Fundamentals of Chemistry II, Laboratory Manual

SCC202
Fundamentals of Chemistry II
Laboratory Manual
LaGuardia Community College
Compilation by Dr.lvan Rivera-Torres
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SCC202 Fundamentals of Chemistry II © 2009 Cengage Learning

Laboratory Manual
Compilation by Dr.lvan Rivera-Torres
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Acknowledgements
The content of this text has been adapted from the following product(s):
Determination Of Ka For Weak Acids- Seager/Slabaugh

ISBN-10: (0-495-25458-4)
IS~N-13: (978-0-495-25458-4)
ELEC0450: Studying Electrochemical Half-Cells and Half-Reactions

ISBN-10: (0-87540-450-2)
ISBN-13: (978-0-87 540-450-9)
Colligative Properties Of Solutions - Seager/Slabaugh
ISBN-10: (0-495-25454-1)
ISBN-13: (978-0-495-25454-6)
KINE0508: Studying the Kinetics of a Chemical Reaction
ISBN-10: (0-87540-508-8)
ISBN-13: (978-0-87540-508-7)
Chemical Safety and Laboratory Rules - Bishop/Bishop/Whitten
ISBN-10: (0-495-24925-4)
ISBN-13: (978-0-495-24925-2)
The Structure Of Crystals- An Experiment Using Models- Slowinski
ISBN-10: (0-495-25322-7)
ISBN-13: (978-0-495-25322-8)
EQUL1003: Preparation and Properties of Buffers
ISBN-10: (0-495-23885-6)
ISBN-13: (978-0-495-23885-0)
Common Equipment - Bishop/Bishop/Whitten
ISBN-10: (0-495-24927-0)
ISBN-13: (978-0-495-24927-6)
EQUL0494: Monitoring Acid-Base Titrations with a pH Meter
ISBN-10: (0-87540-494-4)
ISBN-13: (978-0-87540-494-3)
THER1003: Energy Changes in Chemical Reactions
ISBN-10: (0-495-24060-5)
ISBN-13: (978-0-495-24060-0)
EQUL0499: Studying the pH of Strong Acid, Weak Acid, Salt, and Buffer Solutions
ISBN-10: (0-87540-499-5)
----------------
ISBN-13: (978-0-87540-499-8)
EQUL0616: Introducing Chemical Equilibrium
ISBN -10: (0-87 540-616-5)
ISBN-13: (978-0-87540-616-9)
Table Of Contents
I. Chemical Safety and Laboratory Rules - Bishop/Bishop/Whitten ............................................ .

2. Common Equipment - Bishop/Bishop/Whitten. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. The Structure Of Crystals - An Experiment Using Models - Slowinski. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4. Colligative Properties Of Solutions -Seager/Slabaugh .................................................... 21
5. KINE0508: Studying the Kinetics of a Chemical Reaction ................................................. 33
6. EQUL0616: Introducing Chemical Equilibrium.......................................................... 57
7. EQUL0499: Studying the pH of Strong Acid, Weak Acid, Salt, and Buffer Solutions ............................ 71
8. Determination Of Ka For Weak Acids- Seager/Slabaugh ................................................. 91
9. EQUL1003: Preparation and Properties of Buffers.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
10. EQUL0494: Monitoring Acid-Base Titrations with a pH Meter. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
11. THER1003: Energy Changes in Chemical Reactions .................................................... 137
12. ELEC0450: Studying Electrochemical Half-Cells and Half-Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
1
CHEMICAL SAFETY
AND LABORATORY RULES
OBJECTIVE To develop a "safety conscious" attitude about working in the laboratory and
to locate safety equipment in your laboratory.
CONCEPT TO BE TESTED The laboratory is a safe place in which to work if appropriate
precautions are taken and sound judgment and common sense are exercised.
References: (1) Safety in Academic Chemistry Laboratories, Department of Educational
Activities, ACS, 1155 16th St. N.W., Washington, D.C. 20036. (2) NIOSH Publications No.
78-104A, 104B and 77-205 on Toxic Effects of Substances and Carcinogens. Superintendent
ofDocuments U.S. Government Printing Office, Washington D. C. 20402. (3) Material Safety
Data Sheets (MSDS) (4) Safe Handling and Disposal of Chemicals, J. T. Baker Inc., 222 Red
School Lane, Phillipsburg, NJ 08865
INTRODUCTION
YOU ARE EXPECTED TO KNOW AND TO ADHERE TO SAFETY PRACTICES
IN THE CHEMISTRY LABORATORY. THERE ARE RISKS AND HAZARDS
INVOLVED IN WORKING IN THE CHEMISTRY LABORATORY JUST AS
THERE ARE IN ANY OF OUR LIVES. THE PURPOSE OF THE EXERCISE IS
TO HELP YOU RECOGNIZE HAZARDS AND RISKS, AND TO SHOW YOU
HOW TO MAKE YOUR EXPERIENCE IN CHEMISTRY SAFE AND ENJOY-
ABLE.
Rule 1: Exercise caution and good judgment!

Rule 2: You must wear departmentally approved safety EYE PROTECTION at all
times you are in the laboratory. Know the penalty for failure to follow this
rule. Keep all reaction vessels well away from your face.
Rule 3: Absolutely no unauthorized experiments are to be performed in the
laboratory. Follow directions and read labels on reagents carefully! Your
Laboratory Instructor is responsible for obtaining MSDS sheets from
supply companies for all the safety and waste disposal information on a
particular compound and for informing you of cautions and hazards.
The experiments in this manual are described for specific chemicals and conditions.
Any changes require adequate information about hazards. Changes are the responsibility of
the laboratory director.
Rule 4: Locate all safety equipment and the first aid kit.
When you first go into the lab, locate and remember where each of the safety devices
is so that you can get to them with your eyes closed if you must. (In case of an accident you
may have to.)
a) the fire extinguisher (Study directions for use.)
b) the emergency shower
c) the eye wash fountain
d) the spill absorbent bucket
e) the fire blanket
f) nearest telephone-ask your laboratory instructor to post near the telephone
the telephone numbers for emergency help.
--------- ------------------ ---------------------------

2 Chemical Safety and Laboratory Rules - Bishop/Bishop/Whitten
Rule 5: Always call for help loudly when an accident occurs.

All accidents must be reported immediately to your laboratory instructor. Accidents
may be prevented if you are aware of the potential causes of accidents. About 75% of all
chemistry laboratory accidents involve injuries to the hands. Most of these hand injuries
involve cuts, thermal burns, and chemical burns. Always protect your hand from sharp
glass edges with a towel or thick gloves. Glass stays hot for a long time. The best treatment
for minor thermal burns is to immerse the burned area in cold water. Ointments are diffi-
cult and painful to remove.
Rule 6: The immediate treatment for contact with corrosive chemical agents is
to wash the exposed area with lots of water for about 15 minutes. More
severe chemical burns should be referred to a physician.
Eye wash fountains are necessary pieces of safety equipment. At all times in the labo-
ratory, you must wear the appropriate eye protection (goggles) required by your laboratory
director and by your state laws. Wearing contact lenses is especially hazardous around
chemicals. Eye contact with chemicals should be immediately followed by gentle irrigation
of the eyes with lots of water (about 15 minutes) by using an eye wash fountain.
Rule 7: Open flames must not be used near flammable substances.

Immediately smother small fires in beakers by covering with a watch glass. Call your
instructor immediately in case of fire. Larger fires require the use of a fire extinguisher.
Leave the lab if the fire is uncontrolled. Call the fire department. A fire blanket is helpful to
smother burning clothing. Learn the location and the use of all safety equipment.
Rule 8: Fume hoods are necessary in the chemical laboratory unless the chemi-
cals are classified as very low risk chemicals.
The hood must have a good air flow but not so turbulent that it extinguishes a burner
flame.
Rule 9: Good Hygiene is essential.

Toxic chemicals may enter your body by inhalation, skin absorption, skin and eye con-
tact, and ingestion. Wash your hands often. Do not eat, drink, or smoke in the labora-
tory.
COMMONLY ACCEPTED SAFETY PRECAUTIONS INCLUDE

THE FOLLOWING:
1. Wear the required safety eye protection (safety glasses) in the laboratory at all times.
Contact lenses must not be worn in the laboratory at any time.
2. Wear shoes at all times that provide protection to your feet, i.e., shoes that "shed"
liquids . Sandals and "open top" shoes are not permitted in the laboratory.
3. Long hair must always be tied back. Long hair is a serious fire hazard.
4. Laboratory aprons or coats provide protection for your clothing. Clothing which
covers most of the body provides the best protection.
5. Never eat, drink, chew gum, or smoke in the laboratory. These activities are strictly
prohibited.
6. Consider all chemicals to be dangerous (hazardous) unless you are specifically
instructed otherwise. Read labels carefully!
7. Never taste chemicals unless specifically instructed to do so. Most laboratory directors
require that students do not taste any chemical in the laboratory. Know the policies
of your laboratory director.
Chemical Safety and Laboratory Rules - Bishop/Bishop/Whitten 3
8. Never smell (inhale) gases or vapors directly. When you are instructed to report the
odor of a chemical, gently waft the vapors with your hand toward your nose and smell
cautiously as described in Laboratory Techniques Section /.1.
9. If hazardous chemicals come in contact with your eyes or skin, wash immediately
with large amounts of water. Call for help while you are washing. Contaminated
clothing should be removed.
10. Never rub your eyes unless you are absolutely certain that there are no chemicals on
your hands. Wash your hands with soap and water often, especially after you
complete the laboratory experiments.
11. Volatile chemicals that are poisonous, irritating to the skin, or that have unpleasant
odors should always be used under the fume hood.
12. Never point a test tube or any other reaction vessel toward yourself or anyone else.
Chemicals undergoing reaction may "spatter" over a large area.
13. Most organic liquids are flammable, as are some gases such as hydrogen. Never use
flammable chemicals near a flame or a "hot" hot plate.
14. Clean up all broken glass immediately. Dispose of broken glass in special receptacles
labeled for broken glass. Do not put broken glass in trash cans. The cleaning crew
may cut themselves. Similarly, spilled chemicals should be cleaned up immediately-
consult your instructor for details.
15. Always pour concentrated acids into water, never water into acid. Some concentrated
acids (sulfuric acid, for example) release enough heat to cause severe spattering. Hot,
concentrated acids are very corrosive.
16. Observe carefully the safety precautions that are included in the experiments. The
section on Laboratory Techniques includes many safety precautions.
17. Always be alert to the possibility of an accident by your neighbors. You could be a
victim of their mistakes. Always advise them of any unsafe practices you observe. If
necessary, inform your instructor immediately.
18. Always maintain an orderly, businesslike attitude and a clean, orderly working
space. "Horseplay" may get you expelled from the course.
19. Students are never to work alone in the laboratory. An instructor must always be
present.
20. Unauthorized experiments and unauthorized modifications of experiments in this
manual are strictly prohibited.
21. If you have any doubt about what to do in any set of circumstances, consult your
instructor.
22. Always keep laboratory drawers and doors to laboratory desks closed except when
you are placing something into or removing something from your drawer or desk.
Open doors and drawers obstruct the aisle-such obstruction may cause serious
accidents.
23. Do not return excess chemicals to their original containers unless instructed to do so.
24. Put paper waste and glass waste in separate waste containers.
25. Report broken equipment to your Instructor immediately.
26. Chemicals are never to be taken from the laboratory.
4 Chemical Safety and Laboratoty Rules - Bishop/Bishop/Whitten
Chemical Safety and Laboratory Rules - Bishop/Bishop/Whitten 5
Name._ _ _ _ _ _ _ _ _ _ _ __ Lab Instructor_ _ _ _ _ _ _ __
ID Number_ _ _ _ _ _ _ _ _ __ Lab Period____________
Laboratory Safety Quiz

Reattach this sheet after grading so that you have the data available for review.
I HAVE READ THE CHEMICAL SAFETY AND LABORATORY RULES. I

UNDERSTAND AND WILL OBEY THESE RULES.
SIGNED_____________________________ DATED___________
1. Which safety devices do you have in the laboratory and where are they located?
2. Are there safety devices located in the area near the laboratory that you can use? If
so what are they and where are they located
3. Which telephone numbers do you need to know and what are they? (fire department,
police, etc.)
6 Chemical Safety and Laboratory Rules - Bishop/Bishop/Whitten
4. What should you do in the following circumstances?

a) The clothing of another student catches on fire?
b) Chemicals spatter from another student's test tube into your eye?
c) You spill a bottle of acid on the floor? on the lab bench? on the reagent table?
d) A small beaker of a flammable liquid has caught fire?
e) A bottle of flammable reagent is spilled?

2
Common Equipment
u u
Plastic
wash bottle
Wide-mouthed
bottle
~
BUchner fUI'IIlel aur--. burner
(Tirrill type)
Buret clamp
A Clay triangle
~
Clamp holder
~
Pinchcoek clamp
lkSaewclamp
~CI\ICible and
cover
eMortar and
pM1Ie
Ring stand
u
Stell
spatula
Test tube
bMih "Test tube
holder
I
Ttlt tube fliCk
I
Tbermometer
ee:
TIWigullr fie
;:pr
WlntgiUZe
8 Common Equipment - Bishop/Bishop/Whitten
(~------)~..
--~-==========
-------------
3
The Structure of Crystals-

An Experiment Using Models
f one examines the crystals of an ordinary substance like table salt, using a magnifying glass or a micro-
I scope, one finds many cubic particles, among others, in which planes at right angles are present. This is the
situation with many common solids. The regularity we see implies a deeper regularity in the arrangement of
atoms or ions in the solid. Indeed, when we study crystals by x-ray diffraction, we find that the atomic nuclei
are present in remarkably symmetrical arrays, which continue in three dimensions for thousands or millions
of units. Substances having a regular arrangement of atom-size particles in the solid are called crystalline, and
the solid material consists of crystals. This experiment deals with some of the simpler arrays in which atoms
or ions occur in crystals, and what these arrays can tell us about such properties as atomic sizes, densities of
solids, and the efficiency of packing of particles.
Many crystals are complex, almost beyond belief. We will limit ourselves to the simplest crystals, those
which have cubic structures. They are by far the easiest to understand, yet they exhibit many of the interest-
ing properties of more complicated structures. We will further limit our discussion to substances containing
only one or two kinds of atoms, so we will be working with the crystals of some of the elements and some
binary compounds.
The atoms in crystals occur in planes. Sometimes a crystal will cleave readily at such planes. This is
the reason the cubic structure of salt is so apparent. Let us begin our study of crystals with a simple exam-
ple, a two-dimensional crystal in which all of the atoms lie in a square array in a plane, in the manner shown
below:
0 0 0 0 0 0 0 0 0 0
r----,
I I
0 o---o 0 I 0 I 0 0
I I /0---;0 0
I I IL . - - - - . J
I
I I /// ///
0
I
o---o
I
0 0 0
o(_ __ cf 0 0
0 0 0 0 0 0 0 0 0 0
The first thing that you need to realize is that the array goes on essentially forever, in both directions. In
this array 0 is always the same kind of atom, so all the atoms are equivalent. The distance, d 0 , between atoms
in the vertical direction is the same as in the horizontal, so if you knew either distance you could generate the
array completely. In crystal studies we select a small section of the array, called the unit cell, that represents
the array in the sense that by moving the unit cell repeatedly in either the x or y direction, a distance d 0 at a
time, you could generate the entire array. In the sketch we have used dotted lines to indicate several possible
unit cells. All the cells have the same area, and by moving them up or down or across we could locate all the
sites in the array. Ordinarily we select the unit cell on the left, because it includes four of the atoms and has
its edges along the natural axes, x andy, for the array, but that is not necessary. In fact, the middle cell has the
advantage that it clearly tells us that the number of 0 atoms in the cell is equal to 1. The number of atoms in
whatever cell we choose must also equal 1, but that is not so apparent in the cell on the left. However, once
you realize that only V4 of each atom on the comers of the cell actually belongs to that cell, because it is
shared by three other cells, the number of atoms in the whole cell becomes equal to V4 x 4, or 1, which is
what we got by drawing the cell in a different position.
10 The Structure Of Crystals- An Experiment Using Models -Slowinski
When we extend the array to three dimensions, the same ideas regarding unit cells apply. The unit cell is
the smallest portion of the array that could be used to generate the array. With cubic cells the unit cell is usu-
ally chosen to have edges parallel to the x, y, and z axes we could put on the array.
IN THIS EXPERIMENT YOUR INSTRUCTOR MAY

Experimental Procedure ALLOW YOU TO WORK WITHOUT SAFETY GLASSES
In this experiment we will mix the discussion with the experimental procedure, since one supports and illus-
trates the other. We will start with the simplest possible cubic crystal, deal with its properties, and then go on
to the next more complex example, and the next, and so on. Each kind of crystal will be related in some ways
to the earlier ones but will have its own properties as well. So get out your model set and let's begin.
Work in pairs, and complete each section before going on to the next, unless directed otherwise by your
instructor.
The Simple Cubic Crystal

You can probably guess the form of the array in the crystal structure we call simple cubic (SC). It is shown on
the Calculations page at the end of this section.
The unit cell is a cube with an edge length equal to the distance from the center of one atom to the center
of the next. The cell edge is usually given the symbol d 0 • The volume of the unit cell is d 0 3 , and is very small,
since d 0 is of the order of 0.5 nm. Using x-rays we can measure d 0 to four significant figures quite easily. The
number of atoms in the unit cell in a simple cubic crystal is equal to 1. Can you see why? Only l/8 of each
comer atom actually belongs to the cell, since it is shared equally by eight cells.
Using your model set, assemble three attached unit cells having the simple cubic structure shown in the
sketch. Use the short bonds (no. 6) and the gray atoms. Each bond goes into a square face on the atom. An
actual crystal with this structure would have many such cells, in three dimensions.
If you extended the model you have made further, you would find that each atom would be connected to
six others. We say that the coordination number of the atoms in this structure is 6. Only the closest atoms are
considered to be bonded to each other. In the other models we will be making, only those atoms that are
bonded, by covalent or ionic bonds, will be connected to one another, so the number of bonds to an atom in a
large model will be equal to the coordination number.
Although the model has an open structure to help us see relationships better, in an actual crystal we con-
sider that the atoms that are closest are touching. It is on this assumption that we determine atomic radii. In
this SC crystal, if we know d 0 we can find the atomic radius r of the atoms, since, if the atoms are touching,
d 0 must equal 2r. Another property we can calculate knowing d 0 is the density, given the nature of the atoms
in the crystal. From d 0 we can easily find the volume V of the unit cell. Since there is one atom per cell, a mole
will contain Avogadro's number of cells. Given the molar mass of the element, we can find the mass m of a
cell. The density is simply m/V. With more complex crystals we can make these same calculations, but must
take account of the fact that the number of atoms or ions per unit cell may not be equal to one.
Essentially no elements crystallize in an SC structure. The reason is that SC packing is inefficient, in that
the atoms are farther apart than they need be. There is, as you can see, a big hole in the middle of each unit
cell that is begging for an atom to go there, and atoms indeed do. Before we go into that, let's calculate the
fraction of the volume of the unit cell that is actually occupied by atoms. This is easy to do. Make the calcu-
lation of that fraction on the Calculations page.
That fraction is indeed pretty small; only about 52 percent of the cell volume is occupied by atoms. Most
of the empty space is in that hole. You can calculate by simple geometry that an atom having a radius equal
to 73 percent of that of the atom on a comer would fit into the hole. Or, putting it another way, an atom bigger
than that would have to push the comer atoms back to fit in. If the particles on the comers were anions, and
the atom in the hole were a cation, the cation in the hole would push the anions apart, decreasing the repul-
sion between them and maximizing the attraction between anions and cations. We will have more to say about
this when we deal with binary salts, but for now you need to note that if r/r_ > 0.732, the cation will not fit
in the cubic hole formed by anions on the comers of an SC cell.
The Structure Of Crystals -An Experiment Using Models - Slowinski 11
Body-Centered Cubic Crystals

In a body-centered cubic (BCC) crystal, the unit cell still contains the comer atoms present in the SC struc-
ture, but in the center of the cell there is another atom of the same kind. The unit cell is shown on the
Calculations page.
Using your model set, assemble a BCC crystal. Use the blue balls. Put the short bonds in the eight holes
in the triangular faces on one blue ball. Attach a blue ball to each bond, again using the holes in a triangular
face. Those eight blue balls define the unit cell in this structure. Add as many atoms to the structure as you
have available, so that you can see how the atoms are arranged. In a BCC crystal each atom is bonded to eight
others, so the coordination number is 8. Verify this with your model. (There are no bonds along the edges of
the unit cell, since the comer atoms are not as close to one another as they are to the central atom.)
The BCC lattice is much more stable than the SC one, in part at least because of the higher coordination
number. Many metals crystallize in a BCC lattice-including sodium, chromium, tungsten, and iron-when
these metals are at room temperature.
There are several properties of the BCC structure that you should note. The number of atoms per unit cell
is two, one from the comer atoms and one from the atom in the middle of the cell, where it is unshared. As
with SC cells, there is a relation between the unit cell size and the atom radius. Given that in sodium metal the
cell edge is 0.429 nm, calculate the radius of a sodium atom on the Calculations page. When you are finished,
calculate the density of sodium metal.
The fraction of the volume that is occupied by atoms in a BCC crystal is quite a bit larger than with SC
crystals. Using the same kind of procedure that we did with the SC structure, we can show that in BCC crys-
tals about 68 percent of the cell volume is occupied.
Close-Packed Structures
Although many elements form BCC crystals, still more prefer structures in which the atoms are close packed.
In such structures there are layers of atoms in which each atom is in contact with six others, as in the sketch
below:
This is the way that billiard balls lie in a rack, or the honeycomb cells are arranged in a bees' nest. It is the
most efficient way one can pack spheres, with about 74 percent of the volume in a close-packed structure filled
with atoms. It turns out that there is more than one close-packed crystal structure. The layers all have the same
structure, but they can be stacked on one another in two different ways. This is certainly not apparent at first
sight. The first close-packed crystal we will examine is cubic, amazingly enough, considering all those trian-
gles in the layers of atoms.
Face-Centered Cubic Crystals

In the face-centered cubic (FCC) unit cell there are atoms on the comers and an atom at the center of each
face. There is no atom in the center of the cell (see the sketch on the Calculations page, where we show the
bonding on only the three exposed faces).
Constructing an FCC unit cell, using bonds between closest atoms, is not as simple as you might think,
so let's do it the easy way. This time select the large gray balls, the ones with the most holes. Make the bottom
face of the unit cell by attaching four gray balls to a center ball, using short bonds, and holes that are in rec-
tangular faces. You should get the structure on the left below:
X--X--X
I
X
I
To make the middle layer of atoms, connect four of the balls in a square, again using short bonds and the holes
in rectangular faces, as in the right sketch. The top layer is made the same way as the bottom one. Then con-
nect the layers to one another, again using holes in the rectangular faces. You should then have an FCC cubic
unit cell. Because the atoms in the middle of adjacent faces are as close to one another as they are to the comer
atoms, there should be bonds between them. There are quite a few bonds in the final cell, 32 in all. Put them
all in. As with BCC there are no bonds along the edges of the cell.
The FCC, or cubic close-packed, structure is a common one. Among the metals with this type of crystal
are copper, silver, nickel, and calcium.
In close-packed structures the coordination number is the largest that is possible. It can be found by look-
ing at a face-centered atom, say on the top face of the cell. That atom has eight bonds to it and would also
have bonds to atoms in the cell immediately above, four of them. So its coordination number, like that of every
atom in the cell, is 12.
Having seen how to deal with other structures, you should now be able to find the number of atoms in the
FCC unit cell and the radius of an atom as related to d0 • From these relationships and the measured density,
you can calculate Avogadro's number. On the Calculations page, find these quantities, using copper metal,
which has a unit cell edge d 0 equal to 0.361 nm and a density equal to 8.92 g/cm 3 •
In the center of the unit cell there is a hole. It is smaller than a cubic hole but of significant size nonethe-
less. It is called an octahedral hole, because the six atoms around it define an octahedron. In an ionic crystal,
the anions often occupy the sites of the atoms in your cell, and there is a cation in the center of the octahedral
hole. On the Calculations page, find the maximum radius, r+, of the cation that would just fit in an octahedral
hole surrounded by anions of radius r_. You should find that the r/r_ ratio turns out to be 0.414.
There is another kind of hole in the FCC lattice that is important. See if you can find it; there are eight of
them in the unit cell. If you look at an atom on the comer of the cell, you can see that it lies in a tetrahedron.
In the center of the tetrahedron there is a tetrahedral hole, which is small compared to an octahedral or cubic
hole. However, in some crystals small cations are found in some or all of the tetrahedral holes, again in a close-
packed anion lattice. The cation-anion radius ratio at which cations would just fit into a tetrahedral hole is not
so easy to find; r/r_ turns out to be 0.225.
The close-packed layers of atoms in the FCC structure are not parallel to the unit cell faces, but rather are
perpendicular to the cell diagonal. If you look down the cell diagonal, you see six atoms in a close-packed tri-
angle in the layer immediately behind the comer atom, and another layer of close-packed atoms below that,
followed by another comer atom. The layers are indeed closely packed, and, as one goes down the diagonal
of this and succeeding cells, the layers repeat their positions in the order ABCABC ... , meaning that atoms in
every fourth layer lie below one another.
Clearly there is another way we could stack the layers. The first and second will always be in the same rel-
ative positions, but the third layer could be below the first one if it were shifted properly. So we can have a close-
packed structure in which the order of the layers is ABABAB .... The crystal obtained from this arrangement of
layers is not cubic, but hexagonal. It too is a common structure for metals. Cadmium, zinc, and manganese have
this structure. As you might expect, the stability of this structure is very similar to that of FCC crystals. We find
that simply changing the temperature often converts a metal from one form to another. Calcium, for example,
is FCC at room temperature, but if heated to 450°C it converts to close-packed hexagonal.
Crystal Structures of Some Common

