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INTRODUCTION  

•  To   early   19th   Century   Chemists,   organic  

CH  121:  ORGANIC  CHEMISTRY  I   chemistry   meant   the   study   of   compounds  
obtainable  only  from  living  matter  
•  Thought   to   have   vital   force   needed   to  
CHEMICAL  BONDS,  LEWIS  STRUCTURES,  
make  these  compounds  
FORMAL  CHARGES,  CURVED  ARROWS  
AND  RESONANCE   •  1828   Friederich   Wöhler   set   out   to  
synthesize   ammonium   cyanate,   NH4OCN  
as  in  the  reaction:  
     
      2  

AgOCN(s) + NH4Cl(aq) AgCl(s) + NH4+OCN- •  The   compound,   white   crystalline   solid  

obtained   from   the   solution   had   none   of  
properties   of   ammonium   cyanate,   even  
O
heat though  it  had  the  same  composition  
NH4+OCN- H2N C NH2
ammonium cyanate urea, a urinary excretion •  The   compound   was   not   ammonium  
"inorganic" of mammals product
" organic" cyanate  but  urea  
 

3   4  

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CHEMICAL  BONDS:  OCTET  RULE  

•  Wöhler   was   excited   and   reported   to  
Berzelius:    
 
  I   must   tell   you   that   I   can   make   urea   •  The   Jirst   explanation   of   the   nature   of  
without   the   use   of   kidneys,   either   man   or   chemical  bonds  was  advanced  by  G.N.  Lewis  
dog.  Ammonium  cyanate  is  urea!!!   (University   of   Califonia,   Berkeley)   and   W.  
Kössel  (University  of  Munich)  in  1912  

5   6  

COVALENT  BONDS  
•  Two  major  types  of  bonds  were  proposed:  
•  Occurs   when   two   atoms   of   the   same   or  
–  Ionic   Bond   (Electrovalent):   formed   by   the  
transfer  of  one  or  more  electrons  from  one  atom  
similar   electronegativities   react   whereby   a  
to  another  to  create  ions,  results  when  two  atoms   complete   transfer   of   electrons   does   not  
of  different  electronegativities  react     occur   and   form   noble   gas   conJiguration   by  
sharing  of  electrons  
–  Covalent   Bond:   bond   that   results   from   sharing  
of   electrons   by   atoms   to   obtain   octet   structure-­‐ eg:    H           H:H
2 or H H
con8iguration  of  noble  gases  
   
Cl2 Cl:Cl or Cl Cl

7   8  

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H LEWIS  STRUCTURES:  DOT  FORMULA  

H
CH4 H C H or H C H How  to  write  Lewis  structures:  e.g.  CH3F  
H •  Find  the  total  number  of  valence  electrons  
H
of  all  atom  
•  C(4)  +  3H(3)  +  F(7)  =  14  electrons  
H
H •  Use  pairs  of  electrons  to  form  bonds  
NH4 H N H or H N H between  all  atoms  that  are  bonded  to  each  
H other   H
H
H C F

      H
9   10  

Exceptions  of  the  Octet  Rule  

•  Add  the  remaining  electrons  in  pairs  so  as  to  
give   each   hydrogen   two   electrons   (a   duet)   •  The   octet   rule   only   applies   to   elements   of  
and  every  other  atoms  8  electrons  (an  octet)   the   3rd   period   and   beyond   have   d-­‐orbitals  
  that  can  be  used  for  bonding  
H

H C F •  These   can   accommodate   more   than   eight  

electrons  in  their  valence  shells  
H

11   12  

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•  Can  form  more  than  four  covalent  bonds,   Write   the   Lewis   structure   of   the   sulfate  
e.g.  PCl5  and  SF6   SO42-­‐  ion:  

•  Total  number  of  valence  electrons  including  

the   extra   two   electrons   needed   to   give   the  
ion  a  negative  charge  

