Free  Radical  Chlorination  of  1-­Chlorobutane   Experiment  #10   Orijit  Kar,  Section  01,  10  May  2011                      

47  ml)  1-­‐chlorobutane  and  22.  inverting.  sealed  with  a  rubber  septum.Kar  2   I.27   g    0.  2.   was  prepared  by  inserting  damp  cotton  to  form  a  rudimentary  seal.       .    The  beaker  was  set  on  a  hot   plate  and  warmed  such  that  the  water  within  reached   approximately  313K.    Finally.    The  reaction  tube  was  set  up  by  placing  4.  tube  B.         II.5   mmol  (0.5  µmol   azobisisobutyronitrile  (AIBN)  catalyst.     A  thermometer  was  clamped  to  a  ring  stand  and  inserted  into  a   150  ml  beaker  containing  water.16  ml)  was  added  to  the  reaction  tube  to  initiate  the  reaction.  Abstract   The  purpose  of  this  lab  is  to  chlorinate  1-­‐chlorobutane  into  a  dichlorobutane  using  chlorine   generated  from  a  radical  reaction.  and  connected  to  tube  B  with  the   polyethylene  tubing.  Experimental   To  begin.    The  reaction  tube  was   placed  in  the  water  bath.0  mmol  sulfuryl  chloride  (0.    A  second  tube.  experimental  setup  was  prepared  as  seen  below.  and  placing   polyethylene  tubing  as  shown  in  the  image  above.42  g    0.    This  process  is  known  as  free-­‐radical  chlorination.

   GC  analysis  showed  the  following  contents  in  the  product:     IV.    The  remaining  organic   layer  was  then  washed  with  500µl  of  5%  NaHCO3  and  500µl  H2O.       III.    Vociferous  bubbling  was   observed  for  the  first  few  minutes.    This  not  only   absolutely  stopped  the  reaction.  but  it  also  allowed  for  a  clear  separation  of  organic  and   aqueous  layers.  bubbling  became   less  enthusiastic  as  the  reaction  progressed.251  g  of  product  was  placed  in  a  vial  and  submitted  for  gas   chromatography  analysis  (GC).    The  reaction  tube  was  removed  from  the   water  bath  after  30  minutes  and  allowed  to  cool  to  room  temperature. The chlorine radical reacted with a hydrogen in the 1-chlorobutane.    500µl  of  CH2Cl2  and   500µl  of  H20  were  added  dropwise  to  the  reaction  tube  after  it  had  cooled. chlorine can react with any of the hydrogens that are attached to the four .  indicating  the  evolution  of  N2  and  SO2.  Discussion   In lab. As shown in the equation in the abstract.Kar  3     The  reaction  was  allowed  to  proceed  for  30  minutes. a chlorine radical was generated through by decomposing sulfuryl chloride (SOCl2).    The  aqueous  layer  was  removed  from  the  solution.  Results   0.    Finally  calcium  chloride  was  added  to  dry  the  organic  content  from  any   remaining  water  before  0.  removing  the  aqueous   layer  each  time.251  g  of  product  was  created.

