A General Chemistry Lab Manual

The
Rediscovery
Book

CHM 202
Spring 2017
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

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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

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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 measuring the mass of solids. This
method has been chosen because it is especially foolproof. If you always use it you will
never have any trouble obtaining the mass of a solid 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 known 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 he 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

4
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.

The Laboratory Notebook - 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 notebook must be:

- Of the approved type, and have tear out copy pages.
- Data must be recorded in ink.
- It must be current and consecutive, and all your work must be in one place.
- Record everything that is relevant at the time you make the measurement.
- Take your notebook everywhere. Never write anything related to the
experiment on scrap paper, your hand, etc.
- Never, never tear out pages (except copy pages): 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. Remember, this information
must be recorded directly in your notebook. Even if it is transferred once, there is a
danger of, for example, digits being interchanged, so be sure to take your notebook
everywhere you go.

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. You may be tested on the facts you have observed. You
will be permitted to have your notebook for reference during the lab 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 tum 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.

5
A good notebook will state everything that was done, and what you observed during
the experiment. Good records will allow you or anyone to repeat the experiment.

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 be performed to answer this question?
3. What pitfalls exist? What variables are keep constant?
4. What hazards are involved?

You will be given detailed instructions as to what is to be done before lab. These should
be followed! 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 Your Notebook Before Coming to Lab

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.

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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 one forms. Let the solution cool and settle.

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. and shake 30 seconds.
Solid should form, redissolve. If solid 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.
Let solution cool, and solid settle. Remove liquid with disposable dropper, discard into "Hg
waste."
Add 2 to 4 mL of H2O. Heat to boil in H2O bath.
After solid settles, remove and 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.

7
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.

WORKING SAFELY

We have done our best to build safety into the design of the experiments and work
areas, but working in the lab still has risks. Your instructor will undoubtedly bring
safety rules to your attention. The ones listed below, which are universal, serve as a
starting 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. If you refuse to wear eye protection, you
cannot come to lab. It is that simple.

2. 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. 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.

3. 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.

4. 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!

5. Do not perform any unauthorized experiments. Ask permission first. The difference
between using potassium chlorate and chloride may be an explosion!

6. Report even trivial injuries to your teaching assistant or lab supervisor. What seems
minor can have major complications.

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7. 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.

8. 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!

9. Do not, as a rule, bring visitors into the laboratory. Ask permission before bringing
them, and see that they obey the roles. You can always talk in the hall.

10. 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.

9
Running a Reaction

To run a reaction, you will need to combine the chemicals (called reagents) and possibly
to mix 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 stones 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.

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.

10
 Figure 1

MEASURING MASS

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 measure the mass of a solid, you will be given a range of
mass values. Any mass in this range will work, as long as you know exact mass of the
solid transferred.

“Weighing by difference.” Put the solid in a vial, put the top on the vial (to keep out
moisture and dust), and take an initial reading, this is called the tare. Reset the tare to
zero, and 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. Remeasure the mass of the sealed vial. The negative reading on the
balance is the mass of the sample transferred. If the amount transferred is not sufficient,

11
transfer more to the beaker and remeasure the mass of the vial. If you have added too
much, clean out the beaker and start over. Do not transfer the solid back to the initial
vial lest you contaminate the entire sample. Alternately, you can record the initial and
final mass of the sample, and the difference between the two masses is the mass of the
sample transferred.

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).

12
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, notify
your TA or instructor.

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 a Volumetric Flask

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. Swirl the flask to thoroughly mix the solution after each addition
of rinsings. For good control, add the final drops of the liquid with a pipet, not a squirt
bottle. After filling up to the mark (a circular ring etched on the neck, insert the
stopper, and invert the flask to thoroughly mix the solution. 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).

Figure 2 A Volumetric Flask

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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.

An Interpretation of the Hieroglyphics on a Volumetric Flask

A
TC 250 mL ± 0.12 mL
20 °C
Pyrex® USA No. 5640

A volumetric flask is calibrated to contain a certain volume of solution at 20 °C when

the diluted to mark. 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 rinsed 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.

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).

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

14
 Figure 3 Buret Reading

Pipeting

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.

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.

15
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.

16
Experiment 5: Lewis Acids and Bases

In this experiment, you will make an iron compound, demonstrate a few of its
properties, and complete a semi-microanalysis. The experiment also illustrates some
neutralizations of Lewis acids and bases. General chemistry textbooks cover the basic
Lewis acid-base concept.

Essential Chemistry of Iron

Iron is a gray metal that oxidizes in air and is dissolved by strong acids, although the
rate of reaction is slow with concentrated HNO3. It has two common oxidation states,
Fe2+ (ferrous) and Fe3+ (ferric), and both ferrous and ferric salts are known. Even mildly
basic solutions will precipitate the hydroxides from solutions of the salts.

The conversion of Fe2+ to Fe3+ is easy, even in acid solution. Oxygen in the air can cause
the reaction. Hence, solutions of ferrous ion usually contain some ferric ion as well.
The ferric ion is a strong Lewis acid. The vacancies in the 3d, 4s, and 4p orbitals can be
used to receive donated electron pairs. A vast number of compounds of iron and
various Lewis bases are known, and some are of biological importance.

A. How to Prepare the Compound and Do the Preliminary Testing

To do the tests you will need to make at least a quarter of a gram of pure compound, by
allowing the strong Lewis acid FeCl3 to react with potassium oxalate. The oxalate ion is
a good Lewis base.

CAUTION:
Potassium permanganate, KMnO4, will oxidize any organic matter it comes in contact
with paper, clothes, and skin. If you spill any on your skin, wash it off with large
amounts of water. Permanganate stains on glassware can be removed with dilute
sodium bisulflte, NaHSO3.

You will also be using 3 M sulfuric acid. This will attack skin and clothes. If any
acid is spilled on your skin or clothes, wash immediately with generous amounts of
water.

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How to Prepare the Compound

1. Mix 6 g of potassium oxalate (K2C2O4) with 20 mL of water, and warm to dissolve the
substance. Then add 2 mL of 1.5 M FeCl3 solution to the hot mixture. Note the color
change as the neutralization reaction takes place. Allow the solution to cool in an ice
bath. Crystals of the product formed by the reaction will precipitate.

2. Collect the crystals with a Buchner filter. The filtrate, which contains impurities and
excess reactants, may be discarded. You do not need to get all of the crystals into the
filter, so do not use a jet of water to transfer the last dregs. The addition of excess water
will dissolve the crystals.

Purification of the Unknown Crystals:

You will purify the solid by using a process known as recrystallization. The product
and the impurities are soluble in hot water, but if you cool the solution most of the
product crystallizes out, leaving the impurities in solution. Scrape the crystals out of
the filter into a 50 mL beaker, and add the hot water drop wise with a disposable pipet
until all the solid dissolves. Let the solution cool in an ice bath, and collect the crystals,
as before.

This method of purification works because of the effect of temperature on solubility.

The capacity of a solution to hold solute (dissolved material) decreases at lower
temperatures, and the excess solute begins to precipitate. Under carefully chosen
conditions the precipitated solid will be very pure; as the crystals grow, they usually
(although not always) add identical molecules to maintain the atomic array regular.

You should keep the material in the dark, because light causes an irreversible chemical
change. This property has been exploited in blue printing, a primitive method of
reproducing documents, used before the invention of the photocopying machine.
You are now ready to find out some facts about the compound.

Testing

The only way to find out what a positive test looks like is to try it on a solution known
to contain the ion. The tests are designed to work on solutions that are about 0.05 to 0.1
M in the ion being tested for. It is essential to write down your observations in some
detail. The interpretation can come after the lab.

18
Test 1
For oxalate ion. To about 1mL of Ca2+ (0.1 M), add a few drops of the solution being
tested. If it contains oxalate ion, calcium oxalate will precipitate by an exchange of
partners reaction.

