greenkorn
Lydersen, Greenkorn,
y Hougen
Greenkorn, and
and Hougen23
23 desarrollaron una correlación de estados correspondientes con dos
Lydersen,
Lydersen, Greenkorn,
Greenkorn, andHougen
and Hougen23
Hougen 23developed
developed
developed a aatwo-parameter
two-parameter
two-parameter corresponding-states
correlation
parámetros for
para la estimación estimation of
del volumen liquid volumes. It provides a correlation of reduced density as redu-
ρrr as
correlation
correlation
correlation for estimation
for estimation
for estimation of liquidde
liquid
of liquid
of volumes.líquidos.
volumes.
volumes. It Ésta proporciona
provides
It provides
It provides a correlation
aa correlationuna of
correlation of correlación
reduced
of reduced
reduced de densidad
density
density
density ρ as
ρρrr as
a
a function
cida r r como
function of
una función
of reduced
reduced temperature
de latemperature
temperaturaand
temperature and
and pressure.
y lapressure. By
presión reducidas.
pressure. By definition,
definition, Por definición,
aa function
function of reduced
of reduced temperature and pressure. By definition,
By definition,
ρ Vc
≡ ρ ρρ= = VcV Vcc
(3.74)(3.74)
ρrr ≡
ρ (3.74)
(3.74)
ρρrr ≡≡ρρcc = =V V (3.74)
ρ
ρcc V
V
donde rwhere
c es laρ
where ρdensidad
is the en el punto
the density
density the crítico.
at the critical La correlación
point. The generalized generalizada
generalized se muestra
correlation is shownen laby
shown byfigura
Fig. 3.16.
3.16. Ésta es
where
where ρis
ccρ is the
cc is the density
density at at the
at the critical
critical
critical point.
point.The
point. The generalized
The generalized correlation
correlation
correlation is is shown
is shown by
byFig.
Fig.
Fig.3.16.
3.16.
3.16.
posible This
usarla
This de
figure
figure manera
may
may be
bedirecta
used
used con
directly
directly la ecuación
with
with Eq.
Eq. (3.74)
(3.74)
(3.74) para
for
for determinar
determination
determination los volúmenes
of
of liquid
liquid de
volumes
volumes los líquidos
if
if the si se
the
This figure may be used directly with Eq. (3.74)
This figure may be used directly with Eq. (3.74) for determination of liquid volumes if the for determination of liquid volumes if the
conoce value
el valor
value of del
of the volumen
the critical crítico.is
critical volume
volume isUn mejor procedimiento
known.
known. A better
A better procedure
procedure consiste toenmake
is to
is usar use
make un volumen
use of aa single
of singlelíquido
known
known conocido
value of the critical volume is known. A better
value of the critical volume is known. A better procedure is to make use of a single known procedure is to make use of a single known
(estado liquid
1) y emplear
liquid volumela(state
volume identidad,
(state 1) by
1) by the the identity,
identity,
liquid
liquid volume (state
volume (state 1) by
1) by the the identity,
identity,
ρr11
V22 =
V =V V ρrρρ rr11 (3.75)
(3.75) (3.75)
V22 =
V = 11V Vρρ11rr22 (3.75)
(3.75)
ρ
ρrr22
where
where V
V 2V= = required
required volumevolume
donde wherewhere V2 = volumen2V22 == required requerido
required volume
volume
V = = known
known volume volume
V1 =V11volumen
V11 ==
V known
known conocido
volume
volume
ρ 11 ,, ρ ρrr22 = = reduced
reduced densities
densities read read from from Fig. Fig. 3.16
3.16
r r1,ρrrrρρr rr211= densidades
,, ρρ = reduced
rr22 = reduced reducidas
densitiesleídas
densities read from
read de
fromla Fig.
figura 3.16
Fig. 3.16
3.16
This method
This method gives gives good
good results
results and and requires
requires only only experimental
experimental data data that
that are
are usually
usually available.
available.
This method
This method gives gives good
good results results and and requires
requires only only experimental
experimental data data that
that are
are usually
usually available.
available.
Este método
Figure
Figure da3.16
3.16buenosmakes
makes resultados
clear
clear the
the y sólo
increasing
increasing requiere de
effects
effects información
of
ofof both
both experimental
temperature
temperature and
and que
pressure
pressure usualmente
on
onon liquid
liquid está
den-disponi-
den-
Figure
Figure 3.16
3.16 makes
makes clear
clear the
the increasing
increasing effects
effects of both
both temperature
temperature and
and pressure
pressure on liquid
liquid den-
den-
ble. La sity
figura
sity as
asas 3.16
the
the muestra
critical
critical de
point
point forma
is
is is clara
approached.
approached. los efectos al aumentar la temperatura y la presión sobre la densi-
sity
sity as the
the critical
critical point
point is approached.
approached.
dad del líquido conforme
Correlations
Correlations se
for acerca
forforthe
the molar
molar al punto crítico.
densities
densities as
asas functions
functions of
ofof temperature
temperature are
are given
given for
forformany
many pure
pure
Correlations
Correlations for the
the molar
molar densities
densities as functions
functions of temperature
temperature are
are given
given for many
many pure
pure
Las correlaciones
liquids
liquids by Daubert
by Daubert paraand
andlascoworkers.
densidades
coworkers. 24
24 molares
24
24 como funciones de la temperatura se conocen para varios
liquids by
liquids by Daubert
Daubert and and coworkers.
coworkers. 24
líquidos puros por Daubert y colaboradores.
22 H. G. Rackett, J. Chem. Eng. Data, vol. 15, pp. 514–517, 1970; see also C. F. Spencer and S. B. Adler, ibid.,
22 H. G.G.
22 H.
22 Rackett,
G. J. J.
Rackett, Chem.
J. Chem.
Chem. Eng. Data,
Eng. Data,vol. 15,15,
vol. pp.pp.
15, 514–517,
pp. 1970;
514–517, seesee
1970; also
see C.C.
also F. F.
C. Spencer
F. and
Spencer andS. S.
B.B.
S. Adler,
B. ibid.,
Adler, ibid.,
vol.
vol. 23,H.pp.
23,
Rackett,
pp. 82–89,
82–89, 1978,
1978,
Eng.
for aa review
for review Data, vol.
of available
of available 514–517,
equations.
equations.
1970; also Spencer and Adler, ibid.,
vol. 23, pp. 82–89, 1978, for a review of available equations.
vol. 23, pp. 82–89, 1978, for a review of available equations.
22 H. G. Rackett, J. Chem. Eng. Data, vol. 15, pp. 514-517, 1970; véase también C. F. Spencer y S. B. Adler, ibid., vol. 23, pp. 82-89,
23 A. L. Lydersen, R. A. Greenkorn, and O. A. Hougen, “Generalized Thermodynamic Properties of Pure Fluids,”
23 A.
23A.
23 L.L.
Lydersen, R.R. A.A.
Greenkorn, and O.O.A.A.
Hougen, “Generalized Thermodynamic Properties of of
Pure Fluids,”
1978, para una Wisconsin,
Univ. revisión
A. L. deEng.
las ecuaciones
Lydersen,
Lydersen, R.
Expt.
A. disponibles.
Greenkorn,
Greenkorn,
Sta. Rept.
and
and
4, 1955.
1955.
O. A. Hougen,
Hougen, “Generalized
“Generalized Thermodynamic
Thermodynamic Properties
Properties of Pure
Pure Fluids,”
Fluids,”
Univ. Wisconsin,
Univ. Eng.
Wisconsin, Eng.Expt. Sta.
Expt. Rept.
Sta. 4,
Rept. 4, 1955.
23 A. L. Univ. Wisconsin,
Lydersen, Eng. Expt.ySta.
R. A. Greenkorn Rept.
O. A. 4, 1955.
Hougen, “Generalized Thermodynamic Properties of Pure Fluids”, Univ. Wisconsin, Eng.
24 T. 4,
Expt. Sta. Rept.
24 E. 1955.
Daubert, R.
R. P.
P. Danner,
Danner, H.
H. M.
M. Sibul,
Sibul, and
and C.
C. C.
C. Stebbins,
Stebbins, Physical
Physical and
and Thermodynamic
Properties of
of Pure
Pure
T. E.
24T.
24 T. Daubert,
E.
E. Daubert, R.
Daubert, R. P.
P. Danner,
Danner, H.
H. M.
M. Sibul,
Sibul, and
and C.
C. C.
C. Stebbins,
Stebbins, Physical
Physical and
and Thermodynamic
Properties of
of Pure
Pure
Chemicals:
24 T. Chemicals:
E.Chemicals:
Daubert, Data
R. P.
Data Compilation,
Danner, H.
Compilation, Taylor
M. Sibul
Taylor &yFrancis,
& Francis,
C. C. Bristol,
Stebbins,
Bristol, PA, extantand
Physical
PA, extant 1995.
Thermodynamic
1995. Properties of Pure Chemicals: Data
Chemicals: Data
Data Compilation,
Compilation, Taylor
Taylor &
& Francis,
Francis, Bristol,
Bristol, PA,
PA, extant
extant 1995.
1995.
Compilation, Taylor & Francis, Bristol, PA, existente 1995.

110 110 CAPÍTULO
Properties deFluids
3.5
3.5
TrT�0.3
0.3
3.5 rr
0.40.3
Tr0.4
�
0.5
0.50.4
3.0
3.0 0.6
0.60.5
3.0 0.7
0.70.6
0.8 0.7
0.8
2.5
2.5 0.9 0.8
0.9
1.0 0.9
 2.5 Tr  0.95 1.0
�r r Trr � 0.95
1.0
�r Tr � 0.95
2.0
2.0
0.97
2.0 0.97
0.99
0.97
0.99
1.5 0.99
1.5
1.5 Líquido saturado
Saturated Liquid
Saturated Liquid
1.0
1.0 0 1 2 3 4 5 6 7 8 9 10
0
1.0 1 2 3 4 5 6 7 8 9 10
Pr
0 1 2 3 4 Pr 5 6 7 8 9 10
Pr
Figura 3.16: Correlación de densidad generalizada para líquidos.

Figure 3.16: Generalized density correlation for liquids.
Figure 3.16: Generalized density correlation for liquids.
Example
Ejemplo 3.13 3.13
Example 3.13
For ammonia at 310 K, estimate the density of:
Para el amoniaco a 310 K, calcule la densidad de:
For ammonia at 310 K, estimate the density of:
(a) The saturated liquid; (b) The liquid at 100 bar.
a) El líquido saturado;
(a) The b) El liquid;
saturated líquido (b)
a 100
Thebar.
liquid at 100 bar.
Solution
Solución 3.13 3.13
Solution 3.13
(a) Apply Eq. (3.72) at the reduced temperature, Tr = 310/405.7 = 0.7641. With
a) Aplique laApply
Vc(a)
= ecuación and(3.72)
72.47 Eq. Z c =a0.242
(3.72) atlathe
temperatura
reduced reducida,
temperature,
(from Table = 310/405.7
B.1), Tr T=r 310/405.7 = 0.7641.
= 0.7641. Con V C = 72.47
With
y ZC = 0.242
V =
c (de la tabla B.1),
72.47 and Z c = 0.242 (from Table B.1),
2/7 2/7
V sat = Vc Z c(1−Tr ) 2/7= (72.47)(0.242)(0.2359) 2/7= 28.33 cm3 mol−1
saturado
V V sat = Vc Z c(1−Tr ) = (72.47)(0.242)(0.2359) = 28.33 cm3 mol−1
For comparison, the experimental value is 29.14 cm3 mol−1 , a 2.7% difference.
−1 , a 2.7% difference.
Para comparación, el valorthe
For comparison, experimental
experimental es value
de 29.14 cm3 mol
is 29.14 cm3–1mol
, y difiere en 2.7%.
(b) The reduced conditions are:
b) Las condiciones reducidas son:
(b) The reduced conditions are:
100
Tr = 0.764 Pr = 100 = 0.887
Tr = 0.764 Pr =112.8 = 0.887
Sustituyendo el valorthe
Substituting = 2.38ρ(de
r rvalue, r =la figura
2.38 3.16),
(from VC 112.8
Fig.y3.16),
enand
la ecuación (3.74),
Vc into Eq. se gives:
(3.74) obtiene:
Substituting the value, ρr = 2.38 (from Fig. 3.16), and Vc into Eq. (3.74) gives:
Vc 72.47
V = Vc= 72.47= 30.45 cm3 mol−1
V =ρr =2.38 = 30.45 cm3 mol−1
ρr 2.38

Problems 111
Problems
Problems 111
111
Problemas
Problems 111 111
In comparison with the experimental value of 28.6 cm mol , this result is higher 3 −1
In comparison
comparison with the experimental value of 28.6
28.6 cm 3 mol−1 , this result is higher
En In
comparación
by 6.5%. con elthe
valor experimental de of 28.6 cmcm3 mol
3 mol–1,−1este resultado eshigher
mayor en 6.5%.
In comparison with
with the experimental
experimental value
value of 28.6 cm 3 mol −1 , this result
resultisis
by
Si 6.5%.
comenzamos
If we startcon with el valor
the experimental
experimental valuede 29.14
of 29.14cm 3
cmmol –1,,this
3 mol −1 for
para el líquido
saturated
higher
saturado
liquid a 310
by 6.5%.
by 6.5%. −1 for saturated liquid
If
K, se puede we start
usar
K, lawith the experimental
ecuación experimental
(3.75). be Paravalue
elFor ofthe
líquido 29.14 cm33 mol
saturado mol
a −1=for 0.764, = 2.34 r(de
atwe
If 310start Eq.
with (3.75)
the may used.
value of saturated
29.14 cm 3 mol−1T
liquid at T =r
saturated
r for saturated
r 0.764,
liquid
r1 liquid ρ 1 =la figura
at 310If we
310 K, start
Eq. with the
(3.75) may experimental
be used. Forvalue
For ofsaturated
theknown 29.14 cmliquid atEq. = 0.764,
Tr (3.75) 0.764, ρr1 = =
3.16).
at Con
2.34la(from
K, sustitución
Eq. (3.75) de los
Fig. 3.16).
may be valores
Substitution
used. conocidos
of
the envalues
saturatedla ecuación
intoat
liquid (3.75)
T = se obtiene:
gives:
ρ
at 310
2.34 K, Eq.
(from Fig.(3.75)
3.16).may be used. of
Substitution For the saturated
known values liquid
into Eq.at Trr =gives:
(3.75) 0.764, ρrr11 =
2.34 (from Fig. 3.16). Substitution
2.34 (from Fig. 3.16). Substitution of known
of known � �
values into Eq. (3.75)
values into Eq. (3.75) gives: gives:
ρr1 � 2.34
�
V2 =ρV r 1 �
= (29.14)� 2.34 �� = 28.65 cm3 mol−1
V = V ρ r 1 ρ=r (29.14) 2.34 2.38 = 28.65 cm333 mol
mol−1 −1
VV22 = V 1 ρr1 = (29.14)
1 2 2.34 = 28.65 cm
1 ρ
2 = V1ρr 2 = (29.14) 2.38
r 2.38 = 28.65 cm mol−1
En esencia,
This este
resultresultado concuerda
ρr22 agreement
is in essential con el 2.38
valorthe
with experimental.
experimental value.
La aplicación
This
This result
Direct
result is indirecta
is in application
essentialde la
essential ofcorrelación
agreement withLee/Kesler
the Lee/Kesler
agreement with thecorrelation
the con los
experimental
experimental with valuesdeofZ 0Z y0 Z
valores
value.
value. and1 interpolados
Z 1 inde
This
las tablas result is in
E.1 application
y E.2 essential
conduce agreement
aE.1
un valor with
deleads the
33.87tocmexperimental
3 mol –1 value.
,33.87
que tiene
0 and 1 in-
Direct
Direct application
terpolated from of
Tables
of the
the Lee/Kesler
and E.2
Lee/Kesler correlation
correlation with
a value
with values
ofvalues cmZ 0un
of
of Z
3 mol
and error
−1Z
Z,
0 and Z 1 in- importante,
1which
in- is sin
duda, Directafrom
debido
terpolated application
la naturaleza
Tables of
E.1 the Lee/Kesler
altamente
and polar correlation
E.2owing
leads del
to amoniaco.ofwith values 3 of Z −1
significantly
terpolated from in error,
Tables E.1 noanddoubtE.2 leads totoaathe
value
highly
value of 33.87
polar cm
33.87 cm
nature3
mol
3 mol of−1
−1 ,,,which
which is
ammonia. is
terpolated from
significantly in Tables
error, no E.1
doubt andowing
E.2 leads
to theto highly
a valuepolar
of 33.87
nature cmofmol ammonia. which is
significantly
significantlyin inerror,
error,no nodoubt
doubtowing owingto tothethehighly
highlypolar
polarnature
natureof ofammonia.
ammonia.
PROBLEMAS
PROBLEMS
PROBLEMS
PROBLEMS
PROBLEMS
3.1. Exprese
3.1. Express la expansión
the volume volumétrica
expansivity y la andcompresibilidad
the isothermal isotérmica como funciones
compressibility as functions de laof
densidad
3.1.r Express
y sus
density the
derivadas ρvolume
and its expansivity
parciales.
partial Para eland
derivatives.agua the a isothermal
50
For °C
water y 1at bar,
50 ◦k
compressibility
C =
and44.18
1 bar,× as
10
κ –6
functions
= bar
44.18–1. ¿A
× of
10 −6 presión
qué
3.1.
3.1. Express
Express−1 the
the volume
volume expansivity
expansivity and
andFor the isothermal
thewaterisothermal compressibility as functions of
density
debe bar ρρ .and
comprimirse
density and its
To its
whatpartial
el agua derivatives.
pressure
partial a 50must°C para
derivatives. water
For que at 50
besucompressed
water 50◦◦C
densidad
at Ccompressibility
and
cambie
andat 501
◦bar,
1 bar,
C1%? == as44.18
toκκ change
Suponga
functions
44.18 ×que
its× 10−6−6of
k−6esbyindepen-
density
10
density
−1 ρ and its partial derivatives. For water at 50 ◦ C and◦ 1 bar, κ = 44.18 × 10
bar−1
diente
bar 1%?... To
de To
P. what pressure
Assume pressure
that κ ismustmust water be
independent beofcompressed
compressed
P. at 50◦ C C to change
change its densitydensity by
bar−1Assume
1%? To what
whatthat pressure
κ is must water
independent water of be
P. compressed atat 50 50◦ C to to change its its density by by
1%?
1%? Assume
Assumethat thatκκ isisindependent
independentof of P.P.
3.2. Por
3.2.loGenerally,
general, elvolume coeficiente de expansión
expansivity β andvolumétrica b y la compresibilidad
isothermal compressibility κ depend isotérmica
on T and k depen-
3.2.
3.2.den deP.T
Generally, y P.
Prove Demuestre
volume
that: que:
expansivity β and isothermal
� isothermal
�
compressibility
�compressibility
�
κ depend on T and
3.2. Generally,
Generally,
P. Prove that:
volume
volume expansivity
that: expansivity ββ and and isothermal compressibility κκ depend
depend on on TT andand
P. Prove � �
� �∂β =�
� − ��∂κ
P. Prove that: ∂β
�∂β ∂�P � ∂κ �
∂β =T−
= − ∂κ ∂κ ∂ T P
∂ P
∂∂PP T T = − ∂ T
∂∂TT PP
3.3. The Tait equation for liquids is written T for an isotherm P as:
3.3.
3.3.
3.3. The
Para Tait
una equation
isoterma, lafor liquids
ecuación is
de written
Tait para for an isotherm
líquidos
� isotherm se as:
escribe
as:� como:
3.3. The
TheTait
Taitequation
equationfor forliquids
liquidsisiswritten
writtenfor foran an isotherm A� P as:
�
V =��V0 1 − ��
AP
A PB + P
V = V 1 − A P
VV = 0
= VV00 11− −B B+ +P P
where V is molar or specific volume, V0Bis+the P hypothetical molar or specific vol-
where
whereume VV is
atel molar
isiszero
molar or
pressure, specific
and volume,
A and B V V
are0 isis the
positive hypothetical
constants. molaranor
Find orexpression
specific vol- vol-
for the
donde where
ume V
at es
V
zero molar or
volumen
pressure,
specific
ormolar
specific
and A
volume,
o and
específico
volume,
B are yV0V
positive
the
0 0isesthe
hypothetical
elconstants.
volumen
hypothetical molar
Find
molar
molar
an or specific
o específico specific
expression hipotético
for the a presión
vol-
ume
cero, isothermal
at zero compressibility
pressure, and A andconsistent
B are with
positive this equation.
constants. Find an expression for the
umemientras
isothermal que A y B and
at zerocompressibility
pressure, son constantes
A and B are
consistent positivas.
with positive Encuentre una
constants.
this equation.
equation. Findexpresión
an expression para laforcompresibilidad
the
isothermal
isotérmica que compressibility
sea consistente consistent
con esta
isothermal compressibility consistent with this equation. with
ecuación.this
3.4. For liquid water the isothermal compressibility is given by:
3.4. For liquid
liquid water water the the isothermal
isothermal compressibility
compressibility is is given
given by: by:
3.4.
3.4. For
3.4.Para
Forelliquid
agua water líquidathe la isothermal
compresibilidad isotérmicaisces
compressibility conocida
given by: por:
κ= c
= cc(P + b)
V
κκκ ==V V (P
(P + + b)
where c and b are functions of temperature V (P +b) b)only. If 1 kg of water is compressed
where
where c and
isothermally
cyc band b are
and functions
bbúnicamente
are reversibly
functions of
of temperature
from 1
temperature to 500 only.
bar
only. atIfIf6011◦ C,
kghowof water
water
muchis iswork
compressed
is required?
donde where c
isothermally ◦andsonand are functions
reversibly funciones
fromof 1 to de
temperature
500 la temperatura.
bar only.
3at −1
60 ◦
◦ C, Sikg
If 1how seof
kg comprime
of
much waterwork is1compressed
is kg de agua de manera
compressed
required?
At
isothermally60 C, b
and = 2, 700
reversibly bar and
from c =
11 to 0.125
500 cm
bar at g 60 .
◦C, how much work isrequiere?
required?
isotérmica
isothermally
At 60 ◦
60◦ C, y
C, bb = reversible
and
= 2,2, 700
700 bar desde
reversibly
bar and 1
from
and cc = hasta
= 0.125 cm 500
to 500 bar3bar
cm3 g−1 . a
−1 60
at °C,
60 C,¿cuánto
how trabajo
much se
work is required? A 60 °C, b =
At
2 700
At 60bar ◦ C,y bc ==0.1252, 700cm bar –1. c = 0.125
3 gand 0.125 cm3 gg−1..

112 112 CAPÍTULO
3. Volumetric volumétricas
Properties de fluidos puros
of Pure Fluids
3.5. Calcule el trabajo reversible hecho al comprimir 1(pie)3 de mercurio a una temperatura constante de
3 of mercury
3.5.32(°F),
Calculate
desdetheuna
reversible
presión work
de done
1(atm) in compressing
hasta 3 000 (atm). 1(ft)
La compresibilidadatisotérmica
a constantdel mercurio
temperature of 32(◦ F) from 1(atm) to 3,000(atm). The isothermal compressibility of
a 32(°F) es:
mercury at 32(◦ F) is:
κ/(atm)−1 = 3.9 × 10−6 − 0.1 × 10−9 P(atm)
3.6.
3.6.Cinco
Five kilogramos
kilograms ofdeliquidtetracloruro
carbon de carbono líquido
tetrachloride undergose asometen a un cambio
mechanically de estado
reversible, iso- isobárico,
mecánicamente reversible a 1 bar, durante el cual la temperatura varía de
baric change of state at 1 bar during which the temperature changes from 0 C to 20◦ C. 0 a 20
◦ °C. Determine DV t,
t
Q, DH y �V t
DU t ,. W
Suponga
W,Determine , Q, �Hque las �U
t , and siguientes propiedades
t . The properties fordel tetracloruro
liquid de carbono líquido a 1
carbon tetrachloride
bar –3 K–1, C = 0.84−3 −1–1, K–1, y r =
at 1 bar and 0 C may be assumed independent of temperature: β = 1.2 × 10 kJKkg
y 0 °C son independientes
◦ de la temperatura: b = 1.2 × 10 P
1C590 kg m .–3 −1 K−1 , and ρ = 1,590 kg m−3 .
P = 0.84 kJ kg
3.7. Una
3.7. sustancia for
A substance para la que
which κ isk aes una constante,
constant se an
undergoes somete a un proceso
isothermal, isotérmico,
mechanically mecánicamente
reversible
reversible
process from initial state (P1 , V1 ) to final state (P2 , V2 ), where V is molar volume.molar.
del estado inicial (P 1 , V1 ) al estado final (P 2 , V2 ), donde V es el volumen
a) (a)A Starting
partir dewith
la definición de k of
the definition demuestre
κ, show que
that la
thetrayectoria
path of thedel proceso
process está descrita
is described by: por:
VV ==A(T)exp(-k P) P)
A(T ) exp(−κ
b) (b)Determine
Determine una
an expresión exacta which
exact expression que proporcione el trabajo work
gives the isothermal isotérmico hecho
done on 1 molsobre
of 1 mol de
esta sustancia con k constante.
this constant-κ substance.
3.8.
3.8.Un
Onemolmole
de gas
of ideal congas
an ideal = (7/2)R
CP with CP = y C(7/2)R
V = (5/2)R
and se
C Vexpande de Pexpands
= (5/2)R 1 = 8 barfrom
y T1 =
P1600
= K a P2 = 1
bar por cada una de las trayectorias siguientes:
8 bar and T1 = 600 K to P2 = 1 bar by each of the following paths:
Volumen
a)(a) constante;
Constant temperatura
volume;b)(b) constante; c) (c)
Constant temperature; en forma adiabática.
Adiabatically.
Assuming mechanical
Suponiendo reversibility,
reversibilidad mecánica, calculate
calcule W,WQ,
, Q,
DU�U , and
y DH for proceso.
�Hcada
para each process.
Dibuje cada tra-
Sketch each path on a single
yectoria en un solo diagrama PV.P V diagram.
3.9.Un
3.9. Angas
ideal gasinicialmente
ideal, initially at 600 K and
a 600 K y1010bar undergoes
bar, se sometea four-step
a un ciclomechanically
mecánicamente reversible
reversible de cua-
cycle in a closed system. In step 12, pressure decreases isothermally
tro etapas en un sistema cerrado. En la etapa 12, la presión decrece isotérmicamenteto 3 bar; in stepa 3 bar; en la
23, pressure
etapa decreases
23, la presión at constant
disminuye volume
a volumen to 2 bar;
constante a 2 in step
bar; en 34, volume
la etapa decreases
34, el volumenatdisminuye a
constant
presión pressure;y en
constante, andlainetapa
step 41,
41,elthe gas
gas returnsenadiabatically
regresa to itsainitial
forma adiabática state.inicial.
su estado Take Considere:
C = (7/2)R and C
CP = (7/2)R y CV = (5/2)R.
P V = (5/2)R.
(a) Sketch the cycle on a P V diagram.

a) (b)Dibuje el ciclo
Determine en ununknown)
(where diagrama PV.
both T and P for states 1, 2, 3, and 4.
b) Determine (donde no se tienen ) tanto a T como a P para los estados 1, 2, 3 y 4.
(c) Calculate Q, W , �U , and �H for each step of the cycle.
c) Calcule Q, W, DU y DH para cada etapa del ciclo.
3.10. An ideal gas, C P = (5/2)R and C V = (3/2)R, is changed from tP = 1 3bar and
3.10. Un gas ideal,3con CP = (5/2)R y CV = (3/2)R, cambia de P = 1 bar y V 1 = 12 m a P2 = 12 bar y V 2t
V1t =
3 12 m to P2 = 12 bar and V2t = 1 m3 by the following mechanically reversible
= 1 m mediante los procesos mecánicamente reversibles siguientes:
processes:
a) (a)Compresión
Isothermalisotérmica.
compression.
b) (b)Compresión adiabática seguida
Adiabatic compression porby
followed enfriamiento a presiónpressure.
cooling at constant constante.
c) (c)Compresión adiabática seguida por enfriamiento a volumen
Adiabatic compression followed by cooling at constant volume.constante.
d) (d)Calentamiento a volumen constante seguido por enfriamiento a presión constante.
Heating at constant volume followed by cooling at constant pressure.

