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20   I / CENTRIFUGATION/ Derivatization


                                                           meters that govern settling velocity. They show that
                                                           the sedimentation rate (i.e. limiting velocity) of a par-
                                                           ticle in a centrifugal Reld:

                                                             increases as the square of the particle diameter and
                                                             rotor speed, i.e. doubling the speed or particle
                                                             diameter will lessen the run time by a factor of
                                                             four;
                                                             increases proportionally with distance from the
                                                             axis or rotation; and
                                                             is inversely related to the viscosity of the carrier
                                                             medium.
                                                           These are the fundamental premises that a practi-
                                                           tioner must know in order to develop a rational
                                                           approach to centrifugal separation.
                                                           Sedimentation Coef\cient
                                                           Since the terms r,   P ,   M and   as given in
           Figure 1 Forces acting on a particle in a centrifugal field: F b ,
           buoyancy; F f , frictional; F c , centrifugal; and F g , gravitational.  eqns [13]}[15] are constant for a given particle in
                                                           a homogeneous medium, the sedimentation rate,
                                                                                  2
                                                           dx/dt, is proportional to   x. This proportionality is
           forces equals the centrifugal force:            often expressed in terms of the sedimentation coef-
                                                           Rcient, S, which is simply a measure of the sedimenta-
                                                     [10]
                             F c "F b #F f
                                                           tion velocity per unit of centrifugal force. For a given
                                                           set of run conditions, the sedimentation coefRc-
           Substituting eqns [2], [4] and [7] into eqn [10] gives:
                                                           ient, S r , may be calculated as:
                                 2
                       2
                    m  x"V P   M   x#6  r(dx/dt)     [11]
                                                                  S r "(dx/dt)/(  x)"2r (  P !  M )/9   [16]
                                                                                      2
                                                                               2
                                                  4
                                                     3
           Assuming a spherical particle and substituting 3  r for
           volume gives:                                   The sedimentation coefRcient, S, has the dimen-
                                                           sions of seconds and is expressed in Svedberg units
                                                                      13
                    3
                             4
                 4
                        2
                                3
                                     2
                ( 3  r )  P   x"( 3  r )  M   x#6  r(dx/dt) [12]  equal to 10  s. Its value is dependent on the particle
                                                           being separated, the centrifugal force and the proper-
           Then solving for dx/dt:                         ties of the sedimentation medium. While adequate for
                                                           a given set of run conditions, it is sometimes useful to
                               2
                     dx/dt"[2r (  P !  M )  x]/9     [13]  compare sedimentation coefRcients obtained un-
                                         2
                                                           der  differing  conditions  and/or  sedimentation
           Eqn [13] is more commonly expressed in terms of  media by reference to the behaviour of the particle in
           particle velocity, v, and particle diameter, d:  water at 203C, S 20,w :
                                      2
                            2
                       v"(d (  P !  M )  x)/18 )     [14]
                                                                S 20,w "S T,M   T,M (  P !  20,w )/  20,w (  P !  T,M ) [17]
           Eqn [14] may be integrated to determine the time  where the subscripts T and M denote the experi-
           required for a particle to traverse a radial distance  mental temperature and medium, respectively.
           from x 0 to x 1 :
                                                           Rotor Ef\ciency
                             2
                                       2
                   t"[18 /(d (  P !  M )  )] ln (x 1 /x 0 )  [15]
                                                           The time required for a particle to traverse a rotor is
           where x 0 is the initial position of the particle and x 1 is  known as the pelleting efRciency or k-factor. The
           the Rnal position of the particle.              k- or clearing factor, which is calculated at the max-
             While modiRcations can be made to eqns [13]}[15]  imum rated rotor speed, is a function of rotor design
           to account for speciRc rotor design, liquid}liquid,  and is a constant for a given rotor. k-Factors provide
           density-gradient separations, etc., these equations de-  a convenient means of determining the minimum
           scribe the relative impact of the more signiRcant para-  residence time required to pellet a particle in a given
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