Test 2
For iron. To a few drops of the solution being tested, add one drop of 0.01 M
sulfosalicylic acid. You do not need to know how to write an equation for this reaction,
its nature is described further on in the manual.

Test 3
For oxalate. To a test tube containing a few mL of 3 M H2SO4, add a drop of KMnO4.
Mix well, and add a few drops of the solution being tested. Heat to nearly boiling in a
beaker of boiling water. Use tongs to move the test tube in and out of the water. The
oxalate is oxidized to CO2 and the permanganate reduced to Mn2+.

Test 4
For potassium. Heat a nichrome wire over a Bunsen burner until the flame returns to
its original color. Cool the wire with deionized water, and plunge it, still wet, into the
solid to be tested. Note the color of the flame produced when the wire is reheated.
Complete the blank test on solid KCI.

Test 5
For iron. Add a few drops of the solution being tested to a few mL of NaOH. Try this
on both Fe2+ and Fe3+ solutions. (A solution of Fe2+ has to be made by the student
because it will not keep. Add a few crystals of a soluble ferrous salt to water.) This is
an exchange of partners ionic reaction, which can help distinguish between Fe2+ and
Fe3+.

Test on the Standards

Tests 1 and 3 are both test for the presence of oxalate ion. The solution being tested is
the standard potassium oxalate solution. Test 2 is a test for ferric ions, and the solution
being tested is standard FeCl3 solution. Test 5 is test for the presence of both ferric and
ferrous ions. For Fe2+ ions, a solution of ferrous sulfate is made right before performing
the test 5. The source of Fe3+ ions is the standard FeCl3 solution.

Tests on the Compound

Dissolve a few crystals of compound in a few mL of water to make a solution that is just
barely colored. Then test this solution in Tests 1 through 4, using a single drop each
time. You may find that the test results do not agree on the presence or absence of an

19
ion, continue, in any case. Test 5 (the reaction of the compound with base) is done in
the next step.

Tests on the Compound After Treatment with Base.

Make a solution of the compound of the same approximate strength as described above.
Add one or two mL of concentrated aqueous NH3. Record any color changes, then heat
briefly in a beaker of hot water in the hood.

The solid is now dispersed through the liquid. To separate it, you will use a centrifuge.
This device whirls the test tube around at high speed, and the centrifugal force
developed pushes the solid to the bottom. There are many different kinds of centrifuge,
and your teaching assistant will demonstrate your school's particular model.

Load the centrifuge by putting the test tube with the iron compound on one side of the
rotor and a test tube of equivalent size containing roughly the same amount of water on
the other side. This balances the rotor and prevents destructive vibrations that can
otherwise break the test tube. After the test tube has been centrifuged, remove the
supernatant liquid with a dropper. Then divide the solution into four portions and do
Tests 1, 2, 3 and 5.

B. The Microanalysis of the Compound

You are to determine the ratio of oxalate to iron in the compound. Use a small pinch
(~100 mg) of the compound for this microanalysis. The measurement need not be exact.
If you use too much, it takes much longer to do the experiment. In spite of the small
sample size, you can derive an exact formula!

Caution: NaOH is a strong base. If you spill any on your skin, wash it off
immediately

1. Dissolve ~100 mg of compound in 5 mL of H2O and add 5 mL of 1 M NaOH slowly.

2. Heat the beaker containing the precipitate to the boiling temperature.

3. Transfer ALL of the contents to a gravity filter. (Your teaching assistant will
demonstrate Gravity filtration). Rinse the filter with a little cold water.

The filtrate contains oxalate and potassium ions, the precipitate contains the iron ions.
First we will analyze the filtrate for oxalate ion.

20
Analysis of the filtrate for Oxalate

4. Add 10 mL of 3 M H2SO4 and heat it to nearly boiling. Keep H2SO4 off skin and
clothes, and do not let the solution overheat and spatter. Test the solution with pH
paper or litmus to be sure it is acidic.

5. Add 0.1 M KMnO4 solution with an eyedropper, counting the drops, and stirring
continuously. When the oxalate is used up, the first drop of unreacted KMnO4 will
color the solution. This is the end point of this "titration." Use care in discarding this
solution. Wash off immediately any that spills on your skin or clothes.

Analysis of the solid Iron

6. Add 1M NaHSO4 solution to the funnel until the last trace of residue has
disappeared (as seen by the color). To the resulting solution, add 5 mL of 0.01 M
sulfosalicylic acid. The red color is very faint because the solution is too acidic.
Neutralize excess acid drop-wise with NH3 under the hood. When the solution first
turns burgundy red, it has reached about the correct acidity for titration. If the solution
is brown or cloudy and produces a basic test with litmus, consult your TA, your
solution is too basic. Warm the solution, and then add 0.1 M EDTA solution from the
same eyedropper as used in the KMnO4 titration, counting the drops until the red color
changes to pure yellow, which indicates that all of the iron has been used up. If you are
in doubt about the end point, add 1 or 2 drops more and see if there is a further color
change. Your instructor may prepare a standard "bottled end point" for comparison.

If your sample used less than 10 drops of either reagent, work through the analysis
again with a larger sample. If you have time, make duplicate determinations.

From the ratio of drops and the stoichiometry, you should be able to report the ratio of
iron to oxalate in the compound you prepared. Recall that the KMnO4 loses strength on
standing, and so its concentration may be lower than the stated, 0.1 M

Understanding How the EDTA Titration Works

The molecule EDTA (ethylenediaminetetraacetic acid) is shown below. EDTA is an

interesting substance that forms compounds with a large number of metals. It is used
as a food additive, since discoloration and oxidation are catalyzed by traces of metal
ions. It is used in medicine as a treatment for poisoning by heavy metal (e.g., mercury,
plutonium); the Ca-EDTA compound is administered, and the heavy metal EDTA
compound is excreted.

21
You have shown that sulfosalicylic acid will form a colored compound with the iron in
your compound. However, this compound is not as strong as the iron-EDTA
compound. As the EDTA is added to the solution, it ties up the iron, and the
sulfosalicylic acid-iron compound dissociates, restoring the equilibrium.

The experiment will not work in extremely acid solution because only the
sulfosalicylate ion will react, and in strongly acid media, the weak acid, sulfosalicylic
acid, is formed. The EDTA-iron complex is extremely stable, and only an extremely
small amount of free iron remains in the solution at the end point.

Figure 5.1 EDTA (Ethylenediaminetetraacetic Acid)

HO O C
C H2C OH
H2
H2C C N
N C CH2
H2

HO CH2 C
C O OH

The other interesting thing about the EDTA-iron titration is that it is another Lewis
acid-base neutralization. EDTA is an electron donor. In contrast to normal acid-base
reaction, no water is formed in the EDTA-metal ion reaction; an electron pair donation
is made from the N's and O's of the EDTA to the metal.

REPORTING THE RESULTS

1. The results of the tests you have completed should be displayed in tabular form.
What ions are present in the compound? If any test for an ion is positive, then the ion is
present.

2. The ratio of iron to oxalate should be worked out. You are reminded that the
equation for the reaction of oxalate and permanganate is

16 H+ + 2 MnO4– + 5 C2O42_ 10 CO2 + 2 Mn2+ + 8 H2O

22
The determination as to whether the iron is in the Fe2+ or Fe3+ oxidation state can be
made by reference to the test results. Your tests also indicate the existence of another
ion that can be used for charge balance. Report a charged balanced formula.

In your discussion, explain

3. Why every student does not get the same number of grams of compound, even
though everybody started with the same amount of materials.

