GENERAL CHEMISTRY

LABORATORY II
MANUAL

Spring Semester

1
 INDEX

Experiment 1: Determination of Water Hardness 3

Experiment 2: Synthesis of Soap 15

Experiment 3: Molecular Models and Covalent Bonding 19

Experiment 4: Steam Distillation 29

Experiment 5: Molecular Weight Determination From Freezing Point Depression 36

Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions 46

Experiment 7: Chemical Equilibrium 54

Experiment 8: Weak acids, Weak bases and Their Salts 61

Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation 74

Scores of the General Chemistry Laboratory II Experiments 83

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 Experiment 1: Determination of Water Hardness

1. Determination of Water Hardness

INTRODUCTION
Water quality is evaluated by using a number of parameters, including total ionic content, pH,
total dissolved solids, organic compounds, and water hardness. Water hardness is a measure of
the concentration of all the polyvalent cations dissolved in the water. Water that contains certain
dissolved minerals in relatively large amounts is said to be hard. Although hard water is not
necessarily unhealthy, there are two common problems associated with it. First, hard water
contains certain cations, such as Ca2+, which form water insoluble compounds with soaps. The
formation of these precipitates reduces the cleaning ability of the soap and, at the same time,
results in the formation of unsightly “scum” on clothing and in tubs and sinks. If Fe3+ is present, a
red-brown deposit might form on the surfaces of sinks and tubs. Second, hard water encourages
the buildup of boiler scale in water heaters, pipes, etc., which can cause considerable damage to
expensive equipment and require time and expense for periodic cleaning.
The major ions responsible for natural water hardness are Ca2+, Mg2+, Fe3+ and HCO3 - . The
presence of bicarbonate ion is classified as temporary hardness because the water may be
“softened” by boiling. Heating removes HCO3- and CO2(g), but also produces boiler scale when
CO32- ion is formed and precipitates with Ca2+, Mg2+, and Fe3+ ions. The equilibrium in an
aqueous solution of carbonate ion is summarized in the following chemical equations, and the net
equation represents the heating reaction that can serve to reduce temporary hardness.

HCO3-(aq) + H2O H3O+ + CO32-(aq)

CO3-(aq) + H3O+ H2O + H2CO3(aq)
HCO3-(aq) H2O +CO2(g)
Net equation: 2HCO3-(aq) H2O + CO32-(aq) + CO2(g) [1]
Water that contains ions that cannot be removed by heating, such as Ca2+, Mg2+, Fe3+, and SO42-
, is said to be permanently hard.
Hardness is defined as calcium and magnesium ion content. Since most analyses do not
distinguish between Ca2+ and Mg2+, and since most hardness is caused by carbonate mineral
deposits, hardness is usually reported as parts per million (ppm) of calcium carbonate (by
weight).

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 Experiment 1: Determination of Water Hardness

Figure 1. Water Hardness Scale

The purpose of this experiment is to determine the concentration of permanent hardness in
water by titration with a standard solution of ethylenediaminetetraacetic acid, EDTA. This
reagent is a weak acid that can lose four H on complete neutralization; the structural formula of
the tetraprotic EDTA molecule follows:

Figure 2. Structural Formula of EDTA

This acid acts as a polydentate ligand for most metal cations in aqueous solutions. The four acid
oxygen sites and the two nitrogen atoms have unshared electron pairs, which can form bonds to a
metal ion forming a complex ion or coordination compound. Most of the complexes formed are
quite stable and, therefore, the use of EDTA as a titrant in chemical analysis has found
widespread application.
Often the term H4Y is used to indicate the above substance. Because H4Y is a polyprotic acid,
several ionization equilibriums are involved. The most important are:
H4Y H+ + H3Y- Ka1 = 1.00 x 10-2 [2]
H3Y- H+ + H2Y2- Ka2 = 2.16 x 10-3 [3]
H2Y2- H+ + HY3- Ka3 = 6.92 x 10-7 [4]
HY3- H+ + Y4- Ka4 = 5.50 x 10-11 [5]

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 Experiment 1: Determination of Water Hardness

Because the parent acid H4Y is only sparingly soluble in water, the relatively soluble and
readily available disodium salt (Na2H2Y.2H2O) serves as the starting material for the preparation
of standard EDTA solutions used in titrimetry. Since the predominant species in a solution of this
salt is the H2Y2- ion, the pH of the resulting solution of this salt is approximately ½(pK2+pK3), or
4.4. The distribution of EDTA among its undissociated and dissociated forms varies considerably
with pH. At any particular pH the distribution of EDTA species may be calculated from the four
acid dissociation constants. These calculations can be plotted graphically as a distribution
diagram. For example, by using the EDTA distribution diagram in Figure 1, which plots the
fractional amount of each species as a function of pH, it can be seen in the 9-12 pH range only
Y4- and HY3- are present in significant concentrations, and in the 6-9 pH range, H2Y2- and HY3-
predominate.

Figure 3. Distribution of EDTA Species as a Function of pH

The Y4- ion forms very stable, one-to-one complexes with practically every metal ion,
depending on pH and other conditions. Above pH=12, the Y4- species predominates, and it is
available to coordinate metal cations.

Mn+ + Y4- MYn-4 [6]

An example of a six-coordinated species of an octahedral central metal ion and an EDTA

molecule is the cobalt (III)-EDTA complex, CoY- , whose structure is shown in Figure 4.

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 Experiment 1: Determination of Water Hardness

Most metal ion-EDTA titrations are performed in neutral or alkaline solutions because, although
metal-EDTA complexes formed in titrations are quite stable, they can undergo dissociation in the
presence of acid, which causes the equilibrium to shift away from the formation of the complex.
This equilibrium (eqn 7) will lie to the left if the pH is maintained at a neutral or alkaline level.

Figure 4. Cobalt (III)-EDTA Complex Ion

MYn-4 + 2H+ Mn+ + H2Y2- [7]
As can be seen from Figure 3, the predominant species in neutral and slightly alkaline solutions
are H2Y2- and HY3- , and the net titration reactions can be written as in the following two
equations:
Mn+ + H2Y2- MYn-4 + 2H+ [8]
Mn+ + HY3- MYn-4 + H+ [9]
The precise titration reaction, of course, depends upon the exact pH of the solution. The
liberation of H+ ions during titration would cause the pH to decrease and adversely affect the
formation of the metal-EDTA complex. Therefore, in practice, a large excess of an inert buffer
system, such as NH3/NH4Cl, is used to keep pH near the desired value for the particular
application. In addition to maintaining the desired pH, the NH3 system forms stable complexes
with some metal ions, such as Cd2+, Cu2+, Ni2+, and Zn2+, and thus serves to prevent the undesired
precipitation of these ions as metal hydroxides.
A very large number of indicators has been studied and employed for complexometric
titrations. The term metallochromic indicator is frequently used to describe these substances
because they form stable, highly colored complexes with most of the metal ions of interest. They
are acid-base indicators as well, and the combination of their metal ion and acid-base indicating
properties is used to obtain the indicator behavior desired in complexometric titrations. For
example, Eriochrome Black T (EBT) forms a wine-red complex with most metal ions, such as
Ca2+.

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 Experiment 1: Determination of Water Hardness

Ca2+ + EBT Ca(EBT)2+ [10]

If EDTA is added to this solution, the Ca2+ is gradually removed from the Ca-EBT complex
and forms more stable CaY2- complex ion.
Ca(EBT)2+ + Y4- CaY2- + EBT [11]
wine-red blue
Thus, the uncomplexed free form of the EBT increases in concentration as it is displaced by the
EDTA titrant. When almost no Ca-EBT complex remains, the pure blue color of the free EBT
predominates and denotes the end point (The end point color change is sharpened by the presence
of Mg2+ ion).

SAFETY PRECAUTIONS
None of the reagents in this procedure is particularly dangerous. However, the normal safety
precautions should be followed. Wear eye protection and never pipette by mouth. Always use a
suction device when drawing solution into a pipette.

PROCEDURE
Required Laboratory Materials
Chemicals Glassware
0.01 M Ca2+ Solution Erlenmayer Flask (100 mL, 250 mL)
0.01 M EDTA Solution Graduated Cylinder (10 mL, 50 mL)
NH3-NH4Cl Buffer Sol. Pipette
Eriochrome Black T Suction Device
Top Water Stand
Burette-Burette Clamp
Spatula
Funnel

A. Standardization of 0.01 M EDTA Titrant

1. Rinse a 10.00-mL pipette with small portions of standard 0.0100 M Ca2+ solution, and then
pipette a 10.00-mL aliquot of the solution into a clean 250-mL Erlenmeyer flask.
2. Add 2.00 mL of NH3-NH4Cl buffer solution from a graduated cylinder and dilute the mixture
to approximately 50 mL with distilled water.
3. Add small portion of Eriochrome Black T indicator.

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 Experiment 1: Determination of Water Hardness

4. Rinse a 50-mL burette with small (5-10 mL) portions of the EDTA solution. Then fill it with
EDTA solution, and record the initial position of the meniscus. Read the volume to the nearest
0.01 mL.
5. Titrate the Ca2+ solution with EDTA until the wine-red color of the Ca indicator complex
changes from purple-red to the pure blue color of the free form of the indicator. If you are not
certain of the color change, go to the window and use natural sunlight to see it or compare it to
the color of titrated blank sample (see Note). Add titrant in drops and fractions of a drop until the
color change from wine-red to pure blue is permanent. Record the final position of the meniscus
after waiting 30 sec for the burette to drain.
Note: Sometimes it is difficult to tell if the exact end point color has been reached. The actual
color at the end point can be seen if you make a blank sample containing 90.00 mL of distilled
water, 10.00 mL of buffer, and indicator. Then add several drops of titrant, and if the water is not
contaminated with minerals, t he color formed will be the blue of the free, uncomplexed indicator.
Titrate at least three samples of the standard Ca2+ solution with EDTA. Calculate the
concentrations of EDTA as follows. In all titrations using EDTA, only one EDTA molecule is
used for each metal ion. Thus,

B. Determination of Permanent Hardness (as ppm CaCO3)

1. Thoroughly rinse the pipette with the water sample and then pipette exactly 10.00 mL of the
water sample into a clean 250-mL Erlenmeyer flask.
2. Add 2.00 mL of buffer solution (which brings the pH to about 10) and enough indicator (EBT)
to get a distinct color.
3. Refill the 50-mL burette with more of the EDTA titrant used in the standardization titrations
and record the initial volume.
4. Titrate the sample solution with EDTA solution until the color changes from purple-red to the
first color of pure blue. Be sure to swirl the solution after each addition of titrant. Also, near the
end point, rinse down the walls of the flask with distilled water and add the EDTA dropwise.
5. Repeat the titration procedure two times.
Disposal: All solutions are non-hazardous and may be flushed down the sink with running water.
Hardness Calculation
It is not convenient to determine the concentration of each cation separately, so assume that all
the hardness is due to the presence of only Ca2+ ions in the form of calcium carbonate, CaCO3.
The concentration can be expressed in terms of molarity of CaCO3, but it is expressed more
commonly as mg CaCO3 per liter of water.