Binary Compounds
We have now dealt with all of the possible cubic crystal structures for metals. It turns out that the structures
of binary ionic compounds are often related to these metal structures in a very simple way. In many ionic crys-
tals the anions, which are large compared with cations, are essentially in contact with each other, in either an
SC or FCC structure. The cations go into the cubic, or octahedral, or tetrahedral holes, depending on the
cation-anion radius ratios that we calculated. The idea is that the cation will tend to go into a hole in which it
will not quite fit. This increases the unit cell size from the value it would have if the anions were touching,
which reduces the repulsion energy due to anion-anion interaction and increases to the maximum the cation-
anion attraction energy, producing the most stable possible crystal structure. According to the so-called radius-
ratio rule, large cations go into cubic holes, smaller ones into octahedral holes, and the smallest ones into
tetrahedral holes.
The deciding factor for which hole is favored is given by the radius ratio:
If r)r_ > 0.732 cations go into cubic holes

If 0.732 > r)r_ > 0.414 cations go into octahedral holes
If 0.414 > r+lr- > 0.225 cations go into tetrahedral holes
The NaCI Crystal

To apply the radius-ratio rule to NaCI, we simply need to find r)r_, using the data in Table 16.1. Since rNa+=
0.095 nm, and rc1-= 0.181 nm, the radius ratio is 0.095/0.181, or 0.525. That value is less than 0.732 and
greater than 0.414, so the sodium ions should go into octahedral holes. We saw the octahedral hole in the
center of the FCC unit cell, so Na+ ions go there, and the CI- ions have the FCC structure. Actually, there are
12 other octahedral holes associated with the cell, one on each edge, which would be apparent if we had been
able to make more cells. An Na+ ion goes into each of these holes, giving the classic NaCl structure shown on
the Calculations page. (Again, only the ions and bonds on the exposed faces are shown.)
Make a model of the unit cell for NaCl, using the large gray balls for the CI- ions and the blue ones for
Na+ ions. Clearly the Na+ ion at the center of the cell is in an octahedral hole, but so are all of the other sodium
ions, because if you extend the lattice, every Na+ ion will be surrounded by six CI- ions. The coordination
number of Na+, and of CI-, ions is 6. The crystal is FCC in CI- and also in Na+, because you could put Na+
ions on the corners of the unit cell and maintain the same structure. The unit cell extends from the center of
one CI- ion to the center of the next CI- along the cell edge; or, from the center of one Na+ ion to the center
of the next Na+ ion.
On the Calculations page find the number of Na+ and of CI- ions in the unit cell.
The CsCI Crystal

Cesium chloride has the same type of formula as NaCI, 1:1. The Cs+ ion, however, is larger than Na+, and has
a radius equal to 0.169 nm. This makes r)r_ equal to 0.933. Because this value is greater than 0.732, we would
expect that in the CsCl crystal the Cs+ ions will fill cubic holes, and this is what is observed. The structure of
CsCl will look like that of the BCC unit cell you made earlier, except that the ion in the center will be Cs+ and
those on the corners CI-. If you put gray balls in the center of each BCC unit cell you made from the blue
balls, you would have the CsCl structure. This structure is not BCC, because the corner and center atoms are
not the same. Rather it consists of two interpenetrating simple cubic lattices, one made from CI- ions and the
other from cs+ ions.
The Zinc Sulfide Crystal

Zinc sulfide is another 1: 1 compound, but its crystal structure is not that of NaCl or of CsCI. In ZnS, the Zn 2+
ions have a radius of 0.074 nm and the S2- ions a radius of 0.184 nm, making r)r_ equal to 0.402. By the
radius-ratio rule, ZnS should have close-packed S2- ions, with the Zn 2+ ions in tetrahedral holes. In the ZnS
unit cell, we find that this is indeed the case; the S2- ions are FCC, and alternate tetrahedral holes in the unit
cell are occupied by Zn 2+ ions, which themselves form a tetrahedron.
To make a model for ZnS, first assemble an SC unit cell, using blue balls and the long bonds. Use gray
balls for the zinc ions, and assemble the unit shown below, using the short bonds and the holes in triangular
faces:
Attach this unit to two comer atoms on the diagonal of the bottom face. Make another unit and attach it
to the two comer atoms in the upper face that lie on the face diagonal that is not parallel to the bottom face
diagonal. The gray balls should then form a tetrahedron. Then attach the four other FCC blue balls to the gray
ones. In this structure the coordination number is four (the long bonds do not count, they just keep the unit
cell from falling apart). If the gray balls in the unit cell are replaced with blue ones, so that all atoms are of
the same element, we obtain the diamond crystal structure.
These are the three common cubic structures of 1:1 compounds. The radius-ratio rule allows us to predict
which structure a given compound will have. It does not always work, but it is correct most of the time. On
the Calculations page, use the rule to predict the cubic structures that crystals of the following substances will
have: KI, CuBr, and TlBr.
The Calcium Fluoride Crystal

Calcium fluoride is a 1:2 compound, so it cannot have the structure of any crystal we have discussed so far.
The radii of Ca2+ and p-are 0.099 and 0.136 nm, respectively, so r/r_ is 0.727. This makes CaF2 on the
boundary between compounds with cations in cubic holes or octahedral holes. It turns out that in CaF2 , the p-
ions have a simple cubic structure, with half of the cubic holes filled by Ca2+ ions. This produces a crystal in
which the Ca2+ ions lie in an FCC lattice, with 8 p- ions in a cube inside the unit cell.
Use your model set to make a unit cell for CaF2 • Use gray balls for the Ca2+ ions and red ones for F-. The
cations and anions are linked by short bonds that go into holes in nonadjacent triangular faces. The Ca2+ ions
on each face diagonal are linked top- ions as shown below:
To complete the bottom face, attach two red and two gray balls to the initial line, so that the four red balls
form a square and the gray ones an FCC face. The top of the unit cell is made the same way. Attach the two
assemblies through four gray balls, which lie at the centers of the other faces. When you are done, the red balls
should form a cube inside an FCC unit cell made from gray balls. Extend the model into an adjacent unit cell
to show that every other cube of p- ions has a Ca2+ ion at its center.
When you have completed this part of the experiment, your instructor may assign you a model with which
to work. Report your results as directed. Then disassemble the models you made and pack the components in
the box.
Name Section
Experiment 16
Data and Calculations: The Structure of Crystals
Table 16.1
Atom Molar Mass, g!mole Atomic Radius, nm Ionic Radius, nm
Na 22.99 0.095
Cu 63.55 0.096
Cl 35.45 0.099 0.181
Cs 132.9 0.262 0.169
Zn 65.38 0.133 0.074
s 32.06 0.104 0.184
K 39.10 0.231 0.133
126.9 0.133 0.216
Br 79.90 0.114 0.195
Tl 204.4 0.171 0.147
Some Cubic Unit Cells
sc
NaCII±Ifi
Simple Cubic Crystal
Fraction of volume of unit cell occupied by atoms
Volume of unit cell in terms of d 0
Number of atoms per unit cell
Radius r of atom in terms of d0
4 3
Volume of atom in terms of d 0 ( V = 1t r )
3
Volume of atom/volume of cell
(continued on following page)

16 The Structure Of Crystals -An Experiment Using Models - Slowinski
Body-Centered Cubic Crystal

a. Radius of a sodium atom
In BCC atoms touch along the cube diagonal

(see your model)
Length of cube diagonal if d 0 = 0.429 nm _ _ _ _ _ nm
4x rNa = length of cube diagonal
b. Density of sodium metal
Length of unit cell, d0 , in em (I em = 107 nm) _ _ _ _ _ em
Volume of unit cell, V _ _ _ _ _ cm 3
Number of unit cells per mole Na
Mass of a unit cell, m _____ g
Density of sodium metal, m!V (Obs. 0.97 g/cm 3 ) _ _ _ _ _ g/cm 3
Face-Centered Cubic Crystal

a. Number of atoms per unit cell
Number of atoms on comers ____ Shared by ____ cells ____ x _ _ __
Number of atoms on faces ____ Shared by ____ cells ____ x ____
Total atoms per cell _ _ _ __
b. Radius of a Cu atom
In FCC atoms touch along face diagonal (see your model and ASA)
Length of face diagonal in Cu, where d 0 = 0.361 nm _ _ _ _ _ nm
Number of Cu atom radii on face diagonal _ _ rcu = - - - - - nm

c. Avogadro's Number, N
Length of cell edge, d 0 , in em, in Cu metal em
Volume of a unit cell in Cu metal cm 3
Volume of a mole of Cu metal (V =mass/density) cm3
Number of unit cells per mole Cu
Number of atoms per mole, N
d. Size of an octahedral hole
Below is a sketch of the front face of a face-centered cubic cell with the NaCl structure. The ions are
drawn so that they are just touching their nearest neighbors. The cations are in octahedral holes.
Show the length of d 0 on the sketch. (See your model.)
What is the relationship between r_ and d 0 ?
r = ______ x d0
What is the equation relating r+, r_, d 0 ?
do=------
What is the relationship between r+ and d0 ?
What is the value of the radius ratio r/r_? Express the ratio to three significant figures.
r/r_ = ______

NaCI Crystal
Number of CI- ions in the unit cell (FCC)
Number of Na+ ions on edges of cell ______ Shared by ______ cells
Number of Na+ ions in center of cell _ _ _ _ _ Shared by _ _ _ _ _ cell(s)
Total no. Na+ ions in unit cell
Radius-ratio rule (data in Table 16.1)
KI r)r__ _ _ _ _ Predicted structure ______ Obs. NaCl
CuBr r)r______ Predicted structure ______ Obs. ZnS
TlBr r)r__ _ _ _ _ Predicted structure _ _ _ _ _ Obs. CsCl
Report on unknown
The Structure Of Crystals - An Experiment Using Models - Slowinski 19
Name Section
Experiment 16
Advance Study Assignment: The Structure of Crystals
1. Many substances crystallize in a cubic structure. The unit cell for such crystals is a cube having an edge
with a length equal to d 0 •
Face diagonal
a. What is the length, in terms of d 0 , of the face diagonal, which runs diagonally across one face of the
cube?
b. What is the length, again in terms of d 0 , of the cube diagonal, which runs from one comer, through
the center of the cube, to the other comer? Hint: Make a right triangle having a face diagonal and an
edge of the cube as its sides, with the hypotenuse equal to the cube diagonal.
2. In an FCC structure, the atoms are found on the comers of the cubic unit cell and in the centers of each
face. The unit cell has an edge whose length is the distance from the center of one comer atom to the
center of another comer atom on the same edge. The atoms on the diagonal of any face are touching. One
of the faces of the unit cell is shown below.
a. Show the distance d 0 on the sketch. Draw the boundaries of the unit cell.
b. What is the relationship between the length of the face diagonal and the radius of the atoms in the
cell?
Face diagonal = _ _ _ _ __

20 The Structure Of Crystals -An Experiment Using Models - Slowinski
c. How is the radius of the atoms related to d 0 ?
r= ______
d. Silver metal crystals have an FCC structure. The unit cell edge in silver is 0.4086 nm long. What is
the radius of a silver atom?
______ nm
4
COLLIGATIVE PROPERTIES OF SOLUTIONS
In this experiment, you will
0 Demonstrate the movement of solvent through a membrane as a result of osmotic pressure.

0 Measure the depression in freezing point for water resulting from the addition of a solute
and evaluate the freezing-point constant for water.
0 Measure the elevation in boiling-point for water resulting from the addition of a solute, and
evaluate the boiling point constant for water.
INTRODUCTION
Certain properties of solvents change when a solute is dissolved in the solvent to form
a solution. The freezing point of saltwater, for example, is lower than the freezing point
of pure water. Properties of this type, called colligative properties, also include the
vapor pressure, boiling point, and osmotic pressure of solutions. All colligative
properties depend on the concentration of solute particles present in a solution. For
example, a 1 molar (M) solution of potassium chloride (KCl) has a lower freezing point
than a 1 M solution of sugar. This difference occurs because 1 mol of KCl dissociates
and produces 2 mol of solute particles ( K+ and Ct ions), whereas 1 mol of sugar
produces only 1 mol of undissociated sugar molecules upon dissolving.
~~ EXPERIMENTAL PROCEDURE
A Osmosis and Osmotic Pressure