4. What color changes you observed during the formation of the compound, and what
chemical reactions caused them.

5. Why the EDTA titration could not be done on the solution left over after treating the
compound with KMnO4.

6. It has been proposed that the iron is bonded tightly to the oxalate to make a
"complex ion." The iron-EDTA might be considered to be an example of such a
"complex" ion. Compare the results of your reaction of iron-EDTA and your compound
with sulfosalicylic acid. Are your test results consistent with this hypothesis? What
circumstances cause breaking of the complex? Do your results prove the existence of
this complex ion? If not, can you suggest a test that would prove it?

23
Experiment 6: Preparation of a Sodium Thiosulfate Solution

For several experiments and for the Practical Exam II exam you will need a stock
solution of sodium thiosulfate, Na2S2O3, of known concentration. This solution cannot
be made by a weighing experiment; the solution must be standardized.

How to Prepare the Solution

To make the required solution, boil 600 mL of deionized water for 2 min to sterilize it.
Then add 7 – 8 grams of the Na2S2O3•5 H2O crystals (this mass can be measured on a
beam balance) and also about 25 mg (a trace) of Na2CO3 as a preservative. Let cool.
Store in a clean plastic bottle. Shake for one full minute as vigorously as possible, then
standardize.

The sterility is required for a rather amazing reason. A remarkable breed of bacteria
derives almost all of their energy from various sulfur compounds and need little
organic "food," unlike almost all of the other organisms on this planet. Many ways have
been devised to discourage these bacteria. They don't seem to like basic solutions, so a
trace of Na2CO3 is added as a preservative.

Why isn't measuring the mass sufficient to make a solution of accurate concentration?
Why can't the beautiful crystals of Na2S2O3•5 H2O be considered to be a primary
standard? Unfortunately, they have a tendency to slowly lose their water of
crystallization. The white spots on the crystals are the anhydrous salt beginning to
form. Since the exact amount of water of crystallization varies among bottles, the
molecular mass varies, and so the exact concentration can never be known from a
measured mass. You can demonstrate this transformation by putting a few Na2S2O3•5
H2O crystals in a watch glass, and observing them again at the end of the period.

How to Standardize the Sodium Thiosulfate

The primary standard for this titration will be potassium iodate, KIO3. Take care in
making the primary standard solution. If it is incorrectly prepared, the rest of the
experiment will produce closely clustered results, all of which will be wrong.

1. Measure the mass of the KIO3 vial on an analytical balance, and transfer between
0.8000 and 1.2000 g of solid to a clean 250 mL beaker. Measure the mass the vial again
to determine the exact amount transferred.

24
2. Dissolve the solid in deionized water, ~100 mL, and transfer COMPLETELY to a 250-
mL volumetric flask. Mix thoroughly, using your best technique. Bring to the mark
with deionized H2O. Invert 20 times (The air bubble moving from bottom to top of the
flask does the mixing.) Clean a storage bottle, taking care to remove any brown
permanganate stains. Rinse the storage bottle with a little of the KIO3 solution, then
add the rest of it.

To standardize, measure 10.00 to 15.00 mL of your KIO3 solution into a 250 mL conical
flask containing about 50 mL of H2O. Use a buret to obtain the precise volume of KIO3
solution added. Add about 0.5 to 1.0 g of NaI, then 10 mL of 1 M HCl.

3. Titrate with Na2S2O3 until the solution is a pale yellow color. Then add 3 – 5 drops
starch solution, and continue drop-wise to the end point.

If you notice black flecks of solid during this titration, these are I2 solid. Add more NaI,
and they will dissolve, forming the soluble I3– ion.

To quickly check your titration consistency, compute the ratio of volume of Na2S2O3 to
volume of KIO3 for each titration. The two numbers should ideally be within 1% of
each other. This is a check of the titration precision, not its accuracy.

How This Standardization Works

The iodate ion IO3– reacts with the iodide I– to produce I2.

6 H+ + IO3– + 5 I– 3 I2 + 3 H2O

As the titration proceeds, the brown iodine I2 is reduced to the colorless I– ion by the
thiosulfate ion in the following half reactions:

I2 + 2 e– 2 I–
2 S2O32– S4O62– + 2 e–

When the equivalence point is reached, all of the I2 has been reduced by the thiosulfate
ion. Two moles of thiosulfate ion will reduce 1 mol of I2. The number of moles of I2 is
related by stoichiometry to the primary standard KIO3. Hence, by this involved chain
of logic, it is possible to calculate the concentration of the thiosulfate ion from the moles
of KIO3 used.

25
What Does the Boiled Water Do in This Titration?

Boiled water is often suggested to eliminate dissolved oxygen, which will also oxidize
iodide ion as follows:

Any dissolved oxygen will make additional I2 and hence increase the amount of
thiosulfate used.

2 H+ + 2 I– + 1/2 O2 I2 (s) + H2O (l)

What is the Starch Used For?

The starch is an indicator. As the I2 gets less concentrated the brown color becomes
fainter and fainter and it's difficult to see when it disappears completely. However,
there is a reversible reaction between I2 and starch as follows:

I2 + starch blue complex (composition uncertain)

The blue color of the complex is quite intense so that even a trace is highly visible.
When the blue color fades, you are certain of the end point. Note that the above
equilibrium is not instantaneous, and you should proceed slowly when you are near the
end point. The starch-I2 reaction does not work reversibly in high concentrations of I2;
hence, it is necessary to add the starch late in the titration when most of the I2 has been
used up.

Doing the Calculation

The exact concentration of Na2S2O3 can be calculated from the number of moles of KIO3
used. Remember that each mole of KIO3 uses up 6 mol of S2O32–, so that at the end point
there are six times as many moles of thiosulfate as KIO3 in the flask.

! vol KIO3 $
M Na S O = 6 (M KIO3 ) # &
2 2 3
" vol Na 2S2 O3 %

Also, preform an uncertainty calculation for the concentration for your sodium
thiosulfate solution. You will also need to take account for the absolute error of the
volumetric flask. For a 250 mL volumetric flask, the error is ± 0.12 mL. Show two
consistent concentration values to your teaching assistant before using the solution in
any experiment.

26
Experiment 7: The Iodine Clock Reaction

This experiment is a truly classic one in which the rate of the reaction of persulfate ion,
S2O82–, with iodide I– is measured:

S2O82– + 2 I– I2 + 2 SO42-

The reaction will be run in the presence of delayed indicator solution. This solution will
cause the mixture to turn blue after a fixed amount of I2 has been produced. The time it
takes to turn blue is therefore a valid measure of the speed of the reaction. You will
measure the blue time under various conditions of concentration and temperature.

A. Determination of the Concentration Dependence of Rate

The first step for this project is the preparation of solutions of known concentration.

Preparing the Solutions

1. The S2O82– solution will be prepared for you at the correct concentration. Record all
label information, including the batch number, if there is one.

2. You will use the sodium thiosulfate, Na2S2O3, solution previously standardized in the
Preparation of a Sodium Thiosulfate Solution experiment. This must be diluted by a factor
of 10. Check to see if the stock solution is cloudy or smells strongly of sulfur before
diluting it. This cloudiness indicates bacterial decomposition and probably means you
did not put enough preservative in or did not use a clean bottle for storage.

To prepare the diluted solution, use a volumetric pipette to withdraw exactly 10.00 mL
of stock solution. Use a pipette bulb to withdraw the solution. Then dilute to the mark
on a 100 mL volumetric flask. Shake thoroughly.

3. To make the potassium iodide solution, measure out between 7.000 and 10.000 g of
KI into a clean, dry 250 mL beaker using an analytical balance to record the exact mass.
Dissolve in ~100 mL deionized distilled water and transfer to the 250 mL volumetric
flask. Fill to the mark with distilled water. Remember to invert 20 times to mix.

Solutions of KI will not keep and must be made on the day they are to be used. In the
first week, you must use the same KI solution for Runs 1, 2, and 3; the second week, the
KI concentration must be the same for all of the runs.

