UNIVERSIDAD SIMÓN BOLÍVAR Departamento de Termodinámica y Fenómenos de Transferencia Materia : Profesor : Capítulo :
Fenómenos de Transporte I (TF-1221) M. Aguilera - D. González - A. López - L. Matamoros - C. Oronel 1
ESTIMACION DE PROPIEDADES DE TRANSPORTE: VISCOSIDADES
Realizado por: Profs. María E. Aguilera, Aguilera, Dosinda GonzálezGonzález- Mendizabal Aura López de Ramos, Ramos, Luis Matamoros Matamoros y César Oronel
Sartenejas, Septiembre del 2000
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INDICE Pág. 1.
Introducción
3
2.
Objetivo
4
3.
Unidades de viscosidad
5
4.
Correlaciones para estimar viscosidades 4.1 Gases 4.2 Líquidos
6 6 7
5.
Bibliografía
9
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1. INTRODUCCIÓN
El curso de Fenómenos de Transporte I (TF1221) está diseñado para formar en el área de Fluidos a los estudiantes de las carreras de Ingeniería Química, Materiales y Producción.
Esta guía presenta el resultado de una revisión bibliográfica exhaustiva sobre los diferentes métodos que están reportados en la literatura especializada para calcular el coeficiente de viscosidad dinámica o cinemática de un fluido.
En el curso de Fenómenos de Transporte I, el profesor de la materia dedicará la primera parte del curso en ilustrar cómo se utiliza en forma general esta guía; sin embargo, el estudiante deberá leerla con detenimiento para familiarizarse con las diferentes técnicas de cálculo: lectura de gráficas, nomogramas y tablas o uso de correlaciones. Al final de esta guía el estudiante encontrará algunos ejercicios propuestos que serán de mucha utilidad en el proceso de aprendizaje de este tema.
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2. OBJETIVO Seleccionar el método adecuado para estimar la viscosidad dinámica y cinemática de ciertos fluidos. Una vez seleccionado el método, calcular la viscosidad y estimar el error cometido en el cálculo.
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3. UNIDADES DE VISCOSIDAD
1 P = 1 poise 2 1 P = 1 dyn.s/cm 1 P = 1 g/s.cm 2 1 P = 10 cP 6 1 P = 10 µP -2 1 P = 6,72 . 10 lbm/ft.s -3 2 1 P = 2,09.10 lbf.s/ft -1 1 P = 10 Pa.s
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4. CORRELACIONES PARA ESTIMAR VISCOSIDADES 4.1 Gases -
Ecuación de Chapman-Enskog: Válida para gases poco densos (bajas presiones):
µ = 2,6693 ⋅ 10 −5 ⋅
M⋅T
σ2 ⋅ Ωµ
donde: µ = viscosidad (P) M = peso molecular T = temperatura (K) o
σ = diámetro de colisión, característico de cada molécula en A (10-8 cm) Ωµ = función integral de colisión σ y Ωµ se determinan de acuerdo al siguiente criterio: a) Gases polares: potencial de Stockmayer (Tablas 1 y 2) b) Gases no polares: potencial de Lennard-Jones (Tablas 3 y 4)
-
Mezclas de Gases: Ecuación de Wilke (error ≈ 2%) n
µm =
∑ i =1
Xi
⋅ µi
n
∑ X j ⋅ φij
j=1 1/ 2 −1 / 2 µ M 1 φ ij = ⋅ 1 + i ⋅ 1 + i µ j 8 M j
φ ji =
1/ 4
M j ⋅ M i
2
µ j M i ⋅ ⋅φ µ i M j ij
donde: n = número de especies químicas existentes en la mezcla. Xi, X j = fracciones molares de las especies i,j.
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-
Variación de la viscosidad de los gases con la temperatura 0,5 µ T = Por cinética de los gases: µ o T o Ley de la Potencia:
Para el aire:
µ µ o
µ T = µ o To 0 , 76 T = T o
n
n= constante
intervalo de temperatura de 300 a
900 ºR.