In general. This trend was more or less reflected in the data. one would expect (1. or (1.     . thereby increasing the BDE.Kar  4   carbons in butane. However. although relative abundances of (1. tertiary alkyl groups have lower bond dissociation energy (BDE) than secondary alkyl groups. The other and more important factor determining relative abundance is the bond dissociation energy of the hydrogens bound to carbon.4dichlorobutane. With that in mind. This also affects the C2 carbon but less so.4)-dichlorobutane were nearly equal.2) and (1. The local intermolecular environments of each carbon (C1-C4) varies slightly and so do those of their constituent hydrogens. Considering this factor. Based on the gas chromatograph. The relative abundance of each isomer depends on both the number of hydrogens attached to each carbon and the bond dissociation energy of the carbon hydrogen bond. (1. one should expect a maximum relative abundance of 1.3) dichlorobutane to be relatively most abundant.2-dichlorobutane. followed by 1. (1. it strengthens the bond between the C1 carbon (to which it is attached) and its hydrogens. For example a carbon with three bound hydrogens has one more hydrogen available for reaction than a carbon with two bound hydrogens.8%)  than  products.3-dichlorobutane. Yield  was  rather  low  as  less  than  21%  of  the  analyzed  product  (which  was  itself  only   43.    This  may  have  occurred  for  a   number  of  reasons. forming (1.2) and (1.    Perhaps  the  reaction  was  not  allowed  to  proceed  long  enough. and finally minimal 1.2). As such. 1.1).5%  of  theoretical  yield)  contained  the  desired  chlorination  products  and  there  was  a   greater  concentration  of  reactant  (26. and they were. it is also important to keep in mind that the chlorine in 1-chlorobutane is very electronegative and considered an electron withdrawing group.1-dichlorobutane. One primary objective in this experiment was to elicit the relative abundance of each isomer of dichlorobutane formed by the chlorination of 1-chlorobutane.3). which in turn have lower BDE than primary alkyl groups.4) dichlorobutane.

  V.    A  third   possibility  would  be  a  series  of  small  errors  in  measurement.  which  is  modified  from:   Williamson.”  University  of  Pennsylvania.  the  experiment  was  successful  because  the  reaction  occurred  and   products  formed  at  ratios  very  close  to  expected  and  theoretical  relative  abundances.E.    When  working  with  small   quantities.  in  order  to   maximize  yield.   Seiple.  unfortunately.  “Chlorination  of  1-­‐chlorobutane.  one  should  take  extra  care  to  ensure  accurate  measurement  and  proper   experimental  setup.    In  such  controlled  settings  as  a  laboratory  with  proper  equipment.  2003.  K.”  University  of       Pennsylvania.  “Free  Radical  Chain  Chlorination  of  1-­‐chlorobutane.Kar  5   Perhaps  a  bad  seal  in  the  apparatus  allowed  some  product  to  escape  into  the  hood.  disappointingly  low  for  reasons  discussed  above.    This  experiment   demonstrates  the  relative  ease  of  further  halogenating  a  halogenated  alkane  using  free-­‐ radical  generation.    Yield   was.  this   method  can  be  both  easier  and  more  practical  than  using  chlorine  gas.       Procedure  from  lab  manual.     Houghton  Mifflin.  indicating  that  equilibrium  does  not  heavily   favor  product  formation.  Susan  W.  accurate  measurement  becomes  particularly  imperative.    It  should  be  noted  that  even  in  the  literature.  yield  for   this  reaction  is  not  particularly  high  (35-­‐40%).  Macroscale  and  Microscale  Organic  Chemistry  Experiments.  given  that  even  small   errors  are  proportionally  magnified.   VI.  Conclusions     Qualitatively.  4th  ed.  References   Mburu.  Boston.   Appendicies  A  and  B  follow   .  Scott.    In  future.

 4.5  mmol  =  0.886  g/ml  =  0.47  ml)   Theoretical  yield:   MW  dichlorobutane  =  127.    Looking  that  the  GC   readout.5  mmol  of  dichloromethane  product  total  from  4.  4.7%  *  21%  =  9.  Appendix  B  –  see  attached  GC  Chromatograph   .251  g   %  yield  =  (actual  yield  /  theoretical  yield)  *  100%   %  yield  =  43.575  g.    0.  we  should  expect  4.  this  assumes  all  of  the  product  formed  was  dichlorobutane.5  mmol  =  0.5  mmol  of  1-­‐ chlorobutane  reactant.42  g  /  (0.  Appendix  A  –  Calculations  of  Yield   Stoichiometry  =  1:1  (reactants:  products)   Thus.  this  is  not  the  case.     MW  1-­‐chlorobutane  =  92.    43.Kar  6     VII.42  g.     Actual  yield  =  0.6  g/mol.  notwithstanding  relative  distribution  of  isomers.7   However.0  g/mol.18%  yield     VIII.

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