27
Be sure to observe the following precautions in performing this experiment:

• Use deionized water. Stray ions in tap water (especially Cu2+) catalyze the reaction.
A small trace of EDTA, a substance that binds metal ions into a complex, is used in
some of the reagents to provide extra protection.
• Change one variable at a time. The rate of reaction depends vitally on the
concentration and temperature. All variables except the one being studied must be
held constant if the data are to be interpretable.
• Maintain good records. Record all buret readings (not net values) and elapsed time.
It is difficult to write up this experiment unless your records are perfect.

Doing a Run Under Standard Conditions

You will need three 250 mL beaker. Label them KI, S2O82–, mixing. It is essential that
the same beakers always be used for the same items. Now, do a run according to the
following procedure:

1. Use a buret to measure 20.00 mL of KI solution of known concentration into the

beaker marked KI.

2. Use the other buret to measure 20.00 mL of S2O82– solution, into the beaker so
marked.

3. Prepare the "delayed indicator" solution in the mixing beaker. Use a volumetric
pipette to transfer exactly 10.00 mL of your diluted S2O32– solution into the mixing
beaker, add a 3 - 5 drops of starch solution and the thermometer from your desk
drawer.

4. Frist add the contents of Beaker A containing S2O32– solution into the 250 mL mixing
beaker. Next add the contents of Beaker B containing KI solution into the 250 mL
mixing beaker, and gently swirl the solution to produce complete mixing. Record the
time between the instant of mixing and the instant the solution turns blue. Record the
thermometer temperature to ± 2 °C. Rinse all the beakers before the next run.

You have now completed Run 1. The blue time should not exceed 3 min nor be less
than 20 sec.

The Effect of Changing the Persulfate (S2O82-)

The total number of ions in the solution is an important variable. To keep this constant,
we will add SO42– ions as an ionic “filler”

28
In Run 2, you should keep everything the same as it was in the standard run, except
that the contents of the S2O82- beaker are to be 10 mL of 0.1 M K2SO4 solution (measure
with a graduated cylinder) and 10.00 mL of S2O82- solution measured with a buret.
Otherwise, the run should duplicate the standard run.

In Run 3, place 14 mL of 0.1 M K2SO4 solution (measured with a graduated cylinder)

and 6.0 mL of S2O82- solution (measured with a buret) in the S2O82- beaker. Otherwise,
the run should duplicate the standard run.

Note that there are three sulfur-containing ions in this experiment: thiosulfate, S2O32-,
persulfate, S2O82-, and sulfate, SO42–. They all perform different functions and must not
be accidentally interchanged.

Two things must be held constant during Runs 1 through 3 – the concentration of KI
and the temperature. Hence, you must use the same KI solution throughout.
Normally, all the solutions will be close to room temperature, and so temperature
variations should be ± 1°C or less, which is tolerable.

Check your results: Does the blue time lengthen as the concentration of reactant is
reduced?

The Effect of Varying Iodide Ion Concentration

Again, ionic fillers are important. You will use potassium chloride, KCl, to provide
spectator ions. If you run out of KI solution and need to make more, that is all right, as
long as you record the weight of the KI used, and which batch you used for each run.
Keep the temperature within ± 1°C of that for the standard run.

For Run 4, put 10 mL of 0.2 M KCI solution (graduated cylinder measurement is

acceptable) and 10.0 mL of KI solution (buret measurement required) in the KI beaker.
Otherwise, duplicate the standard run.

For Run 5, put 14 mL of 0.2 M KCI solution (graduated cylinder measurement) and 6.0
mL of KI solution (buret measurement required) in the KI beaker. Otherwise, duplicate
the standard run.

Run 5a tests the effect of the ionic filler. Put 14 mL of distilled water (graduated
cylinder measurement) and 6.0 mL of KI solution (buret measurement required) in the
KI beaker. Otherwise, duplicate the standard run.

29
B. Determining the Temperature Dependence of Rate

The effect of temperature can be studied by doing the standard run, only at different
temperatures. (The KI may be of a different batch, as long as it is of known
concentration and is the same throughout Runs 6 through 9.)

It is not necessary to have a particular set of temperatures, as long as they are known
exactly and there is a reasonable range between the highest and lowest.

Doing Runs 6 Through 9

Run 6 should be at a temperature less than 50 °C but greater than 35 °C. The easiest
way of sufficiently warming the solutions is probably to replace the S2O82- and KI
beakers with test tubes similarly labeled, and immerse them in a large beaker of water
at about 60 °C. When the contents are mixed with the cold indicator solution, the final
temperature will be about right.

Record the temperature of the entire mixture in the mixing beaker as soon as possible
after the solution turns blue.

Run 7 should be within the range of 25° to 40°C. Warm the S2O82- and KI containers so
that they are warm to the touch, but not uncomfortable to handle. Then perform the
standard run.

Run 8 should be slightly colder than room temperature. Cool the S2O82- and KI
containers under running cold water or briefly in an ice bath. Perform the standard
run.

Run 9 should be ice cold. Chill the S2O82-, and KI containers and the mixing beaker with
the indicating solution in an ice bath, swirling for 10 min. Go ahead with the standard
run. Ideally, you should have four runs that are identical except for temperature. Most
reactions are more rapid at higher temperatures. Is that true here?

C. Reporting the Results

How the "Delayed" Indicating Solution Works

The reaction for which the rate is to be measured is

S2O82– + 2 I– I2 + 2 SO42-

30
This reaction produces I2. Normally, the I2 would build up in the solution. However,
the indicating solution contains S2O32– ions, and this rapidly reduces the I2 back to I–.

Eventually, all the S2O32– is used up. However, the main reaction shown above is
continuing to produce I2. The first trace of this I2 turns the starch blue.

Thus, the blue time is the amount of time the reaction uses to produce a fixed number of
moles of I2. To produce a fixed number of moles of I2 requires a fixed number of moles
of S2O32– the main reaction. The rate of reaction is defined as the number of moles of
S2O82– used per second. It is like timing a horse race over a fixed length. You can
calculate the speed of the horse by dividing the distance covered (S2O82– concentration
change) by the time (number of seconds elapsed from mixing until the blue color
appears).

Much less S2O82– is used than either S2O32– or I–. Only a small fraction of the S2O82– is
used up by the time the mixture turns blue. Because the I– is regenerated by reduction
until the moment when the blue color appears, it stays constant in concentration.

Doing the Calculations

There is a lot of data here and it is essential to lay it out in tabular form as much as
possible.

1. Note first that the concentration of the species after mixing will be different because
of dilution. For example, if you add 20 ml of 0.1 M KI solution to 30 mL of other
ingredients, the final concentration of I– will be

! 20 mL $
0.1M * # & = 0.04M
" 50 mL %

The change caused by dilution takes place as a separate step before any chemical
reaction begins. Set up a table for Runs 1 through 5, converting your observed blue
times to rates, as shown in Table 7.1.

Table 7.1
Concentration Concentration
of Solution Volume of Solution
Before Mixing Added After Mixing Rate
2–
S2O8
KI
S2O32–

31
The rate is computed by dividing the change in S2O82– concentration between mixing
(after dilution) and blue time, by the blue time. Thus,

diluted concentration - blue time concentration

rate = 
blue time

However, you do not know the blue time concentration of S2O82–. You do know,
however, that for each mole of S2O82– used, two moles of S2O32– were used to destroy the
resulting iodine. The change in S2O32– concentration is

∆[ S2O32–] = initial diluted concentration of S2O32– – blue time concentration of S2O32–

Because the blue time concentration of S2O32– = 0, this reduces to

∆[ S2O32–] = initial diluted concentration of S2O32–

so that the change in S2O82– concentration = ½ (initial diluted concentration of S2O32–)

Thus, the rate of reaction is

(0.5)(diluted concentration of S2 O 2– )
rate = 3

blue time

where the phrase "diluted concentration of S2O32– refers to the value calculated in Table
7.1. Make a table for each run. You can save time by noting where calculations repeat.

