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70  Chapter 3  Mass Transfer and Diffusion


                  N2 over the length of the tube,                    The factor (1 - xA) accounts for the bulk-flow effect. For a
                                                                     mixture dilute in  A,  the bulk-flow  effect is  negligible  or
                                                                     small. In mixtures more concentrated in A, the bulk-flow
                                                                     effect can  be  appreciable. For  example, in  an  equimolar
                                                                     mixture of  A and B, (1 - xA) = 0.5 and the molar  mass-
                                                                     transfer flux of A is twice the ordinary molecular-diffusion
                        = 9.23 x   molls   in the positive z-direction
                                                                     flux.
                     nH2 = 9.23 x   moVs   in the negative z-direction
                                                                        For the stagnant conlponent, B, (3-13) becomes
                  (b)  For equimolar counterdiffusion, the molar-average velocity of
                  the mixture,  UM, is 0. Therefore, from (3-9), species velocities are
                  equal to species diffusion velocities. Thus,





                                                                     Thus, the bulk-flow flux  of  B  is equal but  opposite to its
                                                                                                                        I
                               0.0287                                diffusion flux.
                             --        in the positive z-direction
                             -
                                                                        At quasi-steady-state conditions, that is, with no accumu-
                                xN2
                                                                     lation, and with constant molar density, (3-27) becomes in   1
                  Similarly,                                         integral form:                                     I
                              0.0287
                            = -
                                       in the negative z-direction
                                XH2
                  Thus,  species  velocities  depend  on  species  mole  fractions,  as                                  I
                                                                     which upon integration yields
                  follows:                                                                                               I
                                                           ,
                       Z, cm     XN1    -%I    VN* , CII~/S VH~ cm/s
                      0 (end 1)   0.800   0.200   0.035 1   -0.1435
                      5         0.617   0.383   0.0465   -0.0749
                                                                     Rearrangement to give the mole-fraction variation as a func-
                      10        0.433   0.567   0.0663   -0.0506
                                                                     tion of z yields
                      15 (end 2)   0.250   0.750   0.1148   -0.0383
                  Note that species velocities vary across the length of the connect-   XA  = 1 - (1 - XA~) exp [NA2biZ1)]   (3-32)
                  ing tube, but at any location, z, VM = 0. For example, at z = 10 cm,
                  from (3-8),
                                                                     Thus, as shown in Figure 3.lb, the mole fractions are non-
                                                                     linear in distance.
                                                                        An  alternative and  more  useful  form of  (3-31) can be
                                                                     derived from the definition of  the log mean. When z  = 22,
                                                                     (3-3 1) becomes
                  Unimolecular Diffusion

                  In unimolecular diffusion (UMD), mass transfer of compo-
                  nent A occurs through stagnant (nonmoving) component B.
                  Thus,
                                                                     The log mean (LM) of (1 - xA) at the two ends of the stag-
                                      NB = 0                 (3 -24)   nant layer is

                  and
                                      N = NA                 (3-25)
                  Therefore, from (3-  12),



                                                                     Combining (3-33) with (3-34) gives

                  which can be rearranged to a Fick's-law form,
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