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Arrhenius  (Sweden)  -­‐  1884  
 
•  An   acid   is   a   substance   that   dissociates   in  
water  to  form  hydrogen  ions  (H+);  that  is,  an  
acid   increases   the   concentration   of   H+   ions  
ACIDS  AND  BASES   in  an  aqueous  solution  
•  A   base   is   a   substance   that   dissociates   in  
water  to  form  hydroxide  (OH−)  ions;  that  is,  
a   base   increases   the   concentration   of   OH−  
ions  in  an  aqueous  solution  

2  

B r ø n s t e d   ( D e n m a r k )   &   L ow r y  
(England)  -­‐  1923    
•  All   Arrhenius   acids   and   bases   are   also  
•  An   acid   is   any   compound   or   ion   which   can  
give  up  a  proton     Bronsted-­‐Lowry   acids   and   bases,   but   the  
–  Examples:  HCl  +  H2O  =  H3O+  +  Cl-­‐   opposite  isn't  true    
–  The   hydrogen   on   the   hydrogen   chloride   donates   •  An  Arrhenius  acid/base  must  be  a  substance  
its   hydrogen   proton   to   the   water,   resulting   in   a  
cation  of  H3O+  and  an  anion  of  Cl-­‐   dissolved  in  water  
•  A   base   is   any   compound   or   ion   which   can   •  A   Bronsted-­‐Lowry   acid/base   can   be  
accept  a  proton   dissolved   in   water,   like   the   Arrhenius   acid/
–  Example:  NH3  +  H2O  =  NH4+  +  OH-­‐     base,  but  it  does  not  have  to  be    
–  The   ammonia   accepts   a   proton   from   the  
hydrogen  of  water  (H2O)  to  become  NH4+  
3   4  

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Lewis  (America)  -­‐  1923   Summary  

•  Arrhenius  acid:  Produces  hydronium  ion  in  
•  Lewis   acid   is   a   substance   that   accepts   an  
electron  pair  to  form  a  covalent  bond   water  
•  A   strong   acid   is   a   hydrogen   donor,   or   acid,   •  Arrhenius  base:  Produces  hydroxide  ion  in  
that  completely  dissociates  in  water     water  
•  A  base  is  a  hydrogen  ion  acceptor  -­‐  it  lowers   •  Brønsted-­‐Lowry  acid:  Donates  a  proton  
the  hydrogen  ion  concentration  in  a  solution   •  Brønsted-­‐Lowry  base:  Accepts  a  proton  
while  increasing  the  pH  of  that  solution.    
•  Lewis  acid:  Accepts  electrons  
•  A   strong   base   is   a   hydrogen   ion   acceptor  
that  can  completely  dissociate  in  water     •  Lewis  base:  Donates  electrons  

5   6  

Conjugate  Acids  and  Bases  

•  Conjugate  acid:  an  acid  that  forms  when  a   [H 3O + ][Br ! ] [H 3O + ][Br ! ]
Ka = = = 1.58 "10 !6
base  gains  a  proton     [HBr][H 2O] [HBr]
•  Conjugate  base:  a  base  that  forms  when  an  
acid  loses  a  proton    
pK a = ! log(K a ) = !5.8
Proton Proton
acceptor donor Conjugate acid/base
pKa   tells   us   how   acidic   (or   not)   a   given  
H O H + H Br H3O + Br hydrogen   atom   in   a   molecule   is   (acid  
strength)  
Conjugate acid/base
7   8  

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•  Instead   of   using   Kb   to   compare   base  

strength,   the   pKa   of   the   conjugate   acid   (a  
•  Example:   Comparison   of   the   basicity   of  
base   in   its   protonated   form),   pKaH   is  
ammonia   and   pyridine   is   easily   done   by  
considered  
considering  their  conjugate  acids    
•  Example:   Lithium   diisopropylamine   is   a   H
common  base  with  pKaH  =  42  (pKa  =  42)   N
H H N
Ammonia Pyridine
Li
N +H+

N N
LDA: Lithium
diisopropyl amine
9   10  

Factors  affecting  acid  strength  

•  Bond  strength:  Better  orbital  overlap  leads  
•  The   pKa   value   for   the   conjugate   acid   of  
to   stronger   bonds,   less   likely   a   proton   to  
ammonia   (ammonium   ion)   is   9.3   whereas  
come  off,  consider  the  following  series:  
that   of   the   conjugate   acid   of   pyridine  
(pyridinium  ion)  is  5.2                          H-­‐F  <  H-­‐Cl  <  H-­‐Br  <  H-­‐I  
•  Thus   the   conjugate   acid   of   ammonia   is   pKa  =        3.1    -­‐3.9    -­‐5.8    -­‐10.4  
weaker   than   that   of   pyridine,   implying   that   •  HI   is   more   acidic   compared   to   the   other  
ammonia   is   a   stronger   base   compared   to   halogens   because   the   bond   between  
pyridine   hydrogen   and   iodine   is   weaker   due   to   the  
atomic  size  
11   12  