µ o (T / To ) 3 / 2 (To + S) Ley de Sutherland: µ = T +S -
S=constante.
Variación de la viscosidad de los gases con la presión
La Ecuación de Chapman-Enskog es valida para él calculo de viscosidades a bajas presiones, por lo cual no es recomendable utilizarla a presiones elevadas. En este caso la viscosidad se obtendrá por las Figuras 1 y 2. donde:
Pc = Presión crítica Tc = Temperatura crítica Pr = Presión reducida Tr = Temperatura reducida µο = Viscosidad a bajas presiones (puede ser un dato experimental o un valor calculado a partir de una ecuación de la teoría de los gases o nomogramas (Figura 1)) µ = Viscosidad a la presión y temperatura deseada µc = Viscosidad crítica, la cual se obtendrá por las siguientes ecuaciones
µ c = 61,6 ⋅ (M ⋅ Tc )1 2 ⋅ Vc −2 3
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n
Tcm
=
∑
x i ⋅ Tci
i =1 n
µ cm =
∑
xi
⋅ µ ci
i =1
4.2 Líquidos - Ecuación de Eyring: (Válida para líquidos líquidos no polares, error ≈ 25%) T µ = ξ ⋅ h ⋅ exp 3,8 ⋅ b T donde:
µ = viscosidad (P)
-27
h = constante de Planck = 6,624.10 erg.s T b = temperatura normal de ebullición (K) T = temperatura (K) N ξ = = N ⋅ ρ V 23 -1 con N = Nº de Avogadro = 6,023.10 (gmol) 3 V = volumen molar (cm /gmol) ρ = densidad molar (gmol/cm3) - Ecuación de Gambill: (Para líquidos puros, orgánicos e inorgánicos a T b)
µ b = 0,324 ⋅ ρ b1/ 2 donde el subíndice b indica a la temperatura normal de ebullición.
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µ = A ⋅ e − BT A y Β son constantes que se encuentran al ajustar datos a una curva para un líquido particular. - Mezcla de Líquidos:
µ1m/ 3 = x1 ⋅ µ11/ 3 + x 2 ⋅ µ12/ 3 x = x = fracciones molares. Para la determinación de la viscosidad de líquidos se presenta un nomograma aplicable a presiones cercanas a la atmosférica (figura 2), cuyas coordenadas se encuentran en la tabla 7.
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5. ANEXOS RELACIONES DE PRESION, VOLUMEN Y TEMPERATURA
Tabla 1. Parámetros del Potencial de Stockmayer
H2O NH3 HCl HBr HI SO2 H2S NOCl CHCl3 CH2Cl2 CH3Cl CH3Br C2H5Cl CH3OH C2H5OH n-C3H7OH i-C3H7OH (CH3)2O (C2H5)2O (CH3)2CO CH3COOCH3 CH3COOC2H5 CH3 NO2
Notas:
Momento Dipolar µ , debyes 1,85 1,47 1,08 0,80 0,42 1,63 0,92 1,83 1,013 1,57 1,87 1,80 2,03 1,70 1,69 1,69 1,69 1,30 1,15 1,20 1,72 1,78 2,15
σ , A
ε O /k , K
bO,, cm3/gmol
t *
δ max max
2,52 3,15 3,36 3,41 4,13 4,04 3,49 3,53 5,31 4,52 3,94 4,25 4,45 3,69 4,31 4,71 4,64 4,21 5,49 3,82 5,04 5,24 4,16
775 358 328 417 313 347 343 690 355 483 414 382 423 417 431 495 518 432 362 428 418 499 290
