216 Lab Manual 2003-2004

The University of Western Ontario
Faculty of Engineering Science
DEPARTMENT OF CHEMICAL AND BIOCHEMICAL

ENGINEERING
INDUSTRIAL ORGANIC CHEMISTRY

C.B.E. 216
LABORATORY MANUAL
Instructor: P.A. Charpentier
2nd Edition
Copyright P. Charpentier 2003

E.S. 216 Industrial Organic Processes Laboratory Manual
Prof. P. Charpentier 2003-2004
TABLE OF CONTENTS
1 INTRODUCTION ............................................................................................... 3
1.1 CONVERSION FACTORS ............................................................................... 4
1.2 COMMON ITEMS OF GLASSWARE AND APPARATUS ........................... 5
1.3 A NOTE TO THE STUDENT ............................................................................ 9
1.4 PERSONAL CONDUCT .................................................................................. 11
1.5 HANDLING CHEMICALS AND EQUIPMENT ............................................ 12
1.6 GENERAL HOUSEKEEPING ......................................................................... 14
1.7 GUIDELINES FOR PREPARATION OF LABORATORY REPORTS ......... 14
LABORATORY 1 - THE FRACTIONATION OF HYDROCARBONS

AND GAS CHROMATOGRAPHY (GC) ......................................................... 20
LABORATORY 2 - ANALYSIS OF PETROLEUM FRACTIONS .............. 29
LABORATORY 3- REDUCTION OF A KETONE TO A SECONDARY

ALCOHOL ……………………………….…………………………………….48
LABORATORY 4- CATALYTIC HYDROGENATION OF SQUALENE (A

POLYUNSATURATED HYDROCARBON) .................................................. 51
LABORATORY 5- EPOXIDATION OF 1-TMP AND IODINE

TITRATION…………………………………………………………………..60
LABORATORY 6 - SYNTHESIS OF AZO-DYES AND UV-VIS

SPECTROSCOPY............................................................................................. 73
LABORATORY 7 - SYNTHESIS OF DICUMYL ETHER AND NMR

SPECTROSCOPY ……………………………………………………………....80
LABORATORY 8- SOXHLET EXTRACTION OF CAFFEINE FROM

BEVERAGE PLANTS…………………………………………………………..87
APPENDIX 1……………………………………………………………………90
2
1 INTRODUCTION
1.1 CONVERSION FACTORS FOR SOME
COMMONLY USED UNITS OF MEASUREMENT
Acceleration m/s2 ft/s2 3.281X100 3.048X10-1

g (accel. of gravity) 1.020X10-1 9.807X100
Area m2 ft2 1.076X101 9.290X10-2
inch2 1.550X103 6.452X10-4
2
yard 1.197X100 8.361X10-1
Density kg/m2 g/cm 1.000X10-3 1.000X103
lb/gallon 8.345X10-3 1.198X102
lb/ft3 6.242X10-2 1.602X101
Energy J btu 9.484X10-1 1.054X103
(includes work) calorie 2.387X10-1 4.184X100
(thermochemical)
erg 1.000X107 1.000X10-7
ft-lb 7.375X10-1 1.356X100
kW-hr 2.778X107 3.600X10-6
Force N dyne 1.000X105 1.000X10-5
pound force 2.248X10-1 4.448X100
Heat capacity J/kg*K btu/lb*oF 2.390X10-4 4.184X103
(includes entropy) cal/g*oC 2.390X10-4 4.184X103
Length m Å 1.000X1010 1.000X10-10
in 3.937X101 2.540X10-2
ft 3.281X100 3.048X10-1
micron 1.000X106 1.000X10-6
mile 6.213X10-4 1.609X103
yard 1.094X100 9.144X10-1
Mass kg ounce 3.527X102 2.835X10-1
lb 2.205X100 4.536X10-1
Power W btu/hr 3.414X100 2.929X10-1
btu/sec 9.484X10-4 1.054X101
cal/sec 2.390X10-1 4.184X100
ft-lb/sec 7.376X10-1 1.356X100
horsepower 1.341X10-1 7.457X102
(550 ft*lb/sec)
Pressure Pa atm 9.869X10-6 1.013X105
(76cm Hg)
bar 1.000X10-5 1.000X105
cm of Hg 7.506X10-3 1.333X103
3
dyne/cm2 1.000X101 1.000X10-1

in of Hg 2.961X10-4 3.337X103
kg force/cm2 1.020X10-5 9.807X104
CONVERSION FACTORS FOR SOME
COMMONLY USED UNITS OF MEASUREMENT CONT’D
lb/in2 (psi) 1.450X10-4 6.895X103

torr 7.501X10-3 1.332X102
(mm of Hg)
Volume m3 ft3 3.531X101 2.832X102
(includes capacity) in3 6.102X10-1 1.639X10-5
gallon (U.S.) 2.642X102 3.785X10-3
L 1.000X103 1.000X10-3
ounce (U.S.) 3.381X104 2.957X10-5
psig ≡ pounds per square inch gauge

psia ≡ ponds per square inch absolute
4
1.2 COMMON ITEMS OF GLASSWARE AND

APPARATUS
Most of the apparatus used will be familiar to you, but the following notes may help you
in identifying and using specific pieces.
The ERLENMEYER or CONICAL FLASK is used for handling solutions,

and for titrations. It is designed with a narrow neck to minimize loss of
solution through splashing or evaporation.
The FILTER or BUCHNER FLASK is used in conjunction with the Buchner

funnel for vacuum-assisted filtration. It is heavy-walled to give pressure resistance; for
this reason, a Buchner funnel should never be used to heat a
solution. Attach it to the vacuum line or water aspirator with heavy-
wall rubber tubing. For any operation involving vacuum, always
use heavy walled rubber tubing - never use soft tubes like
Tygon. If a water aspirator is used, an empty flask should come
between the filter and the pump to avoid ‘suck-back’ if the water
pressure falls. The Buchner assembly is top-heavy and should be
supported when in operation.
The BUCHNER FUNNEL is used for filtration. It fits through a rubber bung
or cone into the Buchner flask. To use, assemble the flask and funnel, place
a filter-paper flat across the perforated porcelain plate, and wet the paper
with the solvent being used (usually distilled water). Turn on the vacuum
and make sure the paper is correctly seated in the funnel; the filter paper should be cut
slightly smaller than the funnel, but make sure it covers all the holes. Stir the suspension
to be filtered and quickly pour it onto the center of the paper, using a glass rod to guide it.
Filtration will go more quickly if you keep liquid in the funnel. If all of the liquid is
filtered off, the residual solid will pack down into a solid cake, slowing filtration. To
empty the funnel after the solid cake has been washed and sucked as dry as possible,
5
loosen the cake around the edge with a spatula, carefully invert the funnel onto a watch-
glass and tap it gently.
The EVAPORATING DISH is used to provide a large surface area to speed up

evaporation. It can be heated on the steam-bath but should never be heated with a
direct flame.
The BURETTE accurately measures volumes to 0.1ml accuracy. When titrating, always
fill the burette to the zero milliliter marking. Your eye should be level with the bottom of
the meniscus in order to take a proper reading of the liquid level.
The TRANSFER PIPETTE accurately delivers one volume (e.g. 5 or10 or25ml).
The PASTEUR or DROPPING PIPETTE is for transferring a few drops.
The SEPARATORY FUNNEL is used for the separation of

liquids with differing densities and for washing. The funnel
should have a properly working stopcock and a stopper of the
correct size. The solution to be separated is poured into the funnel
with the stopcock closed and the funnel stoppered. It is then
shaken vigorously with two hands; one holding the bottom of the
flask between first and second fingers and the other on the stopper
so it does not fall out. This maneuver is performed with the flask
upside down and the stem directed away from people standing by
in case of any splashing. The pressure which may build up inside
the flask is released by holding the funnel upside down and opening the stopcock. Next,
the funnel is placed in a proper size support ring. Enough time is given for the solutions
6
to separate into two distinct layers after which the bottom layer can be removed and the
procedure repeated until necessary. (It is assumed that one knows which layer is to be
kept!)
GAS CYLINDERS with the safety cap off need to be securely strapped to the wall or a
desk in order to prevent them from falling. There is considerable pressure in these
cylinders and care must be taken to control the flow of gases from them. The main
cylinder or tank valve should be closed when not in operation. This valve measures the
pressure present in the tank (i.e. how much gas is left in the tank). The control valve,
usually the second one, gives the pressure reading present in the line connected to the
tank. This is usually a backwards valve, meaning that to reduce pressure it needs to be
turned in the counterclockwise direction. A BUBBLER is usually inserted in the gas line
between the cylinder and the connection to the apparatus to be filled with the gas. This
is advantageous for two reasons: 1) the flow of gas is actually seen as it bubbles through
the oil in the bubbler and 2) this is an outlet for the gas if the pressure becomes too high
so that it exits via the bubbler rather than blowing the glassware or connecting tubes.
When working with gas cylinders it is very important that you know and understand how
everything is connected and what function each piece of equipment has.
There are many different shapes of CONDENSERS available

for use. All of them serve the same purpose in conjunction
with distillation apparatus. Their purpose is to cool the vapors
inside the condenser usually with water as coolant. The
condenser is placed before and is tilted toward the receiving
flasks. The glass is blown so that the cooling liquid is
separated from the vapors which are to be condensed. To have
good cooling cold water should flow through the condenser at
all times. This is achieved by connecting the water inlet to the
bottom end of the condenser and the outlet to the top so the
water flows from the bottom up the condenser and out the top.
7
ERROR DATA
Volumetric flasks Volumetric pipettes

Volume (ml) Error Volume (ml) Error
10 ±0.04 1 ±0.006
25 ±0.06 2 ±0.006
50 ±0.10 5 ±0.01
100 ±0.16 10 ±0.01
8
1.3 A NOTE TO THE STUDENT
The following introductory paragraphs are intended to be for your benefit and safety.
The objective of this laboratory is to introduce the student to basic organic reactions and
analytical instrumentation, as used in industrial operations and processes. By performing
the prescribed experiments the student will become familiar with a typical organic
chemical laboratory and the operation of typical analytical instruments. She/he will also
obtain a feeling and routine for generation of analytical results and the technical
capabilities of various instruments. The generated knowledge will enable the student to
better understand the basic chemical principles and control of industrial processes, which
is essential for proper operation of individual units in the plant and the management of
processes for optimum performance and product quality, and environmental effects.
Whether in management, processing, design or laboratory, an engineer should have good
knowledge and understanding of the chemistry, measurements and instrumentation being
used in the plant. The important decisions and modifications that an engineer must make
in industry will be based on the results obtained from the laboratory. A good
understanding of possible errors in procedures and instruments is also required and
particularly a good understanding of variables that could affect a result. A lack of this
understanding very often results in erroneous judgments that can affect considerably both
production and quality of the final product.
Although this laboratory does not involve extensive manipulation of hazardous

chemicals, materials that will be analyzed are often flammable and volatile as well as
toxic. Each student must therefore follow strictly all safety procedures and not perform
any unauthorized manipulations with these chemicals prior to consultation with the
instructor or the demonstrator.
Remember: ACCIDENTS ARE CAUSED AND CAN BE PREVENTED!
9
A few rules are listed below. A ‘Handbook of Safety Practices in Engineering’ is supplied
in the laboratory and each student should be familiar with its contents.
The students will work in groups of two or three and enough time will be provided to
finish all the prescribed experiments. If any piece of equipment fails or does not function
properly, students are required to report the problem immediately to the demonstrator or
the instructor and are not allowed to attempt to fix the instrument on their own.
ALL STUDENTS MUST HAVE A LABORATORY BOOK IN WHICH TO RECORD

ALL LAB DATA DURING THE LABORATORY PERIOD. The lab book used in
industry is a legal document. Loose papers for recording of data or comments are not
allowed and will be removed from the lab.
Each student must read the instructions for the particular experiment PRIOR to coming to
the laboratory. He/she should understand the whole procedure and what must be done in
the experiment. This knowledge will be checked periodically by the instructor or the
demonstrator and it will be evaluated.
Equations for all reactions should be written out in your lab notebook before coming to
the laboratory. Also, any calculations required (e.g. theoretical yield, preparation of
solutions) should be written in full in your laboratory notebook before coming to the
laboratory. Record all observations in the lab book including any color changes,
unexpected events, smells, etc. The notebook will be marked from time to time during the
term. Plan your working time in the laboratory! By doing this your laboratory will be a
useful and pleasant experience rather than a frustrating one.
Develop good working habits. Keep your area clean and tidy. Your working area reflects
your working habits and also the quality of your work and results. You are working with
precise instruments and generating accurate data --keep this in mind!
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ALL FLASKS, BEAKERS, CONTAINERS WITH ANY CHEMICALS IN THEM

MUST BE CLEARLY LABELED WITH THE NAME OF THE CHEMICAL AND
DATE!
NO SMOKING, EATING OR DRINKING IS ALLOWED IN THE LABORATORY!
LEAVE YOUR WORKING SPACE, APPARATUS AND GLASSWARE CLEAN AND
IN ORDER BEFORE LEAVING THE LAB!
The demonstrator will sign your lab book ONLY after you have fulfilled this
requirement.
ALL LABORATORY EXPERIMENTS MUST BE DONE DURING THE
ALLOCATED TIME PERIOD. THERE WILL BE NO EXTENSION OF THE LAB
AND NO ADDITIONAL TIME PERIOD AVAILABLE FOR THE EXPERIMENTS,
except under special circumstances such as illness verified by a doctor’s note.
1.4 PERSONAL CONDUCT
(1) Eye protection (safety glasses with side shields) is mandatory.