If two solutions of different concentration are separated by a semipermeable
membrane through which solvent (but not solute) can flow, solvent will flow from the
dilute solution into the concentrated solution. The pressure necessary to prevent
solvent flow between such a pair of solutions is called the osmotic pressure of the
system and depends on the solute concentration difference between the two solutions.
Jn this part of the experiment, the magnitude of the osmotic pressure will not be
measured, but the associated flow of solvent through membranes will be illustrated.
PROCEDURE
1. Prepare a sugar solution by dissolving about 10 g of sucrose (table sugar) in
about 90 mL of distilled water contained in a 125-mL flask.
2. Mix the resulting solution thoroughly by swirling the flask.
22 Colligative Properties Of Solutions - Seager/Slabaugh
3. Obtain two 8-cm lengths of dialysis tubing from the stockroom. Moisten each
piece in water and open it.
4. Tie one end of each piece tightly closed with string to form a tube.
5. Put 5 mL of the sugar solution prepared in Step 1 into one tube, then tie the
tube tightly closed while excluding most of the air. Make sure no solution can
leak out.
6. Put 5 mL of distilled water into the other tube and tie it closed, again making
sure that it doesn't leak.
7. Identify the tubes in some way to remind you of their contents.
8. Rinse both tubes under running water for a short time, then pat them dry care-
fully with a towel. Do not attempt to completely dry the strings.
9. Weigh each tube on a centigram or electronic balance.
10. Record the mass of the water-filled tube in Table 10.1 and the mass of the sugar-
solution-filled tube in Table 10.2.
11. Put the remaining sugar solution from Step 1 into a 250-mL beaker.
12. Put about 100 mL of distilled water into another 250-mL beaker.
13. Label the beakers so you know what each contains.
14. Put the water-filled dialysis tube into the beaker of sugar solution and the sugar-
solution-filled tube into the beaker of water.
15. Obtain two dried prunes (nonpitted), rinse them in water, and wipe off the ex-
cess water with a towel.
16. Weigh each prune on the same balance used in Step 9.
17. Record the mass of one prune in Table 10.1, then put the prune into the beaker
containing the sugar solution.
18. Record the mass of the second prune in Table 10.2, then put the prune into
the beaker containing distilled water.
19. Let all samples remain in the beakers for at least 1 hour. A longer time will
improve your results. Go on to other parts of the experiment while the samples
soak in the beakers.
20. After at least 1 hour, remove all samples, being careful to note which beaker
they were in.
21. Rinse the samples in water, wipe off excess water, and weigh them on the same
balance used for the earlier weighings.
22. Record the masses of the samples from the beaker containing sugar solution in
Table 10.1 and those from the beaker containing distilled water in Table 10.2.
4ili\
~~~
Beaker contents and dialysis-tubing contents in sink. Used prunes
\,~ '~
Disposal in wastebasket.
B. Freezing-Point Depression
The freezing point of a solution is lower than the freezing point of the pure solvent.
The difference in temperature, L!t 1 , between the pure solvent and solution freezing
points is
Eq. 10.1
In this expression, m is the molal concentration of solute in the solution and k1 is the
freezing-point constant of the solvent. Numerical values of k1 are different for each
Colligative Properties Of Solutions - Seager/Slabaugh 23
solvent and must be determined experimentally. For example, k1 is 4.90 for benzene
and 3.90 for acetic acid.
The molal concentration (m) used in Equation 10.1 is defined below and can
be calculated as follows:
m = the number of moles of solute dissolved in 1 kg of solvent
moles of solute
m=------- Eq. 10.2
kilograms of solvent
In this part of the experiment, you will collect data that will enable you to esti-
mate the value of k1 for water.
PROCEDURE
1. Accurately weigh a clean, dry, empty 100-mL beaker on a centigram or
electronic balance. Record the mass in Table 10.4 in the blank corresponding to
sodium chloride as the solute.
2. Add enough crushed ice to fill the beaker 1/2 full.
3. Use your graduated cylinder and add about 25 mL of distilled water to the
beaker. Weigh the beaker on the same balance used in Step 1. Record the mass
in Table 10.4 in the blank corresponding to sodium chloride solute.
4. Use a thermometer and measure the lowest temperature resulting in the stirred
ice-and-water mixture (estimate to the nearest 0.1 oq Record this temperature,
which is the freezing point of pure water.
5. Accurately weigh about 5 g of sodium chloride on a centigram or electronic
balance. Use the difference technique and record the empty container mass
and the container-plus-sample mass in Table 10.4.
6. Add the salt to the ice-and-water mixture in the beaker.
7. Put your thermometer into the mixture and hold it there while you stir the
mixture steadily with a glass stirring rod. Continue the steady stirring until the
unmelted floating ice in the beaker forms a thin layer that covers 1/2 to 2/3 of
the surface of the liquid. At that point, read the thermometer without removing it
from the mixture. The temperature at that point is the solution freezing point.
Record the freezing point in Table 10.4. The process of stirring until the freezing
point is obtained will take approximately 5-8 minutes, but be patient and get a
good temperature reading.
8. Empty, rinse, and dry the beaker. Repeat Steps 1 to 4, but record the data in the
blank corresponding to the ethylene glycol solute. Set the mixture aside and
proceed with Steps 9 and 10. Record the data in Table 10.4 under the ethylene
glycol solute heading.
1fl'
\~-~
Beaker contents in sink;.
Disposal
9. Weigh an empty, dry 50-mL beaker on the centigram or electronic balance

used in the repeated Steps 1 and 2. Record the mass.
10. Using a dry graduated cylinder, put about 4.5 mL of ethylene glycol into the
50-mL beaker, reweigh, and record the combined mass.
11. Add the ethylene glycol sample to the ice-and-water mixture from Step 8. You
might have to rinse the last traces of ethylene glycol from the weighing beaker,
using a little of the water from the ice-water mixture. Pour any such rinsings
back into the ice-water mixture. Stir the resulting mixture steadily as you did
before. Record the freezing point of the solution in Table 10.4 under the ethyl-
ene glycol solute heading.
Beaker contents in container labeled •Exp. 1o. Used Ethylene

Disposal glycol Parts B and C'.
C. Boiling-Point Elevation
The boiling point of a solution is also different than the boiling point of the pure
solvent. However, the boiling point of the solution is higher, and the difference, ~tb , is
given by Equation 10.3, where m is the molal concentration of solute in the solution
and kb is the boiling-point constant for the solvent:
Eq.l0.3
We see that the M values for boiling and freezing points of solutions are calculated
using similar equations-only the k's are different. The boiling point constant, kb,
can be evaluated experimentally by procedures similar to those used to evaluate k 1 .
PROCEDURE
1. Put about 50 mL of distilled water into a 100-mL beaker and add 1 or 2 boiling
chips.
2. Heat until the water boils steadily.
3. Measure the boiling point by completely submerging the thermometer bulb in
the boiling water, without the thermometer bulb touching the bottom of the
beaker.
4. Record in Table 10.6 the maximum steady temperature reading from the ther-
mometer (the boiling point of pure water). Once again, estimate the thermome-
ter reading to 0.1 °C.
5. Empty and dry the beaker.
6. Use your graduated cylinder and put exactly 50.0 mL of distilled water into the
beaker. Add 1 or 2 boiling chips. Record the volume of water used in Table 10.6
under the sucrose solute heading.
7. On a centigram or electronic balance, accurately weigh by difference a sample
of sucrose (table sugar) equal to about 20 g. Record the appropriate data in
Table 10.6.
8. Add the sucrose sample to the water in the beaker and stir well.
9. Stirring carefully, heat the mixture until it boils steadily, then measure and
record the boiling point as before. Measure the temperature as soon as the
mixture boils steadily and the thermometer reading becomes steady to avoid
boiling solvent from the mixture.
10. Empty, rinse, and dry the beaker.
~ Beaker contents in Scink.

Disposal
11. Repeat Steps 6 to 9, but substitute 20 mL of ethylene glycol for the sucrose.
Using a 50-mL beaker as a container, weigh the ethylene glycol by difference.
Rinse the last traces of ethylene glycol from the weighing beaker by pouring a
little of the water sample into the weighing beaker, swirling, and returning the
rinse material to the rest of the water sample in the 100-mL beaker. Record the
data in Table 10.6 under the ethylene glycol solute reading.
Beaker contents in container labeled "Exp. 10"·· Used Ethylene

Disposal glycol Parts: B .and c.·
I~ CALCULATIONS AND REPORT
A Osmosis and Osmotic Pressure

1. Use the masses recorded in Tables 10.1 and 10.2 to determine whether each
sample gained or lost mass. Indicate your results in Table 10.3, with a + for a
gain and a - for a loss.
2. Use the results of Step 1 and determine the direction of solvent flow for each
sample: into the sample (+) or out of the sample (-). Record your conclusions.
3. On the basis of these conclusions, decide whether the concentration of sugar
solute inside the sample was higher (+),or lower(-), or about equal (0) to that
of the surrounding liquid. Remember that, during osmosis, solvent flows
through membranes from the dilute solution into the concentrated solution.
Record your conclusions.
1. The total mass of water in each sample equals the mass of ice plus the mass of
water added from the graduated cylinder. Determine this total mass from data
in Table 10.4. Record the total mass of the water sample in Table 10.5.
2. Calculate and record the mass of the sodium chloride solute sample used.
3. One mole of sodium chloride weighs 58.5 g. Use this value and the sodium
chloride sample mass to calculate the number of moles of sodium chloride in the
sample (Equation 10.4). Record the result in Table 10.5.
1 mol NaCl
moles NaCl =mass NaCl x - - - - Eq. 10.4.
58.5 gNaCl
4. Calculate and record M 1 by subtracting the freezing point of the solution from
the freezing point of pure water.
5. Express the total mass of the water sample in kilograms and record the result.
6. Calculate the molality of the solution by dividing the number of moles of sodium
chloride by the number of kilograms of water in the sample (Equation 10.2).
Record the result.
7. Note that Equation 10.1 can be rearranged into the form
Eq. 10.5
Use this equation, the calculated M 1 and the calculated molality of the solution
to evaluate k 1 . Record the result of this calculation in Table 10.5.
8. Repeat the above calculations, using the data collected in Table 10.4 for ethyl-
ene glycol (1 mol= 62.0 g). Record the results.
1. The mass of water in each sample is obtained from the volume used (50.0 mL)
and the water density of 1.00 g/mL. Use data from Table 10.6 and calculate and
record this mass in Table 10.7.
2. Using data from Table 10.6, calculate and record the mass of sucrose solute
added to the water.
3. One mole of sucrose weighs 342 g. Use this value and the mass of the sucrose
sample to calculate the number of moles of sucrose in the sample (use Equa-
tion 10.4, but substitute sucrose information in place of NaCl). Record this
result.
4. Calculate and record Mb by subtracting the boiling point of pure water from
the boiling point of the solution.
5. Express the mass of water in the sample in kilograms and record the result.
6. Calculate the molality of the solution by using Equation 10.2.
7. Rearrange Equation 10.3 to allow you to evaluate kb from Mb and m, then
calculate kb . Record the result.
8. Repeat the above calculations, using the data collected in Table 10.6 for ethyl-
ene glycol (1 mol= 62.0 g). Record the results in Table 10.7.
Name Section Date

-------------------------- ------------- -----
Experiment 1 0 ... Pre-lab Review

1. Are any specific safety alerts given in the experiment? List any that are given.
2. Are any specific disposal directions given in the experiment? List any that are given.
3. List the steps used to weigh a sample of material using the difference technique.
4. What special precautions should be taken when you prepare dialysis tubes full of liquid in
Part A?
5. In Part A, why is it important to note which centigram or electronic balance is used when the
liquid-filled dialysis tubes and the prunes are first weighed?
6. To what extent should you estimate your thermometer readings when making temperature
measurements in this experiment?
7. In Part B why must the 100-mL beaker used in Step 1 be dry?

8. How do you know what temperature to record as a freezing point in Part B?
9. What precaution is taken in this experiment to make sure that boiling occurs smoothly without
spattering?
10. In Parts B and C, how do you make certain that all of the weighed ethylene glycol sample is
added to the water solution?
11. How do you know what temperature to record as a boiling point in Part C?
Name Section Date

-------------------------- ------ -----
Experiment 1 0 ... Data and Report Sheet
A. Osmosis and Osmotic Pressure

Table 10.1 Samples Placed in Sugar Table 10.2 Samples placed in Water
Solution (data) (data)
Mass Mass Mass Mass
Before After Before After
Sample Soaking Soaking Sample Soaking Soaking
Dialysis tubing Dialysis tubing

containing water containing sugar
solution
Prune
Prune
Table 10.3 (report)

Cone. of
Sugar
(inside sample
relative to
Surrounding Change in Direction of surrounding
Sample Liquid Sample Mass Solvent Flow liquid)
Dialysis tubing + water Sugar solution
Dialysis tubing + sugar solution Pure water
Prune Sugar solution
Prune Pure water

Table 10.4 (data) Table 10.5 (report)

Sodium Ethylene Sodium Ethylene
Chloride Glycol Chloride Glycol
Solute Solute Solute Solute
Mass of beaker + ice Total water mass

+water
Mass of solute
Mass of empty
beaker Moles of solute
Freezing point of
pure water
Water mass in kg
Mass of container
+sample Solution molality
Mass of empty
container
Freezing point
of solution
Table 10.6 (data) Table 10.7 (report)

Ethylene
Boiling point of pure water Sucrose Glycol
Solute Solute
Ethylene
Sucrose Glycol Total water mass
Solute Solute
Mass of solute
Volume of water used - - - -
Moles of solute
Mass of solute +
container
Mass of empty Water mass in kg

container
Solution molality
Boiling point of
solution
QUESTIONS
1. Suppose that in Part A of the experiment you confused the dialysis tube samples and put them
into the wrong beakers. What results would have been observed?
a. Both samples would increase in mass.
b. Both samples would decrease in mass.
c. One sample would increase and the other would decrease in mass.
d. Both samples would remain essentially constant in mass.
Explain your a n s w e r : - - - - - - - - - - - - - - - - - - - - - - - - - -
2. In the calculations used to obtain the k1 values tabulated in Table 10.5, one fact has not been
taken into account. This will cause a significant difference between the k1 value obtained
using NaCl solute and the value obtained using ethylene glycol solute. What is this fact?
a. NaCl dissociates in solution while ethylene glycol does not.
b. NaCl is solid while ethylene glycol is a liquid.
c. NaCl is less soluble in water than ethylene glycol.
d. NaCl has a higher melting point than ethylene glycol.
3. How should the k1 value obtained with NaCl as the solute and recorded in Table 10.5 be modi-
fied before it is equivalent to the value obtained using ethylene glycol solute?
a. It should be multiplied by 2.
b. It should be divided by 2.
c. No modification is needed.
4. Suppose in Part C that a student ignores the direction in Step 9 to measure the boiling point as
soon as the mixture boils steadily. As a result, a significant amount of the solvent (water) boils
away and is lost. How would this mistake influence the measured boiling point compared to
the correct value it would have if the mistake was not made?
a. Measured value would be lower than correct value.
b. Measured value would be higher than correct value.
c. Measured value would not be different from correct value.
5. Suppose you want to purchase a syrup containing water and sugar and you have two brands
from which to choose. If you want to purchase on the basis of highest sugar content, which
should you buy?
a. The syrup with the highest freezing point.
b. The syrup with the highest boiling point.
Explain your a n s w e r : - - - - - - - - - - - - - - - - - - - - - - - - - - - -
6. How would the freezing and boiling points of distilled water and seawater compare?
a. Both the freezing and boiling points of seawater would be lower.
b. Both the freezing and boiling points of seawater would be higher.
c. The seawater freezing point would be lower and the seawater boiling point higher.
d. The seawater freezing point would be higher and the seawater boiling point lower.
7. Ethylene glycol is the active ingredient in most commercial automobile antifreeze. Why
wouldn't sodium chloride be used in a similar way?
a. Sodium chloride solute does not lower the freezing point of water.
b. Sodium chloride does not dissolve in water.
c. Sodium chloride lowers the freezing point of water but has other undesirable characteris-
tics.
d. Sodium chloride is a solid while ethylene glycol is a liquid.
5
KINE
Studying the Kinetics

of a Chemical Reaction
Prepared by Paul C. Moews, Jr., Royal Institution of Great Britain,
Ralph H. Petrucci, California State University, San Bernardino, and
Judith C. Foster, Bowdoin College
PURPOSE OF THE EXPERIMENT

Determine the rate law, activation energy, and collision frequency factor
for the reaction of peroxodisulfate ion with iodide ion. Determine the effect
of copper(II) nitrate on the rate constant.
BACKGROUND INFORMATION
Kinetics Kinetics is the study of the rates and mechanisms of chemical reactions.
The overall rate of a chemical reaction is the speed with which the
reaction proceeds. The mechanism of a reaction is a series of one or
more interactions, called steps, through which the reactants are
converted to products. The rate of the overall reaction is determined
by the rate of the slowest step, which is called the rate-limiting step.
Monitoring the disappearance of one of the reactants or the appearance
of one of the products allows us to determine a reaction rate.
For most reactions to occur, reactant species must collide. The overall
reaction rate is affected by conditions that influence the frequency and
energy of these collisions, namely reactant concentrations and tempera-
ture. Only by experiment can the extent to which these variables affect the
rate of a specific chemical reaction be determined.
Describing the Kinetics A. The Rate Law

of a Chemical Reaction
A mathematical equation known as the rate law expresses the rate of a
chemical reaction as a function of the concentrations of substances in the
chemical equation. For the hypothetical reaction
A+B+C--+D+E+F
the rate law usually takes the form shown in Equation 1.

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Q)
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Q)
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u © 1999 Cengage Learning. ALL RIGHTS RESERVED. No part of this work covered by the copynght herein may be reproduced,
CENGAGE
m transmitted, stored, or used in any form or by any means graphic, electronic, or mechanical, including but not limited to photocopying,
8l Learning·
recording, scanning, digitizing, taping, Web distribution, information networks, or information storage and retrieval systems, except as
@ permitted under Section 107 or 108 of the 1976 United Slates Copyright Act, without the prior written permission of the publisher.
34 KIN£0508: Studying the Kinetics of a Chemical Reaction
(Eq. 1)
The symbol [ ] signifies the molar concentration (mol/L, or M) of the

species in the brackets. x, y, and z are the order, or power to which each
concentration term must be raised in the rate law. k is the rate constant, a
proportionality constant that is independent of reactant concentrations, but
changes with changes in temperature.
While the sp:xies appearing in a rate equation are usually reactants,
they could also include one or more of the products if a reverse reaction
occurs to a significant extent. Sometimes not every reactant has an effect on
the reaction rate. In such cases the rate law does not include a term for each
of the reactants. Occasionally, species that do not appear in the overall
stoichiometric equation for the reaction may appear in the rate law. Such
species would be reaction intermediates involved in the rate-limiting step.
The order (x, y, z) of the reaction with respect to each substance in the rate
equation must be determined experimentally. These exponents are often
small positive integers, but may be fractional or negative. If x = 1 and y = 2 in
Equation 1, the reaction is first order with respect to A and second order with
respect to B. If a reaction is first order with respect to one particular reactant
and that reactant's concentration is doubled without changing other con-
ditions, the reaction rate will double. If the reaction is second order with
respect to a pm:ticular reactant, then doubling that reactant's concentration
will cause the reaction rate to quadruple. The sum of the exponents, x + y + z,
in the rate law is the overall order of the reaction.
B. Activation Energy
The rate constant k is constant only if the temperature is constant and the
reaction mechanism does not change. As the reaction temperature increases,
the frequency of collisions between reactant species increases, resulting in an
- increased reaction rate without an increase in reactant concentrations. It is not
unusual for a ten-degree temperature increase to result in a doubling or
tripling of a reaction rate. We cannot account for this dramatic rate increase
solely by the increase in collision frequency, which is proportional to v'T,
where Tis in kelvins (K). For example, a change from 298 to 308 K represents a
3% increase in temperature and only a 1.5% increase in the collision frequency.
The Swedish chemist Svante Arrhenius (1859-1927) suggested that
some minimum collision energy is required for a reaction to occur. We call
this minimum energy the activation energy, Ea. The activation energy for a
specific reaction is constant as long as the mechanism does not change.
Reacting species with a total kinetic energy 2': Ea can successfully react.
Therefore, the activation energy is a barrier that reactants must overcome
to become products.
Figure 1 shows the distribution of kinetic energies of the reacting
species at two slightly different temperatures.
Figure 1 indicates that the percent increase in the proportion of reactant
species with kinetic energy 2': Ea is vastly greater than the percent increase
in the square root of the temperature, v'T. Thus, the concept of an
activation energy accounts for the large observed rate increase resulting
from a relatively small temperature increase.
KINE0508: Studying the Kinetics of a Chemical Reaction 35
low temperature
Figure 1 kinetic energy Ea

Distribution of kinetic energies species with kinetic energy > Ea at low temperature
of the reacting species at two
temperatures species with kinetic energy > Ea at high temperature
A mathematical interpretation of the activation energy concept led to

the Arrhenius equation, shown in Equation 2, relating k and the Kelvin
temperature, T. In Equation 2, R is the ideal gas constant, 8.314 J/mol · K,
and A is the collision frequency factor for the reaction, which is related to
the collision frequency and the complexity of the reaction.
(Eq. 2)
Of more practical use is the logarithmic form of Equation 2, shown as

Equation 3.
ln k = ln A- (Ea/R) (1/T) (Eq. 3)
Equation 3 shows that the linear relationship between ln k and 1 /Tis of the
formy = mx + b, where y =Ink, x = 1/T, m = -Ea!R, and b = ln A. Thus, if
the rate constants of a reaction are determined at different temperatures
and ln k is plotted against 1/T, a straight line should be obtained. From the
slope and y-intercept of this line, we can calculate the activation energy
and the collision frequency factor for the reaction. These constants, along
with the rate law, describe the kinetic behavior of the reaction system.
The rates of some reactions increase in the presence of catalysts.
Catalysts are substances that facilitate a less energy-demanding mechan-
ism without themselves undergoing any net change during the reaction.
Consider again the distribution of kinetic energies (Figure 1). Lowering the
Ea would increase the proportion of reactants with sufficient kinetic energy
Ol
to successfully react.
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.5 The Chemical Reaction You In this experiment, you will study the reaction of peroxodisulfate ions, also
~ WiiiStudy called persulfate ions, 52 0 82 -, with iodide ions, r, shown in Equation 4.
Ol
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u
(J)
(J)
(Eq. 4)
(J)
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36 KINE0508: Studying the Kinetics of a Chemical Reaction
You will use ammonium peroxodisulfate, (NH4 hS 20 8, and potassium

iodide (KI) solutions to supply these ions.
Because each reactant and product is clear and colorless in aqueous
solution, it will be impossible for you to visually follow the reaction
progress. To solve this problem, you will add starch solution and a
constant amount of sodium thiosulfate (Na 2S20 3 ) to each reaction mixture.
Starch forms a deep blue complex with triiodide ions (13 -) and, as you will
see, the presence of a measured amount of thiosulfate ions (S20l-) will
allow you to make accurate reaction time measurements.
The moment you mix the reagents, 13 - will be produced so the blue
starch-h- complex will immediately form, regardless of the reaction rate.
Therefore, you will time a second reaction to indicate when the S2 ol-- 1-
reaction produces a predetermined amount of 13-.
The reaction of 13 - with S20}- is shown in Equation 5.
(Eq. 5)
Thus, in addition to varying volumes of S2082- and 1- solutions, each

reaction mixture will contain constant volumes of Na 2S20 3 and starch
solutions. The added S20 32- in the reaction mixture serves a dual purpose.
First, the reaction of S2032- with 13- prevents the reverse reaction in
Equation 4 from occurring because [13-] is kept low. Therefore, the data you
collect will reflect only the rate of the forward reaction in Equation 4.
Second, as long as S20 32- is present in the reaction mixture, 13- cannot
accumulate in the solution to complex with the starch. However, as soon as
all of the S2032- has reacted, 13- can accumulate and its presence will be
indicated by the dark blue color of the starch-13- complex.
Because the same amount of S2032- is present in each experiment, the
amount of 13- produced prior to the color change will be the same in all
determinations.
The reaction time will be the elapsed time between the moment of
mixing and the appearance of the blue color. If more time elapses before
the solution in determination 2 turns blue than is the case for
determination 1, then the reaction in determination 2 proceeded more
slowly and has a lower reaction rate. You will use the elapsed time in each
determination and Equation 6 to calculate the reaction rate for that
determination.
change in S208 2- concentration

rate=- .
elapsed hme
a[S2082-] (Eq. 6)
At
For each determination, a[S2082-] is the number of moles of S2082-
required to produce enough 13- to consume the S2032- in solution, divided
by the volume of the reaction mixture. Because the number of moles of
S20 32- and total volume of each reaction mixture is the same, a[S20 82-] is
constant throughout all the determinations. The minus sign is used
because reaction rates are defined to be positive, and in this instance the
concentrations of the reactants are measured as they decrease during the
reaction. Therefore, the reaction rate and the rate constant are positive.
Both the S20t-:.__ 13- and the 13- -starch reactions occur virtually
instantaneously. Therefore, the elapsed time between mixing and the
appearance of the blue color only represents the reaction time for the
S20l--1- reaction.
Determining the Rate You will use the method of initial rates to study the S2ol--I- reaction.
2
Equation for the 5 2 0 8 - -•- You will measure the reaction rate under conditions such that the number
Reaction of moles of S2082- and of 1- consumed is small relative to the number of
moles of these reactants present in the mixture. Thus, the concentration
changes that occur in the measured time intervals do not significantly alter
the reaction rate so the reaction rate is constant during the measured time
interval.
The rate equation for the S2082-- r reaction takes the form shown in
Equation 7.
(Eq. 7)
In brief, to determine x, you will compare the rates of a series of

determinations in which you keep [1-] constant and vary [520 82-]. To
determine y, you will compare the rates of determinations in which you
keep [S2ol-l constant and vary u-l. Once you know X andy, you can use
data from any one determination to calculate k.
A. Calculating the Initial Reactant Concentrations

Suppose we perform two determinations, using the solution concentra-
tions and volumes shown in Table A.
Because rates are determined by the concentrations of reactants present