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 Experiment 1: Determination of Water Hardness

(parts per million CaCO3 = ppm CaCO3 = mg CaCO3/L)

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 Experiment 1: Determination of Water Hardness

Name____________________________Department______________________Group____

DATA
A. Standardization of EDTA solution

Molarity of Ca2+ solution = _________ M

Trial 1 Trial 2 Trial 3

Initial burette reading (±0.1mL)

Final burette reading (±0.1mL)

mL of EDTA used

B. Hardness titration

Trial 1 Trial 2 Trial 3

mL of water sample

Initial burette reading (±0.1mL) Final

burette reading (±0.1mL)

mL of EDTA used

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 Experiment 1: Determination of Water Hardness

Name____________________________Department______________________Group____
CALCULATIONS
A. Standardization of EDTA Solution

CALCULATIONS RESULT

Trial 1
Molarity of
EDTA solution

Trial 2
Molarity of
EDTA solution

Trial 3
Molarity of
EDTA solution

Average
Molarity of
EDTA

Relative
Average
Deviation
(R.A.D.)

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 Experiment 1: Determination of Water Hardness

Name____________________________Department______________________Group____
B. Hardness Titration

CALCULATIONS RESULT

Trial 1 ppm
CaCO3 in
solution
(mg/L)

Trial 2 ppm
CaCO3 in
solution
(mg/L)

Trial 3 ppm
CaCO3 in
solution
(mg/L)

Average ppm
CaCO3

Relative
Average
Deviation
(R.A.D.)

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 Experiment 1: Determination of Water Hardness

Name____________________________Department______________________Group____
QUESTIONS

1. If the pH became too low during the titration of unknown by EDTA, how would the titration
reaction’s equilibrium is affected?

2. Water sample A and water sample B are identical except that B contains less iron (III) ion.
How would the value of ppm CaCO3 of A compare to that of B (larger, smaller, the same)?
Explain.

3. In step 4 of the procedure to standardize the EDTA solution a student forgets to rinse the
burette with a small portion of EDTA solution (The burette contains water droplets from
washing). If this incorrect concentration of EDTA is used to calculate the ppm CaCO3 of a
hard water sample, will the resulting value be too high, too low, or correct? Explain briefly.

4. Why does the Eriochrome Black T indicator change from red to blue when EDTA is added to a
solution of cations? Describe what is responsible for the color change.

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 Experiment 1: Determination of Water Hardness

Name____________________________Department______________________Group____
PRELAB QUESTIONS
1. Boiler scale may be composed of what three compounds?

2. At pH=8, which acid form of EDTA is predominant in the solution?

3. When temporarily hard water is boiled,

a) What gas is evolved?

b) What solid product is formed?

4. 25.00 mL of 0.01 M Ca2+ is titrated to an Eriochrome Black T (EBT) end point with EDTA
solution. If the pure blue end point color occurs at 27.50 mL, what is the molarity of the
EDTA?

5. A 100.0 mL water sample requires 22.25 mL of 0.01 M EDTA to reach an Eriochrome Black
T end point. Calculate the hardness of this sample in units of ppm CaCO3.

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 Experiment 2: Synthesis of Soap

2. Synthesis of Soap (Saponification)

INTRODUCTION

Soap is made by mixing lye and water with fats or oil. Through a complex chemical reaction lye
which is also called sodium hydroxide (a base) converts Fats or Oil (an acid) to soap. This
process is called saponification. When oil or fats (acid) come into contact with the lye or sodium
hydroxide (base) the saponification process begins with the lye turning the oil/fat into a thicker
and more uniform solution. The point at which the solution begins to thicken is called a trace.
Any oils/fats or other ingredients added at this point will not be substantially converted and will
basically remain in the soap in their original form. At the trace stage (in this stage, any essential
oil and dye can be added 1-2 drop) the soap can be poured into molds where it will continue to
harden.

The process that the home soap maker will use is referred to as “cold process soap making”.
Even though it is called a cold process, heat is required for the chain reaction to take place. This
heat is provided by the chain reaction of the water and the lye and their incorporation into the oil
or fat. (You will notice that when the lye is poured into the water it heats up immediately)
Stirring the oil/fat/lye mixture helps this process to continue and to be uniform.

Soap is prepared by carrying out a hydrolysis reaction in which an ester is treated with water
using a base catalyst to give a carboxylic acid and alcohol. When a base is used as the catalyst
this process is often called saponification-literally soap making. Fats and oils are esters of
glycerol, (CH2OHCHOHCH2OH), a tri-alcohol, and three long chain fatty acid. There are
therefore three ester groups per molecule, and thus fats or oils are often called triglyceride. The
following reaction is called as saponification

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 Experiment 2: Synthesis of Soap

The soap molecule has two different ends, one that

is hydrophilic (polar head) that binds with water
and the other that is hydrophobic (non-polar
hydrocarbon tail) that binds with grease and oil.
When greasy dirt or oil is mixed with soapy water,
the soap molecules arrange themselves into tiny
clusters called micelles. Since the micelle is soluble
in water, it can easily be washed away.

Soaps do not work well in hard water containing calcium and magnesium ions, because the
calcium and magnesium salts of soap are insoluble; they tend to bind to the calcium and
magnesium ions, eventually precipitating.

SAFETY PRECAUTIONS

In this experiment, the normal safety precautions should be followed. Wear eye protection and
never pipette by mouth. Always use a suction device when drawing solution into a pipette.
NaOH: Ulceration of the nasal passages and irritation of the skin, eyes can occur when into
direct contact with sodium hydroxide.

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 Experiment 2: Synthesis of Soap

Required Laboratory Materials

Chemicals Glassware
20 grams of olive oil Erlenmeyer Flask (250 mL)
20 mL Ethyl alcohol Graduated Cylinder (50 mL)
5M NaOH solution Heater
Saturated NaCl solution Buchner Flask and Funnel
Filter Paper
Vacuum Pump.

PROCEDURE

1. Place 20 grams of olive oil in a 200 mL Erlenmeyer flask.

2. Add 20 mL of ethyl alcohol.
3. SLOWLY AND CAREFULLY (this staff is dangerous) add 25 mL of 5M sodium
hydroxide.
4. Gently heat this mixture under low heat, (maintain a constantly boiling mixture), stirring with a
glass stirring rod until the base has completely reacted with the oil (about 20 to 30 minutes).
5. After all of the base has reacted, cool the mixture and add 100 mL of saturated sodium
chloride solution.
6. Let this new mixture cool completely. The solid cake is the soap. (What is left, if you do it out
chemically, is glycerol)
7. Filter the cooled mixture.

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 Experiment 2: Synthesis of Soap

Name____________________________Department______________________Group____

PRELAB QUESTIONS

1. Draw out the structure of a general soap molecule.

2. Describe how soap cleans.

3. Describe the words below:

a) Saponification:

b) Esterification

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 Experiment 3: Molecular Models and Covalent Bonding

3. Molecular Models and Covalent Bonding

INTRODUCTION
Much of the chemical behavior of matter can be related to the detailed structures and shapes
of molecules. Structural theory is useful when one wishes to relate experimental evidence to
the more theoretical concepts of chemical bonding. The arrangement of atoms and ions in
molecules and crystals is related to the distribution of bonding electrons within the structure.
Molecules often are represented by pictures or molecular models in which balls or some other
geometrical centers represent atoms and sticks, or tubes represent the bonds between the
atoms.
The purpose of this experiment is to use molecular models to help understand fuller the
theoretical concepts of covalent bonding and molecular structure. Lewis structure of
molecules, covalent bonding, hybridization, polarity and Valence Shell Electron Repulsion
Theory (VSPER) will be discussed using molecular models.
Molecular models are designed to reproduce molecular structures in three-dimensional space.
If models are correctly assembled, many subtle features concerning shapes of molecules (such
as, dipole moment, polarity, and bond angle) become clearer to us. One aspect of molecular
structure is called isomerism. The most obvious type of structural isomerism is that in which
there exists more than one way to assemble the atoms of a compound correctly. Sometimes
only one of the possible structures is the stable form of a compound, but many times two or
more structures are stable enough to exist in more than relatively small amounts. An example
of a structural isomer is that of ethyl alcohol and dimethyl ether, shown in Figure 1. Note that
both have the same molecular formula, C2H6O.

Figure 1. Two structural isomers of C2H6O.

Determining Lewis Structure of Molecules
Lewis structures are a simple way to find out bonding electrons, non-bonding electrons, and
formal charges in molecules. Lewis structure of a molecule is important factor in determining
its structure, stoichiometry, and properties. To make a Lewis structure follow these steps:
1. Find total number of valence shell electrons of molecule. Add 1 additional electron per
negative charge if the structure is an anion. Subtract 1 electron per positive charge if
the structure is a cation.

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 Experiment 3: Molecular Models and Covalent Bonding

2. Use the formula of the molecule or ion to help you determine the arrangement of the
atoms in molecule.
3. Predict the central and terminal atoms. In general, central atom has lower
electronegativity and terminal atom has higher. But hydrogen is always terminal atom
and carbon is always central atom.
4. Beginning with the terminal atoms, add enough electrons to each atom to give each
atom an octet (two for hydrogen). If any electrons are left over, place them on the
central atom.
5. Use valence electrons to make 2-electron bonds to connect the atoms in the structure.
If the central atom has fewer electrons than an octet, use lone pairs from terminal
atoms to form multiple (double or triple) bonds to the central atom to achieve an octet.
You can make single bonds (2 electrons), 2 bonds or a double bond (4 electrons), 3
bonds or a triple bond (6 electrons) in some cases. Be sure that you don't exceed the
maximum.
6. Use the remaining electrons to make lone pairs of electrons on atoms. When there is
an odd number of electrons, there will be a single electron on some atom (radical).
7. There may be more than one possible Lewis structure. If so, the one with the fewest
formal charges is usually the best. A correct Lewis structure always includes the
formal charges.

Formal Charge
Formal charge can show us the electron rich and electron poor regions of a compound. It is an
important part of the Lewis structure. For each atom in the structure:
1. Sum 1/2 of all electrons in bonds to that atom and add any other non-bonding electrons.
2. Formula of calculating formal charge is:
Formal charge on an atom [F.C] = [total number of electrons in the free atom] – [total number
of non-bonding (lone pair) electrons] -½[total number of bonding(shared pair) electrons]
3. Compare that number to the number of formal charges of atoms and determine the best
Lewis structure.