(2) Eating and drinking in the lab are strictly forbidden.
(3) Long hair should be tied back.
(4) Laboratory coats are required for cloth and body
protection.
(5) No laboratory work may be performed without the prior permission of Mr.
Milton.
(6) No open toed shoes allowed.
(7) No shorts allowed.
VIOLATION OF ANY OF THESE REGULATIONS WILL MEAN THAT YOU WILL

NOT BE PERMITTED TO WORK IN THE LABORATORY.
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1.5 HANDLING CHEMICALS AND EQUIPMENT
1. Do not taste chemicals.
2. Do not pipet any chemicals by mouth. Use rubber bulb (propipette).
3. Do not pour liquids that are flammable or that do not mix with water into sinks. Pour
them into the provided and labeled containers.
4. Do not mix incompatible chemicals.
5. Do not heat flammable liquids with an open flame.
6. Operations involving volatile or toxic materials are to be conducted in the fume hood.
7. Dispose of solid wastes in garbage pails. Do not use the sinks.
8. Clean up spills (solid or liquid) at once.
9. Return chipped or broken glassware to the demonstrator.
10. Be sure the apparatus is placed properly. Do not move instruments without proper
consultation with the demonstrator.
11. When heating a test tube make sure that it is not pointing towards yourself or other
people in the vicinity, so no damage will result if the contents suddenly ‘dump’ out.
12. Never apply force to any glass apparatus. Many serious cuts are caused by the sudden
fracture of glass under strain from misuse. In particular, never use force in an
attempt to push a thermometer or glass tube through a hole in a cork or rubber.
12
13. Never heat a tightly stoppered flask even if it is empty-----it will explode.
14. Do not attempt to buttress a laboratory assembly with makeshift supports such as
books, pencils and the like. Use several ring stands if necessary. Round bottom flasks
cannot stand freely on the bench----use a special cork support or place the flask into a
beaker.
15. Do not attempt to break up a solid in the bottom of a flask by punching the solid with
a glass stirring rod. The rod may either fracture in your hand or puncture the bottom
of the flask.
16. Avoid shortcuts! If you have an idea for an improvement talk it over with your
demonstrator; if no objections, try it; if it is successful, tell us about it!
17. There are certain necessary precautions associated with particular chemicals or
experiments. Your demonstrator will point these out when required.
18. If you are not familiar with a piece of apparatus or an experimental procedure ask
for help. Don’t just try to muddle through without knowing what you are doing.
19. Chemical waste should be disposed of in the labeled waste containers

provided. Halogenated chemicals must be disposed of separately from non-
halogenated chemicals. Nothing should go down the drain! Dispose of all chemicals
in the bottles marked for the specific lab.
13
1.6 GENERAL HOUSEKEEPING
1. Keep benches clean and orderly and sinks clean. You must leave your portion of the
bench clean at the end of the lab period.
2. Aisles and floors are to be kept free of obstructions. Keep cupboard doors and
drawers closed when not in use.
3. Hang coats on the rack. No coats are permitted on tables or benches.
4. Laboratory doors MUST be unlocked during lab period.
1.7 GUIDELINES FOR PREPARATION OF LABORATORY REPORTS
Laboratory reports should be written as though they were short technical reports. Thus
Tables and Figures should always be referred to in the prose text of the report, i.e. they
should not appear on their own.
The report should be written in the past tense, since it is a description and a correlation of
past observations. The present tense may be used in referring to laws of nature, properties
of materials etc. which are independent of time. Thus, for instance, in a particular
experiment “The ambient temperature equaled 22 °C”; on the other hand, “The ambient
temperature equals about 20 °C ”.
TITLE PAGE
Title of experiment
Name of person writing the report
Name of experimenters
Date when the experiment was performed
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All Formal reports must be TYPED
ABSTRACT
The Abstract should summarize the entire report. It should state clearly and briefly the
objectives, methods, results and conclusions of the lab.
Objective: State the objective or purpose of the lab

Method: In one or two sentences, summarize the methods, including scientific and
common names of organisms and techniques used.
Results: Summarize what was found in the study
Conclusions: State the significance of the results in relation to the objective.
INTRODUCTION
The Introduction should describe the scope and the purpose of the lab and include any
background information necessary to understand the experiment.
State the general problem. Give a brief statement of why the general topic is relevant and
important. Define any specialized terms or concepts (e.g. the concept of distillation)
likely to be encountered later in the lab report. Supply sufficient background (historical
and theoretical) information to allow the reader to evaluate and understand the results of
the study without needing to refer to other publications.
State the specific objective or purpose of the lab and the approach to be used. The
purpose states what you are investigating and why; how you perform the investigation
should be described later in the Methods and Materials.
15
MATERIALS AND METHODS
The Methods section should describe what was done and how it was done. It should be
written in the past tense with active voice, and in paragraph form.
The Materials and Methods section should provide only enough detail to permit a
competent worker to evaluate the validity of the experiment and to repeat it, if necessary.
It should not be simply a recipe of all the steps involved. State the names (IUPAC if
possible) of the chemicals used, the instruments, equipment and pattern of replication.
Describe any unusual numerical calculations and state the statistical technique used to
analyze the data.
RESULTS
The Results section should present the data collected in a summarized form and describe
only the key features of these data, emphasizing trends or patterns that are relevant to the
hypotheses being tested. Interpretation of the data is reserved for the discussion section.
Do not present the same data in both a table and figure i.e. place table of raw data in an
appendix and place figure in the results section. Titles of tables and figures should
contain enough information to understand the contents without reference to the text. The
number and title are placed at the top of a table, and at the bottom of figure.
Guide the reader through your figure (s) and table (s) in a logical and systematic manner,
pointing out trends and differences that pertain to the objective (s) of the report. Simply
state what you found in your study, without inference or reference to "expected" results.
16
DISCUSSION
The Discussion section should provide an explanation and interpretation of your results
and indicate the significance of the results to the hypothesis being tested. Results of
previous studies on the same topic should be compared with yours, with an explanation of
why your results are different from previous studies, if necessary.
State how and why your results either support or do not support the objectives and
hypotheses. REMEMBER: results are results, they are never wrong simply by being
different from either your expectations or from other investigations. Draw conclusions
about the hypotheses (objectives) of your study, based on all data available in the current
studies.
APPENDIX
Includes all raw experimental data, e.g. time vs. temperature data points, sample
calculations, and any other information or data used for the experiment and calculations.
REFERENCES
The Reference section should be a list of all books, journals, and other materials cited in
the body of the paper.
The surname of the author(s) and the year of publication should be inserted in the text at
an appropriate place:
"Smith (1991) compared..." or "... have been recently compared (Smith, 1991)."
If the reference has more than 2 authors, include only the surname of the first author,
followed by "et al."
17
"Smith et al. (1991) compared..." or "... have been recently compared (Smith et al.,
1991)."
When listing more than one citation at a given point in the text, list them in
chronologically by first author, but for 2 (or more) papers, published in the same year, list
these alphabetically:
"(Jones, 1978; Black et al., 1989; Smith, 1989; Jones and Smith, 1991)"
If an author or group of authors has published more than one article in a given year, you
can distinguish between these articles by placing a letter postscript after the publication
year:
"(Black and Smith, 1990a; Black and Smith, 1990b)"
List all references in alphabetical order, sorted by the author(s)' last name(s). In cases
where the same author or group of authors has/have published multiple papers that you
have cited, then arrange these references in chronological order.. All authors must be
given in the reference list - the abbreviation "et al." Is used only in the text. The following
are examples of the punctuation, style and abbreviations that may be used for references
(note: the headings given here are not to be included in your reference list).
Journal article:
Jones, R.S., E.J. Gutherz, W.R. Nelson and G.C. Matlock. 1989. Burrow utilization by
yellowedge grouper, Epinephelusflavolimbatus, in the northwestern Gulf of Mexico. Env.
Biol. Fish. 26: 277-284.
Chapter in a Book:
18
Gross, M.T. 1984. Sunfish, Salmon and evolution of alternative reproductive strategies
and tactics in fishes. Pp. 55-57. In: G.W. Potts and R.J. Wooten (eds.) Fish reproduction:
strategies and tactics. Academic Press, London.
Book:
Siegel, S. 1956. Nonparametric statistics for the behavioral sciences. McGraw-Hill, New
York. pp. 312.
19
ORGANIC CHEMISTRY LABORATORIES
LABORATORY 1 - THE FRACTIONATION OF HYDROCARBONS AND GAS

CHROMATOGRAPHY (GC)
(2 LAB PERIODS)
I. INTRODUCTION
Mixtures of organic compounds can be separated by distillation. One such mixture is

crude oil. Oil refineries fractionate crude oil by distillation into products such as gasoline.
Separation by distillation is based on the difference in boiling points. The composition
and uses of crude oil fractions is summarized in Table 1.1
Table 1.1 Petroleum constituents
FRACTION DISTILLATION CARBON NUMBER GENERAL USES

TEMPERATURE (bp),
o
C
Gas below 20 C1-C4 uses as for natural gas
Petroleum ether 20-60 C5-C6 solvent, dry-cleaning
Ligroin (light 60-100 C6-C7 useful as fuel or
naphtha) chemicals feedstock
Natural gasoline 40-205 C5-C10, cycloalkanes straight run gasoline
Kerosene 175-325 C12-C18, aromatics jet, tractor, heating fuel
Gas oil above 275 C12 and higher diesel and heating fuel
Lubricating oil non-volatile liquids long chains attached lubricants or cracked to
to cyclic structures give lighter fractions
Asphalt or non-volatile solids polycyclic structures paving, coating and
petroleum coke structure uses
20
SEPARATION BY DISTILLATION
Simple Distillation:
In a simple distillation, the mixture of compounds to be separated is boiled, and the
vapors are condensed. The vapor phase is always richer in the more volatile compound
(lower boiling point). For instance, if we boil the liquid with a composition of Xo as
shown in Figure 1.1, the vapor will have a composition of Yo, which is richer in the low
boiler. By condensing the vapors we get a ‘head’ product rich in the low boiler, while the
‘bottom’ product will be nearly pure high boiler. This method gives good separation only
if there
Figure 1.1 Simple Distillation
is a reasonably big difference between the boiling points of the high and low boilers. The
method can be further refined by redistilling the condensed head fractions.
Reflux Cooling (Deflegmation):

The head product can be enriched to have more low boilers by using a reflux condenser
shown in Figure 1.2. To achieve this a fraction of the vapors is condensed back to the
21
boiler. This can be understood from Figure 1.3. When we boil a liquid with composition
Xo, the vapors would have a composition of Yo. The reflux cooler condenses a fraction of
the vapors, reducing the temperature to P. This point is in the two-phase region, thus the
vapor separates to the refluxing liquid with a composition of XD, going back to the boiler,
and the ‘head’ product with a composition of YD. It can be easily seen that the head
product is richer in the low boiler than in a simple distillation (Yo).
Figure 1.2 Reflux cooling setup Figure 1.3 Reflux cooling
Rectification:
To further improve the separation, the refluxing liquid can be contacted with the
evaporating vapor - this is called rectification (Figure 1.4). To understand the principle of
rectification lets assume that the composition of the vapor, A, and the refluxing liquid, B,
22
is equal, so we can represent it as P on Figure 1.5. The vertical position of P depends on

the ratio of A to B. P separates into two phases, with compositions XL and YD. This is the
representation of the equilibrium of one ‘theoretical plate’. In the industrial distillation
towers there are a number of plates (with lower efficiency than the theoretical plates). For
the separation of components with similar boiling points, as many as 200 plates are used.
Figure 1.4 Rectification setup Figure 1.5 Rectification
In the present lab, a three component system will be separated by a simplified

rectification. The reflux condenser to be used is called a Vigreux column, and the spikes
serve as plates to force the vapors to bubble through the condensing liquid, thereby
improving the separation. A better lab distillation head shown in Figure 1.6 almost
perfectly simulates the industrial towers (Figure 1.7).
23
Figure 1.6 Laboratory rectification

Figure 1.7 Industrial distillation
head
tower
II. MATERIALS
• unknown mixture of hydrocarbons (prepared by the demonstrator) consisting of
toluene, 2-methyl-butene and hexane
III. EQUIPMENT
• 1000ml round bottom boiling flask
• fractionation column (Vigreux)
• condenser
• distributor (cow)
• 4, 250ml round bottom receiving flasks
• green, plastic glassware clamps
• heating mantle with power control unit
• thermometer
• clamps
• Gas Chromatograph
24
25
IV. PROCEDURE
Before beginning the distillation, make an injection of the hydrocarbon (HC) mixture you
received from the TA into the gas chromatography (GC) unit. Refer to the GC section
under Instrumentation found in this lab manual for background information. The GC will
produce a strip chart with a number of peaks that relate to the volume percent of each of
the HCs in the mixture, as well as some other peaks. Normalize the peak areas of the
three HCs to equal 100 percent of the total peak area. (i.e.: use only the areas of the
peaks that relate to the HC peaks) Then calculate the percentage of each of the fractions
in the mixture as indicated by the GC analysis. These are the values that will determine
the success of your distillation. You can then proceed with the distillation of the HC
mixture.
If you do your distillation correctly, the total volume of the fractions collected plus the
remaining bottom fraction (left in the boiling flask) should equal the volume of the
original mixture. Also, the percentage of each HC in the mixture should correspond to
the original GC analysis. Doing this will require several simple but necessary
calculations. The interesting part of the calculation is that your fractions will probably
be a mixture of several HCs, with one HC dominating. You will have to calculated the
total volume of each HC from the volume of that HC in each of the fractions and the
bottom. (The bottom is what is left over in the boiling flask at the end of the distillation)
Include in your report a table listing the volume of each HC collected in each fraction,
and the sum of each HC in the entire mixture. Convert these volumes to percentages, and
compare this to the original GC analysis of the small sample of the mixture, again in table
format. Remember to title each table and figure appropriately. Proper form and style are
very important, even if you are not satisfied with the results of your experiment.
To perform the distillation, set up the equipment as shown in Figure 1. Pour a measured
volume (300 mL) of a prepared HC mixture into the boiling flask. Prepare a table and
26
take time/temperature measurements throughout the distillation every 60 seconds. This