in the reaction mixture, we must calculate those from the concentrations
and volumes of the solutions mixed. The initial [I-] after mixing but prior
to any reaction can be calculated, using Equation 8. The sample calculation
is shown for determination 1 in Table A.
number of moles of r, mol (Eq. 8)

[KI] = [r]
total reaction volume, L
(2.5 x w- 2 L) (0.20 mol KI/L)
2.s x w- 2 L + 2.s x w- 2 L + 5 x w- 3 L + 1.0 x w- 2 L
3
5.0 X w- mol KI = 7.7 X w-2 M
6.5 x w- 2 L
Table A Reaction volumes for determining the effect of [5 2 0i-1 on the reaction rate
Flask A Flask B
Starch, 1.2 x 10- 2M 0.20M Distilled 0.20M Reaction

D>
Determination mL NazSz03 , mL KI, mL water, mL (NH4)zSzOs, mL time, s
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1 5.0 10.0 25.0 0.0 25.0 24
<lJ
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D> 2 5.0 10.0 12.5 12.5 25.0 48
<lJ
0
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Table B Some data for a kinetic study of the S2 0i- -r reaction at constant
temperature
Determination [r], M Reaction rate, M/s
1 7.7 x 10- 2 7.7 X 10- 2 3.8 X 10-5

2 3.8 X 10- 2 7.7 X 10-2 1.9 X 10-5
A similar calculation for (NH4 hS20 8 gives
B. Determining the Reaction Rate

Equation 6 is used to calculate the reaction rate. To calculate .:l[S2082-], the
number of moles of 520 82- required to produce the 13- that consumed the
520 32- in the reaction mixture is determined. The number of moles of
520 32- in the mixture and the stoichiometric relationships in Equations 4
and 5 determine .:1[520 82-], using Equations 9 and 10. The sample cal-
culation is appropriate for either determination in Table A.
number of moles of S20}- added, mol =

2
l.O x 10 _2 L (1.2 x 10- ~ol Na2S203)
= 1.2 x 10- 4 mol 5 20}- (Eq. 9)
number of moles of S208 2-reacted, mol=

1.2 x 10- 4 )1 mol 13 - ) (1 mol S208 z-)
(
( mol Sz0 2- 2 mol 520 3 2- 1 mol 13 -
3
5 2
= 6.0 x 10- mol Sz08 - (Eq. 10)
For your laboratory determinations, you must calculate the number of

moles of Sz082 - consumed based on the amount of S2032- you added.
To determine .:1[520 82-], the number of moles of Szol- consumed is
divided by the volume of the reaction mixture. The reaction volume in
each determination is the same, 6.5 x 10-2 L for our example.
We can now use Equation 6.
Concentration and rate data for these determinations are summarized in

Table B.
KIN£0508: Studying the Kinetics of a Chemical Reaction 39
Substituting our data into Equation 7, we can write:
3.8 x w- 5 M/s = k[7.7 x w- 2r [7.7 x w- 2JY

and
Dividing the rate expression for the first determination by that of the
second determination gives:
3.8 x w- 5 M/s) = (k[7.7 x w- 2 n7.7 x w- 2JY)

( 1.9 x w- 5 M/s k[7.7 x w- 2 n3.9 x w- 2JY
Because k is constant at constant temperature, and [52ol-lx is identical in
both determinations, the expression is simplified, leaving:
3.8 x w- 5 M/s) = ([7.7 x w- 2]Y)

( 1.9 x w-5 M/s [3.9 x w- 2]Y
This expression further simplifies to 2 = 2Y. We see that doubling [I-]
increased the reaction rate by a factor of 2, so y = 1 and the reaction is first
order in 1-.
A similar study can be carried out holding [r] constant and varying
[52 0 82 -] to determine the reaction order with respect to 52 0 82 -. Using data
from two determinations where the initial [52 0 82 -] changes while the initial
[I-] is held constant allOWS US to calculate a value for X.
We can compare the rates of two reactions for which only the
concentration of one reactant differs. The ratio of the rates is equal to the
ratio of the concentrations, each raised to the power equal to the order of
the reaction for that reactant, as shown in Equation 11.
rate,) = (concentrat~on~) = (concentrat~on,) x (Eq. 11)

( rate concentration~ concentrahon2
2
C. Calculating the Specific Rate Constant, k

The specific rate constant, k, is calculated by substituting experimental
rates and concentrations for any determination into the rate law. The
specific rate constants calculated for individual determinations should be
the same, as long as the reaction temperature is constant.
Calculating the Activation The activation energy, Ea, and the collision frequency factor, A, for the
Energy and the Collision 5 2 0 82 - - r reaction is calculated from data collected after running the
Frequency Factor reaction at different temperatures. First, we calculate the rate constants at
each of the temperatures. Then, a graph is plotted for ln k (oi-t the ordinate)
Ol
c
c versus 1/T (on the abscissa). If the reaction follows the Arrhenius equation
(Equation 3), then the points should fall on a straight line with slope (m) =
'"
QJ
_j
QJ
-Ea/R. The activation energy for the reaction can then be calculated from
Ol
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QJ
u
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8l
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the experimentally determined slope of the line. The y-intercept is equal to

ln A, where A is the collision frequency factor for the reaction and has the
same units as the rate constant.
In This Experiment In this experiment, you will run a series of four reactions of 5 20 82- and l-
in which the u-1 is kept constant and the [Sz082 -] is varied. Then you will
run a second series of four reactions in which the [52 0 82 -] is kept constant
and the [1-] is varied. Next you will run a third series of reactions in which
both the n-1 and the [S2 ol-l are kept constant, but each reaction is done at
a different temperature: 10 oc below room temperature, room temperature,
10 oc above room temperature, and 20 oc above room temperature.
Finally, you will determine the effect of a Cu(N03 )z catalyst on the reaction
rate. In all determinations, you will also add potassium nitrate (KN03 ) and
ammonium sulfate ((NH4 )zS04 ) to keep a constant number of ions in the
reaction mixture. KN03 and (NH4 )zS04 are both inert substances with
respect to the Sz082 --1- reaction.
From these data, you will determine the rate equation for the reaction
and calculate the specific rate constant. Then, you will determine the
activation energy and collision frequency factor for the reaction.
PROCEDURE
~
~
Chemical Alert
Wear departmentally approved safety goggles while doing this experiment.
NOTE: Your laboratory instructor will indicate whether you should use a graduated
pipet, buret, or graduated cylinder to measure the solutions you will use in this
experiment.
I. General Procedure The volumes of reactants required for each determination are given in
Tables 1, 2, 3, and 4. Your laboratory instructor will tell you which
determinations you or your group will carry out during this investigation.
You may be asked to work in groups of four so that each member can
perform, in at least duplicate, the four determinations in one of Tables 1-4.
-------------
Table 1 Reaction volumes for determining the effect of [S 2 oi-J on the reaction rate
Flask A Flask B
0.20M 0.20M
Determina- 1.2 x w- 2M 0.20M KI, 0.20M (NH4hSzOs, (NH4)zS04,
tion Starch, mL Na 2 S2 0 3 , mL mL KN0 3 , mL mL mL
1 1.0 2.0 4.0 4.0 8.0 0.0

2 1.0 2.0 4.0 4.0 4.0 4.0
3 1.0 2.0 4.0 4.0 2.0 6.0
4 1.0 2.0 4.0 4.0 1.0 7.0
Table 2 Reaction volumes for determining the effect of [r] on the reaction rate
Flask A Flask B
0.20M
reaction 0.20M
Determina- 1.2 x w- 2 M 0.20M KI, 0.20M (NH4)zSzOs, (NH4)zS04,
tion Starch, mL NazSz03, mL mL KN0 3 , mL mL mL
5 1.0 2.0 8.0 0.0 4.0 4.0

6 1.0 2.0 4.0 4.0 4.0 4.0
7 1.0 2.0 2.0 6.0 4.0 4.0
8 1.0 2.0 1.0 7.0 4.0 4.0
0.20M Ammonium peroxodisulfate and 2.0 x 10-2 M copper(ll) nitrate are

oxidants and corrosives. 0.20M Ammonium sulfate and 1.2 x 10-2 M sodium
thiosulfate are irritants. 0.20M Potassium nitrate is an oxidant and irritant.
Prevent eye, skin, and clothing contact with these reagents. Notify your laboratory
instructor if you spill any solutions.
The reaction product, triiodide, is a sensitizer. Prevent eye, skin, and clothing
contact.
To facilitate mixing the solutions, add the specified volumes of 0.2%

starch, 1.2 x 10-2M Na2S2 0 3 , 0.20M KI, and 0.20M KN03 to one clean, dry,
labeled, 50-mL Erlenmeyer flask (Flask A). Add the specified volumes of
0.20M (NH 4)zS20 8 and 0.20M (NH 4)zS0 4 to a second clean, dry, labeled,
50-mL Erlenmeyer flask (Flask B).
Place these two flasks in a constant-temperature bath, set at the
Dl
_!;
specified temperature (room temperature, except for determinations 9, 11,
c
(;; and 12), and allow them to equilibrate. Record the water-bath temperature.
..5 Instead of doing determinations 1-4, 5-8, 10 and 13-16 in a constant-
(])
Dl
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Dl
temperature bath, your laboratory instructor may direct you to perform
(])
u them at your laboratory station (in which case, you will record the
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laboratory temperature).
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Table 3 Reaction volumes for determining the effect of temperature on the reaction rate
Flask A Flask B
1.2 X
10- 2M 0.20M 0.20M
Determi- Tempera- Starch, Na 2S 203, 0.20M KI, 0.20M (NH4hS20s, (NH4hS04,
nation ture, oc mL mL mL KN0 3, mL mL mL
9 room- 10 1.0 2.0 4.0 4.0 2.0 6.0

10 room 1.0 2.0 4.0 4.0 2.0 6.0
11 room+ 10 1.0 2.0 4.0 4.0 2.0 6.0
12 room+ 20 1.0 2.0 4.0 4.0 2.0 6.0
Table 4 Reaction volumes for determining the effect of Cu(N03h on the reaction rate
Flask A Flask B
0.20M 0.20M
Determi- 1.2 X 10-2M 0.20M KI, 0.20M (NH4hS20s, (NH4hS04,
nation Starch, mL Na2S203, mL mL KN0 3, mL mL mL
13 1.0 2.0 8.0 0.0 4.0 4.0

14 1.0 2.0 4.0 4.0 4.0 4.0
15 1.0 2.0 2.0 6.0 4.0 4.0
16 1.0 2.0 1.0 7.0 4.0 4.0
Pour the solution from Flask B into Flask A. Record the starting time
when the transfer is complete. Rapidly mix the solutions by pouring the
mixture from one flask into the other four times. Record the final time
when the mixture turns blue.
Perform all trials of each determination at the same temperature.
Between trials, thoroughly rinse the flasks with distilled or deionized water
and dry them. If the reaction times for duplicate trials do not agree within
10%, perform a third trial.
Transfer all reaction mixtures into a container provided by your
laboratory instructor and labeled "Reacted (NH4 hS2 0 8-KI Mixtures".
II. Determining the Effect of A. Determining the Effect of S2 0/- Concentration on the Reaction Rate
Concentration on the Use the reaction volumes listed in Table 1. Follow the steps in Part I,
Reaction Rate General Procedure. Record all data on Data Sheet 1.
B. Determining the Effect of r Concentration on the Reaction Rate

Use the reaction volumes listed in Table 2. Follow the steps in Part I,
General Procedure. Record all data on Data Sheet 2.
Ill. Determining the Effect In determinations 9, 10, 11, and 12, you will keep the KI and (Nt4hS20 8
of Temperature on the concentrations constant, but you will vary the reaction temperature. You
Reaction Rate will run the reaction at 10 ac below room temperature, room temperature,
10 ac above, and 20 oc above room temperature. Use the reaction volumes
listed in Table 3. Follow the steps in Part I, General Procedure. Record your
data, including the temperatures of the constant temperature baths, on
Data Sheet 3.
IV. Determining the Effect of Use the reaction volumes listed in Table 4. Add one drop of 2.0 x 10- 2M
Cu(N03 } 2 , a Catalyst, on the Cu(N03 h to the flask containing the starch, Na 2S20 3 , and KI solutions
Reaction Rate (Flask A) for each determination. Follow the steps in Part I, General
Procedure. Record all data on Data Sheet 4.
Wash your hands thoroughly with soap or detergent before leaving the
laboratory.
CALCULATIONS
Do the following calculations and record the results on the appropriate
Data Sheets. Where necessary, obtain data from your laboratory partner
and/ or other student groups. ·
Preliminary Calculations 1. Calculate the initial KI concentration for each determination, using
Equation 8.
2. Calculate the initial (Nt4hS20 8 concentration for each determination,
substituting (Nt4hS20 8 for KI in Equation 8.
3. Calculate the average reaction time for each determination.
4. Calculate .:l[S20 82-] as described in Determining the Reaction Rate, subs-
tituting the volumes and concentrations you used . .:l[S2082-] is the
same for all determinations. Remember .:l[S20l-J will be negative.
5. Calculate the reaction rate using the average reaction time for each
determination and Equation 6, as described in Determining the Reaction
Rate.
II. Determining the Effect A. Determining the Effect of S2 0i- Concentration on the Reaction Rate
of Concentration on the 6. Find the reaction order with respect to S20 2-, comparing the average
8
Reaction Rate rates you calculated for determinations 1 and 2, 2 and 3, 3 and 4.
Because the ratio of S20 82- concentrations for each of these pairs is 2
and the ratio of 1- concentrations in each of these pairs is 1, then
(Eq. 12)
Cl
.<:::
c
(ij
QJ
_j
Calculate x from each rate ratio. Calculate the average x, rounding
QJ
Cl
to the nearest integer.
"'c
Cl
QJ
u
Q)
g;
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-----------
B. Detennining the Effect of r Concentration on the Reaction Rate

7. Find the reaction order with respect to 1- using Equation 13 and the
rates calculated for determinations 5 and 6, 6 and 7, 7 and 8.
rates) = (rate6) = (rate7) = 2y (Eq. 13)

( rate6 rate7 rates
Calculate y from each rate ratio. Calculate the average y, rounding to

the nearest integer.
Calculating the Rate 8. Write the rate law for this chemical reaction, using your experimen-
Constant tally determined values of x andy, in Equation 14.
(Eq. 14)
Using Equation 15, calculate the rate constant, k, for each determina-
tion using the integer values determined for x and y and data for each
determination.
(Eq. 15)
Ill. Determining the Effect 9. For determinations 9-12, calculate the natural logarithm of the rate
of Temperature on the constant, (ln k).
Reaction Rate 10. For determinations 9-12, calculate the reaction temperature, in kelvins.
Then calculate 1 /T.
11. Prepare a graph with ln k plotted on the ordinate and 1/T on the
abscissa. Draw the best straight line through the points. Using two
points on the line (not necessarily data points), calculate the slope
(D..y I D..x) of the line. Calculate the y-intercept of the line, using the
calculated slope and a point on the line. From the slope and the
y-intercept, calculate Ea and A.
IV. Determining the Effect of 12. Calculate the average rate constant, k, for determinations 5-8 (average
Cu(N0 3 ) 2 , a Catalyst, on the kuncatalyzed) and for determinations 13-16 (average kcatalyzed).
Reaction Rate
13. Calculate the ratio of average kcatalyzed to average kuncatalyzed' using
Equation 16.
average kcatalyzed
(Eq. 16)
average kuncatalyzed
name section date
Post-Laboratory Questions
(Use the spaces provided for the answers and additional paper if necessary.)
1. (a) From the Ea and A you determined in this experiment, calculate the rate constant at 75 oc.
(b) How much time would elapse before the appearance of the blue color at 75 oc, using the solutions
from Part III?
2. How would your observed reaction rates for the 5 2 0 82 --r experiment have varied if you had
doubled the volume of each of the solutions for a particular determination? Briefly explain.
3. An industrial chemical reaction has a rate law: rate= k [C]. The activation energy for the reaction is
3.0000 x 104 J/mol and A= 2.000 x 10-3 . What must be the reaction temperature if a rate of 1.00 x
10-9 M/sis required and [C] must be kept at 0.0300M? Hint: What must be the value of k to achieve
the necessary rate?
4. Sketch the Boltzmann distribution of the kinetic energy of molecules and show how lowering the
activation energy for a reaction increases the reaction rate. (Note that the fraction of molecules with
enough energy to react successfully is equal to the area under the curve to the right of Ea. The rate
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5. In Part IV, you used the rate of the catalyzed reaction and the rate law of the uncatalyzed reaction to
calculate the rate constant of the catalyzed reaction. How could you test whether the same rate law is
valid with and without the catalyst present?
6. Suppose you had pipetted and mixed the solutions for determination 2 but the mixture failed to turn
blue. Then, you realized that you had pipetted only 5 solutions. Which solution might you have
omitted? Is there more than one possibility? Briefly explain.
7. A student uses a miscalibrated graduated cylinder to measure the KI solution in Part liB. Each scale
reading indicates a volume exactly 0.5 mL greater than is actually the case (e.g., the cylinder reads
8.0 mL when it actually contains only 7.5 mL).
(a) What actual volumes will be measured for each of determinations 5-8?
(b) How will the experimentally determined concentrations compare to the concentrations you cal-
culated for these determinations?
(c) Which determination will be the most affected? Briefly explain.

name section date
Data Sheet 1
II. Determining the Effect of Concentration on the Reaction Rate
A. Determining the Effect of S2 0i- Concentration on the Reaction Rate
determination
1 2 3 4
concentration of reactants
after mixing
KI,M
trial 1
initial time
time of color change
reaction time, s
temperature, oc
trial 2
initial time
reaction time, s
temperature, oc
trial 3
initial time
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determination
1 2 3 4
average reaction time for the

determination, s
reaction rate for the determi-

nation, M/s
ratio of rates
order of reaction with respect to S2082-, x
average x, rounded to integer
After you calculate a value for y (Data Sheet 2), calculate the rate constant for each of
determinations 1-4. Remember to round x andy to integers.
rate constant, k
name section date
Data Sheet 2
II. Determining the Effect of Concentration on the Reaction Rate
B. Detennining the Effect of r Concentration on the Reaction Rate
determination
5 6 7 8
concentration of reactants after

mixing
KI,M
(NH4hS20s, M
trial 1
initial time
reaction time, s
temperature, oc
trial 2
initial time
reaction time, s
temperature, oc
trial 3
initial time
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determination
5 6 7 8

determination, s

nation, M/s
rate5 /rate 6
ratio of rates
order of reaction with respect to 1-, y
average y, rounded to integer
Using your average x (Data Sheet 1) andy (above), calculate the rate constant for each of
determinations (5-8). Remember to round x and y to integers.
rate constant, k
rate law: rate =

name section date
Data Sheet 3
III. Determining the Effect of Temperature on the Reaction Rate
determination
9 10 11 12
mixing
KI,M
(NH4 )z5 20s, M
trial 1
initial time
reaction time, s
temperature, oc
trial 2
initial time
reaction time, s
temperature, oc
trial 3
initial time

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determination
9 10 11 12
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ln k
reaction temperature, oc
reaction temperature, K
1/T, K- 1
slope of line
Ea, J/mol
ln A (y-intercept of line)
A, 1/M · s
name section date
Data Sheet 4
IV. Determining the Effect of Cu(N0 3 )~ a Catalyst, on the Reaction Rate
determination
13 14 15 16

mixing
KI,M
(NH4)zS20s, M
trial 1
initial time
reaction time, s
temperature, ac
trial 2
initial time
reaction time, s
temperature, oc
trial 3
initial time

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determination
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nation, M/s
rate constant, k
average kuncatalyzedl determi-

nations 5-8
average kcatalyzed, determina-

tions 13-16
k ratio (average kcatalyzed/

average kuncatalyzed)
name section date
Pre-Laboratory Assignment
1. The following data were collected at 20 oc for the reaction of bromphenol blue (HBPB2 ~) and
hydroxide ions (OH~), shown in Equation 16.
(Eq. 16)
The times required to consume a small but constant amount of HBPB2 ~ at varying initial HBPB 2 ~
and OH~ concentrations were measured and are recorded below.
Determination [HBPB 2 ~], M [OH~], M Time, s
1 7.22 X 10~ 6 1.00 75
2 7.22 X 10~ 6 0.25 290
3 3.63 X 10~ 6 1.00 152
(a) Determine the reaction order with respect to OH~.
(b) Determine the reaction order with respect to HBPB 2 ~.
(c) Write the rate law for the reaction of HBPB2 ~ with OH~.
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2. Assume that the small, constant amount of HBPB2 - consumed in the experiment described in Pre-
Laboratory Assignment 1 corresponds to an HBPB 2 - concentration change of 7.22 x 10- 7M.
(a) Calculate the rate constant for this reaction at room temperature.
(b) What other information do you need to calculate the activation energy for this reaction?
3. Why is it better to transfer one group of solutions into one flask and a second group into a second
flask and then mix them, instead of pipetting the solutions sequentially into the same flask?
4. For which part of the experiment (II, III or IV) would it be most important to keep the flask in the
constant-temperature water bath after mixing? What would happen if the temperature of that reac-
tion mixture were not carefully controlled?
E QU L
Introducing Chemical Equilibrium

Prepared by M. L. Gillette, Indiana University Kokomo, H. A. Neidig, Lebanon Valley College, and
J. N. Spencer, Franklin and Marshall College

Observe the effects of disturbances on three chemical systems at equi-
librium. Consider these effects in relation toLe Chatelier's principle.
BACKGROUND REQUIRED
You should be familiar with basic laboratory techniques for transferring
solids, mixing solutions, and using hot- and ice-water baths. You should
also be familiar with the concepts associated with stoichiometry and
thermochemistry.
Many chemical reactions do not proceed to completion. The reaction shown
in a typical chemical equation is called the forward reaction. In some cases,
the reaction products begin reacting to re-form the original reactants,
while the forward reaction is still going on. We call this reverse process the
reverse or backward reaction. Ultimately, under the right conditions, the
rates of the forward and backward reactions become equal. At this point,
the concentrations of reactants and products stabilize, and we say that the
chemical system has reached equilibrium. When writing the chemical
equation for a system at equilibrium, we use double arrows(~) to indicate
the simultaneous occurrence of forward and reverse reactions. We call
reactions that behave in this way reversible.
Disturbances that alter the concentration of any species in a system at
equilibrium necessarily disturb that equilibrium. We can predict the response
of a chemical equilibrium to such disturbances by using Le Chatelier's
principle. This principle states that a chemical system at equilibrium res-
ponds to a change in conditions by adjusting the relative concentrations of the
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CENGAGE © 2008,1999 Cengage Learning. ALL RIGHTS RESERVED. No part of this work covered by the copyright herein may be reproduced.
a:i Learning· transmitted, stored, or used in any form or by any means graphic, electronic, or mechanical, including but not limited to photocopying,
:5
N recording, scanning, digitizing, taping, Web drstnbution, information networks. or information storage and retrieval systems, except as
@ permrtted under Section 107 or 108 of the 1976 United Stales Copyright Act, without the prior written penmission oft he publisher.
58 EQUL0616: Introducing Chemical Equilibrium
Chemical equilibria also respond to temperature changes, although

such responses are not included in the chemical equations for the equilibria.
For example, an exothermic reaction at equilibrium will respond to a tempe-
rature increase by increasing the concentration of reactants, in order to
adjust to the added heat.
The three chemical systems that you will study in this experiment are
described below.
1. The ionization of acetic acid (HC 2 H 30 2 ) in water to form hydronium ion
(H 3 0+) and acetate ion (C 2 H 3 0 2 -), as shown in Equation 1.
(Eq. 1)
Because all components in this system are colorless, you will add methyl
orange indicator to the equilibrium mixture to help visualize the changes
that occur. Methyl orange turns redder as H 3 0+ concentration increases,
and yellower as H 3 0+ concentration decreases.
2. The conversion of a blue complex ion into a red complex ion, both
formed by the cobalt(II) ion (Co 2 +). The net ionic equation for this
equilibrium is shown in Equation 2.
(Eq. 2)
3. The dissolution of ammonium chloride (NH4Cl) in water, as shown in

Equation 3.
NH4Cl(s) ~N~ +(aq) + Cl-(aq) (Eq. 3)
Example Problem You have a colorless saturated lead (II) chloride (PbC12 ) solution
at equilibrium containing solid PbClz crystals and small
concentrations of Pb 2 + and Cl- ions, as shown in Equation 4.
PbClz(s, white)~ Pb2 +(aq) +2 Cl-(aq) (Eq. 4)
Briefly outline and explain what you would observe if you

disturbed the equilibrium by (a) adding NaCl solution and then
(b) heating the mixture.
Solution (a) If you added a few drops of NaCl solution to the equilibrium
mixture, the solution would become cloudy. The added NaCl
would increase the chloride ion (Cl-) concentration in the
mixture. In response, some of the excess Cl- would react
with Pb 2 + to form fine particles of PbClz. The PbClz particles
would make the solution cloudy.
(b) If you now heat the equilibrium mixture, some of the PbClz
particles would dissolve, making the solution less cloudy.
This is because heat functions as a reactant in Equation 4. The
increased reactant concentration causes the equilibrium to
shift to the right, meaning that more products form. Some
PbClz particles would therefore dissolve, and the Pb2 + and
Cl- concentrations would increase. To represent the new
EQUL0616: Introducing Chemical Equilibrium 59
equilibrium, we can add heat as a reactant to Equation 4,

resulting in Equation 5.
(Eq. 5)
In This Experiment You will observe the responses of three different chemical systems at
equilibrium to species concentration and temperature changes. Then you
will briefly explain these responses in terms of Le Chatelier's principle.
PROCEDURE

Always use caution in the laboratory. Many chemicals are potentially harmful.
Prevent contact with your eyes, skin, and clothing. Avoid ingesting any of the
reagents.
NOTE:
• Mix the solutions in your test tubes using the method described by your laboratory
instructor.
• Dispose of your reaction mixtures and rinses according to your laboratory
instructor's directions.
• Record all of your data on your Data and Observations sheet.
1. Prepare a hot-water bath for use in Step 5. To do so, pour 100 mL of tap
water into a 250-mL beaker. Attach a large support ring to a ring stand.
Place the beaker in the ring. Adjust the ring so that the beaker is
stabilized while sitting on a hot plate. Turn on the hot plate.
2. Prepare an ice-water bath by filling a 250-mL beaker with ice.
I. Studying the Ionization 3. Measure 1 mL of 1M HC 2H 30 2 into each of two clean, dry 15 x 125-mm
of HC2 H3 0 2 in Water test tubes. Add 1 drop of methyl orange solution to each tube. Mix well.
Equilibrium Record the color of the initial equilibrium mixtures. Use one of the
mixtures as a color control.
Q)
4. Add the amount of sodium acetate (NaC 2H 30 2) needed to fill the end of
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a microspatula to one of your test tubes. Mix the solution until the
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aj the solution, using a glass stirring rod. Leave the test tube in the hot-
0
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6. Using a test tube holder, transfer the test tube from Step 5 to your
ice-water bath. Frequently stir the solution in the tube. Allow the tube
to remain in the ice-water bath until the solution changes color. Record
this color change.
7. Pour the contents of both test tubes into the container specified by
your laboratory instructor. Rinse the tubes with tap water, then distilled
or deionized water.
II. Studying the [CoCI 4 ] 2 - /

[Co(H 2 0)6 ] 2 + Equilibrium
8. Measure 3 mL of 0.1M CoCh in 95% ethanol into a clean, dry

15 x 125-mm test tube. Record the color of the solution.
9. Add one drop of distilled water to the test tube, and stir well. Add
additional water dropwise, with stirring, until you see a color change.
Then add 1 final drop of distilled water, and stir well. Record the color
change.
12M (concentrated) HCI is toxic and corrosive, and it can cause burns.
10. Add one drop of 12M HCl to the solution in the test tube. Stir well with
a glass stirring rod. Add additional 12M HCl dropwise, stirring after
each addition, until you see a color change. Then add 1 final drop of
12M HCl, and stir well. Record the color change.
11. Add one drop of distilled water to the test tube, and stir well. Add
additional water dropwise, with stirring, just until you see a color
change. Record the color change.
12. Place the test tube from Step 11 into your hot-water bath. Leave the tube
in the bath, stirring the mixture frequently, until you see a color change.
Record this color change.
13. Using a test tube holder, transfer the test tube to your ice-water bath.
Leave the tube in the bath, stirring the solution frequently, until you see
a color change. Record this color change.
14. Repeat Step 7.
Ill. Studying the Dissolution

of NH 4 CI in Water Equilibrium
15. Measure 3 mL of saturated NI-4Cl solution into a clean, dry 15 x 125-mm

test tube. Record the initial appearance of the solution.
16. Add 1 drop of 12M HCl to the test tube. Stir well. Continue adding 12M
HCl dropwise, stirring after each addition, until you observe a change
in the appearance of the mixture. Record this change.
17. Place the test tube in your hot-water bath. Stir the solution in the test