Figure 2. Lewis Structure of H2O molecule.

Look at the example below for formal charges. There are three possible Lewis structure of N3
molecule. The second structure has resonance, so it is not shown here.

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 Experiment 3: Molecular Models and Covalent Bonding

Figure 3. Formal charges on N3 molecule.

Exceptions to the Octet Rule

Some atoms do not possess octet rule because of the number of valence electrons and formal
charges. Here some examples of molecules with odd electron atoms, incomplete octet and
expanded octet.

Figure 4. Exceptions to octet rule. Odd electron species (left), incomplete octet (middle) and
expanded octet (right).
Resonance
Some compounds cannot be represented by a single definite structure rather more than one
structure. Thus, the various structure written for a compound to explain the known properties
of the compound are called as resonating or contributing or canonical structure. The
phenomenon is resonance.

Figure 5. Resonance structures of Ozone molecule (O3).

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 Experiment 3: Molecular Models and Covalent Bonding

Valence Shell Repulsion theory (VSPER)

Valence shell electron-pair repulsion theory (VSEPR theory) enables us to predict the
molecular structure, including approximate bond angles around a central atom, of a molecule
from an examination of the number of bonds and lone electron pairs in its Lewis structure.
The VSEPR model assumes that electron pairs in the valence shell of a central atom will
adopt an arrangement that minimizes repulsions between these electron pairs by maximizing
the distance between them. The electrons in the valence shell of a central atom form either
bonding pairs of electrons, located primarily between bonded atoms, or lone pairs. The
electrostatic repulsion of these electrons is reduced when the various regions of high electron
density assume positions as far from each other as possible.
General Rules for Predicting Molecular Geometries by Valence Shell Electron Pair
Repulsion Theory [VSEPR]

1. Count the valence electrons in the entire molecule or ion.

2. Adjust this count for charge, if any, by adding (for anions) or subtracting (for cations)
electrons.
3. Arrange atoms in the most symmetrical fashion.
4. Bond each terminal atom to the central atom.
5. Complete the octet on each terminal atom (except H).
6. Any unused electrons go on the central atom as unshared or lone pairs.
7. If the central atom is in periods 2 and 3, complete its octet, using multiple bonds if
necessary.
8. Determine the molecular geometry based on mutual repulsion of electron pairs. Remember
that nonbonding pairs are more repulsive than bonding pairs.
Polarity
Polarity is the phenomenon about the electronegativies of the atoms in molecule. Polar
covalent bonds connect two atoms with different electronegativities. Since the electrons are
pulled toward the more electronegative atom, one atom has a partial positive charge (δ+) and
the other atom has a partial negative charge (δ–).This separation of charge gives rise to a bond
dipole moment. Dipole moment vectors are shown as arrows pointing along the bond from the
less electronegative atom toward the more electronegative atom. If net dipole moment is zero,
the molecule is nonpolar. If dipole moment is greater than zero, than the molecule is said to be
polar. The dipole moment measures the extent of net charge separation in the molecule as a
whole.

Figure 6. Dipole moment on different molecules.

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 Experiment 3: Molecular Models and Covalent Bonding

Hybridization

Hybridization is used to explain the nature of bonds, and shape of the polyatomic molecules.
According to the hybridization, certain atomic orbitals of nearly the same energy undergo
mixing to produce equal number of new orbitals. The new orbitals are called as hybrid
orbitals. The process of mixing of the atomic orbitals to form new hybrid orbitals is called
hybridization. All hybrid orbitals of a particular kind have equal energy, identical shapes and
are symmetrically oriented in space.

Figure 7. sp3 hybridization.

Hybridization rule for central atom in molecules with different electron grup geometries:

Electron group geometry Hybridization

Linear sp
Trigponal Planar sp2
Tetrahedral sp3
Trigonal bipyramidal sp3d
Octahedral sp3d2

PROCEDURE
Perform the following operations, when applicable, on each compound in the list provided by
your instructor.
1. Draw the correct Lewis structure and any resonance forms.
2. Determine if any structural isomers exist.
3. Assemble a molecular model for the compound. Construct a model for each isomer from
step 2 (Resonance structures require only one model).
4. Sketch only one model, using a solid line for a bond in the plane of the paper, a wedge
bond for a bond coming out of or in front of the plane of paper, and a dashed line for a bond
in back of the plane of paper.
5. Indicate the following for each Lewis structure
a. Hybridization on central atom(s) (there may be more than one).
b. Overall molecular geometry and electron pair geometry.
c. Whether the molecule is polar or nonpolar. (Polar in this sense means that the species has a
net dipole. Nonpolar means that there are no dipoles present, or that, if present, they
cancel, resulting in no net dipole moment.)

Example:

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 Experiment 3: Molecular Models and Covalent Bonding

Here is the Lewis structure, sketch of the molecule and molecular shape of CH4 molecule
respectively.

Figure 8. Lewis structure (left), sketch (middle) and molecular shape of CH4 molecule.
Electron group geometry and molecular geometry of methane is both tetrahedral because
there is no lone pair in central atom. Hybridization of carbon atom is sp3 and molecule is not
polar.

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 Experiment 3: Molecular Models and Covalent Bonding

Name Department Group

25
 Experiment 3: Molecular Models and Covalent Bonding

Name Department Group

26
 Experiment 3: Molecular Models and Covalent Bonding

Name Department Group

REPORT QUESTIONS
Consider the molecule

1. Indicate the hybridization employed by each central atom.

a. CA : ________________ b. CB : _____________
c. OA : ________________ d. OB : _____________

2. Indicate the electron pair geometry about each central atom.

a. CA : ________________ b. CB : _____________
c. OA : ________________ d. OB : _____________

3. Indicate the predicted bond angles around each central atom having more than one bond.

a. CA : __________ b. CB : ________ c. OB : __________

4. Describe all the σ and π bonds in this molecule in the form of a hybridization and bonding
scheme. For example, a hypothetical O-H bond = O (2 sp2) – H (1 s).
sigma bond(s) pi bond(s)

5. Which bond is the:

a. shortest? __________________
b. strongest? __________________

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 Experiment 3: Molecular Models and Covalent Bonding

Name Department Group

PRELAB QUESTIONS
1. What are isomers?

2. Sketch the Lewis structures for the isomers of C2H4Cl2 .

3. Under what circumstances in writing Lewis structures for a molecule may one conclude
that the molecule exhibits resonance?

4. A triple bond consists of __________sigma bond(s) and ____________pi bond(s).

5. Under what circumstances is the molecular geometry the same as the electron pair
geometry? Which of the molecules fits this description?

PCl3 or PCl5

28
 Experiment 4: Steam Distillation

4. Steam Distillation

Introduction

Distillation is a process in which the components of a substance or liquid mixture are

separated by heating it to a certain temperature and condensing the resulting vapors.The
process is mainly based upon the boiling point of liquid substances. Some substances (such as
crude oil) have components that vaporize at different temperatures and thus can be separated
by condensing their vapors in turn. Distillation is also used as a purification process in which
non-volatile components are separated from volatile ones and as separation of liquids in
industrial and lab. scales. Distillation is used for many commercial processes, such as
production of gasoline, distilled water, xylene, alcohol, paraffin, kerosene, and many other
liquids. This process can be performed in different ways (at atmospheric pressure, under
vacuum). The liquid formed at the end of distillation is named as distillate and the remaining
in the flask is named as residue. Generally, distillate has lower boiling point compared with
residue. The vapor pressure of a system, composed of immiscible liquid components, is equal
to the sum of vapor pressures of each component. The boiling point of this system is lower
than those of its components.

Many compounds, that have high boiling point and immiscible with water can be
distilled at relatively lower temperatures by passing through water vapor. During boiling, mole
fractions of components in the vapor phase are directly proportional with their vapor pressures.
In other words, the volatile component exists in the vapor phase in a greater amount. The mole
fractions of components can be calculated by separation of components after condensation of the
vapor phase and determining their amounts. If the molecular weight of a component is not
known, it can be estimated from mole fraction.

In this laboratory exercise we will employ steam distillation to isolate an essential oil
from lemon peel. This will involve distilling a mix of lemon peels and water to obtain the oil,

29
 Experiment 4: Steam Distillation

extracting the oil from the water, and then isolating the oil from the extraction solvent. Essential
oils are a mix of fragrant compounds common to a number of plants such as mint, lavender, pine,
etc. which are isolated via steam distillation. Because these oils were once considered to be the
essence of the plant, they were initially sought as possible pharmaceuticals and are a part of early
medicine's contribution to modern chemistry. Today they are used as flavorings, perfumes and
deodorants.

Limonene takes its name from the peel of the lemon. Limonene is a chiral molecule, and
biological sources produce one enantiomer: the principal industrial source, citrus fruit, contains
D-limonene ((+)-limonene), which is the (R)-enantiomer. D-Limonene is obtained commercially
from citrus fruits through two primary methods: centrifugal separation or steam distillation.

PROCEDURE

In this experiment, the molecular weight of limonene will be determined by steam

distillation of limonene-water mixture. Steam distillation is used when organic compound
codistills with water. It is a great way to isolate the organic compounds with high boiling points.

1. First, prepare the distillation set up given in Figure 1. Take three medium lemons and
grate the peels of lemons and measure the mass of the peel. Add the peels to the distilling pot, a
250 mL flat bottom flask (Flask 2), using a wide-mouth funnel and a stirring rod. Add enough
water so that the distilling pot is about 2/3 full. Add boiling chips to the round-bottom flask
(Flask 1) that is full with water prior to passing steam. Then connect the two flasks with a rubber

30
 Experiment 4: Steam Distillation

tube, heat Flask 1- 2. Turn on the condenser water and seal the distilling pot. Start passing steam
through.

2. As the mixture boils and distills, you will be losing water from the distillation mixture. It
is important to watch the water level because of the high concentration of sugar in lemons. If the
water level gets too low, the sugar will carmelize and burn. Keep the heat at a low, steady level.

3. Collect the condensed liquid a tared erlenmayer flask. In the process, all the hot vapors
produced are immediately channelled into a condenser which cools and condenses the vapors.
Therefore the distillate will not be pure. Since water and lemonene are immiscible. (Figure 1.)

Figure 1. Distillation set-up

4. Transfer your distillate to a 100 mL separatory funnel.

Add 10 mL dichloromethane (DCM) and extract the oil.
Drain the DCM layer of into a 100 mL erlenmayer flask
(Figure 2.).

