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TO THE STUDENT

The Rediscovery Book: A General Chemistry Lab Manual contains a set of


investigations originally performed by chemists in their labs many years ago. These
early chemists researched very basic phenomena such as formulas or molecular
weights using methods and apparatus similar to the ones you will use in your
modem-day labs. Whenever you take a lab, you are recreating the research of these
nineteenth-century chemists. It is in this sense that the manual is a "rediscovery"
manual.
Lab teaching at its best is a three-part Socratic dialogue among an instructor, a
student, and nature. The questions this lab manual answers are those that should
be going through your mind as you prepare for an experiment, but it does not
answer the final question being put to nature. While this manual is written to set
the mood of serious scientific inquiry, its purpose is not incompatible with some
down home" informality.
To keep the "research flavor" in the course, you will work with unknowns. This is
not because of some dark need for secrecy; it is a way of letting you approach the
problems posed in an unbiased way. The only way you will find out the answer is
to do the experiment, and you will not be told what it "should be" before, during, or
afterward.
The frequent student complaint that the lab does not connect with the lecture does
not seem very sensible. The lab has a rather different mission: to teach a student to
reason accurately from chemical observation and how to make good measurements.
It does not teach the facts of chemistry as much as how to think about chemistry,
and by extension, how to do science in general.
You see, a lab will not "illustrate" lectures. Scientific concepts cannot be illustrated
or discovered in a single afternoon. Instead, a lab will illustrate the discovery and
measurement of a concept rather than the concept itself. The difference is subtle,
rather like that pointed out by the Yale librarian, who, when the new library was
built, wanted to have written over the door, "This is not the library, the library is
inside."
At this point you, gentle reader, are probably saying to yourself, "Pickering, all that
you are saying is a good idea, but I'm a klutz. Apparatus breaks when it hears me
coming."
Fear not. If you can learn to eat with a knife and fork, you can get good enough
measurements to do well in this course. I make this analogy for several reasons.
One is that it is, in fact, not easy to learn how to eat. (Try chopsticks sometime. or
watch an infant with a spoon.) It is learned gradually. Also, eating is dominated by
habit, and there is no reason why the same principle cannot be employed in the lab.
As you perfect the manipulation of the lab apparatus, you will be able to spend
more time concentrating on the science, in the same way that you eat and carry on
an absorbing conversation at the same time.

The trick with both table manners and lab technique is to learn one method, develop
it into a habit, and refuse to do things any other way, so that the habit becomes
entrenched. In this manual each operation is spelled out in detail the first time you
meet it. The methods are chosen to be "goof-proof" and to work with almost all
substances, almost all of the time. Learn them, and let them become your laboratory
table manners.
You can also avoid trouble by understanding what you are doing and why. If you
have had difficulty in previous labs, be especially careful about prelab preparation.
Your roommate may be able to come into lab unprepared and get away with it, but
do not try it. The extra preparation time you put in will be saved by just one
afternoon your roommate wasted because of a bad day," and you will be ahead.
Last, do not try to beat the clock. People work at different speeds. Since teaching
assistants are paid for the class period, asking them to stay on is an unreasonable
imposition, and legal requirements do not let you work unsupervised. But
sometimes you can come back to another session another afternoon and continue.
Be sure to observe whatever the local tradition is regarding admission to another
section.
At bottom, the idea that scientists have to have exceptional dexterity is a myth. In
practice, experiments are designed to be done with all constraints-dexterity being
one of the more fundamental ones.
When writing a book like this, there is a choice between making it completely
humorless, or allowing some of the personality of the author to come through. I
have chosen the latter to avoid making the text sound like instructions to Form 1040.
I realize that humor is a subtle thing that does not always come across well in
writing, but I very much want you to read and enjoy this manual. Good luck in all
of your scientific endeavors!
Miles Pickering

PART ONE: How to Be Successful in Lab Work


Being successful in the lab is not a matter of exceptional dexterity. If you can handle a
knife and fork, you can obtain good results. The trick in doing lab work is to learn a
particular routine for each basic operation and practice it until it becomes habitual. For
example, in this manual you will find a method for weighing out solids. This method
has been chosen because it is especially foolproof. If you always use it you will never
have any trouble weighing out solids and, in time, any other method will seem strange.
If dexterity is not important, what does matter? Primarily, it is important to understand
what is happening. In any lab, it is tempting to use a "cook-book" approach, but a
student who understands the underlying principles has a profound advantage. He or
she will be able to evaluate the results as they appear, will know when short cuts are
desirable (or fatal) and will have quiet self-confidence, instead of a sense of impending
disaster.
The Role of Measurement in Lab Work
Measurements are made in this course to answer molecular questions. Molecules can
be investigated only indirectly by finding observable information that can be directly
related to the quantity being measured. You never really look at molecules; rather, you
look at meter readings and try to interpret them.
In such an inquiry, it is easy to measure something other than what you expect to
measure, a situation know as systematic error. A major source of systematic error is
various sorts of instrument malfunctions. To guard against this, there are a number of
very quick proof-of-method experiments in the text. These require almost no
calculation, and if the proof-of-method experiment works, you can be reasonably sure
that the method will actually produce "real results, unaffected by instrument
problems. This approach is constantly used in scientific research.
Another source of systematic error is failure to control important variables. If you wish
to know the boiling point of a liquid, the atmospheric pressure is a significant variable.
Usually, it is possible to use controls or blanks to avoid these problems. It is sometimes
possible to compensate for these variables if you have remembered to measure them,
but it is essential to think about them when planning the experiment.
Besides recording experimental results, you should record variables that are controlled
by the experimenter. It may or may not be important to know the concentration of a
solution, for example. One of the reasons for the many repetitions of experiments in
real research is to weed out the various possible systematic errors, until the result can
be stated confidently. In this course, much of this work has been done, but it is still
important to consider how changes in procedure might affect the result.

Getting Ready for Lab


Read the experiment carefully from beginning to end. (Check the schedule to see that
you are preparing for the correct experiment!) Ask yourself some of the following
questions:
1. What question is being asked of nature?
2. What measurements must you do to answer this question?
3. What pitfalls exist? What variables do you have to keep constant?
4. What hazards are involved?
Your instructor will probably give you very detailed instructions as to what is to be
done before lab. These should be followed! If he or she leaves this to you, the simplest
method is to make a summary in your notebook. Aim for telegraphic simplicity. Leave
a lot of space in the notebook, at appropriate places, for measurements.
Preparation does not take place in the notebook, but in your head! Our studies have
shown that students who prepare well go home about 20 percent earlier, on the
average.
To give you an idea of how such a summary is prepared, a section of the lab manual,
together with the resulting student summary, is now presented.
Preparing a Good Notebook
This is in the original procedure, taken from the procedure for the synthesis of
Tetraiodomecurates.
1. You will be given a test tube containing 30 mg of Hg2+ in an acid medium.
This solution is poisonous.
2. To the solution in the original test tube, add 1 mL of 0.5 M KI solution.
Agitate for 30 sec or so. A solid (HgI2) will form and then gradually dissolve to
form Hgl42-. You should not need more than about 1 mL. If the solid does not
completely redissolve after about 30 sec, add more KI solution drop-wise,
agitating after each drop until a transparent solution results.
3. To the resulting solution, add 3 mL of 0.1 M Ag+ or 0.1 M Cu2+ solution,
depending on whether you are trying to make the silver or copper salt. A
precipitate will form. Agitate gently, taking care not to spill.
4. Heat in the water bath to "digest" the precipitate for 5 to 10 min. During
digestion, small crystals dissolve and larger ones form. Let the solution cool and
settle.
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5. With a disposable dropper, remove most of the liquid, discarding the liquid
into the "mercury waste" container in the hood. Add 2 to 3 mL of distilled water
and bring to the boil. Again, cool, let the solid settle, and discard the waste
solution into the mercury waste container.
6. Add a few drops of distilled water. Use the tip of a disposable dropper to stir
up the precipitate and suck up the solid. Transfer it to a clean 50 mL beaker.
Allow the beaker to stand uncovered for a week in your desk. This will allow
the excess H2O to evaporate.
The following is an example of how the procedure appeared in a student's notebook.
Receive test tube with 30 mg of Hg2+ (poisonous).
Add 1 mL of 0.5 M KI sol. shake 30 seconds.
Solid should form, redissolve. If not completely redissolved, add more KI drop-wise until
solution is transparent.
Add 1 mL of 0.1M Ag+ or 0.1 M Cu2+, agitate.
Heat 5 to 10 min in H2O bath.
Remove liquid with disposable dropper, discard into "Hg waste."
Add 2 to 4 mL of H2O. Heat to boil in H2O bath.
Discard H2O into "Hg waste.
Add few drops H2O, stir up solid with dropper, suck up drop into beaker, let stand one
week.
Observe and record colors.
The previous is a good notebook summary because
1. it is broken up into individual steps and has a check-list quality;
2. all key landmarks are present (for example, "solid should form, redissolve") so
that the student can check the results as the work goes on;
3. hazards are included;
4. there is a reminder to record crucial observations.
This summary could be written on the left-hand half of the page, leaving the other half
page for observations. Alternatively, the student could entitle it To Be Done and then
record measurements and observations at the end under the heading What Was
Done.
Keeping Records
Nowhere is habit so important as in keeping accurate records. A number of otherwise
inexplicable student results are caused by scrambled records, and studies of laboratory
exams have shown that this is a major cause of student failure. Therefore, most
teachers are strict about notebooks this is an attempt to save students from
themselves. Your instructor will almost certainly add to the directions in this manual.
Your notebook must be of an approved type and data must be recorded in ink. It must
be current and consecutive, and all your work must be in one place. In many schools,
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notebooks are checked on a weekly basis by the teaching assistant, and a persistently
unsatisfactory notebook counts against your grade.
Never, never tear out pages (except carbons): not if you make a mistake, not if you spill
something, never!
Record three classes of data.
1. All of the numbers pertaining to the experiment. Identify all numbers and follow by a
unit. Be sure to record concentrations of stock solutions. This information must be
recorded directly in your notebook, not on scraps of paper. Even if it is transferred
once, there is a danger of, for example, digits being interchanged, so be sure to take
your notebook whenever you go to the balance. Some teachers enforce this by
picking up all scrap paper. Beware!
2. All the observations you have made. This includes smells, colors, and color changes.
It includes the size and shape of solid crystals, abrupt changes in temperature, or
any other phenomena. When in doubt, record it.
3. Any changes in procedure. If you diluted a reagent down from a concentrated stock
solution, record it. If there was a dead fly in your flask when you did a titration,
record it. When in doubt, record it. In many colleges you will be tested on the facts
you have observed. You may be permitted to have your notebook for reference
during the test, so it will be to your advantage if it is complete and readable.
In some colleges, at the end of each period you must turn in a carbon copy of your
notebook for that period. This is not only to keep you honest; it helps you if your
notebook is lost or stolen, because it serves as a record.
WORKING SAFELY
We have done our best to build safety into the design of the experiments and work
areas, but working in the lab is still not as safe as lying in bed. Your instructor will
undoubtedly bring local safety rules to your attention. The ones listed below, which
are universal, serve as a starling point.
1. Wear eye protection at all times. If you ponder for a moment what would
happen to the rest of your college and professional career if you were accidentally
blinded this very period, I am sure you will agree that the discomfort of safety
glasses is a small price to pay for some added insurance. In any case, you must
wear eye protection because it is mandated by federal regulations (29 CPR
1910.133). If you refuse to wear eye protection, you cannot come to lab. It is that
simple.
2. Do not wear contact lenses to lab. If you wear contact lenses, and chemicals get
into your eyes, much more severe damage will result.

3. Wear shoes that cover your feet (not open-toed shoes or sandals). This, too, is
mandated by federal regulation. Do not wear shorts or skirts in the lab. Uou
should wear long pants. Shoes and clothes provide a first line of defense against
spills. Old blue jeans are a good choice for lab clothes. They resist chemicals, and
stains on them are not noticeable. If all else fails, they can be thrown out at the end
of the semester. You will also be required to wear a lab apron when working in the
lab. You are required to wear a lab apron when working in the lab.
4. Do not eat, or drink, in the lab. As the alchemist Paracelsus remarked, "All things
are poisonous, for there is nothing without poisonous, qualities. It is only the dose
which makes a thing poison." These words are as true now as in the sixteenth
century. If you need to eat, or drink, do it in the hall. Although few chemicals are
absorbed through your skin, avoid touching chemicals whenever possible. Wash
your hands at the end of the lab period.
5. Be aware that burns and fires are serious hazards. Some of the substances that
you work with burn very easily. Also note that hot glassware looks very much the
same as cold glassware, but its effect on your skin is very different!
6. Do not perform any unauthorized experiments. The difference between using
potassium chlorate and chloride may be an explosion!
7. Report even trivial injuries to your teaching assistant or lab supervisor. What
seems minor can have major complications.
8. Work in the lab only if you are being supervised. You can work only during your
scheduled period, unless other arrangements are made, and even then you may
work only in the presence of a teaching assistant.
9. Know the location of emergency exits, emergency showers, eye-wash fountains,
and fire extinguishers. Always know two different ways out of a lab. Do not put
book bags or other things on the floor, where they might impede escape. In a real
emergency, follow the instructions of teaching assistants or supervisors. Move, do
not argue!
10. Do not, as a rule, bring visitors into most laboratories. Ask permission before
bringing them, and see that they obey the rules. You can always talk in the hall.
11. Do not listen to music through earphones. (You want to be able to hear
instructions in an emergency.)
If you are, or might be, pregnant, consult your instructor about postponing your lab.
All chemicals known to cause birth defects at this writing have been excluded, but so
little is known about this topic that a conservative approach seems appropriate. The
threat of birth defects from toxic agents is most serious in the first 3 months; it seems
that the hazard is much less later.

