CHEM

 31.1  MIDTERMS  REVIEWER  

 
Experiment  1:  Solubility  of  Organic  Compounds  

• solubility  –  gives  a  clue  on  the  functional  groups  that  a   § polar  compounds  with  few  h-­‐bonding  
compound  contains   groups/sites  
• information     § IMFA:  van  der  waals  w/  diethyl  ether    
o presence  of  functional  groups  –  polar    or   § –OH,  –NH2,  –COOH,  –CONH2,  
nonpolar   aldehydes,  ketones,  esters  
o specific  information  (ex.  weak  or  strong  acid)   o Class  S2  
o estimation  of  molecular  size  and  composition     § polar  compounds  with  many  h-­‐bonding  
§ 5-­‐carbon  chain  rule  (Kamm’s  rule)   groups/sites  
• types  of  solubility     § salts  of  organic  acids,  RNH3Cl,  amino  
o due  to  miscibility  –  dissolution  due  to  the  same   acids,  carbohydrates    
IMFA  (part  of  the  chart  that  is  soluble  in  H2O)   • Class  A  
o due  to  chemical  reactions  –  dissolution  due  to   ∗ acidic  
+
reactions  with  solvent  that  produces  a  soluble   ∗ H  ready  to  react  with  base  
product  (part  of  the  chart  that  is  insoluble  in   o Class  A1  
H2O)   § strong;  insoluble  in  weak  bases    
• factors  in  solubility     o Class  A2  
o temperature     § weak  
o polarity     • Class  B  
o molecular  size  (↑MW:  ↑IMF:  less  soluble)   o soluble  in  5%  HCl  by  chemical  reaction  
o chain  branching  (↑branching:  ↓IMF:  more   o most  contain  nitrogen  
soluble)   o with  amines  (up  to  tertiary  amines):  R–NH2,  R2–
  NH,  R3–N    
Classes  of  Compounds   • Class  M  
• Class  S   o miscellaneous:  neither  acidic  nor  basic  
∗ water-­‐soluble  compounds  with  H-­‐bonding   o amides  or  nitro  compounds    
functional  groups  (–OH,  –NH2,  –COOH,  –CONH2)   • Class  N  
∗ limited  to  5-­‐carbons  per  H-­‐bonding  group   o react  with  concentration  H2SO4  through  forced  
o Class  S1   protonation  
o with  oxygen  or  unsaturated    
Chem  31.  Midterms  Reviewer   1     /steffigatdula/  
 o ketones,  aldehydes,  alcohols,  alkenes,  alkynes   o saturated  and  aromatic  hydrocarbons    
• Class  I   o alkanes,  aromatics,  alkyl  halides
o no  reaction  with  H2SO4  

Experiment  2:  Recrystallization  and  Melting  Point   o introducing  a  nucleus  