5. Dry the DCM with a little anydrous magnesium sulfate. This is required because trace
amounts of water will dissolve in the DCM. The anhyrous magnesium sulfate will absorb the
water and produce solid magnesium sulfate decahydrate:

31
 Experiment 4: Steam Distillation

6. Allow the system to dry for 10-15 minutes. Decant the liquid into a small beaker (don’t
forget to weigh the empty beaker!) . Keep the beaker in a fume hood at least one day in order to
vaporize the DCM. One day later, weigh the beaker and limonene. Determine the molecular
weight of limonene by using equation 4.1.

32
 Experiment 4: Steam Distillation

Name Department Group

33
 Experiment 4: Steam Distillation

Name Department Group

34
 Experiment 4: Steam Distillation

Name Department Group

REPORT QUESTIONS

1. What is the purpose of application of steam distillation method?

2. A and B liquids form ideal solutions. At the boiling point of solution consists of 0.2 mole B
and 0.6 mole A, pure B has a vapor pressure of 0.650 atm.

a. What is the vapor pressure of A at this temperature?

b. Find the mole ratio of A in vapor phase which is in equilibrium with the solution when
the boiling started.

35
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

5. Molecular Weight Determination from Freezing

Point Depression

INTRODUCTION

In this experiment the student will learn how to determine the freezing point of a
substance and the molecular weight of a solute by freezing point depression of solvent. The
molecular weight of sulfur will be determined by freezing point depression of its solution in
naphthalene.

Freezing of a liquid
The temperature at which the liquid and solid coexist is defined as freezing point of a
substance.

Figure 1. Cooling curve of a liquid

As you can follow from Figure 1, at temperature T1 liquid begins to convert to solid
and during this conversion, from T1 to T2, the temperature remains constant.
During freezing, the particles line up in a definite geometric pattern as they go from
liquid state to solid state, and the potential energy of the substance begins to drop. Therefore,
during freezing, formation of solid particles produces heat, and this energy compensates for
the heat removed by cooling. As a result, until freezing is complete the temperature stays
constant. This phenomenon will help us to determine the freezing point of naphthalene in this
experiment.

Freezing point depression

The addition of a solute will generally raise the boiling point and depress the freezing
point of a solvent. When a substance starts to freeze, the molecules slow down by decreasing
temperature, and the intermolecular forces become stronger. The molecules will then arrange
themselves in a pattern, and form a solid. For example, as water is cooled to the freezing

36
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

point, its molecules slow down and hydrogen bonds become stronger, eventually ice is
formed. If a compound is added to the water, the ions or molecules of this compound attract to
the water molecules and interfere with the formation of ice. In order to solidify, the solution
must be cooled to an even lower temperature.
Freezing point depression is a colligative property; that is, it does not depend on the
identity of the substance itself but depends on the ratio of solute to solvent particles. For dilute
solutions, the freezing point depression of a solvent is directly proportional to total molality of
the solution.
Molality, m, is defined as the number of moles of a solute in 1000 g of solvent.

number of moles of solute (n)

Molality =
1000g of solvent

Freezing point depression is defined by the following formula;

∆T = Kf . m

∆T : change in freezing point depression

Kf : molal freezing point depression constant
m : total molality in this solution

Example 1:

1.17 g of NaCl is dissolved in 2000 g of water. Calculate ∆T.

Kf for water is 1.86oC/m
FWNaCl = 58.5 g/mol

Solution:

(1.17 g) / (58.5 g/mol) = 0.02 moles

NaCl  Na+ + Cl-

0.02 mol 0.02 mol

Total molality = ((0.02+0.02)moles / 2000g H2O ) x 1000 = 0.02

∆T = (1.86)*(0.02) = 0.04 oC

In order to calculate molecular weight, we can express molality in a more convenient

form.

37
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

n1 W1/MW1
m= x 1000 m= x 1000
W2 W2
W1 = weight of solute
n1 = number of moles of solute
W2 = weight of solvent

(1000)(W1)
MW =
(m)(W2)

Therefore;

1000.Kf .(W1)
MW1 =
∆T.(W2)

Example 2:
When 1.15 g of naphthalene is dissolved in 100 g of benzene, the resulting solution has
a freezing point of 4.95oC. What is the molecular weight of naphthalene?
For pure benzene Tf =5.40oC, and Kf =5.12

Solution:
m= ∆T / Kf = (5.40-4.95) / 5.12 = 0.088

W1 = 1.15 g
W2 = 100 g

MW = (1000)*(1.15) / (0.088)*(100) = 128 g/ mol

In Example 1, two distinct solute species are present. When a salt such as NaCl is
dissolved in water, a 1 m solution of NaCl contains 1 mole of Na+ and 1 mole of Cl- ions in
1000 g of solvent. Therefore total molality is 2 m. But in Example 2, only one distinct solute
species which is naphthalene is present; therefore a solution of 1 mole of solute will give a
total molality of 1 m.
In this exercise the solvent is naphthalene. The freezing point is lowered 6.8oC for
every mole of solute dissolved in 1000 g of naphthalene. By dissolving a known weight of
sulfur in a known weight of naphthalene and measuring the freezing point depression we can
determine the molecular weight of sulfur.

38
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

PROCEDURE

Required Chemicals Required Lab. Materials

Naphthalene Thermometer
Sulfur Stirring wire
Acetone (test tube cleaning) Beaker
Large test tube
Bunsen burner
Two-holed cork
Spatula
Clamp
Ring stand

1. Assemble the apparatus as shown in Figure 2. When placing your thermometer in a two-
holed cork or a one-holed cork (with a slit in the side), wrap the cork and thermometer with
a towel and twist the thermometer slowly and gently into the hole. Otherwise you may
break the thermometer.

Figure 2

2. On a previously weighed piece of paper, weigh out about 5 g of naphthalene to the nearest
0.03 g. Pour the naphthalene on the paper before you put the paper on the balance. Record
your weighing as W2, weight of the solvent.
3. Make sure that the tube is not wet before you fill it. Pour the naphthalene into a large test
tube; make sure it gets on the bottom of the tube.
4. Insert the thermometer and wire stirrer, place the test tube in a beaker of water, and heat
gently until all the naphthalene has melted. Melting point should be observed around
85°C.
5. Remove the Bunsen burner and, while stirring, record the temperature for every 30
seconds from 85°C to 65°C. With these data you will plot the cooling curve for
naphthalene.
6. On a clean piece of previously weighed paper, weigh about 1.0 g of sulfur to the nearest

39
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

0.01 g. record your weighing as W1, weight of the solute.

7. Add the sulfur to naphthalene; make sure it gets as far down into the test tube as possible.
8. Heat the mixture in a water bath until the sulfur and naphthalene have formed a clear
solution.
9. Remove the Bunsen burner and record the temperature at 30 seconds intervals from 85°C
to 65°C.
10. To clean the test tube, reheat in water bath until the contents melt, remove the
thermometer, and pour the molten naphthalene into a baker labeled “Waste Naphthalene”
DO NOT POUR LIQUID NAPHTHALENE INTO THE SINK!
11. Plot cooling curves for pure naphthalene and sulfur-naphthalene solution.
12. Determine the freezing points from cooling curves.
13. Kf value for naphthalene is 6.8°C/m, calculate the molarity of the solution, m
14. Calculate the molecular weight of sulfur by using m, W1and W2.
15. The atomic weight of sulfur is 32 g/mol. By using the result from (14), write the
molecular formula of sulfur as Sn. What is n?
16. The actual molecular formula of sulfur is S8. Calculate the theoretical molecular weight of
sulfur and the percent error in your experiment.

40
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

Name____________________________Department______________________Group____

DATA

Weight of naphthalene (solvent) in gram = W2 = __________________

Cooling curve data for pure naphthalene;

t ToC t ToC t ToC

41
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

Name____________________________Department______________________Group____

Weight of sulfur (solute) in gram = W1 = ____________________

Cooling curve data for the solution of sulfur in naphthalene;

t ToC t ToC t ToC

42
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

Name____________________________Department______________________Group____

CALCULATIONS
From graph, determine the following temperatures:

Freezing point of pure naphthalene T1 = …..oC

Freezing point of solution T2 = …..oC
Freezing point of depression from graph ∆T = .....oC

 Molality of solution m =____________

 Molecular weight of sulfur FW =____________ g/mol

 Sn n =_____________

 Molecular formula of sulfur =____________

 Percent error in molecular weight =____________

43
 Experiment 5: Molecular Weight Determination from Freezing Point Depression

Name____________________________Department______________________Group____

PRELAB QUESTIONS

1. What is the unit of concentration in freezing point depression equation?

2. Give at least one example of everyday application of freezing point depression that makes
the life easier for us.

3. Which is the better solvent for molar mass determinations by freezing point depression,
benzene or cyclohexane? Explain.

4. Which is the better method for molar mass determination, freezing point depression or
boiling point elevation? Explain.

44
45
 Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions

6. Kinetic Study of the Reaction Between

Ferric and Iodide Ions

INTRODUCTION

The purpose of this experiment is to study kinetics of the reaction between ferric
(Fe ) and iodide (I-) ions i.e. to determine order of the reaction with respect to both ions.
3+

Reactions to be studied in this experiment is the oxidation of I- by Fe3+ ions or reduction of

Fe3+ ions by I- ions according to equation:

2 Fe3+ + 3 I- ↔ 2 Fe2+ + I 3-

Rate expression for this reaction = -1/2 d[Fe3+ ]/dt = k[Fe3+ ]a [I-]b

Parts A and B of this experiment are concerned with the evaluation of exponents a and
b respectively in the rate expression. The initial rate is determined by measuring the time in
seconds required for 4x10-5 mole of Fe3+ to be reduced to Fe2+. This is indicated by adding
starch solution and a small, constant amount of S2O32- to each mixture. The following
reactions then occur:

-
2 Fe3+ + 3 I- ↔ 2 Fe2+ + I 3 (SLOW)
-
I 2 S O 2- ↔ 3 I- + S O 2-
3+ 2 3 4 6 (FAST)

As soon as the S2O32- has been consumed, any additional I3- formed by the reaction
between ferric and iodide ions will react with the starch to form a characteristic blue color.
Note that when the blue color first appears, the decrease in the concentration of Fe3+ from its
initial value is just equal to the initial concentration of S2O32- in the mixture. Thus the initial
rate, -1/2d[Fe3+]/dt, is equal to 1/2[S2O32-]i/∆t, where [S2O32-]i is the initial concentration of
S2O32- and ∆t is the time in seconds between mixing and the appearance of the blue color. In
order to obtain reasonable reaction times, it is necessary to use initial rate intervals which
allow the Fe3+ concentration to decrease slightly (about 4 to 10 percent) from its initial
value. To compensate for this change, it is suggested that the average Fe3+ concentration
during this time interval be used in place of the initial concentration.