When you notice a fellow student who is not following roles, remind him or her.
Almost certainly, your fellow student would rather be reminded by you than by a
teaching assistant or faculty member! If you are the one being reminded, thank the
person doing it and be glad you did not find out "by accident."
Using Proper Lab Etiquette
Lab work can be made faster, pleasanter, and simpler for everybody if your class can
use peer pressure to encourage people to observe some rules that fall into the category
of etiquette. For example, do not remove tools and reagents that are to be shared. Do
not stick droppers or other tools into stock solution bottles. If you spill something,
clean it up. At the end of the period, sponge off your bench, so that the next user does
not have to start by cleaning up a puddle of colorless liquid, wondering, "Is it water or
sulfuric acid?"
USING THE TOOLS OF THE TRADE
Bunsen burners, beakers and test tubes are a few of the tools you will use for the
following experiments.
Running a Reaction
To run a reaction you will need to mix the chemicals (called reagents) and possibly to
beat them. These basic techniques are covered in this section.
How to Adjust a Bunsen Burner
In order to accurately perform an experiment using a Bunsen burner, the flame needs
the proper mixture of gas and air. The flame will be noisy or blow out if there is too
much air or not enough gas. A smoky or yellow flame indicates that there is too much
gas or not enough air. Regulate the air by adjusting the barrel. Control the gas with a
needle valve in the burner base.
How to Set Up a Beaker or Flask for Boiling
Place a piece of wire gauze on a tripod, then place the beaker or flask on top of the wire
gauze. The gauze helps support the beaker and also spreads the heat. To stop the heat,
remove the lighted burner from under the flask, then let the contents of the container
stop boiling before attempting to pour or remove. Use beaker tongs or crucible tongs to
grasp a hot object.

Bumping
Boiling may be uneven and explosive. This phenomenon, known as bumping, is
controlled by adding boiling chips. These act as nuclei, giving the vapor bubbles a
place to form so that the liquid does not superheat. Before adding boiling chips, always
let the hot liquid cool below the boiling point. Otherwise a burst of boiling will occur
when the chips hit the liquid, often scattering the liquid out of the container.
How to Work With a Test Tube
Many of the experiments in this lab manual are done in test tubes. To mix solutions, or
to get a solid to dissolve, do not seal the test tube with your thumb and invert it. This
will contaminate the solution and may be dangerous to tour skin. Rather, grasp the top
of the test tube firmly and then tap rapidly with a finger from the other hand. Use a
circular stroke, letting your finger quickly slide down the outside of the tube (Fig. 1). If
you do this correctly you can create a vortex in the test tube that will mix it efficiently.
Figure 1 Mixing solutions in a Test Tube.

Never heat a test tube directly. Always immerse it in a hot water bath. Otherwise the
liquid may bump and fly out of the test tube.

Measuring Weight
Many of the measurements in this manual depend on the analytical balance, which is
potentially one of the most accurate instruments available to you. Learn to use this
balance well. Your teaching assistant will explain how to use the particular model of
balance available in the labs
How to Use the Analytical Balance
Whenever you are asked to weigh out a solid, you will be given a range of weights.
Any weight in this range will work, as long as you know exactly how much you
actually weigh out.
Weigh by difference. Put the solid in a vial, put the top on (to keep out moisture and
dust), and take a reading. Then transfer a small amount of the solid into a beaker or
flask and reseal the vial. Pour the solid directly into the beaker or flask; do not use a
spatula lest some of the solid stick to it. Reweigh the sealed vial. If the amount
transferred is not sufficient, transfer more to the beaker and reweigh the vial. If you
have added too much, clean out the beaker and start over. Do not transfer the solid
back to the weighing vial lest you contaminate the entire sample.
Remember that the analytical balance is a very precise instrument. Always record all of
the available decimal places. You can round off the number later.
For precise work, do not weigh hot objects on the balance. A hot object creates
convection currents of air that cause the reading to appear light. Although many books
suggest holding objects only with tissue, this is unnecessary unless you have very
sweaty fingers. Hugging the sample in the palm of your hand is not recommended and
will lead to a steady downward drift as the moisture evaporates.
The area in and around the balance must be kept clean. Spills are expected, and you
will never be penalized if you clean them up. However, leaving a mess for the next
student is discourteous and dangerous.
How to Use the Beam Balance
The beam balance is used for rough measurements only and should not be used unless
specified explicitly in this book. Directions vary from balance to balance, and your
instructor will advise you in using yours.

MEASURING VOLUME
Learning to do good volume measurements is essential, and not difficult.
How to Clean Glassware
Soap and water will remove almost all of the stains you will have on glassware (except
as noted for KMnO4) in this course, although it may take some scrubbing. Labels can
be removed by soaking in hot water and then scraping with a spatula, using the same
motion as that for peeling an apple.
It is not necessary to use a great excess of soap. Excessive amounts are difficult to
remove and require many rinsings, which takes time. Do the final rinsing with a small
amount of distilled water (just enough to thoroughly wet the inside, but not enough to
fill or even halfway fill the container).
How to Take Solutions from Stock Bottles
Use a graduated cylinder to take solutions from stock bottles. Pour the stock solution
from the stock bottle into the graduated cylinder, until you have taken slightly more
than you need. Take the cylinder to your desk, and remove the excess with a dropper.
Never, never pour the excess back into the stock bottle. Never, never put any object
(for example, a dropper) into the bottle. If you encounter difficulty with a bottle, get
assistance from your TA.
Remember this as the "one-way" rule: Things come out of stock bottles but never go
into them!
Do not take stock bottles to your desk. Also, if bottles have been placed in the hoods,
leave them there. The hood helps confine poisonous, smelly, or corrosive spills.
How to Use Volumetric Flasks
A volumetric flask must never be heated, because it will probably break. Even if it does
not break, the volume calibration will be destroyed. Dissolve solids before adding them
to the flask, rinse container used for the solutions with a wash bottle, and add the
rinsings to the flask. Shake thoroughly, then fill up to the mark (a circular ring etched
on the neck) and shake again. You cannot mix too much, but each year many students
have difficulties because they did not mix enough! If you fill the flask past the mark,
discard the solution and start over (Fig. 2).
Do not store solutions in volumetric flasks. The solution may cause the stopper to
"freeze, that is, to become solidly wedged in the flask. If this happens, get assistance
for frozen stoppers.

Figure 2 A Volumetric Flask

AN INTERPRETATION OF THE HIEROGLYPHICS ON A VOLUMETRIC FLASK:


A
250 mL 0.12 mL

TC
20 C
Pyrex USA No. 5640

The inscription above appears on a typical volumetric flask. What does it mean? The
top line, A, means "Class A according to the National Bureau of Standards. The next
line means "To Contain at 20 C, 250 mL with an absolute uncertainty of 0.12 mL."
The third line means "made of Pyrex glass (a registered trademark for a type of
borosilicate glass) made in the United States, Catalog No. 5640." Note that the old
abbreviation ml is now being replaced by mL.
ACCURATELY MEASURING VOLUME WITH A BURET
Beads of water form on the inside of an unclean buret when it is wet, as a result of an
invisible layer of grease. This may interfere with the accuracy of the measurement,
because drops remaining on the side of the buret will be counted as if they had been
delivered. Soapy water and a buret brush are sufficient for cleaning the buret.
After rinsing the buret, including the top, several times with water, rinse it with a little
of the solution you will use. This prevents accidentally diluting the solution. Fill the
buret over the sink, which you should be able to do without a funnel and without
spilling. (Funnels can introduce contamination, unless they, too, are with a little of the
solution to be transferred.) Run some of the liquid until the tip of the buret is filled and
the meniscus is on scale. It is a waste of time to start at 0.00 mL.

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To read the buret, look at the bottom of the liquid meniscus and then guestimate the
last place, so that you have a reading with two places after the decimal. The volume
delivered is the difference between the first reading and the final reading, and is
measured in milliliters (mL). The numbers increase reading down the buret, rather than
up as on a thermometer (Fig. 3).
Figure 3 Buret Reading

If you cannot remove all the air from the tip, you may get a false reading when it fills
up later. To remove an air bubble, hold the buret over the sink, open the valve, and
shake once vertically. Ask the teaching assistant for help if you are having trouble
PIPETTING
Two sorts of pipettes are available: the measuring pipette, which is often used in
clinical medicine and has graduations along the side, and the transfer pipette, which
has a bulge in the center. The latter is much more accurate. To use a transfer pipette,
follow this procedure.
1. Clean it thoroughly to prevent beads of water from clinging to the inside.
These beads count as delivered, even though they remain inside.
2. Hold the pipet with one hand and the pipet bulb with the other, out the air
from the bulb, then loosely attach it to the top of the pipet until the liquid has
been pulled up above the mark. Quickly remove the bulb and put your finger
over the top of the pipette.
3. Slowly let the level fall until the bottom of the meniscus just touches the line.
Release the top of the pipette, and let it deliver the solution into the vessel.
Touch the tip to the side of the container, and hold it there for a few seconds
after it looks as if all the contents have drained out. Do not blowout the
pipette or put your mouth on it at any time.

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What Do To Contain" and To Deliver" Mean?


Volumetric flasks are, of course, calibrated to contain the stated volume. Transfer
pipettes, those with no graduations on the side, are calibrated to deliver and are
marked TD. Other pipettes are usually marked to contain. Transfer pipettes need not
be blown out.
Disposing of Waste
There is a patchwork of state, federal, and local laws about waste disposal, and this is
'constantly changing. Your instructor will inform you of the proper method for
disposing of chemical waste. Please comply with these rules-they make the world safer
for all of us.

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Experiment 1: Co-crystallization of an Organic dye with Kalinite.


A crystalline solid is composed of an identical pattern of atoms, ions and/or molecules.
Usually the crystallization process is selective and atoms, ions or molecules of the
wrong shape or size or charge will not be incorporated into the crystal lattice.
However, a different molecules or ion of the correct size and charge can be
incorporated into the growing crystal through a process called co-crystallization.
Kalinite, KAl(SO4)212 H2O, is a colorless solid that is easily synthesized from Al metal.
Since Kainite readily forms crystals, it is ideal for this experiment. In this experiment
you will synthesize, and purify Kalinite, and then determine which (if any) of two
organic dyes, Bismark Brown and/or Bromo - Cresol Green, cocrystallize with Kalinite.
Since the dyes are colored, while Kalinite is colorless, it is easy to determine if
cocrystallization occurs.
Chemistry of Kalinite Synthesis:
The synthesis of Kalinite starting from Al metal is outlined in the four equations below.
N.B. These reactions are not balanced. You need to balance these reactions for the lab
report.
Al (s) + KOH(aq) -----> KAl(OH)4(aq) + H2 (g) (eqn 1)
KAl(OH)4(aq) + H2SO4(aq) -----> Al(OH)3 (s) + K2SO4 (aq) (eqn 2)
Al(OH)3 (s) + H2SO4 (aq) + K2SO4 (aq) -----> Al2(SO4)3 + K2SO4 (aq) (eqn 3)
Al2(SO4)3 + K2SO4 -----> KAl(SO4)2 12 H2O (eqn 4)
The rapid dissolution of aluminum metal in a warm aqueous solution of potassium
hydroxide (KOH) produces hydrogen gas, and the aluminate ion (Al(OH)4-) in an
exothermic reaction, (eqn 1). Aluminum is an example of an amphoteric metal. It is
soluble in both an acidic and basic solution. Most metals, iron for example, are only
soluble in acidic solution and form precipitates in basic solutions. In equation 1 the
aluminate ion, Al(OH)4- , is the soluble form of aluminum in basic solutions. Since the
desired product is in solution, any insoluble impurities can be filtered away at this step.
Treatment of the filtered solution with sulfuric acid first produces a gelatinous
precipitate of aluminum hydroxide (Al(OH)3) (eqn 2), which then dissolves as more acid
is added (eqn 3).
The kalinite is not very soluble in methanol, so the addition of the solvent will induce
precipitation of the desired material from solution. Isolation of the solid and
purification by recrystallization from water will yield pure Kalinite. (eqn 4).

