Page 34 - Introduction to Colloid and Surface Chemistry
P. 34

Kinetic properties  25

        position  along  a  given  axis  after  a  time  t  is  given  by  Einstein's
        equation:

             JT  =  (2Dtf                                       (2.4)

        where  D  is the  diffusion  coefficient  (see  page 26-7).
          The  theory  of  random  motion  helps  towards  understanding  the
        behaviour of linear  high polymers  in solution.  The  various segments
        of  a flexible linear  polymer  molecule  are  subjected  to  independent
        thermal  agitation,  and  so  the  molecule  as  a  whole  will  take  up  a
        continually changing and  somewhat  random  configuration  (see  page
        8).  The  average  distance  between  the  ends of  a completely flexible
        and random chain made up of n segments each of length / is equal  to
        /(/i) w  (cf.  Einstein's  equation  above).  This  average  end-to-end
        distance  becomes l(2ri)^  if an angle of  109° 28' (the tetrahedral angle)
        between  adjacent  segments  is  specified.
          The  diffusion  coefficient  of a  suspended  material is related  to  the
        frictional  coefficient  of  the  particles  by Einstein's  law of  diffusion:



             Df  = kT                                           (2,5)

        Therefore,  for spherical  particles,

                  kT     RT
             D^      =                                         (2-6)
                 6irpa  6irpaN A

        where N A  is Avogadro's  constant,  and
                         \V4
                   RTt
                                                                (2.1)





          Perrin  (1908) studied  the Brownian displacement  (and sedimenta-
        tion  equilibrium under gravity; see page  35) for  fractionated  mastic
        and  gamboge  suspensions  of  known  particle  size,  and  calculated
                                                            23     1
        values  for  Avogadro's  constant  varying  between  5.5  x  10  mol"
                          1
        and  8  x  10 23  mol" .  Subsequent  experiments  of  this  nature have
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