       S(6)  +  O(4  x  6)  +  e(2)  =  32  

13   14  

•  Add   the   remaining   24   electrons   as   unshared  

•  Use   pairs   of   electrons   to   form   bonds   pairs   of   on   oxygen   and   as   double   bonds  
between   sulfur   atom   and   the   four   oxygen   between   the   sulfur   atom   and   two   oxygen  
atoms   atoms  
–  This   gives   8   electrons   on   oxygen   atoms   and   the  
sulfur  atom  12  electrons    
O

O S O

O
15   16  

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FORMAL  CHARGE  
•  Before   writing   Lewis   structure,   the   atoms  
connectivity  must  be  known:   •  Chemists   have   developed   a   very   simple  
–  e.g.   Nitric   acid   is   usually   written   as   HNO3  , book   keeping   method   to   determine   if   an  
however,   this   is   not   correct.   The   correct   atom  within  a  molecule  or  ion  is  neutral,  or  
structure  is  HONO2  not  HNO3   bears  a  positive  or  negative  charge  
 
O
•  The   method   provides   integer   charges   only,  
H O N these   assigned   integer   charges   are   called  
O formal  charges      
   
17   18  

•  This   method   provides   some   indication   of  

charge  distribution,  it  is  an  excellent  starting   •  A   formal   charge   is   a   comparison   of  
point   for   determining   electron   distribution   electrons   "owned"   by   an   atom   in   a   Lewis  
within  a  molecule  or  ion,  and  hence  gives  us  a   structure   versus   the   number   of   electrons  
starting   point   to   predict   chemical   and   possessed   by   the   same   atom   in   its  
physical  properties   unbound,  free  atomic  state  
   

19   20  

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•  The  procedure  to  determine  formal  charges   •  Formal   charge   is   calculated   using   this  
on  the  atoms  of  an  ion  or  molecule  has  three   formula:    
steps:      
   FC  =  GN  -­‐  UE  -­‐1/2BE    
•  Step   1:   Draw   the   best   Lewis   structure   for  
 
the   molecule,   including   all   unpaired   –  FC  =  Formal  charge    
electrons   –  GN  =  Group  number  (number  of  valence  electrons  
•  Step   2.   Assign   the   formal   charge   to   each   in  free,  non-­‐bonded  atom)    
–  UE  =  number  of  unshared  electrons  
atom  
–  BE   =   number   of   electrons   shared   in   covalent  
•  Step  3.  Check  your  work   bonds.    

21   22  

IMPORTANT  
•  Formal   charges   other   than   +1,   0   or   -­‐1   are  
•  The   best   Lewis   structure   or   resonance   uncommon  except  for  metals    
contributing  structure  has  the  least  number  
of  atoms  with  formal  charge   •  The   vast   majority   of   organic   structures   are  
•  Equivalent   atoms   have   the   same   formal   made   up   of   a   small   set   of   atoms   with   a  
charge.  For  example,  all  the  hydrogen  atoms   limited  number  of  bonding  possibilities    
of   methane   (CH4)   are   equivalent   and  
therefore  have  the  same  formal  charge     •  Recognizing   these   cases   will   allow   you   to  
avoid   formal   charge   calculations   most   of   the  
•  All   six   hydrogens   of   ethane   (H3C-­‐CH3)   have   time,  and  speed  your  understanding  of  how  
the   same   formal   charge,   as   do   the   two   charge   inJluences   reactions   and   properties  
carbon  atoms     of  molecules  
 
23   24  

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CURVED  ARROW  NOTATION  

•  The  curved  arrow  notation  shows  the  

movement  of  electrons  (electron  Jlow)  
•  Electrons  from  the   source  to  the   sink  

e-­‐  pair   Single  e-­‐    

Double-­‐headed  arrow   Fishhook  arrow  
25   26  

•  Non  bonding  pair  to  adjacent  bond  (vertex-­‐

to-­‐edge  transfer)  
A A

Electron source Electron sink Product •  Bonding  pair  to  an  adjacent  atom  (edge-­‐to-­‐
vertex  transfer)  
A A