2. Observe that, in general, for the reaction A + B à C + D

rate = k[A]n[B]m

and taking logs:

log rate = log k + n log [A] + m log [B]

Suppose we hold [A] constant, and n and m are natural constants for every reacting
system,

Log rate =(log k + n log [A]) + m log [B]

y= b +mx

This is the equation of a straight line, and the slope will be the order of the reaction with
respect to B. (The same argument will work for varying A while holding B constant.)

32
3. Make a table of log rate and log [I–] for Runs 1, 4, and 5. Plot the log rate on the y
axis and log [I–] on the x axis. The slope of this line gives you the order with respect to
I–.

4. Make a table of log rate and log [S2O82–] for Runs 1,2, and 3. Plot the log rate on the y-
axis, and log [S2O82–] on the x-axis. The slope of this line will give you the order with
respect to S2O82–

5. Now, knowing the order of reaction with respect to each component, calculate the
rate constant for the Mixtures 1 through 5. Set up a table like Table 7.2.

Table 7.2
[KI] [S2O82–] [KI]m [S2O82–]n
after after after after Rate
Run Rate Mixing Mixing Mixing Mixing Constant

6. For Runs 6 through 9, all the concentration terms are constant and only the
temperature changes. You need to know the rate constant for each run.

k= rate
[KI]m [S2 O82– ]n

The denominator of this fraction should be a constant. Do not forget the effect of
dilution; include the diluted concentrations in the calculation.

Make a table containing the run number, the rate, and the rate constant. Add columns
to the table containing the log of the rate constant, the centigrade temperature, and 1/T,
where T is the absolute temperature.

The temperature effects on reaction rate can be unified and explained by the Arrhenius
equation (below), which is derived in most textbooks.

−Ea
k = Ae RT

33
Taking the natural log of both sides of this equation, you obtain

" −Ea %
ln k = ln A + ln $ e RT '
# &

2
Since the natural log of e raised to a power is the power itself (compare log 10 = 2), then

Ea " 1 %
ln k = ln A − $ '
R #T &

which is the equation of a straight line: y=mx+b, where ln k is y and 1/T is x. The slope
will be –Ea/R, and the y intercept will be ln A. So, if you plot ln k on the y axis and 1/T
(where T is the absolute temperature) on the x axis, you will obtain a straight line for
which slope is –Ea/R. (Check units!)

7. Plot ln k versus l/T, and use the slope to get Ea.

For the Discussion Part of Your Lab Report

Now, look at the blue time for Run 5a. To interpret this result, it is necessary to
consider something called the kinetic salt effect. The rate depends on the ionic strength,
a variable that measures the total concentration of all ions, and is defined as:

i
I = (0.5)∑ M i Zi2
1

where M is the molarity of an ion and Z its charge. Furthermore, it is true that

1. if the reaction does not change speed when spectator ions are added, the species
that react at the rate-determining step are not ionic.

2. if the reaction proceeds slower at higher ionic strength, the species reacting at the
rate-determining step are oppositely charged. This is because the additional charges
in the solution make it difficult for the attraction of the reacting ions to be felt.

3. if the reaction takes place more rapidly at higher ionic strength, the species
reacting at the rate-determining step have the same charge. The masking effect of
the added charges also lowers the repulsion between like-charged reacting ions.

34
Run 5a differs from Run 5 only in that the ionic strength is lower. Does this lead to a
faster or slower reaction, or are the times equal within uncertainty? For your
discussion, draw a conclusion about the nature of the rate-determining step.

Indicate the effects of any systematic errors or mistakes that you made. If you believe
that there are no such systematic errors, discuss the following problem: Sam Superior, a
student taking this course, reports values of the rate constants that are about 5% too
low. His blue times are also too long, so the error is not data reduction. What might
cause this problem? What should he do?

This is the most difficult (or perhaps just the longest) report in this course. The write-up
teaches you how to cope with massive amounts of data in an orderly way, and also
provides you with some useful statistical tricks.

35
Experiment 8: Properties of an Organic Acid

This experiment will measure some properties of an organic acid. The organic acid has
been pre-dried. It will pick up moisture readily, so keep the vial tightly capped. You
may be asked to do the parts in reverse order because the supply of pH meters is
limited.

A. Measurement of Molecular Weight by Freezing Point Depression

This is an interesting, if inexact, way of measuring the molecular weight of your organic
acid.

There are two differences between the freezing of solutions and the freezing of pure
liquids. First, the freezing point of a pure solvent is always higher than the freezing
point of a solution. This is because the particles of solute interfere with the ordering
necessary to produce a solvent crystal. This freezing point depression effect will be ∆T
degrees, where

∆T= Kfm

and m is the number of moles of solute particles per kilogram of solvent and Kf is a
constant for the particular solvent. The number that counts is the number of moles of
solute particles, not molecules. If the molecules clump together, the number of moles of
clumps is the important number.

This effect is useful precisely because it can give us the apparent molecular weight of
the aggregates, and such information is often complementary to the weight obtained by
other methods.

How to Do a Freezing Point Depression Measurement

It is essential to keep everything dry throughout the procedure. Water will dissolve in
the solvent and artificially lower the freezing point. Also, avoid flames - the solvent
burns.

1. Put a large test tube inside a 250-mL flask and use a beam balance to measure the
mass of test tube and flask. The conical flask is needed to keep the test tube upright.
Now obtain some t-butanol (about 8 to 12 g), and record the mass again.

2. Insert a precision thermometer (0.1°C graduations), and cool the test tube slowly.
Prolonged dipping of the tube in cold water cools it too quickly. This results in massive

36
amounts of t-butanol sticking to the walls of the test tube. Use the thermometer to
gently stir, and do not remove it because t-butanol will cling to it. The t-butanol should
freeze at 25.5 °C. Freezing is defined as the first point at which crystals are mixed
throughout the liquid, not the point at which it becomes rock solid. (Uniform
cloudiness is the best objective criterion of freezing.) For a pure liquid, it does not
matter very much at what stage we define freezing; however, in a solution, pure
crystals of solvent freeze first, and as this happens the remaining solution becomes
more concentrated. Consequently, its freezing point is further depressed. (Thus, pure
liquids have sharp freezing points, and solutions display a freezing range.) Measure
the freezing point three times to obtain an idea of the reproducibility.

3. Measure the mass of the vial of acid on the analytical balance. Without removing the
thermometer from the test tube, add between 0.2000 g and 0.4000 g of acid, finding the
exact mass by difference.

4. Warm the t-butanol in hot water. The acid will dissolve quickly at 30° to 35 °C with
stirring.

5. Cool the apparatus slowly with stirring. Record the first freezing (cloudiness
throughout the liquid). If you cool too quickly, solid t-butanol will cling to the sides of
the test tube, and it will be difficult to obtain thermal uniformity throughout the
mixture.

6. Melt the mixture, and freeze if again to get a second measurement of the freezing
point.

7. Your instructor will advise where the t-butanol waste is to be put for disposal.

How to Compute the Molecular Weight

The freezing point depression constant can be shown to be equal to

𝑅𝑇"&
𝐾" =
1000∆𝐻"

where the value of R, the gas constant, is 1.987 cal/deg-mol, ∆Hfus is the heat of fusion
expressed in cal/g, and Tf is the freezing point of the pure solvent expressed in Kelvins.
For t-butanol, the heat of fusion is 21.88 cal/g.

