Table of Contents

I. Check in & General Discussion

1. Common Laboratory Apparatus 2

2. Safety in the Chemistry Laboratory 4

II. EXPERIMENTS:

1. Recrystallization 6
2. Melting Point 13
3. Boiling Point 19
4. Extraction 24
5. Fractional Distillation 30
6. Chromatography 38
7. Dehydration of 4-methyl-2-pentanol 45
8. Tests for Functional Groups 48
9. Make Soap 55
10. Preparation of Aspirin 60
11. Discussion of NMR 63
12. Discussion of IR 64

III. Periodic Table 65

1
 Erlenmeyer Graduate
Round-bottomed (Conical) flask (measuring
flask cylinder
Separating
funnel

Clamp
Buchner Receiver
funnel adaptor

Stillhead Claisen stillhead

Condenser
Fractionating
column

2
 spatula

burner striker

test tube holder

wire gauze with
ceramic center

morter & pestle desicator

extension clamp clay triangle

pinch clamp
clamp holder
`

3
SAFETY POLICY FOR STUDENTS:

The following is in no way a complete and absolute statement of safety to be

followed in the laboratory. Its intent is to make you aware of policies for certain emergency
situations. Your instructors may point out other safety precautions from time to time.

EYE PROTECTION: Safety glasses must be WORN all times when you are in the
laboratory. Contact lenses are not recommended in lab. If you must wear contact lenses,
then you must wear a pair of non-vented safety goggles. (Chemicals splashed into the eye
may get behind the lens and damage the eye before the lens can be removed and appropriate
first aid administered. Also chemical fumes can build up behind contact lenses and damage
eyes without one being aware of the problem.)
If a chemical is splashed into your eye, use an eyewash and irrigate the eye completely for
15 minutes. Be sure you immediately inform your instructor about this incident.

CONDITION OF YOUR WORK AREA: You should maintain a work area that is free of
unnecessary equipment, books, coats, purses, chemical spills, excess chemicals…etc. All
chemical spills should be cleaned up immediately.

DISPOSAL OF WASTE MATERIALS: Waste paper, towels, and other trash should be
discarded in the wastebaskets. Broken glass should be placed in the labeled broken glass
container. Waste chemicals should be discarded in the labeled waste containers.

FIRE ON YOUR PERSON: Immediately use the safety shower or extinguish the fire with a
fire extinguisher or fire blanket. Never use a CO2 extinguisher around the exposed skin or
the head of an individual.

FIRE IN THE LABORATORY: For small fires, we can use a CO2 fire extinguisher. For
large fire, we sound the building fire alarm and evacuate the building.

CHEMICAL SPILLS ON YOUR BODY: A safety shower is located in each laboratory and
should be used to wash chemicals from your body if washing in a sink is not sufficient. All
contaminated clothing should be removed as soon as possible while you are under the
shower. Remember: Speed in washing is most important in reducing the extent of injury.

PIPETING LIQUIDS: Always use a rubber suction bulb to pipet liquids. Never use your
mouth.

4
EATING OR DRINKING: Since there is a possibility of food substance becoming
contaminated with toxic chemicals, no eating or drinking will be allowed in the laboratory.
Never taste any chemical in the laboratory, unless directed to do so by your instructor.

SMOKING: Smoking is not allowed in or near the laboratory.

UNAUTHORIZED EXPERIMENTS: Under no circumstances should you conduct an

experiment other than those that have been assigned unless you obtain a written consent
from your instructor. Under no circumstances should you work in the laboratory alone or
without supervision.

HEATING LIQUIDS: When heating liquids always point the opening of the container away
from yourself and the workers in the area. Never heat a closed system. Never use an open
flame in heating flammable liquids.

HANDS: Always wash your hands whenever you have touched a chemical and before you
leave the laboratory.

LABORATORY CONDUCT: You should be courteous and exercise common sense and
good judgment in the laboratory. There will be no practical joking, jogging, running, or
pushing in the laboratory.

CHEMICALS: Never use a chemical from an unlabeled container. Never

substitute a chemical in an experiment unless you have been directed to
do so by your instructor. Always treat unfamiliar chemicals as if they are dangerous.

5
EXPIREMENT 1
RECRYSTALLIZATION

1.1 OBJECTIVES

1. To recrystallize an impure organic compound (benzoic acid) using water as the

solvent.
2. To get acquainted with the filtration techniques (gravity and vacuum).

1.2 INTRODUCTION

Crystallization is a method used for purification. It is the first recommended

technique to be thought of for purifying organic compounds that are solid at room
temperature. The general technique is based on the fact that most solids are more soluble in
hot solvents than cold solvents and that different materials are soluble to different extents in
various solvents.
Recrystallization involves dissolving the material to be crystallized in a hot solvent
and cooling the solution slowly. Upon cooling, solid separates again because it is less
soluble at lower temperature. The process is called crystallization if the crystal grows
slowly and incorporates only product molecules; and it is called precipitation if the crystal
grows rapidly and incorporates impurities as well as product.
solid + solvent  solution
Crystallization is an equilibrium process and produces pure material. When the hot,
saturated solution is allowed to cool slowly, a small seed crystal is formed initially, and it
then grows layer by layer as the solubility of the dissolved material is decreased by cooling.
If at any time during this process the temperature is held constant, equilibrium is established,
that is, the molecules leaving the crystal and molecules attaching to the crystal are equal in
number. Equilibrium encourages the growth of crystals made up of just one kind of
molecule because orientation of molecules in crystal lattice is an exacting and selective

6
 process. In a sense, the crystal “selects” the correct molecules from the solution. In
precipitation, the crystal is formed so rapidly that impurities are trapped within the lattice.
Precipitation usually occurs by rapid cooling. Therefore, in any attempt at purification, too
rapid a process should be avoided. Too slow a process should be avoided. The time scale
for crystal formation should be in the tens of minutes or hours, rather than seconds or days.
The two principle mistakes that can be made are (1) cooling the solution too rapidly and (2)
suddenly adding an incompatible solvent to the solution. Both of these mistakes will be
considered in this technique.

1.3 SOLUBILITY

Fig. 1.1. C (good solvent)

Soubitity vs temperature * very soluble at elevated temp.
*sparingly soluble at room temp.

B (poor solvent)
grams soluble

A (poor solvent)

temperature

The most crucial step in performing a crystallization is selecting a solvent in which the solid to be
crystallized exhibit reasonably high solubility in hot solvent and low solubility in cold solvent. The
solubility curve should be steep, as can be seen in line B of Figure 1.1. A curve with a low slope
(line A) would not give significant crystallization when the temperature of the solution was
lowered. A solvent in which the material was very soluble at all temperature (line B) would not be
suitable crystallization solvent. The solvent presented in steep line C is an ideal crystallization
solvent. Solvents are selected either by consulting the chemical literature or by trial and error
7
based on one’s knowledge of solvent and product structures.
The solubility of organic compounds depends on the polarities and sizes of the solute and
solvent molecules. A general rule of thumb states, “like dissolves like”. That is, if solute is a polar,
a polar solvent is required to dissolve it. If it is nonpolar, a nonpolar solvent will be needed.
Usually compounds having functional groups that can form hydrogen bonds, such as -OH, -NH, -
COOH, -CONH, will be more soluble in hydroxylic solvents such as water or methanol than in
hydrocarbon solvents such as benzene or hexane. However, if the functional group is not the
major part of the molecule, the solubility behavior may be reversed. For instance, dodecyl alcohol,
CH3(CH2)10CH2OH, is almost insoluble in water; its 12-carbon chain causes it to behave more like
a hydrocarbon than an alcohol. The list found in Table 1.1 gives an approximate order for
decreasing polarity of organic functional groups.

TABLE1.1. Solvents, in Decreasing Order of Polarity

Class of Solvent General Structure Example

R = alkyl or aryl
_________________________________________________________________________
Water H2O water
Organic acids RCO2H acetic acid
Amides RCONH2 N,N-dimethylformamide
Alcohols ROH methanol, ethanol
Amines RNH2 triethylamine, pyridine
Ketones RCOR acetone
Esters RCOOR ethyl acetate
Halides RX CH2Cl2>CHCl3>CCl4
Ethers ROR diethyl ether
Aromatics ArH benzene, toluene
Alkanes RH hexane, petroleum ether

Let’s choose a solvent for recrystallizing benzoic acid. Benzoic acid, C6H5CO2H, has a
polar functional group, -CO2H, which is attractive to the polar functional groups that we find in

8
water, alcohols, amines, aldehydes, ketones, amides, and other acids. However, the phenyl ring of
benzoic acid is nonpolar and is attracted to less polar solvents such as ethers, benzene, and
alkanes. We should guess that benzoic acid will be too soluble in benzyl alcohol, C6H5CH2OH,
because of structural similarities. We should expect to be marginally soluble in water, partly
soluble because of the polarity likeness of the two carboxylic groups, and partly insoluble because
of the differences in polar carboxyl and nonpolar phenyl.

TABLE 1.2. Commonly Used Solvent Pairs

Ethanol-Water
Acetic Acid-Water
Acetone-Water
Dioxane-Water
Chloroform-Methanol
Petroleum ether-Diethyl ether
Petroleum Ether-Toluene
Ligroin-Toluene
_______________________________________________________________

When you cannot find a single common solvent that is satisfactory for recrystallization, you
can use a solvent pair. You can make a solvent in which crystals are too soluble less solubilizing
by adding a second miscible solvent in which the crystals are much less soluble. Table 1.2 lists a
number of common solvent pairs. The ligroin and petroleum ether listed in Table 1.2 are actually
hydrocarbon mixture. Pentanes and hexanes predominate in petroleum ether, whereas higher
boiling hydrocarbons predominate in ligroin.

