JULIAN S.

DE LARA January 19, 2011

Lab Partners: (Fumeheads) Kyle de Leon, Michaela Chua, Kim Lagrama, Jolo Mirasol

EXPERIMENT 9: RELATIVE RATES OF ELECTROPHILIC AROMATIC SUBSTITUTION

I. OBJECTIVES
 Be familiar with aldehydes and ketones
 Know more about carbonyl compounds
 Reintroduce nucleophilic addition reactions

II. SCHEMATIC DIAGRAM OF THE PROCEDURE

MATERIALS:
 50 mL beaker  Micro test tubes
 Bunsen burner  Pasteur pipettes
 5 mL Measuring Pipettes

REAGENTS:
 Formalin (40% HCHO in H2O)  10% NaOH
 2,4-dinitrophenylhydrazine (solid)  0.1 M CH3COOH
 2,4-dinitrophenylhydrazine in HCl  0.1 M HCl
 Tollens’ reagent  1.0 M HCl
 Schiff’s reagent  95% CH3CH2OH
 Benedict’s reagent  I2 in KI

REACTION WITH 2,4-DINITROPHENYLHYDRAZINE (2,4-DNPH)

Place 5 drops of 95% ethanol in three To all three, add 1 mL 2,4-DNPH in HCl
micro test tubes. To one, add 2 drops of solution. Record the color of the
acetone. To another, add 2 drops of precipitate formed. If no precipitate, let it
benzaldehyde stand for a while

TOLLENS’ TEST

Place 5 drops of Tollens’ reagent in 3 micro test Observe the formation of a silver mirror. Warm in
tubes. To one, add a drop of formalin; to the a water bath if no reaction is observed. As soon
second, add a drop of acetone; and to the last a as the silver mirror is formed, pour out the
drop of benzaldehyde contents of the test tube and rinse with water.

SCHIFF’S TEST
Place 4 drops of Schiff’s reagent in 3 micro test
tubes. To one, add a drop of formalin; to the Shake and Observe the color that develops in 3-4
second, add a drop of acetone; and to the last a minutes
drop of benzaldehyde
BENEDICT’S TEST

Place 5 drops of Tollens’ reagent in 2 micro test

tubes. To one, add 2 drops of formalin; and to the Place the test tubes in a hot water bath. Note the
last, 2 drops of benzaldehyde brick red precipitate that forms.

IODOFORM TEST

Place 5 drops of 10% NaOH in 2 test tubes. To one, add 2 Warm the solution in a water bath. If the solution turns
drops of acetone; and to the last 2 drops of 95% ethanol. To colorless after heating, add more iodine-iodide solution and
both, add I2 in KI solution until the solution becomes pale take note if it turns yellow again. Record the color after
yellow. addition of iodine-iodide before and after heating

EFFECT OF ACID CONCENTRATION ON THE RATE OF ADDITION OF 2,4-DINITROPHENYLHYDRAZINE

Place 5 drops of the prepared 2,4-DNPH into 4 micro test

Weigh 0.15 g of 2,4-DNPH in a beaker and dissolve in 15 mL tubes. To one, add 1 drop 0.1M acetic acid, to the 2nd, add 1
acetone. Decant if there are undissolved solids. drop 0.1M HCl and to the third add 1 drop 1.0 M HCl. Note
the time of mixing and the time when crystals appear.

III. TABLE OF REAGENTS/PRODUCTS

REAGENT/
STRUCTURE PHYSICAL PROPERTIES HAZARDS
PRODUCT
Melting point: 16.7 C  Substances to be avoided include alcohols,
Boiling point: 118 C aldehydes, halogen-halogen compounds,
Specific gravity: 1.05 oxidizing agents, metals, alkali hydroxides,
Vapour density 2.07 anhydrides, nonmetallic halides,
Acetic Acid Vapour pressure 11 mm Hg at 20 C, 20 mm permanganates, peroxides, ethanolamine,
Hg at 30 C and carbonates. Flammable.
Flash point: 40 C  This material is strongly corrosive and
Explosion limits: 4% - 16% causes serious burns. Very harmful if
Ignition temperature 426 C swallowed.
An Aqueous Solution of:
copper (II) sulfate,
Appearance: liquid  Harmful if swallowed or inhaled and in
Benedict’s Reagent sodium carbonate,
Density (g cm-3): 1.19 contact with the skin.
sodium citrate dihydrate
and 2,5-difluorotoluene.
Appearance: red powder
 Stable when wet, but explosive when dry.
Melting point: 200 - 202 C
May be shock sensitive when dry. Highly
2,4- Solubility:
flammable. Incompatible with strong
dinitrophenylhydrazine Slightly soluble in water.
oxidizing agents.
Melting Point:
 Harmful if swallowed.
198 - 202C (388 - 396F) Decomposes.
Physical State: Clear liquid  Causes severe eye irritation. Flammable
Ethyl Alcohol
Appearance: colorless liquid and vapor. Causes respiratory tract
 Odor: Mild, rather pleasant, like wine or
whis
pH: Not available.
Vapor Pressure: 59.3 mm Hg @ 20 deg C
Vapor Density: 1.59
irritation. This substance has caused
Evaporation Rate: Not available.
adverse reproductive and fetal effects in
Viscosity: 1.200 cP @ 20 deg C
humans. May cause central nervous
Boiling Point: 78 deg C
system depression. May cause liver, kidney
Freezing/Melting Point:-114.1 deg C
and heart damage. Causes moderate skin
Decomposition Temperature: Not available.
irritation.
Solubility: Miscible.
Specific Gravity/Density:0.790 @ 20°C
Molecular Formula:C2H5OH
Molecular Weight:46.0414
 Strong reducing agent, especially in alkaline
solution. Substances to be avoided include
strong bases, strong acids, strong oxidising
agents, aniline, phenol, isocyanates,
Appearance: colourless liquid, typically 37%
anhydrides. Combustible. Light and air
formaldehyde in water
sensitive. Polymerizes spontaneously.
Boiling point: 96 C
 Causes burns. Very toxic by inhalation,
Specific gravity: 1.083
ingestion and through skin absorption.
Vapour pressure: 55 mm Hg at 37 C
Formaline Readily absorbed through skin. Probable
Vapour density: 1 (air = 1)
human carcinogen. Mutagen. May cause
Flash point: 56 C
damage to kidneys. May cause allergic
Explosion limits: 7% - 73%
reactions. May cause sensitisation. May
Autoignition temperature: 572 F
cause heritable genetic damage.
Water solubility: substantial
Lachrymator at levels from less than 20
ppm upwards. Very destructive of mucous
membranes and upper respiratory tract,
eyes and skin.