13

CAUTION:
Potassium Hydroxide, KOH, and Sulfuric Acid, H2SO4, are corrosive and must not be
allowed to touch the skin, eyes or clothes. Methanol, CH3OH, and Ethanol C2H5OH
burns easily; keep fire and flames away when working with them.
Preparation of Kalinite:
1. Accurately weigh between 0.20 - 0.25 g of alloy chips and transfer to medium size
test tube. Add 10 mL of 1.4 M KOH solution (be careful not to get any KOH solution
on your skin. If you do, immediately wash with water), and warm the solution in a
warm water bath. Be careful not to BOIL this solution. After 20 -30 min remove the test
tube from the water bath and allow the test tube to cool. Remember to record all
observations (i.e. color changes, evolution of gases).
2. Gravity filter the cooled solution into a small beaker. To the filtrate carefully add 5
mL of 9 M H2SO4 (be careful not to get any H2SO4 solution on your skin. If you do,
immediately wash with water). If a precipitate still remains after all the acid has been
added, warm the solution again, until all the solid is dissolved.
3. Get 10 mL of methanol from the hood. Before bring the methanol back to your
bench, make sure there are no flames in the immediate vicinity. Methanol Burns! Place
the beaker in an ice bath, add the 10 mL of methanol to the solution, and allow the
solution to cool for 10-20 min. During this time crystals will form. Collect the crystals
by vacuum filtration using a Buchner funnel. Your TA will demonstrate how to
perform a vacuum filtration. You can obtain a Buchner funnel from the stockroom.
Purification of the Kalinite:
The crude kalinite contains a small excess of K2SO4 impurities, and these crystals will be
purified via recrystallization from water. Recrystallization is the most common method
for purifying a solid material. This method take advantage of the differences in
solubility of a compound in hot and cold solvent. The impure solid is dissolved in the
minimal amount of hot solvent and as the solutions cools the pure product crystallizes
from solution leaving the impurities behind in solution.
Heat some distilled water. Place your Kalinite in a small 50 mL beaker, and add the
hot water drop wise with a disposable pipet until all the solid dissolves. It may be
necessary to warm the solution of water and Kalinite if it becomes too cool. When all
the solid is in solution, remove from the heat and allow the solution too cool. You can
place the beaker in an ice bath to speed the cooling process, but if you allow the
solution to cool slowly you will get larger crystals. Collect the solid on a Buchner
funnel. Obtain an exact weight of the dry crystals.

14

Cocrystallization with Organic Dyes:


Dissolve ~ 0.10 g of purified KAl(SO4)212 H2O in a few mL of water. (At this step it is
OK to add an excess of water to dissolve all the solid.) Divide the solution into three
portions, placing the portions on three separate labeled watch glasses. Add 2-4 drops
of dye solutions to two of the watch glasses, keeping the third as a control. Allow the
watch glasses to stand for a week in your locker. The following week wash the crystals
with methanol in the hood. Note any color changes in the crystals.
For the Lab Report
1. Write balanced the equations for the formation of KAl(OH)4 (eqn. 1),
Al(OH)3 (eqn 2), Al2(SO4)3 (eqn 3), and KAl(SO4)212 H2O (eqn. 4).
2. The percent yield is a measure of the efficiency of a chemical reaction, and is defined
below. The actual yield is the number of grams of dry crystals of Kalinite you recorded.

% yield =

actual yield
100
theorectical yield

The theoretical yield is the number of grams of product that would be obtained if the
reaction went to 100% completion and produced only the desired product. The
theoretical yield forthis reaction can be determined as follows:
a. Since the aluminum is the limiting reagent, calculate the number of moles of
aluminum that you started with. The alloy chips used in this experiment are 92
% pure aluminum.
b. Since the mole ratio of Al : Kalinite is 1:1, calculate the number of grams of
Kalinite produced if the reaction went to 100% completion. Molecular weight
for Kalinite is 474.39 g/mol
" wt Al chips %" 1 mole KAl(SO 4 ) 2 12 H 2O %" 474.39 g %
theoretical yield = 0.92$
'$
'$
'
# atomic wt Al &#
&# mole &
1 mole Al

From the above formula and your data, calculate the percent yield for this reaction?
3. The ion Fe3+ is very similar in size to Al3+ and can replace it in the crystal lattice of

kalinite, so that kalinite with an iron impurity is common. How can one produce pure
kalinite from contaminated kalinite? (Hint: dissolve the kalinite in water then add
something that will precipitate the iron.)

15

Experiment 2: Preparation of a Standard Sodium Hydroxide


Solution
This experiment describes the preparation and the standardization of a Sodium
Hydroxide (NaOH) solution, and the titration of an unknown acid to check the
accuracy of the NaOH solution.
Why not just weigh out and Dissolve the NaOH?
Sodium hydroxide has the awkward property of absorbing moisture and CO2 from the
atmosphere. It is impossible to make a solution of an exact molarity by weighing the
sodium hydroxide alone because the sodium hydroxide pellets contain an unknown
quantity of impurities.
The easy way to solve this problem is to titrate the NaOH solution against a primary
standard. A good primary standard should be a high molecular weight solid that is
easy to handle and weigh. Also the primary standard should not pick up moisture
from the air. In this experiment, potassium hydrogen phthatlate (pronounced
thallate, and abbreviated KHP) will be used as the primary standard.
Chemistry:
The reaction of NaOH with KHP is shown below. The balanced equation shows there
is a 1:1 stoichiometric relationship between NaOH and KHP. The molarity of the

COOH

COONa
+ NaOH

+ H2O

COOK

COOK

NaOH solution can be calculated from the recorded volume of NaOH solution required
to neutralize a know weight of KHP. This method of determining precise concentration
of an unknown NaOH solution is called Standardization.
The procedure requires on knowing exactly when the neutralization has occurred. This
problem is solved by using an indicator, a dye that will undergo a rapid, reversible
molecular rearrangement in solution. There is a conspicuous color difference between
the molecular forms in acidic and in basic solutions, and the colors are so bright that
only a little of the indicator need be used. A single drop of NaOH solution will convert
some of the dye from its acidic form to its basic form so the first excess of NaOH not
used to neutralize the acid will convert the dye to its basic form, which is brightly
colored. This result indicates that neutralization reaction has occurred. This point is
known as the end point of the titration.

16

How to measure volume accurately.


This experiment hinges on the accurate measurement of volume, which can be done
most easily by using a buret. Learn to use this tool efficiently and accurately.
Beads of water will form on the inside of an unclean buret when it is wet, because of an
invisible layer of grease. This interferes with the accuracy of the measurement, since
drops remaining on the side of the buret will be counted as though they had been
delivered. To clean the buret, soapy water and a buret brush are sufficient.
After you have rinsed the buret (including the top) several times with deionized water,
rinse with a little of the solution you will use. This prevents the accidental dilution of
the solution you are adding. Fill the buret over the sink. You should be able to do this
without a funnel and without spilling. (If you must use a funnel, rinse it with a little of
the solution to be transferred.) Run the liquid until the tip of the buret is filled and the
meniscus is on scale. If an air bubble persists in the tip, open the valve and shake the
buret once vertically with a snap of the wrist. There is no need to start at exactly 0.00
mL.
To read the buret, look at the bottom of the liquid meniscus and then guestimate" the
last place, so that you have a reading with two places after the decimal. The volume
delivered is the difference between the first reading and the final reading and is
measured in milliliters (mL). Note that the numbers increase as you read down the
buret, not up as on a thermometer. See the figure below.
Figure 2.1 Reading a Buret

Last, be sure, when filling, to write down the concentration and any other information
appearing on the stock bottle label.

17

CAUTION:
Sodium Hydroxide, NaOH, is corrosive and must not be allowed to touch the skin,
eyes or clothes. Clean up any spills, and rinse skin with water. Inform your TA of
any spills.
Part A: How to prepare the NaOH solution.
A stock solution of concentrated NaOH will be provided. Add about 30 mL of this
solution to 900 mL of distilled water in a clean plastic bottle, stopper and mix well.
Mixing well means shaking the bottle for at least 1 full minute with, as much vigor as
you can muster more shaking does no harm. The diluted NaOH, while poisonous, is
not nearly as corrosive as the concentrated solution.
Part B: Standardizing the NaOH solution with KHP.
Take the plastic vial containing your KHP to the balance with a conical flask. Weigh
the vial to get the exact weight. Then transfer between 0.5000 g and 0.8000 g of solid to
the first flask, recording the final weight of the vial, to obtain the exact amount
transferred by difference. Add about 50 to 100 mL of deionized water to the conical
flask. Warm to dissolve, and add between 3-5 drops of phenolphthalein indicator.
Fill a buret with NaOH, check for air bubbles, and then record the initial reading. Now
add NaOH solution from the buret to the flask, quickly at first. The pink color of the
indicator will persist for an increasingly longer time, and will finally spread through
the solution. It is useful to swirl with your dominant hand and control the volume on
the buret with your nondominant hand. Continue adding the solution drop-wise as
you approach the end point.
You will probably need to repeat this procedure several times before you find two
satisfactory end points, but it goes quickly after the first run. Compute the exact NaOH
concentration, and label your bottle. Keep the NaOH in your desk. You will need it for
subsequent work.
Calculating the Concentration of Sodium Hydroxide
The calculation depends on the important fact that one mole of KHP will neutralize
exactly one mole of NaOH. At the endpoint then, the moles NaOH will equal the moles
of KHP.
1. The molecular weight of KHP is 204.22 g/mol. Compute the number of moles of
KHP weighed out.
The volume must be expressed as liters (1 mL is 0.001 L) if the units are to work out.
The concentration of NaOH is simply the number of moles of KHP per the number of
liters of NaOH solution run out of the buret.

18

The concentration or Molarity (M) of the NaOH solution can be calculated, and the unit
for Molarity is mol/Liter:

Molarity NaOH =

%
weight KHP "
1
$
'
204.22 g/mol # vol. NaOH &

2. Do the uncertainty calculations. Start by calculating the upper and lower limits for
your best run. If uncertain as to which is best, choose the last one because practice may

cause an improvement.
For KHP samples weighed by difference, the uncertainties in
weight of KHP will be 0.0010 g. The two worst cases for the Molarity of the NaOH
solution will be

upper - limit Molarity NaOH =

%
upper - limit weight KHP "
1
$
'
204.22 g/mol
# lower - limit vol. NaOH &

lower - limit Molarity NaOH =

%
lower - limit weight KHP "
1
$
'
204.22 g/mol
# upper - limit vol. NaOH &

You should be able to explain why these formulas work.

3. Are the two concentrations identical within uncertainty? If not, shake the NaOH,
refill the buret, and do a third run to see if you can obtain agreement. (The shaking is
recommended only because incomplete mixing is the most common student error.)
4. To determine if two titrations experiments agree within uncertainty, look at the range
of concentrations. One titration of NaOH should fit inside the range of uncertainty just
calculated. For example if your range is 0.0876M to 0.0888M and your first value is
0.0879M, you have agreement. If not, at most one run can be correct.
Part C: A Proof of Method test of your NaOH Solution
The purpose of this little experiment is (1) to provide you with a yardstick by which to
measure your titration technique before you embark on the titration of real unknowns,
and (2) to give you an idea of what the lab practical exam will be like.
You will be given a sample of an unknown acid and are to report the apparent
molecular weight. Remember to record the Unknown Acid Number written on the vial
label in your notebook.
Weigh a sample of 0.5000 g to 1.5000 g of unknown acid into a conical flask, recording
the exact weight. Add 50 100 mL de-ionized H2O to the conical flask, and swirl to
dissolve the solid. Add between 3-5 drops of phenolphthalein indicator.
You handle the unknown acid in the same way you handled the KHP. The first run
will probably be overshot, but weigh out another sample. Initially you can go quickly
until you're close, then drop-wise.
19

Calculating the Molecular Weight of the Unknown Acid.


The Unknown Acid has one replaceable hydrogen, and at the endpoint the moles of
NaOH will equal the moles of Unknown Acid. The molecular weight is the number of
grams per mole. Since we know the number of grams of Unknown Acid we started
with, and we measured the volume of NaOH solution to reach the pink endpoint, we
can calculate the molecular weight of the Unknown Acid by:

Molecular Weight Unknown Acid =

weight Unknown Acid


Molarity NaOH (vol. NaOH)

There is no uncertainty analysis required for the Unknown Acid titration. Your TA will
tell you where to check your value of the Unknown Acid molecular weight. If your
agrees, then you have accurately determined the molecular weight. If your value
value
does not agree, then perform another titration.
For the Report
1. Make a table containing the net weights of KHP and net volume of NaOH solution
used in each titration. You should include data for all titrations performed.
2. Also include the concentration of the NaOH solution from each titration and an
uncertainty analysis for each run. Remember that the error for a net weight of KHP is
0.0010 g and the error for a net volume of NaOH is 0.10 mL. You need to write out,
in detail, one example of how you calculated the concentration, and include the
calculations of the upper and lower limits of the concentration.
3. If you do have agreement between two runs, the final concentration is the average of
the two runs. Also report the error limits for the average. Average the upper limits of
the two runs to obtain the upper limit of the average. Likewise average the lower limits
to obtain the lower limit of the average. Again, do not average two runs that do not
overlap.
4. Report the molecular weight for your Unknown Acid. Make a table containing the
net weights and net volumes for all the titration. Write out one example calculation of
the molecular weight. You do not need to perform an error analysis for this part.
Remember to include the Unknown number of your acid.