raw data will be plotted and submitted with the report. (do not submit the raw data)
Slowly heat the mixture until you have achieved a gentle boil and a steady reflux in the
Vigreaux column. As soon as you begin to see condensation occurring in the condenser,
the first temperature plateau has been reached. Maintain this temperature and collect the
liquid (first cut) in a collection flask. Usually a waste cut is taken to eliminate impurities,
but in this case we want to recover as much of the HC mixture as possible. Also, past
distillation experiments have shown that the majority of the low boiler is fractionated
very early in the experiment.
When the dripping stops, you have exhausted the first cut. Increase the temperature and
repeat the procedure. Keep up with the time/temperature data. When the second cut is
exhausted, you will be left with the third cut (bottom cut) in the boiling flask. Never let
the boiling flask run dry! At this point you will have completed the distillation. Turn
off the heat. After the equipment has cooled it can be dismantled and returned to the
storage bins underneath the lab benches. In the meantime, measure and record the
volume of each cut, and prepare a sample of each cut for storage in the lab fridge. Make
sure you have identified your samples in such a manner that anybody would be able to
continue with the experiment.
A portion of the samples you have collected will be injected into the GC. This is a pretty
straightforward operation. You will identify the fractions based on the time it takes for
the material to pass through the system. Different substances pass through the system at
different lengths of time, depending on their interaction with the G.C. column packing
material.. This is the basis of GC. Once you have created a GC trace for each cut, you
can then complete the calculations as outlined, and prepare your report in compliance
with the Guidelines for Preparation of Laboratory Reports included in your lab manual.
V. PRELAB QUESTIONS
Submit to the TA prior to beginning the laboratory session.
27
1) Draw the structures of toluene, 2-methyl-butene, and hexane. List their physical
properties (molecular weights, density, boiling point, refractive index and melting
point)
VI. SUMMARY OF REQUIREMENTS FOR REPORT
1) In table form show the calculated percentages of each fraction in the mixture prior
to distillation.
2) In table form show the time/temperature measurements recorded throughout the
distillation ( every 60 seconds). Plot the above.
3) Submit the GC trace for each cut and the basis for identification of the fraction
4) Tabulate the volume of each HC cut collected and the volume sum of all the HC
fractions in the entire mixture. Convert volumes to percentages, and compare to the
original sample analyzed prior to distillation.
28
EXPERIMENT 2: ANALYSIS OF PETROLEUM FRACTIONS
(2 LABORATORY PERIODS)
Purpose: To familiarize the student with the instruments and analysis used in the
petroleum and petrochemical industries.
PART 1. ASTM DISTILLATION OF PETROLEUM PRODUCTS (ASTM D86-61).
This method of testing is intended for use in the distillation of motor gasolines, aviation
gasolines, aviation turbine fuels, naphthas, kerosene’s, oils, distillate fuel oils, and similar
petroleum products.
Definitions:
Initial Boiling Point -The thermometer reading which is observed at the instant that the
first drop of condensate falls from the lower end of the condenser tube.
End Point -The maximum thermometer reading attained during the test, which usually
occurs after the evaporation of all liquid from the bottom of the flask. The term
"maximum temperature" is a frequently used synonym.
Dry Point -The thermometer reading which is observed at the instant the last drop of
liquid evaporates from the lower point in the flask. Any drops or film of liquid on the side
of the flask or on the thermometer are disregarded.
Decomposition Point -The thermometer reading which coincides with the first indications
of thermal decomposition of the liquid in the flask.
29
NOTE: Characteristic indications of thermal decomposition are an evolution of fumes

and erratic thermometer readings which usually show a decided decrease after any
attempt is made to adjust the heat.
Percent Recovered -The volume in milliliters of condensate observed in the receiving

graduate, in connection with a simultaneous thermometer reading.
Percent Recovery -The maximum percent recovered, as observed in accordance with

Procedure.
Percent Total Recovery -The combined percent recovery and residue in the flask, as
observed in accordance with Procedure.
Percent Loss -100 minus the percent total recovery.
Percent Residue -The percent total recovery minus the percent recovery, or the volume of
residue in milliliters if measured directly.
Percent Evaporated -The sum of the percent recovered and the percent loss.
Outline of Method
A lOO-ml sample is distilled under the prescribed conditions which are appropriate to its
nature (Table 1). Systematic observations of thermometer reading and volume of
condensate are made, and from these data the results of the test are calculated and
reported.
Apparatus -A typical assembly of the apparatus is shown in Figure 1.
30
Preparation of Apparatus
(a) Fill the condenser box to cover the condenser tube with chopped ice. Add sufficient
water to cover the condenser tube. Prepare a similar cold-water bath for the graduate.
(b) Remove any residual liquid in the condenser tube by swabbing with a piece of soft,
lint-free cloth attached to a cord or copper wire.
(c) Measure 100 ml of the sample in the graduated cylinder and transfer it as completely
as practicable to the distillation flask, taking care that none of the liquid flows into the
vapor tube.
(d) Fit the thermometer, provided with a snug-fitting, well-rolled cork, tightly into the
neck of the flask so that the bulk is centered in the neck and the lower end of the capillary
is level with the highest point on the bottom of the inner wall of the vapor tube.
(e) Place the flask containing the 100-ml charge in its support; and by means of a cork
through which the vapor tube has been passed, make a tight connection with the
condenser tube. Adjust the flask so that it is in a vertical position and so that the vapor
tube extends into the condenser tube for a distance of 1 to 2 in.
31
(f) Place the graduate that was used to measure and charge, without drying, into its bath
under the lower end of the condenser tube so that the end of the condenser tube is
centered in the graduate and extends therein for a distance of at least 1 in, but not below
the 100-ml mark. Cover the graduate closely with a piece of blotting paper so similar
material, suitably weighted, which has been cut to fit the condenser tube snugly. Maintain
the level of the bath around the graduate so that it is at least as high as the 100-ml mark.
(g) Note and record the prevailing barometric pressure, and proceed at once with the
distillation as directed in the following section.
1.4 Procedure
Apply heat to the distillation flask and contents. Immediately after observing the initial
boiling point, move the graduate so that the tip of the condenser touches its inner wall.
Continue to regulate the heating so that the rate of condensation into the graduate is 4-5
ml/min.
In the interval between the initial boiling point and the end of the distillation, observe and
record whatever thermometer readings at prescribed percentages recovered, and/or
percentages recovered at prescribed thermometer readings are necessary for the
calculation and reporting of the results of the test as prescribed in the following section.
Record all volumes in the graduate to the nearest 0.5 ml and all thermometer readings to
the nearest 1.0°F (0.5°C).
NOTE: In cases in which no specific data requirements have been indicated, record the
initial boiling point, the end point or dry point or both, and thermometer readings at 5%
and 95% recovered and at each multiple of 10% recovered from 10% to 90% inclusive.
If either a thermometer reading of 700°F (371°C) or a decomposition point is observed,

discontinue the heating and resume the procedure as directed in the second paragraph
following. Otherwise, continue the heating until the end point is reached.
32
Observe and record the end point or dry point or both, as required, and discontinue the
heating. At the end point, observe if all the liquid has evaporated from the bottom of the
flask. If not, include a note of this fact in the report as prescribed in the following section.
While the condenser tube continues to drain into the graduate, observe the volume of
condensate at 2-minute intervals until two successive observations agree. Measure this
volume accurately and record it, to the nearest 0.5 ml, as percent recovery. If the
distillation was previously discontinued under the conditions given in the second
paragraph preceding, deduct the percent recovery from 100, report this difference as
"Percent Residue and Loss", and omit the procedure given in the next two paragraphs.
After the flask has cooled, pour its contents into the condensate in the graduate and allow
to drain until no appreciable increase in the volume of liquid in the graduate is observed.
Record this volume, to the nearest 0.5 ml, as percent total recovery.
Deduct the percent total recovery from 100 to obtain the percent loss.
1.5 Calculations and Reporting

Report (and plot) the data specified under section 1.1 and the pressure under which the
measurements were made.
1.6 Question
(a) How many components are present in the sample? What are they?
PART 2. API GRAVITY OF PETROLEUM AND ITS PRODUCTS (ASTM D287-

55)
This method describes a procedure for the determination by means of a glass hydrometer
of the API gravity (in vacuum) of crude petroleum and of petroleum products normally
handled as liquids and having a Reid vapor pressure of 26 lbs. or less. Results are
determined at 60°F or converted to values at 60°F by means of standard tables.
33
Definition -API Gravity is defined by the following equation:

API Gravity. deg. = (141.5/ (sp.gr.60/60°F )) -131.5
2.1 Apparatus
The following apparatus is required:
Hydrometers, of glass, graduated in degrees API (in vacuum) as listed in Table l and
conforming to the Tentative Specifications for ASTM Hydrometers (ASTM Designation:
EI00). For routine. testing of petroleum products, the long form of hydrometer (IH to
10H) should be used.
Thermometer, having a range of -5°F to +215°F and conforming to the requirements for
Thermometer 12F as prescribed in ASTM Specifications El.
Hydrometer Cylinders, made of metal, clear glass, or plastic. For convenience in

pouring, the cylinder may have a lip on the rim. The side diameter of the cylinder shall be
at least 25 mm greater than the outside diameter of the hydrometer used in it. The height
of the cylinder shall be such that the length of the column of sample it contains is greater
34
by at least 25 mm than the portion of the hydrometer which is immersed beneath the
surface of the sample.
Temperature of Test -The gravity determined by the hydrometer method is most

accurate at or near the standard temperature of 60°F; use this or any other temperature
between O°F and 195°F for the test, so far as it is consistent with the type of sample and
necessary limiting conditions shown In Table 2.
35
2.2 Procedure
Pour the sample into the clean hydrometer jar without splashing so as to avoid the
formation of bubbles and to reduce to a minimum the evaporation of the lower-boiling
constituents of the more volatile samples. For the more volatile samples, transfer to the
hydrometer cylinder by siphoning. Remove any air bubbles formed, after they have
collected on the surface of the sample, by touching them with a piece of clean filter paper
before inserting the hydrometer. Place the cylinder containing the sample in a vertical
position in a location free from air currents. Take precautions to prevent the temperature
of the sample from changing appreciably during the time necessary to complete the test.
During this period, the temperature of the surrounding medium should not change any
more than 5°F.
Lower the hydrometer gently into the sample, and when it has settled, depress it about
two scale divisions into the liquid and then release; keep the rest of the stem dry as
unnecessary liquid on the stem changes the effective weight of the instrument and so
affects the reading obtained. With samples of low viscosity, a slight spin imparted to the
instrument on releasing assists in bringing it to rest, floating freely away from the walls
of the hydrometer cylinder. Allow sufficient time for the hydrometer to become
completely stationary and for all air bubbles to come to the surface. This is particularly
necessary in the case of the more viscous samples.
When the hydrometer has come to rest, floating freely, and the temperature of the sample
is constant to O.2°F, read the hydrometer to the nearest scale at which the surface of the
liquid cuts the scale. Determine this point by placing the eye slightly below the level of
the liquid and slowly raising it until the surface, first seen as a distorted ellipse, appears to
become a straight line cutting the hydrometer scale.
To make a reading with nontransparent oils, observe the point on the hydrometer scale to
which the sample rises above its main surface, placing the eye slightly above the plane
surface of the liquid. This reading requires a correction. Determine this correction for the
36
particular hydrometer in use by observing the height above the main surface of the liquid
to which the oil rises on the hydrometer scale when the hydrometer in question is
immersed in a transparent oil having a surface tension similar to that of the sample under
testing.
Observe the temperature of the sample to the nearest O.25°F immediately before and
after the observation of the gravity, the liquid in the cylinder being thoroughly but
cautiously stirred with the thermometer, the whole of the mercury thread being immersed.
Should these temperature readings differ by more than 1°F, repeat the temperature and
gravity observations when the temperature of the sample has become more stable. Record
the mean of the thermometer reading before and after the final hydrometer reading, to the
nearest degree Fahrenheit, as the temperature of the test.
NOTE: When thermo-hydrometers are used, stir the sample by carefully raising and
lowering the hydrometer. It is satisfactory in this case to read the thermometer scale after
the hydrometer reading has been observed.
2.3 Result
Report the API gravity of the petroleum sample provided.
PART 3. SAYBOLT VISCOSITY (ASTM D88-56)
This method describes procedures for the empirical measurement of Saybolt viscosity of
petroleum products at specified temperatures between 70°F and 210°F. A special
procedure for waxy and resinous materials is also included.
NOTE: A fundamental and preferred method for measuring viscosity is by the use of
kinematic viscometers as outlined in ASTM Method D445, Test for Kinematic Viscosity.
This method requires smaller samples, less time, and gives greater accuracy.
37
Saybolt Universal and Saybolt Furol viscosities may be obtained from kinematic
viscosity values by the use of conversion tables given in ASTM Method D446 -
Conversion of Kinematic Viscosity to Saybolt Universal Viscosity; and ASTM Method
D666 -Conversion of Kinematic Viscosity to Saybolt Furol Viscosity, respectively.
Definition
(a) Saybolt Universal Viscosity -The efflux time in seconds of 60 ml of sample flowing
through a calibrated Universal orifice under specified conditions.
(b) Saybolt Furol Viscosity -The efflux time in seconds of 60 ml of sample flowing
through-a calibrated Furol orifice under specified conditions.
The Furol viscosity is approximately one-tenth the Universal viscosity and is

recommended for those petroleum products having viscosities greater than 1000 seconds
(Saybolt Universal), such as fuel oils and other residual materials.
The word "Furol" is a contraction of fuel and road oils.
3.1 Outline of Method