Problemas 113
Problems 113
Problems 113
e) Enfriamiento a presión constante seguido por calentamiento a volumen constante.
(e) Cooling at constant pressure followed by heating at constant volume. Problems
Calcule(e) Cooling Q, W,atDU constant
t y DH pressure
t para cada followed
uno deby losheating
procesos, at constant
y dibujevolume.
las trayectorias de todos los pro-
Calculate Q, W , �U t , and �H t for each of these processes, and sketch the paths of
cesos en un solo diagrama PV.
t , and �H t for each of these processes, and sketch the paths of
Calculate
all processes Q, Won, �U a single P V diagram. (e) Cooling at constant pressur
all processes on a single P V diagram.
3.11. El gradiente térmico ambiental dT/dz caracteriza la variación local de la temperatura con la altura
3.11.enThe environmental lapseLarate dT /dz characterizes Calculate Q, W , �U t , and �H
la atmósfera terrestre. presión atmosférica varíathe con local variation de
la elevación of acuerdo
temperature con la fórmula
3.11. The withenvironmental
elevation in the lapse rate atmosphere.
earth’s dT /dz characterizes Atmospheric the local variation
pressure variesofwith temperature
elevation all processes on a single P V di
hidrostática.
with elevation in the earth’s
according to the hydrostatic formula, atmosphere. Atmospheric pressure varies with elevation
according to the hydrostatic formula, 3.11. The environmental lapse rate d
dP with elevation in the earth’s atm
dP = −Mρg
dz = −Mρg according to the hydrostatic for
dz
where M is molar mass, ρ is molar density, and g is the local acceleration of gravity.
donde where
Asssume esmolar
M isthat lathemasa mass, molar,
atmosphere rises
ρ is molar anlaidealdensidad
density, gas,and molar
with gT y glocal
is related
the estolaacceleration
Paceleración
by the polytropic oflocal de
gravity. for-la gravedad.
Suponga
Asssume que
that la
theatmósfera
atmosphere es un
is gas
an ideal,
ideal gas,con T
with relacionada
mula, Eq. (3.35c). Develop an expression for the environmental lapse rate in relation T related toa PP byporthe la fórmula
polytropic politrópica,
for- ecua-
ción
mula, (3.35c).
Eq. Desarrolle
(3.35c).
to M, g, R, and δ. Develop una expresión
an expression para el
for gradiente
the térmico
environmental ambiental
lapse rate en
in relación
relation con
where M ,isg,molar mass, ρ is m
RtoyM, d. g, R, and δ. Asssume that the atmosphere is
3.12. An evacuated tank is filled with gas from a constant-pressure line. Develop an expres- mula, Eq. (3.35c). Develop an
3.12. Se
3.12. An llena
sionevacuatedcon gas
relating tank un tanque previamente
is filled withofgas
the temperature thefromgas invacío mediante
a constant-pressure una
the tank to the temperature línea a
line. Developpresión
T of� constante.
anthe
expres-
gas in Desarrolle
to M, g, R, and δ.
una
sion expresión
the relating
line. Assume que relacione
the temperature
the gas is ideal la temperatura
of the withgasconstant del
in the tank gas en el tanque
heattocapacities,
the temperature con la
and ignore temperatura
�
T ofheat T ′
the transfer
gas in del gas en la
línea.
the Suponga
line. Assume que the el gas
gas is es ideal
ideal withcon capacidades
constant
between the gas and the tank. Mass and energy balances for this problem are3.12. heat caloríficas
capacities, constantes
and ignore e
heat ignore
transfer la
treated transferencia
An evacuated tank is filled with
de incalor
between
Ex. 2.13.entre
the gas el gas
andythe el tanque.
tank. Mass Los and balances
energy de balances
masa y energía for thispara problemeste problema
are treatedse consideran
sion relating the temperature of
en
in el
Ex.ejemplo
2.13. 2.13. the line. Assume the gas is idea
3.13. Show how Eqs. (3.36) and (3.37) reduce to the appropriate expressions for the four between the gas and the tank. M
3.13. Demuestre
3.13. Show cómo
how values
particular Eqs. (3.36)las ecuaciones
of δ listedand (3.37) (3.36)
following reduce y (3.37)the appropriate expressions for the fourin Ex.para
Eq.to(3.37). se reducen a las expresiones apropiadas 2.13. los
cuatro valores particulares de
particular values of δ listed following Eq. (3.37). d enumerados después de la ecuación (3.37).
3.14. A tank of 0.1-m3 volume contains air at3 25◦ C and 101.33 kPa. The tank is connected 3.13. Show how Eqs. (3.36) and (3.3
3.14.
3.14. Un tanque contiene un volumen
3 volume de 0.1 m 25de◦ Caire 25 °C ykPa.
a 101.33 101.33 kPa. Elistanque estáparticular
conectadovalues a of δ listed follo
Atotanka compressed-air line which supplies air at the constant conditions of 45◦ C and
of 0.1-m contains air at and The tank connected
una línea
to1,500 de aire
a compressed-air comprimido
line which que proporciona
supplies air aire
at theen condiciones
constant constantes
conditions of de
45 ◦ 45
C °C
and y 1 500 kPa.
kPa. A valve in the line is cracked so that air flows slowly into the tank until
Una
1,500 válvula
kPa. A en valve
la línea se theagrieta, is así que elso aire fluye air con bastante lentitud thehacia dentro del tanque
of 0.1-m3 volume conta
the pressure equalsinthe linepressure.
line cracked If thethat process flows
occurs slowly
slowlyintoenough tank until
3.14.
that A tank
the
hasta que la presión se equilibra con la presión de la línea. Si el proceso ocurre muy lentamente, de
the pressure equals
temperature in the tank the line remains at 25◦ C,
pressure. If how
the process
much heat occurs
is lostslowly
from the enough tank?that Assume theto a compressed-air line which
tal manera
temperature quein la
thetemperatura
tank remains se mantiene
at 25 ◦ C, howa 25 °C,
much ¿cuánto
heat is calor
lost se
from pierde
the tank? desde el
Assume tanque?
1,500 Supon-
kPa. A valve in the line
air to be an ideal gas for which C P = (7/2)R and C V = (5/2)R.
ga
airque
to be el an
aireideal
es un gas gasforidealwhich paraC Pel= que CP = (7/2)R
(7/2)R and C Vy = = (5/2)R.
CV(5/2)R. the pressure equals the line pre
3.15. Gas at constant T and P is contained in a supply line connected through a valve to temperature a in the tank remains
3.15.
3.15. Gas
Gas aatTconstant
y P constantesT and está
P is contenido
contained en
in una
a línea line
supply de suministro
connected conectada,
through a mediante
valve to a unatoválvula,
air be an ideal gas for which
closed tank containing the same gas at a lower pressure. The valve is opened to allow
aclosed
un tanque tank cerrado
containing que the contiene
same el
gas mismo
at a gas apressure.
lower una presión The menor.
valve Laopened
is válvulatoseallow abre permitiendo
flow of gas into the tank, and then is shut again.
que
flowelofgas gasfluya
into hacia
the tank, dentro anddelthen tanque
is shuty again.
después se cierra una vez más. 3.15. Gas at constant T and P is con
(a) Develop a general equation relating n 1 and n 2 , the moles (or mass) of gas in the closed tank containing the same
(a) Desarrolle
a) Develop
tank at athe una ecuación
general
beginning equation generalendque
and relating of relacione
n 1 and
the na2 ,nthe
process, y nmoles
1to 2, las
the moles
(or mass)
properties (oUmasas)
1of andgas de
in
U 2
gas
,the
the en eloftanque
flow gas into the tank, and th
altank
principio
at the
internal y al final
beginning
energy of theand del proceso,
gas end
in theoftank con
the at las propiedades
process, U
to the properties
the beginning and y U ,
1 end2ofUthe la energía
1 and interna
U2 , the
process, and del gas al
principio
internal yenthalpy
H � , theenergy al finalof delthethe
of proceso,
gasgasin intheythetank laatentalpía
H ′,supply theline, del gas
beginning
and and
to Q, enthe
la
endlínea
of the
heat de suministro
process,toand
transferred y(a)
the a Q,Develop
el calor a general equation
transferido
�
Hmaterial a
, the enthalpy la sustancia
in the tank of the en el
gas inthe
during tanque
theprocess. durante el proceso.
supply line, and to Q, the heat transferred to the tank at the beginning and
b) Reduzca
material la
in ecuación
the tank generalthe
during a su forma más simple para el caso especial de un gas ideal conenergy of the gas in
process.
(b) Reduce the general equation to its simplest form for the special case of an ideal internal
capacidades
(b) Reduce caloríficas
theconstant
generalheat constantes.
equation to its simplest form for the special case of an ideal H � , the enthalpy of the gas
gas with capacities.
c) Además, reduzca la ecuación de b) para el caso n 1 = 0. material in the tank during
(c)gas with constant
Further reduce the heat capacities.
equation of (b) for the case of n 1 = 0.
d) (c) Después
Further reduzcathe
reduce la equation
ecuación of de(b) c) para
for theel caso
case en
of nque, = también
0. Q = 0. (b) Reduce the general equatio
(d) Further reduce the equation of (c) for the case in which, 1 in addition, Q = 0.
(d) Further reduce the equation of (c) for the case in which, in addition, Q = 0. gas with constant heat capa
(c) Further reduce the equation
(d) Further reduce the equation

e) Considerando al nitrógeno como un gas ideal para el que CP = (7/2)R, aplique la ecuación apro-
piada para el que una alimentación estable de nitrógeno a 25 °C y 3 bar fluye hacia dentro de un
tanque vacío de 4 m3 de volumen, y calcule las moles de nitrógeno que fluyen hacia dentro del
tanque para igualar las presiones para dos casos:
1) Suponga que no fluye calor del gas al tanque o a través de las paredes del mismo.
2) El tanque pesa 400 kg, está perfectamente aislado, tiene una temperatura inicial de 25 °C,
cuenta con calor específico de 0.46 kJ kg–1 K–1 y es calentado por el gas, por lo que siempre
estará a la temperatura del gas en el tanque.
3.16. Desarrolle ecuaciones para determinar la temperatura final del gas que permanece en un tanque,
después de que se extrajo gas desde una presión inicial P1 hasta una presión final P2. Las cantidades
conocidas son la temperatura inicial, el volumen del tanque, la capacidad calorífica del gas, la capa-
cidad calorífica total del contenido del tanque, P1 y P2. Suponga que el tanque siempre está a la
temperatura del gas que permanece en éste y que está perfectamente aislado.
3.17. Un tanque rígido no conductor, con un volumen de 4 m3, se divide en dos partes desiguales separa-
das por una membrana delgada. Un lado de la membrana, que representa 1/3 del tanque, contiene
gas nitrógeno a 6 bar y 100 °C, y el otro lado, que representa 2/3 del tanque, está vacío. La mem-
brana se rompe y el gas llena el tanque.
a) ¿Cuál es la temperatura final del gas? ¿Cuánto trabajo se hace? ¿El proceso es reversible?
b) Describa un proceso reversible mediante el cual el gas pueda regresar a su estado inicial. ¿Cuán-
to trabajo se hace?
Suponga que el nitrógeno es un gas ideal para el que CP = (7/2)R y CV = (5/2)R.
3.18. Un gas ideal, inicialmente a 30 °C y 100 kPa, experimenta los siguientes procesos cíclicos en un
sistema cerrado:
a) En un proceso mecánicamente reversible, primero hay una compresión adiabática a 500 kPa, a
continuación un enfriamiento a presión constante de 500 kPa hasta 30 °C, y al final una expan-
sión isotérmica hasta su estado original.
b) El ciclo experimenta los mismos cambios de estado, pero cada etapa es irreversible con una
eficiencia de 80% en comparación con la del correspondiente proceso mecánicamente reversi-
ble. Nota: la etapa inicial puede no ser más larga que el adiabático.
Calcule Q, W, DU y DH para cada etapa del proceso y para todo el ciclo. Considere CP = (7/2)R y
CV = (5/2)R.
3.19. Un metro cúbico de un gas ideal a 600 K y 1 000 kPa se expande hasta alcanzar cinco veces su
volumen inicial de la siguiente manera:
a) Mediante un proceso isotérmico mecánicamente reversible.

b) Mediante un proceso adiabático mecánicamente reversible.

Problemas 115
c) Mediante un proceso adiabático, irreversible, en el cual la expansión se hace contra una presión
restringente de 100 kPa.
Para cada caso calcule la temperatura y presión final y el trabajo realizado por el gas. CP = 21 J
mol–1 K–1.
3.20. Un mol de aire, inicialmente a 150 °C y 8 bar, se somete a los cambios mecánicamente reversibles
siguientes. Se expande isotérmicamente a una presión tal que cuando se enfría hasta 50 °C a volu-
men constante, su presión final es de 3 bar. Suponga que el aire es un gas ideal para el que CP =
(7/2)R y CV = (5/2)R. Calcule W, Q, DU y DH.
3.21. Un gas ideal fluye en estado estacionario por un tubo horizontal. No se añade calor ni se hace tra-
bajo de flecha. El área de la sección transversal del tubo cambia con la longitud, lo cual hace que
cambie la velocidad. Deduzca una ecuación que relacione la temperatura con la velocidad del gas.
Si por una sección del tubo pasa nitrógeno a 150 °C a una velocidad de 2.5 m s–1, ¿cuál es su tem-
peratura en otra sección donde su velocidad es de 50 m s–1? Sea CP = (7/2)R.
3.22. Un mol de gas ideal, inicialmente a 30 °C y 1 bar, cambia a 130 °C y 10 bar mediante tres distintos
procesos mecánicamente reversibles:
a) El gas se calienta primero a volumen constante hasta que su temperatura es de 130 °C; a conti-
nuación, se comprime isotérmicamente hasta que su presión es de 10 bar.
b) El gas se calienta primero a presión constante hasta que su temperatura es de 130 °C; a con
tinuación, se comprime isotérmicamente hasta 10 bar.
c) El gas se comprime primero isotérmicamente hasta 10 bar; a continuación, se calienta a presión
constante hasta 130 °C.
Calcule Q, W, DU y DH en cada caso. Considere CP = (7/2)R y CV = (5/2)R. En otro caso, con-

sidere CP = (5/2)R y CV = (3/2)R.
3.23. Un mol de gas ideal, inicialmente a 30 °C y 1 bar, experimenta los cambios mecánicamente rever-
sibles siguientes. Se comprime de manera isotérmica hasta un punto tal que cuando se calienta a
volumen constante hasta 120 °C, su presión final es de 12 bar. Calcule Q, W, DU y DH para el pro-
ceso. Tome CP = (7/2)R y CV = (5/2)R.
3.24. Un proceso consta de dos etapas: 1) un mol de aire a T = 800 K y P = 4 bar se enfría a volumen
constante hasta T = 350 K. 2) Después el aire se calienta a presión constante hasta que su tempera-
tura llega a 800 K. Si este proceso de dos etapas se reemplaza por una sola expansión isotérmica del
aire desde 800 K y 4 bar hasta una presión final P, ¿cuál es el valor de P que hace que el trabajo de
los dos procesos sea el mismo? Suponga reversibilidad mecánica y considere el aire como un gas
ideal con CP = (7/2)R y CV = (5/2)R.
3.25. El siguiente es un esquema para encontrar el volumen interno V Bt , de un cilindro de gas. El cilindro
se llena con un gas a baja presión P1, y se conecta mediante una línea y válvula pequeñas a un tan-
que de referencia evacuado y de volumen conocido V At .

116 is opened, and gas flows through the CAPÍTULO line into the3. Propiedades
reference tank. volumétricas
After the system de fluidos puros
is opened,
returns to its and gas flows
initial temperature,througha the line into
sensitive the reference
pressure transducer tank. After athe
provides system
value for
returns toseits initial temperature, alathe
sensitive pressure transducer provides t value
VaBthe for
Lathe isválvula
opened,
pressure abre
and y elflows
gas
change gas fluye
�P thepor
inthrough cylinder.línea
line hacia
into
Determine elthe tanque
reference
the de referencia.
cylinder tank. After
volume Después from dethe
system que el sistema
the
regresa
returnspressure
following a tosudata: change
temperatura
its initial temperature, in the un
�Pinicial, cylinder.
atransductor
sensitive Determine sensible
pressure the acylinder
la presión
transducer volume VaBt value
proporciona
provides fromunthe valor para el
for
tV t from the
following
cambio
the pressurede data:
presiónchange DP en
�P el
in cilindro.
the Determine
cylinder. Determine el volumen
the del
cylinder cilindro
volume V B B a partir de la informa-
• V At =data: 256 cmt3 . 3; b) AP/P = –0.0639.
ción siguiente:
following t
• V A = 256 cmA . a) V 3= 256 cm 1
• �P/P t 1 = −0.0639. 3
•• �P/P
3.26. Un cilindro
V A = 256 cm .
1 = −0.0639.
horizontal, no conductor y cerrado, contiene un pistón flotante no conductor y sin fric-
3.26.ción, •que
A closed, �P/P divide 1 = al−0.0639.
nonconducting, cilindro en horizontal
dos secciones, cylinderA is y B. fitted Laswithdos asecciones
nonconducting,
contienen friction-
masas iguales de
3.26.aire,
A closed,
less, floating
inicialmente nonconducting,
piston
en las which
mismas horizontal
divides thecylinder
condiciones, cylinder T1is=into
fitted with
300Sections
K y Pa1 nonconducting,
=A 1(atm).
and B. En Thelatwo friction-
sec- A se activa
sección
less,
3.26.untions
Aelemento floating
closed,contain depiston
nonconducting,
equal whichhorizontal
masses
calentamiento divides
ofeléctrico thecylinder
ycylinder
air, initially isinto
at the
la temperatura fitted
sameSections
with Aaumenta
and TB.1 =
a nonconducting,
conditions,
del aire The 300 two K sec-
friction-
lentamente: andTA en la sec-
tions
P
ción1 =
less, contain
A floating
1(atm).apiston
debido equal
An masses
which divides
electrical
la transferencia of air,
heating initially
the
element
de calor, y Tat
cylinder in the into
Section
en lasame A
sección conditions,
Sectionsis A and
activated,
B debido TB.
1and
a =
laThe 300two
the airKtem-
compresión and adiabática
sec-
B
P
tions = 1(atm).
contain
peratures por
provocada
1 slowly An
equal electrical
masses
increase: T Alento
el movimiento heating
of air,
in Sectionelement
initially
del pistón. in
at
A because Section
the
Considere same A
of heat is activated,
conditions,
el transfer,
aire como T
and and
=
1unTgas the
300 air
B inideal K tem-
Sectionand
con CP = R, y
peratures
seaP =
B 1nbecause
el1(atm).slowly
número of An increase:
adiabatic
de electrical
moles T
compression
de in
heating
aire
A Sectionelement
by
contenidos theA because
in
slowly
en Section
la of
moving
sección heat
A is transfer,
activated,
piston.
A. Para and
Treat
el andT
air
proceso Bthein
as Section
air
an tem-
ideal
descrito, evalúe uno
A
Blosbecause of 7
adiabatic compression by number
theA slowly
peratures
degas with
conjuntos P =
Cslowly de27increase:
R, and
cantidades T Ansiguientes:
let in Section
A be the because of movingof heat
moles ofpiston.
air in Treat
transfer, and air
Section TBA. as
in an ideal
Section
For the
gas
B because
process P =
withasCdescribed,
of 2 R, and
adiabatic let n one
compression
evaluate A beofthe thenumber
by the slowly
following of moving
moles
sets ofof air in Treat
piston.
quantities: Section air A. as an Forideal
the
process as described, 7 evaluate one of the following sets of quantities:
gas with
a) (a)TAT, T,B Ty Q/nC =
P A, si R, and let
2 P(final) = 1.25(atm).n A be the number of moles of air in Section A. For the
process , and
A asB described, Q/n , if P(final)
Aevaluate one = 1.25(atm).
of the following sets of quantities:
b) (a)TBT, AQ/n AB ,yand Q/n Asi, ifTAP(final)
P(final), = 425 K.
(b) TB ,, T Q/n A , and P(final), if T A = = 1.25(atm).
425 K.
c) (b)
(a)T , Q/n
ATB , T Q/n y
A , andP(final),
, andQ/n si T
P(final),
, if = 325
BP(final)
if T K.= 425 K.
= 1.25(atm). K.
(c) T AA, Q/n B A , and P(final),
A A if TB =A 325
–1.
d) (c)TAT , TB, Q/ny P(final),, and siP(final),
Q/nA = if 3 kJT mol
=
(b)
(d) T AAB, TB , and A P(final), if Q/n B A = 3 kJ K.
A
325
425 mol−1 .
(d) T
(c) A Q/n , T , and P(final),
B A , and P(final), if TB if Q/n A = 3 kJ
325 K. mol−1 .
3.27. Un mol
(d) Tmole
3.27. One de
A , TB
un gas
of, and
an ideal ideal
P(final), con
gas with capacidades
if Q/n A = 3heat
constant caloríficas
kJ mol −1 . constantes se somete a un proceso arbitrario
capacities undergoes an arbitrary mechan-
3.27.mecánicamente
One mole of an reversible.
ideal
ically reversible process. Show that: gas Muestre
with que:
constant heat capacities undergoes an arbitrary mechan-
ically reversible process. Show that:
3.27. One mole of an ideal gas with constant heat capacities undergoes an arbitrary mechan-
ically reversible process. Show that: 1
�U = 1 �(P V )
�U = γ − 1 �(P V )
γ− 11
�U = �(P V )
3.28.
3.28.Deduzca
Derive an unaequation
ecuaciónfor paratheelwork trabajo hecho γ −por
of mechanically 1 la compresión isotérmica compression
reversible, isothermal mecánicamente reversi-
3.28.bleDerive
of de
1 mol anofequation
1 mol de gas,from
a gas for an
desde theuna work
initial of mechanically
presión
pressure inicial P1 Pto1 ahasta reversible,
final una isothermal
presión
pressure whenPcompression
P2final 2thecuando
equation la ecuación de
of
3.28.estado 1 mol
Derive
of state es anlaof
is a virial
gas from
expansión
equation
the for an
virial
expansiontheinitial
[ecuación
work [Eq.pressure(3.11)]
of(3.11)] Ptruncated
mechanically to a final
1 truncada to:a:pressure
reversible, P2 when compression
isothermal the equation
of state
1 molisof thea virial
gas from expansion
an initial [Eq. (3.11)] Ptruncated
pressure 1 to a final to:pressure P2 when the equation
�
of state is the virial expansion [Eq. (3.11)] truncated Z = 1 + B P to:
Z = 1 + B� P
How does the result compare with the = 1 + B � P equation for an ideal gas?
Z corresponding
How does the result compare with the corresponding equation for an ideal gas?
3.29.¿Cómo
How
A certainse compara
does theisresult
gas este
described resultado
compare by the withcon the la corresponding
equation ecuación
of state: que corresponde
equation foral angas ideal?
ideal gas?
3.29. A certain gas is described by the equation of � state: �
3.29.
3.29.Cierto gas segas describe mediante la ecuación de estado:
�bstate: θ
A certain is described byPthe V = equation
RT + of − θ �P
P V = RT + �b − RT � P
RTθ
Here, b is a constant and θ is P aV = RT of
function + T bonly. − For this P gas, determine expressions
RT
Here,
for thebisothermal
is a constant and θ is a function
compressibility κ andofthe T only.
thermal Forpressure
this gas,coefficient
determine (∂ expressions
P/∂ T )V .
for
Here,
These thebexpressions
isothermal
is a constant compressibility
and
should θ is a
contain κ and
function
only T of
, the
T
P, thermal
only.
θ , dθ/dT For pressure
this
, and gas, coefficient
determine
constants. (∂ P/∂ T )V .
expressions
Aquí, b es una constante y q es una función sólo de T. Para este gas, determine las expresiones para
These
for the expressions
isothermal should contain only
compressibility κ and T ,theP, thermal
θ , dθ/dTpressure , and constants.
coefficient (∂ P/∂ T )V .expresiones
la compresibilidad isotérmica k y el
◦ C the second
coeficiente de presión térmica (∂P/∂T) V . Estas
These
3.30.deben
For expressions
methyl
contener chloride
sólo T, should
atP,100 q,contain
dq/dT yonly T and
constantes., P, third
θ, dθ/dT virial, coefficients
and constants. are:
3.30. For methyl chloride at 100◦ C the second and third virial coefficients are:
B = −242.5 ◦Ccmthe 3
mol −1 C =virial 25,200 cm6 mol−2
3.30.Para
3.30. ForelmethylclorurochloridedeB metilo at 100a 100 °C,3 elsecond
segundo
−1
and ythirdtercer coefficients
coeficientes are:
viriales
−2 son:
= −242.5 cm mol C = 25,200 cm6 mol
B = −242.5 cm3 3mol−1 C = 25,200 cm6 mol−2
B = –242.5 cm mol–1 C = 25 200 cm6 mol–2

Problems 117
Problems 117
Problems
Problemas 117 117
Problems 117
Calculate the work of mechanically reversible, isothermal compression of 1 mol of
Calcule Calculate the work
el trabajo defrom of mechanically
compresión1 bar toisotérmica, reversible,
100◦ C. isothermal
at mecánicamente compression
reversible of
deon1of
mol 1 de
mol of de meti-
methyl
Calculate chloride
the work of mechanically 55 bar reversible, Base calculations
◦ C.isothermal compression the molcloruro
1 following
of
Calculate
methyl the
chloride work
from of 1 mechanically
bar to 55 bar reversible,
at 100 isothermal
Base compression
calculations on of
the 1 mol of
following
lomethyl
desde
forms1chloride
hasta
of 55from
the virialbarequation:
a1100bar °C.to 55Apoyebar at sus100cálculos
◦ C. Baseen las formas
calculations de la
on ecuación
the virial
following siguientes:
methylofchloride
forms the virialfrom 1 bar to 55 bar at 100◦ C. Base calculations on the following
equation:
forms of the virial equation: B C
forms of the virial equation:
a) (a) Z = 1 +B +C 2
(a) Z = 1 + BBV+ CC2V
(a)(b) ZZ = 1 + V B+� PV+ � 2
(a) Z ==1 1++ V +V2 C P

b)(b)
(b) ZB = 1 + BV�� P +VC2�� P22 C − B 2
Z = 1 + B �P + C �P� 2
(b)where �
B � = B Z = 1 +and B P + C�CP=C − B22 2
where B� = B B RT and C = CC − (RT B
− )B22)
donde where B � = RT and
B = y CC�� =
and = (RT
where
Why don’t both equations give RT exactly the same result? (RT )22
RT (RT )
Why don’t both equations give exactly the same result?
¿Por Whyqué no
don’t se
bothobtiene
equations el mismo resultado
give exactly
Why don’t both equations give exactly the same result?
theconsameambas ecuaciones?
result?
3.31. Any equation of state valid for gases in the zero-pessure limit implies a full set of virial
3.31. Any equation ofShow
coefficients. state thatvalidthe forsecond
gases inand the zero-pessure limit implies a full settheof generic
virial
3.31.
3.31.Cualquier
Any equationecuaciónof statede valid
estado, forque gases in thethird
es válida para virial
gasescoefficients
zero-pessure enlimit
el límite
impliesimplied
a fullby
de presión setcero, implica un con-
of virial
3.31. coefficients.
Any equation
cubic equation of
Show state
of that valid
state, the for
secondgases and in the
thirdzero-pessure
virial limit
coefficients implies
implied a full
by set
the of virial
generic
junto completo
coefficients. de
Show that theEq.
coeficientes (3.42),
second viriales.
and are:Demuestre
third que el
virial coefficientssegundoimplied y tercero
by thecoeficientes
generic viriales
coefficients.
cubic equation Show that Eq.
of state, the (3.42),
second are: and third virial coefficients implied by the generic
implícitos
cubic equationen la ecuación
of state, Eq.
cubic equation of state, Eq.a(T de estado
(3.42),cúbica
(3.42),
) are:
are: genérica, ecuación (3.42), son:
(� + σ )ba(T )
B = b −a(T ) C =2b2 +(� + σ )ba(T )
B = b − a(TRT ) C = b + (� + σσ)ba(T RT ))
B = b − a(T RT ) C = b22 + (� + RT )ba(T
B = b − RT C =b + RT
Specialize the result forRT B to the Redlich/Kwong equation RT of state, express it in re-
Specialize
duced form, the result for B to the
and compare Redlich/Kwong equation of state, express it in re-
Specialize the result for B toitthe numerically
Redlich/Kwong with the generalized
equation of state, correlation
express itforin Bre-for
Adapte Specialize
duced form,
el theand
resultado result
compare
para for B itto the Redlich/Kwong
numerically
B aitDiscuss
lanumerically
ecuaciónwhatde with
estadothe equation
generalized of state, express
correlation forit B
in for
re-
simple
duced fluids,
form, andEq. (3.65).
compare you
with the de
find. Redlich/Kwong,
generalized correlation expréselo
for B en forsu forma re
duced
simple
ducida form,
fluids, and
Eq. compare
(3.65). it
Discuss numerically
what you with
find. the generalized correlation for B for
simpleyfluids,
compárelo numéricamente
Eq. (3.65). Discuss what conyou la correlación
find. generalizada para B para fluidos simples,
simple fluids, Eq. (3.65). Discuss what you find.
ecuación
3.32. Calculate(3.65). Z andAnalice
V forsus resultados.
ethylene at 25◦ C and 12 bar by the following equations:
3.32. Calculate Z and V for ethylene at 25◦ C and 12 bar by the following equations:
3.32. Calculate Z and V for ethylene at 25◦◦C and 12 bar by the following equations:
3.32. Calculate
(a) The Ztruncated
and V for ethylene
virial equation at 25[Eq. C and 12 bar
(3.40)] withbythethefollowing
followingexperimental
equations: values
3.32. Calcule
(a) The yV
Z truncatedpara elvirial
etileno a 25 ºC[Eq.
equation y 12(3.40)]
bar mediante
with thelas ecuaciones
following siguientes:values
experimental
(a) The of truncated
virial coefficients:
virial equation [Eq. (3.40)] with the following experimental values
(a) of
The truncated
virial virial equation [Eq. (3.40)] with the following experimental values
coefficients:
a) Laof virial coefficients:
ofecuación virial truncada [ecuación
virial coefficients: (3.40)], con los valores experimentales siguientes de los
B = −140 cm 3
mol−1 C = 7,200 cm 6
mol−2
coeficientes viriales: B = −140 cm mol 3 −1 C = 7,200 cm mol 6 −2
B = −140 cm33 mol−1 −1 C = 7,200 cm66 mol−2
(b) The truncated = −140
B virial cm3 mol
equation [Eq. (3.38)],
–1
C = a7,200
with value cmof B
6 mol
mol−2
–2 from the generalized
(b) The truncated B = –140
virial equation cm mol C = 7 200 cm
[Eq. (3.38)], with a value of B from the generalized
(b) The Pitzer correlation
truncated virial [Eq.equation (3.63)].
(b) Pitzer
The truncated
correlation virial[Eq. equation
(3.63)]. [Eq. (3.38)], with a value of B from the generalized
b) (c)LaPitzer
ecuación
The correlationvirial truncada
Redlich/Kwong [ecuación (3.38)], con un valor de B obtenido de la correlación ge-
equation.
[Eq. (3.63)].
Pitzer
(c)neralizada
The correlation
Redlich/Kwong [Eq. (3.63)].
equation.equation.
(c)(d)TheThe de Pitzer [ecuación
Soave/Redlich/Kwong
Redlich/Kwong equation.(3.63)].
(c) The
(d) The Soave/Redlich/Kwong
Redlich/Kwong equation. equation.
LaThe
c) (d)(e) ecuación
The de Redlich/Kwong.
Peng/Robinson
Soave/Redlich/Kwong equation.equation.
(d)
(e) The
d) (e)LaThe Soave/Redlich/Kwong
ecuación
The de Soave/Redlich/Kwong.
Peng/Robinson equation. equation.
Peng/Robinson equation.
e) (e)Calculate
3.33. LaThe Peng/Robinson
ecuación de Peng/Robinson.
Z and
equation.
V for ethane at 50◦ C and 15 bar by the following equations:
3.33. Calculate Z and V for ethane at 50◦◦ C and 15 bar by the following equations:
3.33. Calculate Z and V for ethane at 50 ◦C and 15 bar by the following equations:
3.33.Calcule
3.33. Calculate
(a) TheZ y ZV and
paraVelfor
truncated ethane
virial
etano 50at°C50y [Eq.
aequation C
l5 and 15 bar
bar(3.40)]
con by
with
las the
thefollowing
ecuacionesfollowing equations:
experimental values
siguientes:
(a) The truncated
of truncated virial equation [Eq. (3.40)] with the following experimental values
(a) The virial equation [Eq. (3.40)] with the following experimental values
(a) of
The truncated
virial virial equation [Eq. (3.40)] with the following experimental values
coefficients:
a) Laof ofecuación virial truncada [ecuación
virial coefficients: (3.40)], con los valores experimentales siguientes de los
coeficientes viriales: B = −156.7 cm 3
mol−1 C = 9,650 cm 6
mol−2
B = −156.7 cm mol 3 −1 C = 9,650 cm mol 6 −2
B = −156.7 cm33 mol−1 −1 C = 9,650 cm66 mol−2 −2
B= −156.7 cm3 mol –1 C =a 9,650 cmB–2mol
(b) The truncated virial equation
B = –156.7 cm mol [Eq. (3.38)], with
C = 9 650 cm6 of
value mol from the generalized
(b) The truncated
Pitzer virial equation
correlation [Eq. (3.38)], with a value of B from the generalized
(b) The truncated virial [Eq.equation (3.63)].
(b)
b) (c) The
Pitzer
LaPitzer truncated
ecuación correlation virial[Eq.
virial truncada equation
(3.63)]. [Eq. (3.38)],
[ecuación (3.38)],withconaun value
valor ofdeB Bfrom the generalized
obtenido a partir de la correla-
The correlation
[Eq. (3.63)].
(c)(d)Pitzer
ción
The correlation
generalizada
Redlich/Kwong de [Eq.
Pitzer(3.63)].
equation. [ecuación (3.63)].
(c) The The Soave/Redlich/Kwong
Redlich/Kwong equation.equation.
(c)LaThe
c) (d)
(d) The Redlich/Kwong
ecuación de Redlich/Kwong.
Soave/Redlich/Kwong equation. equation.
(e)TheThe Peng/Robinson
Soave/Redlich/Kwong equation.equation.
(d) The
d) (e)LaThe Soave/Redlich/Kwong
ecuación de Soave/Redlich/Kwong.
Peng/Robinson equation. equation.
(e) The Peng/Robinson equation.
e) (e)LaTheecuación de Peng/Robinson.