20,2 39,5 47,8 50,0 88,9 83,2 53,6 55,5 189 117 77,2 96,9 111 63,4 101 132 126 94,2 209 209 70,1 162 182 90,8
0,7 0,5 0,24 0,10 0,20 0,30 0,15 0,3 0,05 0,14 0,35 0,3 0,3 0,35 0,2 0,14 0,14 0,13 0,06 0,9 0,14 0,11 1,6
1,0 0,7 0,34 0,14 0,029 0,42 0,21 0,4 0,07 0,2 0,5 0,4 0,4 0,4 0,5 0,3 0,2 0,2 0,19 0,08 1,3 0,2 0,16 2,3
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Tabla 2. Integrales de Colisión Ωv para viscosidad como se calcularon con el empleo del potencial de Stockmayer. 2 3 δ = (Momento dipolar) /2εoσ * T = kT/εo *
0
0,25
0,50
0,75
1,0
1,5
2,0
2,5
4,1005 3,2626 2,8399 2,5310 2,2837 2,0838 1,9220 1,7902 1,6823 1,5929 1,4551 1,3551 1,2800 1,2219 1,1757 1,0933 1,0388 0,99963 0,96988 0,92676 0,89616 0,87272 0,85379 0,83795 0,82435 0,80184 0,78363 0,76834 0,75518
4,266 3,305 2,836 2,522 2,277 2,081 1,924 1,795 1,689 1,601 1,465 1,365 1,289 1,231 1,184 1,100 1,044 1,004 0,9732 0,9291 0,8979 0,8741 0,8549 0,8388 0,8251 0,8024 0,7840 0,7687 0,7554
4,833 3,516 2,936 2,586 2,329 2,130 1,970 1,840 1,733 1,644 1,504 1,400 1,321 1,259 1,259 1,209 1,119 1,059 1,016 0,9830 0,9369 0,9030 0,8780 0,8580 0,8414 0,8273 0,8039 0,7852 0,7696 0,7562
5,742 5,74 2 3,914 3,914 3,168 3,168 2,749 2,749 2,460 2,460 2,243 2,243 2,072 2,072 1,934 1,934 1,820 1,820 1,725 1,725 1,574 1,574 1,461 1,461 1,374 1,374 1,306 1,251 1,251 1,150 1,150 1,083 1,083 1,035 0,9991 0,9473 0,9114 0,8845 0,8632 0,8456 0,8308 0,8308 0,8065 0,8065 0,7872 0,7872 0,7712 0,7712 0,7575 0,7575
6,729 4,433 3,511 3,004 2,665 2,417 2,225 2,070 1,944 1,838 1,670 1,544 1,447 1,370 1,370 1,307 1,193 1,117 1,062 1,021 0,9628 0,9230 0,8935 0,8703 0,8515 0,8356 0,8101 0,7899 0,7733 0,7592
8,624 5,570 4,329 3,640 3,187 2,862 2,614 2,417 2,258 2,124 1,913 1,754 1,630 1,532 1,451 1,304 1,204 1,133 1,079 1,005 0,9545 0,9181 0,9181 0,8901 0,8901 0,8678 0,8678 0,8493 0,8201 0,7976 0,7794 0,7642
10,34 10,34 6,637 6,637 5,126 5,126 4,282 4,282 3,727 3,727 3,329 3,329 3,028 3,028 2,788 2,788 2,596 2,596 2,435 2,435 2,181 2,181 1,989 1,989 1,838 1,838 1,718 1,718 1,618 1,618 1,435 1,435 1,310 1,310 1,220 1,153 1,058 0,9955 0,9505 0,9164 0,8895 0,8676 0,8676 0,8337 0,8337 0,8081 0,8081 0,7878 0,7878 0,7711 0,7711
11,89 7,618 5,874 4,895 4,249 3,786 3,435 3,156 2,933 2,746 2,451 2,228 2,053 1912 1,795 1,578 1,428 1,319 1,236 1,121 1,044 0,9893 0,9482 0,9160 0,8901 0,8504 0,8212 0,7983 0,7797
T
0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0 1,2 1,4 1,6 1,8 2,0 2,5 3,0 3,5 4,0 5,0 6,0 7,0 8,0 9,0 10,0 12,0 14,0 16,0 18,0