The efflux time in seconds of 60 ml of sample, flowing through a calibrated orifice, is
measured under carefully controlled conditions. This time is corrected by an orifice factor
and reported as the viscosity of the sample at that temperature.
3.2 Apparatus
Viscometer and Bath -The viscometer shall be constructed entirely of corrosion-

resistant metal. The orifice tip, Universal or Furol, may be constructed as a replaceable
unit in the viscometer. Provide a nut at the lower end of the viscometer for fastening it in
the bath. Mount vertically in the bath and test the alignment with a spirit level on the
plane of the gallery rim. Provide a cork or other suitable means to prevent the flow of
sample until the start of the test; a small chain or cord may be attached to the cork to
facilitate rapid removal. The bath serves both as a support to hold the viscometer in a
vertical position as well as the container for the bath medium. Equip the bath with
38
effective insulation, with a coil for heating and cooling, and with thermostatically
controlled heaters capable of maintaining the bath within the functional parameters given
in Table 3. The heaters and coil should be located at least 3 in. from the viscometer.
Provide a means for maintaining the bath medium at least 1/4 in. above the overflow rim.
The bath media are given in Table 3.
39
40
3.3 Preparation of Apparatus

Use a Universal orifice for lubricants and distillate materials with efflux times greater
than 32 seconds to give the desired accuracy. Liquids with efflux times over 1000
seconds are not conveniently tested with this orifice.
Use a Furol orifice for residual materials with efflux times greater than 25 seconds. The
Furol eff1ux is approximately one-tenth the Universal efflux time.
41
42
NOTE: The Universal orifice is used at 70°, 100°, 130° and 210°F. The Furol orifice is
used at 77°, 110°, 122° and 210°F.
Set up the viscometer and bath where they will be free from drafts and rapid changes in
air temperature. Locate them so that the sample will not be contaminated by dust or
vapors during the test.
Viscosity determinations shall not be made at temperatures below the dew point of the
room's atmosphere. Room temperatures up to 100°F will not introduce errors in excess of
1.0 percent. For standardization and referee tests, the room temperature shall be kept
between 68° and 86°F and the actual temperature recorded.
Fill the bath at least 1/4 in. above the overflow rim of the viscometer. Table 4 lists
recommended bath media for each test temperature.
Provide adequate stirring and thermal control for the bath so that the sample will not
fluctuate more than ± 0.05°F after reaching the test temperature.
Clean the viscometers with an effective nontoxic solvent and remove all solvent from the
gallery and viscometer.
NOTE: The plunger commonly supplied with the viscometer should never be used for
cleaning as the overflow rim and walls of the viscometer may be damaged by its use.
43
Calibration of Viscometer
Calibrate the Saybolt Universal viscometer at periodic intervals by measuring the efflux
time at 100°F of an appropriate viscosity standard, following the procedure for standards
given below.
Viscosity standards are available from two sources. These standards may be used with
equal confidence provided they are used immediately after opening and not stored for re-
use as permanent viscosity standards.
Standards Conforming to ASTM Saybolt Viscosity Standards
Viscosity Oil Standards conforming to the requirements of ASTM Viscosity Oil

Standards for viscometer calibration having certified Saybolt viscosity values established
by cooperative determinations of kinematic viscosity values. The kinematic values are
converted to Saybolt Universal and Saybolt Furo1 viscosity values by means of
conversion tables given in ASTM Methods 0446 and 0666, respectively. The Viscosity
Oil Standards are oils with approximate Saybolt viscosities as shown in Table 5.
3.4.2 NBS Viscosity Standards
National Bureau of Standards liquid viscosity standards having accurate values supplied
with each sample. Standard SB has a Saybolt Universal viscosity of approximately 300
sec. at 100°F. Standard SF has a Saybolt Furol viscosity of approximately 100 seconds at
122°F.
3.4.3. Routine Calibrations
The viscosity standards may also be used for routine calibrations at other temperatures as
shown in Table 5.
44
3.4.4 Other Viscosity Standards
Other reference liquids, suitable for routine calibrations, may be established by selecting
stable oils covering the desired range and determining their viscosities in a viscometer
calibrated with a standard conforming to ASTM requirements or an NSB standard as
described herein.
The efflux time should equal the certified Saybolt viscosity value. If the efflux time
differs from the certified value by more than 0.2%, calculate a correction factor, F, for the
viscometer as follows:
F = V/T
where F = certified Saybolt viscosity of the standard, and
45
t = efflux time in seconds at 100°F.
NOTE: The correction factor applies to all viscosity levels and for all temperatures,
provided the calibration is based on viscosity standard having an efflux time between 200
and 600 sec.
Calibrate the Saybolt Furol viscometer at 122°F in the same manner as above, using a
viscosity standard having a minimum efflux time of 90 seconds.
Viscometers or orifices which have corrections in excess of 1.0 percent shall not be used
for routine testing.
3.5 Procedure
If the test temperature is above room temperature, the test may be expedited by
preheating the sample to not more than 3°F of its flash point (see ASTM Method D93).
Test for Flash Point by Means of the Pensky-Martens Closed Tester), as volatility losses
may alter its composition.
Insert a cork stopper, having a cord attached for its easy removal, into the air chamber at
the bottom of the viscometer. The cork shall fit tightly enough to prevent the escape of
air, as evidenced by the absence of oil on the cork when it is withdrawn.
Filter the prepared sample through a 100-mesh screen directly into the viscometer until
the level is above the overflow rate.
Stir the sample until its temperature remains constant within 0.05°F of the test
temperature during 1 minute of continuous stirring. Stir with a viscosity thermometer
equipped with a thermometer support (Figure 3). Use a circular motion at 30 to 50 r.p.m.
in a horizontal plane.
46
NOTE: Never adjust the temperature by immersing hot or cold bodies into the sample.
Such thermal treatment may affect the sample and the precision of the test.
Remove the thermometer from the sample. Quickly remove the oil from the gallery until
its level is below the overflow rim. This is done by placing the tip of the withdrawal tube
at one point in the gallery and applying suction. Do not touch the overflow rim with the
withdrawal tube, or the effective head of the sample will be reduced.
Place the receiving flask where the stream of oil from the bottom of the viscometer will
just strike the neck of the flask. The graduation mark on the flask shall be between 10 and
13 cm from the bottom of the viscometer tube.
Snap the cork from the viscometer using the attached cord. At the same instant start the
timer. Stop the timer the instant the bottom of the meniscus reaches the graduation mark.
Record the efflux time in seconds.
Report the corrected time in seconds as the Saybolt Universal viscosity or Saybolt Furol
viscosity of the oil at the temperature at which the test was made.
Report the values below 200 seconds to the nearest 0.1 second. Report all values of 200
seconds or higher to the nearest whole second.
47
EXPERIMENT 3: REDUCTION OF A KETONE TO A SECONDARY ALCOHOL
(1 LABORATORY PERIOD)
INTRODUCTION
This experiment is intended to serve as an example of how to carry out an organic
reaction. You will find a reaction which may appear as one line in a textbook actually
involves several steps, including the essential ones of isolating and purifying the product.
You should review the technique for taking a melting point and recrystallizing a
compound BEFORE COMING TO THE LABORATORY. The procedure is explained
in the Appendix I.
The carbonyl group of aldehydes and ketones may be converted to a hydroxyl group by a
process known as reduction. Aldehydes may be reduced to primary alcohols, while
ketones yield secondary alcohols.
You will notice that the process of reduction involves the addition of a molecule of
hydrogen across the double bond of the carbonyl group.
The most general method of reducing compounds with carbon-oxygen double bonds is
reaction with lithium aluminum hydride. In this experiment, however, you will use
sodium borohydride to reduce a ketone (benzophenone) to an alcohol (benzhydrol).
Lithium aluminum hydride and sodium borohydride will both reduce aldehydes and
ketones to alcohols; the main difference between the two reagents is that lithium
aluminium hydride is a much more reactive reducing agent than sodium borohydride,
which makes it more difficult to handle safely. For example, lithium aluminium hydride
48
reacts explosively with water and readily decomposes in moist air, whereas with sodium
borohydride the hydrolysis in water is sufficiently slow at room temperature to allow its
use as a reducing agent in an aqueous medium.
Very many organic compounds are insoluable in water, so it is necessary to use ethanol
as a co-solvent in sodium borohydride reductions. However, sodium borohydride reacts
rapidly with ethanol and it is therefore necessary to use a large excess of sodium
borohydride to overcome the effect of this solvolysis and to ensure that enough is present
to reduce the carbonyl group.
Theoretically, one mole of sodium borohydride will reduce four moles of benzophenone
to yield a borate ester.
4C6H5COC6H5 + NaBH4 → Na[(C6H5)2CHO]4B (3)
This borate ester may be hydrolyzed with aqueous sodium hydroxide to yield benzhydrol.
The sodium hydroxide acts as a catalyst for the hydrolysis.
Na[(C6H5)2CHO]4B + 4H2O → 4C6H5-CH.C6H5 + NaB(OH)4 (4)
|
OH
The product benzhydrol is soluble in the ethanol-water mixture which was used for the
reaction but is insoluble in water. Thus, if the reaction mixture is diluted with cold water
the product will precipitate. Sodium borate remains in solution since it is a salt and very
soluble in water.
PROCEDURE:
In a 100 ml Erlenmeyer flask, dissolve 6.0 g of benzophenone in 50 ml of ethanol. In a 50
ml beaker dissolve 0.6 g of sodium borohydride in 25 drops of distilled water, and using a
medicine dropper add this solution drop-wise, with swirling, to the solution of
benzophenone. Swirl the mixture from time to time for 15 minutes. Add 4 ml of a 6N
aqueous sodium hydroxide solution and boil the reaction mixture, using a boiling chip, on
49
a steam bath for 10 minutes. Pour the reaction mixture into 100 ml of cold water and ice
(100 ml total) and
collect the resulting precipitate of benzhydrol on a Buchner funnel. Dry the crude product
for 15 min. at 60°C under suction, weigh it, and then recrystallize from a minimum
volume of 95% ethanol (b.p. 78.2°C).
Weigh your recrystallized product and determine the percentage yield of crude product
and of recrystallized product and the melting point of your pure benzhydrol product.
Submit a sample for grading.
Take an infrared spectrum of your starting material (benzophenone) and your purified
final product (benzhydrol). Discuss differences and point out characteristic absorption
peaks.
50
LABORATORY 4 - CATALYTIC HYDROGENATION OF SQUALENE (A

POLYUNSATURATED HYDROCARBON)
(1 LAB PERIOD)
I. INTRODUCTION
Hydrogenation is the general method of converting a carbon-carbon double bond or triple

bond (π-bonds) into a carbon-carbon single bond (σ-bond). The energy of activation for
the reaction is very high. Therefore, a catalyst is needed to reduce this activation energy
and enable the reaction to proceed at room temperature.
Hydrogenation is frequently used in the food industry to convert unsaturated fats such as
soybean oil and cottonseed oil into saturated solids. This is done to increase the ‘shelf-
life’ of oils by removing the oxidation-sensitive double bonds. Saturated ‘oils’ (fats) are
solids having a consistency similar to that of lard. However, from the nutritional point of
view, saturated fats are less healthy because they are harder to break down and cause
deposition on the arterial wall; unsaturated oils, especially polyunsaturated oils, are
considered to be healthier.
Table 2.1 lists the fatty acid content of several commonly consumed oil products.
Table 2.1 Approximate fatty acid content of some fats (percentages)
ACID BUTTE COTTON OLIVE PALM LINSEE
melting point. R FAT SEED OIL OIL D
(oC) OIL OIL
Butyric, C3H7COOH 3-4
Caproic, C5H11COOH 1-2
Caprylic, C7H15COOH 1-2
Capric, C9H19COOH 2-4
Lauric, C11H23COOH 3-5
Myristic, C13H27COOH 9-11 1-4 0.2
Palmitic, C18H31COOH 22-30 20-23 7-15 35-45 5
62.9
51
Stearic, C17H35COOH 7-15 1-3 1-4 1-8 4

69.9
Oleic, CH3(CH2)7CH=CH(CH2)7COOH 29-40 24-30 70-85 40-50 6-12
16
Linoleic, C17H33COOH 3-5 42-54 4-12 2-11 26-46
-5
Linolenic, 36-50
CH3(CH2)4CH=CHCH2CH=CH(CH2)7CO
OH
For the purpose of the following lab a polyunsaturated hydrocarbon, squalene, will be
hydrogenated in the presence of 10% palladium on carbon support as a catalyst.
Squalene is a naturally occurring polyunsaturated hydrocarbon. Whale oil is rich in
squalene. It is built from polyisoprene blocks. Note that isoprene (2-methyl-butadiene)
is the basic building block of several natural compounds, including cholesterol and
steroids. The multiple double bonds of squalene (6) will disappear due to the addition of
hydrogen, and IR analysis results will show an obvious distinction between the
hydrogenated (saturated), and unhydrogenated (unsaturated) squalene.
CH3 CH3 CH3