46
 Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions

CAUTIONS:
1. Be careful about performing in all the experiments at the same temperature since temperature
changes affect the rate constant; use water bath to keep temperature constant.
2. HNO3 does not participate in the reaction between ferric and iodide ions but it is used to prevent
hydrolysis of the Fe3+ in the water environment.
3. Use 50 mL burettes to dispense H2O, Fe(NO3)3, and HNO3 solutions; 10 mL pipettes to
dispense the KI and Na2S2O3 solutions, and a 10 mL graduated cylinder to dispense the starch
solution.

PROCEDURE

Required Chemicals Required Lab. Materials

0.04 M Fe(NO3)3 Beaker (250 & 100 mL)
0.15 M HNO3 Graduated Cylinder
0.04 M KI Water Bath
0.004 M Na2S2O3
Starch
Distilled Water

PART A. Reaction order with respect to Fe3+

1. Prepare the mixtures for experiment 1 by adding the solution specified in Table 1 to 250
and 100 mL beakers, respectively.
2. Swirl the contents of each beaker briefly and place the beakers in a constant temperature
water bath set at room temperature to reach temperature equilibrium. (Allow 10 to 15
minutes for this.)
3. Meanwhile, prepare the solution for experiment 2 in a second set of beakers, and place
these also in the water bath. By this time the solutions for experiment 1 should be at
bath temperature.
4. Measure and record the initial temperature of the solutions then simultaneously start the
timer and add (rapidly) the contents of the 100 mL beaker to the 250 mL beaker. You
may remove the solution temporarily from the water bath for this.
5. Swirl the solutions until mixed, and then return the 250 mL beaker to the bath.
6. Stop the timer at the first appearance of the blue color. Again measure the temperature, and
calculate the average temperature of the solution during the reaction. Record the time
interval, ∆t, and the average temperature in the table in the data part.
7. Clean and dry the beakers, add the solutions for experiment 3, and place the beakers in the
water bath.
8. Then measure the temperature of the solutions for experiment 2, mix the solutions and
follow the reaction as you did for experiment 1.
9. Continue in this manner through experiment 5.

PART B. Reaction order with respect to I-

1. This part is performed exactly as in Part A, except that the concentration of ferric ion is
kept constant while the concentration of iodide ion is varied. The composition of the
various reaction mixtures to be used is given in Table 1, experiments 6, 7 and 8.
47
 Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions

Table 1

250 mL beaker 100 mL beaker

EXP 0.04 M 0.15 M H2O, 0.04 M 0.004 M Starch, H2O,
Fe3+, mL HNO3, mL mL KI, mL S2O32-, mL mL mL
1 10 20 20 10 10 5 25
2 15 15 20 10 10 5 25
3 20 10 20 10 10 5 25
4 25 5 20 10 10 5 25
5 30 0 20 10 10 5 25
6 10 20 20 5 10 5 30
7 10 20 20 15 10 5 20
8 10 20 20 20 10 5 15

DATA

Temperature (°C): ……….

Table 2

EXP ∆t (s)
1
2
3
4
5
6
7
8

48
 Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions

Name Department Group

CALCULATIONS

By performing the calculations, fill up Table 3.

1. Calculate [S2O32-]i which is constant in all experiments.

[S2O32-]i = 0.004 M x 10 mL / 100 mL

2. Calculate the initial reaction rate by using time data.

Rate = 1/2 [S2O32-]i / Δt

3. Take logarithm of the rate.

4. Calculate initial Fe3+ concentration. Take the volume of Fe3+ according to the
corresponding assignment number.

[Fe+3]i = ............... mL Fe3+ x 0.04 M /100 mL

5. Calculate average Fe+3concentration by using the equation below:

[Fe+3]av = [Fe+3]i – 4x10-4/2 = [Fe+3]i – 2x10-4

49
 Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions

Name Department Group

6. Take logarithm of average Fe+3concentrations.

7. Calculate initial I- concentration. This will be equal to average I- concentration.

[I-]i = ............... mL I- x 0.04 M /100 mL

8. Take logarithm of average I- concentrations.

9. Plot log rate vs. log [Fe+3]avg for experiments 1 to 5 to your graph paper.

10. Find the slope of the line; this will be equal to a, reaction order with respect to ferric ion.

11. Plot log rate vs. log [I-] for experiments 1, 6, 7, 8. to your graph paper.

12. Find the slope of the line; this will be equal to b, reaction order with respect to iodide ion.

50
 Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions

Name Department Group

Table 3

EXP [S2O32-]i Rate= 1/2[S2O32-]i/∆t log rate [Fe+3]i

1
2
3
4
5
6
7
8
EXP [Fe+3]avg log [Fe+3]avg [I-]avg log [I-]avg
1
2
3
4
5
6
7
8

QUESTIONS

1. What is the overall rate of this reaction?

2. How would you evaluate reaction rate constant, k, of this reaction?

51
 Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions

Name Department Group

PRELAB QUESTIONS

1. Define the Rate Law.

2. What is the unit that is used to describe reaction rate?

3. What are the factors that affect the reaction rate? List four of them.

4. What is the order of reaction if the rate of reaction is independent of concentration of the
reactants?

52
 Experiment 6: Kinetic Study of the Reaction Between Ferric and Iodide Ions

Name Department Group

53
 Experiment 7: Chemical Equilibrium

7. Chemical Equilibrium
INTRODUCTION

Until now, we have stressed reactions that go to completion and concepts of

stoichiometry that allow us to calculate the outcomes of such reactions. This time you will
investigate chemical equilibrium where two opposing reactions take place at equal rate.
In this experiment you will take a quantitative look at the reaction between ferric and
thiocyanate ions (Eqn 1). You will determine the concentration of each of the ions at
equilibrium, and then seek an expression that relates these quantities mathematically in a
simple, convenient manner.

Fe3+ (aq) + SCN − (aq) ↔ FeSCN2+ (aq) (Eqn 1)

The determination of the concentration of red colored iron-thiocyanate complex will

be done colorimetrically. A colorimeter is a light-sensitive instrument used in colorimetry for
measuring the color intensity of an object or color sample. In your laboratory simple
colorimeter will be build using diffuse light source and reference colored solution (known
concentration of FeSCN2+) for comparison of the solution with varied concentration of same
compound. If you have ever looked critically at a glass full of colored liquid, such iced tea,
you know that the color intensity as viewed through the sides of the glass is much less than
the color intensity as viewed from the top down. This is because the color intensity depends
upon the concentration of the colored substance and on the depth of the solution (Figure 1).
Thus, 1 cm depth of a 1 M colored solution will appear to have the same color intensity as a 2
cm depth of a 0.5 M solution of the same material. The concentration of two such solutions
may be compared by altering their relative depths until the color intensity appears the same.
the ratio of the concentrations is found to be the inverse of the ratio of the depths. Note that
this procedure gives only relative values for the concentrations. To get absolute values, a
standard solution of known concentration must be used.

Figure 1. Effect of concentration and depth

of solution on color intensity of solutions
h ( [C]: concentration of colored compound,
h/2
N: number of molecules in tube of colored
compound and I: color intensity observed)

54
 Experiment 7: Chemical Equilibrium

PROCEDURE

In preparing the standard solution in step a of this experiment, you will use a low,
known concentration of thiocyanate ion, SCN-(aq), and add a large excess of ferric ion,
Fe3+(aq). You can assume that essentially all of the thiocyanate ion will be used in forming
complex thiocyanoiron(III) ion, FeSCN2+(aq), and the equilibrium concentration of the
FeSCN2+(aq) ion will be essentially the same as the concentration of the SCN-(aq) ion with
which you started.

Arrange your data sheet so that you can record the depth of the solution in each test
tube and the depth of the standard solution compared with each of the other test tubes.

a. Line up five clean test tubes, all of the same diameter, and label them 1, 2, 3, 4, 5. Add
5.0 ml of 0.001 M potassium thiocyanate, KSCN, to each of these five test tubes. To test
tube 1 add 5.0 mL of 0.1 M ferric nitrate, Fe (NO3)3 . This tube will be used as the
standard.
b. Measure 10.0 ml of 0.2 M Fe (NO3)3 in your graduated cylinder and dilute it to the 25.0
ml with distilled water. Pour the solution into a clean dry beaker to use it as a stock
solution. Pipette 5.0 ml of this solution and pour it into test tube 2. (Save the remainder
of the Fe (NO3)3 solution for Part c.) Calculate the concentration of this solution.
c. Measure 10.0 mL of the stock solution from the beaker into your graduated cylinder and
dilute it to 25.0 mL with distilled water. Pour the solution into a clean dry beaker and
pipette 5.0 mL of this solution into test tube 3. Continue dilution in this manner until
you have 5.0 mL of successively more dilute solution in each test tube. Calculate the
concentration of each of the solutions.

After preparation of the solutions, compare the color intensities of solutions in each of
the test tubes with the standard tube (number 1) in order to determine the concentration of the
thiocyanoiron(III) ion, FeSCN2+(aq).

Wrap a strip of a paper around test tubes 1 and 2 to exclude light from the side. Look
vertically down through the solutions toward a diffused light source, as shown in Figure 2.

• If the color intensities appear the same, measure the depth of each solution to the
nearest millimeter and record this.
• If the color intensities do not appear the same, remove some of the solution from the
standard tube with a medicine dropper until the color intensities are the same. (Put the
portion you removed into a clean dry beaker, since you may have to use some of this
solution later.) In fact, the matching may be accomplished by removing more standard
than seems necessary and then replacing part of it drop by drop. When the color
intensities are the same in each test tube, measure the depth of both solutions to the
nearest millimeter.

Repeat the procedure with test tubes 1 and 3, 1 and 4 and finally 1 and 5.

55
 Experiment 7: Chemical Equilibrium

Figure 2. Comparing the color of two samples over a diffuse light source

56
 Experiment 7: Chemical Equilibrium

Name Department Group

DATA & CALCULATIONS

Depth of the Standard Tube Depth of the Solution Ratio

Solution (Tube 1)(mm) (mm)
Number

Assume in your calculations that:

a. the ferric nitrate and the potassium thiocyanate exist in their respective solutions entirely as
ions;
b. In the standard tube (number 1), essentially all the thiocyanate ions have reacted to form
thiocyanate-iron (III) complex ions. Also remember that both solutions are diluted on mixing.

The symbol [ ] will be used to represent the equilibrium concentration in moles per
liter. The formula within the brackets denotes the species. Thus the notation [Fe3+] stands for
the equilibrium concentration of the ferric ion, Fe3+ (aq) in moles per liter.

