Exp.

8: Classification tests for

ORGANIC HALIDES

mrsantiago(Chem 200 lab, AY 2014-2015)

ORGANIC HALIDE
CnH2n+1X
X is more e- than C so it
pulls the electrons in
the bond closer to itself,
gaining a partially
negative charge, making
the carbon it is bonded
to partially positive (or
electron deficient)

mrsantiago(Chem 200 lab, AY 2014-2015)

1. BEILSTEIN TEST
General Test for halides
Produces green colored flame except F2 which
is non-volatile

mrsantiago(Chem 200 lab, AY 2014-2015)

NUCLEOPHILIC SUBSTITUTION (SN)

One covalent bond is broken as a new
covalent bond is formed
The general form for the reaction is
Nu:- + R-X R-Nu +
X:-

Nucleophile +

haloalkane Substituted Product + Leaving group/halide

mrsantiago(Chem 200 lab, AY 2014-2015)

What is a NUCLEOPHILE?
A nucleophile is a molecule or ion that has a high electron
density, so its attracted to atoms in molecules with a lower
electron density.
It may replace another group in an organic molecule.
They are attracted to the electron deficient carbon in the
haloalkane
Typical nucleophiles: H2O, OH-, NH3, CN-

mrsantiago(Chem 200 lab, AY 2014-2015)

mrsantiago(Chem 200 lab, AY 2014-2015)

mrsantiago(Chem 200 lab, AY 2014-2015)

NUCLEOPHILIC SUBSTITUTION
UNIMOLECULAR (SN1)

1.
2.

2-Step reaction:
Dissociation of RX to C+ and XAttachment of Nu- to R+
Reactivity is based on stability of C+

Rate of reaction is dependent on RX

mrsantiago(Chem 200 lab, AY 2014-2015)

SN1 REACTION
Order of reactivity is affected by nature of
alkyl halide
Leaving group (more electronegative, better
leaving group)
F > Cl > Br > I > OH > NH2
Degree of branching
30 > 20 > 10

mrsantiago(Chem 200 lab, AY 2014-2015)

mrsantiago(Chem 200 lab, AY 2014-2015)

NUCLEOPHILIC SUBSTITUTION
BIMOLECULAR (SN2)
1-step reaction

Reactivity is dependent on the steric effect of the rear end of the functional C

Rate of reaction is dependent on RX and Numrsantiago(Chem 200 lab, AY 2014-2015)

SN2 REACTION
Order of reactivity is affected by:
Degree of branching (steric hindrance)
10 > 20 > 30
Strength of nucleophile
-NH2 > -OH >

mrsantiago(Chem 200 lab, AY 2014-2015)

Summary (Expt 8)
SAMPLE

BEILSTEIN
TEST

Ethanolic
AgNO3 (SN1)

NaI in
acetone
(SN2)

Green flame

(3)+++

(1)+

Green flame

(2)++

(2)++

Green flame

(1)+

(3)+++

Green flame

(4) +/-

NR (-)

mrsantiago(Chem 200 lab, AY 2014-2015)

Exp 9: Classification test for

HYDROXYL AND CARBONYL
CONTAINING COMPOUNDS

mrsantiago(Chem 200 lab, AY 2014-2015)

HYDROXYL CONTAINING
HYDROCARBON DERIVATIVES

mrsantiago(Chem 200 lab, AY 2014-2015)

SOLUBILITY OF ALCOHOLS IN WATER

Polar hydroxyl group

Non-polar/hydrophobic hydrocarbon chain
#C, hydrophobic, polar, soluble in H2O
branched, hydrophobic, soluble in H2O

Solubility in water:

3 0 > 2 0 > 10
mrsantiago(Chem 200 lab, AY 2014-2015)

Lucas Test (SN1)

Substrates that easily give rise to cationic character at the carbon bearing the
hydroxyl group undergo the Lucas test readily.

Alkyl halide appears as a second liquid layer

+ Test: Formation of insoluble layer or emulsion in 5-10 min
Note: Primary alcohols do not give positive result.

mrsantiago(Chem 200 lab, AY 2014-2015)

CARBONYL CONTAINING
HYDROCARBON DERIVATIVES

mrsantiago(Chem 200 lab, AY 2014-2015)

OXIDATION OF ALCOHOLS AND

ALDEHYDES

No rxn

No rxn
mrsantiago(Chem 200 lab, AY 2014-2015)

Oxidation tests
1. Jones or Chromic acid test
2. Tollens or Silver mirror test
3. Fehlings test

mrsantiago(Chem 200 lab, AY 2014-2015)

CHROMIC ACID TEST

(JONES OXIDATION TEST)
Differentiating test for oxidizable carbons

No Reaction
mrsantiago(Chem 200 lab, AY 2014-2015)

TOLLENS (SILVER MIRROR) TEST

Test for oxidizable carbon
Reduction of Ag+ to Ag

No rxn
mrsantiago(Chem 200 lab, AY 2014-2015)

FEHLINGS TEST

Test for oxidizable carbon

Differentiating test for aliphatic(+) and aromatic (-)

aldehydes

Components:
Fehlings A: CuSO4(aq)
Fehlings B: potassium sodium tartrate, NaOH

No rxn
mrsantiago(Chem 200 lab, AY 2014-2015)

FEHLINGS TEST

mrsantiago(Chem 200 lab, AY 2014-2015)

2,4-DNPH TEST
Test for presence of carbonyl group (aldehydes and
sterically unhindered ketones)

formation of hydrazone

Reagent: 2,4-dinitrophenyl hydrazine

Can be used to differentiate aromatic and

aliphatic carbonyl containing organic compound
Aromatic: red orange ppt
Aliphatic yellow orange ppt
mrsantiago(Chem 200 lab, AY 2014-2015)

IODOFORM TEST
Test for methyl carbonyl
Enolate formation of methyl carbonyl group
Reagent: 10% KI/NaClO

mrsantiago(Chem 200 lab, AY 2014-2015)

Sample

n-butyl
alcohol
sec-butyl
alcohol
tert-butyl
alcohol
acetaldeh
yde
nbutyralde
hyde

benzalde
hyde
acetone
acetophe
none
Isopropyl
alcohol

Solubility Lucas
in H2O

Jones

Tollens

Fehlings

DNPH

Iodoform