CH3
H3C
CH3 CH3 CH3
Squalene
52
CH3 CH3 CH3

CH3
H3C
CH3 CH3 CH3
Squalane
Figure 2.1. Squalene & Squalane
By knowing the stoichiometry of one hydrogen molecule reacting with each double bond,
hydrogenation can also be used as a quantitative tool to determine the number of double
bonds in an organic compound.
II. MATERIALS
• squalene
• hydrogen (already set up)
• chloroform
• catalyst (10% Pd on carbon support)
III. EQUIPMENT
• Hydrogenation Apparatus as seen in Figure 2.2
53
IV. PROCEDURES
BE CAREFUL WITH HYDROGEN GAS. IT IS HIGHLY FLAMMABLE! Mixed

with oxygen in a 2:1 ratio it forms an explosive gas.
Before you start, study the apparatus and compare with the one in the notes. Stopcock A
is 3-way so gas can be allowed to fill different parts of the system. Also read the
introduction on GAS CYLINDERS found at the beginning of this manual.
The hydrogenation reaction takes place in a closed system made up of the gas burette
connected to the reaction flask. However, the system is full of air and this needs to be
exchanged with hydrogen before the reaction is started.
The hydrogen cylinder is equipped with a two-stage regulator. The high pressure gauge
(closer to the cylinder) shows the pressure in the cylinder when you open the main valve
on the cylinder.
The low pressure gauge (second stage) will show the pressure of the gas going to your
apparatus. Open the first stage to tank pressure and set the second stage to about 2.5
pounds per square inch pressure. DO NOT EXCEED 6 POUNDS/INCH2 ON THE
SECOND STAGE. Open the needle valve which connects the cylinder to your apparatus.
The pressure on the low gauge may drop. Readjust it.
To clear air out of the system: first open stopcock B and turn stopcock A (3-way) so that
it connects the gas burette to the exhaust line. See Figure 4 of 2.2. Expel all air present in
the gas burette by holding the reservoir up until the oil pushes all the air out;
approximately 1cm below stopcock A. Then turn stopcock A (3-way) so that H2 gas can
flow through the system and exit via the exhaust tube without entering the gas burette.
See Figure 2 of 2.2. Flush the system with hydrogen and shut off flow at the regulator
needle valve.
To prepare the gas burette with hydrogen ready for the reaction:
54
Turn the three way stopcock A to the position which allows H2 to enter the gas burette
See Figure 3 of 2.2. Carefully turn on the hydrogen flow and fill the burette with
hydrogen gas 5-6cm from the bottom of the burette.
55
Figure 2.2 Hydrogenation apparatus
56
Once the burette is full of hydrogen, turn stopcock A back to the bypass position (Figure
2 of 2.2).
To set up the reaction flask: pipette 1ml of squalene into 19 ml. Chloroform. Place 5 ml.
Of this mixture into the reaction flask along with a magnetic stirrer. Add about 80mg of
10% palladium on charcoal to the reaction flask. This is the catalyst.
Flush the flask with hydrogen for 2-3 minutes using the gas inlet. When flushing, be sure
to hold the glass stopper loosely to allow the hydrogen to enter the flask and the air to
leave out the sides.
Before starting the reaction record the volume of H2 in the gas burette. This is done by
matching the levels of oil in the burette and the reservoir. Then move the reservoir to its
maximum height to exert a small pressure on the hydrogen in the closed system.
To start the reaction close the main valve on the H2 cylinder. Place the gas inlet tube
snugly into the flask and turn the three-way stopcock A to connect the gas burette with
the reaction flask (see Figure 4 of 2.2). Stopcock C should also be open to allow
hydrogen into the reaction flask. Turn on the magnetic stirrer and let the reaction proceed
until there is no longer a change in H2 volume (about one-half hour). Check the extent of
the reaction by matching the oil in the burette and reservoir. Record the amount of H2
every 5 minutes.
During the reaction observe whether the flask is cooling or warming up.
Stop the stirrer when there is no longer a decrease in H2 over a 5-10 minute period.
Match the oil level in the gas burette with that in the oil reservoir and record the final
volume of hydrogen and the room temperature. Close the stopcocks and remove the
reaction flask. By matching the oil levels before and after the reaction, the final volume
reading is obtained at a pressure of 1 atm.
57
Release the pressure from the apparatus through the exhaust line by opening stopcocks A
and B and loosening the membrane valve (second stage) all the way. Both gauges should
read zero psig.
Filter off the catalyst using vacuum filter apparatus and buchner funnel. Place the
catalyst in the vessel for Pd residues.
V. INFRARED ANALYSIS
For the theory of infrared analysis refer to the Appendix.
Procedure:
1. Rinse IR cell with CHCl3 and run CHCl3 sample, scanning from 300 to 700.
2. Run sample of original unsaturated squalene and CHCl3.
3. Run sample of hydrogenated squalene and CHCl3.
Compare differences in peaks around area where double bonds are detected. Note, this
will only provide you with a qualitative analysis, not a quantitative analysis.
Make photocopies of the three IR charts for each member of the lab group and submit
them along with the formal lab report. Remember to properly label the figures and
clearly indicate the observed changes in the peaks.
VI. PRE-LAB QUESTIONS
To be completed before starting the laboratory –please check with T.A. for proper
calculations
1) Write down the structure of isoprene and squalene. List the physical properties of
squalene ( mol. wt., density, boiling point, melting point) and write the stochiometric
equation for the hydrogenation of squalene.
2) Calculate the theoretical volume of H2 required to completely hydrogenate your
58
squalene sample (hint: use ideal gas law).
VII. SUMMARY OF REQUIREMENTS FOR LABORATORY REPORT
1) From the volume of hydrogen used, calculate the number of grams and moles of
hydrogen consumed in the reaction.
2) Given that squalene has a density of 0.858 g/cm3 at 250C, how many grams of
hydrogen were taken up per 100g of squalene? How many moles of H2 are taken up
by 1 mole of squalene? (Use the molar weight, MW = 410.73gmol-1 of squalene for
your calculations.)
3) How many moles of hydrogen reacted per mole of palladium present?

Is hydrogenation exothermic or endothermic and why?
59
LABORATORY 5 EPOXIDATION OF 1-TMP AND IODINE TITRATION
(2 LAB PERIODS)
I. INTRODUCTION AND THEORY

O
Compounds containing the three-membered ring CH CH , are called

epoxides. Epoxides are ethers with unusual properties due to the strained ring structure
present. One method to prepare them is to use peroxybenzoic acid to oxidize alkenes or
double bonds in chloroform, dichloromethane or ether as solvent. Once prepared, the
three-membered ring easily undergoes acid- and base-catalyzed cleavage. An example of
the mechanism and orientation during the cleavage of isobutylene oxide, a substituted
epoxide is shown:
Acid-catalyzed cleavage:
CH3 CH3
+ H+
H3C C CH2 HOH H3C C CH2OH
O OH
Base-catalyzed cleavage:
CH3 CH3
CH3ONa
H3C C CH2 + CH3OH H3C C CH2 OCH3
O OH
The following experiment makes use of the fact that each double bond reacts with one
mole of peroxyacid to form the epoxide ring. The reaction for 2,4,4-trimethylpentene-1
(TMP-1) is shown:
60
H 3C CH 3 CH 2 OH
O
C O
C C + Cl
H 3C C CH 3
H2
1-TM P 3-Chloroperoxybenzoic acid
H 3C CH 3 H 2C OH
O O
C
C C Cl
+
H 3C C CH 3
H2
1-TM PO xide 3-Chlorobenzoic acid
The mol% unsaturation can be calculated by back-titration of any unreacted peracid. This
is done by reacting the leftover (unreacted) acid with potassium iodide, which will release
I2 exactly equivalent to 2 mols of peroxiacid:
OH
O O
C O C OK
Cl Cl
+2KI + I2 + H2O+ 1/2O2
2 2
The liberated I2 is then titrated with Na2S2O3. The reaction for the titration is:
I2 + 2 Na2S2O3 → Na2S4O6 + 2 NaI (3)
From reaction (3) it is clear that 2 mol Na2S2O3 is equivalent with one mol I2 (1N
Na2S2O3 = 0.5M Na2S2O3)
Iodine titration is used very often in industry for double bond titration; it is also used for
water analysis at the ppm level (Carl-Fischer titration).
61
II. MATERIALS
• 3-Chloroperoxybenzoic acid, (CPBA)

• sodium phosphate
• potassium dihydrogen phosphate
• dichloromethane
• glacial acetic acid
• 10w% potassium iodide
• 0.1N sodiumthiosulfate
• starch indicator
• water bottle with distilled water
III. EQUIPMENT
• 3, 1L beakers
• stirring plate and magnetic stirrers
• vacuum oven or desiccators
• 100ml volumetric flask
• 3, 250ml Erlenmeyer flasks
• 1ml, 10ml pipettes
• timer
• 4, 5ml and 1, 10ml graduated cylinder
• watch-glasses
• burette
• nitrile gloves
62
IV. PROCEDURES
PART A (WEEK 1)
A) PURIFICATION OF PERACID:
During storage 3-Chloroperoxybenzoic acid decomposes to give a mixture of the peroxy

(a) and the carboxylic (b) O O
Cl Cl
acids. Therefore, purification C O OH C OH
is needed to remove the
carboxylic acid by a ‘buffer’ 3-Chloroperoxybenzoic acid and 3-Chlorobenzoic acid
(a) (b)
which selectively dissolves
the acid but leaves the desired peroxyacid or peracid insoluble.
Step 1: Prepare the buffer solution
Dissolve 67.1g of sodium phosphate (Na2HPO4.7H2O) in 500ml of distilled water. Do the

same with 34g of potassium dihydrogen phosphate (KH2PO4) in a separate beaker. Once
the solids are completely dissolved mix the two solutions.
Step 2: Washing of the peracid
Take 50g of raw (∼50% purity) 3-Chloroperoxybenzoic acid (CPBA) and place it in a
large beaker. Add about 200ml of buffer and stir it well using a stirring rod. Let the solid
settle down and decant the liquid. Repeat 4 more times. (The settling of the solid takes
time so set up the Buchner funnel). Next, wash the peracid 3 times the same way with
distilled water. The last 2 washes should be done on a Buchner funnel to filter the solid
(see discussion on Buchner funnel at the beginning of the lab notes).
63
Step 3: Drying of the peracid
Weigh an empty beaker, sufficient in size to hold all of your peroxyacid. Transfer the
peroxyacid from the Buchner funnel into the beaker. This is the pure peroxyacid, which
should be dried. Label the beaker with the name of compound, your name, group number
and date. Place in a desiccator. The following week the peracid should be dry and ready
to use. Measure the amount recovered and do a %yield calculation.
PART B (WEEK 2)
B) EPOXIDATION OF 1-TMP AND IODINE TITRATION
FOR YOUR PROTECTION PLEASE WEAR NITRILE GLOVES (BLUE) FOR

STEP 4/a OF THIS EXPERIMENT. The dichloromethane used in this experiment
dissolves the latex gloves and is harmful to your skin.
Step 4a) Preparation of 0.1M CPBA
In a weighing boat measure out the amount needed to make 50ml of 0.1M CPBA from
the one that you made last week. Record the exact weight used to 4 decimal point
accuracy. UNDER A FUMEHOOD transfer this amount into a clean, dry, 50ml
volumetric flask using a funnel. Rinse the boat and the funnel with dichloromethane
(CH2Cl2), and add some more CH2Cl2 to dissolve the solid. Wait until complete
dissolution and fill up the volumetric flask to the mark. Calculate the exact molarity of
your peracid solution and record it in your notebook. Stopper the flask, label it, wrap it in
aluminum foil and label it on the outside again. Peroxyacid is heat and light sensitive and
every precaution should be taken to prevent it from decomposing.
Step 4b) Epoxidation and iodine titration
64
The TMP-1 is epoxidized by reacting it with excess CPBA in a dichloromethane solution.

After 10 minutes reaction time the amount of leftover peracid is determined by reacting it
with excess KI and backtitrating the liberated I2 with sodium thiosulfate (Na2S2O3). By
knowing the stoichiometry of each reaction, the extent of the epoxidation can be
determined.
2 mols of peracid releases 1 mol of I2. 1 mol of I2 reacts with 2 mols of Na2S2O3. Thus, 1
mol of peracid will be equivalent to 1 mol of Na2S2O3. The Na2S2O3 is normalized
against I2 so 1 mol I2 is equivalent to 2 mols Na2S2O3. Therefore, the normality of 1 M
Na2S2O3 = 2 N. Also, 10ml of 1 M m-CPBA will be equivalent to 10ml of 1 M Na2S2O3
or 20ml of 1 N Na2S2O3. (See reaction equations in the INTRODUCTION section).
Step 4b.1) Blank titration
Since one can never make an exact 1 M solution, the exact amount of the peracid in the
0.1 M solution made in Step 4 a will be determined by a ‘blank’ titration. Thus, 10ml of
peracid solution is reacted by excess KI, and the liberated I2 is backtitrated by Na2S2O3. If
the peracid solution were ‘perfect’, 10ml of peracid should be equivalent to 20ml of 0.1 N
sodium thiosulfate. The Thiosulfate is already normalized by the supplier. Na2S2O3 is
light- and heat sensitive!
Each student should do at least one titration. For each titration: to a 250ml Erlenmeyer
flask add 10.00ml CH2Cl2. This is the solvent. Add exactly 10.00ml of the above
prepared 0.1M CPBA using a 10.00ml transfer pipette. This is the known amount of
peracid which can react to form the epoxide. Add 2ml 10wt% KI (1 g. in 10 ml H2O),
50ml distilled water and 5ml glacial acetic acid. Pour some 0.1N sodium thiosulfate
(Na2S2O3) into a clean, dry beaker. Using a funnel, pour enough of this solution to fill a
clean, dry burette. At the start of each titration the solution level should be at the zero
mark (the bottom of the meniscus is read and should be sitting exactly on the zero line).
Start titrating. You should observe two layers of liquid. In the organic phase, the I2 is
pink, and in the aqueous phase, the I2 is brown. Because the reaction occurs in the
65
aqueous phase, you have to mix it very well to get all of the I2 out of the organic phase
and into the water phase. Titrate slowly! The H2O is added to force the reaction out of
the organic phase. The reaction with Na2S2O3 only takes place in the H2O phase. Glacial
acetic acid is added to help force the I2 out of the organic phase. Make sure you swirl the
flask enough after each addition of sodium thiosulfate that it has a chance to react. Wait
until there is no more color change and then add more of the thiosulfate solution. Titrate
until the solution becomes pale yellow. At this point you are not too far from the end-
point, so slow down and take care not to overshoot the titration! Add a drop or two of
starch indicator. The solution turns dark blue. The rest of the titration should be done
drop-by-drop, washing down each drop into the flask with a water bottle containing
distilled water. The end-point is reached when the solution becomes clear, colorless (both
phases).
Calculate the exact concentration of the peracid. This will be Ao mol.
Step 4b.2) Epoxidation and iodine titration
Each student should do at least one titration. Prepare a solution containing 99 ml CH2Cl2
and 1 ml of TMP-1. For each titration mix 10 ml of this solution with 10 ml of peracid in
a 250ml Erlenmeyer flask equipped with a magnetic stirring slug. The reaction is started
when the TMP-1 is mixed with the peracid (0.1 ml TMP-1 = 0.63 mmol). Turn on the
timer when the TMP-1 is added. Place the flask on a magnetic stirrer and turn it on. Set
the stirring speed so there is no splashing; cover the flask with a small watch-glass. Let
the reaction proceed for 10 minutes.
After 10 minutes add, 2ml of 10w% KI to stop the reaction, followed by the addition of
50ml distilled water and 5ml glacial acetic acid. Titrate with 0.1N Na2S2O3 following the
same procedure as for the ‘blank’ titration.
66
Calculate the amount of leftover peracid (A10 mols). The difference between the ‘blank’,
Ao and the leftover peracid, A10 will give the amount of peracid in moles that reacted with
the 0.63mmol of 1-TMP.
67
V. PRE-LAB QUESTIONS
Submit to the TA prior to beginning the laboratory session.
Write the formulas of all the starting materials (except H2O and starch). List their
physical properties.
1. Define molarity and normality.
What is a buffer?
2. In a blank titration of 10 ml. of 1M (nominal) m-Cl- perbenzoic acid (CPBA) 19.2 ml.
0.1 N Na2S2O3 is consumed. What is the exact concentration of the CPBA solution?
3. Using the following example calculate the amount of peracid in your ‘blank’ solution,
Ao, the amount of acid leftover after 10 minutes of reaction time, A10, the amount of
acid that reacted with the TMP-1, Arxn and the amount of epoxidized TMP-1, and the
extent of the reaction (%).
Example calculation:
Suppose the nominal concentration of CPBA is 0.1M. Ten milliliters are titrated. The
‘blank’ titration end-point is reached after addition of 18.29ml of 0.1N Na2S2O3.
Titration of the epoxidized 1-TMP reaction required 11.40ml of 0.1N Na2S2O3.
• 10ml m-CPBA (0.001mol nominal) ≡ 18.29ml Na2S2O3 ⇒ 0.0009145mol = Ao