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•  When   comparing   atoms   of   equal   formal  

charge  the  larger  atom  provides  more  space   •  Smaller   atoms   have   a   greater   driving   force  
for  the  charge   to   share   electron   density   because   of  
•  Therefore,   in   a   larger   atom   the   negative   increased   charge   concentration   and   are  
charge   is   more   dispersed   and   the   charge   thereby  stronger  bases  
density  decreases    
•  As  a  result  negative  charges  prefer  to  rest  on  
large  atoms  rather  than  being  localized  on  a  
small  atom  (due  to  increase  stability)    

13   14  

Electronegativity:    
•  The   more   electronegative   the   element   on  
•  Atoms   with   greater   s   character   are   more  
which   the   negative   charge   is   located,   the  
electronegative,   therefore   are   better   able   to  
more   stable   the   conjugate   base,   and   the  
stabilize  the  negative  charge  
stronger   the   acid,   i.e.   more   electronegative  
atoms   can   better   stabilize   the   negative  
charge   of   the   conjugate   base   than   less  
electronegative  
       CH4  <  NH3  <  H2O  <  HF  
 pKa  =      50    38      15.7    3.7  
15   16  

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Hybridization:    
•  The  s  orbitals  are  closer  to  the  nucleus  than   •  Such   atoms   are   less   willing   to   share   their  
p   orbitals,   this   is   why   the   more   s   character   a   electron   density   and   thereby   have   greater  
hybrid   orbital   has   the   closer   are   the   acidic  character  
electrons  to  the  atom    
•  Therefore,   there   is   a   direct   relationship   H H
between   s   character   and   electronegativity;   <
the   greater   the   s   character   of   the   hybrid  
H3C
sp3
CH3 C
sp2
C < H C
sp
C H

H H
orbital,   the   greater   is   the   electronegativity   50 43 25
of  the  atom  
17   18  

•  Hyperconjugation  (σ-­‐donation):    
H
•  Hybridisation  has  an  effect  on  pKa,  s  orbitals   OH
OH
are  closer  to  the  nucleus  than  p  orbitals,  and   OH
< < OH
< H H
therefore  lower  in  energy   18 16.5 16 15.5
•  This   means   that   the   more   s   character   an   +
-H
-H+

orbital   has,   the   more   tightly   held   are   the   H

electrons  in  it   O O
H H
Destabilized by C-C bonds Much weaker !
pushing electron density donation from C-H
toward charge bonds
Strong ! donation
19   20  

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Resonance  Delocalization:    
•  Spreading   the   charge   (positive   or   negative)  
•  Polarizability:   Large   atoms   are   more  
over  more  than  one  atom  is  most  important  
diffuse,   are   better   able   to   stabilize   the  
factor  in  determining  acidity/basicity    
negative  charge  over  bigger  space  
•  Resonance   can   either   increase   or   decrease  
         H2O  <  H2S  <  H2Se  
the   electron   density   at   the   atom   that   will  
   pKa  =    15.7      7.0      3.9   actually  share  electrons  with  the  proton  
•  Additionally,   resonance   delocalizes   the  
electron   density   and   thus   leads   to   greater  
stabilization  
21   22  

•  Inductive   effects:   Pull   of   electron   density  

O
O
from   the   negative   charge   through   inductive  
H2O < < HO S OH
effect  leads  to  stabilization  of  the  charge  
OH -3.0 O
15.7 4.8
O •  Induction  occurs  through  the  σ-­‐network  
-H+
-H+ HO S O •  Nearby   atoms   may   add   to   or   detract   from  
O O O the   electron   density   of   the   atom   sharing  
O O
HO S O HO S O electrons  with  the  proton    
O O O O •  This   in   turn   indluences   its   driving   force   to  
share   electron   density,   and   ultimately   its  
basicity    
23   24  

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•  In  many  cases,  electronegative  atoms  near  a  

molecule  pull  away  the  electron  density  and  
make   it   less   basic   because   its   driving   force   •  Charge:   A   base   with   a   negative   formal  
to  share  electron  density  is  decreased   charge   has   a   greater   driving   force   to   share  
O O
O O
electron  density  then  a  neutral  base  
Cl
Cl
OH
Cl
OH •  The   greater   the   electron   density   (in   this  
OH < OH < < Cl case   due   to   negative   charge),   the   stronger  
Cl Cl
4.8 2.9 1.3 0.65 the  base  and  the  weaker  the  conjugate  acid  
O -H+

Cl
The 3 chloride pull the electron density O
from the -ve charge hence stablizing it Cl Inductive occurs
Cl through ! network
25   26  

O N
H H H

NaNH2 Charged, Less stable.