SAVE THE NAOH SOLUTION! YOU WILL NEED IT FOR


FUTURE WORK.

20

Experiment 3: Formula of a Mineral


You are a nineteenth-century chemist. A geologist has just returned from a far away
placed called California. Among the collection of mineral samples is one believed to be
novel. Preliminary tests confirm that the mineral is a sulfate. It probably contains
water of crystallization, but what metal does it contain? What is the formula of the
mineral? Perhaps it contains a hitherto unknown element (which you will have the
honor of naming).
The mineral has the following components: (1) a metal ion or ions, which is positively
charged, (2) the sulfate ion, which is negatively charged, and (3) the water of
crystallization. Over the next three lab periods, you will analyze your mineral to
determine the number of grams of each of these components in the sample. From this,
the formula of the unknown mineral and the atomic weight of the metal ion(s) can be
deduced.
Some of the minerals used in this experiment have an unfortunate property, that is, the
tendency to lose or gain water if exposed to the atmosphere for a prolonged period.
Keep the mineral sample in a sealed container. Only open it for only the minimum
necessary amount of time.
The analysis of the sample will take three 3-hr periods. It is recommended that you do
the calculations for each section as you complete it, so that if something looks odd, you
can consult your teaching assistant. Note that all of the measurements should contain
at least four significant figures; rounding off can yield strange results.
This seems to be a difficult experiment, primarily because for many students it is their
first attempt at a precise chemical analysis. Plenty of time is allowed; if you blunder
somewhere, you can repeat a step. The reward at the end is the intellectual satisfaction
of being able to identify confidently the composition of this white powder.
Part A: Flame Test, a Quick Preliminary Test
Take a clean nichrome wire, make a loop and heat a single crystal of the mineral in a
flame. Your teaching assistant will demonstrate this operation. For comparison, heat
samples of NaCl and KCl to observe a positive test for Na+ and K+ ions. If your mineral
gives a bright color to the flame, it may be possible to decide whether
1. It has sodium.
2. It has potassium.
3. It has an unknown element (another color flame or no color at all).
Note that if the flame test is positive for sodium, potassium may or may not also be
present. The sodium flame obscures the potassium color. Viewing the flame test
through a piece of cobalt glass, you should be able to see the potassium flame even if

21

sodium is also present. This test takes only 5 or 10 min and can provide useful
information.
Part B: Analysis for Water of Crystallization
A certain number of water molecules are needed to hold together the mineral crystal.
They are weakly bonded to the ions, and heating or sometimes simply exposure to a
dry atmosphere causes them to be lost. Usually the water of hydration has a definite
stoichiometric ratio to the ions in the salt. This loose bond between the water and the
rest of the ions is signified by the dot as, for example, in CaSO4 2 H2O. This is the
formula for gypsum and states that the crystal contains two water molecules for each
Ca2+ or SO42- ion. Often the color and hardness of the hydrated form of the crystal and
the anhydrous (water-free) form are strikingly different. A practical use for the
hydration phenomenon is the setting of plaster of Paris CaSO4 H2O. When mixed
with water, it slowly turns into solid gypsum.
How to Measure the Water of Hydration
You will do the reverse of the reaction just described in the plaster of Paris example.
You will take a hydrate and heat it until it is anhydrous.

MSO4 x H2 O MSO4 + x H2 O
1. Heat a small crucible (not a filter crucible) for about 2 min on a clay triangle to dry it
thoroughly. When it is cool, determine the precise weight of the crucible and cover.
to handle the hot crucible.
Use crucible tongs
2. Record the sample unknown number immediately upon obtaining the sample.
Weigh the sealed vial, transfer between 0.5000 and 2.0000g of mineral to the crucible,
and reweigh the vial to find the exact weight transferred.
3. Place the crucible on the triangle, and put on the top, so that it does not completely
cover the crucible but sits jauntily like a beret. Heat gently at first, and keep the flame
moving to avoid hot spots. Increase the heat moderately but do not permit the crucible to
become red hot. Overheating may cause the salt to decompose. Using tongs,
occasionally remove the cover to see if the dehydration appears to be complete.
Observe any change in the appearance of the powder caused by the loss of the water
molecules. When the dehydration is complete (15 min), continue to heat for another
five min.
4. Check your desiccator. This is a device to keep objects free from atmospheric
moisture, and depends on a chemical drying agent, CaCl2. Is the CaCl2 drying agent
caked or moist? If so, it should be replaced. If the seal is not tight, a little grease will
help.

22

5. Allow the crucible and contents to cool in the desiccator to prevent stray moisture
from being picked up. Weigh the sample accurately when cool, then reheat for 10 min
and see if a further decrease in weight occurs.
6. Repeat until the weight is the same, within uncertainty limits. Then you may be
certain that all the moisture has been driven off. This procedure is called drying to
constant weight. Remember that objects seem lighter when they are hot because of air
currents near the balance pan. Be sure to wipe off any stray drying agent clinging to
the outside of the crucible before weighing.
Strictly speaking, we have not shown that the only chemical change is loss of water.
This might be hard to prove. One could condense the water vapor and show that the
weight of water is equal to the loss of sample weight. Or, one could show that if water
is added to the anhydrous salt, the product is chemically identical to the original
mineral.
How to Do the Calculations for This Part
The calculations in this section exactly parallel the coal example in mathematical
operations section. Make a table showing the net weight of wet mineral and of dry
mineral, the net weight loss, and the grams of H2O per gram of mineral (Gwater), and the
moles of water per gram of mineral (Mwater). These values are calculated by

Gwater =

wt. water
wt. sample

M water =

moles water
Gwater
=
wt. sample 18.015 g/mol

where wt. water is the weight lost by the sample, and wt. sample is the weight of the
wet mineral sample at the start of the analysis. The value for the molecular weight of
water is 18.015 g/mol.

Show all the worst cases, and compute the range in the final number Gwater and Mwater.
Only the net weight of water lost and wet mineral sample have errors associated with
them.
Part C: Sulfate Analysis
We need to know how many grams of each gram of mineral are sulfate. Clearly, it is
not possible to separate the SO42- ion and weigh it.
In this situation, chemists use a technique called gravimetric analysis. One forms an
insoluble compound with the ion in question and collects the precipitate from the
solution. Your analysis will exploit the fact that BaSO4 precipitates out until virtually
all the sulfate ion has been removed from the solution. Then it is a simple matter to
filter out the solid BaSO4 and weigh it. The number of moles of BaSO4 formed will
equal the number of moles of SO4 2- present. The balanced equation is shown below.

23

Ba 2+ (aq) + 2 Cl - (aq) + M2+ (aq) + SO24 - (aq) BaSO4 (s) + M2+ (aq) + 2 Cl - (aq)

Note that the BaCl2 totally dissociates to the Ba2+ and Cl- ions, and no harm is done if an
excess of Ba2+ ions are added to the solution.
A gravimetric analysis can be made very accurate because the analytical balance if
potentially one of the most accurate instruments we have available. An accurate
weight of BaSO4 is all that is needed to calculate accurately the number of moles of
sulfate in the original mineral sample.
CAUTION:
Concentrated Hydrochloric Acid, HCl, is corrosive and must not be allowed to touch
the skin, eyes or clothes. Clean up any spills, and rinse skin with water. Inform
your TA of any spills.
How to Do the Sulfate Analysis
1. Weigh the original sealed vial containing your original mineral sample. Transfer
about 0.2000 to 0.5000 g to a clean but not necessarily dry 250 mL beaker. Reseal the
vial and reweigh to find the amount of sample transferred. (If you go modestly over
0.7 g, you can still save the experiment by adding proportionately extra BaCl2 . More
than 0.7 g will yield so much product that filtering will be very slow. Clean out the
beaker and begin again.) If your sulfate mineral is only marginally soluble in water,
you may find that even 0.2 g is too much and that you need much smaller samples.
2. To the beaker add 100 mL of deionized water and 3 - 5 drops of concentrated HCl.
Bring to the boiling point, then using beaker tongs remove the burner so that the liquid
stops boiling. Obtain 10 mL of BaCl2 solution in your graduated cylinder. Once all of
your compound has dissolved, add a drop of 0.5 M BaCl2 solution, and swirl. Then add
the remaining 10 mL of BaCl2 solution. This method creates larger and more easily
filterable crystals of BaSO4. Cover the beaker with a watch glass and boil gently for at
least 5 min. Then let the beaker stand for a few minutes. The boiling process enables
the small crystals of BaSO4 to dissolve and larger ones to form, a process called
digestion.
3. While you are waiting for the digestion process to take place, examine a filter
crucible. Check to see if they have cracks in the fritted bottom by holding them up to
the light. If it is necessary to clean them, put them in the oven to dry for 1 hr afterward.
Do not weigh with a wet frit! Weigh a clean, dry filter crucibles. When the digestion
process is completed, filter the suspensions of BaSO4 through the crucible. Your
teaching assistant will demonstrate the best method. Speed up the filtration by
allowing the solid to settle and pouring the supernatant liquid through the filter first
(see figure below).

24

Figure 3.1 Final Transfer of BaSO4 to Filter Crucible

Use a rubber policeman to scrub the inside of the beaker, and use the jet of water from a
wash bottle to direct the solid into the crucible. You must transfer ALL of the solid to
the filter crucible, and if any is spilled, discard the sample. Run about 5 mL of water
through the filter, crucible to "wash" the sample, that is, to remove any ions clinging to
the solid. Your teaching assistant will show you how to use the aspirator to dry the
crucible. Put your crucible in a 100 mL beaker, and give your teaching assistant the
beaker with a scrap of paper inside that has your name on it. The sample will be oven
dried to eliminate the last traces of water. Then you will weigh the crucible (when cool)
to determine the weight of BaSO4 .
One can do a gravimetric analysis only when no interfering ions are present. In this
precipitation, acid (HCl) is added to destroy any carbonate ion (by converting it to
carbon dioxide (CO2), which will bubble off) and any hydroxide ion (by converting it to
water). Both barium hydroxide (Ba(OH)2) and barium carbonate (BaCO3) are insoluble
in water and would be collected on the filter with the BaSO4 desired. Thus, hydroxide
and carbonate are "interfering" ions for this analysis. The interfering ions are different
for each type of precipitation. Systematic errors result whenever the reagent
precipitating the ion you wish to measure precipitates stray ions as well.
How to Do the Calculations for this Part
The calculation relies on the known relationship between the weight of BaSO4 and the
amount of sulfate in the sample. From the balanced equation, we see that the BaSO4
and SO42- have a stoichiometric ratio of 1:1.

25

1. Convert the weight of BaSO4 to the number of moles of BaSO4 by using the molecular
weight (233.4 g/mol). Then note that the number of grams of SO42- in this material is
the number of moles of BaSO4 multiplied by 96.06 g/mol. This is also the number of
grams of SO42- in the original mineral sample. Divide the weight of SO42- by the weight
of sample used in this part of the analysis to get the fraction of sulfate, Gsulfate.

" wt. BaSO %" 96.06 g/mol %


4
Gsulfate = $
'$
'
wt.
sample
#
&# 233.4 g/mol &
2. Calculate the moles of sulfate per gram of mineral, Msulfate , by dividing Gsulfate by the
molecular weight of SO42-.

moles sulfate
Gsulfate
Msulfate =
=
wt. sample
96.06 g/mol
3. Calculate the upper and lower limits for the values of Gsulfate and Msulfate. Only the net
weight of BaSO4 and mineral sample have errors associated with them.

Part D: Analysis of Metal Ion


This section of the experiment requires a NaOH solution of a precisely known
concentration. You will use your solution prepared in Experiment 2: Preparation of a
Standard Sodium Hydroxide Solution. Complete that experiment first!
The Problem in Brief
You need to know how much of the mineral is metal ion. This isn't easy because all the
elements are different. If you don't know what the element is, how can you choose a
method-one that would work for any of them?
The answer is ion exchange. Instead of analyzing the metal ion directly, we will
"exchange" the metal ions for H+ ions, which we do know how to analyze. An ion
exchange resin has the remarkable property of exchanging any ion for an H+ on a
charge equivalent basis.
How "Ion Exchange" Works
Ion exchange is a process in which ions of the same type of charge (positive or negative)
are traded (exchanged) between a solution and an insoluble solid. Clays are among the
common solids that show this property, which is important for the retention of plant
nutrients like potassium. Chemists have improved on nature by creating ion-exchange
"plastics" or resins; these resins are porous and" have a large" capacity for holding ions.

