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Chapter One

Review of Diffusion and Mass Transfer Theories


1. Introduction:
When a system contains two or more components whose concentrations vary from point to point, there is a natural tendency for mass to be transferred, minimizing the concentration differences within the system and moving it towards equilibrium.

(a) Mass Transfer:


Transport of one component from a region of high concentration to a region of low concentration.

(b) Dail !ife "#a$ples:


Numerous of our daily activities involve mass transfer phenomena such as: 1. iffusion of perfume through air. !. iffusion of coffee smell through air. ". issolution and diffusion of sugar throughout a cup of coffee. #. $aundry hanging under the sun during a breezy day.

(c) Industrial "#a$ples:


%ass Transfer plays an important role in many industrial processes. & group of operations for separating the components of mi'tures is based on the transfer of material from one homogeneous

phase to another. These methods (i.e. %ass Transfer )perations* include +as &bsorption, istillation, ,umidification, $iquid -'traction, &dsorption, and %embrane .eparations.

%ote:
The driving force for mass transfer in these operations is a concentration gradient.

&. Diffusivit : (a) 'ic()s !aw:


/lu' of %ass transfer by molecular diffusion is proportional to concentration gradient.

na
Where

C a X

na = - D
g mole cm ! . sec

C a X

na: /lu' of %ass transfer,


C a X

D: iffusivity coefficient and its function in temperature and pressure, : 0oncentration gradient,
g mole 1 cm " cm

cm! sec

%otes:

1. /ic23s law proportionality factor 4 5 is 2nown as the diffusion coefficient or diffusivity. 6ts fundamental concept is identical to the other transport properties as 2inematic viscosity (718* and thermal diffusivity 9. !. The mass diffusivity is usually reported in units of cm !1s or m!1s. The diffusion coefficient depends upon the pressure and temperature.

". -'perimental values for the diffusivities of gases, liquids, and solids are tabulated. #. ue to the molecules mobility, the diffusivities are generally higher for gases (: ;.<=1; >< to 1.;=1;>< m!1s* than for liquids (: 1;>1; to 1;>? m!1s* which are higher than the values reported for solids (: 1;>1# to 1;>1; m!1s*. <. 6n the absence of e'perimental data, semi>theoretical e'pressions have been developed which give appro'imated values, which sometimes as valid as e'perimental values due to the difficulties encountered in their measurements.

'or ideal *ases:


.ince PV = nRT 0@
P RT

P=

n RT V

P = C RT

where

n =C V

na = - (D/RT)(PA / x)

(b) Calculation of Diffusivit coefficient +D, fro$ other ph sical properties:


(i) -ases: -illiland Correlation:
D AB = ;.;;#"T 1.< 11 " 11 " ! P (V A +VB * 1 1 + M A MB
cm " gmole cm ! sec

T: A

P: atm

VA, VB:

MA, MB: molecular weight

"#a$ple:
"

0alculate the mass diffusivity of mi'ture 0) ! B )! at ; o0 and 1 atm using +illiland 0orrelation. .tudy the effect of temperature and pressure as: (a* 6ncrease the temperature from ; to 1;; o0 in 1; o0 increment at constant pressure. (b* 6ncrease the pressure from 1 to 1; atm in 1 atm increment at constant temperature. When diffusion 4D15 is 2nown at T1 B P1, D!" can be calculated at T! B P! from:
P1 T ! D ! = D1 P ! T 1
1 .<

.irschfelder et al. Correlation: ,irschfelder et al. (1?#?* used the $ennard>Cones potential to evaluate the influence of intermolecular forces, presented an equation for the diffusion coefficient for gas pairs of non>polar and non>reacting molecules as: 1.< ;.< G&D! H * &D @ (;.;;!EE T * 1 (F %&D Where %&D @ ! (11 %& I 11 %D*>1 ! %& B %D : molecular weight of & B D &D : diffusion coefficient, cm 1s T : temperature, A F : pressure, bar o G&D : collision diameter, & H : diffusion collision integral, dimensionless H is a function of temperature and intermolecular potential field for & and D molecules. H is usually tabulated as a function of T=. T= @ ( 2 T 1 J&D*

Where

2 : Doltzmann constant (1."K=1;>1E erg1A* J&D : energy of molecular interaction for & and D erg

& very accurate appro'imation of H can be obtained from (Neufield et al., 1?L!* as: H @ (a 1 T= b* I (c 1 e'p d T=* I (e 1 e'p f T=* I (g 1 e'p h T=* Where a @ 1.;E;# b @ ;.1<E1 c @ ;.1?"; d @ ;.#LE# e @ 1.;"<? f @ 1.<!?? g @ 1.LE#L h @ ".K?#1 /or a binary system composed of non>polar molecular pairs: G&D @ (G& I GD* 1 ! J&D @ (J& JD *;.<

<

(ii) !i/uids:
A: solute B: solvent @ (?.?E = 1;>1E T* 1 (7D M&;."""* @ O11L." = 1;>1K (P %D*;.< TQ 1 (7D M&;.E* for VA N ;.< m" 1 2 mol for VA R ;.< m" 1 2 mol

0to(es 1 "inestein correlation:


&D

2il(e 1 Chan*:
&D

Where DAB: diffusivity of 4A5 in very dilute solution in solvent B, m!1sec MB: %olecular weight of solvent T: temperature, A #B: solvent viscosity, 2g 1 m . s VA: solute molal volume, m"12mol P : solvent association factor (,!) is !.!E, 0,"), is 1.?, 0!,<), is 1.<, etcS*

(c) 0tead state one3di$ensional diffusion:

n& @ >

( d 0& 1 d '*

4. Mechanis$ of Mass Transfer:


There are two types: (a* %olecular iffusion (b* 0onvective (as in mi'ing*

When a mi'ture of gases or liquids is contained such that there concentration gradient of one or more of the constituents across the system, there will be a mass transfer on a microscopic level as a result of diffusion from regions of high concentration to regions of low concentration. %ass is also transported from one place to another due to convection in the flow system. This type of mass transfer occurs on a macroscopic level.