tube frequently, while heating the tube for 3-4 min. Record your
observations of the mixture.
When done, turn off the hot plate.
18. Using a test tube holder, transfer the test tube to your ice-water bath.
Stirring the solution frequently, leave the tube in the ice-water bath until
you see a change in the solution. Record the change.
19. Use a microspatula to add enough NH4 Cl crystals to a second clean, dry
15 x 125-mm test tube to cover the bottom. Add distilled water
dropwise to the N~Cl crystals in the tube, stirring well after each
addition. During this process, feel the bottom of the test tube to
determine whether or not the dissolution of solid NH4 Cl produces a
temperature change. Record your observations.
20. Repeat Step 7.
laboratory.
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Name Partner Section Date
1. (a) Explain how the reactant and product concentrations in a system at equilibrium can remain
constant, even though the chemical reactions continue to occur.
(b) List two ways we can disturb a chemical system at equilibrium. Using your own data, give
specific examples of the two ways.
(c) Explain what we mean when we say that an equilibrium "shifts" in response to a disturbance.
2. A catalyst is a substance that increases the rate of a chemical reaction but is not consumed by the
reaction. A catalyst works by lowering the activation energy for a reaction, making it easier for
reactants to form products. What effect, if any, would a catalyst have on a system already at
equilibrium? Briefly explain.
3. The reaction of hydrogen (Hz) with nitrogen (Nz) to form ammonia (NH3), known as the Haber
process, is an important reaction in industry. This reversible reaction as shown in Equation 6 is
endothermic.
Nz (g) + 3Hz (g) ;=O 2 NH3 (g) (Eq. 6)

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(b) What change in the concentration of H 2 will occur if we add N 2 to the equilibrium mixture shown
in Equation 6? Briefly explain.
(c) What change in the concentration of H 2 will occur if we add NH3 to the equilibrium mixture?
Briefly explain.
(d) What change in the concentration of N 2 will occur if we add heat to equilibrium mixture?
Briefly explain.
Data and Observations

I. Studying the Ionization of HC2 H3 0 2 in Water Equilibrium
color of original equilibrium mixture:
color change after addition of NaC 2 H 3 0 2 :
color change after heating mixture:
color change after cooling mixture:
11. Studying the [CoCI 4 ] 2 - I [Co(H 2 0)6 ] 2 + Equilibrium

color of original equilibrium mixture:
color change after addition of distilled water:
color change after addition of 12M HCl:
color change after addition of distilled water:
color change after heating mixture:

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initial appearance of equilibrium mixture:
change after addition of 12M HCl:
change after heating mixture for 3-4 min:
change after cooling mixture:
observations of dissolution of solid NH4 Cl in water:

Calculations and Conclusions

Write your chemical equations and answers to the questions in the spaces provided.
I. Studying the Ionization of HC2 H3 0 2 in Water Equilibrium
(Eq. 1)
1. Based on the initial solution color, is the H 3 0+ concentration in the original equilibrium mixture
relatively high or relatively low? Briefly explain.
2. What experimental evidence do you have that the equilibrium is affected by the addition of solid
NaC 2H 3 0 2? What must have happened to the H 30+ concentration to produce this evidence?
3. NaC 2H 3 0 2 is not a component of the HC 2H 3 0 2 equilibrium. Explain why the equilibrium is affected
by the addition of solid NaC2H3 0 2.
4. When the equilibrium mixture was heated, did the H 3 0+ concentration increase or decrease? Briefly
explain.
5. Based on your answer to Calculation 4, is the forward reaction exothermic or endothermic? Rewrite
the equilibrium reaction to include the heat term.
II. Studying the [CoCI 4 ] 2 -/[Co(H 2 0)6 ] 2 + Equilibrium
(Eq. 2)
6. Use Le Chatelier's principle to account for the color change you observed when you added 12M HCl
to the equilibrium mixture.
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7. Based on your answer to Calculation 6., would you expect to observe the same color change if you
added a saturated NaCl solution instead of adding the 12M HCl? Briefly explain.
8. After the equilibrium mixture was cooled in the ice-water bath, what was the predominant cobalt(II)
species present in the solution, [CoC14 f- or [Co(H2 0) 6 f+? Briefly explain your answer.
9. Based on your answer to Calculation 8., is the forward reaction exothermic or endothermic? Rewrite
the equilibrium reaction to include the heat term.
Ill. Studying the Dissolution of NH4 CI in Water Equilibrium
NH4Cl(s) ;=ONH4 +(aq) + Cl-(aq) (Eq. 3)
10. Based upon your observations of the dissolution of NH4 Cl in water, is the dissolution of NH4Cl
exothermic or endothermic? Briefly explain.
11. Rewrite the chemical equation for the dissolution of N~Cl in water to include the heat term.
1. What hazards should you be aware of when working with the following substances?
(a) 12M HCl
(b) 0.1M CoClz in 95% ethanol
2. Each of the components of the HC 2 H 3 0 2 equilibrium system you will be studying is clear and
colorless.
(a) What will you add to this equilibrium mixture to help visualize the changes that occur?
(b) What will you observe if the H 3 0+ concentration becomes relatively high?
(c) What will you observe if the H 3 0+ concentration becomes relatively low?
(d) What will you observe if the H 3 0+ concentration is in between the concentrations described in
(b) and (c)?
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7
EQ UL
Studying the pH of Strong Acid,

Weak Acid, Salt, and Buffer Solutions
Prepared by Norma Robinson North, State University of New York at Potsdam, and
M. L. Gillette, Indiana University Kokomo

Compare calculated and measured pHs of a series of hydrochloric acid and
acetic acid solutions. Based on the pH measurements, calculate the acid
dissociation constant of acetic acid.
Measure the pH of various salt solutions. Using your pH measure-
ments, calculate the hydrolysis constant of ammonium chloride.
Compare measured and calculated pHs of: a buffer solution; the same
buffer solution mixed with HCl solution and mixed with NaOH solution;
distilled water; and distilled water mixed with HCl solution and mixed
with NaOH solution.
Water and Aqueous Many compounds dissolve in water, forming aqueous solutions. In some of
Solutions these cases, water molecules simply surround, or solvate, molecules or ions
in the solution. In other cases, the water molecules and the solute molecules
or ions react.
In pure water, a small percentage of the molecules take part in the
chemical equilibrium shown in Equation I.
(Eq. 1)
As a result, small amounts of hydronium ion (H3 0+) and hydroxide ion
(OH-) are present in water. The equilibrium constant expression for this
reaction, Kw, sometimes referred to as the ion product of water, is shown in
Equation 2. We use square brackets to indicate the molar concentration
(mol/L, M) of the enclosed species.
(Eq. 2)
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u CENGAGE © 1998 Cengage Learning. ALL RIGHTS RESERVED. No part of this work covered by the copyright herein may be reproduced,
co Learning· transmitted, stored, or used in any form or by any means graphic, electronic, or mechanical, including but not limited to photocopying,
8l recording, scanning, digitizing, taping, Web distribution, 10lormation networks, or information storage and retrieval systems, except as
permitted under Section 107 or 108 of the 1976 United States Copyright Act, withoutthe prior written permission of the publisher.
72 EQUL0499: Studying the pH of Strong Acid, Weak Acid, Salt, and Buffer Solutions
From Equation 1 we can see that, in pure water, [H30+] and [OH-] are
equal. Using Equation 2, we can determine these concentrations. If
[H30+] = [OH-], 1.0 X 10- 14M = [H3o+f, and [H3o+] = 1.0 X 10- 7M.
Strong Acids and Strong Acids in aqueous solution release one or more hydrogen ions (H+) per
Bases molecule to water molecules, forming H 30+. In this context, we refer to the
release of H+ as dissociation. The extent to which a specific acid dissociates
in water is a measure of acid strength. When essentially every molecule in
an acid sample dissociates, we say the acid is strong.
For example, if we bubble a measured amount of gaseous hydrogen
chloride into water to prepare a hydrochloric acid (HCl) solution, the
reaction shown in Equation 3 occurs.
(Eq. 3)
Hydrochloric acid is a strong acid, which means that essentially all of

the HCl molecules dissociate. Therefore, [H 30+] in the above solution
equals the concentration of the originally added HCl gas. Other strong
acids include nitric acid (HN03), sulfuric acid (H 2S04), and hydrobromic
acid (HBr).
Strong bases are compounds that either: dissociate essentially
completely in water to form one or more cations and OH-; or otherwise
react with water to produce a solution with a high [OH-]. Sodium
hydroxide (NaOH) and potassium hydroxide (KOH) are examples of strong
bases. The dissociation of NaOH in water is shown in Equation 4.
water
NaOH(s) ~ Na+(aq) + OH-(aq) (Eq. 4)
In a NaOH solution, [OH-] is the same as the calculated concentration of

oH- based on the mass of the added NaOH.
In aqueous solutions, [H30+] and [OH-] can have widely different
values, although their product must always equall.O x 10- 14, as shown in
Equation 2. For example, in a O.lOM HCl solution, [H30+] = 1.0 x 10- 1M,
and [OH-] = (1.0 x 10- 14)/0.10 = 1.0 x 10- 13M. In 1909, Danish chemist
Se~rensen proposed using an exponential system to ease comparison and
graphing of [H30+] and [OH-], given the widely varying magnitudes of
these terms. The abreviation Se~rensen suggested for expressing [H30+] was
pH, in which p represents "negative logarithm of". Mathematically, we
define pH as shown in Equations 5 and 6.
(Eq. 5)
(Eq. 6)
We can write similar expressions for [OH-], shown in Equations 7 and 8
pOH =-log [OH-] (Eq. 7)
[OH-] = 10-pOH (Eq. 8)
-------~-----
EQUL0499: Studying the pH of Strong Acid, Weak Acid, Salt, and Buffer Solutions 73
pH 01234567891011121314
increasing
acidity i
neutral
decreasing
acidity
pOH
.------------ l --------·
14131211109876543210
increasing decreasing
acidity acidity
Figure 1
pH and pOH scales
Thus, for a 0.10M HCl solution,
pH= -log (1.0 X w- 1 ) = 1.0

and
pOH = -log (1.0 X w- 13 ) = 13.0
In accordance with Equation 2, the product of [H3 0+] and [OH-] must
equall.O x 10- 14. Therefore, we can write the expression:
pH+ pOH = 14.00 (Eq. 9)
The pH scale, pOH scale, and their relationship to each other are shown
in Figure 1.
WeakAcidsandWeakBases In aqueous solution, only 10% (or less) of the molecules of most acids
dissociate to release H+. We call such acids weak acids. In solutions of
weak acids, [H3 0+] is far lower than the calculated concentration of the
added acid.
Hypochlorous acid (HClO) is a typical weak acid. The dissociation of
HCIO in water is shown in Equation 10.
(Eq. 10)
In a weak acid solution, the relationship of [H3 0+] to the acid equilibrium
constant expression, Ka, for the acid can be defined by Equation 11.
(Eq. 11)
Note that, in this expression, we raise the reaction product concentrations to

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u water, the solvent, remains virtually unchanged as a result of the
~ dissociation of any weak acid.
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Table 1 Some Weak Acids and their Kas
acid chemical formula
acetic HC2H302 1.8 X 10~ 5

butyric HC4H~2 1.5 X 10~ 5
carbonic H2C03 4.3 X 10~ 7
formic HCHO 1.8 X 10~ 4
hypochlorous HClO 3.0 X 10~ 8
monohydrogen HC03~ 5.6 X 10~ 11
carbonate
nitrous HN02 4.6 X 10~ 4
propionic HC3H 5 0 2 1.3 X 10~ 5
The larger the value of its Ka, the greater is the dissociation of an acid in
water. Acid dissociation equilibrium constants of several weak acids are
listed in Table 1.
We can use the value of Ka and Equation 11 to calculate the equilibrium
[H30+], hence the pH, of any weak acid solution. Because the percent of
acid molecules that dissociate is so small, it is usually satisfactory to assume
that for typical weak acids the initial acid concentration equals the
equilibrium concentration of the undissociated weak acid. In the case of
HClO, we know that [H30+] = [ClO~], based on Equation 10. Therefore,
[H30+][Cl0~] = [H3o+f. The following equations illustrate these calcula-
tions for a 0.10M HClO solution.
~8 [H30+] [ClO~] [H30+] 2

3.0 X 10 = 0.10 = 0.10
[H30+j2 = 3.0 X 10~ 9
[H3o+] = 5.5 x 10~ 5
pH= -log (5.5 X 10~ 5 ) = 4.26
A pH of 4.26 is evidence that [H30+] of an 0.10M HClO solution is much

less than the [H30+] of an 0.10M HCl solution, a strong acid solution with a
pH of 1.0.
Alternatively, we can use the measured pH of a weak acid solution of
known concentration to calculate the Ka of the acid. For example, we can
calculate the Ka of propionic acid, HC3H 50 2, if we know that the pH of a
0.15M HC3H 50 2 solution is 2.85, and we assume that [H30+] = [C3H 50 2~].
2.85 =-log [H30+]

[H30+] = 10~ 2 · 85 = 1.4 x 10~ 3
(1.4 X 10~3)2 2.0 X 10~6 = 1.3 X 10~5

Ka = 0.15 0.15
Weak bases are compounds that partially react with water to produce
small amounts of OH~. In contrast to strong bases, only a small percent of
the molecules in a weak base dissociate in water. For example, when we
bubble ammonia (NH3) gas, a weak base, into water, the reaction shown in
Equation 12 occurs.
(Eq. 12)
We can write the base equilibrium constant expression, Kb, for the reaction
in Equation 12 as shown in Equation 13.
(Eq. 13)
In the case of this reaction, we know that [NH4+] = [OH-], based on

Equation 12.
Interactions of Salts with Many ionic compounds are salts, composed of negatively-charged anions
Water and positively-charged cations. When an ionic compound dissolves in water,
the ions are separated and surrounded by water molecules. Some kinds of
ions react with water molecules in a process we call hydrolysis; others do
not. When anions hydrolyze, they attract H+ from water molecules. When
sodium hypochlorite (NaClO) is added to water, the salt dissociates into
hypochlorite ion that hydrolyzes, as shown in Equation 14.
(Eq. 14)
Therefore, the pH of an NaClO solution is greater than 7.0. The equilibrium

shown in Equation 14 occurs because the product, HClO, a weak acid, has
only a very slight tendency to release H+ back to the water. Sodium ions do
not hydrolyze to a measurable extent.
The anions of strong acids, such as N03-, sol-, and Br-, and the
cations of strong ionic bases, such as Na+, K+, and Ca2+, do not hydrolyze
measurably. When little or no hydrolysis of the ions occurs, the pH of
the resulting solution is 7.0, as established by the reaction in Equation 1.
In general, we can divide salts into four categories, based upon whether
it is the cation, the anion, or both that hydrolyze or not. These categories are
described in Table 2.
Table 2 Four types of salts and the pH characteristics of their aqueous solutions
1. Neutral salts: Salts that are a product of the reaction between a strong
base and a strong acid; no measurable hydrolysis occurs; solution is
neutral. Examples: NaCl, KBr, KN03.
2. Basic salts: Salts that are a product of the reaction between a strong base
and a weak acid; only the anion hydrolyzes; solution is basic. Examples:
KClO, KC 2H 30 2, NaC4H,,z.
3. Acidic salts: Salts that are a product of the reaction between a weak
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(;;
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NH4Cl0, NH4C2H30z.
------ --- - - - -
Equation 15 shows the hydrolysis equilibrium constant expression,

Kh, for the reaction in Equation 14.
Kh = [HClO] [OH-] (Eq. 15)

[ClO]
l.O x w-14 = 3.3 x w-7

3.0 x w- 8
We can calculate Kh for any anion from the Ka of the resulting weak acid and
Kw. Because the magnitude of most hydrolysis constants is small, we can
reasonably consider the equilibrium concentration of the hydrolyzing anion
(Clo- in Equation 14) equivalent to the initial anion concentration. Note,
too, that [OH-] and [HClO] will be equal (per Equation 14). Based on these
assumptions, we can calculate the pH of 0.23M NaClO as follows:
2
K = _7 = [HClO] [OH-] = [OH-]
33 10
h . X [CIO l 0.23
[OH-] 2 = 7.6 X w- 8 M
[oH-l = 2.8 x w- 4M
pOH = -log (2.8 X w- 4) = 3.55
pH= 14.0-3.55 = 10.45
Some cations hydrolyze measurably. For example, in an ammonium

chloride solution (NH4Cl), a small percent of the ammonium ions (NH 4+)
react with water, as shown in Equation 16, forming NH3 and H 3 0+.
(Eq. 16)
The hydrolysis of NH 4+ reduces the solution pH to below 7.0, due to the

production of H 30+. We can calculate Kh for NH4+using Equation 17.
K _ [NH3][H30+] _ Kw
h- [NH4+] - Kb (Eq. 17)
As in the case of the hydrolysis of Clo-, the extent of NH4+hydrolysis

is small enough that we can reasonably consider the equilibrium [NH4+]
equal to the initial [NH4+]. Based on the pH of an NH4Cl solution of known
concentration, we can use Equation 17 to calculate Kh of NH4+.
Buffer Solutions Solutions that undergo only a minimal pH change when limited quantities
of acid or base are added are called buffer solutions. Human blood is an
extremely complex buffer solution, with a normal pH range of 7.35-7.45.
Variations in blood pH of as little as 0.1 produce serious health problems.
We can prepare a buffer solution by mixing a weak acid and a salt
containing the anion of this acid: for example, HCIO and NaClO. We can
also prepare a buffer solution by mixing a weak base and a salt containing
the cation of this base: for example, NH3 and NH4Cl.
Consider the behavior of O.lOM HClO to which we have added

sufficient NaClO to make the [ClO-] O.lOM. The equilibrium and Ka
expressions for this buffer solution are shown in Equations 10 and 11.
However, it is no longer true that [H30+] = [ClO-] in Equation 11, because
now the [ClO-] is largely contributed by NaClO, not HClO. Substituting the
buffer solution conditions into Equation 11, we can calculate the buffer
solution pH, as shown in Equation lla.
x _8 = [H3o+][clo-] = [H3o+][o.Io]
30 10
. [HClO] [0.10]
[H3o+J = 3.o x 10-s
pH= -log (3.0 x 10-8 ) = 7.52 (Eq. lla)
Addition of a small amount of HCl solution to our buffer solution

results in the conversion of ClO- into HClO, as shown in Equation 18.
(Eq. 18)
Because the added H 30+ from the HCl solution reacts with Clo- in the
buffer solution, the [H30+] does not increase appreciably. Hence, the pH
does not change significantly.
Addition of a small amount of aqueous NaOH to our buffer solution
results in formation of more ClO-, as shown in Equation 19.
OH-(aq) + HClO(aq) ___, ClO-(aq) + H20(l) (Eq. 19)
Because HClO in the buffer solution reacts with the added OH- from
NaOH, the [OH-] does not increase.
As long as both Clo- and HClO are present in the buffer solution to
react with added H 30+ and OH-, respectively, the pH of the buffer solution
will change only slightly as a result of such additions. Consider the
following example. One liter our buffer solution contains 0.10 mol HClO
and 0.10 mol NaClO. If we add 0.010 mol H 30+ to our buffer solution, 0.010
mol Clo- will react with the H 30+ to form 0.010 mol HClO and water (see
Equation 18). The new [HClO] will be 0.11M (0.10 + 0.01 = 0.11). The new
[ClO-] will be 0.09M (0.10 - 0.01 = 0.09). We can calculate the new pH of
the buffer solution using Equation 11.
_8 = [H3o+](o.o9)
3 .0 X
10 (0.11)
10-8 )(0.11) =
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(i; H 30 (0.09) 3 .7 X
10
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This pH is close to the pH of the original buffer solution (7.52).
PROCEDURE
Preview
• Prepare HCl solutions of various concentrations
• Use pH meter to determine pH of HCl solutions
• Prepare HC 2H 30 2 solutions of various concentrations
• Use pH meter to determine pH of HC 2 H 3 0 2 solutions
• Use pH meter to determine pH of several aqueous salt solutions
• Prepare a HC 2H 30 2 /NaC 2H 30 2 buffer solution
• Add HCl and NaOH solutions to separate samples of buffer solution,
and to distilled or deionized water
• Determine pH of the buffer solution and water samples after addition of
HCl and NaOH solution
• Treat discarded solutions for safe disposal
0.1 OM acetic acid-irritant

6.0M hydrochloric acid-toxic and corrosive
0.1 OM hydrochloric acid-irritant
phenolphthalein solution-flammable and toxic
6.0M sodium hydroxide-toxic and corrosive
I. Preparing HCI Solutions

and Determining pH
0.1 OM HCI is irritating. Prevent eye, skin, and clothing contact.
1. Label four 16 x 125-mm test tubes "1", "2", "3", and "4".
2. Obtain 10 mL of 0.10M HCl in a clean, dry 10-mL graduated cylinder.
3. Transfer exactly 5.0 mL of this solution into test tube 1.
4. Transfer the remaining 5 mL of HCl solution into a clean, dry 50-mL
graduated cylinder. Rinse the 10-mL cylinder with small quantities of
distilled or deionized water, and add the rinses to the 50-mL cylinder.
Dilute the solution in the 50-mL cylinder to exactly 50 mL with distilled
water. Thoroughly mix the solution with a glass stirring rod.
5. Transfer 5 mL of the solution prepared in Step 4 to test tube 2.
6. Transfer 5 mL of the solution prepared in Step 4 to a second 50-mL
graduated cylinder. Transfer the remaining 40 mL of solution from the
first 50-mL cylinder to a 400-mL beaker labeled "Discarded Solutions".
Rinse the empty cylinder. Add the rinses to the discard beaker.
7. Dilute the solution in the 50-mL cylinder to exactly 50 mL with distilled

water. Transfer exactly 5 mL of this solution to test tube 3. Transfer
5 mL into a clean, 50-mL graduated cylinder. Transfer the remaining
40 mL of diluted solution to the "Discarded Solutions" container, as
in Step 6.
8. Dilute the 5 mL of solution in the 50-mL cylinder to exactly 50 mL with
distilled water. Transfer exactly 5 mL of the diluted solution to test tube
4. Discard the remaining 40 mL of solution as in Step 7.
NOTE: Your laboratory instructor will describe and demonstrate the proper use of
the pH meters and combination electrodes available in your laboratory. Be certain
to thoroughly rinse the electrode with distilled water before placing it in any solution.
To ensure accurate pH measurement, periodically re-calibrate the pH meter, using
pH-7.0 buffer solution. Allow sufficient time for the pH meter reading to stabilize
before you record it.
9. Use a pH meter to measure the pH of the four solutions in the test tubes.
Begin by transferring the solution from test tube I into a clean, dry 50-mL
beaker. Thoroughly rinse the electrode with distilled water. Carefully
lower the electrode into the beaker until the glass bulb is completely
beneath the solution surface. Carefully swirl the beaker so that the
solution makes good contact with the electrode. Read and record the
solution pH on Data Sheet I.
Repeat the above procedure using the solutions in the other three
test tubes.
Transfer all HCl solutions and rinses into the "Discarded Solutions"
beaker.
Rinse and drain the graduated cylinders and test tubes, transferring
the rinses into the "Discarded Solutions" beaker. Thoroughly rinse the
electrode with distilled water and store it as directed by your laboratory
instructor.
II. Treating Discarded

Solutions for Safe Disposal
Phenolphthalein solution is flammable and toxic. Do not use near open
flame. Prevent eye, skin, and clothing contact.
6.0M NaOH is toxic and corrosive. Prevent eye, skin, and clothing contact. If
you spill any solution, immediately notify your laboratory instructor.
NOTE: Phenolphthalein is a pH indicator that is colorless in solutions with pH < 8.2

and pink in solutions with pH > 8.2.
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.5 Solutions" beaker. If the resulting mixture is not colorless, consult
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mixture stays pink for 30 s. Discard the solution into the drain, diluting
with a large amount of running water. Wash and drain all glassware.
------~--
Ill. Preparing HC2H302

Solutions and
Determining pH 0.1 OM HC 2 H3 0 2 is irritating. Prevent eye, skin, and clothing contact.
11. Obtain 10 mL of 0.10M HC 2 H 30 2 in a clean, dry 10-mL graduated

cylinder.
12. Repeat Steps 3-10, using the HC 2 H 30 2 solution in place of the HCl
solution. Record all pH readings on Data Sheet 1.
IV. Determining the pH of 13. Obtain 5-mL samples of the following aqueous salt solutions in six
Various Salt Solutions clean, dry, appropriately labeled 16 x 125-mm test tubes: 0.10M NaCI,
0.10M NaC 2 H 30 2 , 0.10M NaHC03, 0.10M Na2 C03, 0.10M NH4 Cl, and
0.10M NH4CzH30z.
14. Transfer the NaCI solution into a clean, dry 50-mL beaker.
15. Use the pH meter to measure the pH of the NaCI solution. Record this
pH on Data Sheet 2. Transfer the solution into the "Discarded
Solutions" beaker.
16. Rinse the beaker twice with distilled water. Transfer the rinses into the
"Discarded Solutions" beaker. Following the directions of your
laboratory instructor, clean the electrode.
17. Repeat Steps 14-16 using each of the five remaining salt solutions.
18. Repeat Step 10. Rinse and drain all glassware.
V. Preparing a Buffer 19. Weigh a clean 150-mL beaker to the nearest 0.1 g.
Solution
NOTE: Ask your laboratory instructor to verify the mass of NaC 2 H3 0 2 you should use
in Step 20.
20. Add 2.0 g of solid anhydrous NaC 2 H 30 2 to the beaker.
6.0M HC2 H3 0 2 is corrosive. Prevent eye, skin, and clothing contact. If you
spill any acid, immediately notify your laboratory instructor.
21. Remove the beaker from the balance. Using a 10-mL graduated
cylinder, add 4.0 mL of 6M HC 2 H 30 2 to the beaker.
22. Using a 50-mL graduated cylinder, add 46 mL distilled water to the
beaker. Stir the solution until the NaC 2 H 30 2 has completely dissolved.
This solution will contain 2.4 x 10-2 mol each of NaC 2 H 30 2 and
HC 2 H 30 2 in 50 mL of solution.
VI. Observing pH Changes in 23. Label four clean, dry 50-mL beakers "1", "2", "3", and "4".
Water and Buffer Solutions 24. Using a 50-mL graduated cylinder, pour 25 mL of distilled water into
upon Addition of HCI and beakers 1 and 3.
NaOH Solutions
25. Using a graduated cylinder, add 25 mL of the buffer solution each to
beakers 2 and 4.
26. Measure the pH of the solutions in beakers 1 and 2, rinsing the electrode
with distilled water after each measurement. Record the data on Data
Sheet 2.
6.0M HCI is corrosive and toxic, and it can cause burns. Prevent eye, skin,
and clothing contact. If you spill any acid, immediately notify your laboratory
instructor.
Your laboratory instructor will describe and demonstrate a satisfactory
method for transferring 0.5 ml (3 x 1o- 3 mol) each of 6M HCI and 6M NaOH into
your beakers.
27. Transfer 0.5 mL of 6M HCl each to beakers 1 and 2. Thoroughly mix

with a glass stirring rod, rinsing the rod with distilled water after
mixing each solution. Measure the pH of each solution. Record the data
on Data Sheet 2. Transfer the solutions into the "Discarded Solutions"
beaker.
28. Transfer 0.5 mL of 6M NaOH each to beakers 3 and 4. Thoroughly mix
with a glass stirring rod, as in Step 28. Measure and record the pH of
each solution on Data Sheet 2. Transfer the solutions into the
"Discarded Solutions" beaker.
29. Repeat step 10.
30. Following the directions of your laboratory instructor, prepare the pH
meter for use by the next student.
laboratory.
CALCULATIONS
Do the following calculations, and record the results on your Data Sheets.
I. Preparing HCI Solutions 1. Calculate the theoretical pH of each HCl solution, using Equation 5.
and Determining pH
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Ill. Preparing HC2H 3 02 2. Calculate the theoretical pH of each HC2 H 30 2 solution, using Equation 5
_,:;
c Solutions and and the Ka value given in Table 1.
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Determining pH 3. Calculate Ka for HC 2H 30 2 using your measured pH values for each
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solution and the model of Equations 10 and 11. Assume that the
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---·-----·
IV. Determining the pH of 5. Classify each salt, based on Table 2. Briefly explain why the pH of each
Various Salt Solutions salt solution does or doesn't vary from 7.0.
6. Calculate Kh for NHtCl, using Equation 17. Assume that [Nfit +j is
equivalent to initial [NH4 Cl].
VI. Observing pH Changes in 7. Calculate the pH of each of the following solutions based upon the
Water and Buffer Solutions theoretical [H3 0+].
upon Addition of HCI and (a) distilled water, using Equations 1, 2, and 5
NaOH Solutions
(b) original buffer solution, using Equation 11a as a model
(c) distilled water with added 6M HCl, using Equations 2 and 3 as
models
(d) buffer solution with added 6M HCl, using Equations 11a and 18 as
models
(e) distilled water with added 6M NaOH, using Equations 2 and 4 as
models
(f) buffer solution with added 6M NaOH, using Equations 11a and 19
as models
Name Section Date
(use the spaces provided for the answers and additional paper if necessary.)
1. Briefly explain why the pH of 1.0 x 10-2M HCl is different from that of 1.0 x 10-2M HC 2H 30 2 .
2. (a) Calculate the percent error in your experimentally determined Kas for the HC 2 H 3 0 2 solutions in
Part III, using Equation 20.
(calculated Ka-literature Ka) ( OO )

percent error, 01
1o = r1terature Ka 1 % (Eq. 20)
(b) Are the magnitudes of your percent errors random, or do you see a pattern? Briefly explain.
3. Briefly explain why the pH change that resulted when you added 6M NaOH to the buffer solution
was of a different magnitude than the pH change that resulted when you added aqueous NaOH to
distilled water.