26

There are two types of resins. Cation exchange resins are materials that contain many
SOOH or COOH groups that can exchange the cation H+ for other positive ions.
Anion exchange resins have groups such as -N(CH)3+OH- or -N(CH3)+Cl- that exchange
OH- or Cl- anions for other negative ions. Each location where exchange can occur is
called an exchange site. One long chain molecule may have many exchange sites.
When one ion is exchanged for another, electrical neutrality must be preserved. Ion
exchange resins work by substituting one type of cation (anion) for an electrically
equivalent quantity of another cation (anion). For example, if a table salt (NaCl)
solution is passed through a cation exchange column, HCl emerges from the column
since the Na+ ions are replaced by H+ ions. Conversely, NaOH emerges if NaCl is
passed through an anion exchange column because OH ions replace the Cl- anions.
(Water is "deionized" by passing it first through a cation exchange column and then
through an anion exchange column. The first converts NaCl to HCl and the second
changes HCl into HOH, water.)
Figure 3.2 Ion Exchange Column

SO3 H
SO3 H

SO3 H
+ H+

+ M2+

SO3 M+

before exchange

after exchange

Since the reaction of ion exchange is reversible, it is possible to "recharge" an exchange


column that has exhausted its supply of exchange ions by treating the resin with a more
concentrated solution of H+ (or OH-) ions in the reverse process. These cations are
exchanged for Na+ (or Cl-) ions on the column.
Ion exchange columns are used
1. To produce ultrapure deionized water for laboratory use and to desalt sea water.
2. To convert the salt of an acid (base) into the corresponding acid (base). The
concentration of the original salt solution can then be accurately determined by
titrating the acid (base).
3. To convert one salt into another, for example, to exchange K + for Na+, a process
often important in making pharmaceuticals.

27

CAUTION:
Sodium Hydroxide, NaOH, and Hydrochloric Acid, HCl, are corrosive and must not
be allowed to touch the skin, eyes or clothes. Clean up any spills, and rinse skin
with water. Inform your TA of any spills.
How to Run the Ion exchange on the Mineral
You will be loaned an ion-exchange column containing resin. Throughout this
experiment the column must not be allowed to run dry, because this creates channels
through which solution can run without being exposed to the resin.
The ion-exchange column should be filled with H+, although it is best to convert it
again, in case the previous user has been sloppy. Check to see that there are no air
bubbles in the resin before beginning. Drain the liquid until it is within 0.5 cm of the
top of the column. Add about 15 mL of 3M HCl to the column, and then allow it to
drain slowly. Continue to add HCl to the column until 100 mL have passed through it.
Then wash the resin with at least 100 mL of deionized water. After the rinsing, collect a
drop of the water emerging from the column (the eluate.) This drop should become
only faintly cloudy when a drop of silver nitrate solution is added. We have now filled
all of the exchange sites on the resin with H+ and removed all excess acid.
Weigh the vial containing the mineral and transfer a new sample of not more than 0.3 g
to a clean, but not necessarily dry, beaker. Reweigh the vial to find the exact amount of
mineral that was transferred. Add about 40 mL of water to the mineral, and add all of
the resulting solution to the column. Collect the eluate in a clean conical flask. Rinse
the beaker with a wash bottle and add the rinsing to the column. Also run 100 mL of
distilled water through the column, and collect in the same conical flask. Run all
substances through the column slowly. (How slow is slow? You should be able to count
the drops.) Keep the eluate in a conical flask, and store until you are ready to titrate. (If
you need to run a second sample through the column, separately collecting the eluates.
It is not necessary to regenerate the column between samples.)
How to Analyze the Eluate
The eluate now contains as many H+ as there were positive charges in the mineral
sample. According to the equation below
NaOH (aq) + H+ (aq) H2 O (aq) + Na + (aq)

each mole of NaOH will react with exactly 1 mol of H+. Because each mole of doublepositive metal ions in the mineral will produce two moles of H+ ions, we can easily
moles of metal ions from the number of moles of NaOH consumed.
calculate the
You have already determined the concentration of your NaOH solution by allowing it
to react with a known weight of KHP. Titrate the eluate with this standardized
solution of NaOH.
28

If you overshoot the end point, all is not lost! Add a known amount of solid KHP, and
then titrate carefully to the end point. The bookkeeping may be a bit more difficult, but
it sure beats starting over!
Doing Calculations and Uncertainty Analysis
The calculation here is not mysterious. It is really very similar to the calculations done
in the standardization of NaOH.
1. You should have computed the concentration of your NaOH solution and its upper
and lower limits when you were standardizing the solution.
2. Compute the moles of H+ in the eluate sample from the moles of NaOH required for
neutralization. Remember to correct for any back titration. Compute the number of
moles of metal ion in the sample you used; remember that the ion exchange column
releases two H+ ions for each M2+ ion exchanged. Then calculate Mmetal the number of
moles of metal ion per gram of mineral.

M metal =

1/2 (MolarityNaOH vol. NaOH)


moles M2+
=
wt. mineral
wt. mineral

3. Compute upper and lower limits for the number of moles of metal ion in your
sample by following the same procedure as that in Step 2. The upper limit of Mmetal will
be theupper limit of the number of moles of metal ion divided by the lower limit of the
weight of mineral sample used. With this hint, you should also be able to work out the
lower limit.
For the Report
Now you are ready to work out the formula of the mineral.
1. To obtain the formula, compute the following, if you have not already done so.
Mwater = the number of moles of water per gram of mineral
Msulfate = the number of moles of sulfate per gram of mineral
Mmetal = the number of moles of dipositive metal ion per gram of mineral*-+.
Make a table containing the upper and lower limits for all your M and G values.
2. Charge Balance: The correct formula must have an equal number of positive and
negative charges. If the experiment has been carried out correctly, the limits for Msulfate
and Mmetal should overlap. Choose one best value, since it is clear that Msulfate must
equal Mmetal by charge balance.

29

3. Water of Crytalization: To calculate the number of Waters of Crystallization (WC)


divide Mwater by your best value of Msulfate or Mmetal. You also need to calculate the upper
and lower limits for this value.
4. If we use Gmetal to denote the number of grams of metal ion per gram of mineral, then
it is true that

Gmetal = 1 - Gsulfate - Gwater


where Gsulfate and Gwater stand for the number of grams of sulfate per gram of mineral
and the number of grams of water per gram of mineral, respectively. Compute Gmetal

and the upper and lower


limits of Gmetal .
5. The molecular weight of the metal ion will be simply
MWmetal =

Gmetal
M metal

What are the upper and lower limits of the molecular weight of the metal ion?

For your discussion


1. Are your results consistent with each other? For example, do you have charge
balance? If not, explain why not. Discard runs where blunders have been made, but
explain in the discussion why the run is being discarded. You may have to choose the
better value of Mmetal or Msulfate and set the other one equal to it. If so, explain which is
the better value and why.
2. If your results support one of the formulas in the Table 3.1 , state which one, and
also state any that can't be ruled out. Note that mineral samples can often be mixtures
of the same material with different amounts of water of hydration (a mixture of
mirabilite and thenardite, for example, is a reasonable result.)
3. If your results do not support the choice of a mineral below, you should report the
formula of the mineral and the apparent atomic weight of its M2+ ion. Note that the ion
may not really be M2+. If it is M3+, your atomic weight will appear to be only two-thirds
of the true value. If it is M+, then your atomic weight is twice the true value.
4. A student taking this course finds that Msulfate is larger than Mmetal. It is known that
the value of Mmetal is the correct one. What might have happened to produce this
discrepancy?
This is a long report, but when you have finished it, you will understand uncertainty
analysis, which is a useful tool for planning any scientific experiment.

30

Table 3.1 Some Common Sulfate Minerals


Mineral
Simple Sulfates
epsomite
bexahydrite
leonardite
mirabiJite
rhenardite
Double Sulfates
leonite
schonite
loweite
kalinite

Apparent Atomic
Weight of M2+ (g/mol)

MgSO47 H2O (M2+ = Mg2+)


MgSO46 H2O
MgSO44 H2O
Na2SO410 H2O (M2+ = 2Na+)
Na2SO4

24.31
24.31
24.31
45.96
45.96

K2Mg(SO4)24 H2O
K2Mg(SO4)26 H2O
Na2Mg(SO4)22 H2O
KAl(SO4)212 H2O

51.28
51.28
35.13
33.04

31

Experiment 4 Determination of an Equilibrium Constant


In this experiment you will measure the value of an equilibrium constant and its
dependence on temperature. The reaction chosen is that of the dye xylenol orange with
Al3+ ions. The dye structure is shown in Figure 4.1 below. It is an interesting molecule
because it can undergo acid-base reactions and combine to form complexes with metal
ions.
Figure 4.1 The Structure of Xylenol Orange
CH2COOH

CH2COOH

H3C

HO

CH2COOH

H2C

CH2

HOOCH2C
C

CH

HC

C
C
H

C
H

C
HC

HC

CH3

SO3H

CH
C
H

In this structural formula, only one of the many possible resonance forms is shown.
The " systems of all three rings overlap to form a continuous delocalized system, and
the electrons can migrate allover this network. This gives rise to unoccupied low-lying
electronic states and to the absorption of visible light. The compound can also undergo
significant rearrangements in acidic or basic media. (It has structural elements similar
to those of phenophthalein.)
The protons of the four -COOH groups are easily lost, and so we will think of xylenol
orange as a tetraprotic acid and abbreviate it H4Q.
What is the reaction you will Study?
H4Q (aq) + Al3+ (aq)

QAl (aq) + 4 H+ (aq)

Because the only colored species in this reaction are the QAl complex and the H4Q, you
should be able to follow the reaction by monitoring one of them. You will do this by
measuring the intensity of the color of the QAl complex.
32

The intensity of color is related to the concentration by Beer's Law. This relationship
and the use of the Spectronic 20, which is the instrument used in this experiment, are
discussed in the first section of Instrumentation.
Measuring the Equilibrium Constant
To measure the equilibrium for the above reaction we need to be able to determine the
concentration of the QAl molecule. Luckily, the H4Q is not the same color as the QAl,
so we will make our observations at a wavelength of 550 nm, which is close to the
maximum absorbance of the QAl molecule. Nevertheless, there will be some
absorbance due to the unreacted xylenol orange, and a "blank" or control must be used
to overcome this.
1. Clean three test tubes of 1 cm diameter. Pipette exactly 2.0 mL of xylenol orange into
each. The easiest way to provide suction for the small pipet required is to use a syringe
and to connect it with a small section of rubber tubing. After the xylenol orange, pipet
exactly 2.0 mL of Al3+ into the three test tubes. One of these test tubes will remain at
room temperature, at which no reaction takes place, and will be a control. The other
two test tubes will be heated in a water bath.
2. Add about 150 mL of water to a 250 mL beaker, immerse two of the test tubes, and
bring the water to the boil. Continue to boil the water for at least 5 min to allow the
equilibrium to be established. Then use tongs to remove one of the test tubes and place
it in an ice bath. Using the tongs, place the second test tube in a test tube rack. Use the
beaker tongs to pour off the hot water into a thermocup (put one Styrofoam cup inside
another). Still using tongs, transfer the test tube from the rack to the thermocup, which
will slow the cooling process. Use a thermometer to measure the water temperature.
When the water cools to about 90 85 C, make the first measurement. Then repeat
every 5C or so, until the sample reaches 50C.
3. To make a measurement, put your control test tube of xylenol orange into the
Spectronic 20 and adjust for 100% transmittance. Pull out the test tube in the hot water
bath, noting the temperature. Wipe it dry with a paper towel, and put it into the
Spectronic 20 sample holder. Read the % transmittance of the mixture, and then replace the test tube into the water bath. Be careful not to bum yourself or to spill the
solution into the Spectronic 20. Perform this operation quickly to avoid the solution
cooling while in the Spectronic 20.
At the end of the experiment you should have a series of measurements of the %
transmittance for at least six temperatures. You can repeat the experiment any number
of times by reheating the contents of the tube to 100 C, waiting 5 min, and letting the
tube cool slowly. Be sure to record the concentrations of the solutions used and all the
other label information.
4. The last and, in many ways, the most interesting experiment measure the %
transmittance of the test tube that has cooled in the ice bath.