118118 CHAPTER 3. 3.
CHAPTER Volumetric
Volumetric
Properties
Properties
of of
Pure
Pure
Fluids
Fluids
3.34.
3.34.
Calculate
Calculate
Z and
Z and
V Vforfor
sulfur
sulfur
hexafluoride
hexafluoride at ◦75
at 75 C◦and
C and
1515
barbar
byby
thethe
following
following
equa-
equa-
3.34. Calcule
tions: Z
tions: y V para el hexafluoruro de azufre a 75 °C y 15 bar mediante las ecuaciones siguientes:
a) La
(a)(a)
Theecuación
The
truncatedvirial
truncated truncada
virial
virial [ecuación
equation
equation
[Eq.
[Eq. (3.40)],
(3.40)]
(3.40)]
withcon
with los
thethe valores experimental
following experimentales
following experimental siguientes
values
values de los
coeficientes
of of
virial
virial viriales:
coefficients:
coefficients:
3 3 −1 −1 6 6 −2 −2
B ==
B =
−194
−194
B–194 cm
cm 3 cmmol
mol mol
–1 C =15
C =C =
15,300
15,300
300 cm6cm
cm mol
molmol
–2
(b)(b)
b) The
La The
truncated
truncated
ecuación virial
virialvirial
equation
equation
truncada [Eq.
[Eq.
(3.38)],
[ecuación (3.38)],
with
(3.38)], with
a value
con a value
un of of
valor Bdefrom
BBfrom
thethe
generalized
obtenido generalized
de la correlación ge-
Pitzer
Pitzer
correlation
correlation
[Eq.
[Eq.
(3.63)].
(3.63)].
neralizada de Pitzer [ecuación (3.63)].
c) (c)(c)
The
La The
Redlich/Kwong
Redlich/Kwong
ecuación equation.
equation.
de Redlich/Kwong.
(d)(d)
d) The
La The
Soave/Redlich/Kwong
Soave/Redlich/Kwong
ecuación equation.
equation.
de Soave/Redlich/Kwong.
La
e) (e)(e) ecuación
TheThe de Peng/Robinson.
Peng/Robinson
equation.
Tc T= 3 mol −1 ,−1and
3 mol
ForFor
sulfur
sulfur
hexafluoride,
hexafluoride, c =
318.7
318.7 Pc P=
K, K, =37.6
37.6 V V= =
bar,bar, 198198
cmcm , and
Para el hexafluoruro de azufre, Tc = 318.7 K, Pc c = 37.6 bar, cVc c= 198 cm3 mol–1, y w = 0.286.
ω= ω= 0.286.
0.286.
3.35. Determine Z y V para el vapor a 250 °C◦ C◦y 1 800 kPa a partir de lo siguiente:
3.35.
3.35.
Determine
Determine
Z and
Z and
V for
V for
steam
steam
at 250
at 250 and
C and
1,800
1,800
kPakPa
byby
thethe
following:
following:
a) Mediante
(a)(a)
TheThe la ecuación
truncated
truncatedvirial virial
virial
equationtruncada
equation[Eq.
[Eq. [ecuación
(3.40)]
(3.40)]
with (3.40)]
with
thethe con losexperimental
following
followingvalores experimentales
experimental values siguien-
values
tes de
of of los
virial coeficientes
virial
coefficients: viriales:
coefficients:
= 3 3mol
3 –1−1 6 6mol
6 –2−2 −2
B –152.5
BB = =
−152.5 cm
−152.5cmcm mol
mol −1 C =C
C =–5
= 800
−5,800cm
−5,800
cmcm molmol
b) Con
(b)(b)
The latruncated
The ecuación
truncatedvirial
virial
virialtruncada
equation
equation [ecuación
[Eq.
[Eq. (3.38)],
(3.38)],
(3.38)],
with
withcon
a valueunofvalor
a value of B de
B from
from obtenido
Bthethe de la correlación
generalized
generalized
generalizada
Pitzer
Pitzer de Pitzer
correlation
correlation
[Eq. [ecuación
[Eq.
(3.63)].
(3.63)].(3.63)].
c) Mediante las tablas de vapor (apéndice F).
(c)(c)
TheThe
steam
steam
tables
tables
(App.
(App.F).F).
3.36. Con respecto a las expansiones viriales, ecuaciones (3.11) y (3.12), demuestre que:
3.36.
3.36.
With
With
respect
respect
to to
thethe
virial
virial
expansions,
expansions,
Eqs.
Eqs.
(3.11)
(3.11)
andand
(3.12),
(3.12),
show
show
that:
that:
��
∂ Z∂ Z ∂ Z∂ Z
B � B=� = and y
and B = B=
∂ P∂ PT,P=0
T,P=0 ∂ρ∂ρT,ρ=0
T,ρ=0
where
donde rρ ≡≡
where ≡
1/V
1/V
ρ1/V. . .
3.37.
3.37.
3.37. Equation
Equation
Cuando la(3.12)
(3.12)
when
ecuación when
truncated
truncated
(3.12) to four
se truncatoafour
terms
terms
cuatro accurately
accurately
términos, represents
represents
describe conthethe
volumetric
volumetric
exactitud data
data
la información volu-
forfor
methane
methanegas
gas
at 0
at◦C
0◦with:
C with:
métrica para el gas metano a 0 °C con:
3 3 −1 −1 6 6 −2 −2 9 9 −3 −3
B=
BB=
−53.4
= −53.4
cmcm
–53.4 cmmol
3 mol ===
mol–1 CCC 2,620
2 2,620
620cm
cmcm
6mol
mol
mol =5=
D =D
–2 D 5,000
5,000
000 cm9cm
cm mol
molmol
–3
(a)(a)
a) Use
UseUsethese
estathese
data
data
to to
información prepare
prepare
para apreparar
plot
a plot
of of
Z
unavs.
Z gráfica
vs.
P for
P for
methane
de methane at 0at◦ C
Z en función 0◦from
C
defrom0 to
0 to
P para 200200
bar.bar.
metano a 0 °C de 0 a
200 bar.
(b)(b)
ToTo
what
whatpressures
pressuresdo do
Eqs.
Eqs.
(3.38)
(3.38)
andand
(3.39)
(3.39)
provide
providegood
goodapproximations?
approximations?
b) ¿Para qué presiones las ecuaciones (3.38) y (3.39) proporcionan buenas aproximaciones?
3.38.
3.38.
Calculate
Calculatethethe
molar
molarvolume
volumeof of
saturated
saturatedliquid
liquid
andandthethe
molar
molar volume
volumeof of
saturated
saturated
3.38. Calcule
vapor
vaporelby
by volumen
thethe molar del líquido
Redlich/Kwong
Redlich/Kwong equation saturado
equation forfor y of
oneonedelof
volumen
thethe molar
following
following anddel
and vapor
compare saturado
compare results mediante la
results
ecuación
with
with de Redlich/Kwong
values
valuesfound
foundbyby para
suitable
suitable una de lascorrelations.
generalized
generalized condiciones
correlations. y sustancias siguientes y compare los resul-
tados con los valores encontrados mediante el empleo de las correlaciones generalizadas adecuadas.
(a)(a)
Propane
Propane at ◦40
at 40 C◦where
C whereP sat
P sat
= 13.71
= 13.71bar.bar.
a) Propano a 40 °C donde P saturado = 13.71 bar.

Problemas 119
b) Propano a 50 °C donde P saturado = 17.16 bar.

c) Propano a 60 °C donde P saturado = 21.22 bar.
d) Propano a 70 °C donde P saturado = 25.94 bar.
e) n-butano a 100 °C donde P saturado = 15.41 bar.
f) n-butano a 110 °C donde P saturado = 18.66 bar.
g) n-butano a 120 °C donde P saturado = 22.38 bar.
h) n-butano a 130 °C donde P saturado = 26.59 bar.
i) Isobutano a 90 °C donde P saturado = 16.54 bar.
j) Isobutano a 100 °C donde P saturado = 20.03 bar.
k) Isobutano a 110 °C donde P saturado = 24.01 bar.
l) Isobutano a 120 °C donde P saturado = 28.53 bar.
m) Cloro a 60 °C donde P saturado = 18.21 bar.
n) Cloro a 70 °C donde P saturado = 22.49 bar.
o) Cloro a 80 °C donde P saturado = 27.43 bar.
p) Cloro a 90 °C donde P saturado = 33.08 bar.
q) Bióxido de azufre a 80 °C donde P saturado = 18.66 bar.
r) Dióxido de azufre a 90 °C donde P saturado = 23.31 bar.
s) Dióxido de azufre a 100 °C donde P saturado = 28.74 bar.
t) Dióxido de azufre a 110 °C donde P saturado = 35.01 bar.
3.39. Use la ecuación de Soave/Redlich/Kwong para calcular el volumen molar del líquido y del vapor
saturados, para la sustancia y condiciones conocidas por uno de los incisos del problema 3.38, y
compare sus resultados con los valores que se encuentran mediante las correlaciones generalizadas
adecuadas.
3.40. Use la ecuación de Peng/Robinson para calcular los volúmenes molares del líquido y del vapor satu-
rados para la sustancia y condiciones dadas por uno de los incisos del problema 3.38, y compare sus
resultados con los valores que se encuentran mediante las correlaciones generalizadas adecuadas.
3.41. Calcule lo siguiente:
a) El volumen ocupado por 18 kg de etileno a 55 °C y 35 bar.

b) La masa de etileno contenida en un cilindro de 0.25 m3 a 50 °C y 115 bar.
3.42. El volumen molar de la fase vapor de un compuesto particular se reporta como

23 000 cm3 mol–1 a 300 K y 1 bar. Ninguna otra información está disponible. Sin que suponga com-
portamiento de un gas ideal determine una estimación razonable del volumen molar del vapor a 300
K y 5 bar.
3.43. Con una buena aproximación, ¿cuál es el volumen molar del vapor de etanol a 480 °C y 6 000 kPa?
¿Cómo se compara este resultado con el valor que corresponde a un gas ideal?
3.44. Se utiliza un recipiente de 0.35 m3 para almacenar propano líquido a su presión de vapor. Las con-
sideraciones de seguridad dictan que a una temperatura de 320 K el líquido no debe ocupar más de
80% del volumen total del recipiente. Bajo estas condiciones determine las masas de vapor y de lí-
quido dentro del recipiente. A 320 K la presión de vapor del propano es 16.0 bar.

3.45. Un tanque de 30 m3 contiene 14 m3 de n-butano líquido en equilibrio con su vapor a 25 °C. Estime
la masa de vapor del n-butano contenida en el tanque. La presión de vapor del n-butano a la tempe-
ratura dada es 2.43 bar.
3.46. Calcule:
a) La masa de etano contenida en un recipiente de 0.15 m3 a 60 °C y 14 000 kPa.

b) La temperatura a la que 40 kg de etano, almacenados en un recipiente de 0.15 m3, ejercen una
presión de 20 000 kPa.
3.47. ¿A qué presión debe llenarse un recipiente de 0.15 m3 a 25 °C para guardar 40 kg de etileno?
3.48. Si 15 kg de H2o se calientan a 400 °C en un recipiente de 0.4 m3, ¿que presión se genera?
3.49. A un recipiente de 0.35 m3 contiene vapor de etano a 25 °C y 2 200 kPa. Si el recipiente se calienta
a 220 °C, ¿qué presión se genera dentro de él?
3.50. ¿Cuál es la presión en un recipiente de 0.5 m3 cuando se carga con 10 kg de dióxido de carbono a
30 °C?
3.51. A un recipiente rígido, lleno a la mitad de su volumen con nitrógeno líquido en su punto normal de
ebullición, se le permite calentarse a 25 °C. ¿Qué presión se desarrolla? El volumen molar del ni-
trógeno líquido en su punto normal de ebullición es 34.7 cm3 mol–1.
3.52. El volumen específico del isobutano líquido a 300 K y 4 bar es 1.824 cm3 g–1. Calcule el volumen
específico a 415 K y 75 bar.
3.53. La densidad del n-pentano líquido es 0.630 g cm–3 a 18 °C y 1 bar. Estime su densidad a 140 °C y
120 bar.
3.54. Calcule la densidad del etanol líquido a 180 °C y 200 bar.
3.55. Estime el cambio de volumen en la vaporización del amoniaco a 20 °C. A esta temperatura, la pre-
sión de vapor del amoniaco es 857 kPa.
3.56. La información PVT es posible adquirirse mediante el procedimiento siguiente. La masa m de una
sustancia de masa molar M se introduce en un recipiente de volumen total V t conocido y térmica-
mente controlado. Al sistema se le permite alcanzar el equilibrio, y se miden la temperatura T y la
presión P.
a) Aproximadamente, ¿qué porcentajes de error se pueden permitir en las variables observadas (m,
M, V t y P) si el error máximo permisible en el factor de compresibilidad Z es ±1%?
b) Aproximadamente, ¿qué porcentajes de error se permiten en las variables observadas si el error
máximo permisible en los valores calculados del segundo coeficiente virial B es ±1%? Suponga
que Z 0.9 y que los valores de B se calculan mediante la ecuación (3.39).

Problems
Problems
Problemas 121
121 121
3.57.
3.57.Para
3.57. Forun
For gasdescribed
aa gas
gas descrito por
described byla
by theecuación
the de Redlich/Kwong
Redlich/Kwong
equation andy para
and for aauna
for temperatura
temperature
temperature mayor
greater
greater que Tc, desa-
than
than
rrolle expresiones
TTcc,, develop
develop para lasfor
expressions
expressions dosthe
for pendientes
the two límite,
two limiting
limiting slopes,
slopes,
��
� �
∂∂ZZ ∂∂ZZ
lím
lim
lim lím
lim
lim
P→0 ∂∂ P
P→0 P TT P→∞ ∂∂ P
P→∞ P TT
Observe
Note quein
Note that
that inen ellimit
the
the límiteas
limit asconforme
PP → 0, VVP →
→ 0, 0,Vand
→ ∞,
∞, and thatyin
→ ∞,
that inque
theen
the el límite
limit
limit as conforme
as PP →
→ ∞, P→
∞, VV →
→ b. ∞, V → b.
b.
3.58.
3.58.SiIf
3.58. 140(ft)333 de
If140(pie)
140(ft) of gas
of metano
methane
methane gasa at
gas 60(◦◦F)
60(°F)
at 60( yF)1(atm)
and es equivalente
and 1(atm)
1(atm) is a 1(gal)
is equivalent
equivalent to de gasolina
to 1(gal)
1(gal) of comoas
of gasoline
gasoline ascombustible
para
fuelunfor
fuel formotor
an de automóvil,
an automobile
automobile ¿cuál
engine,
engine, whatsería
what el volumen
would
would be
be the del tanque
the volume
volume of theque
of the tankserequired
tank necesitato
required topara
holdmantener el
hold
metano
methane
methane a 3at000(psia)
at y 60(°F)
3,000(psia)
3,000(psia) and en◦◦una
and 60(
60( F)
F) inincantidad
an equivalente
an amount
amount equivalent
equivalenta 10(gal)
to
to 10(gal)
10(gal)de of
gasolina?
of gasoline?
gasoline?
Problems 121
3.59.
3.59.Determine
3.59. Determine
Determine una buenaestimate
aa good
good estimación
estimate for paracompressibility
for the
the el factor de compresibilidad
compressibility factor
factor ZZ of Z de vapor
of saturated
saturated saturado
hydrogen
hydrogen va-de hidróge-
va-
nopor
a 25
por atK
at 25yK
25 K3.213
and bar. Por
and 3.213
3.213 comparación,
bar.
bar. For
For comparison,un valor
comparison, an experimentalvalue
an experimental
experimental es Z is
value =
is 0.7757.
ZZ =
= 0.7757.
0.7757.
3.57. For a gas described by the Redlich/Kwong equation and for a temperature greater than
3.60.
3.60.LaThe
3.60. temperatura
The Boyle temperature
c , develop es
is aquella
de Boyleexpressions
BoyleTtemperature is the
the parathe
temperature
temperature
for la two
que:
for
for which:
which: slopes,
limiting
�
��
� � �
∂∂∂ZZZ ∂Z
lím
lim
lim
lim =
= 00 lim
P→0 ∂∂∂P
P→0
P→0 PP TTT P→∞ ∂ P T
a) (a) Muestre
(a) Show
ShowNote que
that el
that the
the
thatsegundo
second
second coeficiente
virial
in the limitvirial P→
coefficient
ascoefficientvirial
0, VBBB→ eszero
is
is ceroand
∞,
zero ata the
at la
the temperatura
Boyle
thatBoyle
in the deas
temperature.
temperature.
limit Boyle.
P → ∞, V → b.
b) (b) Use
(b) Use
Usela the
correlación
the generalized
generalized generalizada
correlation
correlation para
for B,ecuación
forB,B, Eq.
Eq. (3.63),
(3.63),(3.63),
to para estimar
to estimate
estimate the la temperatura
the reduced
reduced Boyle de Boyle
Boyle
reducida
3.58.
temperatureIfpara
temperature 140(ft)for3simple
fluidos
for of simples.
simplemethane fluids.gas at 60(◦ F) and 1(atm) is equivalent to 1(gal) of gasoline as
fluids.
fuel for an automobile engine, what would be the volume of the tank required to hold
◦ F) in an amount equivalent to 10(gal) of gasoline?
3.61.
3.61.SeNatural
3.61. entregagas
Natural gas
gas naturalat(suponga
methane
(assume
(assume 3,000(psia)
pure
pure methane) metano
methane) andis puro)
is60( a unato
delivered
delivered ciudad
to cityavia
aa city través
via de unat
pipeline
pipeline conducto
at aa volumetriccon una relación
volumetric
volumétrica ◦◦F) promedio
rate
rate of 150de
of 150 150 millones
million
million standardde
standard piesfeet
cubic
cubic cúbicos
feet per estándar
per day.
day. Average
Average por día. Las condiciones
delivery
delivery conditions
conditions are de50(
are entrega
50( F)
son
and 50(°F)
and 3.59. yDetermine
300(psia).
300(psia). 300(psia).
Determine:
Determine: aDetermine:
good estimate for the compressibility factor Z of saturated hydrogen va-
por at 25 K and 3.213 bar. For comparison, an experimental value is Z = 0.7757.
a) (a) LaThe
(a) The volumetric
volumetric
relación de entrega delivery
delivery rate
rate in
volumétrica in actual
actual
en pies cubic
cubic feet
cúbicosfeet per
per
reales day.
day.por día.
(b)
(b) The
b) La3.60.The molar
molar
relación Thede delivery
delivery
entrega
Boyle rate
rate in
in kmol
kmol
molar eniskmol
temperature per
per hour.
hour.
por hora. for which:
the temperature
c) (c)LaThe
(c) The gas
gas velocity
velocidad velocity
del gas at
atadelivery
delivery conditions
las condicionesconditions de inin mm�
entrega ss−1
−1..
en�m s–1.
∂Z
The
The pipe
pipe is is 24(in)
24(in) schedule-40
schedule-40 steel steel withwith an an lim
inside
inside∂ P diameter
diameter = 0of
of 22.624(in).
22.624(in). Standard Standard
Laconditions
tubería es
conditions are de acero ◦
◦
60( F)
are 60( de
F) and 24(in),
and 1(atm).
1(atm).cédula 40, con P→0 un diámetro T interior de 22.624(in). Las condiciones
estándar son 60(°F) y 1 atm.
(a) Show that the second virial coefficient B is zero at the Boyle temperature.
3.62.
3.62. SomeSome corresponding-states
(b) Use the generalized correlations
correlations use
use the
correlation thefor critical
critical
B, Eq. compressibility
factor ZZ
(3.63), to estimate cc,, rather
the rather
reduced Boyle
3.62. Algunas
than thecorrelaciones
than the acentric
acentric factor
factordeω, estados
ω, as
as aa correspondientes
third
third parameter.
parameter. The
The usan
two
two eltypes
factor
types of
ofde compresibilidad
correlation
correlation (one
(one basedcrítica Zc, más
based
temperature for simple fluids.
que
on el factor acéntrico
on TTcc,, PPcc,, and
and ZZcc,, the w,
the othercomo
other on un tercer
on TTcc,, PPcc,, andparámetro.
and ω) ω) would Las
would be dos clases
be equivalent de
equivalent were correlación
were there
there aa one-one- basado en
(uno
,to-one
Pc y Zcorrespondence
Tcto-one c , el otro en T , P y w) serían equivalentes donde exista una correspondencia uno a uno
Natural gas c(assume
3.61.correspondence c
between
between pure and
ZZcc methane)
and ω. ω. The The data
data of
is delivered of App.
App. B
B allow
to a city allow aa test
test of
via pipeline ofatthis
this
a volumetric
entre Z c y
correspondence.w. La información
Prepare del
aa plot apéndice
ofof ZZccubic B permite una prueba de esta correspondencia. Prepare
◦ F)
correspondence. rate of 150 Prepare
million plot
standard c vs. ωω to
vs. feet topersee how
seeday.how well
well ZZcdelivery
Average c correlates
correlates with
with ω.
conditions ω.are 50(
una gráfica
Develop
Develop aaand de Z
linearc
linear en función
correlation
correlation
300(psia). Determine: de(Z
(Z w
cc =
= para
aa ++ver
bω)
bω)qué for
for tan bien
nonpolar
nonpolar Z c se correlaciona
substances.
substances. con w. Desarrolle una
correlación lineal (Zc = a + bw) para sustancias no polares.
3.63.
3.63. Figure
Figure 3.3 3.3(a) The volumetric
suggests
suggests that
that the delivery rate
the isochores
isochores in actual
(paths
(paths of
of constantcubic volume)
constant feet per day.
volume) are
are approximately
approximately
figura
3.63. Lastraight 3.3
straight lines
lines sugiere
(b) onThe
on que
aa PPmolar las
TT diagram.
diagram. isocoras
delivery Show
Show (trayectorias
rate that
in kmol
that the de volumen
per hour. models
the following
following constante)
models imply
imply linear
linearsonisochores.
líneas casi rectas en
isochores.
un diagrama(c) PT.TheMuestre que los siguientes modelos
gas velocity at delivery conditions in m s . implican −1isocoras lineales.
(a)
(a) Constant-β,
Constant-β, κκ equation equation for for liquids.
liquids. (b) (b) Ideal-gas
Ideal-gas equation.equation. (c) (c) Van
Van der der Waals
Waals
a) Ecuación
equation.
equation. Theparapipelíquidos
is 24(in) k, –b constante.
schedule-40 steel with b) Ecuación
an inside dediameter
gas ideal. c) Ecuación
of 22.624(in). de van
Standard
der Waals. conditions are 60(◦ F) and 1(atm).
3.62. Some corresponding-states correlations use the critical compressibility factor Z c , rather
than the acentric factor ω, as a third parameter. The two types of correlation (one based
on Tc , Pc , and Z c , the other on Tc , Pc , and ω) would be equivalent were there a one-
to-one correspondence between Z c and ω. The data of App. B allow a test of this
correspondence. Prepare a plot of Z c vs. ω to see how well Z c correlates with ω.
122
122
122122 CAPÍTULO
CHAPTER
CHAPTER 3.3.3.
Volumetric
Volumetric
Properties
Properties ofofPure
Properties ofPure
Pure de
Fluidsfluidos puros
Fluids
Fluids
3.64. A continuación se muestra el árbol de decisión de la ecuación de estado. Para cada elemento discu-
3.64.
3.64.
3.64. Shown
Shown
Shown below
below isisthe
below isthe
theEquation
Equation
EquationofofState
ofState Decision
State
Decision Tree.
Decision
Tree. For
Tree.
For each
For
each
eachitem
itemitemdiscuss
discuss the
discuss
the condi-
the
condi-
condi-
ta tions
las condiciones
appropriate
másits apropiadas para su uso.
tions
tions
appropriate
appropriate totoits use.
to its
use.
use.
��
� (a)(a)
(a) Ideal
Ideal gas
Ideal
gasgas ideal
a) Gas
��
� (b)
(b) 2-term
(b)
2-term Ecuación
b) virial
2-termvirial virial de dos términos
equation
virial
equation
equation
Gas�
Gas
Gas
Gas��
��
� (c)(c)
(c) Cubic
Cubic
CubicEcuación
c)equation
equation
equation cúbica
ofof
ofstate
state de estado
state
d) Tablas de Lee/Kesler, apéndice E
��
� (d)
(d) Lee/Kesler
(d)
Lee/Kesler tables,
Lee/Kesler
tables, Appendix
tables,
Appendix EE E
Appendix
¿Gas o Gas Gas ororor �
Gas ��
líquido? liquid?
liquid?
liquid?
��
� (e)(e)
(e) Incompressible
Incompressible
Incompressible liquid
liquid
liquid
e) Líquido incompresible
��
� (f) Rackett
(f) (f)
Rackett equation,
Rackett
equation,
equation,Eq.
Eq.Eq.(3.72)
(3.72)
(3.72)
Liquid
�
Liquid ��
Liquid f) Ecuación de Rackett, ecuación (3.72)
Líquido
��
� (g)
(g) Constant
(g)
Constant
Constant βand
ββand κκ κ
and
g) b y k constantes
��
�
(h)
(h) Lydersen
(h)
Lydersen etetal.
Lydersen etal.al.
h) Diagrama chart,
chart, Fig.
chart,
de Fig. 3.16
Fig.
3.16
Lydersen, 3.16
et al., figura 3.16
3.65.
3.65.
3.65. Un
3.65.An
An gas
An ideal,
ideal
ideal gas,
ideal
gas, inicialmente
initially
gas,
initially atat25
initially a◦25
at25 ◦25
CC◦and°C
Cand1y1bar,
and 1 bar,
bar,
1bar, se somete
undergoes
undergoes the
undergoes
the alfollowing
the siguiente
following
following proceso
cyclic
cyclic
cyclic cíclicoininen
processes
processes
processes aina un
a sistema
cerrado:
closed
closed
closedsystem:
system:
system:
a) (a)En
(a) InInprocesos
(a) mechanically mecánicamente
Inmechanically
reversible
reversiblereversibles
processes,
processes,
processes, ititprimero
isitisfirst
isfirst se comprime
compressed
first
compressed
compressed de manera to
adiabatically
adiabatically
adiabatically adiabática
to5to5bar,bar,a 5 bar, a
5bar,
continuación
then cooled seataenfría a presión constante de 525 bar ◦hasta
25◦25 ◦ C, 25 °C yexpanded
por últimoisother-
seisother-
expande isotér-
thenthen
cooled
cooled at ataconstant
aconstant
constantpressure
pressure
pressure ofof5of5bar
5bar toto
bar to C,
C, and
andandfinally
finally
finallyexpanded
expanded isother-
micamente
mally
mally
mally a its
totoits
toitssuoriginal
presión
original
original original.
pressure.
pressure.
pressure.
b) (b)El
(b)
(b)
Theciclo
The
The es
cycle
cycle irreversible
cycleisisirreversible y
isirreversible cada
irreversible and
and etapa
and each
each tiene
each step
step step una
has
has has eficiencia
ananan
efficiencyde of
efficiency
efficiency80%
ofof en
80%
80% 80% comparación
compared
compared
compared con el corres-
with
withwith
pondiente
the
the the proceso
corresponding
corresponding
corresponding que es mecánicamente
mechanically
mechanically
reversible
reversiblereversible.
process.
process.
process.El ciclo
The
TheThe completo
cycle
cycle
cyclestill
still consiste
consists
still
consists en
ofofan
consists una
an etapa de
ofan
compresión
adiabatic
adiabatic
adiabatic adiabática,
compression
compression
compression una etapa
step,
step, ananan
step, de enfriamiento
isobaric
isobaric
isobaric cooling
coolingcooling isobárico
step,
step, and
step,
andand y
anananuna expansión
isothermal
isothermal
isothermal isotérmica.
expansion.
expansion.
expansion.
Calculate
Calcule Q, W,
Calculate
Calculate
Q, ∆U
Q,Q,
WW,W ,∆H
y,�U
�U , ,para
�U and
and cada
, and
�H�H
�H for
etapa
for each
for del
each
eachstep
step ofofof
proceso
step the
y the
the process
para
process
processand
el ciclo.
andandfor
for the
Considere
for
the cycle.
the
cycle. CTake
que Take
cycle. = (7/2)R y CV
PTake
P=
CPC P=(7/2)R
=(7/2)R
=C(5/2)R. and
and
(7/2)R V=
CCVC
and V=(5/2)R.
=(5/2)R.
(5/2)R.
3.66.
3.66.
3.66. Demuestre
3.66.Show
Show
Showthat
that que
the
that
the los
the segundos coeficientes
density-series
density-series
density-seriessecond
second
second viriales
virial
virial
virial en serie
coefficients
coefficients
coefficients
candebebe
can
can densidad
bederived
derived pueden
derivedfrom
from
from obtenerse
isothermala partir de
isothermal
isothermal
información
volumetric
volumetric
volumetricvolumétrica
data
data
datavia
via the
via
the isotérmica
expression:
the
expression: mediante la expresión:
expression:
B==
BB= lím
lim
lim (Z(Z
lim
(Z 1)/ρ ρρr(densidad
−−1)/ρ
−1)/ρ ρ(molar
(molar
(molar molar)
≡≡1/V
density)
density)
density) 1/V)
≡1/V
1/V
ρ→0
ρ→0
ρ→0
3.67.
3.67.
3.67. Haga
3.67.Use
Use Useuso
the
the de
the la ecuación
equation
equation
equation ofofthe del
ofthe
the problema
preceding
preceding
preceding anterior
problem
problem
problem yand
and ladata
and información
data from
data
from
from deF.2
Table
Table
TablelaF.2
tabla F.2
totoobtain
F.2 para
toobtain obtener
value un valor
a avalue
obtain avalue
de B para
ofofof
BBfor
Bforel
for agua
water
water
water a una
atatone
atone de
ofofthe
one las
ofthe
thesiguientes
following
following
following temperaturas:
temperatures:
temperatures:
temperatures:
300
a)(a)
(a) °C
300 ◦C
◦C ◦ C(b)
(b) 350
350 ◦C
◦C ◦ Cb) 350
(c) 400 ◦C
°C
◦C ◦C c) 400 °C
(a)
300300 (b) 350 (c) (c)
400400

