Free  Radical  Chlorination  of  1-­Chlorobutane  

Experiment  #10  

Orijit  Kar,  Section  01,  10  May  2011  

 
 Kar  2  

I.  Abstract  

The  purpose  of  this  lab  is  to  chlorinate  1-­‐chlorobutane  into  a  dichlorobutane  using  chlorine  

generated  from  a  radical  reaction.    This  process  is  known  as  free-­‐radical  chlorination.      

II.  Experimental  

To  begin,  experimental  setup  was  prepared  as  seen  below.    

A  thermometer  was  clamped  to  a  ring  stand  and  inserted  into  a  

150  ml  beaker  containing  water.    The  beaker  was  set  on  a  hot  

plate  and  warmed  such  that  the  water  within  reached  

approximately  313K.    The  reaction  tube  was  set  up  by  placing  4.5  

mmol  (0.42  g    0.47  ml)  1-­‐chlorobutane  and  22.5  µmol  

azobisisobutyronitrile  (AIBN)  catalyst.    A  second  tube,  tube  B,  

was  prepared  by  inserting  damp  cotton  to  form  a  rudimentary  seal,  inverting,  and  placing  

polyethylene  tubing  as  shown  in  the  image  above.    Finally,  2.0  mmol  sulfuryl  chloride  (0.27  

g    0.16  ml)  was  added  to  the  reaction  tube  to  initiate  the  reaction.    The  reaction  tube  was  

placed  in  the  water  bath,  sealed  with  a  rubber  septum,  and  connected  to  tube  B  with  the  

polyethylene  tubing.      
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  The  reaction  was  allowed  to  proceed  for  30  minutes.    Vociferous  bubbling  was  

observed  for  the  first  few  minutes,  indicating  the  evolution  of  N2  and  SO2;  bubbling  became  

less  enthusiastic  as  the  reaction  progressed.    The  reaction  tube  was  removed  from  the  

water  bath  after  30  minutes  and  allowed  to  cool  to  room  temperature.    500µl  of  CH2Cl2  and  

500µl  of  H20  were  added  dropwise  to  the  reaction  tube  after  it  had  cooled.    This  not  only  

absolutely  stopped  the  reaction,  but  it  also  allowed  for  a  clear  separation  of  organic  and  

aqueous  layers.    The  aqueous  layer  was  removed  from  the  solution.    The  remaining  organic  

layer  was  then  washed  with  500µl  of  5%  NaHCO3  and  500µl  H2O,  removing  the  aqueous  

layer  each  time.    Finally  calcium  chloride  was  added  to  dry  the  organic  content  from  any  

remaining  water  before  0.251  g  of  product  was  placed  in  a  vial  and  submitted  for  gas  

chromatography  analysis  (GC).      

III.  Results  

0.251  g  of  product  was  created.    GC  analysis  showed  the  following  contents  in  the  product:  

IV.  Discussion  

In lab, a chlorine radical was generated through by decomposing sulfuryl chloride

(SOCl2). The chlorine radical reacted with a hydrogen in the 1-chlorobutane. As shown in the

equation in the abstract, chlorine can react with any of the hydrogens that are attached to the four
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carbons in butane, forming (1,1), (1,2), (1,3), or (1,4) dichlorobutane. The local intermolecular

environments of each carbon (C1-C4) varies slightly and so do those of their constituent

hydrogens. One primary objective in this experiment was to elicit the relative abundance of each

isomer of dichlorobutane formed by the chlorination of 1-chlorobutane. 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. For example a carbon with three bound hydrogens has one more hydrogen available for

reaction than a carbon with two bound hydrogens. The other and more important factor

determining relative abundance is the bond dissociation energy of the hydrogens bound to

carbon. In general, tertiary alkyl groups have lower bond dissociation energy (BDE) than

secondary alkyl groups, which in turn have lower BDE than primary alkyl groups. With that in

mind, one would expect (1,2) and (1,3) dichlorobutane to be relatively most abundant, and they

were. However, it is also important to keep in mind that the chlorine in 1-chlorobutane is very

electronegative and considered an electron withdrawing group. As such, it strengthens the bond

between the C1 carbon (to which it is attached) and its hydrogens, thereby increasing the BDE.