33

For the Report


1. Convert your % transmittance numbers to absorbances by using the usual formula,

" % transmittance %
A = log10 $
'
#
&
100
The equilibrium concentrations of QAl are computed from Beer's Law:
=
The extinction coefficient, , is 25,000 L/mol cm for this compound (a very intense
color, comparable to that of permanganate). Take the path length as 0.9 cm.
2. The concentration of H+ is from the pH marked on the container and will be virtually
unchanged throughout the reaction.
3. The concentration of the other two species can be obtained by means of
stoichiometry:

!"Al3+ #$ = !"Al3+ #$
!"QAl- #$
and [ H 4Q ]equil = [ H 4Q ]initial !"QAl- #$
equil
initial
equil
equil
Remember that the initial concentrations are referring to the starting reagent
concentrations in the test tubes. These concentrations are half those marked on the
bottles because of dilution.
3. From these equilibrium concentrations, compute the equilibrium constant (K) at each
temperature.
4

!"QAl- #$!"H + #$
K=
[ H 4Q]!"Al3+ #$

4. The fact that the equilibrium constant depends on temperature is useful, because it
allows you to measure values of G, H, and S for the reaction. You can easily
obtain the equilibrium constant from the concentrations. You know that
G = RT ln K

Therefore you can calculate a value of G at any temperature if the equilibrium


constant K is known.
It is also true that
G = H - TS

34

If these two equations are combined, we obtain


-RT lnK = H - TS
This equation can be rearranged very slightly to yield

ln K =

H # 1 & S
% (
R $T' R

which has the form of a straight line:


y = mx + b
where m is the slope and b is the intercept. Hence, if one plots lnK on the y axis
versus 1/T on the x axis, the slope of the resulting straight line will be -H/R
and its intercept will be S/R.
Note that R = 8.313 J/mol-deg and that T must be in Kelvins (celsius + 273.15.) This
argument does assume that H and S are independent of temperature over the
small range of measurement. For extended discussions of the meaning of G and H,
refer to your textbook.
5. Plot ln K on the y axis, and the reciprocal temperature (1/T) on the x axis, and
remember to report the temperature in Kelvins. Draw the best straight line through the
points. Sometimes there is a slight curvature at the ends of the line. The middle few
points are usually the most reliable ones.
6. Calculate H, and S from the slopes and y intercept of the line. Note that the units
must work out, if you take ln K to be dimensionless.
Discussion Questions
In the discussion part of your lab report, consider the following questions:
a. Compute the equilibrium constant of the tube that has been quickly cooled. Which
of the equilibrium constants measured in Step 3 does this seem closest to, and what was
the corresponding temperature in Step 3. How do you account for the fact that this
temperature is much higher than that of ice water?
b. Is the sign of H correct? (Recall that the reaction seems to be displaced toward
QAl at high temperatures.)
c. What would you expect in regard to the sign of S. Did the experimental facts
support your idea? Do not worry if you predicted the opposite sign for S. The
reaction is not simply an ordering" by chelation. To accurately predict S, you would
need to know a great deal about the ordering or disordering of the solvent molecules as
well.

35

Practical Exam I: Percent Oxalate in an Unknown


The practical exam is viewed by most people as a challenge, and many claim to enjoy it
more than any other experiment. It provides an effective test of lab technique and skill.
Luck actually plays a very small role, and chance always favors the prepared mind.
Use your best technique, and demonstrate here that you are now at home in the world
of precise measurement.
Rules for the Practical Exam
1. You may not talk to one another, compare results, or share calculators. The exam is
"closed-book," unless otherwise announced, but you may bring your lab notebook, and
the report form.
2. The teaching assistant who is present is a time keeper and safety monitor and will
not answer questions about end points, which values to discard, or other such
decisions. You should make these judgments yourself. The teaching assistant may
help you if you have an equipment problem beyond what you might reasonably be
expected to cope with.
3. Eye protection and proper attire are required at all times. You will be asked to leave
the lab and therefore fail the exam if you do not wear them.
4. To obtain a sample, you must turn in a signed receipt. You will not be issued
another sample if the first one is damaged, lost, or destroyed.
5. Come on time. Once you start the exam, you may not come again on another day.
(Time is not normally a problem for most students taking this exam.)
6. No visitors will be admitted to the rooms where the exam is held.
7. Bring a calculator (one with working batteries). If you use your report form, you
will not be penalized for mathematical errors, but you are the person best qualified to
choose the best value.
An extra lab session is scheduled the previous week, so that you can make certain
solutions and do other essential chores. We suggest that on the day of the exam you
copy a set of explicit directions into your notebook. There will be no instructions on the
Whiteboard.

36

The Problem You are to Solve


You will be given a sample containing an unknown amount of oxalate (C2O42-.) You
will be expected to tell us the percentage of C2O42- very accurately by doing a titration
with the strong oxidizing agent KMnO4. The balanced equation for this reaction is

10 CO2 + 2 Mn2+ + 8 H2O

5 C2O42- + 2 MnO4 + 16 H+

This reaction can be used for titration only if the solution temperature is at least 70 C
to 90 C.
Because this exam was run as a contest for many years, the most common causes of
failure seem to be
1. Failing to understand the instructions.
2. Preparing solutions poorly, or "mistreating" them. This category breaks down into a
number of subproblems, such as not mixing the solutions thoroughly. The average
student seriously underestimates the shaking required to mix things in a volumetric
flask. The solutions must be absolutely uniform it is impossible to shake them too
much.
Contaminating the primary standard. This can happen by placing the solution in a
container that is wet on the inside, because the beads of water can cause significant
dilution. Primary standard solution should not be poured back from the buret into the
storage bottle (this practice is dangerous and introduces contamination or stray water).
Adding the primary standard to a buret or funnel containing stray beads of water can
also introduce contamination.
3. Not allowing the primary standard solution to cool before diluting to the mark (the
H2SO4 solvent contracts as it cools).
Mixing up records. (This is inexcusable, but it keeps happening. Make sure it does not
happen to you.)
4. Making blunders in the use of, for example, the buret and the balance. The practical
exam is extremely efficient at finding people who, for example, do not know how to
read the balance correctly. If you have any lingering doubts, ask your teaching
assistant, even if you think you really ought to know.
Averaging good runs with those in which blunders occurred. Averaging does not
reduce systematic errors; it only means that good data are spoiled. Only average your
results if you are reasonably sure that no blunders occurred that could affect them. It is
far better to have one good standardization and one good titration of the unknown than
to have three poor runs.

37

Preparing the Solutions


CAUTION: This experiment involves two dangerous chemicals. One is potassium
permanganate, KMnO4, which oxidizes any organic matter it comes in contact with papers, clothes, and skin. If you spill any on your skin, wash it off with large
amounts of water. Permanganate stains of glassware can be removed with a dilute
sodium bisulfate solution, NaHSO3 .
Also, you will be using 3M sulfuric acid. This attack skin and clothes. If any acid is
spilled on your skin or clothes, wash immediately with generous amounts of water.
What you do today affects your results. Be sure to complete the following:
1. You should make up 400 mL of KMnO4 solution. Weigh out between 2.000 and
4.000 g of KMnO4. This can be done on a beam balance.
Dissolve the KMnO4 in a 600 mL beaker with 400 mL of H2O (this can be measured with
a graduated cylinder). Cover the beaker with a watch glass; warm it, but do not boil,
stirring occasionally. Allow the solution to cool until it is comfortable to handle, and
then cool it further by running cold water over the outside. Pour the KMnO4 solution
into a reagent bottle for storage. Solutions of KMnO4 deteriorate, and for precise work
the concentration must be determined on the day of use. Shake thoroughly for one full
minute before using.
2. Make up 250 mL of oxalate solution. Weigh out between 4.0000 and 5.0000 g of
sodium oxalate (be sure the weight is known exactly), into a 250 mL beaker. Dissolve
in about 100 mL of 3M of H2SO4 warming if necessary. With the aid of a funnel,
transfer all of the solution to a 250-mL volumetric flask. Rinse the beaker with 3M
H2SO4 and add the rinsings to the flask.
You may bring the flask to the mark with water as long as most of the solvent is 3M
H2SO4, because the acid is in great excess. Do not heat the volumetric flasks they are
fragile. If warming is necessary, use a stream of hot water. Before diluting to the mark,
let the solution cool. After diluting to the mark, mix by inverting the flask another 20
times. You cannot over mix.
Store this primary standard solution in a clean reagent bottle. Rinse the bottle with a
little of the solution it will contain before putting the bulk of the solution in. Repeat
this step until it is correct. The best technique in the world will not save you on the
exam if the primary standard concentration is not correct.
3. Do a dry run. Titrate 30 mL of the standard oxalate solution with KMnO4 solution in
a conical flask. The end point is the faintest of pinks, and it is important to do a run to
see the color before beginning the exam itself. Raise the temperature of the mixture
being titrated to 70C to 90C to speed the reaction, but do not let it boil lest some be
lost by spattering. If you put a thermometer into the mixture, be sure to rinse it into the
mixture being titrated. It is difficult to see the end point unless you titrate the oxalate

38

with the KMnO4. The reverse procedure does not work as well; compute the ratio of
volumes used.
SAVE BOTH SOLUTIONS FOR THE EXAM
4. On the day before the practical exam, reread the section of the book called How to
Be Successful in Lab so that you recall all of the special tricks of titration.
Doing the Oxalate Analysis
You will have 2 hrs. and 30 min to do this part.
1. Obtain a sample from the stockroom. A signed receipt is required.
2. Because it gradually deteriorates, the KMnO4 solution must be standardized on the
day it is to be used. Shake the solution vigorously for one full minute before beginning.
Standardize the solution against oxalate in the way described in Step 3 in Preparing the
Solution, above. Do not forget to heat the solution.
3. For the titration of the unknown, place about 1.0000 g of the unknown solid in a
conical flask, recording the exact weight. Weigh out one sample at a time, so that if too
much or too little KMnO4 is used, you can adjust the next sample size to be more
convenient. Dissolve the unknown in at least 25 mL of 3M H2SO4. You may wish to
heat it to speed up dissolution. Remember, the reaction occurs rapidly only when the
solution is hot, so you will have to heat until the temperature of the solution is 70C to
90C before titrating.
4. Ideally, you should do three standardizations and three titrations. The ratio of
KMnO4 to Na2C2O4 should not be drastically different from that on the dry run day.
Work with deliberate speed and do not waste time, but it is much preferred to obtain
one good pair of runs than three poor ones.
5. When "time" is called, stop work and complete the calculations on the report form.
You may choose the mean, the median, or the best value, or you may just guess. If your
answer for oxalate content is not between 10% and 40%, you have probably made a
mathematical error. Your grade will be based solely on how close your number is to
the correct value of the unknown. Give some thought to the choice of mean, median, or
best value.
6. Avoid the following errors:
a) Mixing up burets.
b) Forgetting to heat the solution (end point appears sluggish).
c) Forgetting to add H2SO4 where needed (end point brownish).
7. Before you leave, be sure to clean your work area, wiping up any spills. You will
dispose of the solutions during the Check-out period. Keep the sample vials until then.
39

INSTRUMENTATION: USING THE SPECTRONIC 20


The Bausch and Lomb Spectronic 20 (see Fig. 5.1) is the "workhorse" instrument for all
measurements involving light. It works in the wavelength region of 380 to 620 nm
without modification. To use this instrument, begin by locating the controls. To use
the Spectronic 20, follow these instructions:
1. Switch on the machine. Let it warm up for at least 10 min. You will need two
solutions, a blank, for correcting for the solvent, and the sample solution to be
measured.
2. Select the desired wavelength by using the wavelength control, the knob on
top of the instrument.
3. Set the percent transmittance (top scale on the meter) to zero, using the zero
control.
4. Place a cuvette (or test tube) filled with the appropriate blank in the sample
holder. Close the cover.
5. Use the 100 percent T control to set the needle to 100 percent transmittance.
This adjusts for the transmittance of the solvent, test tube, and so forth.
6. Remove the blank, and close the cover over the sample holder. The needle
should swing back to 0 percent transmittance. If it does not, repeat procedure all
over again.
Figure 5.1: A Spectronic 20

The instrument is now correctly calibrated, but for one particular wavelength only. To
take a reading, place a cuvette containing your sample in the sample holder, close the
cover, and record the transmittance after the needle has settled down. The cuvette
must be free of fingerprints, bubbles, and other dirt.
When you are using the Spectronic 20, keep the test tube or cuvette clean; avoid leaving
fingerprints on the bottom part where the light passes through. There should be no air
bubbles on the inside, and solutions with suspended material will result in odd
readings.
The cuvette is cylindrical and therefore acts as a lens, focusing the light to some extent.
The cuvette should therefore be lined up in the same way each time. There is a mark on

40

some cuvettes, which can be lined up with a line on the cell holder. If there is no mark,
make a small one at the top of the tube using a wax pencil.
The calibration with the blank must be redone at each new wavelength and should be
repeated every few minutes, even at the same wavelength, to compensate for any drift
in the electronics.
Remove the cells in order to fill them. Water and electricity do not mix!
How the Spectronic 20 Works
You will be measuring the amount of light absorbed at a chosen wavelength. The
Spectronic 20 is a typical absorption spectrophotometer, and it has the following basic
parts:
1. A source of light. For the Spectronic 20, this is a tungsten lamp. White light
comes out of the bulb, and lenses focus it into a narrow, parallel beam.
2. A monochromator. This is a device used to break up the light into several
wavelengths and to block off all but the wavelength of interest. In your
instrument, the light is broken up by a diffraction grating and sorted by an exit
slit, which stops all but one wavelength band.
3. A cell holder to hold a cuvette or sample test tube. In the Spectronic 20 there is an
occluder to prevent light from passing through if there is no sample in the holder.
4. A photocell or other device used to "see" the light and to give a numerical value to its
intensity. The phototube will measure all the light remaining after the sample
has done the absorbing.
All spectrophotometers have the same basic parts, but obviously different sources of
radiation and types of receptors are needed for different regions of the electromagnetic
spectrum. One of the reasons for taking time to understand the Spectronic 20 is that
once this instrument is understood, mastery of more complicated but basically similar
instruments is easy.
How the Spectronic 20 Controls Do Their Job
The wavelength controller adjusts the position of the diffraction grating so that different
colors of light are selected by the slit.
The zero control adjusts the electronics. With the sample compartment cover down and
no sample, this should be adjusted until the meter reads 0 for transmittance. This
control adjusts for the so-called dark current, the current transmitted by the photocell in
the dark.
The 100 percent T control, a knob on the right, controls the amount of light output. A
mechanical linkage is used to drive a wedge into the light beam. This should be
adjusted so that with a test tube full of solvent in the sample holder, the transmittance is