Determination  of  Benzoic  Acid     o +  small  amount  of  
  crystals  to  initiate  
• recrystallization     recrystallization  
o slow  process;  high  percent  purity     ∗ scratching  
• ideal  solvent     o introduces  sites  of  
o at  elevated  temperature:  dissolves  solute   nucleation  
(recrystallization)     o creates  imperfect  spaces  
o at  room  temp:  sparingly  soluble     where  recrystallization  
§ can  selectively  dissolve  solute   may  occur  
§ does  not  react  with  solute   cool  in  ice  bath   • allows  formation  of  more  
§ sufficiently  volatile  (dry)     ↓   crystals    
§ solvent’s  BP  >  solute’s  MP   filter  in  pre-­‐weighed  filter   • washing  with  cold  solvent  
  paper   removes  adhering  mother  
Methodology:     ↓   liquor  and  prevents  
  dissolution    
Single  Solvent   melting  point    
  determination  and  %  
crude  benzoic  acid  +  H2O   • H2O:  recrystallization   recovery  
↓   solvent    
• formation  of  saturated   Mixed  Solvent  
solution     • solvents  should  be  miscible  in  all  proportions  
heat  mixture   • increases  solubility   • compound  should  be  soluble  in  first  solvent  
↓   • compound  should  be  insoluble  in  second  solvent    
+  charcoal/activated   • removes  colored  impurities     • impurities  can  be  removed;  less  time  consuming;  costly  
carbon   • small  amount  only;    
↓   •  too  much  adsorb  (cling  to   Melting  Point  Determination  
surface  of)  solute   • if  MP  is  ±2°C  of  reported  value  →  pure  
hot  filtration   • fluted  f.p.:  maximizes  SA,   • wide  MP  range  indicates  impure  compound  
↓   faster  rate  of  filtration   • benzoic  acid  MP:  122  ±2°C  
• short-­‐stemmed  funnel:   • getting  the  range  
lessen  contact  areas  with   o appearance  of  first  drop:  first  value  
benzoic  acid  to  prevent   o completely  liquid:  second  value  
premature  recrystallization    
• wire:  to  reduce  pressure,   Advantages/Disadvantages  of  Mixed  Solvent  vs.  Single  
conduct  heat,  and  allow  air   Solvent  
to  flow   • advantages  
• pre-­‐heated  receiving  flask:   o less  time  consuming  
avoid  premature   o effective  way  of  removal  of  impurities  (filtration  
recrystallization   and  dissolution)    
cool  filtrate  to  room   • slow  cooling  allows  particle   o better  for  some  compounds  
temperature   growth,  bigger  filterable   • disadvantages  
↓   crystals;  otherwise,   o costly,  2  solvents  
impurities  can  penetrate   o more  cautious  execution  of  procedure  
crystals   o  
• rate  of  growth  >  rate  of    
nucleation    
• no  recrystallization:  solution    
might  be  supersaturated    
• ideal  saturation:  ↑solute,    
↓solvent    
∗ seeding      
Chem  31.  Midterms  Reviewer   2     /steffigatdula/  
Experiment  3:  Extraction  and  Purification  of  Caffeine  
  o biodiesel  
• solvent  extraction   o metal  recovery  
o processing  of  perfumes   o nuclear  reprocessing    
o production  of  vegetable  oils  
o    
  • qualities  of  a  good  solvent  
weigh  coffee  (or  tea)       o able  to  separate  the  components  effectively  (i.e.  
↓   good  resolution)  
+  boiling  water   • extracts  caffeine  from   o moderately  volatile  
↓   sample   o cheap  
• highly  soluble  in  water  at   o relatively  less  toxic  
elevated  temperatures    
• other  polar  compounds   • stationary  phase:  water  adsorbed  on  cellulose  
such  as  tannins  are  also   • mobile  phase:  chromatographic  solvents  
extracted   o can  be  a  mixture  of    2  or  more  solvents  
filter   • removes  undissolved  solids    
↓  
extraction  with  ethyl   • separates  caffeine  from  
acetate/dichloromethane   other  polar  compounds  
↓   • salt  solution  can  be  added  
to  enhance  
separation/remove  
emulsion  due  to  saponins  
 