Do all of the calculations for each test tube 2 through 5 as follows in the calculation
tables:

1. a) Calculate the ratio of depths in the color comparison.

Depth of standard matched with tube 2

Ratio =
Depth of liquid in tube 2

b) From these ratios calculate the equilibrium concentration of thiocyanate-iron (III) ion,
[FeSCN2+]:
[FeSCN2+] = (Ratio of depth) x (Conc. of standard)

57
 Experiment 7: Chemical Equilibrium

Name Department Group

2. From your dilution data calculate the initial concentration of Fe3+(aq) ion.
3. Calculate the equilibrium concentration of Fe3+(aq), [Fe3+], by subtracting the equilibrium
concentration of the FeSCN2+(aq) ion from the initial concentration of Fe3+(aq) ion.

Tube
[FeSCN2+]e [Fe3+]i [Fe3+]e
Number

4. Calculate the equilibrium concentration of SCN-(aq), [SCN-], in the same manner for the
Fe3+(aq) ion. Subtract the equilibrium concentration of the FeSCN2+(aq) ion from the
initial concentration of SCN-(aq) ion.

Tube
[SCN-]i [SCN-]e
Number

58
 Experiment 7: Chemical Equilibrium

Name Department Group

5. Now try to find some constant numerical relationship between the equilibrium
concentrations of the ions in each test tube by multiplying and dividing the values obtained
in each test tube in various concentrations.

[SCN ]−
[FeSCN ]
2+
Tube
Number [Fe ]⋅ [FeSCN ]
3+ 2+
[Fe ]⋅ [FeSCN ]⋅ [SCN ]
3+ 2+ −

[Fe ]⋅ [SCN ]
3+ −

QUESTIONS

1. Which of the combinations of concentrations, (a), (b) or (c), gives the most constant
numerical value? This form is known as the equilibrium constant expression.

2. Restate this expression, in words, using the terms reactants and products.

3. Give a possible explanation as to why such a relationship might exist.

59
 Experiment 7: Chemical Equilibrium

Name Department Group

PRELAB QUESTIONS

1. Describe the chemical equilibrium process.

2. How can you know that an equilibrium is dynamic?

3. Briefly explain why equilibrium constant expression do not contain concentration terms for
pure solids or pure liquids phases?

4. What is the concentration unit used in equilibrium constant expressions for the liquids?
(Kc)

60
 Experiment 8: Weak Acids, Weak Bases and Their Salts

8. Weak Acids, Weak Bases and Their

Salts

INTRODUCTION

The purpose of this experiment is to determine the pH values of various concentrations

of acids, bases, and salts. The pH values are determined by one of three methods.

1. Matched indicators
2. pH paper
3. pH meter

These data will be used to determine the acid-base dissociation constants of the
substances being investigated. The variation of the degree of ionization of a weak acid and of
a weak base using concentration also will be determined.

A. Strong Acids and Strong Bases

When a strong acid such as HCl or strong base such as NaOH is dissolved in water, it
dissociates completely into ions as shown in equations [1] and [2].

HCl(g) + H2O H3O+(aq) + Cl-(aq) [1]

NaOH(s) + H2O Na+(aq) + OH-(aq) [2]

As a result, the concentration of hydronium ions, [H3O+], or the concentration of

hydroxide ions, [OH-], essentially is equal to the concentration of the strong acid or the strong
base, respectively.
Hydronium ion concentrations commonly range from 1.0 M to 10-14 M and frequently
are expressed on logarithmic scale of pH.

pH = -log [H3O+] [3]

Furthermore, [OH-] is related to [H3O+] by the ion product of water, Kw, which at 25oC
has the value

Kw = [H3O+][OH-] = 1.0 x 10-14 [4]

61
 Experiment 8: Weak Acids, Weak Bases and Their Salts

The relationship between pH and pOH (-log[OH-]) is obtained from equation [4].

-log Kw = -log[H3O+] –log [OH-] = +14.00

pKw = pH + pOH = 14.00 [5]

Consequently, if one of pH, pOH, [H3O+], or [OH-] is known, the other three may be
calculated by using equations [3], [4] and [5].

B. Weak Acids and Weak Bases

In contrast to strong acids and bases, weak acids and weak bases do not dissociate
completely in solution. They ionize only partly, as shown for nitrous acid (HNO2) and
hydrazine (N2H4) in equations [6] and [7].

HNO2(aq) + H2O H3O+(aq) + NO 2-(aq) [6]

N2H4(aq) +H2O OH-(aq) + N2H5+(aq) [7]

The equilibrium constants for these reactions are known as dissociation or ionization
constants. For a given weak acids or weak bases, the ionization constant has a definite value
at a specific temperature. The ionization constant expressions and their values at 25oC for
nitrous acid and hydrazine are:
[H3O+] [NO2—] [8]
Ki = Ka (HNO2) = = 4.5x10—4
[HNO2 ]

[OH—] [N2H5+] [9]

Ki = Kb (N2H4) = = 9.8x10—7
[N2H4 ]

Where Ki is ionization constant, Ka is an acid ionization constant, and Kb is a base

ionization constant.
Ionization constants are determined experimentally by a method very similar to that
used in this experiment. The pH of a solution of weak acid or base of known concentration is
determined, and these data are used to calculate the value of the ionization constant.

EXAMPLE: The pH of a 1.0 M solution of benzoic acid, C6H5COOH, is 2.11. Calculate the
ionization constant of benzoic acid.

A pH of 2.11 is equivalent to [H3O+] = 0.0078 M. The ionization reaction follows, and

the initial and equilibrium concentrations are given below each species

C6H5COOH(aq) + H2O C6H5COO- (aq) + H3O+(aq)

Initial: 1.00 M - -
Equilibrium: (1.00 – 0.0078) M 0.0078 M 0.0078 M

62
 Experiment 8: Weak Acids, Weak Bases and Their Salts

Since only equilibrium concentrations are used in the ionization constant, Ka becomes

[H3O+] [C7H5O2—] (0.0078)(0.0078) [10]

—5
Ka = = (1.00 — 0.0078) = 6.1x10
[HC7H5O2]

Because weak acids and bases only partially ionize, the degree of ionization, α, of a
weak acid or base often is calculated. For example, if a weak base, B, ionizes according to
Eqn. 11,

B(aq) + H2O BH+(aq) + OH-(aq) [11]

[BH+]eq [OH—]eq [12]

α= =
[B]init [B]init

The subscript “eq” indicates equilibrium concentration and the subscript “init”
indicates initial concentration. While the ionization constant of a given acid or base depends
only on temperature, the degree of ionization also varies inversely with concentration.

C. Salts of Weak Acids and Weak Bases

Although soluble salts dissociate completely into their ions when they dissolve in
water, the fate of these ions depends on the acid or base from which they are derived. The
anions of strong acids and the cations of strong bases do not react with water except to
become hydrated – surrounded by water molecules. On the other hand, the anions and cations
of weak acids and bases react with water by a process sometimes known as hydrolysis.

Thus, the salt sodium nitrite, NaNO2, first dissociates completely in water

NaNO 2(aq) + H O Na+(aq) + NO -

(aq) [13]

and then the nitrite ion acts as a weak base, accepting proton from water to form its conjugate
acid, HNO2.

NO2-(aq) + H2O HNO2(aq) + OH-(aq) [14]

The equilibrium constant, Kb, for equation [14] is

[HNO2 ] [OH —] [15]
Kb =
[NO2 —]

Values of Kb for anions are rarely tabulated since they may be calculated from the
ionization constants of the corresponding conjugate acids. Algebraic manipulation of equation
[15] shows the relationship between Ka and Kb of a conjugate acid–base pair.

63
 Experiment 8: Weak Acids, Weak Bases and Their Salts

[HNO2] [OH —] [HNO2] [H3O +] = [HNO2] x[[H O + — 1 Kw [16]

x 3
Kb = [NO2—] [H O ]
+ [H O +][NO —] ][OH
3 3 2 ] = x Kw =
Ka Ka

For the salt hydrazine iodide, N2H5I , the equations analogous to [13]-[16] are [17]-[20].

N 2H 5I + H 2 O N2H5+(aq) + I-(aq) [17]

N 2H 5+ (aq) + H 2O N 2H 4(aq) 3
+
(aq)

[N2H4] [H30 +] [19]

Ka =
[N2H 5+]
Kw [N2H4] [H30 +] [20]
K= + —
a K = [H30 ][0H ] x
b [N2H5+]

The pH and concentration of a salt dissolved in water are the data necessary to
determine the values of Ka and Kb for a weak conjugate acid–base pair.

EXAMPLE: A 1.00 M solution of sodium benzoate, NaC7H5O2, has a pH of 9.11. What is

the value of Kb for the benzoate anion (the conjugate base of benzoic acid) and the acid
ionization constant of benzoic acid?

A pH = 9.11 is equivalent to pOH = 4.89 or [OH-] = 1.3 x 10-5 M. The hydrolysis

reaction as follows:

C7H5O2- + H2O  HC7H5O2 + OH-

Initial: 1.00 M
Equlibrium: (1.0 – 1.3 x 10-5) M ̴ 1.00 M 1.3 x 10-5 M 1.3 x 10-5 M

Then Kb for benzoate anion and Ka or benzoic acid can be determined. Note that for
any conjugate acid-base pair, KaKb = Kw .
[0H —][HC7H502] (1.3x10 —5M)(1.3x10 —5M) —10
Kb = [C H 0 = = 1.7x10
7 5 2 —] 1.00 M

Kw 1.00x10 —14 5
Ka = = = 5.9x10
Kb 1.7x10 —10

64
 Experiment 8: Weak Acids, Weak Bases and Their Salts

PROCEDURE

You can determine the pH of the solutions investigated in this experiment using one of
the three methods below.

Method I. pH Determination Using Indicators

Obtain about 200 mL of distilled water and boil it for 5 min to remove carbon dioxide.
Carbon dioxide dissolved in water is a weak acid that will seriously affect the results of this
experiment if it is not removed. For each solution to be tested, proceed as follows.

1. Rinse each of five very clean small test tubes three times with about 2 mL of boiled
distilled water
2. Rinse each test tube once with about 2 mL of the solution to be tested.
3. Place about 5 mL of the solution to be tested into each of the five test tubes.
4. Add 3 or 4 drops of one of the indicators given in Figure 1 to the test tubes. Use a different
indicator in each test tube.
5. Record the color in each test tube and, using the data of Figure 1, determine and record the
pH of the solution to the nearest 0.3 pH unit. (You will have to estimate the last digit.)
6. Repeat steps 1-5 for each solution making sure to carefully rinse all test tubes and as
directed in step 1.