Appearance: Clear, colorless liquid.

Odor: Pungent odor.
Solubility: Infinitely soluble.
 Corrosive. Liquid and mist cause severe
Density: 1.05 @ 15 C (59 F)
Hydrochloric Acid burns to all body tissue. May be fatal if
pH: For HCL solutions: 0.1 (1.0 N), 1.1 (0.1
swallowed or inhaled.
N), 2.02 (0.01 N)
% Volatiles by volume @ 21C (70F): 100
Boiling Point: 101 - 103C (214 - 217F)

I I

 Causes severe irritation or burns to every

Appearance: Clear, reddish brown liquid.
area of contact. May be fatal if swallowed
Odor: Iodine odor.
or inhaled. Vapors cause severe irritation to
Solubility: Infinitely soluble.
skin, eyes and respiratory tract. Oxidizer.
I2 in KI Specific Gravity: 1.37
Contact with other material may cause fire.
% Volatiles by volume @ 21C (70F): ca. 60
Affects the cardiovascular and central
Boiling Point: ca. 100C (ca. 212F)
nervous systems. May cause allergic skin
Melting Point: ca. 0C (ca. 32F)
or respiratory reaction.

Schiff’s Reagent Appearance: Clear, colorless liquid.
Odor: Pungent odor of sulfur dioxide.
Solubility: Complete (100%)
Specific Gravity: 1.00
pH: 1.1 - 1.5
% Volatiles by volume @ 21C (70F): 100
 May cause irritation to skin, eyes, and
respiratory tract. Possible cancer hazard.
Contains pararosaniline which may cause
cancer based on animal data. Risk of
cancer depends upon duration and level of
exposure.
 Boiling Point: ca. 100C (ca. 212F)
Melting Point: ca. 0C (ca. 32F)
Vapor Pressure (mm Hg): Essentially the

same as water.
Evaporation Rate (BuAc=1): Essentially the
same as water.
Physical State: Liquid
Appearance: colorless
Odor: practically odorless
pH: 13-14
Vapor Pressure: Not available.
Vapor Density: >1.0  Corrosive. Causes eye and skin burns. May
Evaporation Rate: Not available. cause severe respiratory tract irritation with
Viscosity: Not available. possible burns. May cause severe digestive
Sodium Hydroxide H3O+ OH-
Boiling Point: > 100 deg C tract irritation with possible burns. Eye
Freezing/Melting Point:> 0 deg C contact may result in permanent eye
Decomposition Temperature: Not available. damage.

Solubility: Soluble.
Specific Gravity/Density:>1.0
Molecular Formula: NaOH
Molecular Weight: Not available.
 Tollen's reagent contains ammonium
hydroxide which is corrosive and harmful if
you swallow it. It can also cause damage if
splashed into the eyes.
[Ag(NH3)2]+  If spilt upon the skin, the silver ions in
Form: colourless liquid
Tollen's solution may, over the course of
Stability: Stable, but only for a few hours, so
one or two days, produce a black stain on
Tollens’ Reagent this reagent is best freshly prepared for
the skin. This is not likely to be harmful, nor
each use
will it be permanent, but may be unsightly.
Specific gravity: close to 1
 There is a small risk of forming explosive
fulminating silver, if Tollen's reagent is left
unused for a period of time. To avoid this,
neutralise unused reagent with a little nitric
acid and discard.

IV. WASTE DISPOSAL

 All Waste Solutions – Non-Halogenated Waste Jars