wash  with  6M  NaOH  and   • NaOH  dissolves  low  MW   • most  cases:  normal  phase  chromatography    
dH2O   acidic  tannins       o stationary  phase:  H2O  in  cellulose  (polar)  
↓   • tannins  can  also  be   o mobile  phase:  petroleum  ether  (nonpolar)  
removed  by  boiling  with   • reverse  phase  chromatography    
CaCO3  to  cut  ester  bonds   o stationary  phase:  relatively  nonpolar  
(converts  to  water-­‐soluble   o mobile  phase:  relatively  polar  
sugars)    
+  anhydrous  CaCl2   • drying;  removes  water   • 1.5cm  line  
↓   o avoid  component  dissolution;  otherwise,  
steam  bath   • removes  excess  solvent   separation  will  not  occur    
↓   • chromatographic  chamber  
sublimation     • purification     o closed  system  
  § avoid  solvent  evaporation  
Principle:   § avoid  contamination    
• solids  sublime  if:  with  high  vapor  pressure  at   § allow  saturation  to  prevent  solvent  
temperature  below  melting  point  for  volatile  solids   evaporating  of  paper  
o MP  caffeine:  238°C   • retention  factor  
o sublimation  temperature:  178°C   o qualitative  parameter  
  o good  resolution:  Rf  =  0.4  –  0.8    
  recrystallization   sublimation   o each  spot  has  a  unique  Rf  
procedure   tedious   simple  and  easy   o solvent  dependent  (indicate  solvent  used)  
involves  many   involves  only  one   distance  travelled  by  spot
R! =  
steps   step  and  doesn’t   distance  travelled  by  solvent
require  the  use  of    
solvents   • advantages:    
%  yield   high   low   o simple  set-­‐up    
%  purity   low   high   o easy  to  do    
  o not  time  consuming    
Experiment  4:  Paper  Chromatography   o cheap  
  • limitations:  
• columnar  or  planar  chromatography   o for  mixtures  with  colored  compounds  only  
• components  separated  based  on  relative  solubilities  in  M    
and  S  phase    
Chem  31.  Midterms  Reviewer   3     /steffigatdula/  
Visualizing  Techniques   Experiment  6:  Preparation  and  Purification  of  an  Alkyl  
• iodine  chamber   Halide  
o multiple  bonds  (double/  triple)/unsaturated    
compounds   Alkyl  Halides  
o electrophilic  addition   • compounds  in  which  a  halogen  atom  replaces  a  H  atom  
• UV  lamp   of  an  alkane  
o conjugated  double  bonds   • also  called  haloalkanes    
3
o aromatic  compounds   • R-­‐X  where  X  =  Br,  Cl,  I,  F  (sp  hybridized)  
  • classified  as  primary,  secondary,  tertiary  
Dimensional  Techniques   o based  on  the  C  atom  the  hydrogen  is  directly  
attached  
 
Physical  Properties  
• most  are  inert  →  used  as  common  solvents  
 
Reactions    
• nucleophilic  substitution    
• elimination    
 
Side  Reactions  
• di-­‐tert-­‐butyl-­‐ether  
• 2-­‐methlypropene  
• reversion  back  to  alcohol/solvolysis  
 