4. (a) Write the chemical equation for the reaction that occurred when you added 6M NaOH to the
buffer solution.
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(b) Write the chemical equation for the reaction that occurred when you added 6M HCl to the buffer
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Name Section Date
Data Sheet 1
I. Preparing HCI Solutions and Determining pH
concentration of HCl, M measured pH theoretical pH
1.0 X 10- 1
1.0 X 10- 2
1.0 X 10-3
1.0 X 10- 4
Ill. Preparing HC2 H3 0 2 Solutions and Determining pH
measured pH theoretical pH
1.0 X 10- 1
1.0 X 10- 2
1.0 X 10-3
1.0 X 10- 4
calculated Ka of HC2H302
based on pH data
1.0 X 10- 1
1.0 X 10- 2
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Data Sheet 2
IV. Determining the pH of Various Salt Solutions
explanation for difference

salt salt type measured pH between measured pH and 7.0
NaCl
Calculated Kh for O.lM NH4 Cl, based on measured pH and Equation 17:
I. Observing pH Changes in Water and Buffer Solutions upon Addition of HCI and NaOH Solutions
solution measured pH calculated pH
distilled water
original buffer solution
distilled water with added

6MHC1
buffer solution with added

6MHC1
distilled water with added

6MNaOH
buffer solution with added

6MNaOH
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Name Section Date
1. Briefly explain
(a) why you must use caution when you work with HCl solutions.
(b) how you are going to process for disposal the HC 2 H 3 0 2 solutions you have discarded.
2. Briefly distinguish between the following terms, as they pertain to this experiment.
(a) strong acids and strong bases
(b) strong acids and weak acids
3. Calculate
(a) the pH of a solution in which [H30+] = 1.5 x 10- 3M
(b) the pH of a solution in which [OH-] = 3.1 x 10-4M
~ (d) [H30+] when pOH = 5.58

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4. Butyric acid (HC4 HtD2 ) is a weak acid with the stench of rancid butter.
(a) Write the equation for the dissociation of HC 4HtD 2 in water.
(b) The pH of O.SOM HC4 HtD2 is 2.56. Calculate Ka of butyric acid.
(c) Write the equation for the hydrolysis of C 4 HtD2-.
(d) Calculate Kh for C4 HtD2 -.
(e) Calculate the pH of a buffer solution in which [HC 4 HtD2] = 0.36M and [C4 HtD2-] = 0.31M.
8
DETERMINATION OF Ka FOR WEAK ACIDS
In this experiment, you will
0 Prepare a solution of NaOH if one is not available.

0 Titrate a solution of unknown acid to the half-reacted point and use the pH of the solution
at that point to determine K 0 for the unknown acid.
0 Titrate a solution containing a weighed amount of solid unknown acid to the half-reacted
point and use the pH of the solution at that point to determine K0 for the unknown acid.
I q~ INTRODUCTION
The dissociation of a weak acid that is dissolved in water can be represented by the
following general equation, where HA represents that part of the acid that is dissolved
but not dissociated and A- is the anion produced by that part of the dissolved acid
that has dissociated:
Eq. 14.1
The equilibrium constant for this reaction is
K = (H 3 0+ ](A-]
Eq. 14.2
[HA)[H 2 0]
In Equation 14.2, the brackets, [],indicate molar concentrations. The molar concentra-
tion of water, the solvent, is essentially constant for dilute solutions, so Equation 14.2
may be written as follows:
Eq.l4.3
Ka is called the acid dissociation constant, and the brackets again denote molar
concentrations.
The strength of weak acids is indicated by the extent to which the process repre-
sented by Equation 14.1 occurs when an acid is dissolved in water. The stronger an
acid, the greater is its tendency to donate H+ ions to water to form H 3 0+ ions. Thus,
solutions of stronger acids have higher H 3 0+ and A- concentrations and lower HA
92 Determination OfKa For Weak Acids -Seager/Slabaugh
concentrations at equilibrium than do solutions of weaker acids. Thus, according to

Equation 14.3, stronger acids will have larger Ka values.
The value of Ka for a weak acid can be determined by a straightforward
experimental procedure. If a solution is prepared that contains HA, H 3 Q+, and A-
in equilibrium and if the concentrations are adjusted so that the concentrations of
undissociated acid (HA) and acid anion (A- ) are made equal to each other, then the
value of Ka will be equal to the concentration of H 3 0+ as shown in Equation 14.4:
Eq. 14.4
In Equation 14.4, the [A-] and [HA] cancel because they have the same value.
The neutralization reaction that occurs between an acid and a base can be used
to establish the condition in which [A-] = [HA]. The neutralization reaction is written
as
HA(aq) + NaOH(aq) ---t H 2 0(/) + Na + (aq) +A- (aq) Eq. 14.5
In Equation 14.5, the salt (NaA) is written in the dissociated form it takes when it is
dissolved in water. If a solution is made by dissolving some weak acid (HA) in water,
very little of the acid will dissociate, and so very little A- will be present at equilibrium.
If half the dissolved acid is reacted with NaOH to form the salt, the concentration of
A- from the salt that is produced will be the same as the concentration of unreacted
acid that remains in solution (remember, dissolved salts dissociate completely). Thus,
in a weak acid solution that is half-reacted, [A-] = [HA]. Of course, this is only true if
the amount of weak acid undergoing dissociation according to Equation 14.1 is
negligible and provides only a negligible amount of A- . This assumption is valid for
most weak acids.
~\
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EXPERIMENTAL PROCEDURE
A Preparation of a Solution of NaOH

In this experiment, you will titrate your acid samples with a solution of NaOH that is
about 0.1 M. You can use the standardized solution you prepared and standardized in
Experiment 13, a solution that is provided in the laboratory, or you can prepare a
solution by following the steps given below. Check with your lab instructor for direc-
tions.
PROCEDURE
1. Use your 10-mL graduated cylinder to put 3.5 mL of 6 M sodium hydroxide so-
lution (NaOH) into a clean 250-mL beaker.
2. Use a 50- or 100-mL graduated cylinder to add 200 mL of distilled water to the
beaker. Stir the resulting solution well with a glass stirring rod and mark the
beaker in some way so you remember that it contains your NaOH solution.
Determination Of Ka For Weak Acids -Seager/Slabaugh 93
B. Determination of Ka for an Unknown Acid in Solution

In this part of the experiment, you will titrate a specific volume of a solution that
contains a dissolved weak acid. You will completely titrate two samples to the phenol-
phthalein end point in order to determine the volume of base that will be required to
titrate a sample to the half-reacted point. You will then titrate a sample to the half-
reacted point and measure the pH of the half-reacted sample. The unknown will either
be available in the reagent area of the lab, or you will get a sample of unknown from
the stockroom.
PROCEDURE
1. Obtain about 50 mL of unknown acid solution in a clean, dry 100-mL beaker.
Obtain the unknown from either the lab reagent area or from the stockroom. If
you are given an identification (ID) number for your sample, record it in the
appropriate blank of Table 14.2.
2. Obtain a 25- or 50-mL buret from the stockroom. Wash it and rinse it with no
more than 5 mL of the NaOH solution you will use for the titration.
Rinse solution in sink~

Disposal
Mount the buret on a ringstand, fill it with the NaOH solution you will use, and
prepare it for use in a titration. See Experiment 13, Part A, Steps 17 to 20 for a
review if necessary.
3. Obtain a 10-mL pipet from your locker equipment or the stockroom. Rinse the
pipet with about 5 mL of the unknown acid solution.
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Rinse solutiQn in sink
Disposal
4. Pipet a 10.00-mL sample of unknown acid solution into a clean 125-mL flask,
add 25.0 mL of distilled water (use a graduated cylinder), then add 3 drops of
phenolphthalein indicator.
5. Put the flask under the buret you set up in Step 2 and titrate the sample of acid
to the phenolphthalein end point. Remember, this end point is reached when a
single drop of NaOH solution from the buret causes the solution in the flask to
have a pink color that remains for at least 15 seconds while the solution is
swirled. Note and record in Table 14.1 the initial and final buret readings.
6. Repeat Steps 4 and 5 for a second 10.00-mL sample of the unknown acid so-
lution. Record the initial and final buret readings in Table 14.1.
Titrated sample,s il_l sJnk.

Disposal
'-------- -----------
94 Determination Of Ka For Weak Acids - Seager/Slabaugh
7. Use the initial and final buret readings recorded in Table 14.1 to determine the
volume of NaOH solution required to completely titrate each 10.00-ml sample
of unknown acid solution. Record these volumes in Table 14.1. The two values
should agree within 0.2 mL. If they do not, repeat Steps 4 and 5 for a third sam-
ple. Average the two NaOH volumes that agree most closely with each other (do
not titrate more than three samples). Record the average in Table 14.2.
8. Divide the average value recorded in Step 7 by 2, and record this value in
Table 14.2. This is the volume of NaOH solution that would be required to
titrate a 10.00-ml sample of unknown acid solution to the half-reacted point.
9. Pipet a 10.00-ml sample of unknown acid solution into a clean 125-ml flask,
add 25.0 ml of distilled water, and use your buret to carefully add the volume
of NaOH solution required to titrate the sample to the half-reacted point. Record
the initial and final buret readings in Table 14.2.
10. Mix the half-reacted sample well, then use long-range (1 to 11) pH paper to
determine the approximate pH of the sample. Record the measured pH in
Table 14.2.
11. Obtain a short-range pH paper that includes the pH value you measured in
Step 10. Measure the sample pH with the short-range paper and record the
value in Table 14.2.
12. If a pH meter is available, measure the pH of the half-reacted sample to the
precision available on the meter. Obtain directions from your lab instructor
before you attempt to use the pH meter. Record the pH value in Table 14.2.
Half-reacted sample in sink.

Disposal
c. Determination of K0 for an Unknown Solid Acid

In this part of the experiment, you will weigh samples of an unknown solid acid,
dissolve the samples in water, and completely titrate the dissolved samples to the
phenolphthalein end point. You will use the mass of the samples and the volume of
NaOH solution required to titrate them to calculate the amount of NaOH solution
needed to titrate another weighed sample to the half-reacted point. You will then
measure the pH of the half-reacted sample and use the data to calculate Ka for the
unknown solid acid.
PROCEDURE
1. Obtain about 1 g of unknown solid acid from the reagent area of the lab or
from the stockroom. If you are given an ID number for your sample, record it
in the appropriate blank of Table 14.4.
2. Use a centigram or electronic balance to weigh out two samples of the un-
known solid acid with masses in the range of 0.20 to 0.25 g. Record the
masses in Table 14.3, then put each sample into a clean 125-ml flask. Identify
the flasks in some way so you can tell which sample each one contains.
3. Add 25.0 ml of distilled water to each flask and 3 drops of phenolphthalein
indicator. Swirl the flasks to speed the dissolving of the solid samples.
4. After the solid samples have dissolved, use your buret to titrate each sample to
the phenolphthalein end point. Record the initial and final buret readings in
Table 14.3.
-----~----
Determination OfKa For Weak Acids -Seager/Slabaugh 95
Titrated samples in sink.

Disposal
5. Use the buret readings recorded in Table 14.3 to calculate the volume of NaOH
solution required to completely titrate each sample. Record the volumes in
Table 14.3.
6. Divide the volume of NaOH required for each sample by the mass of the
sample expressed in grams. This gives the volume of NaOH required to titrate
each gram of sample (the vol-per-gram value). Record this value in Table 14.3.
The two values should agree to within 1 mL of each other. If they do not agree,
weigh out and titrate a third sample of unknown solid acid. Do the appropriate
calculations and enter the values in Table 14.3.
7. Average the two vol-per-gram values calculated in Step 6 that agree most
closely (do not titrate more than three solid acid samples). Record the average
value in Table 14.3.
8. Weigh out and dissolve in 25.0 mL of water another sample of solid unknown
acid in the range of 0.20 to 0.25 g. Record the mass of the sample in Table 14.4.
Multiply the mass of the sample by the vol-per-gram value you calculated in
Step 7. This will give you the volume of NaOH solution required to completely
titrate the sample you just weighed out. Record the volume in Table 14.4.
Divide this volume by 2 and enter the value in Table 14.4 in the blank corre-
sponding to the volume required to half-react your sample.
9. Use your buret and add to the dissolved sample the volume of NaOH solution
required to half-react the sample. Record the initial and final buret readings in
Table 14.4.
10. Mix the half-reacted sample well, then use long-range pH paper, short-range pH
paper, and a pH meter (if available) as you did for your half-reacted sample in
Part B, Steps 10 to 12. Record the appropriate pH values in Table 14.4.
Titrated sample, unqsed solid Ltnknown, and excess NaOH solution

Disposal in sink.
CALCULATIONS AND REPORT
B. Determination of Ka for an Unknown Acid in Solution

As described earlier, the value of Ka is equal to [ H 30+] in a half-reacted sample of
weak acid. In the experiment, you measured the pH of the half-reacted samples. Thus,
it is necessary to convert pH to [ H 3 0+ ]. The relationship between pH and [ H 3 0+] is
Eq. 14.6
Thus, the value of [ H 3 0+ ] is obtained by taking the antilog of -pH. On most

calculators, this is done by the following steps:
1. Enter the pH value.

2. Change the sign of the pH value to negative.
3. Push the second function or inverse function key.
4. Push the log key.
Remember when you do this calculation, the calculated [ H 3 0+ ] value will have one
less significant figure than the total number of figures used to express the pH. Thus, a
pH value of 4. 75 will give a value of 1.8 x w-s for [ H 3 0+ ].
1. Note in Table 14.2 the pH values obtained for the half-reacted sample using
short-range pH paper and the pH meter. Convert each of these two pH values
into a value for [ H 3 0+ ]. Remember that the [ H 3 0+] value is the same as the
value of Ka for the weak acid and record the Ka values in Table 14.2.
C. Determination of Ka for an Unknown Solid Acid

1. Note in Table 14.4 the pH values obtained for the half-reacted sample using
short-range pH paper and the pH meter. Convert each of these two pH values
into a value for [H 3 0+] and record the Ka values in Table 14.4.
Name
--------------------------- Section ------------ Date - - - - -
Experiment 14 ... Pre-Lab Review
DETERMINATION OF K0 FOR WEAK ACIDS

1. Are any specific safety alerts given in the experiment? List any that are given.
2. Are any specific disposal directions given in the experiment? List any that are given.
3. What are the possible sources of the NaOH solution needed in the experiment?
4. In Part B, why do you titrate some samples completely but only half-react one sample?
5. What indicator is used in all titrations that are done to completion?
6. How do you know when you have titrated to the proper end point in the complete titrations
done in the experiment?
7. What two different methods are used to measure samples to be titrated in Parts B and C?
8. What size samples are titrated in Parts B and C?
9. Describe how the pH of half-reacted samples is measured using pH paper.
----~- ----------- ------------------

Name Section - - - - - - Date

-------------------------- -----
Experiment 14 ... Data and Report Sheet
DETERMINATION OF Ka FOR WEAK ACIDS
B. Determination of Ka for an Unknown Acid 1n Solution
Table 14.1 (data)

Sample 1 Sample 2 Sample 3
Final buret reading
Initial buret reading
Vol. of NaOH required for complete titration
Table 14.2 (data and report)
Unknown ID number
Average volume for complete titration
Volume required to half-react sample
Final buret reading
Half-reacted sample pH (long range)
Half-reacted sample pH (short range)
Half-reacted sample pH (pH meter)

100 Determination OfKa For Weak Acids -Seager/Slabaugh
C. Determination of Ka for an Unknown Solid Acid

Table 14.3 (data)
Sample 1 Sample2 Sample 3
Sample mass
Final buret reading
Vol. of NaOH required for complete titration
Vol-per-gram. value
Average vol-per-gram value
Table 14.4 (data and report)
Unknown 10 number
Sample mass
Volume of NaOH required for

complete titration
Volume of NaOH required to

half-react sample
Final buret reading
Half-reacted sample pH (long range)
Half-reacted sample pH (short range)
Half-reacted sample pH (pH meter)

Determination Of Ka For Weak Acids - Seager/Slabaugh 101
QUESTIONS
1. Suppose you had to prepare some NaOH solution according to the directions given in Part A
However, while using a 50-mL graduated cylinder to add the distilled water, you miscounted
and only added 150 mL instead of 200 mL. How will this mistake influence the Ka value
determined in Part B?
a. Make it larger than the correct value.
b. Make it smaller than the correct value.
c. Will not influence it.
2. Suppose in Part B a stockroom employee gave you a 15-mL pipet to use rather than the 10-mL
type called for in the experiment. Without noticing the mistake, you use the pipet and do every-
thing else in the experiment according to the written directions. How will this mistake influence
the volume of NaOH solution required to titrate the two samples?
a. The volume of NaOH required for the first sample would be greater than the volume re-
quired for the second sample.
b. The volume of NaOH required for the first sample would be less than the volume re-
quired for the second sample.
c. The volume of NaOH required should be the same for the two samples.
3. How would the mistake described in Question 2 influence the K0 value determined in Part B?
b. Make it smaller than the correct value.
c. Will not influence it.
4. Suppose in Part Cone of your samples that was titrated completely had a mass of 0.221 g
(larger than the maximum mass given in the directions). How would this mistake influence
the vol-per-gram value calculated for that sample compared to a sample that had a mass of
0.208 g (within the prescribed range)?
a. The larger sample would have a larger vol-per-gram value than the smaller sample.
b. The larger sample would have a smaller vol-per-gram value than the smaller sample.
c. The vol-per-gram values of the two samples should be the same.
5. How would the mistake described in Question 4 influence the Ka value determined in Part C?
b. Make it smaller then the correct value.
c. Would not influence it.
6. Suppose in Part B that a student pipets a 10.00-ml sample in Step 9 and adds 25 ml of dis-
tilled water and 3 drops of phenolphthalein indicator. Then, the student realizes that the di-
rections do not call for the addition of any indicator. What should the student do to be most
efficient in using lab time?
a. Discard the sample and start over with a new one.
b. Proceed to add enough NaOH solution to half-react with the sample.
c. Titrate the sample to the phenolphthalein end point.
9
EQU L
Preparation and
Properties of Buffers
Prepared by Larry A. Scheich, St. Norbert College and
Lynn A. Melton, University of Texas, Dallas
Objectives To prepare and examine the properties of buffer solutions and to

determine the buffer capacity of a buffer solution.
Materials 50-mL and 25-mL pipets, 250 mL volumetric flask, 150-mL Erlenmeyer
flask, buret and pH meter. Solutions of 0.10 M NaOH, 0.01 M NaOH,
0.01 M HCl, 0.2 M acetic acid and solid sodium acetate.
Safety All of the chemicals used are acids or bases, and can be caustic at high
concentrations. Even though the concentrations used here are low, normal
precautions for the handling of acid and bases should be followed. Report
any spills to the instructor. Wear safety glasses at all times during this
experiment.
Waste Disposal Any unused stock solutions or solids should be returned to the instructor.
All of the solutions produced may be washed down the drain with copious
amounts of water.
INTRODUCTION
Buffers are solutions with the property of resisting changes in pH when
amounts of strong acid or base are added. Addition of 1 x 10-3 moles of a
strong acid such as HCl to a liter of distilled water will cause a change in
pH of 4 units. (Distilled water has a pH of 7, while the 1 x 10-3 M solution
of strong acid produced would have a pH of 3.) Addition of a similar
amount of strong acid to a buffer solution would generally cause a change
in pH of 0.1 units or less. Many biological functions depend on buffer
systems to control the pH within a small range. For example, human blood
is buffered at a pH of 7.4. Changes in pH as small as 0.1 pH units would
cause a dramatic decrease in the blood's ability to carry the oxygen
required to sustain life.
Solutions that function as buffers are mixtures of a weak acid and its
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© permitted under Section 107 or 108 of the 1976 United Stales Copyright Act, without the prior written permission of the publisher
104 EQUL1003: Preparation and Properties of Buffers
considering the chemical equilibrium between the weak acid (generally

referred to as HA) and its conjugate base (generally referred to as A - 1 ). The
weak acid equilibrium is given by:
HA(aq) H+ 1 (aq) +A - 1 (aq) (equation 1)
The equilibrium constant expression for this reaction is:

[H+ 1 ] X [A- 1 ]
Ka= [HA] (equation 2)
When a buffer is prepared to contain both the weak acid and the weak
base in known concentrations, the concentration of H+ 1 can be found by
rearranging the above expression for Ka:
(equation 3)
The pH of the buffer may then be calculated from the [H+ 1 ]:

(equation 4)
An alternative method commonly used to calculate the pH for buffer

solutions involves taking the negative log of both sides of equation 3 to
give:
This equation is commonly written in the form below (recall that

pKa = -logKa and notice the change in sign in the last log term):
pH= pKa + log([A - 1 ]/[HA]) (equation 5)
Equation 5 is known as the Henderson-Hasselbalch equation.

An important property of any buffer system is its ability to resist
changes in pH. However, this ability is limited by the amount of weak
acid and/ or conjugate base in the buffer. Buffer capacity is used to
measure the ability of a buffer to resist changes in pH when a strong acid
or strong base is added to the buffer. Normally, the buffer capacity is
defined as the amount of strong acid or strong base (in moles) that can be
added to the buffer, resulting in a pH change of one unit. The buffer
capacity for the addition of strong acid depends on the amount of A-1 in
the buffer solution, and the buffer capacity for the addition of strong base
depends on the amount of HA in the buffer solution. In a buffer, the
[A - 1 ] does not have to equal [HA]. Therefore, the buffer capacity for
addition of acid can be different from the buffer capacity for addition of
base.
In this experiment you will prepare a buffer of acetic acid and sodium
acetate by two different methods. In the first method, you will pipet a
known amount of acetic acid into a volumetric flask and add an equal
number of moles of solid sodium acetate. (You will first, of course, be
asked to calculate how much solid sodium acetate is required.) The second
method involves converting some of the acetic acid in a solution into
sodium acetate (in solution). This method uses an acid-base neutralization
EQULl 003: Preparation and Properties of Buffers 105
reaction. In either case, you will have a solution of a weak acid (acetic acid)
and its conjugate base (sodium acetate), which is a buffer.
PROCEDURE
Part 1: Making a Buffer from 1. Pipet 25 mL of 0.20 M acetic acid into a 250-mL volumetric flask.
a Weak Acid and its 2. Calculate the number of moles of acetic acid that are in the 250-mL
Conjugate Base volumetric flask. (This is molarity x volume, and is described as cal-
culation #1. There is space provided on your Report Form for this
calculation.)
3. Calculate the weight of sodium acetate that will give the same number
of moles as the number of moles of acetic acid that you added to the
volumetric flask. (This is a gram-mole conversion, and there is space
provided on your Report Form for this calculation.)
4. Weigh out the amount of sodium acetate that you calculated in step 3,
add it to the acetic acid in the volumetric flask, and swirl to dissolve all
of the solid. Add distilled water to fill the volumetric flask about 2/3
full and mix well. Add distilled water to the mark and mix well. This
solution is a buffer.
Ring Stand
Buret Clamp
or Finger Clamp
Lead to pH Meter
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5. Using the pH meter provided, measure the pH of the solution and

record it on your Report Form.
6. Pipet 25 mL of the buffer solution that you have just prepared into a
150-mL Erlenmeyer flask.
7. Set up a buret and fill it with 0.010 M HCL Record the initial buret
volume on your Report Form.
8. Add about 4 mL of the 0.010 M HCl from the buret to the buffer in the
150-ml Erlenmeyer flask. Record the new buret volume on your Report
Form.
9. Mix well, measure the pH, and record the pH on your Report Form.
10. Repeat steps 8 and 9 four more times, each time adding another 4 mL
portion of 0.010 M HCl to the same buffer solution.
11. Repeat the above procedure (Steps 6-10), substituting 4 mL portions of
0.010 M NaOH in place of the 0.010 M HCL
Part II: Making a Buffer from 1. Pipet 50 mL of 0.20 M acetic acid into a 250-mL volumetric flask.
a Weak Acid and a Strong 2. Into the same 250-mL volumetric flask, pipet 50 mL of 0.10 M NaOH.
Base Mix the solution.
3. Fill the volumetric flask to the mark using the procedure described in
Part I. Be sure that the solution is well mixed. This solution is also a
buffer (as you will see when you complete the calculations).
4. Pipet 25 mL of the buffer solution that you have just prepared into a
150-mL Erlenmeyer flask.
5. Measure the pH of this buffer solution and record it on your Report
Form.
6. Fill a buret with 0.010 M HCl and record the initial buret volume on
your Report Form.
7. Add about 4 mL of the 0.010 M HCl from the buret to the buffer in the
150-mL Erlenmeyer flask. Record the new buret volume on your
Report Form.
8. Mix well, measure the pH, and record the pH on your Report Form.
9. Repeat steps 7 and 8 four more times, each time adding another 4 mL
portion of 0.010 M HCl to the same buffer solution.
10. Repeat the above procedure (steps 4-9) substituting 4 mL portions of
0.010 M NaOH in place of the 0.010 M HCL
CALCULATIONS
Show all of your work on your Report Form.
Part 1: Making a Buffer 1. Calculate the number of moles of acetic acid added to the 250-mL
from a Weak Acid and its volumetric flask. You added 25.00 mL of 0.20 M acetic acid. The num-
Conjugate Base ber of moles are given by:
Molarity (moles/liter) x Volume (in liters)= moles of acetic acid

0.20 M x 0.02500 L = _ _ _ _ moles of acetic acid
2. Calculate the grams of sodium acetate equal to the number of moles of

acetic acid. This is:
moles of NaCzH302 x molar mass of NaCzH302 = grams of NaCzH302

3. Calculate the theoretical pH of the solution using the Henderson-
Hasselbalch equation. This requires the concentrations of acetic acid and
sodium acetate:
[HC2H 30 2] =moles of acetic acid/0.2500 L

(Remember that the solution ends up in a 250-mL volumetric)
[NaC2H 30 2] = moles of NaC 2H 30 2/0.2500 L
(Again, the solution ends up in a 250-mL volumetric)
Then:
4. The determination of the buffer capacity requires the calculation of the

total volume of 0.010 M HCl added to the buffer from the buret at the
end of each addition. After each addition, the total volume of HCl
added is the final buret reading minus the initial buret reading.
5. In order to find the buffer capacity with respect to HCl, you need to
plot the measured pH of the solution (on the y-axis) vs. the total vol-
ume of HCl added (on the x-axis). Draw a smooth curve through the
data points and estimate the volume of HCI that would be required in
order to change the pH by one unit (from the measured pH of the
original buffer that you prepared).
/Initial pH
pH
Buffer Capacity jt-o•t---------.•~1 mL of HCl (or NaOH)

inmL ~
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required to change the pH by one unit, so you need to convert the
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u Molarity of HCl x volume of HCl from the plot (in liters) = moles of HCI
~ 0.010 M x liters= moles of HCl
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6. In order to find the buffer capacity with respect to NaOH, repeat cal-
culations 4 and 5 using the data for the addition of NaOH.
Part II: Making a Buffer 1. Calculate the number of moles of acetic acid added to the 250-mL
from a Weak Acid and a volumetric flask. You added 50.00 mL of 0.20 M acetic acid. The number
Strong Base of moles are given by:
Molarity (moles/liter) x Volume (in liters) = moles of acetic acid
0.20 M x 0.0500 L = _ _ _ _ moles of acetic acid
2. Calculate the number of moles of NaOH added to the 250-mL volu-
metric flask. You added 50.00 mL of 0.10 M NaOH. The number of
moles are given by:
Molarity (moles/liter) x Volume (in liters) =moles of NaOH
0.10 M x 0.0500 L = moles of NaOH
3. When a weak acid and strong base are mixed, an acid-base neutraliza-