37
The next task is to compute the number of grams of solute that would be in 1000 g of
t-butanol. From this number, it is easy to compute the molecular weight. To do the
uncertainty analysis, neglect all uncertainties except the uncertainties in ∆T and in the
mass of t-butanol. Consider the analytical balance measurement as exact.

B. Preperation of NaOH Solution for pH titration.

CAUTION: Concentrated NaOH solutions are dangerous and lead to severe burns.
If they are splashed on your skin, wash them off immediately with copious amounts
of water. Wear eye protection.

Measure 30 to 35 mL of the stock NaOH solution with graduated cylinder accuracy, and
add 275 mL of deionized water. Stir well. Standardize this by using the procedure in
the fourth section of this experiment, but do the third section first because it is less
demanding of your technique.

C. Titration of the Unknown Acid

First, calibrate a pH meter. The inner workings of the meter are described in the
Instrumentation section. Only the use of the instrument is described here. Keep the
meter electrode wet at all times. Once it dries out, the measurements become erratic.

How to Calibrate a pH Meter

The following is written for the Analytical Measurements Model 707S pH Meter. The
calibration is used to adjust the meter so that voltages from the probe can directly be
read as pH. You need to obtain about 40 mL of buffer solutions of known pH and a
beaker filled with distilled water; this beaker is used to rinse off the electrode.

1. Rinse off the electrode using the spray from your wash bottle, and place the probe in
the pH 7 buffer solution. Turn the selector switch from "off" to "pH." Adjust the
"calibrate" knob until the meter reads 7.00.

2. Remove the probe from the pH 7 buffer solution, rinse it off with deionized water,
and place the probe into pH 4 buffer solution. Adjust the "temperature" knob so that
the meter reads 4.00.

3. Repeat the cycle of adjusting the calibrate knob when the probe is in pH 7 buffer
solution and the temperature knob when it is in pH 4 buffer solution, until the meter
reads the correct value in both buffer solutions without further adjustment. The process

38
can be somewhat exasperating, but take the time to do it correctly because the results of
the entire experiment depend on it.

The temperature and calibrate controls are essentially "slope" and "intercept" controls.
The temperature control adjusts the amount of amplification used. The electrode
potential changes 59 mV for each pH unit. The amplifier has to convert this into voltage
that just produces a scale jump of 1 pH unit. The calibrate control adjusts the zero of
the voltage.
Be sure to rinse the electrode each time you test a new solution. Also, allow the needle
to stabilize before taking a reading. Excessive movement of this particular pH meter
model can cause the calibration to change!

Taking Measurements on the Unknown Acid

You need to measure the pH as the acid is slowly neutralized to determine the
molecular mass, the number of replaceable hydrogen atoms, and the acid dissociation
constant. All these facts can be obtained easily by plotting the pH of a mixture as a base
of known concentration is added.

Measuring the Mass of the Unknown Acid

Clean a 250 or 400 mL beaker. Measure out 0.2000 to 0.3000 g of the unknown acid into
the beaker. Unfortunately, you cannot use a conical flask because the pH electrode will
not fit. Add 50 mL of distilled water, measured with a graduated cylinder.

Performing the Titration

1. Fill a buret with the NaOH solution that you have prepared, run air bubbles out of
the tip, and then record the initial volume reading.

2. Immerse the pH electrode in the beaker after you have calibrated the meter, and then
record the initial pH before any NaOH is added. Be careful it is very fragile and
expensive.

3. Add the NaOH solution slowly, mixing thoroughly by swirling but taking care not to
spill. Do not use the electrode as a stirrer. Record the pH reading and volume after
each addition. Do not rinse the electrode between additions.

The best method is to swirl the beaker constantly with the dominant hand, keeping
your other hand on the buret valve. Keep your eye on the pH meter. Try to record
every time the pH jumps by 0.5 units. In some areas of the titration curve, this happens
only if several mL of NaOH is added. In other regions, one drop will be enough!

39
Adjust the rate of addition to the rate that the pH is rising, and where it is rising steeply,
take more measurements (after each drop if necessary).

4. After the first end point, the pH again changes less rapidly as NaOH is added.
Continue until you have reached pH 11.

5. Rinse the electrode and replace it in distilled H2O.

6. Sketch a plot pH versus total NaOH volume. Show this plot to your TA.

D. How to Standardize Your NaOH Solution with a pH Meter

This section displays a typical strong acid-strong base titration curve and enables you to
standardize your NaOH solution using the pH meter. It is best to do this after you have
already done some work with the meter, because care in taking the measurements in
the end point region is required.

The standardization of NaOH could be done with potassium hydrogen phthalate as a

primary standard. This is a weak acid, so the titration curve is not as easy to read, as it
would be with a strong acid. So in this part of the experiment you will use sulfamic
acid, H2NSO3H

H2NSO3H + H2O H2NSO3– + H3O+

Sulfamic acid dissociates completely to the sulfamate ion, H2NSO3– in aqueous solution.
It is a pure solid crystalline material. It has only one defect, as a primary standard the
molecular weight is low.

Running the Titration

1. Using a scoop of the correct size, put about 1 g of sulfamic acid in a weighing bottle.
Measure the mass of the bottle exactly on an analytical balance then put not more than
0.4000 g of the solid in a 250 or 400-mL beaker. Measure the mass again to get the exact
mass transferred. Dissolve the acid in 50 mL of distilled water.

2. Fill a buret with the NaOH solution to be standardized. Calibrate the pH meter, and
place the electrode in the beaker. Record the initial volume and initial pH of the
solution before any NaOH is added.

3. Without rinsing the electrode between additions, make a table of pH versus mL of

base added. You may go rapidly, adding up to 5 mL of base at a time until the pH rises
above pH 2.7, then go drop wise until it becomes very high (this is the end point
region). Stop when you reach pH 11.

40
When you plot this data, you will have a perfect example of a titration curve of a strong
acid with a strong base. If you have been careful around the end point region, the curve
will cross pH 7 at the place where the same number of moles of base as acid has been
added. From this you should be able to compute the unknown concentration of the
sodium hydroxide solution. Your report should show the plot and the calculation.

Reporting Your Results

This manual does not cover the details of ionic equilibrium, because such topics are
adequately treated in most genral chemistry texts. If you are not sure what the terms
pH, pKa, and buffer mean, look in the index of your favorite book and give yourself a
crash course.

1. Plot pH versus mL of total NaOH added for the organic acid titration. On the plot,
label the flat buffer regions and the rapidly rising end point regions with roman
numerals. Make a table listing what the major chemical species are in each region

2. How many end points are there? How many replaceable hydrogens does the acid
have? At the first end point, the number of moles of acid present is equal to the number
of moles of NaOH consumed. Because you know the number of grams of acid weighed
out, you can easily compute the number of grams per mole, which is the molecular
mass. What is the molecular mass of the acid?

3. What is the pKa of the acid? If it has more than one replaceable H+, list the
pKa for each replaceable H+.

(Hint: Assume that each hydrogen is neutralized sequentially, that is, all of the first
hydrogen has been neutralized before any of the second one has started to be
neutralized. Thus, in the first buffer region, the first hydrogen is being neutralized, and
at half way to the first end point you will be in the center of the first buffer region. At
half the volume required to neutralize a specific hydrogen, the concentration of anions
will be exactly equal to the concentration of unreacted acid.

Because the equilibrium expression for the acid HA is

[H 3O+ ][A – ]
Ka =
[HA]

for this halfway point

Ka = [H3O+]

41
or
pKa = pH

In summary, then, the first pKa value is given by the pH at the midpoint of the region
from the beginning of the titration to the first end point; the second pKa value is given
by the pH at the midpoint between the first and second end points, and so on.

4. If you make a salt using the unknown acid, neutralizing only the first replaceable
hydrogen, what is the pH of the resulting solution? If you think for a moment, you see
that you can read this off the graph without doing any calculations.