• 11.40ml Na2S2O3 ⇒ 0.0005700mol = A10
• Arxn = Ao - A10 = 0.0009145mol - 0.0005700mol = 0.0003445mol ≡ TMP
equivalent
• [TMP-1]0 = 0.00063mol; TMP-1 reacted = 0.00034mol. Thus 53% of the 1-TMP
was epoxidized after 10 minutes reaction time.
68
1
VI. H NMR SPECTROSCOPY.
For the theory of NMR spectroscopy, refer to the Appendix.

The extent of the reaction can be determined by 1H NMR spectroscopy. For the theory of
NMR, refer to Section 17.9 - 17.12 (Spectroscopy and Structure, p600-610) in Morrison-
Boyd, and your lecture notes.
Figure 3.1 shows the 1H NMR spectra of TMP-1 before and after epoxidation. Describe
the differences! The assignment will be explained during tutorials in more detail.
69
(a )
CH3
H 3C
H 3C (a)
H C H 2 (b )
(d )
H C H 3 (c )
(c) (b)
(d)
ppm 6 4 2 0
Figure 3.1a NMR spectra of TMP-1 before epoxidation
(a)
CH3
H3C
(a)
H3C
H CH2 (b)
(d)
H CH3 (c)
O (c)
(d)
(b)
ppm 4 2 0
Figure 3.1b NMR spectra of TMP-1 after epoxidation
70
71
4)
72
LABORATORY 6 - SYNTHESIS OF AZO-DYES AND UV-VIS SPECTROSCOPY
(1 LAB PERIOD)
I. INTRODUCTION AND THEORY
Synthesis of azo dyes
Dyes play a visible role in many aspects of our day-to-day lives. They are used to color
foodstuff (butter yellow), in the clothing and textile industries (fast red A), in paint
pigments (hansa yellow G), as indicators (methyl orange), in photography (brilliant
yellow) and in medicinal compounds (trypan blue).
Some examples of azo dyes are shown in Figure 5.1.
Figure 5.1 Examples of azo dyes

Figure 5.1 Examples of azo dyes
H3C
N N
H3C N
Butter yellow(food coloring)
H3C O O
N N S
H3C N ONa
Methyl orange (indicator)
O
N C CH3
N CH C NH
O
Hansa yellow (paint pigment)
O O
ONa O
O S S ONa
N H
HO C N
N C OH
H N
Brilliant yellow (printing color)

73
Many dyes contain the azo group, -N=N- which is prepared most directly from diazonium
salts. This is done by reacting the diazonium salt with another aromatic compound, a
reaction called a coupling reaction. The diazonium salt is a cation and hence an
electrophile. It is a weak electrophile and gives good yields only with rings that are
activated. The aromatic ring to be substituted is therefore usually a phenol or aniline
analogue. The reaction goes through a normal electrophilic aromatic substitution, with the
predominant substitution occurring at the para position (ortho if the para position is
blocked by a substituent).
Electophilic aromatic substitution:
+ R+
R+
The rate of the coupling is dependent on the pH of the solution. There are two equilibria
of interest, one involving the diazonium salt and its hydrolysis products and the other
involving the aromatic compound undergoing substitution and its conjugate base or acid.
HO O
OH
activated phenol
beta-naphthol
a phenol
The first azo-dye was prepared by German chemists and this was the beginning of IG
Farbenindustries, now Bayer, BASF and Hüls.
74
ULTRAVIOLET-VISIBLE SPECTROSCOPY
There are many types of instruments available today to describe the structure of
molecules and/or to detect, measure and identify the presence or absence of short-lived
intermediates. One of these is ultraviolet-visible spectroscopy. A schematic of a simple
double-beam UV-Vis instrument is shown in Figure 5.1. The solution to be analyzed is
placed in a cell of set length. Light of different wavelengths and therefore energy is
passed through the solution. When this light is absorbed by the molecule it causes
changes in its electronic states. Table 1 describes the types of quantum transitions
possible in a molecule, and gives the more commonly used spectroscopic methods of
detection, and the range of these on the electromagnetic spectrum.
Table 3. Common spectroscopic methods based on electromagnetic radiation

Type of spectroscopy Wavelength range Wavenumber range, Type of quantum
cm-1 transition
Gamma-ray emission 0.005-1.4Å - Nuclear
X-ray absorption, 0.1-100Å - Inner electron
emission, fluorescence
and diffraction
Vacuum ultraviolet 10-80nm 1X106 to 5X104 Bonding electrons
absorption
Ultraviolet visible 180-780nm 5X104 to 1.3X101 Bonding electrons
absorption, emission
and fluorescence
Infrared absorption and 0.78-300µm 1.3X104 to 3.3X101 Rotation/vibration of
Raman scattering molecules
Microwave absorption 0.75-3.75mm 13-27 Rotation of molecules
Electron spin 3cm 0.33 Spin of electrons in a
resonance magnetic field
Nuclear magnetic 0.6-10m 1.7X10-2 to 1X103 Spin of nuclei in a
resonance magnetic field
The following experiments relate to the synthesis of the dye Orange II.
75
Figure 5.2 Double-beam-UV-VIS spectroscopic instrument
II. MATERIALS
• sulfanilic acid
• 2N HCl
• sodium nitrite
• β-naphthol
• sodium hydroxide
III. EQUIPMENT
• 125ml Erlenmeyer flask

• 25ml Erlenmeyer flask
76
• large plastic container for ice bath

• 2, 25ml beakers
• 2, 250ml beakers
• medicine dropper or Pasteur pipet
• UV-Vis Spectrophotometer
IV. PROCEDURE
Synthesis of Orange II
a) Synthesis of the diazonium salt of sulfanilic acid.

O O O O
S NaNO2 S
NH2 OH N: N OH
Diazonium cation
Sulfanilic acid
In a 125ml Erlenmeyer flask dissolve approximately 1g of sulfanilic acid (weighed to the

nearest 0.1g) in 70ml of water and 3ml of 2N HCl. Heat if necessary. Cool the solution to
0oC using an ice bath. Dissolve 0.5g of sodium nitrite in 10ml of water and cool the
solution to 0oC. Slowly add this solution to the solution of sulfanilic acid using a
medicine dropper until an excess of nitrite ion appears as determined by starch-iodide
paper; until the iodide paper turns blue.
The temperature must be maintained near freezing using salted ice bath to prevent
isomerization of the diazonium salt to an inactive analogue. The dry, solid diazonium
salt is dangerously explosive, hence the solution must not be allowed to dry out at
any stage of the experiment! Add water if the solution looks like it will dry out. The
diazonium salt also decomposes slowly in a basic solution.
77
b) Coupling reaction
O
O
O
S N N
+
OH
HO
HO
N
S
O N
O
Orange II
Coupling takes place in basic solution. Thus, the acid diazonium salt must be added to a
basic solution of the coupling agent. Dissolve 0.83g of β-naphthol in 10ml of 2N NaOH.
Cool to near 0oC and add slowly to the cold solution of the diazonium salt.
ULTRAVIOLET-VISIBLE SPECTROSCOPIC ANALYSIS:
Prepare two separate beakers with 100ml of water and one drop of solution in each. To
one add one granule of NaOH, to the other add 2 drops of HCl. Note and record any color
changes.
Take UV-Vis absorption measurements between (400nm-700nm, in 5nm increments).

Plot the data on one graph. You should see a different peak maximum for the acidic and
basic solutions. Write the chemical equations for the acid-base equilibrium for this case.
V. PRE-LABORATORY QUESTIONS
Submit to the TA at the beginning of the laboratory period.
1. Why is Orange II yellow-orange in colour?
78
2. What is methyl orange and what is it used for?
VI. SUMMARY OF REQUIREMENTS FOR REPORT

Calculate the percentage yield of the azodye (re. to the theoretically expected yield).
79
LABORATORY 7 - SYNTHESIS OF DICUMYL ETHER AND NMR

SPECTROSCOPY
(2 LAB PERIODS)
I. INTRODUCTION
The general formula of ethers is R-O-R, R being any alkyl or phenyl group. The carbon-
oxygen bonds are not linear at 1800C, therefore ethers have a net dipole moment i.e. they
are slightly polar. Also, there is no hydrogen bonding possible since there is no hydrogen
bonded to the oxygen of ethers as there is in alcohols.
In this lab an ether will be prepared by the reaction of the corresponding alcohol with
sulfuric acid. The reaction is called dehydration since a molecule of water is lost for
every pair of alcohol molecules. The general formula for this nucleophilic substitution
reaction is shown below for tertiary and secondary alcohols. A HNMR spectra of DCE is
shown on figure 4.1.
R-OH + H+ R-OH2+
H
ROH
R OH2+ R+ + H2O RO R H+ + ROR
30 and 20 alcohols
CH3 CH3 CH3OH CH3 CH3

(solvent,reactant)
HO C C OH H3CO C C OCH3
H2SO4
CH3 CH3 (catalyst) CH3 CH3
1,4-di(1-hydroxy-1-methylethyl)benzene 1,4-di(1-methoxy-1-methylethyl)benzene
(dicumyl alcohol (DCA)) (dicumyl methyl ether (DCE))
80
[1]
CH3 CH3
H3C [3]
O O
CH3
CH3 CH3
[2]
[3]
[2]
[1]
Figure 4.11HNMR
Figure4.1 NMRofofDicumyl
Dicumylmethyl
methylether
ether(DCE)
(DCE)
Methanol is used both as a solvent and a reagent. While the polar dicumyl alcohol
dissolves in methanol, but it is not soluble inorganic solvents or water. Dicumyl methyl
ether, on the other hand, is soluble in organic solvents. The goal of this experiment is to
make a hydrocarbon-soluble tertiary compound, which is an effective initiator for
carbocationic polymerizations. As a side reaction, the tertiary dicumyl-alcohol may
dehydrate if too much H2SO4 is used:
81
CH3 CH3 CH2 CH2

HO C C OH C C
H2SO4
CH3 CH3 CH3 CH3
dicumyl alcohol (DCA) 1,4-diisopropenyl benzene
II. MATERIALS
a) Synthesis of dicumyl ether:

• α,α,α’,α’-Tetramethyl-1,4-benzene-dimethanol
• reagent grade methanol
• concentrated sulfuric acid
• reagent grade hexane
• anhydrous magnesium sulfate
b) Purification of dicumyl ether:

• Activated alumina column packing
• glass wool
• pentane
III. EQUIPMENT
a) Synthesis of dicumyl ether:

• 1L, one-necked round bottom flask
• condenser
• magnetic stirrer and stirring plate
• heating mantle
• powder funnel
• graduated cylinders
82
• large beaker
• separatory funnel
• funnel and filter paper
• rotavap
b) Purification of dicumyl ether:
• chromatography column
• test tubes for collecting fractions
IV. PROCEDURES
PART A (WEEK 1)
A) Synthesis of dicumyl ether (DCE):

Set up a two necked 1L round bottomed flask with a reflux condenser, a magnetic stirrer
and stirring plate and a heating mantle. (See figure 4.2 below.)
Figure 4.2 Flask-reflux condenser apparatus
83
Using a powder funnel add 20g of α,α,α’,α’- Tetramethyl-1,4-benzene-dimethanol. Add