9
1.4 THEORY OF CRYSTALLIZATION

A (10 g)
10
Figure 1.2.

t
Solubility curves

L solven
B (3 g)
6 (impurity)

e/100 m
g solubl

2.5
1.5
temperature0C
25 50 75

Most recrystallizations involve purifying crude product crystals that have impurities in the
crystal lattice and adhering to the surface. Because impurities generally have solubility
characteristics that are similar to those of the desired product, you can successfully separate the
product from such impurities only when there is either a considerable difference in their
solubilities or when the impurity is present in relatively small quantity. For example, consider the
case shown in Figure 1.2. The solubility curve for product A shows that at 75 0C, 10.0 g are
soluble in 100 mL of solvent, while the solubility curve for the Impurity B shows that at 75 0C,
6.0 g are soluble in 100 mL of solvent. Both curves for A and B have almost similar solubility
curve. If you initially dissolve 10.00 g of A and 3.0 g of B in 100 mL of solvent at 75 0C, cooling
the solution to 25 0C precipitates 8.50 g of A (10-1.5) along with 0.50 g of B (3.0 - 2.5), an
unsuccessful operation. However, if the original solution contains 2.5 g of B or less, the solution
can be cooled to 25 0C without precipitating any of B, and you can recover 8.50 g of pure A. 1.50
g of A and all of impurity B will remain in the leftover solution known as the mother liquor.
Sometimes you must repeat crystallization to obtain pure product crystals, especially when
impurities are present in large amounts. An important aspect of crystallization, that is, it is
wasteful. Nothing can be done to prevent the loss. Some A must be lost along with the impurity B
for the method to be successful.
10
 Other times, even though enough solute will dissolve to produce a saturated solution at the
higher temperature the solute will not precipitate again as the solution is cooled. Such a situation
results in a cold, supersaturated solution, which contains more solute than it required for
saturation. Supersaturation occurs when the first crystals do not form readily.

1.5 APPARATUS & CHEMICALS

Impure benzoic acid Glass rod
Distilled water Watch glass
Two 100 mL Erlenmeyer (Conical) flasks Filter papers
Buchner funnel Hot plate
Filter (Buchner) flask Short-stem funnel

1.6 EXPERIMENTAL PROCEDURE

Compound to be recrystallized is benzoic acid (benzenecarbocylic acid)
Solvent to be used is water.

I. Dissolving
1. Heat the desired solvent to its boiling point.
2. Dissolve 2.00 g of the crude sample in a minimum amount of boiling water (about 40 mL
of water).
3. Add decolorizing charcoal if necessary.
4. Gravity filter the hot solution through a preheated funnel using Fluted Filter Paper to
remove any insoluble impurities or charcoal.
5. Allow the solution to cool.
6. If crystals do not appear, go to II; if crystals appear, go to III.

II. Inducing crystallization

1. Scratch the flask with a glass rod or
2. Seed the solution or

11
3. Cool the solution in an ice-water bath

III. Collecting
1. Collect crystals by vacuum filtration, using a Büchner (Hirsch) funnel
2. Rinse crystals with a small portion of cold solvent.
3. Continue suction for few minutes.

IV. Drying
1. Air-dry the crystals or
2. Place the crystals in a drying oven or
3. Dry the crystals in a vacuum desiccator.

V. Storing the sample

1. Transfer the dried crystals to a clean, pre-weighed vial
2. Weigh the vial and contents.
3. Record the mass of the purified product on the vial.
4. Hand in your purified benzoic acid to the instructor.

12
EXPERIMENT 2
MELTING POINT

2.1. Objectives
1. To determine the melting point of a pure benzoic acid, an unknown compound, and
the benzoic acid you purified in experiment 1.

2. To observe the effect of impurities on melting range.

3. To determine the melting range of an unknown compound.

2.2. Introduction
Melting point for a crystalline compound is the primary index of purity used
by organic chemists. The process of converting solids to liquids upon heating is called
melting. A small amount of material is heated slowly in a special apparatus equipped
with a thermometer, a heating coil or a heating bath, and usually a magnifying eyepiece
for observing the sample. Two temperatures are noted. The first is the point at which the
first drop of liquid forms among the crystals; the second is the point at which the whole
mass of crystals turns into liquid. The melting point is then recorded as melting range.
For instance, that the melting point of a substance is 121-124 0C. That is, the substance
melted over a 30 range.
The melting point of a pure crystalline substance is a physical property of that
substance. Since the vapor pressure of a solid, compared with a liquid, is low, the
melting point is usually insensitive to changes of pressure (within reasonable limits).
This melting point can be used to identify a given substance.

2.3. Melting-Point Behavior

I. Melting Point of Pure Substance
The melting point of a substance is defined as the temperature at which the liquid
and solid phases exist in equilibrium with one another without change of temperature.
Ideally, addition of heat to a mixture of the solid and liquid phases of a pure substance
at the melting point will cause no rise in temperature until all the solid has melted.
Conversely, removal of heat from the equilibrium mixture will produce no decrease in
temperature until all the liquid solidifies. This means that the melting and freezing
points of a pure substance are identical.
The melting point is expressed as the temperature range over which the solid starts
to melt and then is completely converted to liquid. Consequently, rather than a melting

13
point, what is actually measured is a melting range, although the two terms are used
interchangeably. If a solid substance is pure, it should melt over a narrow or sharp
range, which should normally be within 3 0C. Melting may actually begin by softening
as evidence by an apparent shrinking of the solid. Thus, the start of melting is defined
as the temperature at which the first droplet of liquid is observed. Note that it is
improper and inexact to report a single temperature, such as 121 0C for a melting point;
rather, a range of 121 - 123 0C or 121.0 – 122.5 0C, for example, should be reported.

II. Melting Point of an Impure Substance; Mixture

The melting point (or range) indicates purity in two ways. First, the purer the
material, the higher is melting point. Second, the purer the material, the narrower the
melting-point range.
The presence of an impurity generally decreases the melting point of a pure solid
as shown in Figure 2.1. In this melting-point-composition diagram of Figure 2.1, points
(a, b) represent the melting point of pure A and B, respectively. Point E is called the
eutectic point and is determined by the equilibrium composition at which A and B melt
in constant ratio. In Figure 2.1, this ratio is 60 mol % A and 40 mol % B; an impure
solid comprised of A and B in this ratio would be called eutectic mixture. The melting
point of the mixture cannot be depressed below e, the melting temperature of the
eutectic.
Now consider what happens when the melting point of a mixture of 80% A and
20% of B is approached (note, B is the impurity in this case). When the temperature
reaches e, A and B will both begin to melt. Once all of B has melted, only solid A will
be left in equilibrium with the melt. The remaining solid A will continue to melt as
additional heat is supplied, and the percentage of A in the melt will increase. This
increase the vapor pressure of A in the solution according to Raoult’s law and raises the
temperature at which solid A is in equilibrium with the molten solution. The
relationship between the equilibrium temperature and the composition of the molten
solution is then represented by curve EF in Figure 2.1. When the temperature reaches f,
no solid A will remain and melting of the sample will be complete. The impure sample
A exhibits a melting point that extends over the relatively broad temperature range e-f.
Because melting both begins and ends below the melting point of pure A, the melting
point of A is said to be depressed.

14
 The foregoing analysis is easily extended to the case in which substance B
contains A as an impurity. In Figure 2.1, this simply means that the composition of the
solid mixture is to the right of point E. The temperature during the melting process
would follow curve ED or EG, and the melting range would now be e-d or e-g.
A sample whose composition is exactly that of the eutectic mixture (point E,
Figure 2.1) will exhibit a sharp melting point at the eutectic temperature. This means a
eutectic mixture can be mistaken for a pure compound, because both have a sharp
melting point.
The lower end of the melting range will always be e; however, melting will not be
observed at this temperature. An observable melting at e only comes about when a large
amount of B is present. Otherwise, the amount of liquid formed at e will be too small to
observe. Therefore, the melting behavior that is actually observed will have a smaller
range.

b
G g
liquid solution
a A&B

F D d
Temperature C

0
f

liquid & liquid &

solid A solid B
E
e e

Eutectic composition
Solid A & B

mol %A 100 90 80 70 60 50 40 30 20 10 0

mol % B 0 10 20 30 40 50 60 70 80 90 100

Fig. 2.1 Phase diagram for melting in a two-component system

2.4 Mixed Melting Point

The melting point can be used as supporting evidence in identifying a given
compound if an authentic sample of that compound is available for comparison. The
technique is commonly known as a mixed melting-point determination, and is
illustrated by the following example. Assume that an unknown compound X melts at
134-135 0C, and you suspect it is either urea, H2NCONH2, or trans-cinnamic acid,

15
C6H5CH=CHCO2H, both of which melt in this range. If X is mixed intimately with urea
and the melting point of this mixture is found to be lower than that of the pure
compound and pure urea, then urea is acting as an impurity, and the compound cannot
be urea. If the mixture melting point is identical to that of pure compound and of urea,
the compound is identical as urea.