Problemas
Problems
Problems
Problems 123
123
123 123
3.68.
3.68.
3.68.Obtenga
3.68.Derive
Derive
Derive los
the
the
thevalores
values
values
values de
ofof
of
�,W,
�,
�,
�,ψ
�, yand
and
�, Z ZcZcdados
and Zcgivenen
cgiven
given la
ininin tabla
Table
Table
Table 3.1
3.1
3.1
3.1 para:
for:
for:
for:
La
a)(a)
(a) ecuación
(a)The
The
The de estado deequation
Redlich/Kwong
Redlich/Kwong
Redlich/Kwong Redlich/Kwong.
equation
equation
ofofof
state.
state.
state.
La
b)(b)
(b) ecuación
(b)The
The
The de estado de Soave/Redlich/Kwong.
Soave/Redlich/Kwong
Soave/Redlich/Kwong
Soave/Redlich/Kwong equation
equation
equation ofofof
state.
state.
state.
La
c)(c)
(c) ecuación
(c)The
The
The de estado
Peng/Robinson
Peng/Robinson
Peng/Robinsonde Peng/Robinson.
equation
equation
equation
ofofof
state.
state.
state.
3.69. Suponga que se tienen disponibles datos de Z en función de Pr a Tr constante. Demuestre que el
3.69.
3.69.
3.69.Suppose
Suppose
Suppose
segundo ZZZvs.
vs.
coeficiente r data
vs.PPr P data
dataare
rvirialare
are
available
available
available
reducido enatat
at
constant
constant
constant
serie TTr rT. .r Show
de densidad .Show
Showthat
that
puedethat
the
the
the
reduced
reduced
reduced
obtenerse density-
density-
density-
a partir de tales datos
series
series
series
second
second
secondvirial
virial
virial
mediante la expresión: coefficient
coefficient
coefficient
can
can
can
be
be
be
derived
derived
derived
from
from
fromsuchsuch
suchdata
data
data
via
via
via
the
the
the
expression:
expression:
expression:
B̂B̂B̂ lím
===lim
lim
lim
(Z
(Z−−−
(Z 1)Z
1)Z
1)Z
TTr rT/P
/P
r /P
rr r
r →0
PP rP→0
r →0
Sugerencia:
Suggestion:fundamente
Suggestion:
Suggestion:
Base
Base
Base
the
the
the el desarrolloon
development
development
development en
on
on la
the
the expansión
the
full
full
full
virial
virial
virialvirial en densidad
expansion
expansion
expansion ininin completa,
density,
density,
density,
Eq.
Eq.
Eq. ecuación (3.12).
(3.12)
(3.12)
(3.12)
3.70.
3.70.
3.70.Utilice
3.70.Use
UseUse el
the
the
theresultado
result
result
result
ofofofdel
the
the
the problema
preceding
preceding
preceding anterior
problem
problem
problem yand
los
and
anddatos
data
data
data de
from
from
fromlaTable
tabla
Table
TableE.1
E.1
E.1
E.1topara
toto obtener
obtain
obtain
obtain un valor
aavalue
avalueofofof de B̂ para
value
fluidos
B̂B̂B̂
for
for
forsimples
simple
simple
simple con
fluids
fluids T
fluids =
r at
atat 1. Compare
TTr rT==r 1.
=1.1.
Compare
Compareel
Compare resultado
the
the
the
result
resultcon
result
with
withel
with valor
the
thethe dado
value
value
value por
implied
implied
implied la ecuación
by
byby
Eq.
Eq.
Eq. (3.65).
(3.65).
(3.65).
(3.65).
3.71.
3.71.
3.71.La
3.71. siguiente
The
The
The conversación
following
following
following fuewas
conversation
conversation
conversation escuchada
was
was en in
overheard
overheardlos
overheardininpasillos
the
the
the de una
corridors
corridors
corridors aimportante
ofofof
alarge
alarge
large compañía
engineering
engineering
engineering de ingeniería.
firm.
firm.
firm.
Ingeniero
New
NewNew novato:
engineer:
engineer:
engineer: ”Hi,“Hola,
”Hi,
”Hi,
boss.jefe.
boss.
boss.Why
Why
Why¿Por
the
thequé
the
big
big
bigtan
smile?”contento?
smile?”
smile?”
Old-timer:
Old-timer:
Old-timer: ”I
”I”I
finally
finally
finally
won
won
won aawager
awager
wager with
with
with
Veterano: “Por fin le gané una apuesta a Uriel Ortega, Harry
Harry
Harry Carey,
Carey,
Carey,from
from
del from Research.
Research.
Research.He
departamento He
deHebet
bet
bet
meme
methat
that
that Me apos-
investigación.
I I couldn’t
Icouldn’t
couldn’t
tó que no se come
come
come up
up
upwith
with
withaa quick
aquick
quick but
but
butaccurate
accurate
accurate estimate
estimate
estimate for
for
for
the
the
themolar
molar
me podría ocurrir una estimación rápida pero precisa para el volumen molarmolar volume
volume
volume of
ofof
ar-
ar-
ar- del argón
gon
gongon at
atat
30
30◦◦CC
30 ◦C
and
and
and 300
300
300bar.
bar.
bar.Nothing
Nothing
Nothing to
toto
it;
it;it;
I Iused
I
used
used
the
the
the
ideal-gas
ideal-gas
ideal-gas equation,
equation,
equation, and
and
andgot
got
got
about
about
about
a 30 °C33y3 300 −1
−1
bar.
−1
Nada más fácil: utilicé la ecuación del gas ideal y obtuve aproximadamente 83
83
cm 83383cm
cm
molcm–1
mol
mol
.mol . .Harry
Uriel .negó
Harry
Harryshook
shook
shook
con his
his
his
head,
la cabeza,head,
head, but
perobut
butpaid
paid
paid
pagó. up.
up.
up.
¿QuéWhat
What
What do
dodo
piensas you
you
youthink
think
acercathink
deabout
about
about
esto?that?”
that?”
that?”
New
New
Newengineer
engineer
engineer (consulting
(consulting
(consultinghis
his
his
thermo
thermo
thermotext):
text):
text):
”I”I”I
think
think
think
you
you
you
must
must
must
be
bebe
living
living
living
right.”
right.”
right.”
Ingeniero novato (consultando su texto de termodinámica): “Pienso que debe de estar en lo correcto”.
Argon
Argon
Argonatatat
the
the
the
stated
stated
statedconditions
conditions
conditionsisisis
not
not
not
an
anan
ideal
ideal
ideal gas.
gas.
gas.Demonstrate
Demonstrate
Demonstratenumerically
numerically
numerically why
why
why
the
the
the
Elold-timer
argón a won
old-timer
old-timer las
won
won his
his
his wager.establecidas no es un gas ideal. Demuestre numéricamente por qué el
condiciones
wager.
wager.
veterano ganó la apuesta.
3.72.
3.72.
3.72.Cinco
3.72.Five
Five moles
Fivemol
mol de
molofofof carburocarbide
calcium
calcium
calcium de calcio
carbide
carbide
aresecombined
are
are combinan
combined con
combinedwith
with 10
with10 moles
molofofde
1010mol
mol agua
waterinen
ofwater
water ininaaun recipiente
closed,
aclosed,
closed,rigid,cerrado, rígi-
rigid,
rigid,
33internal
3internal 3
do, de alta presión y con un volumen vacío interno de 1 800 cm . Se produce gas de acetileno me-
high-pressure
high-pressure
high-pressure vessel
vessel
vessel
of
ofof
1800
1800
1800cm
cm
cm internal
empty
empty
emptyvolume.
volume.
volume. Acetylene
Acetylene
Acetylene gas
gasgas
isisis
produced
produced
produced
diante
by
byby
thelareaction:
the
the reacción:
reaction:
reaction:
CaC
CaC
CaC 2(s)
22(s)
CaC 2(s)++
(s)++
2H
2H
2H O(l)
22O(l) →→
2 O(l) CC2C
→ H
2H22H (g)
22(g)
(g) ++++
2 (g) Ca(OH)
Ca(OH)
Ca(OH)
22(s)
(s)
2 (s)
ElThe
recipiente
The
Thevessel
vessel
vessel contiene
contains
contains
contains un embalaje
packing
packing
packing with
with
withcon una porosidad
aaporosity
aporosity
porosity ofofof
40%
40%40% de 40%
tototo
prevent
preventpara
prevent evitar ladecomposi-
explosive
explosive
explosive descomposición
decomposi-
decomposi- explo-
siva
tion
tiondel
tion acetileno.
ofofof
the
the
the Las condiciones
acetylene.
acetylene.
acetylene. Initial
Initial
Initial iniciales
conditions
conditions
conditions are son
are
are25 ◦de
2525 ◦CC◦C25
and
and °C
and 11ybar,
1bar,
1bar, bar,
and
andythe
and la
thethereacción
reaction
reaction
reaction llega
goes
goes
goesatoto
completarse.
to
La reacción esThe
completion.
completion.
completion. exotérmica,
The
The reaction
reaction
reaction pero
isisis debido a but
exothermic,
exothermic,
exothermic, la
but transferencia
butowing
owing
owing tototo
heat detransfer,
heat
heat calor,
transfer,
transfer,lathe temperatura
thethe
final
final
final
tempera-final es de sólo
tempera-
tempera-
125
ture
ture°C.
ture Determine
isisis
only
only
only125
125
125◦◦C.
◦la
C.C.presión
Determine
Determine
Determine final
the
theen
the el recipiente.
final
final
final
pressure
pressure
pressure ininin
the
the
thevessel.
vessel.
vessel.
Nota: aAt125 °C◦◦C,
◦ C,
elC,volumen molar delofCa(OH) 333mol –1
−1
−1
−1
2 es de 33.0 cm mol .. .Ignore los efectos de cualquier
Note:
Note:
Note: AtAt
125
125
125 the
the
the
molar
molar
molar volume
volume
volume ofof
Ca(OH)
Ca(OH)
Ca(OH) 3mol
22is 2isis
33.0
33.0
33.0 cm
cmcm mol Ignore
.Ignore
Ignore the
the
theeffects
effects
effects
gas (por
ofofof
any
any
any ejemplo,
gases
gases
gases(e.g.,aire)
(e.g.,
(e.g.,
air)
air)que
air) de manera
initially
initially
initiallypresent
present inicial
present ininin
the
thehaya
the
vessel.
vessel. estado presente en dicho recipiente.
vessel.
3.73.
3.73.
3.73.Se
3.73. requiere
Storage
Storage
Storage almacenar
isisis
required
required
required
for3535,000
for
for 000 kg
35,000
35,000
kg deofofpropano,
kgkg of
propane,
propane,que
propane, es recibido
received
received
receivedasasas como
aagas
agas
gas
atatat
10
10◦◦CC
un
10 ◦C
gas
anda 1(atm).
and 10
and °C y 1(atm). Se
1(atm).
1(atm).
proponen
Two
Two
Two dos opciones:
proposals
proposals
proposals have
have
havebeen
been
beenmade:
made:
made:
◦◦CC
◦ and
a) (a)
(a)
(a)Store
Store
Store
ititas
Almacenarlo itasas
aacomo
gas
agas
gasatatun
at
101010
gasC and
a and
101(atm).
1(atm).
1(atm).
°C y 1(atm).
(b)
(b)
(b)Store
Store
Store
ititas
itasas
aaliquid
aliquid
liquid in
inin
equilibrium
equilibrium
equilibrium with
with
with
its
itsits
vapor
vapor
vapor ◦◦CC
◦C
b) Almacenarlo como un líquido en equilibrio con suatat
at
10
1010
vapor aand
and
10and6.294(atm).
°C6.294(atm).
6.294(atm).For
For
For
y 6.294(atm). this
this
thiseste modo
Para
mode
mode
mode of
of of
storage,
storage,
storage, 90%
90%90% of
ofof
the
the
the
tank
tank
tank
volume
volume
volume is
isis
occupied
occupied
occupied
de almacenamiento, 90% del volumen del tanque es ocupado por líquido. by
by
by
liquid.
liquid.
liquid.

124
124124 CAPÍTULO
3. 3.
CHAPTER
Volumetric
Properties
Properties of Pure
of Pure de fluidos puros
Fluids
Fluids
CompareCompare las dostwo

opciones, discutiendo lospros
puntos acons
favorofy each.
en contraquantitative
de cada una.whereTrate de ofrecer
Compare thethe proposals,
two proposals, discussing
discussing pros andand
cons of each. BeBe quantitative where
argumentos
possible. cuantitativos siempre que sea posible.
possible.
3.74. La definición del factor de compresibilidad Z, ecuación (3.10), puede escribirse de la forma más
3.74.
3.74. TheThe definition
definition of of compressibility
factor Z , ZEq.
, Eq. (3.10),
(3.10), may maybe be written
written in in
thethe
moremore
intuitiva:
intuitive
intuitive form:
form:
V V
Z≡ Z≡
V (gas ideal)
(idealgas)
V (idealgas)
where both volumes are at the same
donde ambos volúmenes se encuentran a las mismas
where both volumes are at the same T T
and and
P. P. Recall
Recall T that
that P. an
y an ideal
gasgas
Recuerde
ideal aismodel
isque aunmodel sub-es una sus-
gassub-
ideal
stance comprising particles with no intermolecular forces. Use the intuitive definition
tancia modelo que tiene partículas sin fuerzas intermoleculares. Utilice la definición intuitiva de Z
stance comprising particles with no intermolecular forces. Use the intuitive definition
of of
para
Z toZ argue
to argue
sostener that:
que:
that:
(a) (a)
a) LasIntermolecular
Intermolecular attractions
atraccionesattractions promote
intermoleculares
promote values
promueven
values of of Z 1.
< 1.
Zvalores
< de Z < 1.
(b) (b)
b) LasIntermolecular repulsions
repulsionesrepulsions
Intermolecular promote
intermoleculares
promote values
promueven
values of of Z 1.
> 1.de Z > 1.
Zvalores
>
(c) (c)
c) AUnbalance
Aequilibrio
balance deattractions
of atracciones
of attractions y repulsiones
andand repulsions
repulsions implica
implies
implies que
thatthat
Z= Z=
Z =1.(Note
1. 1.(Nótese
(Note que
thatthat unideal
an an gas
ideal ideal
gasgas es un caso
especial
is para
aisspecial
a special
caseel que
case
forfor haythere
nowhich
which atracciones
there
areare ni attractions
no no repulsiones).
attractions or repulsions.)
or repulsions.)
3.75.
3.75.
3.75. Escriba
thela
Write
Write theforma general
general
general of de
form
form of una
an an ecuación
equation
equation ofdestate
of state estado
as:as: como:
Z= =+11 Z
ZZ 1= +rep
+ rep(r)
ZZrep
(ρ) − –Z
(ρ) (T,
ZZatr(T,
−attr attr ρ)r)ρ)
(T,
where
where
donde Z (r)
ZZrep rep (ρ)
rep(ρ)
represents
representa
represents la contributions
contribución
contributions from
de
from lasrepulsions,
andand
repulsiones
repulsions, ZZatr(T,
yZ attr (T,(T,
attr r)ρ)
ρ) representsla contribu-
representa
represents
contributions
ción de
contributions fromfrom
las atracciones. attractions.
¿CuálesWhat
attractions. What
son areare
las thethe repulsive
contribuciones
repulsive and attractive
repulsivas
and attractivey de contributions
atracción
contributions detolatoecuación de
the
vanvan
estado
the derder
de van Waals
Waals equation
der equation
Waals? of state?
of state?
3.76.
3.76.
3.76. A Given
continuación
Given below
below se
areare proponen
fourfour cuatro
proposed
proposed modificaciones
modifications
modifications of of avan
la van
thethe ecuación
derder deequation
Waals
Waals estado deofvan
equation of der Waals. ¿Son
state.
state.
razonables
AreAre any algunas
of
any of these these de estas modificaciones?
modifications
modifications reasonable? Explique
Explain
reasonable? Explain de manera
carefully;
carefully; cuidadosa
statements
statements poras,qué
such
such “It las
as, “It afirmacio-
nes del
isn’t
isn’t tipoin“no
cubic
cubic in es cúbica
volume.”
volume.” en el
do
do notnot volumen”, no son válidas.
qualify.
qualify.
RTRT a a
(a)(a)
P=P= −−
V−V b− b V V
RTRT a a
(b)(b)
P=P= −2 −
(V −
(V − b) 2b) V V
RTRT a a
(c)(c)
P=P= − −2 2
V (V
V (V − b) V V
− b)
RTRT a a
(d)(d)
P=P= −− 2
V V V 2V
3.77.
3.77.
3.77. With
Con
With reference
respecto
reference to Pb.
altoproblema
Pb. 2.43,
2.43, assume
2.43, air air
suponga
assume to be
toque
be an
el aire
an ideal
ideal ungas,
esgas, andand
gas develop
ideal an an expression
y desarrolle
develop una expresión en la
expression
giving the household air temperature as a function of time.
que proporcione la temperatura del aire doméstico como una función del tiempo.
giving the household air temperature as a function of time.
3.78.
3.78.
3.78. A garden
AUna
garden
manguerahose
hose dewith
with thethe
jardín water
water
con valve
valve
la shut
válvula shut
andand
del thethe
agua y lanozzle
nozzle closed
closed
boquilla sitssits insethe
in the
cerradas sun,
sun, fullfull
encuentra of
ofexpuesta a los
liquid water. Initially, the water is at ◦10 ◦ C and 6 bar. After some time the temperature
liquid water. Initially, the
rayos del sol y llena de agua water is at
líquida. 10Al C and 6 bar.
principio, el After
agua some
tiene time
una the temperature
temperatura de 10 °C y 6 bar.
of the water rises to ◦40 ◦ C. Owing to the increase in temperature and pressure and the
of the water
Después de rises
cierto totiempo
40 C. la
Owing to the increase
temperatura del aguainasciende
temperature
a 40 and pressure and the
°C. Obedeciendo al incremento de
elasticity
elasticity
temperatura of
of the the hose,
hose,
y presión, the
theasí internal
internal
como ladiameter
adiameter of the
of the
elasticidad hose
de hose
la increases
increases
manguera, el by
by 0.35%.
0.35%.
diámetro Estimate
Estimate
interno de ésta se in-
thethe final
final pressure
pressure of of
the the water
water in in
the the hose.
hose.
crementa 0.35%. Calcule la presión final del agua en la manguera.
Data: β(ave) = 250
= 250 × 10 10−6−1
× −6 K−1 ; κ(ave) = 45= 45 × −6
× ×10 10−6 bar
−1 −1
Data: Datos:β(ave)
b(prom) = 250 × 10–6KK–1; ;κ(ave)
k(prom) = 45 10–6bar
bar–1

Capítulo 4
Efectos térmicos
La transferencia de calor es una de las operaciones más comunes en la industria química. Considere, por
ejemplo, la fabricación del etilenglicol (un agente anticongelante) mediante la oxidación de etileno a óxido de
etileno y de su hidratación posterior a glicol. La reacción de oxidación catalítica resulta más efectiva cuando
se realiza a temperaturas cercanas a 250 °C. Por lo tanto, los reactivos etileno y aire se calientan a esta tem-
peratura antes de que entren al reactor. Para diseñar el precalentador es necesario saber cuánto calor se trans-
fiere. Las reacciones de combustión del etileno con el oxígeno en la cama catalítica tienden a incrementar la
temperatura. Sin embargo, si se elimina el calor del reactor, la temperatura no aumenta más de 250 °C. Las
temperaturas superiores promueven la formación de CO2, que es un producto no deseado. Para el diseño del
reactor se requiere conocer la rapidez de transferencia de calor, y ésta depende de los efectos térmicos asocia-
dos con las reacciones químicas. El producto óxido de etileno se hidrata a glicol por la absorción en agua. El
calor se desprende debido no sólo al cambio de fase y al proceso de disolución, sino también por una reacción
de hidratación entre el óxido de etileno disuelto y el agua. Al final, el glicol se recupera del agua a través de
la destilación, un proceso de vaporización y condensación que origina la separación de una solución en sus
componentes.
Todos los efectos térmicos importantes se ilustran por medio del proceso, relativamente simple, de la
fabricación de una sustancia química. A diferencia de los efectos del calor sensible, caracterizados por los
cambios de temperatura, los efectos térmicos de una reacción química, la transición de fase, así como la for-
mación y la separación de soluciones se determinan a partir de medidas experimentales hechas a temperatura
constante. En este capítulo, la termodinámica se aplica a la evaluación de la mayoría de los efectos térmicos
que acompañan a las operaciones físicas y químicas. No obstante, los efectos térmicos de los procesos de
mezclado, que dependen de las propiedades termodinámicas de las mezclas, se tratan en el capítulo 12.
4.1 EFECTOS DEL CALOR SENSIBLE
La transferencia de calor a un sistema en el que no hay transiciones de fase, ni reacciones químicas o algún
cambio en la composición, provoca que cambie la temperatura del sistema. Nuestro propósito es desarrollar
relaciones entre la cantidad de calor transferida y el cambio de temperatura resultante.
Cuando el sistema es una sustancia homogénea de composición constante, la regla de la fase indica que
al fijar los valores de dos propiedades intensivas se establece su estado. Por lo tanto, la energía interna molar
o específica de una sustancia se puede expresar como una función de las otras dos variables de estado. Cuando
125

126 126 CAPÍTULO
CHAPTER 4. Efectos
4. Heat
Heat Effectstérmicos
126
126 CHAPTER 4.
CHAPTER 4. Effects
Heat Effects
126 CHAPTER 4. Heat Effects
éstas seother
seleccionan
state en forma
variables. Whenarbitraria
these como
are temperatura
arbitrarily selected y volumen
as molar and
temperature o específico,
molar or U = U(T, V).
or specific
specific
other
De donde,
other state
state variables. When these are arbitrarily selected as temperature and molar
volume,
other state
volume, U variables.
U =U
= U (T,
(T, V
variables.
When
V ).
). Whence,
When
Whence,
these are arbitrarily selected as temperature and molar or specific
these are arbitrarily selected as temperature and molar or specific
volume, U = U (T, V ). Whence,
volume, U = U (T, V ). Whence, � � ��
� �
�
� ∂U∂U � � ∂U �
∂U
dU
dU = =
= � ∂U dT +
� dT + � ∂U � dd V V
dU ∂T
∂U
∂ T V dT + ∂∂U ∂VV T dV
dU = ∂ T VVV dT + ∂ V TTT d V
∂T V ∂V T
As aa result
Como resultado
As resultde of
la
of Eq. (2.16)(2.16),
ecuación
Eq. (2.16) this becomes:
this becomes:
ésta será:
As a result of Eq. (2.16) this becomes:
As a result of Eq. (2.16) this becomes: �
� �
�
� ∂U �
∂U
dU =
dU =C C V dT dT + + � ∂U � dd V V
dU =C V dT +
VV ∂V
∂U
∂ V T dV
dU = C V dT + ∂ V TT d V T
∂V T
The final
The final term
final term
term may may
may bebe set
be set equal
set equal
equal to to zero in
to zero
zero in two
two circumstances:
circumstances:
The
Existe laThe
posibilidad in two circumstances:
final termdemay quebeelsettérmino
equal final
to zero seainigual
two acircumstances:
cero bajo dos circunstancias:
• For
• For anyany constant-volume
constant-volume process, process, regardless
regardless of of substance.
substance.
• Para cualquier
• For anyproceso a volumenprocess,
constant-volume constante sin importar
regardless la sustancia.
of substance.
• For any constant-volume process, regardless of substance.
• Whenever the internal energy is independent of volume, regardless of of the
the process.
process. This
This
• Siempre •• Whenever
is
que la energía
Whenever
exactly the
true
interna energy
the internal
internal
for ideal
sea independiente
energy
gases
is independent
is
and
independent del volumen,
incompressible of volume,sinregardless
of volume,
fluids
considerar
regardless
and ofelthe
approximately
proceso.
process.
true for
Esto
This
low-
es verda-
dero para• is
is gases
Whenever
exactly ideales
true for ideal gases and incompressible fluids and approximately true for low-presión.
the
true
exactlygases. y
for fluidos
internal
ideal incompresibles,
energy
gases is
and independent
incompressibley aproximadamente
of volume,
fluids cierto
regardless
and para
of
approximately the gases
process.
true a
forbaja
This
low-
pressure
is exactly
pressure true for ideal gases and incompressible fluids and approximately true for low-
gases.
pressure gases.
pressure gases.
En cualquier
In either caso,
either case, dUdU = =C CVV dT dT
In
In case,
either case, dU
dU =C
= C V dTdT
VV
In either case, dU = � C T V dT
�� T22
y and
and �U =
�U = � T22 CT C V dT dT (4.1) (4.1)
(4.1)
and �U = TT1T2 C V dT
VV (4.1)
and �U = TT11 C V dT1 (4.1)
T1
For
Para unFor
procesoa mechanically reversible
a volumen constante constant-volume
reversiblemecánicamente process,
reversible,
process, QQ Q
Q= ==
∆U,�U
= �U , and
y la and Eq.
ecuación (2.19) may
(2.19) may be escri-
se puede
For
writtenaa mechanically
mechanically
for a unit mass reversible
or a mole:
constant-volume
constant-volume process, �U ,, and Eq. (2.19)
Eq. (2.19) may be be
bir parawritten
unaamol
For foro aamasa
unit unitaria:
mechanically mass reversible
or aa mole:
mole: constant-volume process, Q = �U , and Eq. (2.19) may be
written for unit mass or
written for a unit mass or a mole: � T2
�
Q = �U = � T
TT22 C V dT
Q=
Q = �U �U = = �T T22 C C V dTdT
1 V
V
Q = �U = TTT111 C V dT
T1
Similarly, the the molar
molar or or specific
specific enthalpy
enthalpy may may be expressed
expressed as as a function
function of of temperature
temperature
De manera similar,
Similarly,
Similarly, la
the H entalpía
molar or(T,molar
specific o específica
enthalpy may se expresa
be
be en función
expressed de la temperatura
as aa function of temperature y de la pre-
and pressure. Then = H P), and
sión. Enand tal caso,
pressure. H
Similarly, = H(T,
the
Then HP),=
molar
and pressure. Then H = H (T, P), and y H or
(T,specific
P), and enthalpy may be expressed as a function of temperature
and pressure. Then H = H (T, P), and �
� �
� �
� �
�
� ∂H
∂ H� � ∂H
∂ H�
dHH= = � ∂ H � dT dT + + � ∂ H � dd P P
dd H = ∂∂ T T P dT +
H ∂H
∂ PP T dP
d H = ∂ T PP dT + ∂ P TT d P
P T
∂T P ∂P T
As
As a
a result
result of
of Eq.
Eq. (2.20)
(2.20) this
this becomes:
becomes:
As a result of Eq. (2.20) this becomes:
Como resultado
As a result deof la Eq.
ecuación
(2.20)(2.20), ésta será:
this becomes: � �
�
� ∂H H� �
dHH= =C C P dT dT + ∂
+ � ∂ H � dd P P
dd H =C P
P dT +
P P T dP
∂∂ H
P
d H = C P dT + ∂ P TT d P T
∂P T
Again,
Again, two two circumstances
two circumstances
circumstances allow allow
allow the the final
the final term
term to to bebe setset equal
equal to to zero:
zero:
Again, final term to be set equal to zero:
Una vezAgain,
más, dos
• For
twocircunstancias
For
circumstancespermiten
any constant-pressure
allow theque
constant-pressure process, process,elregardless
final term términoto befinal
regardless seasubstance.
set equal
of the
the igual a cero:
to zero:
• any
• For anyproceso constant-pressure process, regardless of
of the substance.
substance.
• Para cualquier
• For any constant-pressurea presión constante, sin importar
process, regardless la sustancia.
of the substance.
•
• Whenever
Whenever the
the enthalpy
enthalpy of
of the
the substance
substance is
is independent
independent of pressure,
of pressure, regardless
regardless of of the
the
• Cada•vez que la entalpía
Whenever
process. This is de
the enthalpy la sustancia
exactly oftrue
thefor sea
substanceindependiente
ideal is independent
gases and de la presión,
of
approximately sin
pressure, considerar
true regardless
for el of
proceso.
low-pressure the Esto
• process.
WheneverThis
process. the is
This enthalpy
exactlyoftrue thefor
true substance
for ideal gases
gasesis independent of pressure,
and approximately
approximately true regardless of the
for low-pressure
low-pressure
es precisamente
gases. cierto ispara gases ideales,
exactly y aproximadamente
ideal and válido paratrue gases a baja presión.
for
process.
gases.
gases. This is exactly true for ideal gases and approximately true for low-pressure
gases.