t-­‐BuOH  +  cold  conc.  HCl   • why  cold?  
↓   o to  prevent  the  
volatilization  of  product    
o to  minimize  the  
production  of  side  
product  
  • why  in  excess?  
• for  improvement  of  separation     o to  ensure  that  the  
st nd
• 1  run:  vertical  and  2  run:  horizontal   forward  reaction  is  
• different  solvents   favored  
  • why  concentrated?  
Problems   o to  minimize  the  volume  
• tailing     of  HCl  but  retain  the  
o heavy  spot;  heavy  compound   number  of  moles  
• absence  of  spots     mix  in  a  separatory   • relieve  pressure  once  in  a  
o extract  is  too  diluted     funnel   while  by  opening  the  
  ↓   stopcock  
Expected  Elution  Order     +  saturated  NaCl   • minimizes  the  solubility  of  
alkanes  <  R-­‐X  <  dienes  <  aromatic  HCs  <  Ar-­‐X  <  ether  <  ester  <   ↓   the  organic  product  in  the  
ketones  <  aldehydes  <  amines  <  alcohols  <  phenols  <  RCOOHs   aqueous  layer    
<  sulfonic  acid   • “salting  out”;  aqueous  layer  
  will  choose  dissolve  NaCl  
Applications     rather  than  the  organic  
• isolation  of  components   product  
• reaction  monitoring     allow  to  stand  for  20   • aqueous  layer  (bottom)  is  
o time  =  0  →  reagents   minutes   discarded  
o after  1  hour  →  product/s   ↓   • organic  layer  (top)  is  
o after  1  day  →  excess  or  limiting  reagent   collected  
  +  solid  NaHCO3  to  organic   • until  bubble  formation  stops    
  layer   • why  solid?  
  ↓   o to  prevent  introducing  
  H2O  into  the  crude  
product  and  cause  it  to  
Chem  31.  Midterms  Reviewer   4     /steffigatdula/  
 hydrolyze   Ethers  
• to  neutralize  the  acid   • differ  from  alcohols  
+  CaCl2   • add  until  it  no  longer  clumps   • R-­‐O-­‐R  
↓   • this  removes  water  and    
unreacted  alcohols  in  the   Reactivity  of  Ethers  
crude  product   • diethyl  ether  did  not  decolorize  the  neutral  KMnO4  
• also  removes  oxygen   because  ethers  are  inert  to  the  oxidation  by  
containing  compounds   permanganate  and  chromic  acid  
distillation     • distilling  the  crude  product   • lower  boiling  point  and  inertness  to  lots  of  reactions;  
separates  it  from  impurities   good  solvents    
• measuring  the  temperature   • no  α-­‐hydrogens  
of  the  vapor  serves  as  a  way    
of  identifying  the  product     Phenols  
collect  distillate   • in  ice  bath  to  prevent   • alcohols  attached  directly  to  a  benzene  ring  
volatilization    
  Acidity  of  Phenols  
Boiling  Chips?   • the  presence  of  electron  withdrawing  groups  stabilizes  
• prevent  the  solution  from  becoming  superheated  as  it   the  conjugate  base  of  the  phenol:  the  phenoxide  or  
helps  distribute  the  heat  throughout  the  solution   phenolate  ion    
• prevent  the  solution  from  boiling  violently  (i.e.  bumping)   • the  more  electron  withdrawing  groups  →  more  
by  providing  sites  for  bubble  formation     resonance  contributors  →  more  stable  phenoxide  ion  →  
  therefore,  more  acidic  phenol  
+
Continuous  Flow  of  Water  in  Condenser?   • readily  gives  H  
• ensures  that  the  condenser  is  cold  and  is  capable  of    
condensing  vapors   Complexation  with  FeCl3  
• failure  would  result  to  release  of  alkyl  halide  vapors  and   • depending  on  the  presence  of  conjugate  groups  attached  
loss  of  product   to  the  benzene  ring,  color  may  change    
   
Experiment  7:  Alcohols,  Phenols,  and  Ethers   Electrophilic  Aromatic  Substitution    
  • positive  result:  phenol  reacts  with  Br2 ⋅H2O  →  white  
⋅

Alcohols   precipitate  
• have  a  hydroxyl  group  bonded  to  a  saturated  C  atom      
  Oxidation  of  Phenols  
Lucas  Test   • oxidized  to  quinones    
• modified  SN1  mechanism,  meaning  that  the  reaction  rate   • quinones  are  unsaturated  ketones  which  are  usually  
is  determined  by  the  rate  of  formation  of  the  carbocation   colored    
• the  reagent  favors  SN1  because  it  is:   • positive  result:  brown  precipitate  
o acidic    
o it  has  ZnCl2  which  is  a  lewis  acid   Experiment  8:  Aliphatic  and  Aromatic  Hydrocarbons  
o as  a  solvent,  highly  polar  ionic      
• positive  result:  formation  of  layers  and  cloudiness   Hydrocarbons  
o 3°  >  2°  >  1°  >  CH3OH     • aliphatic  –  alkanes,  alkenes,  alkynes  
o benzyl  alcohol  gives  a  false  positive  since  there   • aromatic  
is  formation  of  layers  but  no  reaction    
  • alkanes  –  free  radical  substitution    
Neutral  KMnO4:  Oxidation  of  Alcohols   • alkenes  and  alkynes  –  electrophilic  substitution    
• 1°  and  2°  alcohols  give  the  positive  result,  while  3°   • aromatics  -­‐  unsaturated,  delocalized  pi  electrons  which  
alcohols  will  not  react  at  all     make  them  stable;    to  preserve  the  resonance  stabilized  
• for  a  compounds  to  be  oxidixed,  it  has  to  have  at  least  1   ring,  it  only  reacts  through  substitution    
α-­‐hydrogen  (hydrogen  directly  bonded  to  the  first  carbon    
atom  bonded  to  a  functional  group)   Br2  in  Light  Conditions  
• 1°  alcohols  are  converted  to  carboxylic  acids  and  2°   • free  radical  substitution    
alcohols  to  ketones   • stability  of  free  radicals:  b  ≈  a  3°  >  2°  >  1°  >  CH3OH    
• positive  result:  decolorization  and  brown  precipitate      
  Br2  in  Dark  Conditions  
  • general  test  for  unsaturation    
 