2.5 Packing the Melting-Point Capillary Tube

Thin-walled capillary tubes (1 mm X 100 mm) that have been sealed at one
end are normally used in melting points. To pack the tube with the desired substance,
one presses the open end gently into a pulverized sample of the crystalline material.
Crystals will stick in the open end of the tube. To transfer the crystals to the other end
of the tube, you may do either of the followings a) one drops the capillary, closed end
first, down a one-half to one meter length of glass tubing, which is held upright on the
desk top; or b) By gently tapping the capillary tube on the desk top with the fingers.
The amount of solid pressed into the tube should correspond to a column no more than
1 to 2 mm high.

2.6 Melting Point Techniques

There are two general types of melting point apparatus: a Thiele tube and electrical
devices.
I. Using the Thiele Tube
The Thiele tube (Figure 2.2) is a glass tube designed to contain heating oil
(glycerin, paraffin oil, silicone oil, or cottonseed oil) and a thermometer to which a
capillary tube containing the sample is attached. The shape of the Thiele tube allows
convection currents to form in the oil when it is heated. These currents maintain a
uniform temperature distribution throughout the oil in the tube. The sidearm of the tube
is designed to generate these convection currents and thus transfer the heat from the
flame evenly and rapidly throughout the heating oil. The capillary tube containing the
sample is secured to the thermometer with a rubber band. Suspend the thermometer
with the tube in the oil bath with rubber band sufficiently above the oil level so that
expansion of heated oil will not get in contact with it. Hot oil may soften the rubber and
cause the capillary tubing to fall into the oil.
Heat the Thiele tube with a micro burner. Using a gentle flame and holding the
burner by its base, move the burner slowly back and forth along the bottom of the

16
 Thiele tube arm. The rate of heating should be low near the melting point, about 1 0C
per minute.

Thermometer

One-hole rubber
stopper with
Fig. 2.2 Thiele melting wedge removed
point apparatus

Rubber band or
slice of rubber tubing

Heating fluid (oil)

Sample in
capillary tube

Thiele tube
Microburner

II. Using an Electrical Apparatus

There are many types of melting-point apparatus. Your instructor will show you how to
use the one available in your laboratory. The apparatus is operated by turning the switch
on, adjusting the potentiometric control for the desired rate of heating, and observing
the sample through the magnifying eyepiece. The temperature is read from a
thermometer and the heating rate at the melting point should be about 1 0C per minute.
If the melting point of the substance is unknown, one can often save time by
preparing two samples for melting-point determination. With one sample, one rapidly
determines a crude melting-point value. Then the trial is repeated more carefully, using
the second sample. For the second sample determination, one already has some
approximate idea of what the melting temperature should be.

2.7 Observing and Recording the Melting Point

Some substances may have some degree of unusual behavior before melting.
A substance might undergo decomposition, discoloration, sublimation, softening, and/or
shrinkage at or below the melting point.

17
Certain organic solids, such as amino acids and their salts, salts of carboxylic acids, and
carbohydrates decompose on melting. The melting point or range of a decomposed
substance is recorded as, for instance, 321 0C, d, indicating that this substance melts
with decomposition at 321 0C.
It is not unusual for compounds to soften or shrink just before melting. Such
behavior represents not decomposition but a change in the crystal structure. Actual
melting begins when the first drop of liquid become visible and the melting range
continues until the temperature at which all the solid has been converted to the liquid
state. With experience, one soon learns to distinguish between softening and actual
melting.
Some solid compounds have such a high vapor pressure that they sublime at or
before the melting point. Under such circumstances, the melting-point determination
must be conducted in sealed capillary tubes.

2.8 Experimental Section

You will be given some unknowns to determine their observed melting
point and the mp for pure benzoic acid as well as the purified benzoic acid in
experiment 1.

Procedure
1. Record the identification number of your unknown organic substance.
2. Place a small amount of the unknown sample on a watch glass and grind it
to a fine powder with a clean, dry spatula. Push the open end of the mp
capillary tube into the powdered sample. A small amount of the substance
will be forced into the tube. Invert the tube and tap the sealed end gently so
that the substance collects at the bottom of this closed end. There should
not be more than 1-2 mm of solid in the tube.
3. Place the capillary tube into the one of the holes of the heating block and
switch on the heating using the variable heat control dial. Adjust the rate of
heating to about 2 0C per minute. As soon as the solid starts to melt, record
the temperature. Also record the temperature when all the sample melts.
4. Switch off the heating apparatus and allow the instrument to cool down to 40
0
C before starting the second run.

18
EXPERIMENT 4

EXTRACTION

4.1 Objectives

1. To separate 4-nitroaniline and benzoic acid from a mixture of the two

components.
2. To calculate K for each one the two compounds
3. To determine the melting point range of the separated compounds.
4. To develop a skill for the use of a separating funnel.

4.2 Introduction
Extraction is a technique used for separating two or more components of a
mixture of organic compounds. Or it is used to transfer a solute from one solvent into
another. Two immiscible (none-mixing) solvents are used, often water and organic
solvent. The component to be extracted must be more soluble in the extracting
solvents than in the original other solvent.
Organic acids (RCO2H) and bases (RNH2) are more soluble in organic
solvents than in water and they are easily separated by making them more water-
soluble. Organic acids and bases can be converted into salts RCO 2-Na+ and RNH3+Cl-,
which are more soluble in water than in organic solvents.

HCl NaOH
O2N NH2 O2N NH3+ Cl- O2N NH2

p-nitroaniline Salt of the aniline

Soluble in organic solent Soluble in water

After extraction of the salts into water, the organic acid or base can be regenerated by
the addition of strong acids or bases respectively.

24
4.3. The Distribution Coefficient
Extraction involves the distribution, or partitioning, of a solute between two
immiscible liquid phases. When a solution (a solute in solvent 1) is shaken with
solvent 2 with which it is immiscible, the solute distributes itself between the two
liquid phases. When the two phases have separated again into two distinct solvent
layers, equilibrium will have been achieved such that the ratio of the concentrations
of the solute in each layer defines a constant. This constant, K, is known as the
distribution coefficient (or partition coefficient), defined mathematically by:
K = C2/C1
Where, C1 and C2 are the concentrations (in grams per milliliter) of the solute in
solvents 1 and 2 respectively. The distribution coefficient has a constant value for
each solute considered and depends on the nature of the solvents used in each case.
Let us consider an example of extraction from water into ether for a solute with a
distribution coefficient of 10.0. If the aqueous solution has a concentration of 3.00 g
in 40.0 mL of water and is extracted first with 100 mL of ether and second with two
50-mL extractions with ether. The purpose is to illustrate the effectiveness of two
successive extractions over a single extraction.
1. A single extraction with 100 mL ether.
Let x g be the amount remained in water at equilibrium.
Then, 3-x g will be the amount extracted into the ether layer.
K = Cether / Cwater
10.0 = (3.0 – x)/100  / x/40
x = 0.120 g remaining in the aqueous phase
3.0 – x = 2.88 g extracted into the ether layer
2. Two times extraction with 50 mL each.
A first extraction with 50-mL portion of ether performed on the aqueous layer,
which contains 3.0 g of the solute, will extract an amount of solute given by the
calculation
K = 10 = (3.0 – x )/50  / x/40
x = 0.22 g remaining in the aqueous phase
3 – 0.22 = 2.78 g extracted into the ether layer

25
 A second extraction with another 50-mL portion of ether performed on the
aqueous layer, which contains 0.22 g of the solute, will extract an amount of
solute given by the calculation

K = 10 = (0.22 – x )/50  / x/40

x = 0.0164 g remaining in the aqueous phase
0.222 – 0.0164 = 0.206 g extracted into the ether layer

The total amount extracted into the combined ether layers = 2.78 + 0.206
= 2.98 g solute

4.4. Apparatus and Chemicals

A mixture of benzoic acid & 4-nitroaniline Ethyl acetate
50 mL graduated cylinder 2M HCl
A separating funnel 2M NaOH
Two 250 mL beaker Red & blue litmus paper100 mL
conical flask Filter paper
Büchner funnel Glass rod
Büchner flask

4.5 Procedure

RCO2 H + RNH 2
in ethyl acetate

NaOH HCl

RCOO Na RNH3 Cl

HCl
NaOH

RCOOH RNH2
solid solid

26
1. Label a 250 mL beaker A for organic base and another 250 mL beaker B for
organic acid.
2. Place about 3g of the mixture of 4-nitroaniline and benzoic acid in a 100 mL
conical flask
3. Add about 40 mL of ethyl acetate to the flask and swirl it until the entire solid
has dissolved.
4. Make sure that the stopcock (tap) of the separating funnel is closed. Pour the
solution into the separating funnel.

To separate the 4-nitroaniline

5. Add approximately 20 mL of 2M HCl, place the stopper onto the separating
funnel and shake it pointing the stem away from yourself and others. Release
the pressure (vent) frequently during the shaking process by holding on to the
stopper, turning the funnel upside down and opening the stopcock (Fig. 4.1).
6. Support the separating funnel in a ring on a ring stand, as shown in Figure 6.2.
Remove the stopper and let the two layers separate. After the layers have
separated, drain the lower (aqueous) layer into the beaker labeled A.
7. Repeat steps 5-6 with another 20 mL of 2M HCl, and run off the lower layer
into beaker A. Now the salt of the organic base has been extracted into the
water in beaker A.