tion reaction takes place until all of the reactant in the lesser amount is
used up (i.e., one of the species is the limiting reagent). The reaction in
this case is:
Since the stoichiometry between acetic acid and sodium hydroxide

is 1:1, the species present in the lesser amount is the limiting reagent.
You will find from the calculations above that the NaOH is the limiting
reagent. This means that all of the NaOH is consumed, producing an
equal amount of NaC 2 H 3 0 2 and using an equal amount of HC 2 H 30 2 •
Therefore, after the neutralization reaction takes place:
moles of NaC 2 H 30 2 =moles of NaOH added and
moles of HC 2 H 30 2 = moles of HC 2 H 3 0 2 added
-moles of NaOH added
4. The remaining solution is a buffer, because the neutralization reaction
leaves some unreacted HC 2 H 30 2 and produces some NaC 2 H 3 0 2 . The
theoretical pH of this buffer solution can be calculated using the
Henderson-Hasselbalch equation. This requires the concentrations of
acetic acid and sodium acetate:
[HC 2H 30 2 ] =moles of acetic acid/0.2500 L

[NaC 2H 3 0 2 ] = moles of NaC2 H 3 0 2 /0.2500 L
(Again, the solution ends up in a 250 mL volumetric)
Then:
5. Repeat the calculations described in Part I steps 4, 5 and 6 in order to

determine the buffer capacity of this buffer with respect to HCl and
NaOH. Turn in your graphs with your Report Form.
Pre-Lab Questions
1. Define the terms buffer and buffer capacity.
2. Would each of the following would make a good buffer? Explain each case.
a. HCl and NaOH
c. NaOH and NaF
3. Use the Henderson-Hasselbalch equation to calculate the pH of a buffer containing 0.250 M sodium
propionate and 0.350 M propionic acid. The Ka of propionic acid is 1.34 x 10-5 .
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4. For the buffer described in question 3, which is greater, the buffer capacity with respect to addition of
acid, or the buffer capacity with respect to addition of base? How do you know?
~----------------------
name section date
Preparation and Properties of Buffers

REPORT FoRM
Part 1: Making a Buffer from a Weak Acid and its Conjugate Base
Calculated pH = ______
(Show your work below)
Measured pH = _ _ _ _ _ __
Buret readings Total volume of HCl added pH

initial buret reading _ _ _ _ _ rnL
reading after first addition _ _ _ _ _ rnL first addition _ _ _ _ _ rnL
reading after second reading _ _ _ _ _ rnL second addition _ _ _ _ _ rnL
reading after third addition _ _ _ _ _ rnL third addition _ _ _ _ _ rnL
reading after fourth addition _ _ _ _ _ rnL fourth addition _ _ _ _ _ rnL
.~ reading after fifth addition _ _ _ _ _ rnL fifth addition _ _ _ _ _ rnL

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Addition of HCl
initial buret reading _ _ _ _ _ mL
reading after first addition _ _ _ _ _ mL first addition mL
reading after second reading _ _ _ _ _ mL second addition mL
reading after third addition _ _ _ _ _ mL third addition mL
reading after fourth addition _ _ _ _ _ mL fourth addition mL
reading after fifth addition _ _ _ _ _ mL fifth addition mL
Addition of NaOH
Buffer capacity with respect to HCl _ _ _ _ _ _ mL (from graph)
Buffer capacity with respect to HCl _______ moles
Buffer capacity with respect to NaOH _______ mL (from graph)
Buffer capacity with respect to NaOH _______ moles

EQUL1003: Preparation and Properties of Buffers 113
Part II: Making a Buffer from a Weak Acid and a Strong Base
50 mL of 0.10 M of NaOH = _ _ _ _ _ _initial moles of NaOH
moles of HC 2H 30 2 after neutralization = _ _ _ _ _ __
moles of NaC 2 H 3 0 2 after neutralization= _ _ _ _ _ __
Calculated pH = _ _ _ _ __
(Show your work below)
Measured pH = _ _ _ _ _ __
Addition of HCI

initial buret reading _____ mL
reading after first addition ----- mL first addition _____ mL
reading after second reading _____ mL second addition _____ mL
reading after third addition _____ mL third addition _____ mL
reading after fourth addition _____ mL fourth addition _____ mL

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Addition of NaOH
Buret readings Total volume of NaOH added pH

initial buret reading mL
reading after first addition mL first addition mL
reading after second reading mL second addition mL
reading after third addition mL third addition mL
reading after fourth addition mL fourth addition mL
reading after fifth addition mL fifth addition mL
Buffer capacity with respect to HCl _ _ _ _ _ _ mL (from graph)
Buffer capacity with respect to HCl _______ moles
Buffer capacity with respect to NaOH _ _ _ _ _ _ mL (from graph)
Buffer capacity with respect to NaOH _______ moles
Turn in your graphs with your Report Form.
~------- --~------
Post-Lab Questions
1. Calculate the pH of a buffer that contains 10.0 grams of benzoic acid and 11.5 grams of sodium
benzoate in a total volume of 500.0 mL.
2. Calculate the pH of the buffer in Question 1 if 10.0 mL of 0.20 M NaOH is added.
3. An "ideal" buffer is commonly considered to be one in which the pH of the buffer equals the pKa of
the weak acid in the buffer. Explain why this is the case.
4. How many grams of potassium fluoride must be added to 250.0 mL of 0.15 M HF in order to give a
buffer with a pH of 3.55?
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5. Calculate the buffer capacity with respect to the addition of NaOH for the buffer described in
question 1.
6. Calculate the pH of a buffer that is 0.11 Min sodium phosphate and 0.20 Min sodium hydrogen
phosphate.
7. Briefly describe one buffer that is of biological importance.

10
E QU L
Monitoring Acid-Base Titrations

with a pH Meter
Prepared by John W. Alcock, Quinnipiac College, and
M. L. Gillette, Indiana University Kokomo

Use a pH meter to record titrant solution pH data. Collect titrant volume
for titrations of hydrochloric acid and of acetic acid with standardized
sodium hydroxide solution. Prepare titration curves from the collected
data. Calculate hydronium and hydroxide ion concentrations at various
points throughout the titrations. Use the titration curves and calculations to
compare the behavior of the two acids.
Analysts frequently determine the acid content of solutions such as
rainwater and industrial wastes. To do this, they take advantage of
neutralization reactions between acids and bases. One such example is the
neutralization of hydrochloric acid solution (HCl) with the base sodium
hydroxide (NaOH), shown in Equation 1.
HCl(aq) + NaOH(aq) ____, H20( I)+ NaCl(aq) (Eq. 1)
We can carry out the neutralization quantitatively by titration. Titration is the

addition of a chemically equivalent volume of a solution of known con-
centration, called a standardized solution, to the solution of unknown
concentration being analyzed. We add the standardized solution, the titrant,
from a buret to accurately measure the volume required for the neutraliza-
tion. When the solution being analyzed is acidic, it is convenient to use a
standardized NaOH solution as the titrant.
I. Titrating a Strong Acid with We classify acids as strong or weak depending upon their extent of
a Strong Base dissociation in water. When dissolved in water, virtually every molecule
of a strong acid dissociates, releasing a hydrogen ion (H+) to a water
molecule, producing a hydronium ion (H3 0+). Equation 2 shows the
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reaction of HCl, a strong acid, in water.
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0 CENGAGE © 1997 Cengage Learning. ALL RIGHTS RESERVED. No part of this work covered by Ihe copyright herein rnay be reproduced,
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0)
recording, scanning, digitizing, taping, Web distribution, information networks, or inlorrnalion slorage and retrieval systems, except as
@ permitted under Section 107 or 108 of the 1976 United States Copyright Act, Without the prior written permission ofthe publisher.
118 EQUL0494: Monitoring Acid-Base Titrations with a pH Meter
(Eq. 2)
Sodium hydroxide is a water-soluble ionic compound that completely

dissociates into sodium ions (Na+) and hydroxide ions (OH-). Hence,
NaOH is a strong base. We can more accurately represent the neutralization
reaction of HCl with an NaOH solution in the complete ionic equation
shown in Equation 3.
(Eq. 3)
Sodium ions and chloride ions (Cl-) are spectator ions in this reaction,
appearing unchanged as both reactants and products. Therefore, we can
cancel them from Equation 3 to create the net ionic equation, Equation 4.
(Eq. 4)
We can monitor any acid-base titration by following changes in H 3 0+

concentration in solution. This is convenient, because H 3 0+ concentration is
related to the pH of the solution as defined by Equation 5. Note that the
square brackets represent the molarity (M, mol/L) of H 3 0+.
(Eq. 5)
We monitor pH during a titration using a pH meter equipped with an

electrode responsive to H 3 0+ concentration in solution.
Initially, the pH of the HCl solution will be low, because there are as
many moles of H 3 0+ present as there are moles of HCL As we add NaOH
solution, the reaction in Equation 4 occurs, decreasing [H30+]. This causes a
corresponding increase in solution pH.
This neutralization reaction is complete at the equivalence point, when
the number of moles of OH- added as titrant equals the number of moles of
H 30+ originally present in solution. The pH at the equivalence point is
established by the components of the titration mixture. For the titration of
HCl with NaOH, a strong acid with a strong base, Equation 3 shows that the
only species present at the equivalence point are Na+, Cl-, and H 2 0.
Because neither Na+ nor Cl- react with water (and are, therefore, neutral
ions), the pH of the titration mixture at the equivalence point is established
by the dissociation of water, shown in Equation 6.
(Eq. 6)
The equilibrium constant expression representing this reaction is shown in

Equation 7. At 25 oc, the dissociation constant for water is 1.0 x 10- 14 .
(Eq. 7)
At the equivalence point of our NaOH and HCl titration, H 30+ and OH-
concentrations are equal (Equation 6). Therefore, [H30+] = (1.0 x 10- 14) 112 =
1 x 10- 7M, and the pH of the solution is 7 (Equation 5).
If we continue to add NaOH solution to the titration mixture after the
equivalence point, the pH will continue to increase.
EQUL0494: Monitoring Acid-Base Titrations with a pH Meter 119
12
10
8
equivalence point,
pH
pH= 7.0
6
4 I
I
I
2 - - - _I_ - - - - -
I
QL--L--~--'---L--~~---L--L-~--~
0 5 10 15 20 25 30 35 40 45 50
volume of 0.1 OOM NaOH added, ml
Figure 1
A typical titration curve for a strong acid with O.lOOM NaOH
If we plot the pH of a titration mixture versus volume of titrant added,

we obtain a graph called a titration curve. Figure 1 shows a typical curve for
the titration of a strong acid with NaOH solution. We can locate the equi-
valence point of the titration by drawing a vertical line through the midpoint
of the steep portion of the curve. The titrant volume and pH of the solution at
the equivalence point correspond to the x andy coordinates, respectively, of
the point where the vertical line intersects the titration curve.
II. Titrating a Weak Acid with Most acids are weak. When a weak acid is dissolved in water, only a small
a Strong Base percent of the acid molecules dissociate to produce H 3 0+. Acetic acid
(HC 2H 30 2), the pungent component of vinegar, is a typical weak acid. We
can represent its dissociation in water by Equation 8.
(Eq. 8)
The equilibrium constant expression for the dissociation of HC2H 30 2 is

shown in Equation 9. The dissociation constant for HC 2 H 30 2 at 25 oc
is 1.8 x 10-5 .
(Eq. 9)
The pH of an HC 2H 30 2 solution is higher than that of an HCl solution

of equal concentration, because only about 5% of the HC 2 H 3 0 2 molecules
dissociate, whereas essentially all of the HCl molecules do so.
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If we titrate an HC 2 H 3 0 2 solution with NaOH solution, the reaction
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@ (Equation 12) for this reaction are shown below.
-----· ------------------------
I
12 - - ·- - - l - - -~----~
I
10 I
1 equivalence point,
8 pH =8.8
pH
6
0L--L-L-~-~~--L-L--L-~~
0 5 10 15 20 25 30 35 40 45 50
volume of 0.1 OOM NaOH added, ml
Figure 2
A typical titration curve for a weak acid with O.lOOM NaOH
HCzH30z(aq) + Na+(aq) + OH-(aq)---+ Na+(aq) + CzH302 -(aq) + H 20(l) (Eq. 11)
HCzH30z(aq) + OH-(aq)---+ CzH302 -(aq) + HzO(l) (Eq. 12)
As we add NaOH solution to the HC 2H 30 2 solution, HC 2H 30 2 is

converted into acetate ions (C 2H 30 2-). The solution pH depends upon
the relative concentrations of these two species (Equation 9). As with the
titration of HCl solution with NaOH solution, the pH of the HC 2H 30 2-
NaOH titration mixture at the equivalence point is established by the
components present at that point: C 2H 30 2-, Na+, and H 20.
Sodium ions are neutral in terms of pH, so they do not play a role in pH.
However, because C 2H 30 2- ions are the anions of a weak acid, they react
with H 20, or hydrolyze, as shown in Equation 13.
(Eq. 13)
The equilibrium constant expression, Kh, at 25 oc for the hydrolysis reaction

is shown in Equation 14.
Kh = [OH-] [HCzH30z] = _ x
5 6 1010 (Eq. 14)
[CzH30z-]
The other equilibrium that could occur at this equivalence point is the
dissociation of water, shown in Equation 6. Because Kh is larger than Kw,
the hydrolysis reaction takes precedence. Therefore, the pH of the reaction
mixture at the equivalence point is greater than 7.0, due to the presence of
OH- produced by the hydrolysis of C 2H 30 2-.
A typical titration curve for the titration of a weak acid with 0.100M
NaOH is shown in Figure 2.
Ill. Calculating H3 0+ and We can calculate the molarity of H 30+ and OH- from the pH at any point
OH- Concentrations for on a titration curve. Suppose we find from our titration curve that the
Points on a Titration Curve solution pH is 4.60 when we have added 10.0 mL of 0.100M NaOH to
25.0 mL of an HC 2H 30 2 solution. To determine [H30+] and [OH-] for
the mixture at this point, we substitute 4.60 into Equation 5, and solve
for [H30+].
4.60 = -log[H30+]
-4.60 = log[H30+]
[H3o+] = antilog-4.60 = 2.5 X w- 5M

Using Equation 7, we can calculate [OH-].
[OH-] = 1.0 x 10-14 = 4.0 x 10-IOM

2.s x w-s
Using the same process, we can calculate [H30+] and [OH-] for any point
on the titration curve.
PROCEDURE
Preview
• Calibrate a pH meter
• Fill buret with standardized NaOH solution
• Titrate HCl solution with standardized NaOH solution, monitoring the
reaction mixture pH as titrant added
• Titrate HC 2 H 30 2 solution with standardized NaOH solution, monitor-
ing reaction mixture pH as titrant added
0.1 OOM hydrochloric acid-toxic and corrosive

0.1 OOM sodium hydroxide-toxic and corrosive
I. Calibrating the pH Meter
Glass electrodes are fragile and expensive. Do not bump the glass
membrane against anything solid.
NOTE: Your laboratory instructor will describe and demonstrate a satisfactory

method for calibrating the pH meters available in your laboratory. Depending upon
the model of pH meters available, you will perform this calibration using either one or
two buffer solutions.
@
Consult your laboratory instructor to make sure your electrode is properly vented.
Transfer 50 mL of the designated buffer solution into a 150-mL beaker.

Carefully immerse the electrode(s) in the solution.
Turn the function knob to "pH" or, on some instruments, "read". Turn
the standardize knob until the meter indicates the exact pH of the buffer
solution. Do not turn this knob again during the course of the Procedure.
Turn the function knob to "standby".
On Data Sheet I, record the pH(s) at which you standardized the meter.
II. Titrating HCI Solution with

NaOH Solution
0.1 OOM HCI and 0.1 OOM NaOH are toxic and corrosive. Prevent eye, skin,
and clothing contact.
Obtain 25.00 mL of an approximately O.IOOM HCl solution in a clean,

250-mL beaker. Also obtain 125 mL of an approximately O.IOOM NaOH
solution in a clean, dry 250-mL Erlenmeyer flask. Record the exact molarity
of each solution on Data Sheet I.
Rinse a clean 50-mL buret with three separate 10-mL portions of
distilled water. With the stopcock closed, hold the buret in a nearly
horizontal position, and slowly rotate it so that the water contacts the entire
inner surface of the buret. Drain the rinse water through the buret tip into
the sink. Following the same procedure, rinse the buret with three 5-mL
portions of your NaOH solution. Drain the NaOH solution into a beaker
labeled "Discarded NaOH Solution".
Clamp the buret to a support stand. Fill the buret with your NaOH
solution to a point above the top calibration mark. Drain the solution
through the buret tip into the "Discarded NaOH Solution" beaker until
the meniscus is at a point within the calibrated portion of the buret. The
meniscus does not have to be exactly at the 0.00-mL mark. Remove any air
bubbles in the buret tip. Read the initial solution volume to the nearest
0.02 mL, and record it on Data Sheet I.
NOTE: Your laboratory instructor may tell you to stir your titration mixture with a
magnetic stirrer and stir bar. If so. be certain to position the electrode so that the stir
bar will not hit the glass membrane.
Position the beaker containing the HCl solution so that the glass
membrane of the electrode is immersed in the solution. Position the buret
containing NaOH solution just inside the beaker, with the tip below the rim
but above the solution surface, as shown in Figure 3. Ask your laboratory
instructor to check your equipment setup.
Adjust the function knob of your pH meter from "standby" to "pH", or
"read".
While stirring the HCl solution continuously, begin slowly adding 1- or
2-mL portions of NaOH solution. After each addition, record the pH and
the corresponding buret reading on Data Sheet I.
When successive pH readings begin to increase rapidly, add NaOH
solution dropwise until successive pH readings are increasing only slightly.
When you reach this stage, begin gradually increasing the amount of titrant
you add each time. Stop adding NaOH solution when the pH reaches 11.5.
-----~----
electrode buret
digital display
support
stand sample to be
titrated
function
control
temperature compensation
control
Figure 3
A pH meter-titration apparatus
NOTE: If you are using a magnetic stirrer, do not let the stir bar fall into the drain during
the next step.
After the titration is complete, leave the electrode in place. Add 0.100M
HCl solution to reduce the titration mixture pH to between 4 and 8. Pour
the titration mixture into the drain, diluting with a large amount of runn-
ing water.
Repeat the above procedure with a second 25.00-mL sample of 0.100M
HCl. Record all data on Data Sheet 1.
Ill. Titrating HC2H 3 02

Solution with NaOH Solution
0.1 OOM HC 2 H3 0 2 is an irritant. Prevent eye, skin, and clothing contact.
Follow the Procedure in Part II, using 25.00 mL of approximately 0.100M

HC2H 30 2 in place of the 0.100M HCl. Record the exact molarity of the
HC2 H 3 0 2 solution and all titration data on Data Sheet 1.
0.1 OOM HCI is a toxic, corrosive solution that can cause severe burns.
Prevent eye, skin, and clothing contact. Avoid inhaling the vapors or ingesting the
compound. If you spill any acid, immediately notify your laboratory instructor.
NOTE: If you are using a magnetic stirrer, do not let the stir bar fall into the drain
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(j) beaker. Insert the electrode(s) and stir bar, if you are using one, into the
@ NaOH solution. Add 0.100M HCl dropwise until the solution pH is between
------------·
4 and 8. Pour the solution into the drain, diluting with a large amount of
running water.
Rinse your buret twice using 10-mL portions of tap water, then twice
using 10-mL of distilled water. Drain the buret. With the stopcock open,
clamp the buret to the support stand in an inverted position, so it can drain.
Rinse the electrode with distilled water. Immerse the electrode tip in pH 7
buffer solution.
laboratory.
CALCULATIONS
Do the following calculations, and record the results on the graph paper
supplied and Data Sheet 2.
II. Titrating HCI Solution with 1. Prepare a titration curve. Plot pH (on the y-axis) versus volume of
NaOH Solution NaOH solution added (on the x-axis). If your initial buret reading was
not 0.00 mL, remember to subtract your actual initial reading from each
of your subsequent buret readings before plotting the titration data.
Ill. Titrating HC2 H3 02 2. On a separate piece of graph paper, prepare a titration curve from your
Solution with NaOH Solution data for Part III.
3. Using your titration curves and Equations 5 and 7, calculate [H3 0+] and
[OH-] in the reaction mixture at the following points in each titration:
(1) before you added any NaOH solution

(2) after you added 10.00 mL of NaOH solution
(3) before you added the 0.20 mL of NaOH solution needed to reach
the equivalence point
(4) at the equivalence point
(5) after you added 0.20 mL of NaOH solution past the equivalence
point
(6) after you added the last portion of NaOH solution
Name Section Date
1. Briefly explain why the part of the curve beyond the equivalence point is similar in the graphs from
Parts II and III, even though you titrated a strong acid in Part II and a weak acid in Part III.
2. A student began his Part II titration with an air bubble in the buret tip. The bubble was released,
unnoticed, at some point during the titration. Briefly describe the error that the bubble would have
caused in his titration results if:
(a) the bubble had been released prior to the equivalence point of the titration.
(b) the bubble had been released after the equivalence point.
3. (a) Briefly outline a procedure you could use to determine the HC 2 H 3 0 2 concentration in a vinegar
sample.
(b) Make a rough sketch of the shape of the titration curve for the determination in (a).
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4. (a) Sketch an approximate titration curve for the titration of an NaOH solution with standardized
HCl solution. Briefly explain the shape of the curve before the equivalence point, at the
equivalence point, and after the equivalence point.
(b) What would the pH be at the equivalence point of the titration in (a)? Briefly explain.
Name Section Date
Data Sheet 1
pH(s) at which meter was standardized: _________
II. Titrating HCI Solution with NaOH Solution
concentration of HCl solution, M _ _ _ _ _ _ _ _ __
concentration of NaOH solution, M _________
first determination second determination

initial buret reading, mL _________ initial buret reading, mL _________
buret volume NaOH buret volume NaOH

pH reading, mL added, mL pH reading, mL added, mL
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Ill. Titrating HC2 H3 0 2 Solution with NaOH Solution
concentration of NaOH solution, M

------------------
concentration of HC 2 H 3 0 2 solution, M ________________

initial buret reading, mL _________________ initial buret reading, mL _________________
buret volume NaOH buret volume NaOH

pH reading, mL added, mL pH reading, mL added, mL
Name Section Date
Data Sheet 2
11. Titrating HCI Solution with NaOH Solution

pH pH
(1) before adding NaOH solution
(2) after adding 10.00 mL
(3) 0.20 mL before equivalence point
(4) at equivalence point
(5) 0.20 mL past equivalence point
(6) after last addition
Ill. Titrating HC2 H3 0 2 Solution with NaOH Solution

pH pH
(1) before adding NaOH solution
(2) after adding 10.00 mL
(3) 0.20 mL before equivalence point
(4) at equivalence point
(5) 0.20 mL past equivalence point
(6) after last addition
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Name Section Date
1. Briefly explain:
(a) why you must use caution when working with HCl solutions.
(b) what you will do with the NaOH solution remaining in your buret after you have completed your
titrations.
2. Calculate [H3 0+] and [OH-] in solutions of
(a) pH 4.18
(b) pH 5.70
(c) pH 8.56
3. A student titrated 20.0 mL of 0.410M HCl with 0.320M NaOH and collected the following data.
volume NaOH solution

added, mL pH
0.00 0.39
2.00 0.46
4.00 0.54
6.00 0.62
8.00 0.70
10.00 0.78
12.00 0.87
14.00 0.96
16.00 1.07
18.00 1.19
20.00 1.35
22.00 1.56
24.00 1.93
24.50 2.09
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29.00 12.30
(a) Prepare a titration curve for this titration.
(b) Identify the volume of titrant required to reach the equivalence point of the titration.
(c) What are the pH, [H30+], and [OH-] when 21.50 mL of titrant has been added?
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11
THE R
Energy Changes in
Chemical Reactions
Prepared by Lee R. Summerlin, University of Alabama
Almost all chemical reactions involve either a loss or a gain of heat, although
this may not be readily observable and must be detected and measured with
sensitive instruments. Energy (heat) is required to break bonds, as when
molecules form atoms, and ionic compounds form ions. These reactions that
require energy are called endothermic reactions. On the other hand, when bonds
are formed, as when atoms combine to form molecules, or ions combine to
form ionic compounds, energy is released. These are called exothermic
reactions. When a chemical reaction occurs, bonds are broken and new bonds
are formed. As a net result, the entire reaction may be endothermic or
exothermic. In this experiment, you will explore three processes that involve
changes in energy: First, you will consider the heat of solution, the energy
change that occurs when a solid dissolves in water; secondly, you will conduct
experiments to determine if the overall heat change in a chemical reaction is
endothermic or exothermic, the heat of reaction; finally, you will determine how
much heat is produced when a substance burns. This is the heat of combustion.
This information will allow you to determine the heat content of that
substance, expressed as kilocalories per gram.
A. T H E H E AT 0 F S 0 L U T I 0 N
The Heat of Solution is the amount of heat energy absorbed or released
when a specific amount of a substance is dissolved in a solvent.
Procedure 1. Dissolving Ammonium Nitrate (NH4 N03 )

a. Place 100 ml of water in a styrofoam cup.
b. Measure the temperature and record this on your Report Form.
c. Weigh out about 15 grams of solid ammonium nitrate. Record the
weight.
d. Quickly dump the ammonium nitrate into the water.
e. Note the change in temperature as the solid dissolves. Record the
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change in temperature on your Report Form.
c
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ro
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0 CENGAGE © 2006 Cengage Learning. ALL RIGHTS RESERVED. No part of this work covered by the copyright herein may be reproduced,
<0
Learning· transmitted, stored, or used in any form or by any means graphic, electroniC, or mechanical, including but not limited to photocopying,
:s
N recording, scanning, digitizing, taping, Web distribution, information networks, or information storage and retrieval systems, except as
© permitted under Section 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the publisher.
------~~--
138 THERI 003: Energy Changes in Chemical Reactions
2. Dissolving Calcium Chloride (CaCh)

a. Place 100 mL of water in a clean styrofoam cup.
b. Measure the temperature of the water. Record on your Report Form.
c. Weigh out 15 grams of calcium chloride, CaCh.
d. Dump the calcium chloride in the water and note the change in
temperature as the solid dissolves. Record the change in tempera-
ture on your Report Form.
B. T H E H E AT 0 F R E ACT I 0 N
The Heat of Reaction is the amount of heat absorbed or released when a chemical
reaction takes place.
Procedure 1. The Reaction between Laundry Bleach and Sodium Sulfite

a. Place 50 mL of laundry bleach, in a Styrofoam cup. Laundry bleach
is a 5.25% solution of sodium hypochlorite (NaOCl). Record the
temperature on your Report Form.
b. Place 50 mL of 0.5M sodium sulfite solution in a beaker. Record the
temperature of the sodium sulfite solution. Add this solution to the
bleach in the Styrofoam cup.
c. Record any change in temperature on your Report Form.
2. The Reaction between barium hydroxide and ammonium thiocyanate.
a. Place a small wooden block on your lab bench. Put about 10-15
drops of water on the block to form a puddle. Place the beaker on
top of the puddle.
b. Place 20 g of barium hydroxide, Ba(OHh, crystals in a dry 250 mL
beaker.
c. Add 10 g of ammonium thiocyanate, NH4SCN, to the beaker.
d. Stir the mixture with a wooden splint or a glass rod. Put the beaker
on the puddle of water on the wooden block.
e. Leave it undisturbed for 3-4 minutes.
f. After 3-4 minutes, gently lift the beaker to see if it is frozen to the
board. Record your observations on your Report Form.
C. D E T E R M I N I N G T H E E N E R G Y C 0 N T E N T 0 F A C A N D L E
(HEAT OF COMBUSTION)
It is our common experience that we derive energy from the things that we
burn (coal, wood, oil, etc.), as well as foods that we eat. Chemists and
biochemists are concerned with exactly how much energy is available in
various substances, and these amounts can be easily and accurately
measured. This process is called calorimetry. We will determine the
approximate energy content of a candle that is made of wax, a hydrocarbon
derived from petroleum.
THER1003: Energy Changes in Chemical Reactions 139
Procedure 1. Weigh a small utility candle and an index card on the balance, and
record the weight on your Report Form.
2. Carefully add exactly 100 mL water to a clean cola can. Use a funnel to
be sure that all of the water enters the can. Record this volume on your
Report Form.
3. Place a glass rod through the holes in the sides of the can, and support
it on a ring on a ring stand, as illustrated at right.