100ml reagent grade methanol (MeOH). Separately prepare a mixture of 30ml MeOH
plus 0.015ml conc.H2SO4. Add this mixture to the flask. Turn on the stirrer and slowly
raise the temperature until the mixture is at a reflux. Let the reaction proceed overnight.
Label your experiment with the contents, date, your names and when the reaction was
started. The TA will turn off the heat for you the next day.
b). Preparing the chromatography column for purification
Set up the column with a stopcock at the bottom. In the bottom of the column place some
cotton wool. This is to stop the packing from flowing out of the column. Fill the column
with pentane. Place 50 g of alumina packing material into a large beaker. Add 100 ml
pentane and stir. Pour this slurry into the column while also expelling the initial pentane
so there is no overflow. Stir and shake the column until there are no air bubbles present
and the packing is totally uniform throughout the length of the column. At any time add
pentane if necessary. NEVER LET THE COLUMN GET DRY! There should be 5-8 cm
of pentane on top of the packing at all times. Let out some pentane by opening the
stopcock and pour it into the top of the column and let it go through again. Do this
operation as many times as necessary to get a uniform, air-free packing of the column.
After this is done the column is ready to be used for separation. The prepared column
must be sealed with a rubber stopper to prevent the evaporation of the solvent.
PART B (WEEK 2)
a) Separation of DCE
Transfer the contents of the reaction flask (including the magnetic stirrer) into a large (2
or 3L) beaker. Add 50ml reagent grade hexane and, while stirring, add distilled water
until the beaker is full. Let it stir for 30 minutes.
84
Pour the contents into a proper size separatory funnel and separate the hexane from the
water layer. Place the hexane in a beaker and set aside. For instructions on the use of the
separatory funnel see introductory pages at the beginning of this lab manual. Extract the
water layer again by adding 50ml hexane to it and separating it in the separatory funnel.
Add some anhydrous MgSO4 into the beaker containing the hexane solution and cover it.
Let it sit for 20 minutes to dry.
Filter the solution using a Buchner funnel and filter paper. Pour the contents into a
round-bottomed flask, which fits onto the rotavap, rinsing with a bit of hexane. Remove
the hexane from the dicumyl ether using the rotavap. The TA will help you with this
maneuver. Do not raise the temperature of the bath above 300C, because the product is
heat sensitive. Rotavap until a white powder or a syrup is all that is left in the flask. This
is the dicumyl ether, which can now be purified further.
b) Purification of DCE by chromatography
Dissolve your product in 20ml pentane and gently pour onto column. Allow the liquid to
escape slowly from the bottom. Keep adding pentane to the top of the column in order to
keep fluid level in column above packing level. DO NOT LET THE COLUMN DRY
OUT! Place a drop of the eluent on a watch glass, for example. Your product will appear
when you see a white powdery leftover residue between your fingers. At this time, start to
collect the eluent, and discard the solvent collected up till this point in time. Take 1
fractions of 100?ml each. Pour the first two fractions together. Evaporate the pentane,
using the rotavap, and leaving the DCE powder in the flask. Consult the demonstrator
before beginning this procedure. Place the flask with the product in a desiccator to dry the
product. Calculate the conversion in % (...g dicumyl ether from ... g dicumyl alcohol).
85
V. PRE-LAB QUESTIONS
Submit to the TA at the beginning of the laboratory period.

1) What is the structure of α,α,α’,α’- Tetramethyl-1,4-benzene-dimethanol or 1,4-di(1-
hydroxy-1-methyl ethyl)benzene? Can you think of any other names to identify this
compound?
2) What are the densities of hexane, methanol and water and what are their solubilities
(i.e. which is soluble in the other)?
3) Write the chemical equation for this lab, including the mechanism. What side
reaction can occur during the dehydration. Give the trivial and IUPAC names of all
participants.
4) You want to separate hexane from water using a separatory funnel. Decide which
layer will be on top and why?
5) Is DCA soluble in hexane? Why?
86
LABORATORY 8- SOXHLET EXTRACTION OF CAFFEINE FROM BEVERAGE PLANTS
(1 LAB PERIOD)
Nutraceuticals are becoming very important in our society. A nutraceutical is derived
from a natural product and has properties in-between a pharmaceutical and a nutrient. A
common example of a nutraceutical is caffeine, which has significant pharmacological
and health affects. This lab will explore the extraction of caffeine from coffee beans.
Several procedures can be used for the extraction of caffeine from tea, coffee, and soda
drinks such as HPLC. However, HPLC (and other techniques) do not take into account
the varied nature of beans, nuts, and leaves. A simple extraction may work perfectly well
for one type of sample, but not for another. Soxhlet extraction overcomes problems
related to extractive efficiency by using a combination of heat, solvent, and reflux, and
from a quantitative point of view is much preferred over simpler procedures (28). Soxhlet
extraction is the standard against which other newer techniques such as supercritical fluid
extraction (SFE) are measured. Soxhlet extraction is well suited to the illustrating the
principles of extractive processes in general.
87
Figure 1. Soxhlet Extractor

Experimental Procedure
CAUTION: Gloves and safety glasses should be worn at all times. Exercise care in the
use of ethanol (flammable), sulfuric acid (corrosive), potassium hydroxide (corrosive),
and dichloromethane (narcotic).
1) Crush a quantity of coffee beans or instant coffee supplied by the Teaching Assistant
to a fine powder using a mortar and pestle. Accurately weigh out approximately 10 g of
powder into a Soxhlet extraction thimble, and place this in the extraction apparatus.
2) Use a 250- mL round-bottom flask as a reservoir, and add to this 100 mL of ethanol
and a few boiling chips. Use a heating mantle to reflux the mixture for 1.5–2 h. If
required, the remainder of the procedure can be left until the next class period. Store the
contents of the flask in a sealed container.
88
3) Allow the extract solution to cool before adding it to a 10% (w/v) aqueous solution of
magnesium oxide (this causes tannins to form water-insoluble salts). Evaporate the
ethanol using a steam bath until a brown pasty mass is obtained. Add approximately 125
mL of distilled water,
and then boil this mixture on a steam bath for 30 min. Filter through a cone of coarse
filter paper (for example, Whatman No. 1). Add 10 mL of 0.1 M sulfuric acid solution to
the filtrate and boil this until the volume is reduced to half. Allow to cool.
4) Transfer to a separating flask and add 12 mL of dichloromethane. After shaking,
remove the yellow layer and repeat the procedure two more times with fresh volumes of
dichloromethane. 5) 5) Add 8 mL of 0.1 M potassium hydroxide solution to the combined
extract contained in
a new separating flask. This should be enough to remove the yellow color, but add more
if required. Remove the organic layer and wash the base solution layer twice with 5-mL
volumes of dichloromethane. Add these volumes to the earlier extracts.
6) In a preweighed beaker, evaporate the combined extracts over a steam bath to
approximately
10 mL. Eventually, a white crystalline precipitate should be obtained. Recrystallize from
ethanol.
7) Check the melting point of the dried crystals.
8) When writing up the lab report, show the percent yield of caffeine extraction and the
melting point.
PRELAB QUESTION
Submit to the TA prior to beginning the laboratory session:

Draw the structures of caffeine, ethanol, sulfuric acid, potassium hydroxide, and
dichloromethane. List their physical properties (molecular weights, density, melting
& boiling points, and refractive index).
89
APPENDIX I: RECRYSTlLIZATION AND MELTING POINT

DETERMINATION
A. RECRYSTALLIZATION
1. Theory
(a) General Methods of Recrystallization
Chemical transformations lead invariably to mixtures of products, and therefore various
techniques of separation or purification must be employed to isolate individual
components, in pure form, from the crude reaction mixtures. In the case of solid
substances the most commonly employed technique, at least until the advent of
chromatographic methods, was that of recrystallization (or more simply "crystallization").
As commonly practiced, purification by recrystallization depends upon the fact that most
solids are more soluble in hot than in cold solvents. The solid to be purified is dissolved
in the solvent at~ its boiling point, the hot mixture is filtered to remove all insoluble
impurities, and then crystallization is allowed to proceed as the solution cools. In the
ideal case, all of the desired substance separates in nicely crystalline form and all the
soluble impurities remain dissolved in the mother liquor. Finally, the crystals are
collected on a filter, washed and dried. If a single recrystallization operation does not
yield a pure substance, the process may be repeated with the same or another solvent.
(b) Nature of Suitable Solvents
The single most important factor contributing to a successful recrystallization is the

proper choice of solvent. In general, the most "suitable" solvent for recrystallization
purposes is one in which the compound to be purified is only very slightly soluble at low
temperatures but very soluble at higher temperatures (e.g. at the boiling point of the
solvent). Most compounds exhibit positive temperature coefficients of solubility. Ideally
of course, the impurities to be removed should be readily soluble in the cold solvent in
which they will remain after the crystallization process or almost completely insoluble
even at elevated temperatures.
90
It should be realized that the solvent selected must be inert and not enter into chemical
reaction with the sample. In addition, it is desirable that the solvent be reasonably volatile
(low boiling point) so that it can be fairly easily removed from the crystals by
evaporation. Where two or more solvents are comparable with respect to the properties
already cited, factors such as inflammability, toxicity and cost are to be considered.
The lower the solubility of the compound to be purified in the cold solvent, the greater
will be the recovery of purified material from the crude mixture. The fact that the
solubility of the impurities may be comparable to that of the desired compound does not
preclude the use of a particular solvent, since most impurities are present in relatively
small amounts. As an example, consider the recrystallization of a mixture of solids
consisting of 10 g of A and 1 g of B from a solvent in which the solubility of each is 1.5 g
per 100 ml at room temperature and 10 g per 100 ml at the boiling point. One hundred
milliliters of hot solvent would be required to dissolve the mixture, and upon cooling the
solution would precipitate 8.5 g of A (i.e. 85% recovery) and no B because the solubility
of B had not been exceeded. Only if there were more than 1.5 g of Band 10 g of A would
any B crystallize, and even then a second recrystallization would complete the separation
of up to 2.5 g of B.
(c) Choosing a Suitable Solvent

If no information concerning the solubility characteristics of the substance to be
recrystallized is available, the choice of solvent becomes an experimental problem. It is
necessary to- test various solvents for their suitability according to the criteria outlined
above. As a rule, solvents of decreasing polarity are tried in succession and the solubility
behavior in each case observed. To do this, small-scale trial recrystallizations are carried
out rapidly in micro (10 X 75 mm) test tubes. A few drops of various common solvents
(see table below) are added to small portions of the crude, finely divided solid mixture
and the crystals are stirred and crushed under the cold solvent with a stirring rod. If
solution occurs at room temperature the solvent is obviously unsuitable. If solution does
not occur, the test tube is heated gently on a steam bath or over a small flame with stirring
or shaking. A few more drops of solvent are added if only partial solution has occurred.
91
(Transfer of solvent is most conveniently done with small clean dropping tubes drawn out
at the end like pipettes). If a homogenous solution is obtained it is cooled, and the inside
walls of the test tubes are scratched if crystallization does not occur readily. If no crystals
can be obtained or if solution does not occur on warming, the solvent is unsuitable and
another should be tried. To avoid misleading observations, some care and judgment must
be exercised in choosing the relative amounts of solid and solvent to be used in these
solubility tests.
Choosing a Suitable Solvent

The ultimate proof of the suitability of a particular solvent is in achieving a separation of
the desired component from the unwanted impurities. This can be established by
collecting the crystals which precipitate from the solvent being tested and determining
their melting point.
In many cases it is difficult to predict a suitable solvent. In general, it is said that "like
dissolves like" -that is, a substance will dissolve in a solvent containing similar groups -or
better, that polar solvents will dissolve polar molecules and nonpolar solvents will
dissolve nonpolar molecules; but a good recrystallization solvent cannot be too like the
compound being purified. The accompanying table lists, in order of decreasing polarity,
some of the common solvents used for recrystallization.
92
2. DETAILED DESCRIPTION OF EXPERIMENTAL STEPS AND APPARATUS
(a) Preparation of Hot Solution

At this stage the key words are saturated and minimum. Since the compound to be
purified will invariably be soluble in cold solvent to some extent, however small, the
recovery of pure material will be a maximum only by employing no more solvent than is
absolutely essential to obtain a complete solution at the elevated temperature. By working
at or near the boiling point of the solvent, full advantage is taken of the temperature
coefficient of solubility for that particular solute/solvent combination.
93
Quantitative solubility data are not essential, and the following general approach may be
applied to any solute/solvent combination. The solid is placed in a flask of suitable size
and just covered with a small quantity of solvent (use a volume comparable to that of the
solid phase, but certainly less than will be required ultimately). The flask and contents are
heated gently on a steam bath, shaking or swirling, to a temperature just below the
solvent's boiling point. Heating may then be interrupted, an additional small quantity of
solvent added, and heating resumed. This procedure is repeated until the last bit of solid
just dissolves or until no further decrease in the amount of undissolved material is
apparent. In many instances it will not be possible to obtain complete solution because of
the presence of insoluable impurities in the mixture.
For this and all subsequent operations in the recrystallization sequence, it is convenient to
use the conically shaped Erlenmeyer flask, but never beakers. This particular design
offers many practical advantages. It minimizes both solvent loss (the upper walls acting
as a condenser) and the distribution of crystals on the vessel walls out of reach of the
solvent phase. It is also particularly convenient for handling in the transfer operations or
for corking or fitting with a condenser. In this way, hot, ascending solvent vapor does not
escape but is condensed and continuously returned to the solution flask. This is
particularly important with solvents such as ethyl ether, benzene, and petroleum ether, but
in practice it is advantageous with any solvent because loss of solvent over the period of
time taken by the subsequent filtration step will cause the solution to become
supersaturated prematurely. In fact, it is often desirable to have the solution slightly
below saturation at this point to minimize difficulties in the not filtration (see below).
This is especially true for highly volatile solvents (e.g., b.p.<65°C).
(b) The Use of Decolorizing Charcoal