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Tabla 3. Potenciales de Lennard-Jones determinados a partir de datos de viscosidad Molécula
A He Kr Ne Xe Aire AsH3 BCl3 BF3 B(OCH2)3 Br 2 CCl4 CF4 CHCl3 CH2Cl2 CH3Br CH3Cl CH3OH CH4 CO
Compuesto Argón Helio Criptón Neón Xenón Aire Arsina Cloruro de Boro Fluoruro de Boro Borato Metílico Bromo Tetracloruro de Carbono Tetrafluoruro de Carbono Cloroformo Cloruro de metileno Bromuro de metilo Cloruro de Metilo Metanol Metano Monóxido de
bo, cm3/gmol 46,08 20,95 61,62 28,30 83,66 64,50 89,88 170,1 93,35 210,3 100,1 265,5
σ, A
εo/k, °K
3,542 2,551 3,655 2,820 4,047 3,711 4,145 5,127 4,198 5,503 4,296 5,947
93,3 10,22 178,9 32,8 231,0 78,6 259,8 337,7 186,3 396,7 507,9 322,7
127,9
4,662
134,0
197,5 148,3 88,14 92,31 60,17 66,98 63,41
5,389 4,898 4,118 4,182 3,626 3,758 3,690
340,2 356,3 449,2 350 481,8 148,6 91,7
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Potenciales de Lennard-Jones determinados a partir de datos de viscosidad (Continuación Tabla 3) Molécula Compuesto bo, cm3/gmol σ, A εo/k, °K CH3COOCH 3 n-C4H10 Iso-C4H10 C2H5OC2H5 CH3COOC2H5 n-C2H12 C(CH3)4 C6H6 C6H12 n-C6H14 Cl2 F2 HBr HCN HCl HF HI H2 H2O H2O2 H2S Hg HgBr 2 HgCl2
Acetato metílico n-Butano Isobutano Eter etílico Acetato etílico n-Pentano 2,2-Dimetilpropano Benceno Ciclohexano n-hexano Cloro Fluor Acido bromhídrico Acido cianhídrico Acido clorhídrico Acido fluorhídrico Acido yodhídrico Hidrógeno Agua Peróxido de hidrógeno Acido sulfídrico Mercurio Bromuro mercúrico Cloruro mercúrico
151,8 130,0 185,6 231,0 178,0 244,2 340,9 193,2 298,2 265,7 94,65 47,75 47,58 60,37 46,98 39,37 94,24 28,51 23,25 93,24 60,02 33,03 165,5 118,9
4,936 4,687 5,278 5,678 5,205 5,784 6,464 5,349 6,182 5,949 4,217 3,357 3,353 3,630 3,339 3,148 4,211 2,827 2,641 4,196 3,623 2,969 5,080 4,550
469,8 531,4 330,1 313,8 521,3 341,1 193,4 412,3 297,1 399,3 316,0 112,6 449 569,1 344,7 330 288,7 59,7 809,1 289,3 301,1 750 686,2 750
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Tabla 4. Valores de la integral de colisión Ωv para la viscosidad y de la función de temperatura y viscosidad f viscosidad f 1(kT/ ε ε o ) Basados en el potencial de Lennard-Jones. T* = kT/εo 0,30 0,35 0,40 0,45 0,50 0,55 0,60 0,65 0,70 0,75 0,80 0,85 0,90 0,95 1,00 1,05 1,10 1,15 1,20 1,25
Ωv
f 1(kT/εo)
kT/εo
Ωv
f 1(kT/εo)
kT/εo
Ωv
f 1(kT/εo)
2,785 2,628 2,492 2,368 2,257 2,156 2,065 1,982 1,908 1,841 1,780 1,725 1,675 1,629 1,587 1,549 1,514 1,482 1,452 1,424
0,1969 0,2252 0,2540 0,2834 0,3134 0,3440 0,3751 0,4066 0,4384 0,4704 0,5025 0,5346 0,5566 0,5985 0,6302 0,6616 0,6928 0,7237 0,7544 0,7849