27   28  

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•  Bonding  pair  to  an  adjacent  bond  (vertex-­‐to-­‐

vertex  transfer)  

A A

•  Electron   redistribution   (change   in  

conIiguration)   is   the   origin   of   chemical  
change  (reactivity)   O N O O N O O N O

Notice  that  the  sigma  network  does  not  change  

and  placement  of  atoms  remain  the  same  
29   30  

RESONANCE  
Important  features:  
•  The   Lewis   structures   impose   artiJicial  
locations  on  the  electrons   •  Each  atom  has  a  noble  gas  conJiguration  
•  As  a  result  more  than  one  equivalent  Lewis   •  One   structure   can   be   converted   into   any  
structures   can   be   written   for   many   other   by   changing   only   the   positions   of   the  
molecules  and  ions,  e.g.  CO32-­‐  there  are  three   electrons  
different  but  equivalent  structures  
•  No   need   to   change   the   relative   positions   of  
 
the  atomic  nuclei  

31   32  

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•  Electron   pairs   can   be   moved   by   curved  

arrows   •  Structures   1   –   3   are   not   identical,   they   are  
equivalent  

33   34  

Resonance  Theory  
•  Whenever   a   molecule   or   ion   can   be   •  The   actual   molecule   or   ion   will   be   better  
represented   by   two   or   more   Lewis   represented  by  a  hybrid  of  these  structures  
structures  that  differ  only  in  the  positions  of   •  Resonance   structures,   then   are   not  
the  electrons,  then:   structures   for   the   actual   molecule   or   ion,  
–  None   of   these   structures,   which   are   called   they  exist  only  in  theory  
r e s o n a n c e   s t r u c t u r e s   o r   r e s o n a n c e  
contributors   will   be   a   correct   representation  
for  the  molecule  
–  None   will   be   in   complete   accord   with   the  
physical   or   chemical   properties   of   the  
substance  
35   36  

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RULES  FOR  RESONANCE  STRUCTURES  

•  Resonance  forms  are  imaginary  

•  They   differ   only   in   the   placement   of   π   or  
non   bonding   electrons,   atom   placement   is  
the   same   (Electron   movement   takes   place   in  
the  π  system,  not  σ  system)  
•  Must   be   valid   Lewis   structures   and   obey   the  
rules  of  valence  
Resonance  hybrid  

37   38  

•  Different  resonance  forms  do  not  have  to  be  

energetically   equivalent   (Lower   energy  
resonance   structures   contribute   most   to  
overall  structure  of  the  molecule)  
•  The  resonance  hybrid  (weighted  average)  is  
more  stable  than  individual  resonance  form  
•  Use   double-­‐headed   arrow   between  
structures   and   brackets   around   them,   keep  
track  of  lone  pairs  and  formal  charge  

39   40  

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FUNCTIONAL  GROUPS  

•  The   atom   or   group   of   atoms   that   deJines   the  

structure   of   a   particular   family   of   organic  
FUNCTIONAL  GROUPS,  EMPIRICAL  AND  
compounds   and,   at   the   same   time,  
MOLECULAR  FORMULA  
determines   their   properties   is   called   the  
FUNCTIONAL  GROUP  
•  In   other   words:   A   characteristically   bonded  
group   of   atoms   that   has   about   the   same  
chemical   reactivity   whenever   it   occurs   in   a  
variety  of  compounds  
42

OH

H3C H H O
O
C C H3C C OH H3C C C O C C N
C H
H3C H H OH

Isobutylene Ethyl alcohol Acetic acid Phenol Ether Amine Aldehyde

FG: alkene FG: alcohol FG: carboxylic acid
O O
O
C C C C N C N
C OH
HC CH
Ketone Carboxylic acid Amide Nitrile
Acetylene
FG: alkyne Benzene O
O O O
FG: benzene or other aromatic ring
C O C
C Cl C O C
Acid chloride Anhydride Ester