To separate the benzoic acid

8. Add approximately 20 mL of 2M NaOH to the remaining ethyl acetate
solution in the separating funnel and extract.
9. Support the separating funnel in a ring on a ring stand, remove the stopper and
let the two layers separate. After the layers have separated, drain the lower
(aqueous) layer into the beaker labeled B.
10. Repeat steps 8-9 with another 20 mL of 2M NaOH, and run off the lower layer
into beaker B. Now the salt of the organic acid has been extracted into the
water in beaker B.

27
To regenerate 4-nitroaniline
11. Add 2M NaOH to beaker A until the mixture is strongly alkaline to litmus
paper. This is done by dipping a glass rod into the solution and touching a
piece of red litmus paper to see if it turns blue. A precipitate should form when
the solution is alkaline.
12. Cool the alkaline solution in an ice-water bath if needed. Collect the solid by
suction filtration. Wash the crystals in the funnel with about 10 mL of cold
water. Dry your 4-nitroaniline in an oven at 90 0C, then weigh the sample and
store it in a labeled vial.

To regenerate benzoic acid

13. Add 2M HCl to beaker B until the mixture is strongly acidic to litmus paper
(blue litmus turns red). A heavy, white precipitate should form; if not, add
more HCl.
14. Cool the mixture as in step 12, collect the solid by suction filtration, and wash
the crystals in the funnel with about 10 mL of cold water.
15. Dry the benzoic acid in an oven at 90 0C, then weigh the sample and store it in
a labeled vial.
16. Record the melting range of the dried benzoic acid & 4-nitroaniline.
17. Show your samples of benzoic acid & 4-nitroaniline to your instructor.

SAFETY NOTE: DO NOT POUR ORGANIC SOLVENTS INTO THE

SINK. USE THE PROVIDED WASTE CONTAINER.

28
 Separatory
funnel

more dense
layer less dense
layer

Stopcock

Erlenmeyer
flask

Fig. 4.1 Using the separating funnel Fig. 4.2 Separatory funnel setup

4.6. Problems
1. The partition coefficient for caffeine between water and chloroform is 22. If
150 mL of coffee solution contains 0.80 g of caffeine and you extract once
with 60 mL of chloroform, how much caffeine will remain in the aqueous
layer?
2. How much caffeine will remain in the aqueous layer if two successive
extractions of 30 mL each are used.

29
EXPERIMENT 5

Fractional Distillation

5.1 Objectives
1. To separate a mixture of methanol and water or butyl acetate and ethyl acetate.

2. To determine the percentage composition of each fraction collected.

5.2 Introduction
Distillation is the process of vaporizing a substance, condensing the vapor, and
collecting the condensate in another container. This technique is used for separating a
mixture when the components have different boiling points. There are four different
distillation methods available for chemists:
1. Simple distillation (one vaporization-condensation cycle)
2. Vacuum distillation (distillation at reduced pressure)
3. Fractional distillation (many vaporization-condensation cycles)
4. Steam distillation

Fractional distillation refers to a distillation where a fractionation (fractionating)

column is inserted between boiling flask and the distilling head (stillhead) as shown in
Figure 5.1. The technique is used for the separation of two (or more) liquids differing
the boiling points by less than 40 0C.
The column is filled with suitable packing, such as a stainless steel sponge.
When a mixture of two liquids is heated, the vapors ascend the fractionation column.
The vapors of the higher boiling components will soon condense and return to the
flask as liquid. The ascending vapors will therefore become more and more enriched
in the lower boiling component. The packing in the fractionating column allows the
mixture of liquids to be subjected continuously to many vaporization-condensation
cycles as the vapors move up the column. Finally, nearly pure of the lower boiling
component emerges from the top of the column, condenses, and passes into the
receiving flask as the first fraction. The distillation must be carried out slowly to
ensure numerous vaporization-condensation cycles so as an efficient separation of

30
 Fig. 5.1 Fractional thermometer
distillation apparatus

stillhead condenser

water out
water in
fractionating
packing column

receiver

stillpot or
distilling flask
boiling
chips
the two liquids can be achieved. When nearly all the lower boiling component is
removed, the temperature begins to rise and a small amount of a second fraction,
which contains some of the lower boiling and the higher boiling component, is
collected. When the temperature reaches the boiling point of the second liquid, the
vapor is condensed and collected in another receiving flask as the third fraction.

5.2 Simple and Fractional Distillation

When a simple distillation is performed on an ideal solution of benzene (bp 80
0
C) and toluene (bp 110 0C), the first vapor produced will be enriched in benzene (the
lower-boiling component). Condensation and analyzing the vapor will reveal that the
distillate is not pure benzene since benzene and toluene has a boiling-point difference
of 30 0C. In principle, one could distill a 50:50 mixture of benzene and toluene by
simple distillation and collect the distillate in fractions. The first fraction would
contain the largest amount of benzene and the least amount of toluene and would have
the lowest boiling-point range. The second fraction would contain less benzene and
more toluene than the first fraction and would have a higher boiling-point range. The
last fraction would have the smallest amount of benzene, the largest amount of
toluene, and the highest boiling-point range.
A plot of boiling point vs volume of distillate (condensate) collect can be shown in
Fig. 4.3. Clearly, separation by this method would be poor.

31
 110 fr6
fr5

Temperature C
Fig. 5.3 Temperature-distillate plot 100 fr4
0
for simple distillation of a fr3
benzene-toluene mixture 90 fr2
fr1
80

70

Volume of distillate (fractions)

However, each fraction collected could be redistilled. In the second

distillation, fractions would produce distillate that would contain more benzene than
what was initially present. The residue in the distilling flask would contain more
toluene that what was initially present. More redistillation may be essential to achieve
complete separation. Obviously, the above procedure would be tedious; fortunately,
the series of redistillations can be done “automatically” in a fractionating column. The
column is filled with suitable packing, such as a stainless steel sponge. The packing
allows a mixture of benzene-toluene to be subjected continuously to many
vaporization-condensation cycles as the material moves up the column. With each
cycle within the column, the composition of the vapor is progressively enriched in
benzene, the lower-boiling component. Finally, nearly pure benzene emerges from the
top of the column, condenses, and passes into the receiving flask at the first fraction.
The distillation must be carried out slowly to ensure numerous vaporization-
condensation cycles. When nearly all the benzene is distilled, the temperature begins
to rise and a small amount of a second fraction, which contains some benzene and
toluene, is collected. When the temperature reaches 110 0C, the boiling point of pure
toluene, the vapor is condensed and collected in another receiving flask as the third
fraction. A plot of boiling point vs volume of distillate (condensate) would resemble
Figure 5.4. Clearly, the separation would be much better than that achieved by simple
distillation.
Fig. 5.4. Temperature-distillate
plot for fractional distillation
of a benzene-toluene mixture Fr3
111
Temperature C

Fr2
Fr1
80

Volume of distillate

32
5.4 Vapor-Liquid Composition Diagrams
Figure 5.5 is a boiling point-composition diagram for the cyclohexane-toluene
system. The diagram can be used to explain the operation of a fractionating column
with an ideal solution of two liquids, cyclohexane and toluene. An ideal solution is
one in which the two liquids are chemically similar and totally miscible in all
proportions but do not interact. Such solutions are said to obey Raoult’s law. In the
example given, pure cyclohexane boils at 78 0C while pure toluene boils at 111 0C at
one atmospheric pressure.
The phase diagram relates the compositions of the boiling liquid (lower curve) and its
vapor (upper curve) as a function of temperature. Any horizontal line drawn across
the diagram (a constant-temperature line) intersects the diagram in two places. These
intersections relate the vapor composition to the composition of the boiling liquid that
produces that vapor.
The horizontal and vertical lines shown in Fig. 5.5 represent successive evaporation-
condensation processes in a fractionating column. Each of the horizontal lines (L1V1,
L2V2, L3V3, etc) represents the vaporization step of a given vaporization-
condensation cycle and indicates the composition of the vapor in equilibrium with
liquid at a given temperature. For example, at 95 0C a liquid with a composition of
30% A (L2 on diagram) would yield vapor of composition 57% A and 43% B (L3 on
diagram) at equilibrium. The vapor is richer in the lower-boiling component
cyclohexane than the original liquid was.
Each of the vertical lines (V1L2, V2L3, etc.) represents the condensation step of a
given vaporization-condensation cycle. The temperature does not change as the
temperature drops on condensation. The vapor at V2, for instance, condenses to give a
liquid L3 of composition 57% A and 43% of B with a drop in temperature from 95 to
88 0C.