41

100 percent. This allows the operator to correct for any stray absorbance resulting from
the solvent.
COLOR AND SPECTROSCOPY
When various wavelengths of light enter the eye, we see different colors. The rainbow
is an illustration of a spectrum, in which white light is sorted into its various
component wavelengths, each of which appears as a different color. Such an effect can
also be produced by a prism or diffraction grating.
The range of wavelengths visible as colors for humans is about 700 nm (nanometers,
where 1 nm = 10-9 m) to about 380 nm. It is interesting that some animals can see colors
in the wavelength region beyond violet (ultraviolet) or in the region beyond the red end
of the spectrum (infrared). Humans have to rely on sophisticated instruments to make
observations in these regions of the electromagnetic spectrum.
The color of light transmitted by a solution or reflected by a surface is the light that
remains after some colors have been preferentially absorbed. Chemists are interested in
the region at which light is absorbed, because this can supply information about the
structure of the molecule.
We therefore need to know what wavelength is absorbed most preferentially and also
the intensity of the absorption. The wavelength of absorption is therefore related to the
energy of the light being absorbed by the molecule. Thus, the color of the absorbed
light provides direct information about the kind of molecular transition or the kind of
molecule doing the absorbing. The intensity of absorption is related partly to the type
of molecule, but it also depends on other variables. This section first looks at the color
alone.
The Relationship of Color and Wavelength
In deciding what color something is, you have to distinguish between objects that emit
light and objects that reflect (or transmit) light. A Bunsen burner flame is blue because
the combustion reaction products emit blue light. For such objects, the relationship
between color and wavelength is the same as for sunlight dispersed by a prism. The
solutions you will use are actually involved in the reverse process; instead of emitting
light of a certain wavelength, , they absorb light at wavelength, , and transmit the rest
of the light. So a solution of CuSO4 held up to a light appears blue because the Cu2+ ion
absorbs yellow light and transmits the blue light, which is not absorbed. To figure out
what color light is absorbed if you know what color is transmitted (complementary
colors) use Table 5.1.
The experiment you will do uses solutions that absorb light rather than emit light. The
of the absorbed light is the wavelength of interest to chemists, because it can provide
clues about molecular structure.

42

Our instrument, the Spectronic 20, is calibrated in nanometers (nm), which are
wavelength units. However, the wavelength may also be expressed in Angstrom units
(), which are equal to 10-10 m. Also, infrared workers frequently use cm1 (the
reciprocal of wavelength). This latter unit can be thought of as wave crests per cm and is
really an energy unit.
TABLE 5.1: Relationship Between the Color Seen and the Wavelength of Light
Absorbed Light Absorbed Color You See
Light Absorbed
Wavelength (nm)
400-440
440-480
480-490
490-500
500-560
560-580
580-600
600-610
610-750

Color
violet
blue
green-blue
blue-green
green
yellow-green
yellow
orange
red

Color You See


green-yellow
yellow
orange
red
purple
violet
blue
green-blue
blue-green

The Intensity of Absorption


The intensity of the color will depend on the following variables: (1) the kind of
molecule doing the absorbing, (2) the concentration, and (3) the path length that the
light passes through. To make the idea about color intensity more concrete, you can
define a quantity related to these three variables and call it absorbance A.
! = !"#
This equation says that absorbance is proportional to path length l (if you double the
length of the path of light, you double the opportunities for it to be absorbed) and
proportional to concentration c (doubling the concentration creates twice as many
absorbing centers). To make the units work and to adjust for the type of substance
doing the absorbing, use , the extinction coefficient. The relationship is known as the
Beer-Lambert Law or Beer's Law.
This relationship can be used in many ways. If you know the absorbance for a given
concentration of a substance (at a given wavelength), then the absorbance of an
unknown solution can provide you with the concentration of the unknown, if you are
careful to use the same cell and wavelength.
If you know the absorbance, the path length, and the concentration of a substance, it is
easy to compute the extinction coefficient, and this can provide important clues to the
molecular structures involved in the transition. The extinction coefficient depends, of
course, on the wavelength, but otherwise it is a property of the molecule involved.

43

If the concentration is in stated moles per liter and the path length is in centimeters, the
extinction coefficient will be in liters per mole-centimeter.
The Units of Color Intensity
The meter or chart recorder supplies the intensity of absorption at a given wavelength.
It is calibrated in either or both of the two following ways:
1. Transmittance. This is the fraction of the initial number of photons that pass
through the sample without being absorbed. (Sometimes the transmittance is
expressed as a percentage.)
2. Absorbance. This is the negative logarithm of the transmittance (expressing the
latter as a fraction). It is unitless. Absorbance and optical density (OD) as the
biochemists call it) are the same thing.
The relationship between absorbance A and transmittance T is
A = -log10 T
where T is expressed as a fraction. The following example makes this clearer:
EXAMPLE: A student records a transmittance of 30 percent. What will be the
transmittance if the concentration of the solution is doubled?
Solution: Express 30 percent as a fraction, or 0.30, and compute the corresponding
absorbance,
A = -log(0.30) = 0.52
If the concentration is doubled, the absorbance is doubled (from Beer's' Law). Hence,
the new solution will have an absorbance of 1.04, and a transmittance of 9 percent.

44

Mathematical Operations
This part is largely concerned with uncertainty calculations. You will need to master
the first section to complete most of the lab reports, but the second and third sections
may well be assigned by your professor to deepen your understanding of this topic and
its applications.
If you have had to struggle with uncertainty in a previous lab course, fear not. The
method presented here is a lot simpler, and it works well enough for most student lab
work (and for a good deal of real scientific work as well.) Students who had trouble
with traditional methods can easily cope with uncertainty when it is presented in this
new way, so take heart!
A. CALCULATING UNCERTAINTY BY THE WORST CASE METHOD
There are two sorts of problems with measurements. The first kind is that of systematic
error, the situation in which one is measuring not quite what one supposes, because of,
for example, defects in instruments or technique. Such systematic errors can be
controlled only by improving the design of experiments.
This section discusses the other sort of ambiguity in data, the intrinsic uncertainty due to
the limitations of the instruments. It is assumed here that the desired quantity is in fact
being measured. However, the question is asked: how reproducible would the
measurement be if it were repeated in the same way many times? This reproducibility
or precision is of major importance in planning experiments.
Systematic errors and uncertainties differ in one crucial way. There is no way that
systematic errors can average out. If, for example, a sample from a gravimetric
experiment is not sufficiently dried before weighing, the student can weigh it one
hundred times and the problem will not be cured. However, if a sample is correctly
prepared, more weighings averaged will produce a result of greater precision.
A beginning student has far too much faith in averaging. If the measurements being
averaged contain repetitions of the same systematic errors, the result cannot be purified
by running it through the calculator!
Many classic textbooks draw a distinction between precision (the degree of clustering)
and accuracy (the absence of systematic error). Look at Fig. 6.1 showing a bear target
being shot by a marksman.

45

FIGURE 6.1: The Difference Between Precision and Accuracy

On the average the bear is dead


(accuracy, no precision)

(Precision, no accuracy) You can


average, but it does not help

Computing Uncertainties
Every measurement is uncertain in that it probably cannot be exactly reproduced a
second time. Uncertainty is a technical term for the reproducibility of the measurement.
If, for example, you weigh a copper penny on a balance five times, you will probably
observe some variation in the last decimal place. Such a sequence of results might be
3.0110 g, 3.0114 g, 3.0120 g, 3.0111 g, and 3.0115 g. The average value is about 3.0115 g,
but the range of values is at least 0.0005 g from that value. The number 0.0005 is
called the absolute uncertainty of the measurement. Clearly, the real value (whatever
that is) is somewhere between 3.0110 g and 3.0120 g. These two values are referred to
as worst cases or the upper and lower limits.
Similarly, for any other instrument there is a range of absolute uncertainty in a
measurement related to its observed reproducibility. Some are given below, for the
most common models of instruments in student labs.
buret
balance
360 thermometer

0.05 mL in any single reading.


0.0005 g in any single measurement.
half the difference between the smallest graduations.

The National Bureau of Standards (NBS) sets the following standards for absolute error
tolerable in Class A glassware (Tables 6.1 and 6.2):
When you are confronted with a new instrument and need uncertainty information, it
is sensible to try repeating the same measurement until some idea of the reproducibility
is evident. Then it is easy to choose reasonable values for worst cases. (There is, of
course, some judgment involved.)

46

TABLE 6.1: NBS Specifications for Volumetric Flasks


Capacity

Tolerance Common

Tolerance Class A

10 mL

0.04 mL

0.02 mL

50 mL

0.10 mL

0.05 mL

100 mL

0.16 m

0.08 mL

250 mL

0.24 mL

0.12 mL

500 mL

0.30 mL

0.15 mL

TABLE 6.2: NBS Specifications for Class A Pipettes


Capacity

Tolerance, Transfer

Tolerance, Measuring

1 mL

0.006 mL

0.01 mL

2 mL

0.006 mL

0.01 mL

5 mL

0.01m

0.02 mL

10 mL

0.02 mL

0.03 mL

25 mL

0.03 mL

0.05 mL

Combining Measurements and Computing Worst Cases


The difficult part of performing uncertainty calculations is in the combining of different
sorts of measurements to reach a conclusion. However, by writing down the upper and
lower limits of the individual measurements, it usually becomes clear how these can be
combined to provide worst cases for the results. To save time, remember the following
rules:
1. If the main calculation requires multiplying numbers together or adding
numbers together, multiply or add upper limits to find upper limits, and
multiply or add lower limits to obtain lower limits.
2. Always divide opposite limits. Put an upper limit over a lower limit to obtain
an upper limit. Place a lower limit on top and an upper limit on the bottom, and
the ratio will be the lower limit. If you think about ratios for a moment, you see
why this also is obvious. As long as you remember to combine the opposite
limits, things will work out fine, because it will be quite clear from the values
themselves which limit of the quotient is which.
3. Subtract opposite limits. Again, if you remember to combine opposite limits, it
will be quite clear which limit of the difference is which.

47

4. A corollary: If subtracting two measurements on the same instrument to


obtain a net weight, or net volume, the absolute uncertainty in the net value will
be twice the absolute uncertainty of the individual measurements.
An example shows this very easily: A student measures a value of 5.00 mL using a
buret accurate to 0.05 mL to deliver the volume. Two readings are taken: 4.92 mL
and 9.92 mL (Table 6.3). The volume delivered is 5.00 mL, but what is the range of
uncertainty
TABLE 6.3:

Lower Limit Volume Upper Limit


Final measurement
9.87
9.92
9.97
Initial measurement
4.87
4.92
4.97

Worst cases of the difference are as follows:


Upper Limit: 9.97 4.87 = 5.10 mL
Lower Limit: 9.87 4.97 = 4.90 mL
Hence, the net value delivered is 5.00 0.10 mL.
Some Worst Case Calculations
This section contains a few examples of uncertainty analysis in action.
Calculating Uncertainty in a Weighing Experiment
The energy content of coal, and therefore its price, depends on the water content.
Therefore, it is necessary to determine this content accurately. The coal is placed in a
crucible and heated in an oven so that the water is driven off. Let us assume that the
coal is about 10 percent water and we are using a 0.8000 g sample.
Step 1. Obtain the net weight of wet Coal.
Lower Limit Weight

Upper Limit

Weight of wet coal and crucible

20.7995g

20.8000g

20.8005g

Weight of crucible empty ("tare weight")

19.9995g

20.0000g

20.000g

Net weight of wet coal

0.7990g

0.8000g

0.8010 g

These upper and lower limits are calculated in exactly the same way as in the buret
example:
Upper limit: 20.8005 g 19.9995 g = 0.8010 g
Lower limit: 20.7995 g 20.0005 g = 0.7990 g
So the net weight of wet coal is 0.8000 0.0010 g.
48

Step 2. Obtain the weight loss of coal


Weight of wet coal and crucible 20.7995 g 20.8000 g 20.8005 g
Weight of dry coal and crucible 20.7195 g 20.7200 g 20.7215 g
0.0790 g 0.0800 g 0.0810 g
Weight loss
(or 0.0800 0.0010 g)
(again computed as above)
Step 3. Obtain the percentage of weight loss. The percentage of H2O in the coal
will
percentage =

weight loss
100
original weight

One worst case will


=

upper limit of weight loss


0.0810
100 =
100 = 10.14 %
lower limit of original weight
0.7990

The other worst case will be


=

lower limit of weight loss


0.0790
100 =
100 = 9.86 %
upper limit of original weight
0.8010

Hence, the true percentage of water lost lies between 10.14 percent and 9.86 percent.
This problem could be simplified by realizing that the "net" quantity rule (the corollary,
Rule 4) applies to Steps 1 and 2.
How to Calculate Uncertainty in a Concentration
A solution is made up in an l00 mL volumetric flask. The substance has a molecular
weight of 120.0 g/mol, and 2.6754 g are weighed out. What is the uncertainty in the
concentration?
Concentration =

2.6754 g
(0.10000 L)(120.0

g = 0.2229 !
)
mol

The weight is determined by weighing a vial containing the solid, then transferring the
solid quantitatively to the flask, and reweighing the vial. The absolute uncertainty in
each weighing is 0.0005 g. The weight is a net weight, so the absolute uncertainty of
the net weight is 0.0010 g (by Rule 4).