Frequently, the crude product of a reaction mixture is colored by the presence of certain
impurities which may have arisen through some oxidation, charring, or polymerization
process accompanying the main transformation. Such impurities are usually highly polar
and, even though very soluble in the recrystallization solvent, tend to be adsorbed or
occluded by the growing crystals of the solute. In these instances, a series of wasteful and
94
repetitive recrystallizations can be avoided by the addition of a small quantity of animal

charcoal ("Norite", Darco", "Nuchar", etc.) to the hot solution. This addition permits
selective adsorption of the colored impurities by the active carbon prior to the
crystallization process.
It is important that the solution not be super-heated when the active carbon is to be added,
or excessive frothing and "boiling over" of the flask contents may occur. Usually the
flask is removed from the heat, and after a moment the carbon is added. The contents of
the flask are kept hot and shaken briefly to ensure wetting of the carbon surface.
Adsorption occurs very rapidly, and no advantage is gained by boiling the suspensions
for several minutes. Charcoal is actually less effective at elevated temperatures, and the
only reason for operating at the boiling point is to keep the substance to be crystallized in
solution. The effectiveness of the charcoal in adsorbing the colored impurities is directly
proportional to the solvent polarity and is best in an aqueous solution. The smallest
amount of decolorizing agent that will do the job should be used because the desired
solute may also be adsorbed (thus reducing the yield of product recovered) if the surface
of the adsorbent is not saturated by the coloring matter. For this reason (and since the
color may also be due to the desired compound) the decolorization step is seldom
repeated whatever the results of the single trial. In practice, one seldom uses more than 20
mg of charcoal per gram of dry compound.
(c) Hot Filtration

The hot solution must be filtered to achieve separation from any insoluble impurities or
other undissolved materials. If charcoal is used for decolorization the necessity for
filtration is obvious. If no undissolved material is evident (which is very seldom) this step
may be omitted. The chief difficulty encountered in this operation is that of keeping the
solution hot enough to avoid premature crystallization in the filter. This means that the
filtration must be done as rapidly as possible with minimal cooling of the solution.
Rapid filtration of small quantities of solution is best done by gravity through a fluted
filter paper supported in a stemless glass funnel. Fluting of the filter paper (the technique
of folding will be demonstrated in the laboratory) increases the rate of filtration
95
by presenting a much larger surface area to the solution. If a regular funnel with a stem is
used, there is a good ,possibility of filtrate cooling in the stem, with crystallization
resulting. The relatively narrow stem thus becomes clogged and filtration is impeded. It is
often advantageous to preheat the glass funnel simply by briefly heating it in a flame or
by pouring a quantity of hot solvent through it immediately prior to filtration. If water is
used as the solvent, the filter funnel may be warmed conveniently on a steam bath.
When working with particularly volatile solvents or with solids having very large
temperature coefficients of solubility, it is particularly difficult to avoid premature
crystallization. In these cases it is usually better to prepare the hot solution with excess
solvent (i.e. the solution is not saturated at the boiling point). After the hot solution has
been filtered the excess solvent must, of course, be removed by evaporation before
inducing crystallization.
It should be emphasized that the hot filtration is done by gravity (at least in an elementary
laboratory) and not by suction filtration as described below for the collection of the-
crystallized product. The use of suction for filtering a hot, nearly saturated solution is
nearly always highly unsatisfactory, because the reduced pressure in the filter flask
causes rapid evaporation of the hot solvent; consequently, the solution is not only more
concentrated but it is cooled by the heat of vaporization and becomes supersaturated.
Crystallization in the funnel is then almost inevitable and the funnel may become
completely plugged by the deposited crystals.
In carrying out the actual filtration, the fluted paper is inserted into the stemless funnel so
that the lower tip of the paper projects into the opening at the bottom of the funnel. The
hot solution is decanted quickly but carefully into the paper, keeping the level of
solvent well below the top of the paper. When all of the solution cannot be put into the
funnel at once, the remainder is kept warm on the steam bath or hotplate until it can be
transferred to the funnel.
96
After the solution has run through the paper, a crust of crystals often remains around the
tip of the funnel and ill-formed crystals often form in the body of the cooling filtrate. It is
common practice to rinse the original flask with a little hot solvent and to filter this
through the filter paper to redissolve the crystals adhering thereto. The filtrate which has
been collected in an Erlenmeyer flask should be reheated to redissolve any material that
has crystallized and, if significantly diluted below the saturation point, should be
concentrated to its original optimal volume prior to cooling and crystallization.
If the various precautions outlined above fail to prevent excessive crystallization of the
solute in the filter. paper, the simplest expedient is to return the complete filter paper and
its contents to the original flask, add additional solvent, boil briefly to ensure complete
solution, and begin a new filtration.
(d) Cooling/Crystallization
Crystallization is accomplished by allowing the hot filtrate to cool slowly, undisturbed, to
room temperature (or at least until crystallization has begun) and then chilling the mixture
in ice or cold water to complete the precipitation. The objective is, of course, that the
desired substance be deposited as pure crystals while any "insoluble" impurities remain
dissolved in the "mother liquor". The lower the temperature to which the solution is
cooled, the more the desired substance will crystallize; however, at some point the
impurities may also begin to separate from solution. The size of the crystals which
separate will vary with the rate of cooling and the degree of agitation of the solution.
Rapid cooling with stirring tends to produce small crystals, while slow cooling of an
undisturbed solution tends to give larger crystals. In general, either ~ large or very small
crystals are undesirable. There are problems associated with the collection of very fine
crystals because of clogging of the pores in the filter paper and of adhesion of the small
particles to the walls of the crystallization flask. Moreover, if the solubility of the
impurities is comparable to that of the desired compound, sudden chilling may result in
the co-deposition of the impurities; whereas, with slow, undisturbed cooling these tend to
97
remain in supersaturated solution and more complete separation is effected. On the other
hand, with very large crystals there is a tendency for the mother liquors to be occluded
within the crystals. In the subsequent drying operation, evaporation of the solvent will
leave a deposit of impurities on the crystals.
Yet another problem associated with too rapid chilling of the solution, especially in the
case of low melting solids, is the tendency for the solute to separate first from the solution
as an "oil" which subsequently solidifies to a crystalline cake. If this happens, it is
possible for impurities to be distributed between the solvent layer and the "oily" layer
(see discussion of principles of extraction). The impurities will then be entrapped when
the oil solidifies. For this reason it is often desirable to choose a solvent for
recrystallization whose boiling point is lower than the melting point of the solid being
purified.
(e) Collection of Crystals -Cold Filtration

The important objective in the collection of a purified product is complete separation of
the crystals from the "mother liquor" containing the dissolved impurities. This is achieved
most effectively by employing suction filtration. The necessary apparatus consists of a
Buchner funnel attached to a heavy-walled filter flask which is connected through a
"trap" bottle to the source of suction (water aspirator or vacuum pump) -see
accompanying illustration.
The Buchner funnel is prepared for filtration by attaching it to the filter-flask by means of
a cork or rubber adapter, inserting a piece of filter paper whose diameter is just sufficient
to cover the holes in the filter plate (the paper must not fold up against the sides of the
funnel), wetting the paper with a-small quantity of the solvent being used, then smoothing
the paper snugly against the filter plate by the application of gentle suction.
The cold contents of the crystallization flask are stirred to break up any lumps and
swirled to obtain suspension of crystals. The suspension is decanted quickly into the
funnel in such a way that a layer of uniform thickness is obtained across the whole
98
surface of the filter bed. This is essential for obtaining complete separation of the mother
liquor. It is important, particularly in the early stages, to use only sufficient suction to
obtain a steady flow of filtrate. Very strong suction at this stage will draw the finer
particles into the pores of the paper, clogging them, and slowing the rate of filtration
unnecessarily. The bulk of the crystals remaining in the flask may be transferred to the
funnel with the aid of a metal spatula. Any crystals still remaining are most efficiently
transferred to the funnel by rinsing the flask with a portion of the filtrate (which is
already saturated with solute) rather than using fresh solvent.
When the bulk of the mother liquor has drained through, the cake of crystals is pressed
down quickly with a spatula or glass stopper and the suction is interrupted by removing
the rubber tubing from the filter flask. It is particularly important at this stage not to draw
air through the crystal cake, because this will cause evaporation of the mother liquor and
the impurities that were dissolved therein will be deposited on the surface of the crystals.
If it is intended to use the mother liquor to obtain a second "crop" of crystals after
concentration to a suitable volume, it should be transferred at this point to a separate
vessel (or the Buchner funnel attached to a clean filter flask).
(f) Washing the Crystals

To complete the separation of the mother liquor, the crystalline cake must be washed with
small quantities of fresh, clean solvent. This is done conveniently by covering the filter
cake completely with a thin layer of solvent, with the suction disconnected. If possible
the crystalline cake should be loosened with a spatula to ensure complete wetting by the
wash solvent, but care must be exercised not to disturb the filter paper. The suction is
reapplied and the wash solvent drawn down through the crystals, which are then pressed
down firmly as before to remove the wash liquid as completely as possible. For complete
removal of the mother liquor from the crystals two or three such washes are
recommended; however, to minimize loss of product, the wash portions should be small
in volume and the solvent should be cold. After the last wash, full suction is applied to
draw air through the filter cake to suck it as dry as possible.
99
(g) Drying the Crystals

The final operation in the recrystallization of a product, is the drying of the solid. If the
solvent employed in the recrystallization is rather volatile, it is possible that it will
have evaporated completely during the last stages of the suction filtration. Otherwise,
further drying is necessary. As used here the term "drying" refers to the complete removal
of solvent, be it organic or aqueous.
The cake of crystals is transferred, with the aid of a spatula, to a sheet of glazed paper, a
watch glass, or any suitable container having a relatively large surface area. The solid
sample should be spread out and permitted to stand in air with periodic stirring with a
spatula. In many instances, however, simple "air-drying" as just described will be
inadequate or much too slow. The last traces of solvent (and/or atmospheric moisture) are
removed most conveniently by using a drying oven, a dessicator, or by evaporation under
vacuum. A dessicator is simply a closed vessel with a lower compartment containing an
anhydrous salt such as phosphorus pentoxide which can remove water vapor by forming a
hydrated salt. When using either an oven or a dessicator the rate of drying can be
enhanced even further by reducing the pressure in the system. The temperature
at which the crystalline solid is dried in an oven should, of course,
be significantly lower than the melting point.
100
~.
101

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The University of Western Ontario

Faculty of Engineering Science

DEPARTMENT OF CHEMICAL AND BIOCHEMICAL

INDUSTRIAL ORGANIC CHEMISTRY

Instructor: P.A. Charpentier

Copyright P. Charpentier 2003

LABORATORY 1 - THE FRACTIONATION OF HYDROCARBONS

LABORATORY 2 - ANALYSIS OF PETROLEUM FRACTIONS .............. 29

LABORATORY 3- REDUCTION OF A KETONE TO A SECONDARY

LABORATORY 4- CATALYTIC HYDROGENATION OF SQUALENE (A

LABORATORY 5- EPOXIDATION OF 1-TMP AND IODINE

LABORATORY 6 - SYNTHESIS OF AZO-DYES AND UV-VIS

LABORATORY 7 - SYNTHESIS OF DICUMYL ETHER AND NMR

LABORATORY 8- SOXHLET EXTRACTION OF CAFFEINE FROM

Acceleration m/s2 ft/s2 3.281X100 3.048X10-1

dyne/cm2 1.000X101 1.000X10-1

lb/in2 (psi) 1.450X10-4 6.895X103

psig ≡ pounds per square inch gauge

1.2 COMMON ITEMS OF GLASSWARE AND

The ERLENMEYER or CONICAL FLASK is used for handling solutions,

The FILTER or BUCHNER FLASK is used in conjunction with the Buchner

The EVAPORATING DISH is used to provide a large surface area to speed up

The PASTEUR or DROPPING PIPETTE is for transferring a few drops.

The SEPARATORY FUNNEL is used for the separation of

There are many different shapes of CONDENSERS available

Volumetric flasks Volumetric pipettes

1.3 A NOTE TO THE STUDENT

Although this laboratory does not involve extensive manipulation of hazardous

Remember: ACCIDENTS ARE CAUSED AND CAN BE PREVENTED!

ALL STUDENTS MUST HAVE A LABORATORY BOOK IN WHICH TO RECORD

ALL FLASKS, BEAKERS, CONTAINERS WITH ANY CHEMICALS IN THEM

1.4 PERSONAL CONDUCT

(1) Eye protection (safety glasses with side shields) is mandatory.

VIOLATION OF ANY OF THESE REGULATIONS WILL MEAN THAT YOU WILL

1.5 HANDLING CHEMICALS AND EQUIPMENT

1. Do not taste chemicals.

2. Do not pipet any chemicals by mouth. Use rubber bulb (propipette).

4. Do not mix incompatible chemicals.

5. Do not heat flammable liquids with an open flame.

7. Dispose of solid wastes in garbage pails. Do not use the sinks.

8. Clean up spills (solid or liquid) at once.

9. Return chipped or broken glassware to the demonstrator.

19. Chemical waste should be disposed of in the labeled waste containers

1.6 GENERAL HOUSEKEEPING

1.7 GUIDELINES FOR PREPARATION OF LABORATORY REPORTS

All Formal reports must be TYPED

Objective: State the objective or purpose of the lab

MATERIALS AND METHODS

"(Black and Smith, 1990a; Black and Smith, 1990b)"

ORGANIC CHEMISTRY LABORATORIES

LABORATORY 1 - THE FRACTIONATION OF HYDROCARBONS AND GAS

Mixtures of organic compounds can be separated by distillation. One such mixture is

Table 1.1 Petroleum constituents

FRACTION DISTILLATION CARBON NUMBER GENERAL USES

Figure 1.1 Simple Distillation

Reflux Cooling (Deflegmation):

Figure 1.2 Reflux cooling setup Figure 1.3 Reflux cooling

is equal, so we can represent it as P on Figure 1.5. The vertical position of P depends on

Figure 1.4 Rectification setup Figure 1.5 Rectification

In the present lab, a three component system will be separated by a simplified

Figure 1.6 Laboratory rectification

take time/temperature measurements throughout the distillation every 60 seconds. This

Submit to the TA prior to beginning the laboratory session.

VI. SUMMARY OF REQUIREMENTS FOR REPORT