Figure 1. pH Color Change Ranges of Some Indicators

65
 Experiment 8: Weak Acids, Weak Bases and Their Salts

Method II. pH Determination Using pH Paper

pH paper is filter paper that has been impregnated with one or a mixture of indicators.
The pH paper will display one of a number of colors depending on the pH of the solution to
which it is exposed. pH paper is produced in two types: wide-range and short-range. Wide-
range pH paper covers nearly the entire pH scale, whereas short-range pH paper may display
all its colors within a pH range as narrow as 0.9 pH unit. The general procedure is to test the
pH of a solution using wide-range pH paper to obtain an approximate pH. The short-range pH
paper encompassing this approximate pH is then used to obtain a more exact pH.

Frequently, pH paper is sold in kits. A typical kit contains one wide-range pH paper
with colors as follows.

Color: Red Orange Yellow Green Blue

pH: 2 4 6 8 10

The kit also contains six short-range papers of the following ranges.

Range number: 1 2 3 4 5 6
pH range: 0.0 – 3.0 3.5 - 5.5 6.0 - 8.5 9.0 - 11.0 10.5 - 12.5 12.0 - 14.0

To usage of pH paper to determine the pH of a solution proceed as follows.

1. Obtain 200 mL of distilled water and boil it for 5 min to remove carbon dioxide gas. Place
this distilled water in your wash bottle.
2. Rinse a clean stirring rod with boiled distilled water from your wash bottle and then with
10-15 drops of the solution to be tested.
3. Touch the wet stirring rod to the wide-range pH paper and record the color and
approximate pH in your notebook.
4. Wet the stirring rod again with 5-10 drops of the solution to be tested. Based on the results
of step 4, select the appropriate short-range pH paper and touch the wet stirring rod to it.
Record the color and pH in your notebook. Try to estimate the pH to the nearest 0.1 pH
unit.
5. Repeat steps 3-5 for each solution to be tested. Each piece of pH paper can be reused until
it is covered completely with drops of solution. After it is totally covered, it should be
discarded, and a fresh piece of pH paper then should be used.

Method III. Determination of pH with a pH Meter

pH meters differ greatly in their method of operation, but generally the following steps
should be used.

1. The temperature compensation dial of the pH meter (if there is one) should be set to the
temperature of the solution

66
 Experiment 8: Weak Acids, Weak Bases and Their Salts

2. The electrodes never should be left “high and dry”. They should always be immersed in
liquid except when they are being transferred from one solution to another.
3. The pH meter should be calibrated (if possible) using standard pH buffer solutions. The
buffers should span the range of pH that is to be investigated. Three buffers of pH = 4.0,
7.0 and 10.0 are a particularly useful set.
4. The solution to be investigated should be placed in the smallest container possible. A
combination electrode can measure the solution in a large test tube. Two electrodes can fit
easily in a 50 mL beaker. Using the smallest container possible greatly reduces the amount
of solution that must be used.
5. Electrodes should be rinsed with CO2 free distilled water from a wash bottle between
determinations. Electrodes should never be touched at the bottom with your hands.
6. Many pH meters have a mirror behind the needle. The needle and its mirror image should
be superimposed when reading pH to avoid parallax.
7. Glass electrodes are made of very thin glass at the bottom and are very fragile. Care should
be taken not to bump them on the bottom or sides of the container.
8. Record the pH in your notebook to the nearest 0.01 pH unit.

A. Determination of the pH of the Solutions

Use these three methods to determine the pH of each of the following solutions.

1. Unboiled distilled water

2. Boiled distilled water
3. 1.0 M NaCl solution
4. 1.0 M NaHSO4 solution
5. 1.0 M Na2CO3 solution

Disposal:
Solutions: None of these solutions is particularly hazardous. Mix them all together in
a large beaker and, using pH paper or phenolphthalein as an indicator, neutralize with 1 M
HCl (the first disappearance of pink color) or 1 M NaOH (first appearance of permanent pink
color). Flush the resulting salt solution down the sink with running water.

B. Effect of Concentration on Degree of Dissociation

Use the pH meter described previously to determine the pH of the three solutes given
below at each of the following concentrations: 1.0 M, 0.10 M, and 0.010 M.

1. Acetic acid, HC2H3O2(aq)

2. Ammonia, NH3(aq)
3. Hydrochloric acid, HCl(aq)

If you are using a pH meter do not leave the electrodes immersed in the aqueous
ammonia solutions. Place electrodes in the solution only long enough to determine the pH,

67
 Experiment 8: Weak Acids, Weak Bases and Their Salts

turn the meter to standby, raise the electrodes, thoroughly rinse them with distilled water, and
store them in pH 7 buffer or distilled water. Basic solutions can chemically attack the glass of
the electrode.

Disposal:
Solutions: Follow the same procedure as for Part A.

68
 Experiment 8: Weak Acids, Weak Bases and Their Salts

Name Department Group

DATA&CALCULATIONS

A. Determination of the pH of the Solutions

Based on your observations, fill in the following table.

pH range
thymol methyl methyl bromothymol alizarin pH pH
from
blue orange red blue yellow paper Meter
indicators

Unboiled
distilled
water

Boiled
distilled
water

1.0 M
NaCl

1.0 M
NaHSO4

1.0 M
Na2CO3

Record the pH, [H3O+] and [OH-] of each solution that you investigated.

Solution pH [H3O+] [OH-]

Unboiled distilled water

Boiled distilled water

1.0 M NaCl solution

1.0 M NaHSO4 solution

1.0 M Na2CO3 solution

69
 Experiment 8: Weak Acids, Weak Bases and Their Salts

Name Department Group

For each solute listed below, write the hydrolysis reaction, the expression for the base constant, Kb, if
the solute is a base or the expression for the acid ionization constant, Ka, if the solution is an acid.
Calculate values of Kb and Ka from your data.

Solute Hydrolysis Reaction Expression for Kb or Ka Value of Kb and Ka

NaHSO4

Na2CO3

A. Effect of Concentration on Degree of Ionization

Record the pH, [H3O+] and [OH-] of each solution that you investigated with pH meter.

1.0 M 0.10 M 0.010 M

pH

HCl
[H3O+]

[OH-]

pH

HC2H3O2
[H3O+]

[OH-]

pH

NH3(aq)
[H3O+]

[OH-]

70
 Experiment 8: Weak Acids, Weak Bases and Their Salts

Name Department Group

Using your data, calculate the value of Ka or Kb and the degree of ionization, α, for each of the
solutions you investigated.

1.0 M 0.10 M 0.010 M

Ka
HCl

Ka
HC2H3O2

Ka
NH3(aq)

71
 Experiment 8: Weak Acids, Weak Bases and Their Salts

Name Department Group

REPORT QUESTIONS

1. A solution of carbon dioxide in water is slightly acidic. Show how this can occur by using a
balanced chemical equation for the reaction of CO2 and water.

2. In water, the Ka of phenol, C6H5OH, is equal to 1.3x10-10 at 25 oC. Calculate the value of
Kb for the conjugate base of phenol, the phenolate ion, C6H5O-.

3. NH3 is a stronger base than water. Which of their conjugate acids is stronger, NH4+ ion or
H3O+ ion? Support your answer with an explanation.

4. A 0.100 M solution of a weak mono-functional base, NaNO2, has a pH = 8.18. Calculate

the value of Ka for the conjugate acid of this system, HNO2.

72
 Experiment 8: Weak Acids, Weak Bases and Their Salts

Name Department Group

PRELAB QUESTIONS

1. Classify each of the following according to their pH behavior in water (acidic, basic,
neutral)

a. KNO3 c. N2H4

b. NH4Cl d. NaNO2

2. A solution has a pH of 8.75. Calculate the

a. [H3O+]

b. pOH

c. [OH-]

3. What must be done if strong base solution is spilled on your skin?

4. Why do we avoid leaving glass electrodes immersed in solutions of bases for more than a
brief time?

5. A 0.100 M solution of a weak mono-protic acid, HX, has a pH = 3.25. Calculate the acid
ionization constant, Ka, of HX.

73
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

9. An Investigation of Voltaic Cells:

The Nernst Equation

INTRODUCTION

This experiment investigates the electrical potential (voltage) produced by an

oxidation-reduction reaction and the effect of concentration on that potential. Oxidation is
that process in which the oxidation state of an element increases; the element also loses
electrons. In reduction, the oxidation state of an element decreases; the element gains
electrons. In oxidation-reduction reactions, an oxidation must always accompany a reduction;
neither process can occur alone.

The objectives of this experiment are to:

1. Measure the potentials of cells formed with a variety of different solutions and electrodes.
2. Calculate half reaction potentials using the Cu2+/Cu half reaction as a reference.
3. Measure the effect of changes in concentration on cell potential.
4. Use the Nernst Equation to relate concentration and cell potential.

When an iron nail is placed in a copper (II) nitrate solution and left to stand, the blue
color of the solution fades and a brown-red deposit forms on the nail. If the brown-red deposit
is scraped away, the nail is found to be somewhat smaller and to have an uneven surface.
Chemical analysis reveals that the brown-red deposit is copper metal and Fe2+ ions are in
solution. Some elemental iron, Fe, has become Fe2+ ions, and some Cu2+ ions have become
elemental copper, Cu. These changes are summarized by the following two half-equations.

Fe(s)  Fe2+(aq) + 2 e- (1)

Cu2+(aq) + 2 e-  Cu(s) (2)

Equation [1] represents an oxidation half-reaction, and equation [2] represents a

reduction half-reaction. Another way of stating this is that Fe has been oxidized to Fe2+ and
Cu2+ has been reduced to Cu.

Yet another way to summarize the results of the observation described above is to
write an overall equation. Two different types of equations may be written.

Fe(s) + CuSO4(aq)  FeSO4(aq) + Cu(s) (3)

Fe(s) + Cu2+(aq)  Fe2+(aq) + Cu(s) (4)

74
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

Equation [3] represents the complete reaction for these observations. If the colorless
solution by the reaction were gently evaporated, solid FeSO4 and Cu would be obtained; little
or no CuSO4 would be found in the now colorless solution. Equation [4] summarizes the
essential features of the reaction and eliminates the ion that is changed in the process (SO42- in
this case). Equation [4] is called the net ionic equation for this reaction.
One benefit of using half-equations is now evident; if electron gain and loss are
balanced, two half-equations can be added to yield the net ionic equation for the overall
reaction. Since the net ionic equation can be separated into two-half equations on paper; it is
not surprising that they can be run almost independently in practice.