49

The flask is 100.00 mL nominally and has an absolute uncertainty of 0.08 mL (if it is
Class A). The volume limits, therefore, are 99.92 mL and 100.08 mL. Combining the
upper limit of weight with the lower limit of volume provides the upper limit of
concentration.
Upper limit =

Lower limit =

2.6764 g
(0.09992 L)(120.0
2.6744 g
(0.10008 L)(120.0

g = 0.2232 !
)
mol
g = 0.2227 !
)
mol

The last step of this example illustrates the division rule about division of worst cases.
Problems for You to Solve
1. Jo Superior is a student at a college where the balances are accurate only to 0.005 g.
Into a crucible that weighs 20.100 g empty, she puts some copper powder and reweighs
it, obtaining a reading of 21.100 g. An excess of sulfur is added, and then the mixture is
strongly heated under a hood. The excess sulfur vaporizes, leaving a nonvolatile
compound of copper and sulfur in the crucible. The weight of the crucible and
compound is 21.554 g. The atomic weight of copper is 63.54g/mol; atomic weight of
sulfur is 32.06 g/mol.
Compute the upper and lower limits for the ratio of moles of sulfur to moles of copper.
2. A titration of 0.2686 g of an unknown acid HX requires 23.06 mL of NaOH solution.
The concentration limits of the base solution are 0.0872 M and 0.0884 M. What are the
upper and lower limits for the molecular weight of the HX?
3. A l0 mL Class A pipette is used to deliver a sample of solution of unknown acid HX,
which is titrated with 23.06 mL of NaOH, the concentration of which can be taken as
exactly 0. 01000 M. What are the upper and lower limits for the concentration of the HX
solution?

50

B. A SHORT CUT IN UNCERTAINTY ANALYSIS


In the previous exercises, you have often found the need to calculate worst cases for
results obtained by multiplying and dividing measurements (with known worst cases)
and constants. This method tends to be laborious, and so the following short cut is
offered.
Calculating Relative Uncertainty
Relative uncertainty is defined as the ratio of the absolute uncertainty (defined in the
preceding section) to the quantity being measured.
absolute uncertainty
100
the measurment itself

This is usually expressed as a percentage (which explains the factor of 100). It tells you
what percentage of the measurement is uncertain. This is very useful, because although
absolute error may not be very meaningful it is obvious that a measurement having a 1
percent relative uncertainty is better than one having a 10 percent relative uncertainty.
!" =

Given the formula above, it is easy to compute relative uncertainty in any specific case.
Note that whereas the absolute uncertainty depends on the instrument, the relative
uncertainty depends on the size of a measurement. For example, if you weigh 1.0000 g
by difference, our absolute uncertainty will be 0.0010 g. This absolute uncertainty is
the same if you measure 0.1000 g. However, the relative uncertainty is different:
for 1.0 g !" =

0.0010 g
100 = 0.1 %
1.0000 g

for 0.1 g !" =

0.0010 g
100 = 1.0 %
0.1000 g

If the relative uncertainty is calculated correctly, it should be unitless. (The absolute


uncertainty and the measurement itself will always have the same units.)
Using a Short Cut
If you are computing Y, where Y is derived from measurements by multiplying or
dividing,
Y = kABCDE
and A, B, C,D,E are measurements and k is a constant, then it is approximately true that
RU of Y = sum of relative uncertainties of A through E.

51

Then, if you multiply Y itself by the relative uncertainty of Y, you obtain the absolute
uncertainty of Y and can construct worst case upper and lower limits. In summary,
then, to perform this trick do the following:
1. Convert absolute uncertainties to relative uncertainties for each of the
measurements, to be multiplied or divided.
2. Add all of the relative uncertainties.
3. Compute the absolute uncertainty of the result by multiplying the relative
uncertainty of the result by the result itself.
4. Construct worst case limits for the result.
Understanding Why This Short Cut is Useful
Not only does this short cut save time, it pinpoints the weakest link in the chain of
measurements being used to lead to a conclusion, because this one will have the highest
relative uncertainty.
The result you obtain may not be exactly identical to that from the worst case method,
but it will probably differ only slightly. Because absolute uncertainties are often just
estimates anyway, you do not need to worry.
Remember the limitation of this trick: All measurements must be related to the final
derived value by multiplication or division, or by multiplication or division by a
constant. This short cut does not work for addition or subtraction.
An Example Uncertainty in a Standardization
A student finds that 0.5089 g of potassium acid phthalate exactly neutralizes 23.06 mL
of a NaOH solution of unknown concentration.
Step 1. Calculate the concentration itself. The number of moles of potassium acid
phthalate used is
0.5089 g
= 2.492 10!! mol
204.22 g/mol
Since each mole of this substance reacts with the same number of moles of NaOH,
there must be 2.492 10-3 mol of NaOH in 23.06 mL of solution. So the
concentration will be
2.492 10!! mol
mol
= 0.1080
0.02306 L
L

52

Step 2. Compute relative uncertainties. The potassium acid phthalate was weighed by
difference; hence, the uncertainty in each weighing is 0.0005 g, and the total
absolute uncertainty is 0.0010 g. Thus, the relative uncertainty of the weight of
potassium acid phthalate is
0.0010 g
100 = 0.20%
0.5089 g
This is also the relative uncertainty of the number of moles of potassium acid
phthalate, and, therefore, of the number of moles of NaOH (since we assume that
there is no uncertainty in the molecular weights).
The volume of NaOH is measured by difference. Because the initial buret reading is
uncertain by 0.05 mL and the final reading by 0.05 mL, the total absolute
uncertainty is 0.10 mL. This gives the relative uncertainty on the volume as

0.10 mL
= 0.43 %
23.06 mL

Step 3. Add the relative uncertainties. The relative uncertainty of the NaOH
concentrations will be given by
RU of NaOH concentration = RU of NaOH mol + RU of NaOH vol
RU of NaOH concentration = 0.20% + 0.43% = 0.63%
Step 4. Convert the RU of the result back to an absolute uncertainty. The absolute
uncertainty will clearly be
0.63%
100

0.1080 ! = 0.0007!

Step 5. Construct worst case limits. Thus, the true value of the NaOH lies between
0.1073M and 0.1087 (0.1080 M 0.0007 M).

53

Reporting Lab Results


The point of writing a lab report is to summarize experimental results in a compact
form, to draw conclusions, and to communicate the results to others. Each project in
this course revolves around certain scientific questions. By writing the report, you are
using your data to answer these questions. In the process, you will gain a mastery of
the relevant theory and also learn some data reduction techniques of general scientific
applicability.
Reports need not be typed or elegant. But the information should be presented in a
clear and logical format. You are urged to layout your data and calculations in tabular
form, wherever possible, and graphs must follow the standard conventions of the
scientific journals. In general, however, you may exercise any amount of ingenuity that
you want.
All the projects in this manual have explicit instructions as to what needs to be
reported. Unless your instructor specifies differently, all reports must contain the
following general sections:
1. Title page with your name, your teaching assistant's name, the date, and your
unknown number (if applicable).
2. Purpose. In 50 words or less, state the molecular question that the lab is trying
to answer.
3. Procedure. Normally you can simply cite this manual, giving page numbers;
however, if changes were made-even by the instructor's direction you should
mention them.
4. Results. Layout your data in tabular form, and also show one sample for each
new calculation. You need only tabulate answers, if the same calculation is
repeated. The final results should be shown together with their worst case limits
or absolute uncertainties. The final results should also be stated to an
appropriate number of decimal places (that is, it is foolish to report a value as
8.147 if the real range is from 8.11 to 8.18). Units should be attached. This helps
keep you from making blunders in arithmetic.
5. Discussion. This should contain answers to the specific questions being asked
in the manual. Each project description contains a number of "leading questions"
to start your thinking about what to write in the discussion. Please limit yourself
to a few hundred words.
Using Scientific Notation and Significant Figures
It is useful to report numbers with scientific notation; that is, instead of 0.0203, report
2.03 10-2. Realize also that the number of places reported matters, that is, 2.030

54

implies precision to the last place, and 2.0 implies only that the number is between 1.9
and 2.1.
The digits in a number that are known with certainty, plus one more, are customarily
reported. These are known as significant figures. Thus, the number 2.03 10-2 implies
that the value is between 2.02 10-2 and 2.04 10-2 (if no uncertainty is explicitly stated).
Although there are formal systems for keeping track of significant figures, if you
understand what it means to be "significant," you will never fall into the trap of
reporting 8.6412 for a number that is somewhere between 8.63 and 8.65.
Units should be attached to all numbers that need them, especially final results.
How to Prepare Graphs
A number of lab reports require that you prepare graphs. Over the years, scientific
journals have developed rigid standards for graphs. Your work must conform to these
standards, so that you acquire good habits.
The standards are as follows:
1. The variable being measured (dependent variable) is on the y-axis (vertically).
The variable being adjusted by the experimenter (independent variable) is on the
x-axis. Axes should be labeled in capital letters, with the unit in small letters in
parentheses.
2. Points must be large enough to be seen, and different series of data may be
indicated only by shape and symbol, not by color. There must be a key, caption,
or title explaining what the graph means.
Do not connect the points with a line. Let the shape of the line reflect the underlying
relationship. A linear relationship calls for a straight line; curves may be appropriate if
the underlying relationship is more complicated. Computer generated graph are
acceptable and preferred.
How to Write the Discussion
Most students seem to breeze through the calculations but are stumped by the
discussion part of the lab report. This section contains a report of one experiment, and
a sample discussion, to provide an idea of the possibilities.
Reporting the Data and Calculations of a Sample Experiment
Students were asked to identify the metal in a cylindrical slug by measuring the volume
and weight, and computing the density. The following are the data of the world
famous A Student:

55

weight of slug = 17.0776 g 0.001 g


Volume measurements were done by dropping the slug into a buret partially filled with
H2O and noting the initial and final volume measurements. The volume is therefore a
"net" measurement recorded in the student's notebook as follows:
volume measurement of slug = 40.03 - 34.07 mL
net volume = 5.96 0.10 mL
The data are tabulated in the report in Table 7.1:
Table 7.1:
weight of slug
volume of slug
density of slug

Lower Limit Measurement Upper Limit


17.0771
17.0776
17.078/
5.86
5.96
6.06
2.82
2.86
2.97

Do not worry at this point about how the uncertainty limits are derived; this is
explained in the chapter on mathematical operations.
Discussing the Data of the Sample Experiment
The student's discussion, covering the above data, appears as follows:
The measured density was 2.86 g/mL with the "true" answer in the range of 2 .82 to
2.91 g/mL. This density is closer to that of aluminum (2.6989 g/mL) than to any other
metallic element. However, the density of the aluminum is outside the range of
uncertainty, and we therefore conclude that
1. The sample is not pure aluminum (possibly an alloy of aluminum with a denser
material?)
or
2. There may be an unnoticed systematic error in the measurement. Since the weight
measurement was made on an analytical balance, this could be wrong only if the balance
were improperly calibrated, a remote possibility.
The error, therefore, probably lies in the volume measurement if the hypothesis of
systematic error is correct. The volume would have to appear too small. This could
occur, for example, if the act of dropping the slug into the buret splashed water up onto
the sides, where beads would cling, and thus the rise in the water level would be less than
expected. This was not observed by the experimenter, and the buret was clean enough so
that such beads of water ran down immediately.
Given the extreme simplicity of the experiment, Hypothesis 1 seems more likely.

56

This discussion is a good one because


1. The writer does not jump to conclusions. Just because the value of the density is
close to aluminum does not make the plug aluminum!
2. The writer is not bothered by the fact that his or her results are not quite what was
expected. The discrepancy is simply patiently explained.
3. The writer is specific and does not appeal to vague arguments like "human error,"
"inadequate instruments," or "defective technique." The argument about splashing
proceeds in the proper direction. The writer shows why splashing might result in a
lower volume reading and why this would result in a density that is too high. The
writer argues intelligently about what is the most likely explanation of the findings.

57