33
 110 110
vapor
105 105
V1
L1
100 100
Temperature 0C

V2
95 95
L2

90 V3 liquid 90
L3
85 85
V4
V5 L4
80 L5 80
V6 L6

A. 100% 90 80 70 60 50 40 30 20 10 . 0%
B 0% 10 20 30 40 50 60 70 80 90 100%

Fig. 5.5 phase diagram for a fractional distillation of an ideal two-

component system, A & B

Now consider the phase diagram in Fig. 5.5 for a solution initially 10% in
component A and 90% component B. This solution of 10% A and 90% B composition
is heated (following the dotted line) until it observed to boil at 103 0C L1. The vapor
has a composition V1 of 30% A and 70% B. The vapor is richer in A than the original
liquid was but is by no means pure A. In a simple distillation apparatus, this liquid
would have been condensed and passed into the receiving flask in a highly unpurified
state. However, with a fractionation column, the vapor is condensed in the column to
give liquid L2 of composition 30% A and 70% B. Liquid L2 is revaporized (bp 95 0C)
to give vapor of composition V2 (57% A), which is condensed to give liquid L3 (57%
A). Liquid L3 is revaporized (bp 88 0C) to give vapor of composition V3 (77% A),
which is condensed to give liquid L4 (77% A). Liquid L4 is revaporized (bp 83 0C) to
give vapor of composition V4 (93% A), which is condensed to give liquid L5 (93%
A). Liquid L5 is revaporized (bp 81 0C) to give vapor of composition V5 (98% A),
which is condensed to give liquid L6 (98% A). Finally, liquid L6 is once again
vaporized (bp 79 0C) to give vapor V6 that is mainly pure A. Note, compound A
emerges from the fractionation column, is condensed, and passes into the receiving
flask as a pure A. In the meantime the second component, B, is now concentrated in
the distilling flask and ready to be removed as pure by distillation.

34
5.5 Column Efficiency
Fractionation column efficiency is often given in theoretical plates. One
simple distillation step represents one theoretical plate. So, a one theoretical plate is
equal to one evaporation-condensation cycle. A column would have one theoretical
plate if the first distillate (condensed vapor) had the composition located at L2 in Fig.
5.5. In Fig. 5.5 the distillate apparatus has an efficiency of 6 theoretical plates, five of
which are due to the column.
The higher the number of theoretical plates in a column, the more efficient it
is, and the better it can separate liquids with boiling points close together. So, the
number of theoretical plates necessary for a given separation depends on the
difference in boiling points of the components of the mixture. The number of
theoretical plates necessary to effect practically complete separation can be roughly
calculated from
n = BPA + BPB / 3(BPA - BPB)
where n is the number of theoretical plates, and BP A and BPB are the Kelvin boiling
points of the less volatile and more volatile components, respectively.
For example, in a cyclohexane-toluene system, wherein boiling points are 78 and 111
0
C respectively, n can be calculated.
n = (111 + 273) + (78 + 273)
3[(111 + 273) – (78 + 273)]
n = 7.4, hence eight theoretical plates would be required.

The longer a column is, the more efficient it is.

5.6 Azeotropes: Nonideal Solutions

Many liquids do not form ideal solutions and hence do not conform to
Raoult’s law due to intermolecular attractions or repulsions. Because of molecular
interaction, a mixture of 95.5% (by weight) of ethanol boils below 78.15 0C. The
boiling point of pure ethanol is 78.3 0C. No matter how carefully you distill a mixture
of ethanol and water, ethanol, unlike methanol, cannot be separated completely from
water by distillation. This is because ethanol and water form a binary azeotrope. A
mixture of liquids of a certain definite composition that distills at a constant
temperature without change in composition is called an azeotrope; 95% ethanol is
such an azeotrope.

35
5.7 Apparatus & Chemicals
Distillation apparatus Methanol
Fractionating column Water
Round-bottomed flask (25 mL) Boiling chips or wooden sticks
Electrical heating mantle Graduated cylinder (10 mL)

5.8 Procedure

1. Place 10 mL of methanol and 10 mL of distilled water in a 25 mL round-

bottomed flask and add a few boiling chips.
2. Connect the flask to a fractionating column and condenser as shown in Fig4.1.

3. Clean, dry, and weigh three 10-mL labeled-graduated cylinders.

4. Heat the flask gently so that the distillation occurs slowly (drop by drop). In
each graduated cylinder collect 5.0 mL fraction and record the boiling
intervals.
 The exact volume and weight of each fraction must be obtained to determined
their densities
5. Reweigh the three graduated cylinders to determine the weight of each
fraction, and then calculate the density of the liquids in the fractions.
6. From the graph provided, read off the percentage composition of each
fraction.

36
 Water-Methanol Mixtures vs Density
1.000

0.980

0.960

0.940
Density, g/mL

0.920

0.900

0.880

0.860

0.840

0.820

0.800

0.780
0 10 20 30 40 50 60 70 80 90 100

% H2 O

37
EXPERIMENT 6

CHROMATOGRAPHY

6.1 Objectives
1. To learn chromatography, column & thin-layer, techniques
2. To separate a mixture of dyes using column chromatography
3. To determine the number of components in a mixture.

6.2 Introduction
The word chromatography was first used to describe the colored bands
observed when a solution containing plant pigments is passed through a glass column
containing an adsorbent packing material. The term now encompasses a variety of
separation techniques that are widely used for analytical and preparative purposes.
Chromatography is a separation technique that is used to separate closely
related components of complex mixture. In all chromatographic separations, the
sample is dissolved in a mobile (moving) phase, which may be a gas or a liquid. This
mobile phase is then forced through an immiscible stationary phase, which is fixed
in place in a column or on a solid surface. Separation occurs because the components
of the mixture have different affinities for stationary and mobile phases. Those
components with greater affinity for the stationary phase will be retained in the
stationary phase and will move slowly with the flow of mobile phase. In contrast,
components with less affinity for the stationary phase will move fast with the mobile
phase.

6.3 Types of Chromatography

There are three major types of chromatography that will be studied: column
chromatography (CC), thin-layer chromatography (TLC), and gas chromatography
(GC). All types of chromatography share the following components: injected port,
column, and detector. The exact nature of these depends on the type of
chromatography being done. In column chromatography, the injector port is the
opening in the top of the column into which the sample is poured. In gas
chromatography, the sample is injected through a septum using a hypodermic syringe.
Columns usually contain a finely divided solid material, often in a piece of tubing

38
with small diameter. However, in thin-layer chromatography, the “column” is a layer
of solid attached to a glass or plastic pipette.
A brief introduction to the three types of the above-mentioned chromatography will
be discussed here:

I. Column Chromatography

column

Fig. 6.1 Column

Chromatography

packing
material

cotton

The column, generally a glass tube, is packed with solvent slurry of a uniform
sized, granular, high surface area solid material (silica gel or aluminum oxide). The
column is suspended vertically (see Fig. 6.1); a liquid sample (which is a Mixture of
substances) is introduced at the top of the column. A liquid (often the solvent for the
sample but not necessarily)
is poured in the top of the column and passes through the column, carrying the sample
with it (eluting the sample) and effecting the separation of the mixture of substances
that were added to the top of the column.

II. Thin Layer chromatography

The “column” is a solid material attached in a very thin layer to a glass

or plastic sheet (Fig. 6.2). The material to be separated is spotted onto the thin layer
sheet and the sheet is placed in a closed container containing the solvent to be used for
developing the TLC (Fig. 6.3). The level of the spotted material should be just above
the solvent level to avoid dissolution of the material. The liquid will rise up the plate
by capillary action, carrying the mixture with it (eluting the mixture) and affecting
separation in a manner similar to the column above.

39
 chromatographic
solven front chamber
Thin
layer
plate

sample pencil line

spot solvent
1cm

Fig. 6.2 Thin Layer Fig. 6.3 Chromatographic

Plate Setup Chamber Design

Once the separation of the components of the mixture is complete and the
individual spots have been detected, the retention factor (Rf) of each component may
be calculated using the following equation:

distance traveled by the substance

Rf =
distance traveled by the sovent front

III. Gas Chromatography

Figure 6.4 is a diagram of a typical gas chromatography instrument.
The column (stainless steel, aluminum, or glass tubing) is packed with a solid support
material that is of uniform size and has a very large surface area (3 to 9 square
meters/gram). This solid support material has been coated with a liquid material to a
depth of one to ten molecules. This liquid coating will not come off the column easily
even at high temperatures. The material to be separated is added to the column
(generally by injection); then a carrier gas (normally helium or nitrogen) flows
through the column carrying the mixture with it and effecting separation.

40
 oven recorder
injector port
syringe

He detector
carrier packed column
gas

Fig. 6.4 Schematic diagram og gas chromatography

In all three cases above, there is something in the column that is stationary (a
stationary phase). In column and thin-layer chromatography it is the solid material
and in gas chromatography it is the liquid coated on the solid substrate.
There is also in each case above a moving (mobile) phase; in column and thin-
layer chromatography, it is a liquid phase and in gas chromatography it is a gas phase.
Column and thin layer chromatography make use of a solid stationary phase
and a liquid mobile phase. Gas chromatography makes use of a liquid stationary phase
and a gaseous mobile phase.
The theory involved in any type of chromatography is quite complicated but
one can get an idea of how the separations are accomplished by using a few simple
analogies along with the scientific discussion. Whether one is considering column,
thin layer, gas or high-pressure liquid chromatography (HPLC), the theory of the
separation of substance is essentially the same. All depends on the varying affinity of
the sample being considered to both stationary and mobile phases.