4.1. Sensible Heat Effects 127
4.1.
4.1. Efectos
4.1.
4.1. Sensible
4.1. Sensible
Sensible
del Heat
Heat
calorHeat
Sensible Effects
Effects
sensible
Heat Effects
Effects 127
127
127
127 127
In either case, d H = C P dT
En cualquier
In
In caso,
either
Ineither
In either
either case,
case,
case,
case, dH
ddddH
H
H =
H===C
= C
C
CCPPPPdTdT
dT
dT
dT
� T2P
��
and �H = �� TTTT2T2222C P dT (4.2)
y and
and
and
and �H
�H=
�H
�H == T1 C
= CC dT
dT
CPPPPdT
dT (4.2) (4.2)
(4.2)
(4.2)
(4.2)
P
TTTTT
11111
Por otraMoreover,
parte, Q = Q ∆H= �H paraforprocesos mecánicamente
mechanically reversible,reversibles de sistema
constant-pressure, cerrado, a presión
closed-system processesconstante
Moreover,
Moreover,
Moreover,
Moreover, QQQ =
Qand
==�H
= �H�Hthe
�H for
for
for mechanically
fortransfer
mechanically
mechanically
reversible,
reversible,
reversible, constant-pressure,
constant-pressure,
constant-pressure,
constant-pressure, closed-system
closed-system
closed-system
closed-system processes
processes
processes
processes
[ecuación (2.23)] y para la transferencia de calor en intercambiadores de flujo estableP donde�E
[Eq. (2.23)] for of heat in steady-flow exchangers where �E and ∆EKP are
y ∆EK son
[Eq.
[Eq.
[Eq. (2.23)]
[Eq.(2.23)]
(2.23)]
(2.23)] and for
andfor
and
and for
for the
the transfer
transfer of heat
ofheat
heat in steady-flow
insteady-flow
steady-flow exchangers where
exchangerswherewhere�E�E and
�EPPPPandand�E are
are
�EKKKKare
insignificantes y Wand
negligible s =W =the
the
0 s[ecuacióntransfer
0 [Eq.transfer of
of
(2.33)].
(2.33)]. heat
En inin
In cualquier
either steady-flow
case, caso, exchangers
exchangers where �E P and�E �E K are
negligible
negligible
negligible and
and
negligibleand WWs == 0 0[Eq.
andWWssss==00[Eq.[Eq. (2.33)].
(2.33)].
[Eq.(2.33)]. In
Ineither
either
(2.33)].InIneither case,
eithercase,case,
case,
�
�� TTT222
Q = �H = TTT222 C P dT (4.3) (4.3)
QQ
QQ= =
=�H
= �H�H=
�H =
== T1 C CC dT
CPPPPdT dT
dT (4.3)
(4.3)
(4.3)
(4.3)
P
TTTTT
11111
La aplicación más común
The common de esta application
engineering ecuación enofingeniería
this equation es enislatotransferencia de calor
steady-flow heat en flujo estable.
transfer.
The
The
The common
Thecommon
common engineering
commonengineering
engineering application
engineeringapplication
applicationof
application of
of this
ofthis
this equation
thisequation
equationis
equation isis to
isto steady-flow
tosteady-flow
to heat
steady-flowheat
steady-flow transfer.
heattransfer.
heat transfer.
transfer.
Temperature
Dependencia Dependence
de laDependence of
temperaturaof
dethe Heat Capacity
la capacidad calorífica
Temperature
Temperature
Temperature Dependence
Dependence of the
ofthe
the Heat Capacity
HeatCapacity
Heat Capacity
Evaluation of the integral in Eq. (4.3) requires knowledge of the temperature dependence of
Evaluation
Evaluation
La evaluación ofof the integral
theintegral
integral in Eq.
inEq.Eq.given (4.3)
(4.3) requires
requires knowledge
knowledge of the
ofthethethe temperature
temperature dependence
dependence of
of
the heatdecapacity.
Evaluation
Evaluation laof integral
of the
the This deislausually
integral ecuación
inin Eq. (4.3) (4.3)
(4.3) requiere
requires
requires
by an empirical el conocimiento
knowledge
knowledge of
equation;of the de la dependencia
temperature
temperature
two simplest dependence
dependence de la temperatu-
expressions ofof
the
ra de la ofthe heat
heat
capacidad capacity.
capacity. This
This is
is usually
usually given
given by by an an empirical
empirical equation;
equation; the
the two
two simplest
simplest expressions
expressions
the
the practicalcalorífica.
heat
heat capacity.
capacity.value are:Ésta, por lo general, se proporciona por una ecuación empírica; las dos expresio-
This
This isis usually
usually given
given byby an an empirical
empirical equation;
equation; the
the two
two simplest
simplest expressions
expressions
nes másofofof practical
practical
simples devaluevalue
valueare:
valor are:
are:
C P práctico son:
of practical
practical value are:
CP −2
CCCCPPPP = α + βT + γ T 222 and CC
C CPPPP = a + bT + cT −2 −2
RP = ===ααα++
α + +βT βTβT++
βT + +γγγTTT2 and
γ T 2 2 y
and
and
and RP = ==aaaa+
= + +bT
+ bT
bT+
bT +++cT
cTcT−2
cT −2
−2
RRRR RRR
R
where α, β, and γ and a, b, and c are constants characteristic of the particular substance. With
donde a, where
where
where
the y α,α,α,así
b exception
where g,α, β,
β,β,and
β, como
and
and
and ofγγγthe a,
γ andand
and
and blast ya,
a,
a,a,cb,
b,son
b,
b,
term,
and
and
and
and constantes
ccccare
these
are constants
areconstants
are constants
constants
equations características of thedesame
characteristic
characteristic
characteristic
characteristic
are laof
ofsustancia
the
ofthe
of theparticular
the
form. particular.
particular
particular
particular
We
substance.Con
substance.
substance.
substance.
therefore excepción
combine With del
With
With
With
último the
término,
the
the
the exception
exception
exceptionestas
exception ecuaciones
of
of of
of
them to provide a single expression:
the
thethe
the last
lastlast
last tienen
term,
term,
term,
term, la
these
these
these
these misma equations
equations
equations
equations forma. are
are Por
are
are of
ofof
of lothe
the tanto,
the
the same
same
same
same las combinamos
form.
form.
form.
form. We
We We
We para
therefore
therefore
therefore
therefore proporcionar
combine
combine
combine
combine una
sola expresión:
them
themto
them
them to provide
provideaaaasingle
toprovide
to provide single expression:
singleexpression:
single expression:
expression:
CP −2
CCCCPPPP = A + BT + C T 222+ DT −2 (4.4)
RP = ===AAAA+ + +BT
+ BTBT+
BT ++C
+ CCCTTTT222++ ++DTDTDT−2
DT
−2
−2
−2 (4.4) (4.4)
(4.4)
(4.4)
(4.4)
R
RR R
where either C or D is zero, depending on the substance considered. Because the ratio C P /R
Donde where
ya
where seaeither
where C
eithero DC
either CCesor
C orcero
or D Dis dependiendo
isis zero,
iszero,
zero, depending
depending de laon on sustancia
on the considerada.
substance
thesubstance
substance considered.
considered.Puesto que la the
Because
Because relación
the ratioC
ratio
theratio CCCPPP/R /Rno tiene
P/R
iswhere either
dimensionless, or D
the D units zero, ofdepending
depending
C on the
the
P are governed by the choice of R.
substance considered.
considered. Because
Because the ratio C PP/R/R
dimensiones,
isis las
dimensionless,
dimensionless,
isisdimensionless,
dimensionless, unidades the de
the C
units
units
P dependen
ofof CC are
arede la
governed
governed elección byby de
the
the R.
choice
choice of
of R.
R.
As shown inthe the
Chap.units
units 6,ofoffor PPare
CCPgases
P P aregoverned
governed
the ideal-gas by
bythe thechoice
heat choice
capacity, ofofR. R.
rather than the actual heat ca-
Como se AsAs mostrará
shown
shown en
inin el capítulo
Chap.
Chap. 6, for
6,for 6,
gases
forgasesgases para the los
the gases seheat
ideal-gas
ideal-gas usa capacity,
heat
heat la capacidad
capacity,
capacity, rather
rathercalorífica
than
than the del
actual
theactual gasheat
actual ideal,
heat ca-
ca-en lugar
pacityAs As
is shown
shown
used ininintheChap.
Chap.
evaluation6,6, for gases
of suchthethe ideal-gas
ideal-gas
thermodynamic heat capacity,
properties rather
rather
as the than
than the
the
enthalpy. actual
Theheatheat
reason ca-
ca-
de la capacidad
pacity
pacity
pacity is iscalorífica
used
used in in the real
the en
evaluation
evaluationla evaluación
ofof such
such de las
thermodynamic
thermodynamic propiedades termodinámicas
properties
properties as
as the
the como
enthalpy.
enthalpy. la entalpía.
The
The reason
reason La razón
ispacity
thatisthermodynamic-property
isused
usedininthe theevaluation
evaluationofofevaluation such
suchthermodynamic
thermodynamicis most conveniently properties
propertiesas asthe
theenthalpy.
accomplished enthalpy. inTheThe
tworeasonreason
steps:
es que isla
isis evaluación
that
that
isthat
that termodinámica
thermodynamic-property
thermodynamic-property de la propiedad
evaluation
evaluation
evaluation
evaluationisisideal-gas is
is se
most
most
most consigue
conveniently
conveniently
mostconveniently
conveniently en forma más
accomplished
accomplished
accomplished
accomplished conveniente inin two
inintwo two siguiendo
twosteps: steps: dos
steps:
steps:
first, calculation of values for a hypothetical state wherein ideal-gas heat capacities
pasos: primero,
first,
first,
first,
first, se calculan
calculation
calculation
calculation
calculation of
ofof
of los
values
values
values
values valoresfor
forfor
for aaapara
a un hipotético
hypothetical
hypothetical
hypothetical
hypothetical ideal-gas
ideal-gas
ideal-gas
ideal-gasestado delwherein
state
state
state
state gas
whereinideal,
wherein
wherein en donde
ideal-gas
ideal-gas
ideal-gas
ideal-gas se usan
heat
heat
heat
heat las capacida-
capacities
capacities
capacities
capacities
are used; second, correction of the ideal-gas-state values to the real-gas values. A real gas
des caloríficas
are
are used;
areused;
are used;
used; delsecond,gas ideal;
second,
second,
second, segundo,of
correction
correction
correction
correction ofsethe
the hace
the una corrección
ideal-gas-state
ideal-gas-state valuesde los
values tovalores
to the
thewhen del estado
real-gas
real-gas values.
values. de A gas
AA ideal
real
real gas para que
gas
becomes ideal in the limit as ofP of →the ideal-gas-state
0;ideal-gas-state
if it were to values values
remain toto the
idealthe real-gas
real-gas values.
values.
compressed Atoreal
real
a finitegas
gas
reflejenbecomes
los valores
becomes
becomes
becomes ideal
ideal
ideal
ideal delin gas
in
in
in the
the
thereal.
the limit
limit
limit
limitUnas asgas
as
as PPPPreal
→→ →
→ será
0;
0; 0;
0; ifififideal
if itititwere
it were en to
were
were el
toto
to límite
remain
remain
remain
remain conforme
ideal
ideal
ideal
ideal when
when
when
when P→ 0; si continuara
compressed
compressed
compressed
compressed to
toto
to a siendo
aaafinite
finite
finite
finite ideal
pressure, it would exist in a hypothetical ideal-gas state. In such states gases have proper-
cuandopressure,
se comprime
pressure,
pressure,
pressure, it a presiones
itititwould
would
would
would exist
exist
exist
exist in
in finitas,
in
in a existiría en
aaahypothetical
hypothetical
hypothetical
hypothetical un estado
ideal-gas
ideal-gas
ideal-gas
ideal-gas state.de gas
state.
state.
state. In
InIn
In ideal
such
such
such
such hipotético.
states
states
states
states gases
gases
gases
gases Los have
have
have
havegasesproper- en sus esta-
proper-
proper-
proper-
ties that reflect their molecular structure just as do real gases. Ideal-gas-state heat capacities
dos de ties
gastiesideal
ties
ties that tienen
reflect
thatreflect
that
that reflecttheir
reflect propiedades
their
their molecular
molecular ig que reflejan just
structure
structure su
just
just estructura
asasdodo
dorealreal
realmolecular
gases. al igual que en
Ideal-gas-state
gases.Ideal-gas-state
Ideal-gas-state heat loscapacities
heat gases
capacities
capacities reales. Por
by Ctheir
ig molecular
molecular structure
structure
(designated ig and C ig ig) are thereforejust asas
different do real
for gases.
gases.
different
ig
Ideal-gas-state
ig )gases; although heat
heat capacities
functions of
lo tanto, las capacidades
(designated
(designated
(designated
(designatedby byby
by C C térmicas
ig
P
igig
ig
CCPPPPPare and
andand
and C C Vdel
ig
igig ))
CCVVVVV))are gas
are
are ideal
therefore
therefore
aretherefore
therefore (denotadas different
different
different
differentfor porfor
for C y
different C
different
P
fordifferent V
differentgases; son
gases;
gases; diferentes
although
although
gases;although para gases
functions
althoughfunctionsfunctions
functionsof distintos;
of
of
of
temperature, they independent of pressure.
aunquetemperature,
son funciones
temperature,
temperature,
temperature, theyde
they
they
they la
are
areare temperatura,
independent
independent
arecapacities
independent
independent sonof
of independientes
pressure.
pressure.
ofofpressure.
pressure. de la presión.
Ideal-gas heat increase smoothly with increasing temperature toward an upper
Las capacidades
Ideal-gas
Ideal-gas caloríficas
heat capacities
heatcapacities
capacities delincrease
gas
increase
increase ideal aumentan
smoothly
smoothly with
with deincreasing
manera uniforme
increasing
increasing temperature
temperature conforme
toward
toward seanincrementa
an upper
upper la
limit, Ideal-gas
Ideal-gas
which is heatheat
reached capacities
when all increase smoothly
translational, smoothly with
with
rotational, increasing temperature
and vibrationaltemperature modes toward
toward an
an
of molecular upper
upper
temperatura
limit,
limit,
limit, hacia
which
limit,which which
which un islímite
is reached
reached
isisreached
reached superior,
when
when el
all
all cual se
translational,alcanza
translational, cuando
rotational,
rotational, se excitan
and
and completamente
vibrational
vibrational modes
modes oftodos
of
ig molecularlos
molecular modos de
motion are fully excitedwhen when
[seeall alltranslational,
Eq. translational,
(16.18)]. The rotational,
rotational,
influence and
and
ofvibrational
vibrational
temperature modes
modes
on Cof of
ig
molecular
molecular
for argon,
movimiento
motion
motion
motion
motion molecular
are
are
are
are fullyde
fully
fully
fully traslación,
excited
excited
excited
excited [see
[see
[see
[see rotación
Eq.
Eq. (16.18)].
Eq.(16.18)].
Eq. (16.18)].
(16.18)]. y vibración The
Theinfluence
The
The [véase of
influence
influence
influence la
of ecuación
temperature
oftemperature
of temperature
temperature (16.18)].
on
on onC
on Cig
CC P
ig
P
En
ig
ig for
for laargon,
for
for figura 4.1 se
argon,
argon,
argon,
nitrogen, water, and carbon dioxide is
ig illustrated in Fig. 4.1. Temperature dependence
PPPP is ex-
muestranitrogen,
la influencia
nitrogen,
nitrogen,
nitrogen, water,
water,
water,
water,and de la
and
and
andby temperatura
carbon
carbon
carbon
carbon dioxide en
dioxide
dioxide
dioxide C is
P ispara
illustrated
illustrated
isisillustrated
illustrated el argón, inin
ininhereel
Fig.
Fig.
Fig. nitrógeno,
4.1.
4.1.
Fig.written:
4.1. el
Temperature
Temperature
4.1. Temperature agua
Temperaturedependence y el dióxido
dependence
dependence
dependenceisis de isiscarbono.
ex-
ex-
ex-
ex- La
pressed analytically equations such as Eq. (4.4),
dependencia
pressed
pressed
pressed de la temperatura
analytically
analytically
pressedanalytically
analyticallyby byby se expresa
equations
equations
byequations
equationssuch en
such
such forma
as
suchasasEq.as Eq.
Eq. analítica
Eq.(4.4), (4.4),
(4.4),
(4.4),here here mediante
here written:
herewritten:written:
written: ecuaciones como la (4.4), que aquí se
escribe como: C ig
ig
igig
CCCPPigPig = A + BT + C T 222+ DT −2 −2
C PPP = + + 222 + −2
R = A
==AA++BTA + BT
BT +
BT++CCTT ++DTC C T T + DT −2
DT
DT −2
−2
RRRR

128 CAPÍTULO 4. Efectos térmicos
Los valores de los parámetros se dan en la tabla C.1 del apéndice C para varios gases orgánicos e inorgánicos
comunes. En laofliteratura es posible 1
Values the parameters areencontrar ecuaciones
given in Table C.1 ofmás exactas
App. C for pero más complejas.
a number of common organic
and inorganic gases. More accurate but more complex equations are found in the literature.1
7
CO 2
7
CO 2
6
6
H 2O
5 H 2O
Figura 4.1: Capacidades caloríficas de 5 CPig

gas idealFigure
del argón,
4.1: nitrógeno, agua y
Ideal-gas heat CPig R
N2
bióxido de carbono. argon, nitrogen,
capacities of R 4
water, and carbon dioxide. N2
4
3
3 Ar
Ar
2
500 1 000 1 500 2 000
2
500 1000 T/K
1500 2000
T/K
Como resultado deof

As a result la Eq.
ecuación
(3.19),(3.19),
the twolasideal-gas
dos capacidades caloríficas
heat capacities del gas ideal están relacionadas:
are related:
ig ig
CV C
= P −1 (4.5) (4.5)
R R
ig ig
The temperature dependence of C V /R follows from the temperature dependence of C P /R. ig
La dependencia de la temperatura de CVig/R es consecuencia
ig ig ig
de la dependencia de la temperatura de CP /R.
The de
Los efectos effects of temperature
la temperatura sobreonCPigCoP Cor
V
C Vobtienen
se are determined
de manerabyexperimental;
experiment, most often
con frecuencia, se
from spectroscopic data and knowledge of molecular structure through calculations
calculan mediante métodos de la mecánica estadística a partir de datos espectroscópicos y del conocimiento based on
statisticalmolecular.
de la estructura mechanics. Where
Cuando noexperimental data areexperimental
se tiene información not available,semethods
empleanofmétodos
estimation are
de estimación,
employed, as described by Reid, Prausnitz, and 2
Poling. 2
como los descritos por Reid, Prausnitz, Poling y O’Connell.
AunqueAlthough ideal-gas
las capacidades heat capacities
caloríficas del gasare exactly
ideal son correct
correctas forpara
real gases
gases reales
only atsólo
zeroapressure,
presión cero, la
the departure of real gases from ideality is seldom significant at pressures
desviación de la idealidad de los gases reales rara vez es significativa en presiones por debajo below severaldebars,
varios bar,
ig ig ig
y en esteand
caso CPig
here CyP Cand
V por
C V lo general
are son
usually buenas
good aproximaciones
approximations to de
their sus capacidades
true heat térmicas
capacities. reales.
1 Véase F. A. Aly y L. L. and

Lee,L. vol. 6, pp. 169-179,
1 See F. A. Aly Fluid Phase
L. Lee, Equilibria,
Fluid Phase Equilibria, vol. 6, pp.1981, y su bibliografía;
169–179, 1981, and itsvéase también T.see
bibliography; E. Daubert,
also R. P.
Danner, H.T. E. Sibul
M. y C. R.
Daubert, C. Stebbins,
P. Danner,Physical
H. M. and Thermodynamic
Sibul, Properties
and C. C. Stebbins, of Pureand
Physical Chemicals: Properties Taylor
Data Compilation,
Thermodynamic of Pure& Francis,
Bristol, PA, existente Data
Chemicals: 1995.Compilation, Taylor & Francis, Bristol, PA, extant 1995.
2 J. M. Prausnitz, B. E. Poling y J. P. O’Connell, The Properties of Gases and Liquids, 5a. edición, capítulo 3, McGraw-Hill, Nueva
2
York, 2001. J. M. Prausnitz, B. E. Poling, and J. P. O’Connell, The Properties of Gases and Liquids, 5th ed., chap. 3, McGraw-
Hill, New York, 2001.

Example
4.1. Efectos 4.1
del calor sensible 129
Example 4.1
The parameters listed in Table C.1 require use of Kelvin temperatures in Eq. (4.4).
Example
Ejemplo
The parameters
Equations 4.1
4.1◦◦of the listed
sameinform
Table
mayC.1 require
also use of Kelvin
be developed temperatures
for use in ◦◦C,
in Eq. (4.4).
with temperatures
Equations ◦
The and (ofF),
thebut
(R), parameters same
the form
listed in mayC.1
Table also
parameter be developed
values are
require for use
different.
use of KelvinThewith temperatures
molar heatincapacity
temperatures C,
Eq.in(4.4).
of
Los parámetros
(R), and enumerados
methane
Equations
◦ F), but theen
(inofthe
theideal-gas lastate
form tabla
same parameter mayisC.1 requieren
values
given
also asare
be del usoof
different.
a function
developed de
for temperaturas
The molar
temperature
use with heatKelvin eninla◦ of
capacity
in kelvins
temperatures by: ecuación
C,
(4.4). De esta
methane
(R), forma,
and thetambién
(◦ F),
in these
ideal-gas
but pueden
state
parameter desarrollar
is given as aare
values ecuaciones
function para
Theusarse
of temperature
different. molar incon temperaturas
kelvins
heat by: of en °C,
capacity
(R) y (°F), aunque
methane inson
the diferentes
ig
ig los valores
C PP state
ideal-gas de as
is given losaparámetros.
function La capacidadincalorífica
of temperature molar del me-
kelvins by:
ig =dada −3
−3 −6 22
−6
tano en estado de gas ideal C está 1.702 +
como una
9.081 ×función
10 T −
de la ×
temperatura
2.164 10 T en kelvins por:
R
P −3 −6 2
ig = 1.702 + 9.081 × 10 T − 2.164 × 10 T
CRP −3 −6 T 2
where the parameterR values = 1.702
are+from × 10 C.1.
9.081Table T −Develop
2.164 × 10an equation
ig
ig
for C PP /R for
◦ ig
where in ◦ C. values are from Table C.1. Develop an equation for C Pig/R for
the parameter
temperatures
donde los valores de
temperatures los
in parámetros
◦ C. se toman de la tabla C.1. Desarrolle una ecuación para Cig /R con tempe-
where the parameter values are from Table C.1. Develop an equation for C PP /R for
raturas en °C.
temperatures in ◦ C.
Solution 4.1
Solution
Solución 4.1 4.1
The relation
Solution 4.1between the two temperature scales is:
La relación entre las
The relation dos escalas
between de latemperature
the two temperaturascales
es: is:
T K = t ◦◦C scales
The relation between the two temperature + 273.15is:
TTKK= = tt ◦°C
C ++273.15
273.15
Therefore,
Por lo tanto, como asunaa función
functiondeof t,t, T K = t ◦ C + 273.15
Therefore, as a function of t,
ig
CPPig as a function of t, −3
Therefore,
ig = 1.702 + 9.081 × 10−3 (t + 273.15) − 2.164 × 10−6 −6 (t + 273.15)22
CRP −3 −6 2
ig = 1.702 + 9.081 × 10 (t + 273.15) − 2.164 × 10 (t + 273.15)
CRP −3
= 1.702C PP+ 9.081 × 10 (t + 273.15)
ig
ig − 2.164 × 10−6 (t + 273.15)2
o or R ig = 4.021 + 7.899 × 10 −3
−3 t −6 t22
− 2.164 × 10−6
CR P −3 −6 2
or ig = 4.021 + 7.899 × 10 t − 2.164 × 10 t
CRP
or = 4.021 + 7.899 × 10−3 t − 2.164 × 10−6 t 2
R
Gas mixtures of constant composition behave exactly as do pure gases. In an ideal-gas

Las mezclas
mixture Gasthe de
mixtures gasesofdeconstant
molecules composición
have no compositionconstante
influence onbehave
oneseanother,
comportan
exactlyand asexactamente
do pure
each gasgases. como
exists In losideal-gas
an gases puros.
independent of En
una mezcla
mixture de gases
themixtures ideales
molecules las moléculas carecen de alguna influencia entre sí, y cada gas existe de manera
the others.
Gas The ideal-gas of have
constantno influence
heat capacity
composition onaone
of another,
mixture
behave andaseach
is therefore
exactly do the gasmole-fraction-weighted
pure exists independent
gases. In an ideal-gas of
independiente
the
sum of de
others.the losThe
heat otros. Debidoheat
ideal-gas
capacities a eso,
of the la capacidad
capacity of
individual a calorífica
mixture
gases. is
Thus del gases
gas ideal
therefore
for the
A, de una mezcla
mole-fraction-weighted
B, and C the es la suma
molar heat de las
mixture the molecules have no influence on one another, and each gas exists independent of
capacidades
sum
capacity
the caloríficas
of theofheat
others. aThe ponderadas
capacities
mixture in the
ideal-gas of con la
thecapacity fracción
individual
ideal-gas
heat state mol
gases.
of is:
a mixturede
Thuslos
is forgases individuales.
gases A,
therefore De este
theB,mole-fraction-weighted
and C the molar heat modo, para los
gases A,capacity
B y C
sum of the la capacidad
of aheat mixture calorífica molar
in theofideal-gas
capacities de una mezcla en el estado de gas ideal
state is:gases. Thus for gases A, B, and C the molar heat
the individual es:
ig
ig ig
ig ig
ig ig
ig
capacity of a mixture in the C ideal-gas
PPmixture
mixture
= y AACis:
state PPAA + y BBC P PBB + yC CC P PCC (4.6)
ig ig ig ig
C Pmixture = y A C PA + y B C PB + yC C PC (4.6) (4.6)
mezcla
ig
ig ig
ig ig
ig ig ig ig ig
where C PPAA , C PPBB , and C PPCC are C Pmixture = yAC
the molar PA +
heat y B C PB +
capacities ofypure
C C PCA, B, and C in the ideal-gas (4.6)
ig ig ig ig
ig ig
donde Cwhere ,
state, C C
and
PA PBPA PC y ,
yCAAC , y
PB son
B
B, , las
and
and C ycapacidades
C
C
PC are
are the
mole caloríficas
molar heat
fractions. molares
capacities deof A, B
pure y C
A, puras
B, and en Cestado
in the de gas ideal y yA,
ideal-gas
yB y yCstate,
representan
where and
As igy las
C Pwith ,
A
igfracciones
,Cygases,
B ,, and
and yCC ig
the molares.
are
heat mole
are the fractions.
capacities
molar of solids
heat and liquids
capacities of are
pure found
A, B, by
and experiment.
C in the Param-
ideal-gas
A PB PC
Alstate,
igualfor
eters As que
and theyocurre
with , gases,
Atemperature conthe
y B , and los
yCheatgases, lasfractions.
capacities
dependence
are mole capacidades
of of
C PPsolids caloríficas
and liquids
as expressed by de arelos
Eq. sólidos
found
(4.4) y líquidos
bygiven
are experiment. seParam-
for a few determinan
solids de
maneraeters
experimental.
and for
Asthe
liquids within Los parámetros
temperature
Tables
gases, the dependence
C.2 and C.3
heat para oflaApp.
capacities ofdependencia
CofPC.solids de liquids
asCorrelations
expressed
and la temperatura
byforEq.are(4.4)
the heat
found de
are Cgiven
capacities
by comoforofse
Pexperiment. expresan
amany
few solidsmedian-
solids
Param-
te la ecuación
and
eters for(4.4)
andliquids
liquids theinare están
Tables
given
temperature dados
C.2
by andparaC.3
Perry algunos
and
dependence ofsólidos
ofGreen
App. CC.and
P as
y líquidos
Correlations
by Daubertby
expressed en
for las33(4.4)
the
et Eq.
al. tablascapacities
heat areC.2 y C.3
given ofdel
for many apéndice
a few solids C. Las
solids
correlaciones
and
and liquidspara are
liquids lasTables
in capacidades
given andcaloríficas
by Perry
C.2 andofGreen
C.3 App.deanddiversos
C. sólidoset
by Daubert
Correlations foryal.líquidos
3
the están dadas
heat capacities por Perry
of many solidsy Green,
así como por
33R. Daubert ygiven
colaboradores. 3
and H. Perry
liquids areand D. Green,
by PerryPerry’sand Chemical
GreenEngineers’ Handbook,
and by Daubert al.3ed., Sec. 2, McGraw-Hill, New York,
et 7th
3 R. T.
1997; H.E.Perry
Daubert
and etD.al., op. cit.
Green, Perry’s Chemical Engineers’ Handbook, 7th ed., Sec. 2, McGraw-Hill, New York,
1997;3 R.T.H.
E. Daubert et al., op. cit.
Perry and D. Green, Perry’s Chemical Engineers’ Handbook, 7th ed., Sec. 2, McGraw-Hill, New York,
3 R. H. Perry
1997; T. yE.D.Daubert
Green,etPerry’s
al., op.Chemical
cit. Engineer’s Handbook, 7a. edición, sección 2, McGraw-Hill, Nueva York, 1997; T. E.
Daubert et al., op. cit.