N N
O H Li
Positive charge on O is Positive charge on N, also
very unstable, not likely not ideal, less so because
to form is less electronegative

NH3
N
H
Uncharged, more stable, likely to form.
The difference is ! donation, additional group
(non H) add electron density via !-network,
destabilizing any negative charge making it
more likely to react and become protonated
27   28  

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Lewis  Acids,  Lewis  Bases  and  Organic  

Reaction  Mechanisms   F
F
•  The  Lewis  dedinitions  are  that  an  acid  is  an   + H3CH2C O CH2CH3 F B O CH2CH3
B
electron-­‐pair   acceptor   and   a   base   is   an   F 6e- F Donates 2 F CH2CH3
electrons
electron-­‐pair  donor     Accepts 2
electrons
Lewis Lewis
•  Consider   the   reaction   between   boron   Acid Base
tridluoride  and  diethyl  ether  
•  All  Bønsted-­‐Lowry  acids  are  Lewis  acids  
BF3 + Et2O Et2O BF3
•  All  Brønsted-­‐Lowry  bases  are  Lewis  bases  
Boron Diethyl Boron trifluoride
trifluoride ether ethoxide

29   30  

•  Consider  the  reaction  between  ammonium   •  Consider  the  following  reaction  also:  
ion  with  hydroxyl  ion   CH3 H
CH3
Lewis/Bronsted + H H3C C O H
H Base H C O H
-
H3C 6e CH3
H N H + O H + H O H CH3
N tert-Butyl Lewis Base
H H carbocation
H Lewis Acid Nucleophile
Lewis/Bronsted
Acid Electrophile

31   32  

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Acid  Catalyzed  Alkene  Hydration  

•  Organic  chemists  have  special  names  for   •  Consider  the  hydration  of  isobutylene  (2-­‐
Lewis  acid  and  Lewis  base:   methylpropene)  in  the  presence  of  acid  
–  Lewis  acid  is  called  an  ELECTROPHILE  
H H CH3
–  Lewis  base  is  called  a  NUCLEOPHILE  
H3O
+ H2O H3C C OH

H3C CH3 CH3

2-Methylpropene 2-Methylpropanol
(Isobutylene) (tert-Butanol)

33   34  

•  Step  I:  The  abstraction  of  a  proton  from  the   •  Step   II:   Reaction   between   carbocation  
hydronium   ion   (acid),   isobutylene   is   the   (electrophile/Lewis   acid)   and   water  
source   of   electrons,   thus   a   nucleophile   and   (nucleophile/Lewis   base)   forming   hydrated  
the  hydronium  ion  as  the  electrophile   tert-­‐butyl  (a  Lewis  acid)  
H H
H H CH3
+ H O H H H H H
+ H O H + H O H H3C C O H
H
H3C CH3 H3C CH3
Nucleophile Electrophile Electrophile Nucleophile
H3C CH3 Lewis base
CH3 H
Lewis acid

35   36  

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Acid  catalyzed  alcohol  dehydration  –  

•  Step   III:   Water   (a   Lewis   base)   abstracts   a   Reverse  reaction  
proton   from   the   hydrated   tert   butyl   (Lewis  
acid)   to   form   tert   butyl   alcohol   and   •  Acid   catalyzed   dehydration   of   alcohols  
hydronium  ion  (catalyst  regenerated)   follows   the   opposite   route   to   the   previous,  
CH3
i.e.  hydration  
CH3
H3C C OH + H O H
•  This   is   known   as   the   principle   of  
H3C C O H + H O H
CH3 H
microscopic   reversibility,   ie   reverse   reaction  
Lewis base
CH3 H must   have   the   same   mechanism   as   the  
  Lewis acid forward  reaction  
•  NB:   Compare   with   enzymes   in   biological  
processes  
37   38  

CH3 CH3

H3C C OH + H O H H3C C O H + H2O

CH3 H CH3 H Cl H
Cl vs Cl
CH3 C C
CH3 H Cl H H
+ H O H
H3C C O H C
Cl H
H3C CH3
Cl Cl
CH3 H C C
H Cl H H
H
H H Only 1 H, 3 Cl. Cl more Only 1 Cl, 3 H (all equivalent). Cl
H H electronegative than C. Negative more electronegative than C.
+ H O H +H O H charge is spread over the 3 Cl Negative charge only spread over
atoms through inductive effect the 1 Cl atom
H3C CH3 H
H3C CH3
39   40  

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CH3 H O O
N N
H vs CH3
H2C H2C
NH2 vs OH

CH3 H Amide Carboxylic cid

N N
H vs CH3 O O
H2C H2C
-H+ NH2 vs OH
Amide Carboxylic cid
CH3 N
N CH3 N Deprotonation: Hydrogens on
CH3
heteroatoms are more acidic
Extra C between More stable conjugate base, more O O
N and the Ar ring, acidic. Charge can be delocalized
charge localized to more atoms through resonance H2C H2C
NH O
Any charge needs to be spread to more atoms in the molecule:!
DELOCALIZED! O is more electronegative than N,
41  
H on carboxylic acid more acidic 42  

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