6.5 Apparatus & Chemicals

TLC plates Silica gel or alumina
Chromatographic chambers 95% Ethanol
Columns Dichloromethane
Beakers (400 mL) A dye mixture
Conical Flasks (125 or 250 mL) Pencils
Nichrome wires Rulers

6.6 Experimental Procedure

41
I. Thin Layer Chromatography
1. Add a mixed solvent of ethanol and dichloromethane (7:3) to a depth of 0.5
centimeter in a chromatographic chamber and replace the cap (Fig. 6.3).
2. Lightly mark a line in a pencil on the coating of a thin layer plate (do not press
down with the pencil or the coating on the plate will be destroyed) about 1.0
cm from one end (Fig. 6.2).
3. Using a piece of nichrome wire, spot the dye mixture on the center of the
marked line of the thin layer plate. This is accomplished by dipping the end of
the nichrome wire into the dye solution and then, holding the wire
perpendicular to the plate, momentarily touching the tip of the wire to the thin
layer plate (Fig. 6.2). A very small spot (smaller than a period) works best.
4. Place the thin layer plate in the chromatographic chamber (Fig. 6.3). The dye
spot should be a little above the level of the liquid. Close the lid; the solvent
will then slowly rise up the plate by capillary action. Allow the plate to
develop until the solvent has risen at least one-half but no more than three-
fourths the way up the plate.
5. Remove the plate and immediately mark the solvent front with a pencil.
Measure the distance from the pencil line (spotting line) to the solvent front
and also the distance to the leading edge of each dye sample.
6. Calculate Rf value of each dye.
7. After showing your instructor the thin layer plate, dispose of the waste in the
correct waste containers.

II. Column Chromatography

1. Attach a column to the side of a ring stand clamp using a rubber band (Fig.
6.1).
2. Place a small Erlenmeyer flask under the tip of the column to collect the
ethanol.
3. Pack your column: mix about 5 g of the packing material (alumina or silica
gel) in 10 mL of95% ethanol to form slurry. The packing material will
relatively quickly settle to the bottom. Transfer the slurry using a pipette as a
dropper to the column. While adding the slurry (and until the dyes below are

42
 separated), never allow the level of ethanol in the column to get below the top
of packing material.
4. Obtain a small amount of dye mixture and, using a micropipette, add the dye
mixture to the top of the column (the dye mixture is added to the column when
the ethanol used in preparing the column is about I millimeter above the top of
the packing material).
5. When the dye mixture has just drained onto the top of the packing material,
add carefully, with the aid of a clean disposable pipette, some ethanol to the
column. Continue adding ethanol as needed (till the first dye has come out of
the column). This process is called eluting the column.
6. As the first dye begins to elute (when you start seeing color dripping), replace
the small Erlenmeyer flask with a small sample bottle. After all the first dye is
collected, replace the small sample bottle with the small Erlenmeyer flask.
7. Now start eluting the column with water instead of ethanol. Continue adding
water in small portions until the second dye elutes. Collect the second dye
solution in another small sample bottle.
8. After showing your instructor the separated dye solutions, dispose of the
packing material column and the waste ethanol and water solutions in the
correct waste container.

43
EXPERIMENT 7

Dehydration of Cyclohexanol

Objectives

1. To prepare cyclohexene from cyclohexanol in the presence of phosphoric acid.

2. To test for the presence of a double bond using Baeyer test or Br2/water test.

Introduction

Under acidic conditions alcohols can be dehydrated (removal of water) to

produce alkenes. The reaction is an elimination reaction. This reaction can be
accomplished by heating the alcohol in the presence of a Brønsted acid like sulfuric
acid, phosphoric acid, or a halogen halide. The acid protonates the hydroxyl group
allowing it to dissociate as water. Loss of a proton from the intermediate brings about
an alkene. Since sulfuric acid often causes extensive charring in this reaction, we will
use phosphoric acid since it is comparatively free of this problem.
H
H
+ H2O
OH

If, among other things, the alcohol used in the dehydration is secondary,
tertiary, allylic, or benzylic, the reaction is likely to be an E1 process in which a
carbocation (carbonium ion) is an intermediate. The first step in the mechanism is the
formation of the oxonium ion (I). In this step, the hydroxide group, a poor leaving
group, transforms into water, a good leaving group. Subsequently loss of water
produces the carbocation (II).
H H
H

O H O H

I H II

Finally, one of the Brønsted bases in the solution abstracts one of the protons on
carbon adjacent to the positive center, thereby producing the alkene.
H
H O

II

45
 A reaction competing with the formation of cyclohexene is the SN1 reaction
that forms dicyclohexyl ether (III)
H
H H
O O O
O

III

Although SN1-E1 competition is a common one, we should not expect much

ether to be produced in the cyclohexanol dehydration reaction because the
temperature of the reaction and the method of alkene preparation shift the equilibrium
in favor of the alkene.
The equilibrium that attends this reaction will be shifted in favor of the
product, cyclohexene, by distilling it from the reaction mixture as it is formed. The
cyclohexene (bp 83 0C) will co-distill with the water that is also formed. By
continuously removing the products, one can obtain a high yield of cyclohexene.
Since the starting material, cyclohexanol, is also rather low-boiling (bp 161 0C), the
distillation must be done carefully, not allowing the temperature to rise much above
100 0C.
It is inevitably that small amounts of water and phosphoric acid co-distill with
the product. The acid can be removed by washing the distillate mixture with aqueous
sodium carbonate and the water by drying the product over anhydrous magnesium
sulfate. It is important to remove water because cyclohexene forms a minimum-
boiling azeotrope with water and little or no separation of the two would occur during
purification of cyclohexene by fractional distillation.
You can test for the presence of a double bond by reacting the alkene with the
bromine or potassium permanganate solutions.
H
Br 2 Br
red Br
H
colorless colorless

H
KMnO 4 OH
purple + MnO 2
H
brown
colorless OH

46
Apparatus & Chemicals

A simple distillation set-up Cyclohexanol

Thermometer Anhydrous magnesium sulfate
Beakers (100 mL & 500 mL) Phosphoric acid (85%)
Conical flasks (two 125 mL) Boiling chips
Graduate cylinders (25 mL & 50 mL) Small separating funnel

Procedure

1. In a 50 mL round-bottomed flask (distilling flask), place 10 mL of

cyclohexanol (density 0.96), 3 mL of 85% phosphoric acid, and 3 boiling
chips.
2. Assemble fractional distillation apparatus. The collection (receiving) flask
should be immersed to its neck in an ice-water bath to minimize the possibility
that cyclohexene vapor will escape into the laboratory.
3. Carefully heat the flask over a small flame. The product (cyclohexene) co-
distills with water. The temperature should not rise above 100 0C during the
distillation. Continue the distillation until only 5 mL of liquid is left in the
reaction (distilling flask) flask.
4. Pour the distillate that contains two layers into a small separating funnel.
Remove and discard the lower aqueous layer.
5. Transfer the upper layer (cyclohexene) to a 100 mL beaker. Add about a
teaspoon full of anhydrous MgSO4 or anhydrous CaCl2 and stir the beaker
contents with a glass rod.
6. Weigh a clean, dry 100 mL conical flask and record the mass. Filter the
cyclohexene through a fluted filter paper into this flask. Determine the mass of
cyclohexene obtained.
7. Store your product in a clean, dry vial.

47
EXPERIMENT 8

Tests for Functional Groups

Objectives
1. To observe some tests for alcohols, aldehydes, ketones, carboxylic acids, and
alkenes in known organic compounds.

2. To use the tests to identify the functional groups in an unknown organic

compounds.

Introduction
Organic compounds are generally grouped according to the nature of the
“functional group”. That is the part of the molecule that determines the chemical
reactivity of the compound. Even within a group, there will be a large number of
possible compounds. This arises in part from the properties of carbon, the element
central to all organic compounds.
Functional groups in organic chemistry can be identified in the lab by simple
qualitative experiments performed in test tubes. To see what a positive test looks like
(that is, a test that confirms the presence of a specific functional group) each test is
carried out on a known compound containing that functional group. The same test is
then done on an unknown in a different test tube and a direct comparison can be
made.
Tests For Functional Groups

alcohols: 1 ,2 , 3 alkenes
aldehyde & ketones

Chromic acid Lucas Bromine/water Baeyers'

test test test test
Chromic acid
Tollens
test
test
2,4-dinitrophenyl
hydrazine test

48
The Characterization Tests

I. Characterization of Unsaturated Hydrocarbons

a) The Bromine Test

Unsaturated hydrocarbons react rapidly with bromine in a solution of
tetrachloromethane. The red-brown color of bromine disappears as it is used up in this
addition reaction.
CH3CH=CHCH3 + Br2  CH3CHBrCHBrCH3
colorless red colorless

Procedure for the bromine test

1. Place 10 drops of dioxane, or tetrahydrofurane (THF), or 95% ethanol in a test
tube.
2. Add five drops (or few crystals if solid) of the appropriate hydrocarbon or
unknown.
3. Stir the mixture to dissolve the substance.
4. Add dropwise with shaking a 2% tetrachloromethane (2% Br 2 in CH2Cl2)
solution of bromine.
5. If more than 2 drops of bromine solution are required to give a permanent red
color, unsaturation is indicated. The bromine solution must be fresh.
Cleaning Up: Place the mixture in the halogenated-solvent container.

b) The Baeyer Test

The presence of double or triple bonds can be tested with a reagent of potassium
permanganate. The conversion of the purple color of the permanganate ion, MnO 4 -, to
a brown precipitate of manganese (IV) oxide, MnO2, is an indication of the oxidation
of an unsaturated compound; hence, an indication of a positive test.