43 44

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MOLECULAR  FORMULA  
–  A   qualitative   elemental   analysis:   to   Jind   out  
•  Gives   information   about   what   kinds   of   what  kinds  of  atoms  are  present  in  the  molecule  
atoms   are   there   and   how   many   of   them   –  A  quantitative  elemental  analysis:  to  Jind  out  
make   up   a   molecule,   before   assigning   a   the  relative  numbers  of  the  different  atom,  i.e.  to  
structural   formula   to   a   compound,   we   determine  the  empirical  formula  
must  Jirst  know  its  molecular  formula   –  A   molecular   weight   determination:   which  
shows   the   actual   numbers   of   the   different   kinds  
•  In   order   to   establish   the   molecular   of  atoms  
formula   of   a   compound,   the   following  
must  be  carried  out:  

45 46  

Calculation:  
•  A  qualitative  elemental  analysis:  
•  Only  the  fraction  C/CO2  =  12.01/44.01  of  the  
–  Presence   of   carbon   or   hydrogen   in   a  
compound  is  detected  by  combustion:   carbon   dioxide   is   carbon   and   only   the  
fraction  2H/H2O  =  2.016/18.02  of  the  water  
(C,H) + CuO heat
Cu + CO2 + H2O is  hydrogen  
 Therefore:  
•  A  quantitative  elemental  analysis:  C,  H        Weight  of  C    =  25.53  x  12.01/44.01  =  7.24  mg  
–  Quantitative  combustion  is  used        Weight  of  H    =  21.56  x  2.016/18.02  =  2.41  mg  
–  Example:   A   sample   of   methane   weighing   %  composition:  
9.67  mg  produced  25.53  mg  of  CO2  and  21.56        %C  =  (7.24/9.67)  x  100  =  74.9  
mg  of  H2O,  calculate  the  empirical  formula.  
     %H  =  (2.41/9.67)  x  100  =  24.9  
47 48

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EMPIRICAL  FORMULA  
•  Is   the   simplest   formula   showing   the  
relative  numbers  of  the  different  kinds  of   •  Dividing  by  the  smallest  number:  
atoms  in  a  molecule,  example  in  100  g  of  
methane,   there   are   74.9   g   of   carbon   and    C:  6.24/6.24  =  1,  H  24.7/6.24  =  3.96  (approx.  4),    
24.9  g  of  hydrogen   •  Therefore,  the  empirical  formula  of  methane  
•  Dividing   each   quantity   by   the   proper   if  CH4  
atomic   weight,   gives   the   number   of   moles    
of  each  element:  
   
C:   74.9/12.01   =   6.24   moles,   H:   24.6/1.008   =  
24.7  moles,  therefore,  we  have:  C6.24H24.7  

49 50  

MOLECULAR  WEIGHT:   Practice  Problems  

MOLECULAR  FORMULA   1.  Combustion   of   6.51   mg   of   a   compound   gave   20.47   mg   of   carbon  
dioxide   and   8.36   mg   of   water.   The   molecular   weight   was   found   to   be  
•  Molecular   formula:   is   the   formula   that   84.  Calculate:  
a)  percentage  composition  
shows   the   actual   number   of   each   kind   of   b)  empirical  formula  
atom  in  a  molecule   c)  molecular  formula  of  the  compound  
2.  A  liquid  of  molecular  weight  60  was  found  to  contain  40.0%  carbon  
•  In  order  to  determine  the  molecular  formula   and   6.7%   hydrogen.   What   is   the   molecular   formula   of   the  
compound?  
of  a  molecule  we  need  to  have  the  molecular   3.   Elemental   analysis   of   an   unknown   compound   gave   the   following  
weight,   which   is   determined   by   mass   results  :  C  :  54.53%  H  :  9.15%  and  molecular  weight:  88.  Calculate  :  
spectrometry   i)    the  empirical  formula  
ii)  the  molecular  formula  
 

51   52

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