This also affects the C2 carbon but less so. Considering this factor, one should expect a

maximum relative abundance of 1,3-dichlorobutane, followed by 1,2-dichlorobutane, 1,4-

dichlorobutane, and finally minimal 1,1-dichlorobutane. This trend was more or less reflected in

the data, although relative abundances of (1,2) and (1,4)-dichlorobutane were nearly equal.

Yield  was  rather  low  as  less  than  21%  of  the  analyzed  product  (which  was  itself  only  

43.5%  of  theoretical  yield)  contained  the  desired  chlorination  products  and  there  was  a  

greater  concentration  of  reactant  (26.8%)  than  products.    This  may  have  occurred  for  a  

number  of  reasons.    Perhaps  the  reaction  was  not  allowed  to  proceed  long  enough.    
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Perhaps  a  bad  seal  in  the  apparatus  allowed  some  product  to  escape  into  the  hood.    A  third  

possibility  would  be  a  series  of  small  errors  in  measurement.    When  working  with  small  

quantities,  accurate  measurement  becomes  particularly  imperative,  given  that  even  small  

errors  are  proportionally  magnified.    It  should  be  noted  that  even  in  the  literature,  yield  for  

this  reaction  is  not  particularly  high  (35-­‐40%),  indicating  that  equilibrium  does  not  heavily  

favor  product  formation.  

V.  Conclusions  

  Qualitatively,  the  experiment  was  successful  because  the  reaction  occurred  and  

products  formed  at  ratios  very  close  to  expected  and  theoretical  relative  abundances.    Yield  

was,  unfortunately,  disappointingly  low  for  reasons  discussed  above.    This  experiment  

demonstrates  the  relative  ease  of  further  halogenating  a  halogenated  alkane  using  free-­‐

radical  generation.    In  such  controlled  settings  as  a  laboratory  with  proper  equipment,  this  

method  can  be  both  easier  and  more  practical  than  using  chlorine  gas.    In  future,  in  order  to  

maximize  yield,  one  should  take  extra  care  to  ensure  accurate  measurement  and  proper  

experimental  setup.  

VI.  References  

Mburu,  Susan  W.  “Free  Radical  Chain  Chlorination  of  1-­‐chlorobutane.”  University  of    

  Pennsylvania.  

Seiple,  Scott.  “Chlorination  of  1-­‐chlorobutane.”  University  of  Pennsylvania.      

Procedure  from  lab  manual,  which  is  modified  from:  

Williamson,  K.E.  Macroscale  and  Microscale  Organic  Chemistry  Experiments.  4th  ed,  

  Houghton  Mifflin,  Boston,  2003.  

Appendicies  A  and  B  follow  

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VII.  Appendix  A  –  Calculations  of  Yield  

Stoichiometry  =  1:1  (reactants:  products)  

Thus,  we  should  expect  4.5  mmol  of  dichloromethane  product  total  from  4.5  mmol  of  1-­‐

chlorobutane  reactant,  notwithstanding  relative  distribution  of  isomers.  

MW  1-­‐chlorobutane  =  92.6  g/mol;  4.5  mmol  =  0.42  g.    0.42  g  /  (0.886  g/ml  =  0.47  ml)  

Theoretical  yield:  

MW  dichlorobutane  =  127.0  g/mol;  4.5  mmol  =  0.575  g.    

Actual  yield  =  0.251  g  

%  yield  =  (actual  yield  /  theoretical  yield)  *  100%  

%  yield  =  43.7  

However,  this  assumes  all  of  the  product  formed  was  dichlorobutane.    Looking  that  the  GC  

readout,  this  is  not  the  case.    43.7%  *  21%  =  9.18%  yield  

VIII.  Appendix  B  –  see  attached  GC  Chromatograph