C C C C

MnO 4 MnO 2 OH OH
purple brown

49
Procedure of Baeyer Test
1. Place 10 drops of water, for water-soluble unknowns, or 10 drops of 1,4-
dioxane (or THF), for water-insoluble unknowns, in a test tube.
2. Add five drops (or few crystals if solid) of the appropriate hydrocarbon or
unknown.
3. Stir the mixture to dissolve the substance.
4. Add dropwise with agitation a 1% KMnO4 solution until the solution is light
purple or until a brown precipitate forms.
5. Formation of a brown precipitate constitutes a positive test.

II. Characterization of Alcohols

a) Chromic Acid Test
Primary alcohol can be oxidized to carboxylic acid and secondary alcohol to ketone in
the presence of chromic acid at room temperature. Tertiary alcohol cannot be readily
oxidized.
During the reaction the yellow-orange chromate ion is reduced to green chromic ion,
and appearance of a green chromic sulfate precipitate constitute a positive test. The
test results must be interpreted with caution since other easily oxidized substances
such as aldehydes, phenols, and aniline also may give a positive test.
O

RCH 2 OH R C OH
2
3
CrO 4 Cr

O
OH

R R C R
CH R 2
3
CrO 4 Cr
yellow green

Procedure for the Chromic Acid Test

1. Place 10 drops of acetone in a small test tube
2. Add two drops (or few crystals if solid) of the unknown.
3. Add two drops of chromic acid reagent and shake the mixture.
4. The appearance of an opaque, blue-green color within two seconds is a
positive test.
Reagent preparation: Dissolve 1 g of chromic oxide in 1 mL of concentrated sulfuric
acid. Carefully add the mixture to 3 mL of water.

50
b) The Lucas Test
This test is applicable only to alcohols of no more than six carbons because
larger alcohols are insoluble in the Lucas reagent solution. This test depends on the
appearance of an alkyl chloride as an insoluble second layer when an alcohol is
treated with the Lucas reagent, a mixture of hydrochloric acid and zinc chloride.

ZnCl 2
ROH + HCl RCl + H 2 O

Primary alcohols do not react at room temperature; therefore, the alcohol is

seen simply to dissolve. Secondary alcohols react slowly, whereas tertiary, benzylic,
and allylic alcohols react instantly. Primary carbocations are unstable and do not form
under the conditions of this test. Hence, no results are observed for primary alcohols.

R R H R R
ZnCl 2 Cl
R C OH R C O ZnCl 2 R C R C Cl

R R R R
soluble insoluble

Procedure for the Lucas Test

1. Place 2 mL of Lucas reagent in a small test tube.
2. Add 4 drops of the unknown and agitate the mixture.
3. Tertiary (3o), benzylic, and allylic alcohols give an immediate cloudiness in
the solution as the insoluble alkyl halide separates from the aqueous solution.
4. Secondary (2o) alcohols produce cloudiness within 5 minutes.
5. Primary (1o) alcohols dissolve in the reagent to give a clear solution.

Reagent preparation: Cool 10 mL of concentrated hydrochloric acid in a beaker, using

an ice bath. While still cooling, and with stirring, dissolve 16 g of anhydrous zinc
chloride in the acid.

51
III. Characterization of Aldehydes & Ketones
a) The 2,4-Dinitrophenylhydrazine Test
Most aldehydes and ketones react with 2,4-Dinitrophenylhydrazine to give yellow to
red precipitates called 2,4-dinitrophenylhydrazones. Esters generally do not give this
result; thus, esters can be eliminated by this test

NO2 NO 2
O

+ H2 N NH NO 2 N NH NO 2
OH 2
ppt
The color of the 2,4-dinitrophenylhydrazones (ppt) formed can lead to the
extent of conjugation in the original aldehyde or ketone. For instance, cyclohexanone
(an unconjugate ketone) gives yellow precipitate, whereas benzophenone (a conjugate
ketone) gives orange-to-red precipitate. Compounds that are highly conjugated give
red precipitates. The 2,4-dinitrophenylhydrazine reagent, however, is itself orange-red
and to get a true color of the precipitate, you need to remove it from the reagent
solution and wash it. The reagent can oxidize some allylic and benzylic alcohols to
aldehyes and ketones, hence, these alcohols also give a positive test. Other alcohols
that contain small amounts of oxidation products might also yield a small amount of
precipitate. Therefore slight amount of precipitates can usually be ignored.
Procedure for the 2,4-Dinitrophenylhydrazine Test
1. Place two drops (or few crystals if solid) of the unknown in a test tube along
with 2 mL of 95% ethanol
2. Add 2 mL of 2,4-dinitrophenylhydrazine reagent and shake the tube
vigorously.
3. If no precipitate forms, gently heat the mixture to about 50 0C for up to 10
minutes.
4. A precipitate indicates a positive test.
Reagent preparation: Dissolve 3.0 g of 2,4-dinitrophenylhydrazine in 15 mL of
concentrated sulfuric acid. In a beaker mix 20 mL of water and 70 mL of 95%
ethanol. With vigorous stirring, slowly add the 2,4-dinitrophenylhydrazine solution to
the aqueous ethanol mixture. After thorough mixing, gravity filters the solution using
a fluted filter paper.

52
b) The Tollens Test
Tollens test can be used to differentiate between aldehydes and ketones. Most
aldehydes reduce ammoniacal silver nitrate to yield a precipitate of silver metal,
which appears as a mirror on the test tube wall.
O O

H + 2Ag(NH 3) 2OH OH + Ag + NH 3 + H 2O
(s)

Tollens reagent

Procedure for the Tollens Test

1. Place 3 drops of the prepared reagent in a small test tube
2. Add 3 drops (or a few crystals) of the unknown and agitate the test tube
well to mix the chemicals.
3. Allow the mixture to sit at room temperature for 15 min.
4. If no mirror is deposited on the inner walls of the test tube, warm the
mixture on a 40-50 0C water bath for a few minutes. Be careful not to
agitate the tube after the initial mixing.
5. If mirror is deposited, the test is positive.

The Tollens reagent (5% aqueous silver nitrate and 10% sodium hydroxide solution)
must be prepared and used freshly.
Tollens reagent preparation: Thoroughly scrub and rinse a small test tube
then place 2 mL of 5% aqueous silver nitrate and 2 drops of 10% aqueous
sodium hydroxide in the test tube. Add dropwise with shaking 2M of aqueous
ammonium hydroxide until the dark Ag2O precipitate just dissolves.

c) Chromic Acid (Ceric Ammonium Nitrate) Test

Aldehydes can also be oxidized to carboxylic acid in the presence of chromic
acid at room temperature.

O O

R C H R C OH
2
3
CrO 4 Cr
yellow green

53
 The reagent is the same one used for the characterization of alcohols.
Remember that primary, secondary, allylic, and benzyl alcohols also respond to this
test. What you observe is the change in color from a yellow-orange solution to a green
precipitate. Ketones do not react in this test, hence, a positive 2,4-
dinitrophenylhydrazine test followed by a positive chromic acid test establishes the
unknown as an aldehyde.

Procedure for the Chromic Acid Test

5. Place 10 drops of acetone in a small test tube
6. Add two drops (or few crystals if solid) of the unknown.
7. Add two drops of chromic acid reagent and shake the mixture.
8. The immediate appearance of an opaque, blue-green color is a positive test.

Reagent preparation: Dissolve 1 g of chromic oxide in 1 mL of concentrated sulfuric

acid. Carefully add the mixture to 3 mL of water.

54
EXPERIMENT 9

Preparation of Soap

Objectives
1. To prepare soap from olive oil
2. To investigate some properties of soap

Introduction
A soap is the sodium or potassium salt of a long-chain fatty acid. The fatty
acid usually contains 10 to 20 carbon atoms. Solid soaps usually consist of sodium
salts of fatty acids, whereas liquid soaps consist of the potassium salts of fatty acids.
Soap, such as sodium stearate, consists of a polar end that is soluble in water,
and a nonpolar end (the hydrocarbon chain of the fatty acid) that is insoluble in water.
O

O- Na+
nonpolar, hydrophobic polar, hydrophilic

Soap consists of a molecule containing a polar group, normally ionized, which

is water soluble, and a nonpolar hydrocarbon portion that is water insoluble. When
very small amounts of soaps are put into water, the molecules do not dissolve, but
rather, become concentrated at the water surface with their polar ends immersed in the
water and hydrocarbon chains protruding from the surface. It is this arrangement of
soap molecules that accounts for the lowering of surface tension of water and the
production of bubbles. If the concentration of soap is increased to a certain point, the
mixture becomes turbid because of the formation of colloidal spherical micelles. A
micelle is a submicroscopic grouping of molecules forming a tiny liquid droplet with
the charged groups on the outside and hydrocarbons chain on the inside (Fig 9.1).