130 130
130130 CHAPTER 4.
CAPÍTULO
CHAPTER
CHAPTER Heat
4. 4.Heat Effects
Effects
4. Heat
Efectos térmicos
Effects
130
130 CHAPTER
CHAPTER4.4. Heat
Heat Effects
Effects
130
130 4. Heat
CHAPTER 4.
CHAPTER Heat Effects
Effects
Evaluation
Evaluación de laof
Evaluation
Evaluation of the
the
integral
of theSensible-Heat
Sensible-Heat
del calor sensible
Sensible-Heat Integral
Integral
Integral
Evaluation
Evaluation ofof the
the Sensible-Heat
Sensible-Heat
� Integral
Integral
Evaluation
Evaluation
Evaluation
Evaluation of the
ofof
of
of
thethe
the
the
integral
integral
Sensible-Heat
Sensible-Heat
� �
��CCPPCdT
dT
Integral
Integral
isisaccomplished
accomplished by substitution
bybysubstitution for CCPPCas
forfor as aafunction
function of TT,,T ,
ofof
Evaluation
La evaluación debyintegral
laofformalP dT
integral is accomplished
∫ CP �dT substitution
� Cse consigueP as a function
mediante labysustitución para
Evaluation
followed
Evaluation of the integral
integration.
theintegral
integral CPPPPdTdT
For
dTFor istemperature
is accomplished
accomplished limits substitution
of TT00Tand
bysubstitution
substitution for
TTforthe
forthe CPcomo
CCPresult asasaisisfunción
function
conveniently
de TT,seguida
ofofT,
followed
followed
Evaluation
Evaluation
por la integración
byof by
of formal
the
formal. formal
the integration.
integral
Para integration.
los CC
límites
For
dT temperature
isis
de temperature
accomplished
accomplished
las temperaturas
limits limits
by
by of of
substitution
de T
and
0yand T, Tthe
for
el
result
CCresult
resultado as aaafunction
PPPresult
as function
conveniently
is conveniently
function
se expresa of TTen
of ,, , forma
followed
expressed
followed
expressed by
as:
by
as: formal
formal integration.
integration. For
For temperature
temperature limits
limits of of T T0 0and
and T T the
the result isis conveniently
conveniently
expressed
followed
followed
conveniente como: by as:
by formal
formal integration.
integration. For For temperature
temperature limits limits of of TT00 and0and TT the the result
result isis conveniently
conveniently
expressed
expressed as:as:
expressed
expressed �� T�T as: as: ��
� CTCPPC P BB B22 22 CC C33 33 DD D ��ττ − −τ 1−1 �1�
��TTTTCCP dT dTdT === AT
ATAT 00(τ −
(τ0 (τ −1) −1)1)+ ++ BBTT002T(τ (τ2 −
(τ
2 − 2 1)
−1)1) + ++ CCTT003T(τ (τ 3 −
(τ
3 −3 1)
−
1)1) +
+ +DD� �ττ−−11� � (4.7) (4.7) (4.7)
(4.7)
TT00 TC RRPPPRdT
C dT = = ATAT (τ −
0 0 (τ − 1) + 1) + 2BB
2 T2 T
02
0
(τ
2
2 (τ 2−
22 − 1) +1) + 3
CC3 T
3 T0
3 (τ
3
3 (τ
0 3− 1)
33 − 1) + 0 0 + T T
DD 0 T ττ −
τ−τ 1
1
τ (4.7)
(4.7)
T0T
0 R dT dT =
= ATAT 00 (τ
(τ −− 1)
1) ++ 2 TT 0(τ
(τ −− 1)
1) + + 3 TT (τ
(τ
0 −− 1)
1) +
+ T 0 τ (4.7)
(4.7)
TT00 0 R RR 222 0 0
333 00 TTT 000 τττ
TT T
donde where
where
where ττ ≡ ≡
τ ≡T
where
where ττ≡≡TTT0T 0T
where
where τ≡
τ ≡ TT0 0
Dados T Given
Given y T,Tel
0 Given T00Tcálculo
and
and
0 and de
TT,,Tthe the
, the ∆H es directo.
ocalculation
Qcalculation
calculation ofofof QQ Q orEsor
or �HT
�HT
menos
00�H is is directo
0 is straightforward.
straightforward.el cálculoLess
straightforward. deLess
Less dados
T,direct
direct
direct isisTthe
0the
is ytheQ
cal-
cal- ∆H. En
ocal-
este caso, un Given
culation
culation Given
planteamiento
of
Givenofof T
TTTT,,T0 and
givenand
given TT T, the
iterativo
, and
the
and calculation
QQ es orde
calculation
or �Hutilidad.
�H . of
. of Q
Here,Q
Here, or
Al or �H
factorizar
an
an �H isisstraightforward.
iteration
iteration (τ –
scheme1)
straightforward.
scheme de cada
may
may Less
betérmino
Less
be direct
useful.
direct
useful. del is the
lado
Factoring
is the
Factoring cal-
derecho
cal- de
culation Given T 0, given
and T
and TT, the ,
0 0 T
the and Q
calculation or �H of . Q Here,
or �H an iteration
is
0 calculation of Q or �H is straightforward. Less direct is the cal- scheme
straightforward. may Less be useful.
direct is Factoring
the cal-
culation
la ecuación −(4.7) ofof ,00,given
TTeach and QQ oror�H . . Here, anan iteration scheme may bebeuseful. Factoring
− ofse TTobtiene:
(τ 1)
culation from term
given 0 on the right-hand side of Eq. (4.7) gives:
(τ (τ
culation
culation −1)1) from
of from ,each each
, given
given term TTT
term
00 0 on and
and
and ontheQthe
Q right-hand
or
or �H
�H �H
right-hand .. Here,
side
Here,
Here, side of
an
an ofEq. iteration
Eq. (4.7)
iteration
iteration (4.7) scheme
gives:
gives:
scheme
scheme may
maymay be
be useful.
useful.
useful. Factoring
Factoring
Factoring
(τ(τ−−1)1)from each term on the right-hand side ofofEq. (4.7) gives:
(τ −
(τ − 1) 1) from �from
from
� T�T each eachterm
each termon
term �on�the
�on theright-hand
the right-handside
right-hand sideof
side of Eq.Eq.Eq.(4.7) (4.7)gives:
(4.7) gives:
gives: ��
��T CPPC P CT �� BB B22 2 CC C33 322 2 DD D� �
�� TTTCCP dT dTdT === ��ATATAT 00 + +0+ BBTT002T(τ (τ0 (τ
++1) +1)1) +++ CCTT003T(τ (τ
0 (τ
+ ττ +
2 2+ + τ 1)
+ + +
1)1) + +DD��(τ (τ (τ−−1) −1)1)
TT00 TC CRRPPPRdTdT = = ATAT 0 + + 2
BB
2 T2 T
0 (τ
2 +
22 (τ + 1) + 1) + 3
C C
3 T3 T (τ
3
33 (τ
0 22 + τ + 1) +ττD
+ τ + 1) + TD
Tτ00T0(τ(τ−−1)1)
T0
0 R dT dT = = AT AT00 + 0+ 22TT000(τ (τ + + 1) 1) + + 33TT000(τ (τ + + ττ + + 1) 1) + + ττTT0 (τ (τ − − 1) 1)
TT0T0 0 R RR 22 33 ττTT000
TT − −
T −0T T T 0
Because
Because
Because ττ − τ 1−
− 1= =
1= TT−−TT0 0
Ya que Because τ − 1 = TT T−−T00TT00
Because
Because
Because τττ− −−111= == TT0 0
this
this may
thismay may bebebe written:
written:
written: TT000
this
ésta se puede
thismay be
escribir
may be written:
como: ��
written:
this may
may �be ��
this be �written:
� Twritten: ��
��TT CTCPPC P � � BB B CC C22 22 DD D� �(T
�� TTTCCP dT dTdT == =AA+ ++
A BBTT00(τ T +
(τ0 (τ +1) +
1)1) +++ CCTT002T(τ (τ 2
(τ + 2
+τ+ τ+ +
τ 1)
+
1)1) +
+ +DD (T(T − −T −T00)T) )
TT00 TC CRRPPPRdT dT = = A A + + 2
BB
2 T2 0
T (τ (τ + + 1)1) + + 3
C
C3 T3 T0 (τ
2
22 (τ
0 2 2+ τ + 1)
22 + τ + 1) + 002 0 (T + ττ T
DD
T τ
22
T 2
(T −−TT0 ) )0
T0
0 R dT dT = = AA + + 22TT00(τ 0(τ + + 1) 1) + + 33TT000(τ (τ + + ττ + + 1)1) + + τ T0222 (T (T − − TT00)0)
TT0T0 0 R RR 22 33 τττTTT 000
We
WeWe identify
identify
identify the
thethe quantity
quantity
quantity in
in insquare
square
square brackets
brackets
brackets asasas�C
�C�C PP��HP /R,/R,
H�/R,
where
wherewhere �C
�C�CPP��HP H�H
isis defined
defined
is defined as
asas aa mean
mean
a mean
We identify the quantity in square brackets as �C � H where
/R, �C � is defined as aamean
Identificamos la cantidad entre los inparéntesis rectangulares �CPPP�como
�C � /R,〈C P〉 H /R, �CPdonde
�C � 〈C 〉 se define como una
heat
We
heat capacity:
identify
capacity: the quantity in square brackets as P H /R, where P H is defined as mean
We
We heat
identifycapacity:
identify the quantity
the quantity in square brackets
square brackets as �C
as �HHH/R, where
where �C P�
�
P HH H is
is P
defined
defined H as
as a a mean
mean
capacidadheat capacity:
heatcalorífica
heat
heat capacity:media:
capacity:
capacity: �C
�C�CPP��HP H�H
BB B CC C22 22 DD D
�C�C PP�H � === AA+ ++
A BBTT00(τ T(τ0 (τ++1) +1)1) +++ CCTT002T(τ (τ2 +
(τ
2 +2 ττ +
+ +τ 1)
+
1) ++
1) + DD 22 2
(4.8)
(4.8)
(4.8)
�CRPRP��H
�C RHH ==AA++2BB 2 T2T0 (τ(τ++1)1)++C 3C3 T3T022(τ 20 222+ τ + 1) + ττT
(τ + τ + 1) + D
D
T τ
0 T (4.8)
(4.8) (4.8)
RR = = AA + + 22TT00(τ 0(τ + + 1) 1) + + 33TT000(τ (τ + + ττ + + 1) 1) + + τ T02220 02 (4.8)
(4.8)
RR 22 33 τττTTT 000
Equation
Equation
Equation (4.2)
(4.2)(4.2) may
may may therefore
therefore
therefore be
bebe written:
written:
written:
Equation (4.2) may therefore bebewritten:
aEquation
DebidoEquation
eso, la ecuación
Equation (4.2)may
(4.2)
(4.2) may
may (4.2)therefore
therefore
therefore se escribe be written:
be written:como:
written:
�H == �C= �C�CPP��HP (T (T
H�(T
− −TT00)T) 0 ) (4.9)
H −−
�H �H (4.9)
(4.9)
�H �H ==�C �C PP�H � (T (T − TT0 ) ) (4.9)
(4.9) (4.9)
�H =
�H = �C �CPP��HHH(T (T − − TT00)) 0 (4.9)
(4.9)
The
TheTheangular
angular
angular brackets
brackets
brackets enclosing
enclosing
enclosing CCPPCidentify
identify
P identify
itit as
as
it asaa mean mean
a mean value;
value;
value; subscript
subscript
subscript “H
“H“H ”” denotes
denotes
” denotes aa mean
mean
a mean
The
value
The angular
specific
angular brackets
to enthalpy
brackets enclosingcalculations,
enclosing C CP identify
and
identify it as
distinguishes
it as a a mean
mean value;
this mean
value; subscript
heat
subscript “H
capacity “H ” ”denotes
from
denotes a asimilar
mean
similar
a mean “H”
Los paréntesis
value
The
The valueangular
angular angulares
specific
specific to to
brackets
brackets que
enthalpy
enthalpy contienen
enclosing
enclosing calculations, CCC
calculations,PP PP se and
identify
identify identifican
and distinguishes
distinguishes
it
it as
as aa como
mean
mean su
this this
value;
value; valor
meanmean medio;
heat
subscript
subscript heat capacity
“H“H en
capacity
”” tanto,
from
denotes
denotes fromel a asubíndice
aa similar
mean
mean
value
quantity
value specific
introduced
specific to toenthalpy
in
enthalpy the calculations,
next chapter.
calculations, and and distinguishes
distinguishes this
this mean
mean heat
heat capacity
capacity from
from a a similar
similar
denota value
un
valuevalor
quantity
quantity medio
introduced
specific
specific toespecífico
introduced
to in in
enthalpy
enthalpy thethe para
nextnext
calculations,
calculations, cálculos
chapter.
chapter. and
and dedistinguishes
la entalpía ythis
distinguishes distingue
this mean heat
mean esta capacity
heat capacidad
capacity from
from calorífica
aa similar
similar media de
quantity introduced
Solution of Eq. inin the next chapter.
quantity
una cantidad
quantity
quantity similar
Solution introduced
Solution
introduced
introduced que ofof será
Eq. in(4.9)
Eq.
in (4.9)the
introducida
the
the (4.9) for
next
for
next
next TT
for gives:
chapter.
en
Tgives:
chapter.
chapter. el siguiente capítulo.
gives:
Solution
Solution ofofEq. (4.9)
Eq.(4.9) (4.9) forforT TTgives:gives:
La solución Solution
Solution de laof ofecuación
Eq.
Eq. (4.9) (4.9)
for
for Tparagives:
gives: T da:
�H�H �H+ T
TT = T= = �H ++ T00T0 (4.10)
(4.10)
(4.10)
TT==�C �C �H
�H �H
PP��HP
�C �H++TT0 0 (4.10)
TT = = �C � H ++ TT (4.10) (4.10)
(4.10)
(4.10)
�C
�C �CPP��H�H
P 00
AA starting
Astarting
starting value
valuevalue for
forforTT (andT(and (and hence
hencehence for
forfor ττ = τ= = TTP/T/T HH) allows evaluation of �C � by Eq. (4.8).
T /T00 ) 0allows) allows evaluation
evaluation ofof �C�C PP �HP � byby Eq. Eq. (4.8).
(4.8).
A starting value for T (and hence for τ = T /T 0 )a allows evaluation ofof�C �HH� H by Eq. (4.8).
Un valorAAinicial
Substitution
A starting
Substitution
Substitution
starting
starting para of
value
value
value of Tof(yfor
this
this por
value
for
this
for valueT tanto
TTvalue
(and into
(and
into
(andinto de Eq.
hence
Eq.
hence
hence = T/T
τ Eq. (4.10)for
(4.10)
(4.10)
for
for τ =
0ττ) permite
provides
provides
= T
=provides
TT/T /T00la
/T ) a) evaluación
newallows
new
0) allows
allows value
value
a new evaluation
value ofdeof〈CTPof
evaluation
of
evaluation T T from
from〉of
from
H �C �C�C
whichP
mediante
which
P �HHHby
which
P �
P to
toby
byto la ecuación
reevaluate
Eq.
reevaluate
Eq.
Eq. (4.8). (4.8).
reevaluate
(4.8).
(4.8).
Substitution
�C ofofthis value into Eq. (4.10) provides a new value of TTfrom which totoreevaluate
Al sustituir
�C PP�este
�C
Substitution
Substitution valor
�HPH.�.HIteration
Substitution Iteration
. Iterationofen
of thisla ecuación
continues
this valueinto
continues
this continues
value
value to(4.10)
to
into
into convergence
to Eq.
convergence
Eq.
Eq. se
(4.10)
convergence
(4.10)
(4.10) obtiene on
provides
onon
provides
provides aun anuevo
afinal
final aaanew
final value
new
value
new valor
value of
value
ofof
value
value Tde
T.ofofT.TT
.Tof a partir
fromwhich
from
from delwhich
which cualto tosereevaluate
vuelve a evaluar
reevaluate
reevaluate
�C � . Iteration continues to convergence on a final value of T .
〈CP〉 H. �C
La�CPPH �
�CPPiteración . Iteration
��HHH.. Iteration
Iteration continúa continues
continues hastato
continues la convergence
toto convergenciaon
convergence
convergence onpara
on a un valor
final
aa final
final valuefinal
value
value of TTde
of of T .
.. T.

4.1.
4.1. Sensible
Sensible Heat
Heat Effects
Effects 131
131
4.1. Efectos del calorHeat
4.1. Sensible sensible
Effects 131 131
4.1. Sensible
4.1. Sensible Heat
Heat Effects
Effects 131
131
Example 4.2
Ejemplo 4.2 4.2
Example
Example
Example
Calculate
Calculate the 4.2 required
the 4.2
heat
heat required to
to raise
raise the
the temperature
temperature of
of 1
1 mol
mol of
of methane
methane from
from 260
260
Calculeto
toel600
calor
Calculate
600
◦◦Cnecesario
C in
in
the
a heat para
a steady-flow
steady-flow aumentar
required
process
process la
to raise
attemperatura
at the
a
a pressure
pressure de 1 mol
temperature of 1de
sufficiently
sufficiently
molmetano
low
low
of
that
that de 260from
methane
methane
methane amay
600260
may °C en un
be
be
Calculate
Calculate ◦C the
the heat required
heat required to raise
to raise the
the temperature
temperature of 11 mol
of mol of
of methane
methane from
from 260
260
procesoconsidered
tode flujo
600 ◦
considered◦ estable
in a
an a una presión
steady-flow
ideal gas. lo
process suficientemente
at a pressure baja para
sufficientlyque
lowel metano
that se
methaneconsidere
may be un gas
to
to 600 C
600 in aan
C in ideal gas. process
a steady-flow
steady-flow process at at aa pressure
pressure sufficiently
sufficiently low
low that
that methane
methane may
may be
be
ideal. considered an ideal gas.
considered an
considered an ideal
ideal gas.
gas.
Solution
Solución 4.2
Solution 4.2
4.2
Solution 4.2
Solution 4.2
Solution
La ecuación
Equation
Equation 4.2
(4.3) (4.3)
en
(4.3) combinación
in
in combination
combinationcon la (4.7)
with
with proporciona
Eq.
Eq. (4.7)
(4.7) provides el resultado
provides the requerido.
the required
required result.Los
result. parámetros
Param-
Param-
igEquation (4.3) ig /Rin
ig combination with Eq.temperatures
(4.7) provides the required result. Param-
para CPEquation
/R se
eters obtienen
for
Equation
eters for C C(4.3)
(4.3)
P de la
come
income
/Rin tabla
from
combination
combinationC.1;
from Table las
Table temperaturas
C.1;
withC.1;
with Eq.temperatures
Eq. son:
(4.7) provides
(4.7) provides are:the required
the
are: required result.
result. Param-
Param-
eters for Cig Pig /R come from Table C.1; temperatures are:
ig
eters for CCPPP /R
eters for come from
/R come from Table
Table C.1;
C.1; temperatures
temperatures are: are:
873.15
873.15 1.6377
T00 =
T = 533.15
533.15 K K T=
T = 873.15
873.15 K K ττ = 873.15 =
= 533.15 = 1.6377
T0 = 533.15 K T = 873.15 K τ = 873.15
873.15 = 1.6377
533.15
= 533.15
TT00 = 533.15 K K TT == 873.15
873.15 K K ττ = = 533.15 = = 1.6377
1.6377
�� 873.15 ig ig 533.15
533.15
873.15 C
� 873.15 C PPig dT
Whence,
Whence, Q=
Q �H =
= �H =R R�� 873.15
873.15 C Pig dT
ig
Whence, Q = �H = R 533.15 533.15 CCRPP dT
R
De donde,
Whence,
Whence, QQ= = �H
�H = = RR 533.15 R dT dT
�� 533.15 R
533.15 R
−3
� 9.081 ×
9.081 × 10 −3
10−3 2 22
Q=
Q (8.314)��1.702
= (8.314) 1.702 T (τ −
T00(τ 1) +
− 1) + 9.081 2× 10−3 T
T02(τ(τ − − 1)
1)
Q = (8.314) 1.702 T0 (τ − 1) + 9.081 9.081 × × 10−3 T02022 (τ222 − 1)
2 10
QQ =
= (8.314)
(8.314) 1.702
1.702 TT00 (τ
(τ −
− 1)
1) +
+ 2 TT00 (τ
(τ −
− 1) �
1)
22 −6 �
2.164
2.164 ×
× 10
10 −6
3 3 �
−
− 2.164 3× 10−6 −6 T T0 (τ
3
(τ −
3
1)� =
− 1) � = 19,778
19,778 JJ
2.164 ×
− 2.164 × 10−6 T03033 (τ333 − 1) = 19,778 J
3 10
−
− 3 TT00 (τ(τ −− 1)
1) == 19,778
19,778 JJ
33
Uso de las funciones definidas

Use
Use ofof Defined
Defined Functions
Functions
Use
Use of
of Defined
��
Defined Functions
Functions
Use
The∫(C
La integral
The of Defined
P/R)dT
integral
integral � (C
(C
Functions
a menudo
P /R) dTaparece
/R) dT often en los cálculos
often appears
appears in termodinámicos.
in thermodynamic
thermodynamic Por lo As
calculations.
calculations. tanto,
As por razones
aa matter
matter of de conve-
of conve-
conve-
�� (Cde P
niencia,The
el lado
The
nience,
nience,
The derecho
integral
we
we therefore
integral
integral la define
/R)
(CPPP/R)
therefore
(C /R) ecuación
dT often
define
dT often
dT the(4.7)
the
often
appears
right
right
appears
appears se define
side
side inof
in como
inofthermodynamic
Eq.
Eq. (4.7)
(4.7)
thermodynamic
thermodynamic la función
as
as the
the ICPH(T0,T;A,B,C,D)
calculations.
function,
function,
calculations.
calculations.
As a matter of
ICPH(T0,T;A,B,C,D),
ICPH(T0,T;A,B,C,D),
As aa matter
As matter of of y conve-
se escribe una
conve-
conve-
rutina de computadora
nience,
and
and write
write
nience, we
nience,
weaa para
therefore
computer
computer
we therefore su
therefore define evaluación.
define
routine
routine
the
define the for
for
right
the rightits
its En tal
side caso
of
evaluation.
evaluation.
right side
side of
Eq.
of Eq. la ecuación
(4.7)
Equation
Equation
Eq. (4.7)
(4.7) as
as (4.7)
the
(4.7)
(4.7)
as the then
thenserá
function,
the function, entonces:
ICPH(T0,T;A,B,C,D),
becomes:
becomes:
ICPH(T0,T;A,B,C,D),
function, ICPH(T0,T;A,B,C,D),
and write a computer routine for its evaluation. Equation (4.7) then becomes:
and write
and write aa computer
computer routineroutine��forfor its evaluation.
TT its evaluation. Equation
Equation (4.7) (4.7) then
then becomes:
becomes:
� C CP ICPH(T0,T;A,B,C,D)
�� TTT C PP dT dT ≡ ≡ ICPH(T0,T;A,B,C,D)
ICPH(T0,T;A,B,C,D)
TT0 C CR
RPP dT ≡ ICPH(T0,T;A,B,C,D)
T0 R dT
0 dT ≡ ≡ ICPH(T0,T;A,B,C,D)
ICPH(T0,T;A,B,C,D)
TT00 R R
El nombreThedefunction
The la función
function name
name es ICPH,
is ICPH,
is ICPH, y lasand
andcantidades
the entre paréntesis
quantities
the quantities in
in parenthesesson las
parentheses arevariables
are the T0 y T,T
the variables
variables T00seguidas
and
and TT ,, por los
The
parámetros function name
C yparameters
D. Cuando is ICPH, and the quantities in parentheses are the variables T and T ,
The A,
followed
followed
The B, by
by
function
function parameters
name
name A,a B,
A,
ICPH,
isis ICPH, estas
B, andcantidades
C,
C,
and and
and D.
theD.
the When
When se les
quantities
quantities inasignan
these
these
in valores
quantities
quantities
parentheses
parentheses are
are numéricos,
assigned
assigned
are
are la notación
numerical
numerical
the variables
the variables 0 representa
values,
values,
TT00 and
and TT,,
followed
un valorfollowed
para by parameters
la integral. Así, para A, B,
la C, and D. When these quantities are assigned numerical values,
the
the notation
notation
followed represents
represents
by parameters
by parameters aaA,
A, B,evaluación
value
value
B, for
C,
C, the
forand
andtheD. de
integral.
integral.
D. When
When Q en el ejemplo
Thus,
Thus,
these
these for the 4.2:
for the
quantities
quantities evaluation
evaluation
are assigned
are of
of Q
assigned in
in Ex.
Ex. 4.2:
Qnumerical
numerical 4.2:values,
values,
the notation represents a value for the integral. Thus, for the evaluation of Q in Ex. 4.2:
the notation
the notation represents
represents aa value value for for the
the integral.
integral. Thus,
Thus, for for the
the evaluation
evaluation of of QQ in
in Ex.
Ex. 4.2:
4.2:
Q
QQ= = 8.314 ××
8.314
= 8.314 ICPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0)==
ICPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0)
×ICPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0) =19 19,778
778 J JJ
19,778
Q = 8.314 × ICPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0) = 19,778 J
QQ= = 8.314
8.314 × × ICPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0)
ICPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0) = = 19,778
19,778 JJ
Representative
Representative computer
computer programs
programs for
for evaluation
evaluation of
of the
the integral
integral are
are given
given in
in App.
App. D.
D.integral.
En el apéndice D se dan
Representative programas
computer representativos
programs de computadora
for evaluation of the integral para are
la evaluación
given in as de laD.
App.
For
For added
added flexibility
flexibility the
the programs
programs also
also evaluate
evaluate the
the dimensionless
dimensionless quantity
quantity �C
�C �
� /R
/R as given
given
Para mayor
ForEq.
Representative
Representative
flexibilidad,
added
computer
computer
los programas
flexibility the programs
programs
programs
también
also
for
for evaluation
evaluation
evalúanthe
evaluate la cantidad of
of the
the
dimensionless
integral
integral
adimensional
quantity
are
are〈C
�CPP〉 �HH/R
P
given
given
P H
H in
in App.
App.
/Rcomo
D.expresa
D.
se
as given
by
by
For
For Eq.
added
added (4.8).
(4.8). The
The
flexibility
flexibility right-hand
right-hand
the
the side
side
programs
programs of
of this
this
also
also equation
equation
evaluate
evaluate is
is
the
the another
another function,
function,
dimensionless
dimensionless MCPH(T0,T;A,B,C,D).
MCPH(T0,T;A,B,C,D).
quantity
quantity �C
�C �� /R
/R as
as given
given
mediante bylaEq.ecuación
(4.8). (4.8).
The El lado side
right-hand derecho de equation
of this esta ecuación es otra
is another función,
function, MCPH(T0,T;A,B,C,D).
PP HH
MCPH(T0,T;A,B,C,D). Con
With
With
by
by Eq.this
Eq. this definition,
definition,
(4.8).
(4.8). Eq.
Eq. (4.8)
The right-hand
The right-hand (4.8) becomes:
becomes:
side
side of this
of this equation
equation isis another
another function, MCPH(T0,T;A,B,C,D).
function, MCPH(T0,T;A,B,C,D).
esta definición,
With thisladefinition,
ecuación (4.8)
Eq. (4.8)será: becomes:
With this
With this definition,
definition, Eq. Eq. (4.8)
(4.8) becomes:
becomes:
�C
�C PP ��HH = MCPH(T0,T;A,B,C,D)
�CRP �H = MCPH(T0,T;A,B,C,D)
�CPR
�C P��HH = MCPH(T0,T;A,B,C,D)
MCPH(T0,T;A,B,C,D)
R = = MCPH(T0,T;A,B,C,D)
MCPH(T0,T;A,B,C,D)
RR

132 132 CHAPTER
CAPÍTULO 4. Heat Effectstérmicos
4. Efectos
A specific numerical value of this function is:
A specific numerical value of this function is:
Un valor
A numérico específico
specific numerical de esta
value función
of this es: is:
function
MCPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0) = 6.9965
MCPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0) = 6.9965
�C P � /R for methane in the calculation of Ex. 4.2. By Eq.=(4.9),
representingMCPH(533.15,873.15;1.702,9.081E-3,-2.164E-6,0.0) 6.9965
representing �C P �HH /R for methane in the calculation of Ex. 4.2. By Eq. (4.9),
representando a 〈CP〉�C
representing H /R
P �Hpara el metano
/R for methane eninelthe
cálculo del ejemplo
calculation of Ex.4.2.
4.2.Mediante la ecuación (4.9),
By Eq. (4.9),
�H = (8.314)(6.9965)(873.15 − 533.15) = 19,778 J
�H = (8.314)(6.9965)(873.15 − 533.15) = 19,778 J
�H∆H== (8.314)(6.9965)(873.15
(8.314)(6.9965)(873.15 –−533.15)
533.15)==1919,778
778 J J
Example 4.3
Example
Ejemplo 4.3 4.3
Example
What is 4.3
the final temperature when heat in the amount of 0.4 × 1066(Btu) is added to
What is the final temperature when heat
25(lblamol) of ammonia ◦ in the amount of 0.4 × 10 (Btu) is added to
¿Cuál será temperatura final initially
cuandoat se500( ◦F)
agrega in
una a steady-flow process at 1(atm)?
× 106(Btu) a 25(lb mol)
What
25(lb is theoffinal
mol) temperature
ammonia initiallywhen
at heat
500( F) in a cantidad
in the amountdeofcalor
steady-flow 0.4 ×de100.4
process 6 (Btu)
at is added to
1(atm)?
de amoniaco inicialmente a 500(°F) en un proceso ◦ de flujo estable a 1(atm)?
25(lb mol) of ammonia initially at 500( F) in a steady-flow process at 1(atm)?
Solution 4.3
Solución 4.3
Solution 4.3
Si ∆HSolution
esIfel�Hcambio 4.3
is thede la entalpía
enthalpy change parafor1(lb mol),
1(lb mol),Q= Q n=∆Hn �Hy , and
If �H is the enthalpy change for 1(lb mol), Q = n �H , and
If �H is the enthalpy change Q for ×
0.4 1(lb
10mol),
6 Q = n �H , and
�H = Q = 0.4 × 106 = 16,000(Btu)(lb mol)−1
�H = n = 25 6 = 16,000(Btu)(lb mol)−1
Qn 0.4 × 2510
�H = = = 16,000(Btu)(lb mol)−1
The heat-capacity equationn requires 25 temperatures in kelvins; therefore, conversion
La ecuación
The para la capacidad calorífica requiere que lasintemperaturas estén en kelvins; por lo
of
tanto, seThe allheat-capacity
units
necesita to the equation
convertir SI system
todas
requires
lasrequires
unidades
temperatures
is indicated. Because
al sistema
kelvins;
1 J mol
SI.kelvins;
Puesto
therefore,
que−11 is
J mol
conversion
−1 is equivalent to
–1 es equivalente
of all units to
heat-capacity
0.4299(Btu)(lb the SI system
equation
mol) −1 , divide is
the indicated. Because
temperatures
preceding in
result by 1 J mol
0.4299:therefore,equivalent
conversion to
a 0.4299(Btu)(lb mol) –1, el resultado
0.4299(Btu)(lb
of all units mol)
to the , divideanterior
SI−1system isthe se divide
preceding
indicated. entreby0.4299:
result
Because J mol−1 is equivalent to
10.4299:
0.4299(Btu)(lb mol)�H −1 , divide the preceding result by 0.4299:
∆H= 000/0.4299 ==
= 16,000/0.4299
16 37,218
218 JJJmolmol–1−1
�H = 16,000/0.4299 =3737,218 mol−1
−1
�H = 16,000/0.4299
500 + 459.67= 37,218 J mol
With T0 = 500 + 459.67 = 533.15 K
Con With T0 = 1.8 = 533.15 K
500 +1.8 459.67
With T0 = = 533.15 K
then for any value of T : 1.8
then for any value of T :
A continuación,
then for anyparavalue
cualquier valor de T:
�C P �H of T :
�C P �H = MCPH(533.15,T;3.578,3.020E-3,0.0,-0.186E+5)
�C PR�H = MCPH(533.15,T;3.578,3.020E-3,0.0,-0.186E+5)
R
= MCPH(533.15,T;3.578,3.020E-3,0.0,-0.186E+5)
R
Iteration between this equation and Eq. (4.10) starts with a value T ≥ T0 , and
Iteration between
converges equation and Eq. (4.10) starts with a value T ≥ T0 , and
thisvalue:
on the final
convergesbetween
Iteration on the final equation and Eq. (4.10) starts with a value T ≥ T0 , and
this value:
La iteración entre esta ecuación y la (4.10) comienza con un valor T ≥ T0, y converge al valor
converges on the final T =value: 1,790(◦◦F)
final: 1,250 K or
T = 1,250 K or 1,790( F)
T = 1,250 K or ◦
T = 1 250 K o 1,790(
1 790 (°F) F)