5. For your discussion, consider the following analysis. Either your results for
molecular mass in t-butanol agree with the titration result, or they do not. However,
the t-butanol measurement is subject to important systematic errors as well as a large
intrinsic uncertainty, owing to the difficulty of recognizing the freezing point.

Two systematic errors that will have important effects are (1) recognition of freezing
only after a substantial portion of the t-butanol has frozen out, and (2) admittance of
moisture to the solid. What effect would these have on the freezing point depression
measurement and on the titration data? Could a student eliminate these problems by
repeating measurements?

Can you reconcile your titration numbers with your freezing point depression
numbers?

42
Practical Exam II Antimony in an Unknown

The task to be done on this exam is to measure the percentage of antimony in an

unknown. You will need a primary standard solution of KIO3 and a solution of Na2S2O3
prepared as directed in the experiment on thiosulfate standardization.

How the Procedure Works

Antimony is an interesting element, discovered by an alchemist by the improbable

name of Basil Valentine, about 1600. The name of the element comes from the story that
Valentine fed an antimony compound to pigs, which then grew very fat. He then tried
it on some monks who had been fasting. The monks all died, so the name antimony
comes from roots meaning "anti-monk." Trivalent antimony compounds are still used
in medicine as cures for various parasitic diseases. As Valentine found out, the
difference between curative and toxic levels is small.

Antimony has two common oxidation states, the trivalent SbO+ ion, and the pentavalent
SbO2+ ion. The trivalent ion is converted to the pentavalent ion (in the presence of
tartaric acid or tartrate ion) by a number of oxidizing agents, such as iodate.

3 SbO+ + IO3– 3 SbO2+ + I–

In this procedure, excess iodate is added to oxidize all of the trivalent antimony. The
remaining iodate then oxidizes I– to I2 as in the standardization you have done before.
This excess I2 is reduced with Na2S2O3 and thus the end point is exactly the same as one
you've already seen when standardizing the thiosulfate.

The pH of the mixture should be between 3 and 5 for best results. At high H+
concentrations, a side reaction uses up excess I2. At lower H+ concentrations, the
reaction between IO3– and I– will not work, as this reaction is a net consumer of H+. The
tartrate ion formed as the H+ is used up forms a buffer to stabilize the pH of the
mixture. Thus, the tartrate both catalyzes the oxidation reaction (which is slow at best)
and also stabilizes the pH.

The function of the NaI is to keep the I2 in solution as triiodide ion. Otherwise, it
escapes as a vapor or precipitates as a black solid.

43
A. Preparing for the Exam

You will need a solution of KIO3, which will be the primary standard and therefore
must be of known concentrations, and a solution of sodium thiosulfate, prepared as
directed in the experiment on thiosulfate standardization. Before the exam, you should
obtain a vial of NaI and one of tartaric acid.

Preparing KIO3

This is the primary standard. If it is incorrectly prepared the rest of the experiment will
give closely clustered results, all of which will be wrong.

Measure the mass of your KIO3 vial on an analytical balance, and transfer between
0.8000 and 1.2000 g of solid to a clean 250 mL beaker. Measure the mass of the vial
again to get the exact amount transferred. Dissolve in a ~100 mL of deionized water
and transfer completely to a 250 mL volumetric flask. Mix thoroughly. Use your best
technique here. Bring to the mark with distilled water. Invert 20 times. Clean a storage
bottle. Brown stains can be dissolved with a little cleaning dip, but rinse thoroughly
afterward. Rinse the storage bottle with a little solution to be stored in it.

Preparing Na2S2O3

This is prepared following directions elsewhere in this manual, but if you have not used
the solution for some time since the standardization, check it to see if there are signs of
decomposition for example, cloudiness or a foul smell. Our experience is that properly
prepared Na2S2O3 keeps almost indefinitely. You will need about 150 mL of solution.

If, on the day of the exam, you find that your thiosulfate solution has decomposed, you
can easily make more solution (no need to sterilize the solution if you will use it right
then) and standardize it during the exam.

Preparing Yourself

You saw the end point when you standardized your Na2S2O3 solution.

1. Be sure to record the following in your notebook:

a. The exact concentration of your KIO3 solution

b. The concentration of your Na2S2O3 solution. This is your chance to check your
standardization calculation.

44
2. Reread the section on the tools of the trade regarding the correct use of burets and
other procedures.
3. Obtain a receipt form, fill it in, and have it ready to present in return for your
unknown.

4. Relax!

B. Taking the Exam

Because you may not have taken a practical exam before, note the following rules of
conduct:

1. At most schools you may not talk to one another, compare results, or share
calculators or any other material. You will need to prepare your notebook with detailed
instructions for this experiment.

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 aprons are required at all times. You are expected to follow the
dress code for working in the lab. You will be asked to leave the lab-and therefore fail
the exam-if you violate these rules.

4. Most schools have elaborate procedures to see that each student receives only one
unknown. You will not be given another one if the first is lost, damaged.

5. Come on time. Once you have begun, you may not come back another day.

6. You will have 2.5 hrs to do the measurements. If you decide to prepare additional
solutions, or restandardize your Na2S2O3, you will not be given additional time.

Titrating the Unknown

1. Add 0.5 to 1.0 g of tartaric acid (the amount you could heap on a dime; this can be an
eyeball measurement) to a 250 mL conical flask, and dissolve in 50 mL of distilled
water.

45
2. Add between 0.2500 and 0.5000 g of unknown to this mixture. You must know the
exact mass of unknown added. When the unknown has dissolved, the solution should
not be cloudy. If it is cloudy, add tartaric acid.

3. Add between 0.5 and 1.5 g of NaI. This is an "eyeball" measurement again, about the
amount you can heap on a dime. Surprisingly, KI does not work as well because it is
less soluble. A transient yellow color is occasionally visible at this point.

4. From a buret, add not more than 23.00 to 25.00 mL of KIO3 primary standard,
recording the exact volume used to 0.01 mL. Stop as soon as you see the brownish color
of iodine. If this happens with less than 10 mL of KIO3 solution, this is acceptable, but
for your next run increase both the weight of unknown used and the amount of tartaric
acid. Once the contents of the flask are uniformly brown, you need not add more KIO3
solution.

The color of iodine must be visible at this point. If it is not, did you omit the tartaric
acid or the NaI? If purple iodine vapor is visible over the solution or if there is a dark
precipitate, add more NaI.

5. Let the mixture stand for 2 or 3 min to complete the reaction.

6. Fill a buret with your standard thiosulfate solution and titrate until the solution is
pale yellow. Then add 3 - 5 drops of starch and proceed drop-wise to the end point.
Record the exact volume of thiosulfate solution used.

7. Your instructor will advise you about whether solutions may be discarded down the
drain.

Reporting Your Results

You will use the form provided.

Give some thought to choosing the best value. By this point, it should be clear to you
how much scatter can be ascribed to experimental uncertainty. If the scatter is large, it
is true that, at most, one of the results can be correct. If you average good data with bad
data, you will end up with bad data. There is no law against disregarding one or more
runs if you know that they are defective. Averaging them will certainly not improve
your accuracy. In cases of wide scatter, it is usually best to choose the middle value,
rather than the average, if you have no information on which to base the choice. If,
however, the only scatter is due to experimental uncertainty, the best strategy is to
average the three values.

46
INSTRUMENTATION:

How a pH Meter Works

The first modem pH meter was invented by Professor Arnold Beckman of California
Institute of Technology to measure the pH of citrus fruit, which is obviously important
in California. Beckman's invention largely improved the electronics so that the
previous work on pH could be applied, and the meter went from a laboratory curiosity
to a practical field device. Beckman Instruments went from Beckman's garage to being
one of America's largest corporations in less than 45 years.