1,65 1,70 1,75 1,80 1,85 1,90 1,95 2,00 2,10 2,20 2,30 2,40 2,50 2,60 2,70 2,80 2,90 3,00 3,10 3,20
1,264 1,248 1,234 1,221 1,209 1,197 1,186 1,175 1,156 1,138 1,122 1,107 1,093 1,081 1,069 1,058 1,048 1,039 1,030 1,022
1,0174 1,0453 1,0729 1,0999 1,1264 1,1529 1,1790 1,2048 1,2558 1,3057 1,3547 1,4028 1,4501 1,4962 1,5417 1,5861 1,6298 1,6728 1,7154 1,7573
4,0 4,1 4,2 4,3 4,4 4,5 4,6 4,7 4,8 4,9 5,0 6,0 7,0 8,0 9,0 10 20 30 40 50
0,9700 0,9649 0,9600 0,9553 0,9507 0,9464 0,9422 0,9382 0,9343 0,9305 0,9269 0,8963 0,8727 0,8538 0,8379 0,8242 0,7432 0,7005 0,6718 0,6504
2,0719 2,1090 2,1457 2,1820 2,2180 2,2536 2,2888 2,3237 2,3583 2,3926 2,4264 2,751 3,053 3,337 3,607 3,866 6,063 7,880 9,488 10,958
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Tabla 5.1. Viscosidades de fracciones de petróleo Para rangos de temperatura empleados en el texto las coordenadas deberán usarse con la figura 2: X 14,4 14,0 11,6 10,0 10,3 10,0
75°API gasolina natural 56°API gasolina 42°API kerosén 35°API destilado 34°API crudo continental 28°API gas-oil
Y 6,4 10,5 16,0 20,0 21,3 23,6
Tabla 5.2. Viscosidades de aceites animales y vegetales (figura 2)
Almendra Coco Hígado de bacalao Algodón Lardo Linaza Mostaza Aceite de manitas Oliva
Acido No. 2,85 0,01 ---14,24 3,39 3,42 ---18,35 ----
Grav.Esp. 20/4°C 0,9188 0,9226 0,9138 0,9187 0,9138 0,9297 0,9237 0,9158 0,9158
X
Y
6,9 6,9 7,7 7,0 7,0 6,8 7,0 6,5 6,6
28,2 26,9 27,7 28,0 28,2 27,5 28,5 28,0 28,3
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Tabla 6. Propiedades Críticas de diferentes compuestos. Compound Acetileno Benceno 1,3-Butadieno Clorobenceno Ciclohexano Diclorodifluorometano(freon-12) Diclorodifluorometano (freon-12) Dietil eter Etanol Oxido de etileno Metanol Cloruro de metilo Methyl ethyl Ketone Tolueno Triclorofluorometano (freon-11) Triclorotrifluoroetano Triclorotrifluoroetano (freon-113) Gases elementales Argon Bromo Cloro Helium Hidrógeno
TC (K) 308.3 562.1 425.0 632.4 553.4 385.0 467.7 516.2 469 512.6 416.2 535.6 591.7 471.2 487.2
PC (atm) 60.6 48.3 42.7 44.6 40.2 40.7 35.9 63 71 79.9 65.9 41 40.6 43.5 33.7
VC (cm3/gmol) 113 259 221 308 308 217 280 167 140 118 139 267 316 248 304
ZC 0.271 0.271 0.270 0.265 0.273 0.279 0.262 0.248 0.259 0.224 0.268 0.249 0.264 0.279 0.257
W 0.184 0.210 0.181 0.255 0.214 0.158 0.283 0.635 0.157 0.556 0.158 0.337 0.257 0.295 0.249
150.8 584 417 5.2 33.2
48.1 102 76 2.24 12.8
74.9 127 124 57.3 65
0.291 0.270 0.275 0.301 0.305
0.0 0.132 0.074 0.0 0.0