4.2. Latent
4.2. Calores latentesHeats of Pure Substances
de sustancias puras 133 133
4.2 CALORES LATENTES

4.2 LATENT DE PURE
HEATS OF SUSTANCIAS PURAS
SUBSTANCES
Cuando When
una sustancia pura se convierte
a pure substance al estado
is liquefied from the líquido desdeorelvaporized
solid state estado sólido
from otheseliquid
vaporiza a partir de un
at constant
estado líquido
pressure,a presión
no changeconstante, no hay cambio
in temperature occurs;alguno en lathe
however, temperatura; de cualquier
process requires modo, of
the transfer el proceso
a
requierefinite
la transferencia
amount of de heatunato cantidad finita de
the substance. calorheat
These a laeffects
sustancia. Estos the
are called efectos
latenttérmicos
heat of son llamados
fusion
calor latente de fusión
and the y calor
latent heat latente de vaporización.
of vaporization. De manera
Similarly, there are heatssimilar, existen calores
of transition de transición
accompanying the que
acompañan el cambio
change de una sustancia
of a substance from one desolid
un estado
state sólido a otro;forpor
to another; ejemplo,the
example, el heat
calorabsorbed
absorbidowhen
cuando los
cristalesrhombic
rómbicoscrystalline
de azufre cambian a una estructura
sulfur changes monoclínica
to the monoclinic a 95 °C
structure at y951◦bar es de
C and 360isJ por
1 bar 360cada
J forátomo-
gramo. each gram-atom.
La principal
The característica
characteristic de estos of
feature procesos es processes
all these la coexistencia
is thede dos fases. De
coexistence acuerdo
of two con la
phases. Ac-regla de
fase, un cording
sistema to dethe
dosphase
fases rule,
que está formadosystem
a two-phase por unaconsisting
sola especieof aessingle
univariante,
species yis su estado intensivo
univariant, and se
determinaitspor la especificación
intensive de una sola
state is determined bypropiedad intensiva.
the specification of Así,
just el calor
one latenteproperty.
intensive que acompaña
Thus atheun cam-
bio de fase es heat
latent una accompanying
función sólo dea la temperatura,
phase change isque está relacionada
a function con otras
of temperature only,propiedades deltosistema
and is related
medianteother
una system
ecuación termodinámica
properties exacta:
by an exact thermodynamic equation:
d P saturado
sat
�H = T �V (4.11) (4.11)
dT
where for a pure species at temperature T ,

donde para una especie pura a temperatura T,
�H = latent heat
∆H = calor
�V = latente
volume change accompanying the phase change
∆V = cambio
P sat = de volumen
saturation que acompaña el cambio de fase
pressure
Psaturado = presión de saturación
The derivation of this equation, known as the Clapeyron equation, is given in Chap. 6.
La deducción de estaEq.
When ecuación,
(4.11) isconocida
applied como ecuación de Clapeyron,
to the vaporization se da denP el
of a pure liquid, satcapítulo
/dT is the6. slope of
Cuando
the vaporse aplica la ecuación (4.11) a curve
pressure-vs.-temperature la vaporización de un líquido
at the temperature puro, d�V
of interest, Psaturado /dTdifference
is the es la pendiente
de la curva de presión
between molarde vapor en
volumes of función
saturateddevapor
la temperatura a la liquid,
and saturated temperatura
and �Hde interés, ∆V esheat
is the latent la diferencia
of
entre losvaporization.
volúmenes molares de vapor
Thus values saturado
of �H may ybedecalculated
líquido saturado, y ∆H es el calor
from vapor-pressure andlatente de vaporización.
volumetric data.
Así, los valores de ∆Hheats
Latent se pueden
may alsocalcular a partir de
be measured la presión de vapor
calorimetrically. y de información
Experimental values are volumétrica.
available
Los
at calores
selectedlatentes también
temperatures forsemany
miden de manera
substances. calorimétrica.
4 Correlations forSethe
dispone de valores
latent heats of manyexperimentales
com-
para muchas sustancias a diferentes temperaturas. 4 Las correlaciones para los calores latentes
pounds as a function of temperature are given by Daubert et al.5 Nevertheless, data aredenotmuchos
compuestos en función deatlathe
temperatura están 5 Sin embargo, no siempre
always available temperature of dados porand
interest, Daubert
in manyy colaboradores.
cases the data necessary for ap-
hay información
plication disponible
of Eq. (4.11)a laare
temperatura de interés,
also not known. y enevent
In this muchos casos tampoco
approximate methods se conoce
are usedinformación
for
necesariaestimates
para aplicar
of thelaheat
ecuación
effect (4.11). En esta asituación
accompanying se usanBecause
phase change. métodos aproximados
heats para estimar
of vaporization are el
efecto térmico
by far theque most
acompaña un cambio
important from adepractical
fase. Debido a que
point of losthey
view, calores
havedereceived
vaporización
most son los más im-
attention.
portantesOne
desde un puntois de
procedure usevista
of apráctico, han recibido
group-contribution mayor known
method, atención. Un procedimiento
as UNIVAP. de uso
6 Alternative común es
meth-
el método 6
odsdeserve
la contribución de grupo, conocido como UNIVAP. Los métodos alternativos sirven para uno
one of two purposes:
de dos propósitos:
• Prediction of the heat of vaporization at the normal boiling point, i.e., at a pressure of
• Predicción del caloratmosphere,
1 standard de vaporización en as
defined el 101,325
punto dePa.ebullición normal, es decir, a una presión de 1 at-
mósfera estándar, definida como 101 325 Pa.
4 V. Majer and V. Svoboda, IUPAC Chemical Data Series No. 32, Blackwell, Oxford, 1985; R. H. Perry and
D. Green, op. cit., Sec. 2.
4 5
V. Majer yT.V.E.Svoboda, IUPAC
Daubert et Chemical
al., op. cit. Data Series No. 32, Blackwell, Oxford, 1985; R. H. Perry y D. Green, op. cit., sección 2.
5 T. E. Daubert et al., op. cit.
6 M. Klüppel, S. Schulz, and P. Ulbig, Fluid Phase Equilibria, vol. 102, pp. 1–15, 1994.
6 M. Klüppel, S. Schultz y P. Ulbig, Fluid Phase Equilibria, vol. 102, pp. 1-15, 1994.

134
134 CHAPTER 4.
CHAPTER 4. Heat
Heat Effects
Effects
134 134 CHAPTER
CAPÍTULO 4. 4. Heat Effects
Efectos térmicos
•• Estimation
Estimation of of the
the heat heat of of vaporization
vaporization at at anyany temperature
temperature from from the the known
known value value at at aa
• Estimación •• Estimation
del
Estimation calor of
of dethe
the heat
vaporización
heat of
of vaporization
a cualquier
vaporization at
at any
temperatura
any temperature
temperature a partir from
del
from the
valor
the known
conocido
known value
value a at
at aatempe-
una
single temperature.
single temperature.
• single
Estimation
ratura particular. temperature.
single temperature. of the heat of vaporization at any temperature from the known value at a
single
Rough temperature.
Rough estimatesestimates of of latent
latent heats heats of of vaporization
vaporization for for purepure liquids
liquids at at their
their normal
normal boiling boiling
Estimaciones Rough
Rough estimates
burdas
estimates de los of
of latent
calores
latent heats
latentes
heats of
of vaporization
de vaporización
vaporization for
for pure paraliquids
pure líquidosat
liquids their
their normal
atpuros en
normal boiling
sus puntos
boilingde ebu-
points are
points are given
given by Trouton’s
by Trouton’s rule:
rule:
points
pointsRough
llición normal are
están given
are given dadas by
estimates
bypor Trouton’s
of regla
la
Trouton’s latent rule:
de
rule:heats of �H
Trouton: vaporization for pure liquids at their normal boiling
�Hnn
points are given by Trouton’s rule: �H
�H n∼ ∼ 10 10
RTnnn ∼
RT
�H ∼ 10
10
RT
RTnn ∼ 10
where TTnn is
where is the
the absolute
temperature of of the
theRT normal
normal
n boiling point.
boiling point. The The units
units of of �H
�Hnn,, R, R, and
and TTnn
where T is the absolute temperature of
of the
the normal
normal boiling point. The units of �H n ,, R, and
and TTnn
where
must
must beTnchosen
be n is the so
chosen absolute
so that �H
that �H temperature
/RTnn is
nn/RT is dimensionless.
dimensionless. boiling
Datingpoint.
Dating The
1884,units
from 1884,
from thisof
this �H
rule
rule n R,
still
still provides
provides
must
where
donde Taamust beT chosen
is
es labetemperatura
ncheck
chosenthe so that
absolute �H
absoluta
sowhether
that n /RT
temperaturedel punto
n is dimensionless.
of the normal
de ebullición
is dimensionless. Dating
boilingnormal. from
point. Las 1884,
The units
unidades this of
thisderule
�H∆H still
, R,provides
and
y TnTse
n n, Rprovides n deben
nsimple
simple check on on whether �Hvaluesn /RT
values calculated
ncalculated otherDating
by other
by methods
methods from
are1884,
are reasonable.
reasonable. rule still
Representative
Representative
elegir de a
must
a simple
tal be
forma
simple check
chosen
checkque on
∆H
so
on whether
that
/RT
whether �H novalues
n /RT
tenga
values n calculated
is dimensionless.
dimensiones.
calculated by
by other
Desde
other methods
Dating 1884,
methods from are
esta
are reasonable.
1884,
regla this
reasonable. ruleRepresentative
proporciona still provides
una
Representative comproba-
experimental values n for n
this ratio are Ar, 8.0; N ,
experimental values for this ratio are Ar, 8.0; N22, 8.7; O22, 9.1; HCl, 10.4; C66H66, 10.5; H22S, 8.7; O , 9.1; HCl, 10.4; C H , 10.5; H S,
aexperimental
ción simple simple
de
experimental sicheck
los values
on whether
valores
values for this
calculados ratio
values
ratioson are Ar,
Ar, 8.0;
calculated
arerazonables byN 2 ,, 8.7;
Nother
por O
methods
otros ,, 9.1;
9.1;are
O22métodos. HCl, 10.4;
reasonable.
Valores C
C66HH66,, 10.5;
10.5; H
Representative
10.4; experimentales S,
H22represen-
10.6;
10.6; and
and H
H O,
22O, 13.1. for
13.1. this 8.0; 2 8.7; HCl, S,
tativos de10.6;
10.6; and
experimental
estaOf H
relación
and H 2 O,
O, 13.1.
values
son
13.1. for
Ar, this
8.0; N ratio
, 8.7;are O Ar,
, 8.0;
9.1; N
HCl, , 8.7; O , 9.1;
2 10.4; C26H6, 10.5; H2S, 10.6, HCl, 10.4; C H ,
6 y6 H2O, 10.5;
77 H
13.1.2 S,
Of the the2same
same nature,
nature, but but not 2
not quitequite so2 so simple,
simple, is is thethe equation
equation proposed proposed by by Riedel:
Riedel: 7
Of 7
De10.6;
la mismaOf the
and the same
O,
same13.1.
H2naturaleza, nature,
nature, pero but
butnonot tanquite
not simple,
quite so
so simple,
es la ecuación
simple, is
is thethe equation
propuesta
equation proposed
por Riedel:
proposed by
by Riedel:
Riedel: 7
7
Of the same nature, but not �Hnn
�H quite so simple,
1.092(ln PPcc −
1.092(ln is the equation
− 1.013)
1.013) proposed by Riedel:
�H
�H n= = 1.092(ln
1.092(ln PPc − − 1.013)
1.013) (4.12)
(4.12)
RT
RT nn n =
= 0.930
0.930 −−c TTrr (4.12)
(4.12) (4.12)
�HRT n 1.092(ln
0.930 Pc−−T1.013) r
nn
RTn = 0.930 − Trnn (4.12)
where PPcc is
where is the
the critical pressureRT
critical pressure innbars
in bars and and 0.930
TTrrnn isis − theTrreduced
the reduced
n temperature at
temperature at TTnn.. Equation
Equation
donde Pwhere
c es
where isla presión
P c is the crítica
critical en bar
pressure y T r n es
in la
bars temperatura
and T r is reducida
is the the reduced a Tntemperature
. Resulta sorprendente
at que, para ser
at TTnn.5.5 Equation
(4.12)
(4.12) isPcsurprisingly
is the critical
surprisingly pressure
accurate
accurate forinan
for anbars and Trn expression;
empirical
empirical n
expression; reduced errors
errors temperature
rarely exceed
rarely exceed Equation
percent.
percent.
una expresión
(4.12)
where
(4.12) isto empírica,
is
P c surprisingly
is the la ecuación
critical accurate for an empirical expression; errors rarely exceed 5 percent.al agua
accurate
pressure (4.12)forin es
an
barsexacta;
empirical
and los
T r errores
expression;
is the rara
reduced vez
errors exceden
rarely
temperature a 5%.
exceed
at T Aplicándola
n . 5 percent.
Equation
Applied
Applied tosurprisingly
water itit gives:
water gives: n
se obtiene:
Applied
(4.12) is to water
surprisingly
Applied to water it gives: it gives:
accurate for an empirical expression; errors rarely exceed 5 percent.
Applied to water it gives:�H �Hnn 1.092(ln 220.55
1.092(ln 220.55 − − 1.013)
1.013)
�H
�H n= = 1.092(ln
1.092(ln 220.55
220.55 −− 1.013) =
1.013) = 13.56
13.56
RT n =
RTnn = 1.092(ln 0.930
0.930 −− 0.577
0.577 = 13.56
�HRT n 0.930220.55
− − 1.013) = 13.56
0.577
RTn = 0.930 − 0.577 = 13.56
De donde,Whence,
Whence, �HnnRT
�H ==n(13.56)(8.314)(373.15) 0.930 − 0.577=
(13.56)(8.314)(373.15) = 42,065
42,065 JJ mol mol−1 −1
Whence, �H = (13.56)(8.314)(373.15) = 42,065 J mol −1
Whence, �Hn =−1n (13.56)(8.314)(373.15) = 42,065 J mol −1
−1 −1
−1 −1
This
This
Whence,
Esto corresponde corresponds
correspondsa 2 334 to to
to 2,334
–1
2,334
�H
J g2,334 J
J= g
g
; el Jvalor ;
; the
the steam-table
steam-table
(13.56)(8.314)(373.15) value
value = of
of 2,257
2,257
42,065 JJ g
–1
g
mol is
is loweren
lower by3.4%.
by 3.4 percent.
3.4 percent.
This
This corresponds
corresponds to 2,334
n
J gg−1;;de
−1 the
the
lasteam-table
tabla de vapor
steam-table value
value
deof 2 257
of 2,257
2,257
J gJ g −1
J g
es is
−1 menor
is lower
lower by
by 3.4
3.4 percent.
percent.
Las Estimates
Estimates
estimaciones of
of
del the
thecalorlatent
latent latenteheat
heat
−1 deof
of vaporization
vaporization
vaporización of
of a
a pure
pure
de aunpure liquid
liquid
líquido at
at
puro −1 any
any temperature
temperature
aiscualquier from
from
temperatura the a partir
the
This Estimates
corresponds
Estimates of
ofto the
2,334
the latent
latent J g heat
heat; of
theof vaporization
steam-table
vaporization of
value
of of
pure liquid
2,257
liquid J gat
at any
any temperature
lower by
temperature 3.4 from
percent.
from the
the cono-
known
known
de un valor value
value
conocido at
at aa single
single
a auna temperature
temperature
temperatura may
may
particular, be
be based
based
se puedenonon a
a known
known
hacer experimental
experimental
con base value
value
en temperature
un value
valor or or
or on
on a
a
experimental value
value
known
known value
Estimates
value at
at of
a single
the
single temperature
latent heat
temperature of may
may be
vaporization
be based
based on
ofon a a
a known
pure
known experimental
liquid
88 has at any
experimental value or onfrom
on a
a value
the
value
estimated
estimated
cido o sobre unvalue by
by
valor Eq.
Eq. (4.12).
(4.12).
estimado The
The
por method
method
la ecuación proposed
proposed
(4.12). by
by
El Watson
Watson
método has found
found
propuesto wide
wide
por Watson 8
acceptance:
acceptance:goza
estimated
known
estimated by
byat Eq.
Eq. (4.12).
a single The
The method
(4.12).temperature method mayproposed
be based
proposed by
byon Watsona known
Watson
8
8 has found
found wide
experimental
has widevalueacceptance:
or
acceptance: on adevalue
una amplia
aceptación:
estimated by Eq. (4.12). The method proposed �� by Watson �0.38
� 0.38
8 has found wide acceptance:
�H22
�H �
�111− − TTrr22 � �0.38
�H 2 ==
�H112 = � 111− − T r
−TTTrrr2�0.38
2 0.38 (4.13)
(4.13)
�H
�H
�H = 1 −− T
(4.13)
(4.13) (4.13)
�H211 = 11 −
11
�H − TTrrr211 (4.13)
This equation
This equation is is simple
simple and and fairly
fairly accurate;�H1 its
accurate; its1use− Tis
use isr1illustrated
illustrated in in the
the following
following example.
example.
This
This equation
Esta ecuación es simple
equation is
is simple
ysimple
bastante and fairly
andexacta;fairly accurate;
su uso seits
accurate; use
use is
ilustra
its isenillustrated
el siguiente
illustrated in
in the following
following example.
ejemplo.
the example.
This equation is simple and fairly accurate; its use is illustrated in the following example.
Example 4.4
Ejemplo 4.4 4.4
Example
Example 4.4
Example 100◦◦C −1,, estimate
2,257 JJ gg−1
Given that the4.4
Given that
Given that the
the latent
latent heat
heat of
of vaporization
vaporization of
of water
water at
at 100 C is
is 2,257 estimate
Dado que el
Given calor
latent ◦◦heat of vaporization of water at 100◦◦C is 2,257
that latente
theat de vaporización
latent del aguaof
a water
100 °Cates100
2 ◦257–1 J g−1
C isJ g2,257−1, estimate
, calcule
J g−1 el calor latente a
the
the
the
latent
latent heat
heat at 300
300 ◦heat
C. of vaporization
C. , estimate
the latent
300 °C.Given thatheat
latent at
at 300
the latent
heat ◦C.
300◦heat
C. of vaporization of water at 100 C is 2,257 J g , estimate
the latent heat at 300 C.
77L
7L Riedel, Chem.
Riedel, Chem. Ing.
Ing. Tech.,
Tech., vol.
vol. 26,
26, pp.
pp. 679–683,
679–683, 1954.
1954.
7L Riedel, Chem. Ing. Tech., vol. 26, pp. 679–683, 1954.
L Riedel, Chem. Ing. Tech., vol. 26, pp. 679–683, 1954.
878K.
K. Riedel,
M. Watson,
Watson, Ind. Eng. Chem., vol. 35, 679–683,
pp. 398–406,
398–406, 1943.
8L
7 L. Riedel,
M. Chem. Ing.
Ind. Tech.,
Eng. vol.vol.
Chem., 26, pp.
35, pp. 1954.
1943.
8K.Chem. Ing. Tech.,
M. Watson, vol. 26,
Ind. Eng. pp. 679-683,
Chem., 1954.
vol. 35, pp. 398–406, 1943.
K. M. Watson, Ind. Eng. Chem., vol. 35, pp. 398–406, 1943.
8 K. M. Watson,
8 K. M. Watson,
Ind. Eng.Ind. Eng.vol.
Chem., 35, pp.
Chem., vol.398-406, 1943. 1943.
35, pp. 398–406,

4.3. Standard Heat of Reaction 135
4.3. Calor estándar de reacción 135
Solución 4.4
Solution 4.4
Sean ∆H1 = calor latente a 100 °C = 2◦ 257 J g–1
Let �H = latent heat at 100 C = 2,257 J g−1
∆H2 = calor1 latente a 300 °C ◦
�H2 = latent heat at 300 C
Tr1 = 373.15/647.1 = 0.577
Tr1 = 373.15/647.1 = 0.577
Tr2 = 573.15/647.1 = 0.886
Tr2 = 573.15/647.1 = 0.886
En seguida,
Thenpor
by la ecuación
Eq. (4.13), (4.13),
� �0.38
1 − 0.886
�H2 = (2, 257) = (2, 257)(0.270)0.38 = 1,371 J g−1
1 − 0.577
El valorThe value given en

proporcionado in las
the tablas
steam de
tables is 1,406
vapor J g−1
es 1 406 J g.–1.
4.3 STANDARD HEAT OF REACTION

4.3 CALOR ESTÁNDAR DE REACCIÓN
Heat térmicos
Los efectos effects discussed
analizados so hasta
far have been
ahora hanforsido
physical processes.
sólo para procesos Chemical
físicos. reactions
Las reaccionesalso are
químicas
accompanied either by the transfer of heat or by temperature changes during
también se acompañan, ya sea por una transferencia de calor o por variaciones de temperatura durante the course of el
reaction—in
transcurso some cases
de una reacción, y enby both. These
algunos effects
casos por are manifestations
ambas. Estos efectos son of the differences in de
manifestaciones molec-
las diferen-
cias en ular structure, molecular
la estructura and therefore in energy,
y, en of the products
consecuencia, and reactants.
en la energía For example,
de los productos y dethelosreactants
reactivos. Por
in a combustion reaction possess greater energy on account of their structure
ejemplo, los reactivos en una reacción de combustión poseen una energía mayor que los productos than do the prod-a causa de
ucts, and
su estructura, this energía
y esta energy must
debeeither be transferred
ser transferida a lostoalrededores
the surroundings as heato or
como calor produce obtenidos
productos products a una
at an elevada.
temperatura elevated temperature.
Cada una Eachde of
lasthe vast number
muchas reacciones of possible
químicaschemical
se puedereactions may be
llevar a cabo de carried
diferentesoutmaneras,
in many y cada
different ways, and each reaction carried out in a particular way is accompanied
reacción que se realiza en un procedimiento particular se acompaña por un efecto térmico propio. La tabu- by a particular
heat
lación de effect.
todos Tabulation
los efectos of all possible
térmicos posibles heat
para effects
todas las forreacciones
all possiblerealizables
reactions is es impossible.
poco práctica. WeDebido
a eso, calculamos los efectos térmicos para las reacciones que se realizan de diversas maneras, afor
therefore calculate the heat effects for reactions carried out in diverse ways from data partir de
reactions
información paracarried out inque
reacciones a standard
se realizanway.deThis
modo reduces the required
estándar. data to
Esto reduce al amínimo
minimum. la información re-
querida. The heat associated with a specific chemical reaction depends on the temperatures of
both the reactants and products. A consistent (standard) basis for treatment of reaction heat
El calor asociado con una reacción química determinada depende de la temperatura de los reactivos y
effects results when the products of reaction and the reactants are all at the same temperature.
de los productos. Una base consistente (estándar) para el tratamiento de los efectos térmicos de una reacción
Consider the flow-calorimeter method for measurement of heats of combustion of fuel
se obtiene cuando los productos de una reacción y los reactivos, todos, están a la misma temperatura.
gases. The fuel is mixed with air at ambient temperature and the mixture flows into a combus-
Considere el método del calorímetro de flujo para medir los calores de combustión de los gases com-
tion chamber where reaction occurs. The combustion products enter a water-jacketed section
bustibles. El combustible se mezcla con aire a temperatura ambiente y la mezcla fluye hacia una cámara de
in which they are cooled to the temperature of the reactants. Because no shaft work is produced
combustión donde ocurre la reacción. Los productos de la combustión entran a una sección de enfriamiento
by the process, and the calorimeter is built so that changes in potential and kinetic energy are
con agua, en la que se enfrían a la temperatura de los reactivos. Puesto que no se produce trabajo de flecha
negligible, the overall energy balance, Eq. (2.32), reduces to
debido al proceso, y el calorímetro está construido de tal forma que son insignificantes los cambios en las
energías potencial y cinética, el balance de energíaQtotal, = �H la ecuación (2.32), se reduce a
Thus the heat flowing from the calorimeter Q = ∆H

and absorbed by the water is equal in magnitude to
the enthalpy change caused by the combustion reaction. The enthalpy change of reaction �H
Así, la transmisión del calor desde el calorímetro y que es absorbido por el agua es idéntico en magnitud al
is called the heat of reaction.
cambio de la entalpía causado por una reacción de combustión. El cambio de la entalpía de reacción ∆H se
conoce como el calor de reacción.

136 CAPÍTULO 4. Efectos térmicos
For purposes of data tabulation with respect to the reaction,
For purposes of data tabulation with respect to the reaction,
Con el propósito de tabular la información a A + bB con→ respecto
l L + ma M la reacción,
a A + bB → l L + m M
aA + bB → lL + mM
the standard heat of reaction is defined as the enthalpy change when a moles of A and b moles
the
of standard
B in their heat of
standard se reaction
states is defined
at como
temperature as theTenthalpy
react change
to form when of
l moles a moles
L and of
mAA and bofmoles
moles M in
el calorof
estándar
B in de standard
their reacción define
states at el cambio
temperature T de entalpía
react to form cuando
l moles aofmoles
L and dem y b moles
moles of MdeinB en sus
their
estándarstandard states at the same temperature
reaccionan para formar T .
estadostheir standarda temperatura
states at the T same temperature T . l moles de L y m moles de M en sus estados están-
dar a la misma temperatura T.
A standard state is a particular state of a species at temperature T
Aand standard
at specified state conditions
is a particular state of acomposition,
of pressure, species at temperature and physical T
Un estado and estándar
at specified es un conditions
estado particular of de una especie
pressure, composition, a temperatura and T y en condicio-
physical
condition as,
nes determinadas
e.g., gas,
de presión,
liquid, or solid.
composición y condición física, por ejemplo, gas, líquido o
condition as, e.g., gas, liquid, or solid.
sólido. A standard-state pressure of 1 standard atmosphere (101,325 Pa) was in use for many
years,Aand standard-state
older data tabulationspressure of are1 for
standard atmosphere
this pressure. The (101,325
present standard Pa) wasisin1 use bar for
(105many
5 Pa),
Durante
years, muchos
and older años
data se utilizó como
tabulations are presión
for this de estadoThe
pressure. estándar
present a 1standard
atmósfera is 1estándar
bar (10 (101
Pa), 325 Pa)
but for purposes of this chapter, the difference is of negligible consequence. With5 respect to
y las antiguas
but tabulaciones
for purposes de datos son para esta presión. Ahora el estándar es 1 bar (10 Pa); de cualquier
composition, the of this chapter,
standard the difference
states used in this chapteris of negligible
are states of consequence.
the pure species. With For respect to
gases,
modo, composition,
para los finesthe de standard
este capítulo,states la
useddiferencia
in this tiene consecuencias
chapter are states of insignificantes.
the pure species. Con
For respecto a la
gases,
the physical state is the ideal-gas state and for liquids and solids, the real state at the standard-
composición,
the en estestate capítulo los estados estándar queliquids
se usanand sonsolids,
los estados destate
las especies puras. Para los
statephysical
pressure andisatthethe ideal-gas
system state and for
temperature. In summary, thethe real
standard at the
states standard-
used in this
gases, el estado
state físico
pressure es el estado de gas ideal; y para líquidos y sólidos, el estado real a la presión del estado
chapter are: and at the system temperature. In summary, the standard states used in this
estándarchapter
y a la temperatura
are: del sistema. En resumen, en este capítulo los estados estándar usados son:
• Gases: • Gases:
sustancia The purapure substance
ensubstance
el estado de in the ideal-gas
gasideal-gas
ideal a 1 statestate at 1 bar.
bar.
• Gases: The pure in the at 1 bar.
• Líquidos• Liquids
y sólidos:and líquido
solids: oThe real puro
sólido pure real
liquid a 1orbar.solid at 1 bar.
• Liquids and solids: The real pure liquid or solid at 1 bar.
Los valoresPropertyde una propiedad
values in theen el estado
standard estándar
state se indican
are denoted by the condegree
el símbolo symbol.de grado. Por ejemplo, CP°
For example,
C P◦◦ isProperty
es la capacidad thecalorífica values
standard-stateen el in estado
the
heatstandard
estándar.
capacity. state are denoted
Puesto
Because que by theestándar
the elstandard
estado degree
state forsymbol.
para
gaseslos is For
the example,
gases es el estado de
ideal-gas
C Ppara
gas ideal, is the
state, Clos gases
◦ for gases CP°isesidentical
standard-state idéntica a CPigC
heat capacity.
with , yigla,Because
información
and the
the standard
data deTable
of la tabla state
C.1C.1 forse gases
apply aplica
to the
isal the ideal-gas
estado
standard estándar
state para
P ig
P
los gases.
forTodas
state, C P◦ las
gases. forAllcondiciones
gases
conditions para
is identical for aunwith estado
C P , estándar
standard and
statethearedatason
fixedfijas
of excepto
Table
except C.1 la temperatura,
apply
temperature, to thewhich que
standard siempre
state es la
is always
del sistema.
for Debido
the gases.
temperature Alla eso, las system.
conditions
of the propiedades del estado
for aStandard-state
standard estándar
are fixedson
stateproperties funciones
except
are sólo
temperature,
therefore de lawhich
functions temperatura.
is always
of temperature El estado
estándaronly.
elegido
the Thepara
temperature los gases
standard of statees
the system.hipotético,
chosen ya que
Standard-state
for gases is aahypothetical
1 bar los gases
properties are reales
for atno1 son
therefore
one, ideales.gases
functions
bar actual of Sin embargo,
are not estos
temperature
gases rara
only.vezThe
ideal. se standard
desvíanthey
However, mucho
state de lodeviate
chosen
seldom ideal,
for gasesymuch
enislaafrom
mayoría
hypothetical de los
ideality, one,
and casos son
at 1un
informost barpoco
actual
instances diferentes
gases arelas
enthalpies entalpías
not
for
para el estado
ideal.
the real-gasdel gas
However, staterealata11bar
they barand
seldom y elthe
estado
deviate del gas
much
ideal-gas ideal.
from
state ideality, and
are little different. in most instances enthalpies for
Cuando
the real-gasse proporciona
When state
a heatatof 1 barun and
reactioncalor isde
the reacción
ideal-gas
given paraare
for astate unalittle
particular reacción
different.
reaction, particular,
it applies for éstethe sestoichiometric
ajusta para los coefi-
cientes coefficients
estequiométricos
When a heat
as written.en la ecuación.
of reaction is Si cada coeficiente
given
If each stoichiometric for a particular estequiométrico
reaction,
coefficient it appliesse
is doubled, duplica,
for
the of también
reaction lo
the stoichiometric
heat is hace el
calor decoefficients
reacción.For
doubled. Por ejemplo,the
asexample,
written. la ammonia
If reacción de
each stoichiometric síntesis reaction
synthesis de amoniaco
coefficient mayisbe sedoubled,
puede
written:escribir
the heat como:
of reaction is
doubled. For example, the ammonia synthesis reaction may be written:
1
N + 332 H2 → NH3 �H298 ◦ = −46,110 J
12 2 ◦ = −46,110 J
2 N 2 + 2 H 2 → NH 3 �H 298
or N2 + 3H2 → 2NH3 �H298 ◦ = −92,220 J
◦ = −92,220 J
o or N2 + 3H2 → 2NH3 �H298
The symbol �H298 ◦ indicates that the heat of reaction is the standard value for a temperature
The symbol �H ◦◦ indicates that the heat of reaction is the standard value for a temperature
El símbolo ∆H° Kindica
of 298.15 (25 C).que el calor de reacción es el valor estándar para una temperatura de 298.15 K
298
of 298.15298K (25◦ C).
(25 °C).
4.4 STANDARD HEAT OF FORMATION