- +

FeSO4 CuSO4
solution solution

oxidation: Fe(s)  Fe2+(aq) + 2 e- reduction: Cu2+(aq) + 2 e-  Cu(s)

Figure 1. Apparatus for Measurement of Cell Potentials

The experimental setup is shown in Figure 1. The salt bridge is necessary to complete
the electric circuit by allowing electrical contact between the two solutions. The setup of
Figure 1 can be used to measure the voltage, or potential, of the cell reaction [4]. As seen
from the figure, oxidation occurs at the anode and reduction occurs at the cathode. The
potential changes if a zinc strip is used in place of the iron nail and ZnSO4 solution is used in
place of the FeSO4 solution. Each half-reaction has distinct potential associated with it and the
potential of a cell is the sum of these half-cell potentials.

The Nernst Equation

The concentration of the ions in solution also affects the potential of the half-cell. For
the reaction;

Fe3+(aq) + e-  Fe2+(aq) [5]

75
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

The half-cell potential is given by the Nernst equation;

o 0.0592 [
Fe 2+ ]
Ered = E − log [6]
red
n [
Fe 3+ ]
Where Eored is the standard reduction half-cell potential (the voltage measured when
[Fe2+] = [Fe3+] = 1.00 M) and n is the number of electrons transferred in the half-reaction. In
the case of reaction [5], n=1. For half-reaction [2], the Nernst equation is;

0.0592 1
Ered = o
− log [7]
red
2 [ ]
Cu2+

Frequently, it is easier to use the Nernst equation for the entire cell. For reaction [4],
the Nernst equation is (where Eocell = Eoox + Eored );

o 0.0592 [
Fe 2+ ]
Ecell = E − log [8]
cell
2 [
Cu 2+ ]

Concentration Cells

The Nernst equation also may be used to determine the potential of a cell in which the
net reaction is one of simple dilution.

Cu2+ (1.0M)  Cu2+ (0.050M) [9]

For this reaction Eocell = 0.00 V (since Eoox = Eo re ) and the cell voltage depends only
on concentration.

0.0592 0.050
Ecell = 0.00 − log = 0.0385V
2 1.0

In general, the Nernst equation contains the molar concentrations of the concentrated
and dilute solutions, which are physically separated in the cell by a porous cup or a salt
bridge.
0.0592 [
M n+ (dil.) ]
Ecell = − log n+ [10]
2 [
M (conc.) ]
Equation [10] is the Nernst equation for the reaction and cell shown below;

Mn+(conc.)  Mn+(dil.) M | Mn+(dil.) || Mn+(conc.) | M [11]

76
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

SAFETY PRECAUTIONS

Be very careful in handling chemicals. Wipe all spills promptly with a damp sponge or
towel. If any chemicals get on your hands or clothing, wash immediately with soap and large
volumes of running water. If more than a few drop of chemical solution spill on you, tell your
instructor while you are washing off the spill. Wash your hands carefully and thoroughly at
the end of the experiment before leaving the laboratory.

PROCEDURE

A. Oxidation-Reduction Reactions

1. Add 1.0 M CuSO4 solution into two small test tubes to a depth of 1 cm. Partially immerse a
clean iron nail in one test tube and a strip of zinc in the other. Observe the color of the
solutions and the metals immediately after the metals are immersed.
2. Allow the two test tubes to stand while you setup the apparatus shown in Figure 1 for the
measurement of cell potentials. Note the color of the solutions every five minutes during
the following 15 minute period.
3. Remove the metals and gently scrape and wash off the metallic deposit. Describe the color
and the texture of the metallic deposit as well as the surface of iron nail and the zinc strip.
Especially note any differences between the part of the metal that was immersed in the
CuSO4 solution and the part that was not.

B. Cell Voltages

1. Place approximately 20 mL of 1.0 M CuSO4 solution in a 50 mL beaker.

2. Place approximately 20 mL of 1.0 M FeCl2 solution in another 50 mL beaker.
3. Prepare a salt bridge by soaking a strip of porous paper in a solution of saturated KCl. The
two ends of this salt bridge are dipped into the beakers.
4. Place the iron nail in the FeCl2 solution and a copper strip in the CuSO4 solution. Each
electrode should be long enough (at least 8 cm) so that it is not completely immersed in the
solution. (The electrodes should not be in contact with the paper salt bridge). Connect the
lead from the positive terminal of the voltmeter to the copper electrode using the alligator
clip at the end of the lead. Connect the black lead to the iron nail electrode. Do not allow
the alligator clips to come into contact with the solutions. You will use the same copper
electrode and CuSO4 solution throughout the experiment.
5. Allow the electrodes to sit in solution until the voltmeter reading is stable to ±0.1 V
(fluctuation in the third digit after the decimal will not be significant in this experiment).
Read the voltage to the nearest 0.01 V.
6. A voltaic cell undergoes a spontaneous reaction and will therefore always have a positive
potential. The alligator clips should be connected to the electrodes such that a positive
potential reading is obtained on the voltmeter. The electrode connected to the positive
terminal of the voltmeter is positive and is therefore the cathode. In this first case the

77
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

copper electrode is the positive cathode. The other electrode is negative and is therefore the
anode.
7. Disconnect the alligator clip from the iron nail.
8. Repeat steps 2-7 with each of the solution-electrode pairs given in Table.

Table 1. Electrodes to be investigated

Solution Electrode
1.0 M FeCl2 Iron nail
1.0 M Zn(NO3)2 Zn metal
1.0 M Pb(NO3)2 Pb metal

C. Effect of Concentration

1. Place approximately 20 mL of 1.0 M CuSO4 solution in a 50 mL beaker. This beaker and

solution will be used throughout this part.
2. Place approximately 20 mL of 0.10 M CuSO4 solution in another 50 mL beaker.
3. Dip the two ends of the salt bridge into the beakers.
4. Place a copper strip in the both of solutions and record the potential of the cell.
5. Repeat steps 2-4 with a 0.01 M and 0.001 M CuSO4 solutions.

Disposal of solutions:
Dispose the solutions in a waste bottle labeled heavy metals-solutions.

78
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

Name Department Group

DATA & CALCULATIONS

A. Oxidation-Reduction Reactions

Describe the appearance of the metals and solutions and the deposit with respect to time.

initial 5 min 10 min 15 min

Zn immersed
solution

Fe immersed
solution

Zn metal

Fe metal

B. Cell Voltages

1. For each cell you constructed, record the potential (voltage) of the cell. Write the half cell
equations and the net ionic equation for the reaction that occurred.

Cell Potential (V) Half Reactions Net Ionic Equation

Cu2+/Fe2+

Cu2+/Zn2+

Cu2+/Pb2+

79
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

Name Department Group

2. Use the known standard potential (0.34 V) of the copper half reaction to calculate the
oxidation half cell potential of the studied half reactions.

Cu2+(aq) + 2 e-  Cu(s) 0.34 V

M(s)  M2+(aq) + 2 e- ? Eºox
Cu2+(aq) + M(s)  Cu(s) + M2+(aq) measured potential

Half-Cell Eºox (V) Eºred (V) %Relative Error

Fe2+/Fe

Zn2+/Zn

Pb2+/Pb

80
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

Name Department Group

C. Effect of Concentration

1. For each part, record the potential of the cell. Calculate the diluted Cu2+ concentration
using the measured cell potentials and the Nernst Equation.

Assumed [Cu2+] Cell Potential Experimental [Cu2+] % Relative Error

(M) (V) (M)

0.10 M Cu2+

0.010 M Cu2+

0.0010 M Cu2+

81
 Experiment 9: An Investigation of Voltaic Cells-The Nernst Equation

Name Department Group

PRELAB QUESTIONS

1. Why is it important to keep half of the electrodes out of the solutions when making
measurements in Part A, oxidation-reduction reactions?

2. Calculate the Ecell between two Cu2+/Cu half-cells, one of which contains 0.00100 M Cu2+
and the other contains 1.00 M Cu2+.

3. A Voltaic cell undergoes a cell reaction and has a cell

potential.

4. A voltaic cell is constructed in which a copper wire is placed in a 1.0 M Cu(NO3)2 solution
and a strip of gold is placed in a 1.0 M AuNO3 solution. The measure potential of the cell is
found to be 1.36 V and the copper electrode is negative. Given that the Eo for the Cu2+/Cu
half cell is +0.34 V, calculate the Eo for the Au+/Au.

82
 Scores of the General Chemistry Laboratory II Experiments

Experiment 6: Kinetic Study of the

Experiment 1: Determination of Water Hardness Reaction Between Ferric and Iodide Ions
CHEM 102 CHEM 114 CHEM 102 CHEM 114
Title Page 5 5 Title Page 5 5
Purpose 5 10 Purpose 5 10
Introduction 15 - Introduction 10 -
Procedure 5 10 Procedure 5 5
Data & Results 5 5 Data & Results 10 10
Calculation 25 30 Calculation 25 25
Questions 20 20 Graph 15 15
Conclusion 20 20 Conclusion 15 15
Questions 5 10
Experiment 2: Synthesis of Soap Tidy 5 5
CHEM 102 CHEM 114
Title Page 5 5 Experiment 7: Chemical Equilibrium
Purpose 10 10 CHEM 102 CHEM 114
Introduction 40 40 Title page 5 5
Procedure 15 15 Purpose 5 5
Conclusion 25 25 Introduction 10 -
Tidy 5 5 Procedure 10 10
Data & Results 5 10
Experiment 3: Molecular Models and Covalent Calculations 30 30
Bonding Questions 15 20
CHEM 102 CHEM 114 Conclusion 20 20
Purpose 10 10
Calculation 48 (each 1p) 48 (each 1p) Experiment 8: Weak acids, Weak bases and
Questions 20 (each 4p) 20 (each 4p) Their Salts
Conclusion 5 17 CHEM 102 CHEM 114
Tidy 5 5 Title Page 5 5
Purpose 10 10
Experiment 4: Steam Distillation Introduction 10 -
CHEM 102 CHEM 114 Procedure 10 10
Title page 5 5 Data & Results 10 10
Purpose 5 5 Calculation 30 35
Introduction 10 - Conclusion 20 25
Procedure 5 5 Tidy 5 5
Data & Results 5 5
Questions 20 20 Experiment 9: An Investıgation of Voltaic
Calculation 20 30 Cells-The Nernst Equation
Conclusion 25 25 CHEM 102 CHEM 114
Tidy 5 5 Title Page 5 5
Purpose 5 10
Experiment 4: Molecular Weight Determination Introduction 10 -
From Freezing Point Depression Experimental 5 10
CHEM 102 CHEM 114 Calculation 35 35
Title Page 5 5 Conclusion 25 25
Purpose 10 10 Tidy 5 5
Introduction 10 -
Procedure 5 5
Data & Results 5 5
Calculation 25 30
Conclusion 15 20
Tidy 5 5
Graph 20 20