UNIVERSITI SAINS MALAYSIA

PUSAT PENGAJIAN SAINS KIMIA

KUT 203
Chemistry Practical III
Inorganic Chemistry

NAME

MATRIC NO. :
LECTURER

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KUT 203:

Chemistry Practical lll Inorganic

Students are advised to read this section very carefully and refer to the list of experiments to
be carried out in the following page.
General Introduction
In this practical course there are 8 experiments. All the experiments should be completed
within 12 to 13 weeks. Students will be assigned to groups of not more than two. Students
should complete the practical and hand in the report as a group. Students can choose to
write/type using one-side or both-sided paper. Plagiarism of past students report is strictly not
allowed and will be dealt with appropriately. Illegible handwriting will result in loosing of
marks.
The first practical report should be handed within the 3rd week of the semester. The last
practical report should be handed within the last week of the semester. Reports handed in
later than stipulated time will not be graded.
Grading mechanism:
Practical report
Written test & Quiz

70%
30%

Writing your Lab Report

Cover page of the report should state the number and title of experiment, names of students,
group (Mon-Thurs), date of experiment, and name of instructor/lecturer.
The content of the report should include the following as headings:
Abstract:

A brief description of the experimental result.

Introduction:

A brief introduction of the theory and the experimental background.

Students are advised to read all the references listed and also the most
recent journal papers related to the experiment.

Methodology:

The experimental methodology should be presented in a brief and

concise manner.

Date and Results:

All datapertaining to the experiment should be presented in an

appropriate way. All spectra and analytical results should also be
presented.

Discussion:

The discussion should make use of all the experimental data and
analytical results obtained in the experiment.

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References:

List out all references (only those that you have actually read) using a
suitable style. Follow the style of Journal of Organometallic
Chemistry or Journal of American Chemical Society, etc. Do not
simply copy any reference into your lab report without reading the
original.

Questions:

Answer all question in the practical manual.

I. General Information
1.

Attendance at the laboratory classes is compulsory and attendance is recorded.

2.

Students will generally work in pairs in the laboratory.

3.

Students are expected to follow lab safety rules.

4.

Each student will be expected to complete 3 (three) experiment for the 14 week
laboratory course.

5.

Before starting the experiment, the student must read through the experimental
procedure and familiarize himself/herself with the theory.

6.

Students will be required to keep a laboratory notebook. While you are not required to
adhere to a specific format the following stipulations must be met.
a. The notebook must be bound so that pages cannot be ripped out.
b. The notebook must contain a table of content
c. The pages must be sequentially numbered.
d. All entries must be in ink and dated.
e. Errors are to be lined out: does not use white out
f. All observation must be recorded in the notebook. Do not record your
results on a sheet of paper and then transfer them to your notebook later.
g. Copies of spectra and other computer generated results should be pasted into
the notebook for safekeeping.
h. Upon completion for an experiment, be sure to have the Lecturer or Lab
Technician to sign your notebook.
i. Be prepared to have your notebook inspected at any time.
j. Notebook must be submitted at the end of the laboratory course (week 14).

7.

Each pair must write up a report of the experiment, due the same the following week.
Only One Report need to be submitted by each pair.

8.

Cover page of the report should state the number and the title of experiment, names of
students, group (mon-fri), date of experiment and name of lecture/instructor.

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9.

Grading of Reports and Test

Laboratory reports

70%

Final written practical test (1 hour)

30%

total

100%

The test will focus on understanding the concepts, experimental procedures and
calculation encountered in the laboratory.

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STUDY OF A METAL COMPLEX, POTASSIUM

TRIOXALATOALUMINIUM(III) TRIHYDRATE, K3[Al(ox)3].3H2O

Introduction
Complex compounds comprise of a large group of chemical compounds and is
derived from chemical elements, primarily from metals and in particular transition metals.
Coordination complexes exists in different forms, such as SO42-, MnO4-, [FeCN6]2-, etc. Many
metallic salts exists in the hydrated form, for instance, CoCl2.H2O and consists of the
complex ion such as [Co(H2O)6]2+ where six water molecules act as the ligand bonding
directly to the metal central metal ion, Co2+, by coordinate bond through the donor atom from
the ligand, that is, the oxygen atom from the H2O ligand.
The ligands are arranged in an ordered manner around the central metal atom such
that the stereochemistry can be defined and established. Although there are a number of
stereochemistrys associated with these complexes but the most common ones are those of
coordination number 4 (with tetrahedral or square planar geometries) and 6 (with geometries
that approximate an octahedron).
Many metal complexes are isolated in the solid state, and their stereochemistry and
structure can be determined from X-ray crystallography or assigned based on magnetic
susceptibility, spectroscopic or optical activity measurements. Species of complexes that have
not been established yet can be postulated based on indirect methods such as stability
constant and spectroscopic measurements.
Experimental I:

Preparation of potassium trioxalatoaluminium(III)trihydrate,

K3[Al(ox)3].3H2O

Introduction
The most common method for the preparation of metal complexes is to add excess ligand to
the aqueous of the metallic salt. Since the title complex consists of the K+ ion and the
[Al(ox)3] complex ion, it is soluble in water but not in organic solvents, such as hexane,
ethanol etc. Hence, water soluble organic solvents, e.g. methanol, ethanol, aceton etc. are
often used to precipitate the ionic compound from its aqueous solution.
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Experimental Procedure
A potassium hydroxide solution (3.0 g of KOH dissolved in 25.0 mL water) is added to 0.50
g of aluminium powder in a beaker. Carry out this procedure in a fume cupboard as H2 gas is
liberated. (Reminder: Weigh potassium hydroxide quickly, as KOH reacts rapidly with water
vapour). When the effervescence ceases, heat the solution until it boils and then filter the
residue using a Buchner funnel. Wash the residue with 5.0 mL of lukewarm water.
While stirring the hot filtrate solution add 7.0 g of oxalic acid crystals. Boil and stir the
solution until the initial precipitatate formed re-dissolves in the solution. Cool the solution to
room temperature (use an ice bath).
Slowly pour 30.0 mL of ethanol into the solution with stirring. Occasionally, scratch the
surface of the beaker with the glass rod. A white crystalline precipitate separates from the
solution. Filter the product formed using a Buchner funnel and wash twice with ethanol and
finally once with acetone (CAUTION- ethanol and acetone are flammable and should not be
positioned near a flame).

Place the crystals on an evaporating dish and allow it to dry in air. This takes only a few
minutes and can be hastened by turning the crystals over with a spatula. When the crystals are
dry (no more smell of acetone) weigh it and store in a clearly labelled sample vial.

1.

What is the effect of scratching the wall of the beaker? Explain.

2.

Based on your understanding, why the crystals obtained have to be washed with
ethanol followed by acetone?

3.

Write down all the chemical equations associated with each of the reaction that occurs
during the preparation of the above complex.

4.

Explain why the precipitate formed when oxalic acid is added to the solution.

5.

What are the impurities that may be present in the product?

6.

From the weight of the reactants used, calculate the number of moles of each reactant.

7.

Show that the number of moles that you have calculated is instoichiometry
proportions according to the equations given in question 3.

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8.

Assuming that the reaction go to completion, how many moles of the product are
expected?

9.

From the answer in question 8, calculate the number of grams of product that is
expected (this weight is known as the theoretical yield).

10.

What is the percentage yield of your product? (Note: The calculation above is a useful
indicator of the efficiency of your preparative procedure. Only in a few cases, can the
efficiency achieve 100%. Often the preparative efficiency can be improved, but it
should not be done at the expense of the purity of the compound)

11.

Suggest how the percentage yield can be improved in the experiment above.

Experimental II:

(a)

Analysis of K3[Al(ox)3].3H2O

Preliminary Test

(To find out if the complex decomposes under the conditions in which the analysis is carried
out)
Test to find out how the complex reacts with potassium permanganate (KMnO4) solution.
Prepare two test tubes, each containing about 1mL KMnO4 solution (provided) and diluted
with about 3mL of distilled water:
In the first test tube, add 2 drops of diluted sulphuric acid (H2SO4).
In the second test tube, add 2 drops of sodium hydroxide (NaOH) solution.
To each of the test tube is then added a little of complex K3[Al(ox)3].3H2O. Heat the test
tubes and observe carefully. (You might have to filter the solution in the test tube containing
sodium hydroxide).

Questions:
12.

Write down the ionic equation for the reaction occurring in each of the test tubes.

13.

Your complex will be analyzed based on your observation above. Why is it that
almost all titration involving KMnO4 solutions is carried out under acid conditions?

(b)

Standardization of KMnO4 solution

Prepare a standard solution1of oxalic acid (this acid is used as the primary standard2) by
weighing accurately 1.6 g of oxalic acid (H2C2O4.2H2O) and dissolving and making up to
250.0mL with distilled water in a volumetric flask. Calculate the molarity of the solution.
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By using pipette, transfer 25.0 mL of the oxalic acid solution to a conical flask and add 50.0
mL of dilute sulphuric acid. Heat until 65C and immediately titrate with the KMnO4
solution. Before the end point is reached ensure that temperature of the solution is at least
55C (heat again if necessary). The titration must be carried out at least twice or until
consistent titre is achieved.
The aqueous KMnO4 solution supplied contains about 3.02 gL-1. Calculate its molarity.From
the weight of the oxalic acid (as the primary2 standard) used, the molarity of the oxalic acid
can be calculated accurately. Hence, from the end point volume of the titration, the accurate
concentration of KMnO4 can be determined. Perform your calculations using the mole
concept that is using the concentration expressed as molarity.
Question:
14.