The heart of the pH meter is an electrochemical cell in the probe, which has an
extremely high internal resistance. If a substantial amount of current is drawn, the
voltage observed will drop because of Ohm's Law. It is therefore necessary to use a
voltmeter specially adapted to measuring under these circumstances. An ordinary
meter needs to draw a few microamperes simply to move the needle and needs an
amplifying circuit to isolate the system being measured. The voltage from the cell in the
probe is fed to a field effect transistor. These devices are controlled by the electric field
produced by the voltage and require almost no current flow from the cell, because the
circuit seen by the cell is almost an open circuit. The field effect transistor acts as a
"valve" to control the meter's own power, which is used to move the needle. The probe
contains two half cells connected by a very small salt bridge, usually a glass fiber. One
half cell is a reference cell, designed to give a voltage independent of pH and, as much
as possible, independent of temperature. The other half cell contains a pH-dependent
system.

The Reference Half Cell

The reference half cell is typically a saturated calomel cell. Calomel is a name for
Hg2Cl2, which is sparingly soluble material. The cell contains a platinum wire, dipped
into (or coated with) mercury. So the half cell reaction is

2 Hg Hg22+ + 2 e–

The solution contains both calomel and potassium chloride. The very limited solubility
of calomel in KCl solution means that there is a vast excess of solid calomel in the cell.
As the cell reaction converts it to mercury, its concentration remains the same because
more dissolves. Thus, the half cell potential is not affected by use.

47
The Glass Electrode

The glass electrode is the indicating electrode. A membrane of thin sodium glass will
develop a potential difference if it separates two solutions each having a different pH.
Exactly how this works is not understood on the molecular level. It appears that Na+
ions in the glass are partially replaced by H+ from the solution, and it is known that the
latter are able to migrate through the glass. However, the details of this process are still
very mysterious. The solution inside is held at a fixed pH by means of a buffer, and an
inert electrode, or reference electrode, is used to make contact with the solution. The
glass electrode has a half cell potential that is dependent on H+ differences, as follows:

2.3 RT [H + ] inside
E glass = E° −  log +
F [H ] outside

Since pH = -log [H+],

2.3 RT
E glass = E° −  (pH outside - pH inside)
F

The E° for the glass electrode is called its asymmetry and is due to strains in the glass
and other peculiar effects. Typically, it is close to zero and independent of pH, so

E glass = – 0.059 volt (pH outside – pH inside)

and the overall potential measured by the meter will be

E = E(ref) – E (glass)

Because the reference cell potential is independent of pH, the only part of the probe that
is pH sensitive is the glass electrode. Thus, the measured voltage varies with pH.

The glass electrode and the reference electrode dip into the same solution, so electrical
contact is maintained. The fundamental difficulty with commercial pH meters is the
necessity of making the glass electrode thin for electrical reasons, but this inevitably
means that it is very fragile. The glass electrode should also be kept moist; a hydrated
layer of glass on the surface is important to its functioning, and this hydration takes at
least 24 hr to establish.

Treat your meter with care. It is a remarkable device.

48
Using a pH Meter to Measure Voltage

The pH meter is actually a sensitive voltmeter. If you remove the pH electrode and
attach ordinary wires, you can measure voltage as low as to mv. (A millivolt is 1/1000
of a volt.)

For most meters a single cable is used to connect the pH electrode. This cable actually
contains two wires. To measure voltages, you first attach a separate cable with a fitting
on one end designed to be connected to the pH meter. At the other end of this cable,
there are two clips or two wires, and the source of voltage to be measured is connected
to these two wires.

To take a voltage measurement, first connect the two clips or two wires together.
Change the setting on the meter from pH to mv. Then connect the two wires together.
There will now be zero voltage across the gap between the wires. Adjust the meter
until the voltage reads zero. (Your instructor will tell you how to do this with your
particular meter, and also how to read the voltage from the front face of the meter.)

Unclip the two wires, and then, without further adjustment to the meter, attach them to
the voltage source to be measured. If the meter swings off scale below zero, reverse the
connection to the source. If the meter swings off scale at the upper end of the scale,
disconnect it immediately and seek assistance. You have an adjustment problem.

When measuring voltages, do not place your hands on the electrodes, because you will
short circuit the source being measured. This is not dangerous if the voltages are low
enough, but it does make the measurement inaccurate.

49
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 measuring the mass, the student can measure
the mass one hundred times and the problem will not be cured. However, if a sample is
correctly prepared, averaging more mass measurements 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. 11.1 showing a bear target
being shot by a marksman.

50
 FIGURE 11.1: The Difference Between Precision and Accuracy

On the average the bear is dead You can average, but it does not help
(accuracy, no precision) (Precision, no accuracy)

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 measure the mass of 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 ± 0.05 mL in any single reading.

balance ± 0.0005 g in any single measurement.
360° thermometer ± 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):

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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.)

TABLE 11.1: 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 11.2: 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.

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 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.

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 11.3: Sample Buret Readings

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.

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 Step 1. Obtain the net mass of wet Coal.
Lower Limit Weight Upper Limit
Mass of wet coal and crucible 20.7995g 20.8000g 20.8005g
Mass of crucible empty ("tare weight") 19.9995g 20.0000g 20.000g
Net mass 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 mass of wet coal is 0.8000 ± 0.0010 g.

Step 2. Obtain the mass loss of coal

Mass of wet coal and crucible 20.7995 g 20.8000 g 20.8005 g

Mass of dry coal and crucible 20.7195 g 20.7200 g 20.7215 g
Mass loss 0.0790 g 0.0800 g 0.0810 g
(again computed as above) (or 0.0800 ± 0.0010 g)

Step 3. Obtain the percentage of mass loss. The percentage of H2O in the coal
will

mass loss
percentage = × 100
original mass

One worst case will

upper limit of mass loss 0.0810

= × 100 = × 100 = 10.14 %
lower limit of original mass 0.7990

The other worst case will be

lower limit of mass loss 0.0790

= × 100 = × 100 = 9.86 %
upper limit of original mass 0.8010

Hence, the true percentage of water lost lies between 10.14 percent and 9.86 percent.

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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

mass of 120.0 g/mol, and 2.6754 g are measured out. What is the uncertainty in the
concentration?

2.6754 g
Concentration = g = 0.2229 𝑀
(0.10000 L)(120.0 )
mol

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

2.6764 g
Upper limit = g = 0.2232 𝑀
(0.09992 L)(120.0 )
mol

2.6744 g
Lower limit = g = 0.2227 𝑀
(0.10008 L)(120.0 )
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 with a mass of 20.100 g empty, she puts some copper powder and
measures the mass, 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 mass of the crucible
and compound is 21.554 g. The atomic mass of copper is 63.54g/mol; atomic mass of
sulfur is 32.06 g/mol.

Compute the upper and lower limits for the ratio of moles of sulfur to moles of copper.

55
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 mass 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?

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
𝑅𝑈 = × 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:

0.0010 g
for 1.0 g 𝑅𝑈 = × 100 = 0.1 %
1.0000 g

0.0010 g
for 0.1 g 𝑅𝑈 = × 100 = 1.0 %
0.1000 g

56
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.

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.

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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 × 10RS 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 × 10RS mol mol
= 0.1080
0.02306 L L

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%

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Step 4. Convert the RU of the result back to an absolute uncertainty. The absolute
uncertainty will clearly be
0.63%
0.1080 𝑀 = ± 0.0007𝑀
100

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

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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.

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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 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.

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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 mass, and computing the density. The following are the data of the world famous
A Student:
mass 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 12.1: Identification of an Unknown Slug Data

Lower Limit Measurement Upper Limit

Mass of slug 17.0771 17.0776 17.078/
volume of slug 5.86 5.96 6.06
density of slug 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

62
 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.

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.

63