55
 Na
H O Na
Fig. 9.1 A soap micelle
solvating a droplet of oil Na H
H
O
Na
head
Na H
H Na
tail
O
H
H
Na Na
O H
Na

The importance of micelles is their ability to act as solvents for oil-soluble

substances. When a soap micelle dissolved in water comes in contact with oil
molecules, it absorbs the oil from an aqueous phase into interior by van der Waals
interactions in much the same way that distribution of an organic molecules occurs in
a separatory funnel. In this way, soap micelles in effect make oil and greases soluble
in water and allow them to be washed from skin and clothing.
To be effective in solubilizing oils and greases, micelles must be composed of
soaps containing 10 to 20 carbons. Below 10 carbons there is insufficient van der
Waals interaction to solubilize fats, and above 20 carbons the soap is too insoluble in
water to form a sufficiently concentrated colloidal suspension.
Synthetic detergents have largely replaced soap during the last two decades
because soap has two serious drawbacks. The first disadvantage is that soap becomes
ineffective cleanser in hard water, which contains appreciable amounts of Ca 2+ or
Mg2+. When soap is used in hard water, the insoluble calcium salts of the fatty acids,
and other precipitates are deposited as curds (referred to as bathtub rings).
2C17H35CO2-Na+ + Ca2+  (C17H35CO2)2- Ca2+(s) + 2Na+
soap curd
The other is that, in an acidic solution, soap is converted to free fatty acid and
therefore loses its cleansing action.
C17H35CO2-Na+ + HCl  C17H35CO2H(s) + NaCl

Water softeners are added to soaps to help remove the troublesome hard-water
ions so that the soap will remain effective in hard water. Sodium carbonate or sodium
phosphate or borax (Na2B4O7) will precipitate the ions as the carbonate or phosphate.

56
Unfortunately, the precipitate may become lodged in the fabric of items being
laundered, causing a grayish or streaked appearance.
Ca2+ + CO32-  CaCO3(s)
3 Ca2+ + 2PO43-  Ca3(PO4)2(s)
Na2B4O7 + Ca2+  CaB4O7(s) + 2Na+

Soap Making
Common soaps are made from a variety of fats and oils by a process called
saponification (hydrolysis). This involves boiling the oil or fat in basic solution such
as lye (NaOH) or potash (KOH), until the hydrolysis is complete. The products of this
reaction are glycerol and the soap (the salt of a long-chain fatty acid). In general, the
reverse of esterification (making ester) is called hydrolysis, and hydrolysis of fatty
acid ester (fat or oil) is called saponification.
O

CH2 O C C17 H OH
35 CH2
O O
CH O C C17 H 3NaOH
O 35 CH OH + C17 H 35 C O Na
CH2 O C C17 H sodium stearate
35 CH2 OH
a soap
tristearin glycerol
Optional ingredients that are added to bar soaps include zinc oxide to make the
soap whiter, lanolin to act as an emollient, pumice to help remove heavy soil by
abrasion, and perfumes.

Apparatus & Chemicals

Hot plate Vegetable oil
Ice cubes 95% ethanol
Büchner funnel saturated NaCl
Filter flask (500 mL) 25% NaOH
Filter paper 5% FeCl3
PH paper 5% CaCl2
Boiling chips 5% MgCl2
Glass rod
Graduate cylinder (50 mL)

57
Experimental Procedure

I. Preparation of soap
1. Place 23 mL of a vegetable oil into a 250 mL Erlenmeyer flask.
2. Add 25 mL of 95% ethanol (a solvent) and 20 mL of 25% NaOH solution.
3. Heat the flask with its contents gently in a boiling water bath while stirring the
mixture constantly with a glass rod.
4. After 20 min heating, the odor of alcohol will disappear indicating the
completion of the reaction. A pasty mass containing a mixture of the soap,
glycerol, and excess sodium hydroxide is obtained.
5. Place the flask with its contents in an ice-water bath
6. Add about 150 mL of saturated NaCl solution to the soap mixture while
stirring vigorously to precipitate or salt out the soap. This process increases
the density of the aqueous solution; therefore, soap will float out from the
aqueous solution.
7. Filter the precipitate soap with the aid of suction and wash it with 15 mL of
ice-cold water.

II. Properties of soap

Emulsifying Properties
1. Place 5 mL of water in a small test tube
2. Add 5 drops of the vegetable oil and shake the tube. A temporary emulsion of
tiny oil droplets in water will be formed.
3. In a new test tube, place 5 mL of water and add a small piece of the soap you
have prepared before shaking.
4. Allow both tubes to stand a while. Compare the appearance and the relative
stabilities of the two emulsions.
5. Record your observations in you report.

58
Hard Water Reactions
1. Place 25 mL of water in a 50 mL beaker.
2. Add about one-third spatula-full of the prepared soap.
3. Warm the beaker with its contents to dissolve the soap.
4. Label 5 clean test tubes and place them in a test tube rack.
5. Put about 5 mL of the warm soap solution into each test tube.
6. Put a small amount of each of the following into the tubes as indicated:

Tube # 1: 2 drops of 5% calcium chloride solution

Tube # 2: 2 drops of 5% magnesium chloride solution
Tube # 3: 2 drops of 5% iron (III) chloride solution
Tube # 4: 2 drops of tap water
Tube # 5: will be used later for a basicity test.
Shake the first four test tubes and record your observations in your report.

Alkalinity (Basicity)
Test the soap solution in tube # 5 with a wide-range pH paper. Record the results in
your report.

59
EXPERIMENT 10

Preparation of Aspirin

Objectives

1. To synthesize aspirin by reacting salicylic acid with acetic anhydride in the

presence of sulfuric acid.

2. To purify the product by recrystallization from ethanol/water.

Introduction

Aspirin (acetylsalicylic acid) is a very common household chemical. Aspirin

can be synthesized in one single reaction. Reacting of salicylic acid (2-
hydroxybenzoic acid) with acetic anhydride in the presence of sulfuric acid (a
catalyst) produces aspirin (2-acetoxybenzoic acid) and acetic acid.
CO2H
O O CO2H
OH + H2SO4 O
O + CH3CO2H
acetic anhydride O
salicylic acid aspirin acetic acid

Salicylic acid is a trifunctional compound. It’s aromatic with a hydroxyl group

and a carboxylic group. Hence it can undergo two different types of esterification
reactions, using either the alcohol site or the acid site in the reaction. In the presence
of acetic anhydride, aspirin is formed, whereas in the presence of excess methanol, the
product is methyl salicylate (oil of wintergreen).
O
CO2H CH3
H2SO4 O
OH + CH3OH + H2O
OH

salicylic acid methyl salicylate

In this experiment we shall use the former reaction to prepare aspirin. The
reaction is complicated because salicylic acid has a carboxyl as well as a phenolic
hydroxyl group, and a small amount of polymeric by-product is also formed. Aspirin
will react with sodium bicarbonate to form a water-soluble sodium salt, whereas the
polymeric by-product is insoluble in bicarbonate. This difference in behavior will be
used to purify the product aspirin

60
 CO2H CO2- Na+

O CH3
NaHCO3 O CH3

O O
aspirin salt

OH OH HO2C
HO2C
CO2H
H2SO4 O
+ HO

salicylic acid O
salicylic acid polymeric biproduct
The most likely impurity in the final product is salicylic acid itself, which can
arise from incomplete acetylation or from hydrolysis of the product during the
isolation steps. This material is removed during the various stages of the purification
and in the final crystallization of the product. Salicylic acid, like most phenols, forms
a highly colored complex with iron (III) chloride. Aspirin, which has this group
acetylated, will not give the color reaction. Thus, the presence of this impurity in the
final product is easily detected.

The basic steps utilized in this experiment are the following:

1. Reaction of salicylic acid with acetic anhydride in the presence of a catalyst
(sulfuric acid).
2. Isolation of aspirin by precipitation from solution, followed by filtration.

Acetic anhydride is used rather than some other acetylating agent because it is
inexpensive and because the by-product of the reaction, acetic acid, is non-corrosive.
Sulfuric acid is added as a catalyst to speed up the reaction. The presence of the
sulfuric acid reduces the time required for completion of the reaction from
approximately two hours to fifteen minutes.

Apparatus & Chemicals

2 Erlenmeyer flasks (125 mL) Acetic anhydride
Beaker (500 mL) Salicylic acid
Glass rod Conc. sulfuric acid
Graduate cylinder (25 & 50 mL) 25% ethanol
Büchner funnel Ice
Filtering flask Bunsen burner

61
Procedure
Acetic anhydride gives off irritating fumes, particularly when heated. Use Hood when
working with it.

1. Fill a 500 mL beaker about one-third full with tap water, heat to boiling and
keep it just at the boiling point over the low flame.
2. In a 125 mL conical flask, weigh out to two decimal places about 2.0 g of
salicylic acid. Record the mass.
3. Add 5.0 mL of acetic anhydride and 10 drops of concentrated sulfuric acid.
4. Immerse the flask in the hot water bath for about 15 minutes with occasional
swirling. At this stage all solids should dissolve.
5. Remove the flask from the water bath and add about 30 mL of ice/water to the
hot mixture.
6. Swirl the contents of the flask for a few minutes to hydrolyze the excess acetic
anhydride and to complete the precipitation of the crude product. Keep the
flask in the ice/water bath for at least 10 minutes.
7. Filter off the crude product with suction using a Büchner funnel and a filtering
flask.
8. Wash the crude product with cold water and allow to dry by suction for a few
minutes.

Recrystallization
1. Transfer the crude product to a 125 mL conical flask.
2. Dissolve the solid in a minimum of boiling 25% ethanol
3. Filter the hot solution using fluted filter paper
4. Allow the solution to cool first to room temperature and then in an ice/water
bath for 15 minutes.
5. When crystallization appears complete, filter the product with suction, wash
with a few mL of cold 25% ethanol and dry it by suction for a few minutes.
6. Dry the crystallized product in the oven at about 80 0C for 10 minutes.
7. Record the mass of the product.
8. Record the melting range of the product.
9. Store your product in a clean, labeled vial.

62