4.4 4.4 STANDARD
CALOR HEAT
ESTÁNDAR DEOF FORMATION
FORMACIÓN
Tabulation of data for just the standard heats of reaction for all of the vast number of possible
La tabulación de is
Tabulation
reactions información para
ofimpractical.
data for just losstandard
the calores the
Fortunately, estándar
heats de reacción
of reaction
standard heat for deof
all
of any todas las reacciones
the vast
reaction number
can ofposibles
ifes poco
possible
be calculated
práctica. Por fortuna, el calor estándar de cualquier reacción se puede calcular si se conocen los calores
reactions is impractical. Fortunately, the standard heat of any reaction can be calculated if es-
tándar de formación de los compuestos que participan en una reacción. Una reacción de formación se define

4.4. Standard Heat of Formation 137
4.4. Standard Heat of Formation 137
4.4. Calor estándar de formación 137
the standard heats of formation of the compounds taking part in the reaction are known. A
the standard heats of formation of thereaction
formation compounds takingaspart
is defined in the which
a reaction reaction are known.
forms A
a single compound from its constituent
formation reaction iscomo
defineduna as reacción
a reaction donde
which sólo se
forms forma
a singleun compuesto
compound 1
elements. For1 example, the reaction C + 2 O2 + 2H2 → CH3 OH is the formation a
frompartirits de sus
constituent elementos que lo constituyen.
reaction for Por ejem-
elements. For example,plo,the
la reacción
reaction
methanol. The C + O 2 +
2 reaction 2H 2 H O + 3SO → H SO is not a formation reaction, because it forms H2O +
→ CH OH
OH es
is la
the reacción
formation de formación
reaction for para el metanol. La reacción
2 3 2 4
methanol. The reactionSO3H→ O H + 2SO
2 sulfuricSO no
→ es
H
43 acid not una
SO
2 from 4reacción
is not de
the aelements formación,
formation porque
butreaction,
from other nocompounds.
because forma ácidoFormation
it forms sulfúrico areactions
partir deare los un-
elementos
sulfuric acid not fromsino
thedeelements
otros compuestos.
but from Se
other sobreentiende
compounds. que las
Formation reacciones
reactions
derstood to produce 1 mol of product; the heat of formation is therefore based on 1 mol of the de areformación
un- dan como resultado 1 mol del
derstood to produce 1compuesto;
mol ofcompound por lothe
product; tanto,heat
formed. el calor
of de
formation formación
is thereforese refiere
based a 1
on mol
1 moldel ofcompuesto
the formado.
compound formed. Los calores Heatsdeofreacciónreactiona at cualquier temperatura
any temperature cansebecalculan
calculated a partir
fromdeheat-capacity
la información de ifla the
data capacidad
calorífica
Heats of reaction at anyvalue for one temperature is known; the tabulation of data can therefore be reduced to thereduce a
si se conoce
temperature el
canvalorbe para una
calculated temperatura;
from en
heat-capacity consecuencia,
data if thela tabulación de los datos se
la recopilación
value for one temperature iscompilation
known; dethelosoftabulation
calores
standard estándar
of datade
heats ofcan formación
thereforeat
formation para
be una sola
reduced
a single totemperatura.
the
temperature. The La usual
elección usualfor
choice para esta
temperatura
compilation of standard heats ofes de 298.15
formation
this temperature atK a o 25
single °C. El calor
temperature.
◦ estándar The de formación
usual choice
is 298.15 K or 25 C. The standard heat of formation of a compound at this de
for un compuesto a esta temperatura se
representa
this temperature is 298.15 or por25◦ el
Ktemperature C. símbolo
The ∆H
standard
is represented °
f .
heat El ofsímbolo
formation de grado
of a ◦ indica
compound que at éste
this
by the symbol �H f298 . The degree symbol denotes the standard es el valor estándar, el subíndice f
◦ . 298
muestraby
temperature is represented quethe se trata
symbol de un
�H
value, subscript f fidentifies calor
298
de
The formación,
degree y
symbol el 298 es
denotes la temperatura
the standard
a heat of formation, and the 298 is the approximate absolute absoluta aproximada en kelvins. Las
tablas de
value, subscript f identifies aestos
heatvalores
temperature para sustancias
of formation,
in kelvins. and theofcomunes
Tables 298
theseisvalues
these approximate
encuentran
for common enabsolute
los manuales,
substances maypero las recopilaciones
be found in standard más
extensas
temperature in kelvins. Tables están
of thesedisponibles
values for en trabajos
common especializados
substances may de
be referencia.
found in 9 Una lista de valores abreviada 9se da en
standard
handbooks, but the most extensive compilations available are in specialized 9
reference works.
la tabla
handbooks, but the most C.4abridged
extensive
An delcompilations
apéndicelist ofC.values
available are ininspecialized
is given Table C.4 of reference
App. C.works.
An abridged list of values is Cuando
givenWhen lasTable
in ecuacionesC.4 of químicas
chemical App.
equations C. se arecombinan
combinedpor byadición,
addition,los thecalores
standard estándar
heats of de reaction
reacciónmay también se
When chemicalpueden
equationsalso be added to give the standard heat of the resulting reaction. This is possible because en- es una
sumar are para dar
combined el calor
by estándar
addition, thede una
standard reacción
heats resultante.
of reaction Esto
may es posible porque la entalpía
also be added to givefunción de estado,
the standard
thalpy heat yofsus
is a state cambios
thefunction,
resultingand para ciertos
reaction.
its estados
This
changes is inicialinitial
forpossible
given ybecause
finaland son
en- independientes
final de la trayectoria.
states are independent of En
particular,
thalpy is a state function, and siempre
its changes es posible
for given combinar
initial las
and ecuaciones
final states de
are formación
independent
path. In particular, formation equations and standard heats of formation may always be com- y los
of calores estándar de formación para
producirbined
path. In particular, formation cualquier
equations ecuación
to produce anydeseada
and standard desiredheats(que no sea
of formation
equation (not enitself
sí
may mismaaalways unabeecuación
formation com-
equation) de formación), y ésta se acompa-
and its accompanying
bined to produce anyñadesired
de sustandard
calor
equation estándar
heat of reaction. Equations written for this purpose often include an indication ofuna
(not de
itselfreacción.
a formation Las ecuaciones
equation) escritas
and its para este
accompanying fin con frecuencia incluyen the indica-
ción del
standard heat of reaction. physical state of each reactant and product, i.e., the letter g, l, or s is placed in parenthesesdespués
estado
Equations físico
written de cada
for thisreactivo
purpose y producto,
often include es decir,
an las
indicationletras g,
of l
the o s se ponen entre paréntesis
physical state of eachdereactant
la fórmula
afterand thequímica
product,
chemical para
i.e., indicar
the letter
formula si es
to g,unl, gas,
show or s líquido
whether it isoasólido.
is placed in
gas, a Esto
parentheses
liquid, quizá
or aparezca
solid. This innecesario,
might seem ya que una
especieto
after the chemical formula química
show pura
whether a una
it istemperatura
a gas, a particular
liquid, or a y
solid.a 1 bar
This por
unnecessary, because a pure chemical species at a particular temperature and 1 bar can usually lo
might general
seem puede existir sólo en un estado fí-
unnecessary, becausesico. Sinexist
a pure embargo,
chemical con
species frecuencia
at a se
particular suponen
temperature estados andficticios
1 bar por
can
only in one physical state. However, fictitious states are often assumed for convenience. conveniencia.
usually
Considere
exist only in one physical state. However, la reacción
Consider fictitious de states
the reaction desplazamiento
are often
CO a “gas defor
assumed
2 (g) + H2 (g)◦ → CO(g) + H
agua” CO2(g)
convenience. + H2(g)
2 O(g) at 25→ ◦ C.CO(g)
This +water-gas-
H2O(g) a 25 °C.
Esta reacción
Consider the reaction CO 2 (g) encuentra
+ H 2 (g) →
shift reaction is commonly encountered in the chemical industry, though it takes place aonly
se usualmente
CO(g) + Hen2 la
O(g) industria
at 25 C.química,
This aunque
water-gasse realice únicamente temperaturas
at
mayores
shift reaction is commonly de 25
encountered
temperatures °C. De
in cualquier
the
well chemical
above modo,
25 ◦ la
industry,
C. información
However, though the it que
takes
data se
used emplea
place
are only
for es
25 a
at
◦ 25
C, °C,
and y el
the paso
initial inicial
step in enanycualquier
temperatures well above 25◦calculation
cálculo de However,
C. los efectos ofthe térmicos
heat data used
effects relativos
arethis
for for 25 ◦ C, and the initial step in any
a esta
reaction reacción
is evaluation es para theevaluar
standard el heat
calorofestándar
reactionde la ◦reacción
at 25 C. a
◦ C.
25 °C.for
calculation of heat effects Las reacciones
this reaction de
is formación
evaluation pertinentes
the standard y sus
heat calores
of
The pertinent formation reactions and their heats of formation from Table C.4 are: reaction de formación
at 25 de la tabla C.4 son:
The pertinent formation reactions and their heats of formation from Table C.4 are:
CO2 (g): C(s) + O2 (g) → CO2 (g) �H ◦f298 = −393,509 J
CO2 (g): C(s) + O2 (g) → CO2 (g) �H ◦f298 = −393,509 J
H2 (g): Puesto Because que hydrogen
el hidrógenoisesanunelement elemento �H ◦f = 0
H2 (g): Because hydrogen is an element �H ◦f298 = 0 298 Leyen
CO(g): C(s) + 2 O2◦(g) → CO(g)1 ◦
�H f298 = −110,525 J
CO(g): C(s) + 12 O2 (g) → CO(g) �H f298 = −110,525 J
1
H2 O(g): H2 (g) + 2 O◦2 (g) → H2 O(g) �H ◦f298 = −241,818 J
H2 O(g): H2 (g) + 12 O2 (g) → H2 O(g) �H f298 = −241,818 J
Because the reaction is actually carried out entirely in the gas phase at high temperature, con-
Because the reactionEn vista de carried
is actually que la reacción
venience dictates out entirely se lleva
that the thea gas
cabophase
in standard por completotemperature,
statesatofhigh
en fase gaseosa
all ◦products and reactants con-a muy altas temperaturas, la conve-
at 25◦ C be taken as the
venience dictates thatniencia dicta que
the standard los of
states estados estándarand
all products de reactants
todos los at productos
25 C beytaken reactivosas the a 25 °C se consideren como el estado
de gas ideal a 1 bar, aun cuando en estas condiciones el agua en realidad no exista como un gas.
9 For example, see TRC Thermodynamic Tables—Hydrocarbons and TRC Thermodynamic Tables—Non-
9 For example, see TRC Thermodynamic Tables—Hydrocarbons and TRC Thermodynamic Tables—Non-
hydrocarbons, serial publications of the Thermodynamics Research Center, Texas A & M Univ. System, College
hydrocarbons, serial publications of the Thermodynamics
Station, Texas; “The NBSResearch
Tables ofCenter,
ChemicalTexas A & M Univ.Properties,”
Thermodynamic System, College
J. Physical and Chemical Reference Data,
Station, Texas; “The NBS Tables ofvol.
Chemical
11, Thermodynamic
supp. 2, 1982. See Properties,”
also, T. E. J. Physical
Daubert et and op.
al., Chemical
cit. Reference
Where Data,
data are unavailable, estimates based only on
9 Por ejemplo, véase Thermodynamic Tables—Hydrocarbons y TRC Thermodynamic Tables—Non-hydrocarbons, publicaciones
vol. 11, supp. 2, 1982. See also, T.molecular
E. Daubert et al., may
structure op. cit. Wherebydata
be found theare unavailable,
methods estimates based
of L. Constantinou and only on Fluid Phase Equilibria, vol. 103,
R. Gani,
seriales
molecular structure may be founddelpp.Thermodynamics
by the methods
11–22, of L.Research
1995. Center,
Constantinou andTexas A & Fluid
R. Gani, M Univ. System,
Phase Collagevol.
Equilibria, Station,
103, Texas; “The NBS Tables of Chemical Ther-
pp. 11–22, 1995. modynamic Properties”, J. Physical and Chemical Reference Data, vol. 11, supp. 2, 1982. Véase también T. E. Daubert et al., op. cit.
Cuando no hay datos disponibles las estimaciones se basan únicamente en la estructura molecular y se pueden encontrar con los métodos
de L. Constantinou y R. Gani, Fluid Phase Equilibria, vol. 103, pp. 11-22, 1995.

138 138 CHAPTER 4. 4.
CAPÍTULO Heat Effects
Efectos térmicos
ideal-gas state at 1 bar, even though water cannot actually exist as a gas at these conditions.
Escribir lasstate
ideal-gas reacciones deeven
at 1 bar, formación,
though de tal forma
water cannotque su suma
actually existproduzca
as a gas la
at reacción deseada, requiere
these conditions.
Writing the formation reactions so that their sum yields the desired reaction, requires that
que la reacción de formación
Writing para elreactions
the formation CO2 se escriba a la inversa;
so that their en the
sum yields tal caso el calor
desired de reacción
reaction, requires tiene
that signo
the formation reaction for CO2 be written in reverse; the heat of reaction is then of opposite
contrario a su calor estándar de formación:
the formation reaction for CO 2 be written in reverse; the heat of reaction is then of opposite
sign to its standard heat of formation:
sign to its standard heat of formation:
CO2 (g) → C(s) + O2 (g) ◦ = 393,509 J
�H298
CO2 (g) → C(s) + O2 (g) ◦ = 393,509 J
�H298
1
C(s) + 21O2 (g) → CO(g) ◦ = −110,525 J
�H298
C(s) + 2 O2 (g) → CO(g) ◦ = −110,525 J
�H298
1
H2 (g) + 21O2 (g) → H2 O(g) ◦
H2 (g) + 2 O2 (g) → H2 O(g)
�H298◦ == −241,818
�H298 −241,818 J
J
CO2 (g) + H2 (g) → CO(g) + H2 O(g) �H298 ◦ = 41,166 J

CO2 (g) + H2 (g) → CO(g) + H2 O(g) �H298 ◦ = 41,166 J
The
ElThe meaning
significado of this result is that the enthalpy of 1 mol of COdeplus
CO 1másmol1 of H2deO is greater than que la
meaningde of este resultado
this result es the
is that queenthalpy
la entalpíaof 1demol
1 mol
of CO plus 1 mol mol
of H2 O H O es mayor
is2greater than
the enthalpy of 1 mol of CO2 plus 1 mol of H2 by 41,166 J when each product and reactant is
entalpíathe
de 1enthalpy
mol de CO más of
of 12 mol 1 mol
CO◦ 2de H2 en
plus 41 166
1 mol of HJ2cuando
by 41,166cadaJ producto
when each y reactivo
product and es considerado
reactant is como
taken as the pure gas at 25 ◦C in its ideal-gas state at 1 bar.
el gas puro
takena 25
as °C
the en el estado
pure gas at 25 delCgas in ideal a 1 bar.state at 1 bar.
its ideal-gas
In this example the standard heat of formation of H2 O is available for its hypothetical
En este In ejemplo, se dispone
this example del
the standard calor heat
estándar de formación
of formation of H deOH is2O en su estado
available for itsestándar de gas ideal
hypothetical
ideal-gas standard state at 25 ◦C. One might expect the value2 of the
◦ heat of formation of water
hipotético
to be listed for its actual state as a liquid at 1 bar and 25 ◦C. As a matter of fact, values estado
a 25
ideal-gas °C. Se podría
standard stateesperar
at 25 que C. Oneel valor
mightdel calor
expect de
the formación
value
◦ of thedel agua
heat of se liste
formation para ofsuwater
for real
como un tolíquido
be listed
a 1 for
bar its
y 25actual
°C. Destate as a los
hecho, liquid at 1 para
valores bar and
ambos C. As aestán
25 estados matter
dados of fact,
en la values
tabla for ya que
C.4,
both states are given in Table C.4 because they are both frequently used. This is true for many
both states are given
se usancompounds
con frecuencia. Esto ines Table
cierto C.4 because they are both que
frequently used. This is true for líquidos
many a 25
that normally existpara muchos
as liquids compuestos
at 25 ◦C normalmente
and 1 bar. Cases do arise,existen
however, comoin which
°C y a 1acompounds
bar. that normally exist as liquids 25◦ Csólo
atvalor andestá
1 bar. Cases doelarise, however, incomo
which
value is given only for the standard state as a liquid or as an ideal gas when what is needed isun líqui-
Sin embargo, hay casos en los que un dado para estado estándar
a
do o gasthe valuecuando
ideal is given onlyque for the standard elstate as a liquid or as an ideal
éste gas when what is ejemplo
needed is
other value.loSuppose se necesita
this wereesthe otro
casevalor.
for theSuponga
preceding queexample, fuera el caso
with only del
the standardanterior
the other value. Suppose this were the case for the preceding example, with only the standard
y que sólo
heatseofconociera
formationelofcalorliquidestándar de formación
H O available. del H2then
We would O líquido.
includeAhora debemos
an equation forincluir una ecuación
the physical
heat of formation of liquid H22 O available. We would then include an equation for the physical
para el change
cambio thatfísico que transforma
transforms water el fromaguaitsdesde su estado
standard state asestándar
a liquidcomo
into un
its líquido
standarda su estado
state as anestándar
change that transforms water from its standard state as a liquid into its standard state as an
como un gas gas.
ideal ideal. El enthalpy
The cambio de entalpía
change forpara este proceso
this physical físico
process is es
theladifference
diferenciabetween
entre losthe calores
heats deof forma-
ideal gas. The enthalpy change for this physical process is the difference between the heats of
ción delformation
agua en sus dos
of water estados
in its twoestándar:
standard states:
formation of water in its two standard states:
−241,818 − (−285,830) = 44,012 J
–241 818 −
−241,818 – (–285 830) ==4444,012
(−285,830) 012 J J
This is approximately the latent heat of vaporization of water at 25◦◦C. The sequence of steps
This is approximately
Éste es is
aproximadamente the latent
el calor latenteheat of vaporization
de vaporización delof water
agua a 25at °C.
25 LaC. secuencia
The sequence of steps
de etapas es ahora:
now:
is now: ◦
CO2 (g) → C(s) + O2 (g) �H298 ◦ == 393,509 J
CO2 (g) → C(s) + O2 (g) �H298 393,509 J
C(s) + 121O2 (g) → CO(g) �H298 ◦ = −110,525 J
C(s) + 2 O2 (g) → CO(g) �H298 ◦ = −110,525 J
1
H2 (g) + 21O2 (g) → H2 O(l) �H298 ◦ = −285,830 J
H2 (g) + 2 O2 (g) → H2 O(l) �H298 ◦ = −285,830 J
H2 O(l) → H2 O(g) ◦
H2 O(l) → H2 O(g)
�H298
�H298 ◦ == 44,012
44,012 J
J
CO2 (g) + H2 (g) → CO(g) + H2 O(g) �H298 ◦ = 41,166 J

CO2 (g) + H2 (g) → CO(g) + H2 O(g) �H298 ◦ = 41,166 J
This result is of course in agreement with the original answer.
Por supuesto, este resultado
This result concuerda
is of course con lawith
in agreement respuesta original.
the original answer.
Example
Example 4.5 4.5
Ejemplo 4.5the standard heat at 25◦◦C for the following reaction:
Calculate
Calculate the standard heat at 25 C for the following reaction:
Calcule el calor estándar a 25 4HCl(g)
°C para la
+reacción
O2 (g) →siguiente:
2H2 O(g) + 2Cl2 (g)
4HCl(g) + O2 (g) → 2H2 O(g) + 2Cl2 (g)
4HCl(g) + O2(g) → 2H2O(g) + 2Cl2(g)

4.5. Standard Heat of Combustion 139
4.5. Calor estándar de combustión 139
Solución 4.5
Solution 4.5
Los calores estándar de formación a 298.15 K de la tabla C.4 son:
Standard heats of formation at 298.15 K from Table C.4 are:
HCl(g): –92 307 J H2O(g): –241 818 J
HCl(g): −92,307 J H22O(g): −241,818 J
La combinación siguiente da el resultado deseado:
The following combination gives the desired result:
4HCl(g) → 2H22(g) + 2Cl22(g) ◦◦ = (4)(92,307)

�H298
298
2H22(g) + O22(g) → 2H22O(g) ◦◦ = (2)(−241,818)
�H298
298
4HCl(g) + O22(g) → 2H22O(g) + 2Cl22(g) ◦◦ = −114,408 J

�H298
298
This result is four times the standard heat of combustion of 4HCl(g) (see below).
Este resultado es cuatro veces el calor estándar de combustión de 4HCl(g) (véase más adelante).
4.5 CALOR ESTÁNDAR

4.5 STANDARD DEOF
HEAT COMBUSTIÓN
COMBUSTION
Sólo muy pocas reacciones de formación se pueden llevar a cabo en las condiciones de interés y, por lo tanto,
la información paraformation
Only a few estas reacciones normalmente
reactions can actuallysebe debe determinar
carried out at de
theforma indirecta.
conditions Una clase
of interest, andde reac-
ción que conducedata
therefore de for
manera
thesefácil y pormust
reactions sí misma al be
usually experimento
determinedesindirectly.
la reacción de kind
One combustión, y muchos
of reaction
calores that
estándar de lends
readily formación
itself surgen de los calores
to experiment estándar dereaction,
is the combustion combustión, medidos
and many por calorimetría.
standard heats of Una
reacción de combustión
formation se define
come from comoheats
standard una reacción entre unmeasured
of combustion, elementocalorimetrically.
o compuesto y elAoxígeno para formar
combustion
productos determinados
reaction is defineddeascombustión. Para compuestos
a reaction between an elementorgánicos
or compound que and
están formados
oxygen sólospecified
to form de carbono, hi-
drógenocombustion
y oxígeno,products.
los productos son dióxido
For organic de carbono
compounds madeyup agua, pero elhydrogen,
of carbon, estado deland
agua puedeonly,
oxygen ser vapor o
líquido.the
Laproducts
información siempredioxide
are carbon se basaand
en 1water,
mol debutla the
sustancia
state ofquemada.
the water may be either vapor or
Una reacción
liquid. como
Data are la formación
always based onde n-butano:
1 mol of the substance burned.
A reaction such as the formation of n-butane:
4C(s) + 5H2(g) → C4H10(g)
4C(s) + 5H22(g) → C44H10 10(g)
no puede realizarse en la práctica. De cualquier modo, esta ecuación se obtiene a partir de la combinación de
las reacciones de combustión
is not feasible siguientes:
in practice. However, this equation results from combination of the following
combustion reactions:
4C(s) + 4O22(g) → 4CO22(g) ◦◦ = (4)(−393,509)

�H298
298
5H22(g) + 2 121 O22(g) → 5H22O(l) ◦◦ = (5)(−285,830)
�H298
2 298
4CO22(g) + 5H22O(l) → C44H10 11 ◦◦ = 2,877,396
10(g) + 6 22 O22(g) �H298
298
4C(s) + 5H22(g) → C44H10 ◦◦ = −125,790 J

10(g) �H298
298
This result is the standard heat of formation of n-butane listed in Table C.4.
Este resultado es el calor estándar de formación del n-butano proporcionado en la tabla C.4.

140
140
140 CHAPTER
CHAPTER
CHAPTER 4.
4. Heat
4. Heat
Heat Effects
Effects
Effects
140 140 CAPÍTULO
CHAPTER 4. Efectos
4. Heat Effectstérmicos
◦
4.6 TEMPERATURE DEPENDENCE OF � H ◦◦
4.6 DEPENDENCIA
4.6
4.6 CON LA
TEMPERATURE
TEMPERATURE
4.6 TEMPERATURE TEMPERATURA
DEPENDENCE
DEPENDENCE
DEPENDENCE OF �
� H ◦∆H °
OF �DE
OF H
H
In the
the foregoing
En las secciones anteriores, sections,
los caloresstandard heats of
estándar of reaction
reaction are are discussed for for aa reference
reference temperature
In
In theforegoing
foregoing sections,
sections, standard
standard heats de
heats of reacción
reaction are se analizaron
discussed para
discussed for a una temperatura
reference temperature
temperature de referencia
In the
of foregoing
298.15 K. In sections,
this section standard we heatstheofcalculation
treat reaction areofdiscussed standard for a reference
heats of reaction temperature
at other
other
de 298.15
of K. En esta
of 298.15
298.15 K.K. In sección
In this
this sectionse tratawe
section weel treat
cálculo
treat the thedel calor estándar
calculation
calculation ofof standard de reacción
standard heats aof
heats ofotras
reaction
reactiontemperaturas,
at other pero a
at
of 298.15 K. from
temperatures In this section we
knowledge of treat
the valuethe at calculation
the reference of standard
temperature. heats of reaction at other
partir del conocimiento
temperatures
temperatures from
from delknowledge
valor a la of
knowledge temperatura
ofthethevalue valueat de
atthe referencia.
the reference
referencetemperature. temperature.
temperatures
The general
generalfromchemical
knowledge of the may
reaction valuebeatwritten: the reference temperature.
La reacciónThe
The general químicachemicalgeneral reaction
chemical se puedemay
reaction escribir:
may bebewritten:
written:
The general chemical reaction may be written:
|ν
|ν |A
|ν11|A
|A11 + ++|ν|ν
|ν22|A|A
|A22 + +
+········· → →→ |ν |ν
|ν33|A|A
|A33 + ++|ν |ν
|ν44|A|A
|A44 + ++·········
|ν111|A111 + |ν222|A222 + · · · → |ν333|A333 + |ν444|A444 + · · ·
donde |νwhere
i| es un
where
where |ν
|ν i | is aa stoichiometric
iii||isis a stoichiometric
|νcoeficiente estequiométrico
stoichiometric coefficient
coefficient
coefficient y Ai indicaand
and AAAiiuna
and stands
stands
stands fórmulafor
foraaaquímica.
for chemical
chemicalLas
chemical formula.
formula.especies
formula. The
The
The species
enspecies
la parteon
species on
izquierda

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IntroduccIón a la

00-SmithVanNess Preliminares.ind1 1 8/1/07 12:46:17

misael Flores rojas

MÉXICO • AUCKLAND • BOGOTÁ • BUENOS AIRES • CARACAS • GUATEMALA

00-SmithVanNess Preliminares.ind3 3 8/1/07 12:46:17

Traducción: Efrén Alatorre Miguel

IntroduccIón a la termodInámIca en IngenIería químIca

Prohibida la reproducción total o parcial de esta obra,

DERECHOS RESERVADOS © 2007, respecto a la séptima edición en español por

(ISBN edición anterior: 970-10-3647-6)

Traducido de la séptima edición en inglés de la obra: INTRODUCTION TO CHEMICAL ENGINEERING

Impreso en México Printed in Mexico

00-SmithVanNess Preliminares.ind4 4 8/1/07 12:46:19

2 la PrImera ley y otroS concePtoS báSIcoS 21

3 ProPIedadeS VolumÉtrIcaS de FluIdoS PuroS 64

00-SmithVanNess Preliminares.ind5 5 8/1/07 12:46:19

3.4 Aplicación de las ecuaciones iriales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

4 eFectoS tÉrmIcoS 125

5 la Segunda ley de la termodInámIca 159

6 ProPIedadeS termodInámIcaS de loS FluIdoS 199

7 aPlIcacIoneS de la termodInámIca a loS ProceSoS de FluJo 254

8 generacIón de PotencIa a PartIr del calor 290

9 reFrIgeracIón y lIcueFaccIón 317

00-SmithVanNess Preliminares.ind6 6 8/1/07 12:46:19

9.2 Ciclo de compresión de apor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318

10 equIlIbrIo VaPor/líquIdo: IntroduccIón 338

11 termodInámIca de SolucIoneS: teoría 378

12 termodInámIca de SolucIoneS: aPlIcacIoneS 430

13 equIlIbrIo en reaccIón químIca 483

14 temaS Sobre loS equIlIbrIoS de FaSe 545

00-SmithVanNess Preliminares.ind7 7 8/1/07 12:46:20

14.4 Equilibrio líquido/líquido (ELL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581

15 Análisis termodinámico de procesos 635

16 introducción A lA termodinámicA moleculAr 647

A Factores de conversión y valores de la constante de los gases 677

B propiedades de especies puras 679

c capacidades caloríficas y cambios de propiedad de formación 683

d programas representativos para computadora 688

e tablas de correlación generalizada de lee/Kesler 695

F tablas de vapor 712

G diagramas termodinámicos 788

H método uniFAc 791

i método de newton 798

Índice de autores 803

Índice analítico 807

00-SmithVanNess Preliminares.ind8 8 10/1/07 14:02:01

00-SmithVanNess Preliminares.ind9 9 8/1/07 12:46:21

CP°S Capacidad calorífica estándar media para cálculos de entropía

00-SmithVanNess Preliminares.ind10 10 8/1/07 12:46:22

I Primer potencial de ionización

00-SmithVanNess Preliminares.ind11 11 8/1/07 12:46:22

00-SmithVanNess Preliminares.ind12 12 8/1/07 12:46:23

Ws Trabajo de flecha para procesos de flujo

E Denota una propiedad termodinámica de exceso

α Función en las ecuaciones del estado cúbicas (tabla 3 .1, p .98)

00-SmithVanNess Preliminares.ind13 13 8/1/07 12:46:23

 Profundidad del pozo en la función de potencial intermolecular

c Como subíndice, denota un olumen de control

00-SmithVanNess Preliminares.ind14 14 8/1/07 12:46:24

00-SmithVanNess Preliminares.ind15 15 10/1/07 14:03:43

Alejandro J. Guzmán Gómez, Universidad Nacional Autónoma de México, FES Zaragoza

00-SmithVanNess Preliminares.ind16 16 10/1/07 14:04:50

1.1 EL PANORAMA DE LA TERMODINÁMICA

3.4 Aplicación de las ecuaciones iriales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

9.2 Ciclo de compresión de apor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318

c Como subíndice, denota un olumen de control

Se presenta un tratamiento elemental en el capítulo 6.

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0−5 femto f 0 hecto h

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3 Anders Celsius, astrónomo sueco (70744).

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