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Continuación de la tabla 6. Compuesto Cianuro de hidrógeno Sulfuro de hidrógeno Oxido nítrico (NO) Oxido nitroso (N 2O) Azufre Dióxido de azufre Trióxido de azufre Agua Parafinas: Metano Etano
TC (K) 456.8 373.2 180 309.6 1314 430.8 491 674.1
PC (atm) 53.2 88.2 64 71.5 116 77.8 81 217.6
VC (cm3/gmol) 139 98.5 58 97.4 …. 122 130 56
ZC 0.197 0.284 0.25 0.274 …. 0.268 0.26 0.23
W 0.399 0.100 0.600 0.160 0.070 0.273 0.510 0.348
190.6 305.4
45.4 48.2
99 148
0.288 0.285
0.007 0.091
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Tabla 7. Viscosidades de Líquidos (para usarse como coordenadas de la figura 2) Liquido Acetaldehído Acetato de Amilo Acetato de Butilo Acetato de Etilo Acetato de Metilo Acetato de Vinilo Acetona 100% Acetona 35% Agua Acido Acético 100% Acido Acético 70% Acido Butírico Acido Clorosulfónico
X 15.2 11.8 12.3 13.7 14.2 14.0 14.5 7.9 10.2 12.1 9.5 12.1 11.2
Y 4.8 12.5 11.0 9.1 8.2 8.8 7.2 15.0 13.0 14.2 17.0 15.3 18.1
Liquido Cloruro Estánico Cresol, meta Dibromoetano Dicloroetano Diclorometano Difenilo Eter Etílico Etilbenceno Etilenglicol Fenol Formiato de Etilo Freon 11 Freon 12
X 13.5 2.5 12.7 13.2 14.6 12.0 14.5 13.2 6.0 6.9 14.2 14.4 16.8
Y 12.8 20.8 15.8 12.2 8.9 18.3 5.3 11.5 23.6 20.8 8.4 9.0 5.6
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Continuación de la tabla 7. Clorotolueno. Orto Clorotolueno, meta Clorotolueno, para Cloruro de Etilo Cloruro de Metilo Cloruro de Propilo Cloruro de Sulfurilo
13.0 13.3 13.3 14.8 15.0 14.4 15.2
13.3 12.5 12.5 6.0 3.8 7.5 12.4
Tricloruro de Fósforo Tricloroetileno Tricloroetileno Tolueno Turpentina Xileno, orto Xileno, meta Xileno, para
16.2 14.8 13.7 11.5 13.5 13.9 13.9
10.9 10.5 10.4 14.9 12.1 12.1 10.9
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Tabla 8. Viscosidades de Gases (para usarse como coordenadas de la figura 1) Gas Acetato de Etilo Acetona Acetileno Acido acético Agua Aire Alcohol Etílico Alcohol Metílico Alcohol Propílico Amoniaco Argón Benceno Bromo
X 8.5 8.9 9.8 7.7 8.0 11.0 9.2 8.5 8.4 8.4 10.5 8.5 8.9
Y 13.2 13.0 14.9 14.3 16.0 20.0 14.2 15.6 13.4 16.0 22.4 13.2 19.2
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Continuación de la tabla 8. Pentano Propano Propileno Sulfuro de Hidrógeno Tolueno 2, 3, 3-trimetilbutano 3-trimetilbutano Xenón
7.0 9.7 9.0 8.6 8.6 9.5 9.3
12.8 12.9 13.8 18.0 12.4 10.5 23.0
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6.
•
BIBLIOGRAFIA
Perry-Chilton, "Chemical Engineer's Handbook", 5º edición, Mc Graw Hill, capítulo 3. Reid, R. y T. Sherwood, "Propiedades de los gases y líquidos: su estimación y