(a) Molecular Diffusion:


(i* -quimole > counter iffusion (ii* iffusion of 4&5 in non> diffusing of 4D5

(i) "/ui$ole counter Diffusion of +5, and +6,:


1 mole of 4&5 A ? 1 mole of 4D5 B

n A = n B

nA =

D AB $PA RT $x

and

$C A $x D $PB n B = BA RT $x n A = D

)ne direction

since
P = PA + PB

Then

$PA $PB + =; $x $x D $PA n A = n B n B = BA RT $x

$PA $P = B $x $x D $PA D $PA AB = BA RT $x RT $x

D AB = D BA = D

Conclusion: iffusivity does not depend on concentration.


nA =
nA =

D $PA RT $x
PA1 PA! x x 1 !

n A $x =
1

D RT

$P
1

n A ( x ! x1 ) =

D PA! PA1 RT

D RT

C C A! = D A1 x x 1 !

"#a$ple: & large tan2 filled with a mi'ture of gases &BD at 1 atm and "; o0 is connected to another large tan2 filled with different concentration at 1 atm and "; o0. The connection between the tan2s is ! inch 6. . and 1! ft long. 0alculate the steady state mass transfer rate of gas &

1;

through the tube when the concentration of & in one tan2 is ?; mole T and in the other is < mole T. Ta2e the diffusivity equals to ;.#!< cm!1sec.

(ii) Diffusion of +5, in non3Diffusin* of +6,:


+as 4&5 dissolves in the liquid, however 4D5 does not dissolve in the liquid. n& @ (> nD @ (> .ince 1 U T* d F& 1 d V 1 U T* d FD 1 d V @ ( 1 U T* d F& 1 d V

Liquid

Gas (& and D* nD & (&ID* Dul2 flow


D

n&

(nD* for bul2 flow @ > (nD* for molecular diffusion 1 U T* d F& 1 d V

(nD* for bul2 flow @ (>

.ince (n& bul2 flow 1 nD bul2 flow* @ (F& 1 FD* (n&*bul2 flow @ (> 1UT* (d F&1d V* (F&1FD* (n&*total @ n& I (n&*bul2 flow @ (> 1UT* (d F&1d V* (1 I F&1FD* @ (> 1UT* (d F&1d V* (F&I FD* 1FD (n&*total @ ( 1UT* (F 1 pDm* (F&1 W F&!* 1 (V! W V1*

11

pDm @ (FD! W FD1* 1 $n (pD! 1 pD1* (n&*total @ (0 1 0Dm* (0&1 W 0&!* 1 (V! W V1*

Co$parison between "/ui$ole and 7ni3direction:


6tem /lu' Dul2 flow &pplication -quimole
D PA1 PA ! RT x ! x1

Xni>direction
D P PA1 PA ! RT PBM x ! x1

.maller Not available distillation

$arger &vailable &bsorption -'traction

(b) Convective Mass Transfer:


This mode of transfer involves both the transport properties and the dynamic characteristics of the flowing fluid. The controlling resistance to convective mass transfer is often a thin film of fluid.

1!

6n the turbulent region, particles of fluid no longer flow in the orderly manner found in the laminar sub>layer. 6nstead, large portions of the fluid (called eddies* move rapidly from one position to another. These eddies contribute considerably to the mass transfer process. Decause the eddy motion is rapid, mass transfer in the turbulent region is much more rapid than laminar conditions. This situation can be modeled in terms of mass transfer coefficient. $C a n a = ( D + % D )
$x

where na : /lu' of mass transfer D: iffusivity %D: eddy diffusivity and depend on degree of turbulence
D + %D na = x x C a1 C a! 1 ! D + % D CT na = C a1 C a ! x x ! 1 C BM

-quimole diffusion

Xni>direction diffusion
n a = & C a1 C a!

the above equations can be written as: where &: mass transfer coefficient,
D + %D = x x 1 ! for
cm sec .

-quimole diffusion

1"

D + %D = x x 1 !

CT C BM

for Xni>direction diffusion

& is function in D: diffusivity, V: velocity, ': density, #: viscosity, and (: linear dimension

8. Di$ensional 5nal sis:


%ost practically useful mass transfer situations involve turbulent flow, and for these situations, it is generally not possible to compute mass transfer coefficients from theoretical conditions. 6nstead, we must rely on e'perimental data. The data are limited in scope w.r.t. circumstances and situations as well as to range of fluid properties. Therefore, it is important to be able to e'tend their applicability to conditions not covered e'perimentally. & very useful procedure is dimensional analysis. 6n dimensional analysis, the significant variables in a given situation are grouped into dimensionless parameters which are less than the original variables. Dy combining the variables into a smaller number of dimensionless parameters, the wor2 of e'perimental data is considerably reduced. /rom dimensional analysis, we found that: .h @ a Ueb .cc Where: .h: .herwood number, 2 $1 Ue: Ueynolds number, 8 v $17 .c: .chmidt number, 7 1 8

"#a$ple:

1#

0alculate the mass transfer coefficient for the absorption of .)! from a dilute mi'ture with air in wetted wall column using the given e'perimental data: 6. . @ !< mm Mgas @ !.! m1sec Tgas @ !?" A 7gas @ 1.LK (1;*>< 2g1m.sec 8gas @ 1.!! 2g1m" @ 1!.!(1;*>E m!1sec .h @ ;.;!" Ue;.K< .c;.##

1<