Chem  31.  Midterms  Reviewer   5     /steffigatdula/  
• decolorization  in  dark  conditions  means  unsaturation  is   Electron  Withdrawing  Groups  
present   • characterized  by  having  a  positive  or  partial  positive  
• mechanisms:  electrophilic  addition   charge  
+
• aromatics  do  not  undergo  bromination  addition  reaction   • strong:  –NO2,  –NR3 ,  –CX3  
to  preserve  the  aromatic  ring   • moderate:  –CN,  –COOH,  –COOR,  –CHO,  –COR,  –CONH2,    
  –SO3H  
Baeyer’s  Test     • weak  (only  in  the  ortho-­‐para  positions):  –F,  –Cl,  –Br,  –I  
+
• general  test  for  unsaturation     • ↓  rate  of  E ArS  when  EWG  are  in  the  meta  positions  
• positive  result:  precipitate,  MnO2    
• inconclusive  since  all  easily  oxidizable  organic  
compounds  like  1°  and  2°  alcohols,  aldehydes,  aryl  
halides  and  phenols  give  positive  results  
 
Friedel-­‐Crafts  Alkylation  Test  
• general  test  for  presence  of  aromatic  ring  
• change  in  color  of  AlCl3  crystal  indicates  the  presence  of  
an  aromatic  ring    
• benzene:  yellow  →  orange  
 
Flame  Test    
• combustion  of  hydrocarbons  may  also  suggest  the  type  
of  hydrocarbon  present    
• high  C–to–H  ration  produces  yellow,  smoky,  sooty  flame  
o due  to  the  production  of  C  in  the  form  of  soot  as  
a  result  of  incomplete  combustion  (alkenes,  
alkynes)    
 
Test  for  Alkynes  
• presence  of  terminal  alkynes  detected  by  allowing  it  to  
react  with  [Ag(NH3)2]NO  
• positive  result:  white  to  gray  precipitate  
 
Steam  Distillation  
• steam  distillation:  for  heat  sensitive  liquids  
• immiscible  mixtures  where  steam  is  used  to  provide  one  
of  the  immiscible  phases  
• desired  material  distills  at  >100°C  
• limonene  distills  instead  of  decomposing  
• Patm  =  ↑PT  =  PLIM  +  ↑PSTEAM  
 
Experiment  9:  Relative  Rates  of  Electrophilic  Aromatic  
Substitution    
 
• Br2/CH3COOH  is  the  polarizing  solvent  (distorts  the  
electron  cloud)  
• AlBr3/FeBr3  is  the  catalyst  (lewis  acid)      
 
Electron  Donating  Groups  
• characterized  by  having  lone  pairs    
• strong:  –OH,  –NH,  –NHR,  –NR2    
• moderate:  –OR,  –NHCOOR  
• weak:  –C6H3,  alkyl  (R)  groups  
+
• ↑  rate  of  E ArS  when  EDG  are  in  the  ortho-­‐para  positions  
 
 
 

Chem  31.  Midterms  Reviewer   6     /steffigatdula/