4. Partially enclose the set-up with a large piece of heavy-duty aluminum
foil to prevent excessive heat loss.
5. Measure the temperature of the water in the cola can, and record this
on your Report Form.
6. Place the candle on the index card and put this directly beneath the
cola can so that the flame touches the can.
7. Light the candle and allow it to burn, heating the water in the cola can,
for 2-3 minutes.
8. Extinguish the candle flame and immediately record the temperature
of the heated water. Record this on your Report Form.
9. If any candle wax dripped onto the card beneath it, allow this to
harden. Then weigh the candle and the card as you did before. Record
the weight on your Report Form.
10. When the water in the can has cooled, pour it down the sink and wipe
off any soot that might have accumulated on the bottom of the can.
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140 THERl 003: Energy Changes in Chemical Reactions
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name section date
Energy Changes in Chemical Reactions

REPORT FoRM
A. Heat of Solution
1. Dissolving Ammonium Nitrate, NH4 N03
Volume of water (mL)
Weight of solid ammonium nitrate (grams)
Initial temperature of the solution eC)
Final (lowest) temperature of the solution ec)

Change in temperature ( C) 0
Questions:
a. Is this an endothermic or an exothermic reaction? Explain your answer.
b. Can you think of a practical use for this reaction?
c. Calculate the change in temperature per gram of N~N03 .
d. Write the equation for this reaction:

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142 THER1003: Energy Changes in Chemical Reactions
2. Dissolving Calcium Chloride, CaCh
Volume of water (mL)
Weight of solid CaCh (grams)
Initial temperature of CaCh solution eO

Final (highest) temperature of the solution ( C) 0
Change in temperature ( C) 0
Questions:
a. Is this an exothermic or an endothermic reaction? Explain.
b. Can you think of practical uses for a reaction such as this?
c. What was the change in temperature per gram CaClz?
d. Write the equation for this reaction.

B. The Heat of Reaction

1. The reaction between laundry bleach and sodium sulfite
0
Temperature of laundry bleach ( C)
Temperature of sodium sulfite (°C)
Temperature of mixture ( C)0
Change in temperature (°C)
Is this reaction endothermic or exothermic?
2. Reaction between barium hydroxide and ammonium thiocyanate.
Describe the result of mixing these two solids.
- - - - ~ -------~-
3. Heat of combustion of candle wax
Final temperature of water in can oc

Initial temperature of water in can oc
Change in temperature of water, ~T oc
Final weight of candle + index card grams
Initial weight of candle + index card grams
Amount of candle burned grams
Calorie: Amount of energy (heat) required to increase the temperature of 1 gram (1 mL) of water by 1 degree, oc.
For this experiment,
aT x weight (volume) of water heated= Calories

Calculate the amount of calories produced by the paraffin candle in this experiment.
1. How do your results compare with those obtained by other students in the laboratory?
2. What are some "sources of error" that prevent an accurate determination of the heat of combustion in
this experiment?
3. Another energy unit most often used by chemists is the "joule". If 1.0 calorie= 4.184 J, calculate the
heat of combustion of candle wax in joules.
Post-Lab Questions
1. Define the following: Heat of Solution, Heat of Reaction, Heat of Combustion.
2. Explain how you would determine the number of calories (heat content) of a pecan.
3. Define and distinguish between an "endothermic" and an "exothermic" reaction.
4. Name four reactions from your everyday experience that are exothermic reactions.
5. What improvements could you make to the Heat of Combustion experiment to make it more
accurate?
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6. We most often express heat as kilocalories and kilojoules rather than calories and joules. When
1 pound of fat is burned in the body, 9.4 kilocalories of energy is produced. Express this as
a. calories:
b. kilojoules:
7. A solid is stirred in a beaker of water until the solid dissolves. The water in the beaker becomes
warm. Is this an endothermic or exothermic reaction? Explain.
8. Would you have obtained more or less accurate results for the Heat of Solutions experiment if you
had performed this experiment in a cola can rather than a Styrofoam cup? Explain.
9. If you had accidently spilled some of the water while pouring it into the cola can in the experiment to
determine the heat content of a candle, would this have made your results erroneously higher or
lower? Explain.
10. Are the reactions in the body that utilize carbohydrates, lipids, and proteins endothermic or
exothermic? Explain.
11. Are photosynthetic reactions (say in the potato plant) endothermic or exothermic? Explain.
12
ELEC
Studying Electrochemical
Half-Cells and Half-Reactions
Prepared by Henry D. Schreiber, Virginia Military Institute, James N. Spencer,
Franklin and Marshall College, and H. Anthony Neidig, Lebanon Valley College
PURPOSE OF THE EXPERIMENT:

Construct three half cells. Write equations for the half-reactions and net
oxidation-reduction reactions for your half-cells. Determine net potentials
for the half-cells. Rank the three metals studied according to ease of
oxidation.
Oxidation-Reduction If we place a strip of nickel metal (Ni) in copper(II) sulfate solution

Reactions (CuS04 ), we can see immediate evidence of a chemical reaction. The Ni
begins to dissolve, and a deposit of metallic copper, Cu, appears on the Ni
strip.
We can divide this reaction into two parts, one involving nickel and the
other, copper. In the first part, Ni dissolves into solution as the nickel(II)
ion, Ni2 +. In this reaction, each nickel atom releases two electrons, as
shown in Equation 1:
(Eq. 1)
At the same time, copper(II) ions (Cu2 +) form Cu. This process consumes
electrons, as shown by Equation 2:
(Eq. 2)
The reactant that releases electrons, Ni in this case, is said to be oxidized.

The reactant that gains electrons, Cu2 + ion here, is reduced.
We express the overall reaction by adding the oxidation of Ni
described by Equation 1 to the reduction of Cu2+ ion described by
CENGAGE © 1995 Cengage Learning. ALL RIGHTS RESERVED. No part of this work covered by the copyright herein rnay be reproduced,
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148 ELEC0450: Studying Electrochemical Half-Cells and Half-Reactions
Equation 2. The net reaction involves the transfer of electrons from Ni to

Cu 2 + ion, as shown in Equation 3.
Ni(s) + Cu2+(aq) ---+ Ni2 +(aq) + Cu(s) (Eq. 3)
Reactions that involve the transfer of electrons from one reactant to

another are called oxidation-reduction or redox reactions. Equations 1 and
2 are individually called the oxidation and reduction half-reactions,
respectively, because each constitutes half of the overall reaction. The
electrons appearing in Equations 1 and 2 cancel when we add the half-
equations to yield the overall equation (Equation 3). In any oxidation-
reduction reaction equation, the number of electrons released by the
oxidation half-reaction must equal the number of electrons consumed by
the reduction half-reaction.
If we place a strip of Cu in nickel(II) sulfate solution (NiS04 ), we
observe no evidence of a reaction. This shows that the reverse of the
reaction in Equation 3 does not occur spontaneously. Thus, we may
conclude that Cu 2 + ion has a greater tendency to accept electrons from Ni
than Ni2 + ion does to accept electrons from Cu. In other words, Cu 2 + ion
has a greater reduction potential than Ni2 + ion.
By testing different combinations of metals and aqueous solutions of
metal salts, we can arrange metal ions in order of their relative reduction
potentials. Table 1 ranks selected metal ions by standard reduction
potentials, determined under standard conditions: 25 °C, 1 atm, and 1 molL - l
ion concentration. The standard reduction potential, E 0 red' measured in
Table 1 Selected standard reduction potentials for half-reactions
0
Reduction half-equation E red' V
Mg2 +(aq) + 2 e- ---+ Mg(s) -2.37
Al3 +(aq) + 3 e- ---+ Al(s) -1.66
Cr2 +(aq) + 2 e- ---+ Cr(s) -0.91
Zn2 +(aq) + 2 e- ---+ Zn(s) -0.76
Fe2 +(aq) + 2 e- ---+ Fe(s) -0.44
Ni2 +(aq) + 2 e- ---+ Ni(s) -0.26
Sn2 +(aq) + 2 e- ---+ Sn(s) -0.14
Pb2 +(aq) + 2 e- ---+ Pb(s) -0.13
2 H+(aq) + 2 e- ---+ H 2 (g) 0.00
Cu 2 +(aq) + 2 e- ---+ Cu(s) +0.34
Ag+(aq) + e----+ Ag(s) +0.80

ELEC0450: Studying Electrochemical Half-Cells and Half-Reactions 149
volts (V), provides a quantitative measure of a metal ion's tendency to

accept electrons. The reference point for reduction potentials, 0.000 V, has
been arbitrarily assigned to hydronium ions (H 30+) in aqueous solution
being reduced to hydrogen gas (H 2 ). The greater the reduction potential, the
greater the tendency for reduction. Table 1 shows that Cu 2 + ion does indeed
have a greater reduction potential than Ni2 + ion, as we concluded from the
experiment described previously.
The half-reactions that represent the oxidation of the metals in Table 1
to their respective metal ions are the reverse of the half-reactions in Table 1.
The standard oxidation potential, E 0oxid' of an oxidation half-reaction has
the same numerical value, but the opposite sign, of the corresponding
standard reduction potential. For example, the reduction potential of
magnesium ion, Mg2 +, is -2.37 V, so the oxidation potential of Mg is
+2.37 V. This relatively large positive voltage indicates that Mg is a very
reactive (or active) metal, one that readily donates electrons in an
oxidation-reduction reaction. In contrast, silver metal, Ag, is not especially
active, as indicated by its oxidation potential of -0.80 V.
To illustrate how we can use Table 1 to predict the spontaneity for
specific oxidation-reduction reactions, let's predict what will happen if we
place a Cu strip in silver(l) nitrate solution (AgN03 ) under standard
conditions. We need to determine whether or not the Cu atoms will donate
electrons to the silver ion, Ag+, as part of a spontaneous oxidation-
reduction reaction. The reduction half-reaction for Ag+ ion is shown in
Equation 4. The standard reduction potential for Ag + is +0.80 V (as shown
in Table 1).
Ag+ (aq) + e- -+ Ag(s) (Eq. 4)
The oxidation half-reaction for Cu is shown in Equation 5. Cu has a

standard oxidation potential of -0.34 V.
(Eq. 5)
To obtain the net equation, we add the equations for the two half-
reactions. To equalize the number of electrons in the equations for each
half-reaction, we must multiply Equation 4 by 2. Note that this
manipulation does not change E 0 red for the reduction half-reaction. The
net equation is shown in Equation 6.
2 Ag+(aq) +2 e--'----+ 2 Ag(s) Eored = +0.80V

Cu(s)---+ Cu2 +(aq) +e- £0 oxid = -0.34 V
2 Ag+(aq) + Cu(s)---+ Cu 2+(aq) + 2 Ag(s) E0 net= +0.46 V (Eq. 6)
Because the standard net potential (E 0net), or sum of the standard

reduction and oxidation potentials, is positive for Equation 6, we predict
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Electrochemical Cells Remarkably, oxidation-reduction reactions can even occur between reac-
tants in separate containers. In such cases, electrons are transferred from the
reactant being oxidized to the reactant being reduced through a wire
connecting the two containers.
For example, suppose we place a Ni strip in an aqueous nickel(II) salt
solution. Then we place a Cu strip in an aqueous copper(II) salt solution in
a separate container. Next, we connect one end of a wire to the Ni strip and
the other end to the Cu strip. Electrons will pass through the wire from the
Ni strip to the Cu strip, provided that we make an additional connection
between the containers to complete the electrical circuit. This second
connection is called a salt bridge and is shown in Figure 1. The entire
assembly is an electrochemical cell, a system that utilizes a spontaneous
oxidation-reduction reaction to pump electrons through an electrical
circuit. An electrochemical cell is composed of two parts, or half-cells: in
this case, a nickel half-cell, in which Ni is being oxidized, and a copper
half-cell, in which Cu2 + ion is being reduced. The metal strips are called
electrodes.
Electrons are driven from the nickel half-cell to the copper half-cell by
the net cell potential, which is the sum of the reduction potential of Cu 2 +
ion and the oxidation potential of Ni. We can measure this force by
connecting a voltmeter between the half-cells, as shown in Figure 1. The
magnitude of the net cell potential and the direction of the electron flow
through the wire depend on the relative potentials of the metal-metal ion
couples for donating or accepting electrons, as summarized in Table 1. The
net cell potential for our Ni-Cu cell indicates that the oxidation-reduction
reaction is spontaneous and that the observed voltage should be +0.60 V
under standard conditions.
In this experiment, you will place a zinc strip (Zn) in a CuS04 solution,
a lead strip (Pb) in a CuS04 solution, and a Zn strip in a lead nitrate
solution Pb(N03 h. Then you will observe each chemical system. You will
write equations for the half-reactions and a net equation for each system,
calculate the net cell potential for each system, and predict whether or not
the reaction would be spontaneous. Then you will rank the three metals by
their relative ease of oxidation.
voltmeter
filter paper saturated with

KN0 3 (aq) used as salt bridge
Ni electrode Cu electrode
NiSO4 solution CuS04 solution
Figure 1
A typical electrochemical cell
Next, you will construct Zn-Cu and Fe-Cu electrochemical cells. The
voltmeter for each cell should show a positive reading. For each cell, you
will write equations for each of the half-reactions and the net cell reaction.
Finally, you will calculate the standard net cell potential, based on the
half-cell potentials in Table I.
PROCEDURE
Chemical Alert
Wear departmentally approved eye protection while doing this experiment.
I. Oxidation-Reduction A. The Zn-Cu System

Reactions
NOTE: Reaction indicators will be changes either in the appearance of the metal
surfaces or the solutions. If the metal strips do not appear bright and shiny over their
entire surfaces before the experiment, clean the surfaces with sandpaper.
1. Clean the surface of a Zn strip with sandpaper. Place the strip in a

small test tube.
CuS04 is toxic and irritant. If any of the solution contacts your skin,
thoroughly wash the area.
2. Transfer enough O.lM CuS04 solution into the test tube to completely
cover the Zn strip.
3. After 5 min, record your observations of the Zn-Cu2 + ion system on
Data Sheet I.
4. Place the used Zn strip in the container designated by your laboratory
instructor and labeled "Discarded Zn Metal." Retain the CuS04 solu-
tion for use in Part B.
B. The Pb-Cu System
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5. Clean a Pb strip with sandpaper if necessary. Place the strip in the
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into the container provided by your laboratory instructor and labeled

"Discarded CuS04 Solution."
C. The Zn-Pb System

8. Clean the surface of a Zn strip with sandpaper if necessary. Place the
strip in a small test tube.
Pb(N0 3 )2 solution is toxic. If any of the solution contacts your skin,

thoroughly wash the area.
9. Add 0.1M Pb(N03 )z solution to the test tube until it covers the Zn strip.
10. After 5 min, record your observations of the Zn-Pb2 + ion system on
Data Sheet 1.
11. Place the used Zn strip in the container provided by your laboratory
instructor and labeled "Discarded Zn Metal." Discard the Pb(N03 )z
solution into the container provided by your laboratory instructor and
labeled "Discarded Pb(N03 h Solution." -.
II. Electrochemical Cells A. The Zn-Cu Electrochemical Cell

12. Using a 25-mL graduated cylinder, measure 15 mL of 0.1M zinc(II)
sulfate solution, ZnS04 , and transfer it to a clean 20-mL beaker. Label
the beaker "Zn."
13. Rinse your graduated cylinder and use it to measure 15 mL of 0.1M
CuS04 solution and transfer it to another clean 20-mL beaker. Label the
beaker "Cu."
NOTE: If the metal strips in Steps 14-16 do not appear bright and shiny over their
entire surfaces, sand the metal surfaces until they are shiny.
14. If necessary, clean the surface of a Zn strip using sandpaper.

15. Connect one end of a Cu wire to the Zn strip, and place the strip in the
beaker labeled "Zn." Make certain that the Cu wire does not contact
the solution.
16. If necessary, clean the surface of a Cu strip using sandpaper. Attach
one end of a Cu wire to the Cu strip, and place the strip in the beaker
labeled "Cu." Do not allow the wire to contact the solution.
17. Pour about 50 mL of 0.5M potassium nitrate solution (KN03 ) into a
clean 150-mL beaker.
NOTE: The filter paper saturated with KN0 3 solution serves as the salt bridge for the
cell. The soaked paper makes contact between the half-cells in the two beakers. Do not
allow the filter paper to become dry at any time during the experiment If this should
happen, resoak the filter paper with KN0 3 solution.
---~ -------------
Potassium nitrate solution is an irritant and oxidant. If any of the solution

contacts your skin, thoroughly wash the area.
18. Fold a piece of filter paper to about 1 em wide. Place the filter paper
in the KN03 solution. Allow the filter paper to become thoroughly
soaked.
19. Position the soaked filter paper with tweezers or forceps so that one
end of the paper is in the CuS04 solution and the other end is in the
ZnS04 solution, as shown in Figure 1.
20. Connect the wire attached to the Zn strip to one voltmeter terminal.
Connect the wire from the Cu strip to the other voltmeter terminal.
Check the voltmeter reading. If the reading is negative, reverse the
voltmeter connections.
21. Record the voltage registering on the voltmeter on Data Sheet 1.
22. Disconnect the Cu wires from the voltmeter and from the Zn strip.
Remove the Zn strip and place it in the "Discarded Zn Metal" con-
tainer. Pour the ZnS04 solution into the container provided by your
laboratory instructor and labeled "Discarded ZnS04 Solution." Place
the filter paper in the container labeled "Discarded Filter Paper." Leave
the beaker labeled "Cu" intact.
B. The Fe-Cu Electrochemical Cell

23. After rinsing your 25-mL graduated cylinder, use it to measure 15 mL
of a 0.1M iron(II) sulfate solution (FeS04 ), and pour the solution into a
clean 20-mL beaker. Label the beaker "Fe."
24. If necessary, clean the surface of a Fe strip, using sandpaper. Attach
one end of a Cu wire to the Fe strip, and place the strip in the FeS04
solution. Do not allow the Cu wire to contact the solution.
25. Prepare another salt bridge as in Step 18. Position the filter paper with
forceps so that one end is in the FeS04 solution and the other end is in
the CuS04 solution in the beaker labeled "Cu" from Part A.
26. Connect the wires attached to the Fe and Cu strips to the voltmeter
terminals. Check the voltmeter reading. If the reading is negative,
reverse the voltmeter connections.
27. Record the voltage registering on the voltmeter on Data Sheet 1.
28. Disconnect the wires from the voltmeter and the Fe and Cu strips.
Place the strips in the containers provided by your laboratory instruc-
tor and labeled "Discarded Fe Metal" and "Discarded Cu Metal,"
respectively. Pour the CuS04 , FeS04, and KN03 solutions into the
containers labeled "Discarded CuS04 Solution," "Discarded FeS04
Solution," and "Discarded KN03 Solution," respectively. Place the
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CALCULATIONS
Do the following calculations and record the results on Data Sheet 2.
I. Oxidatio~Reduction A. The Zn-Cu System

Reactions
1. Based on the fact that Zn atoms and Cu2 + ions are the only possible
reactants in this system, write half-equations for the oxidation of Zn
and the reduction of Cu 2 + ion on the spaces provided on Data Sheet 2.
Look up the potential for each half-equation in Table 1. Record these
potentials on Data Sheet 2.
2. Write the net equation and determine the net potential. Predict whether
or not this reaction is spontaneous, based on the sign of the net potential.
Indicate whether or not your experimental observations are consistent
with this prediction.
B. The Pb-Cu System

3. Write the half-equations and potentials for the reduction and oxidation
that occur when Pb is added to CuS04 solution.
4. Add the half-equations and potentials to obtain the net reaction and
net potential. Predict whether or not this reaction is spontaneous.
Compare this prediction with your experimental observations for this
system.
C. The Zn-Pb System

5. Write half-equations and potentials for the reduction and oxidation
that occur when Zn is added to PbN03 solution.
6. Add the half-equations and potentials to obtain the net reaction and
net potential. Predict whether or not this reaction is spontaneous.
Compare this prediction with your experimental observations for this
system.
D. Relative Scales of Reduction and Oxidation Potentials

7. Based on your experimental results, rank Zn2 +, Cu2 +, and Pb 2 + ions in
order of ease of reduction, easiest to hardest. Explain whether or not
this ranking is consistent with the corresponding reduction potentials
in Table 1.
8. Based on your experimental results, rank Zn, Cu, and Pb in order of
ease of oxidation, easiest to hardest. Explain whether or not this ranking
is consistent with the corresponding oxidation potentials in Table 1.
11. Electrochemical Cells A. The Zn-Cu Electrochemical Cell

9. Write the half-equation for the half-reaction initiated in the beaker
labeled "Cu." In order to determine whether Cu(s) is oxidized or
Cu 2 +(aq) is reduced in this half-equation, compare the two possible
half-equations to those of Zn, in order to see which is preferentially
oxidized and which is preferentially reduced, according to the half-cell
potentials listed in Table 1.
10. Determine the half-equation for the half-reaction initiated in the beaker
labeled "Zn."
11. Write the net cell reaction, and calculate the expected cell potential
from the half-cell potentials listed in Table 1.
12. Compare the calculated cell potential to the measured voltage of the
electrochemical cell.

13. Write the half-equation for the half-reaction initiated in the beaker
labeled "Cu." Using Table 1, determine the half-cell potential for this
half-equation.
14. Write the half-equation and the potential for the half-reaction initiated
in the beaker labeled "Fe."
15. Determine the net cell reaction, and calculate the expected cell
potential.
16. Compare the calculated cell potential to the measured voltage of the
electrochemical cell.
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name section date
1. A strip of tin (Sn) is placed in an AgN03 solution.
(I) Predict whether or not a spontaneous oxidation-reduction reaction should occur in this system.
Explain your reasoning.
(2) Write a chemical equation to describe the net reaction, if it is spontaneous.
(3) Indicate the experimental observations you would expect for this procedure.
2. The half-cell reactions that occur in a typical flashlight battery are:
Zn(s) -t Zn2+(aq) +2 e-
2Mn02(s) + Zn2+(aq) + 2 e- -t ZnMn204(s)
Write a chemical equation describing the net cell reaction.
3. An electrochemical cell is constructed in which one half-cell contains AgN0 3 solution in contact with
an Ag strip, and the other half-cell contains magnesium nitrate solution, Mg(N03 h, in contact with a
Mg strip. The two solutions are connected by a salt bridge, and the two metals are connected by a
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(I) Which ion, Mg2+ or Ag+, is more easily reduced in aqueous solution?
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(2) Write the half-equation for the reaction that occurs in the silver half-cell.
(3) Write the equation for the net cell reaction.
(4) Calculate the expected voltage for this cell.

name section date
Data Sheet 1
I. Oxidation-Reduction Reactions
A. The Zn-Cu System

experimental observations:
B. The Pb-Cu System

C. The Zn-Pb System

II. Electrochemical Cells
A. The Zn-Cu Electrochemical Cell

cell voltage:

cell voltage:
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name section date
Data Sheet 2
I. Oxidation-Reduction Reactions
A. The Zn-Cu System

oxidation half-equation __________________
reduction half-equation __________________
net equation ________________________
prediction of spontaneity:
comparison of predicted spontaneity with experimental observations:
B. The Pb-Cu System

oxidation half-equation ___________________
reduction half-equation ___________________
net equation ________________________
C. The Zn-Pb System

oxidation half-equation __________________ E
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oxid = -----
reduction half-equation __________________
net equation ________________________

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D. Relative Scales of Reduction and Oxidation Potentials

ranking of ions by ease of reduction, easiest to hardest:
comparison of ranking with ranking based on reduction potentials in Table 1:
ranking of ions by ease of oxidation, easiest to hardest:
comparison of ranking with ranking based on oxidation potentials in Table 1:
II. Electrochemical Cells
A. The Zn-Cu Electrochemical Cell

Cu half-cell equation _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ Eo= ----------
Zn half-cell equation _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ Eo= ---------
net cell equation ____________________ E

0
net = --------
comparison of observed and calculated cell voltages:

Cu half-cell reaction _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ Eo= ---------
Fe half-cell reaction ___________________ Eo= ---------
net cell reaction ____________________ Eonet = - - - - - - - - -
comparison of observed and calculated cell voltages:

name section date
(Use Table 1 as a source of half-equations and reduction potentials for this assignment.)
1. Rank the following metals by ease of oxidation, from hardest to easiest: Cu; aluminum, Al; Fe; and
chromium, Cr.
2. An Al strip is placed in CuS04 solution.

(1) Would you expect a spontaneous reaction to occur, based on the net potential?
(2) If your answer to (1) is "yes," what would you observe?
(3) Write a chemical equation that describes your predicted observations.
3. Describe what you would observe if you placed an Ag strip in an aluminum nitrate solution,
Al(N03h·
------·------ -
4. Describe an electrochemical cell that would have the following net equation, by answering the
following questions.
Fe(s) + Ni2+(aq)---+ Ni(s) + Fe2+(aq)
(1) Write the reduction and oxidation half-equations for the cell.
(2) Sketch the electrochemical cell. Identify the components of the cell as in Figure 1.
(3) Calculate the expected net voltage for this cell.

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SCC202

Compilation by Dr.lvan Rivera-Torres

SCC202 Fundamentals of Chemistry II © 2009 Cengage Learning

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Determination Of Ka For Weak Acids- Seager/Slabaugh

ELEC0450: Studying Electrochemical Half-Cells and Half-Reactions

I. Chemical Safety and Laboratory Rules - Bishop/Bishop/Whitten ............................................ .

Rule 1: Exercise caution and good judgment!

--------- ------------------ ---------------------------

Rule 5: Always call for help loudly when an accident occurs.

Rule 7: Open flames must not be used near flammable substances.

Rule 9: Good Hygiene is essential.

COMMONLY ACCEPTED SAFETY PRECAUTIONS INCLUDE

Name._ _ _ _ _ _ _ _ _ _ _ __ Lab Instructor_ _ _ _ _ _ _ __

ID Number_ _ _ _ _ _ _ _ _ __ Lab Period____________

Laboratory Safety Quiz

I HAVE READ THE CHEMICAL SAFETY AND LABORATORY RULES. I

4. What should you do in the following circumstances?

d) A small beaker of a flammable liquid has caught fire?

e) A bottle of flammable reagent is spilled?

The Structure of Crystals-

IN THIS EXPERIMENT YOUR INSTRUCTOR MAY

The Simple Cubic Crystal

Body-Centered Cubic Crystals

Face-Centered Cubic Crystals

Crystal Structures of Some Common

If r)r_ > 0.732 cations go into cubic holes

The NaCI Crystal

The CsCI Crystal

The Zinc Sulfide Crystal

The Calcium Fluoride Crystal

Data and Calculations: The Structure of Crystals

Some Cubic Unit Cells

Volume of unit cell in terms of d 0

Number of atoms per unit cell

Radius r of atom in terms of d0

Volume of atom/volume of cell

(continued on following page)

Body-Centered Cubic Crystal

In BCC atoms touch along the cube diagonal

Length of cube diagonal if d 0 = 0.429 nm _ _ _ _ _ nm

4x rNa = length of cube diagonal

b. Density of sodium metal

Length of unit cell, d0 , in em (I em = 107 nm) _ _ _ _ _ em

Volume of unit cell, V _ _ _ _ _ cm 3

Number of atoms per unit cell

Number of unit cells per mole Na

Mass of a unit cell, m _____ g

Density of sodium metal, m!V (Obs. 0.97 g/cm 3 ) _ _ _ _ _ g/cm 3

Face-Centered Cubic Crystal

Number of atoms on comers ____ Shared by ____ cells ____ x _ _ __

Number of atoms on faces ____ Shared by ____ cells ____ x ____

Total atoms per cell _ _ _ __

Length of face diagonal in Cu, where d 0 = 0.361 nm _ _ _ _ _ nm

Number of Cu atom radii on face diagonal _ _ rcu = - - - - - nm

(continued on following page)

Length of cell edge, d 0 , in em, in Cu metal em

Volume of a unit cell in Cu metal cm 3

Volume of a mole of Cu metal (V =mass/density) cm3

ID Number_ _ _ _ _ _ _ _ _ Lab Period__________

Number of atoms on comers Shared by cells x _ _ __

Number of atoms on faces Shared by cells x

Number of Na+ ions on edges of cell Shared by cells

CuBr r)r Predicted structure Obs. ZnS