Why must the oxalic acid solution be heated before it is titrated with potassium
permanganate solution?

(c)

Analysis of complex Determination of percentage of oxalato group

Weigh accurately about 0.2 g (accurate to 0.1 mg) of the complex and dissolve in about
50.0mL dilute sulphuric acid in a conical flask. Heat the solution and titrate as before with
standardized KMnO4 solution. Carry out the analysis twice. Calculate the percentage of the
oxalato group in the sample of the complex. Compare this experimental value with the
theoretical percentage.

Question:
15.

Give possible reasons for the difference between the observed percentage and the
percentage of the oxalato group present in your sample.

What is standard solutions? How do you prepare them? Find out from any analytical books.
What is primary standard? Can you list some of the physical properties of a primary standard?

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PREPARATION AND CONDUCTIVITY OF [Co(NH3)4CO3]NO3 AND

[Co(NH3)5Cl]Cl2

Introduction

In the development of Coordination Chemistry, the important compounds are those of

transition metal complexes. Before 1950, the research in this field involved the investigation
of complex compounds of transition metals with monodentate ligands such as Cl-, Br-, I-,
NH3, pyridine, CN- and NO3- together with bidentate ligands such as ethylenediamine
(H2NCH2CH2NH2), oxalato (C2O4)2-, glycinato (H2NCH2COO-) and carbonato (CO32-). Many
of these complex compounds are still used as starting materials for various researches that are
carried out today. Coordination chemistry is an actively thriving field. Many new compounds
are being discovered every day. Some of the most interesting ligands discovered to date are H, -CH3, CO, H2C=CH2 and C6H6.
Complexes of Co(III) and Cr(III) have attracted attention as they undergo slow ligand
substitution reactions compared with complexes of other transition metals. For example,
under the same conditions, reactions of a complex ions [Co(NH3)6]3+ and [Cr((NH3)6]3+ occur
much slower than that of [Ni(NH3)6]2+. The observation of the differences in rates of
reactions of the various complexes has been explained qualitatively in terms of the ligand
filed theory and molecular orbital theory1. The low reactivity of the Co(III) complex have
made it possible to carry out extensive studies on reactions of complexes. The structure of the
octahedral Co(III) complexes that you will prepare are as follows2.

1
2

Students are advised to read up on the ligand field theory and the molecular orbital theory.
Students should know how to draw 3 dimensional diagrams of coordination complexes.

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An important method to characterize the coordination compounds is to determine the

conductivity of the solution containing the complex ions. The complex having a higher
conductivity in a solution would contain a larger number of ions. For instance, a 1.0M
solution of [Co(NH3)4CO3]NO3 (A) would have a lower conductivity compared with a 1.0M
solution [Co(NH3)5Cl]Cl2 (B). When (A) and (B) are dissolved in water, the complexes will
ionize as follows:

Complex A produces two ions in solution, i.e. [Co(NH3)4CO3]+ and NO3-, while complex B
produces three ions, i.e. one [Co(NH3)5Cl]2+ ions and two Cl ions. The conductivity of the
solution will depend on the total number of ions present in solution. It can then be assumed
that complex B will have a higher conductivity compared to complex A in aqueous solution.
Conversely by measuring the solution conductivity of a compound, we can determine the
number of ions in the compound. This can lead us to the structural formula3 of the
coordination complex. Although the measurement is carried out on the aqueous solution of
the complex, the same information can often be obtained by using organic solvents such as
nitrobenzene or acetonitrile for compounds that are not soluble in water.

Do you remember what structural formulas are? If you dont please revise your KTT
111/112 notes.
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One of the methods to determine the identity of a complex is by using infrared spectroscopy.
This technique gives the vibrational frequencies of functional groups present in the molecule.
The infrared spectra of the two complexes above shows frequencies (usually expressed in
1

wave unit cm-1, i.e. reciprocal ofwavelength ) characteristic of group stretching and bending
modes such as NH3. Although in principal, the Co-N stretching mode can be measured, but

this stretching mode occurs at very low frequencies (less than 650 cm-1) so as to be in the
same region as that of the carbonato group in the [Co(NH3)4CO3]NO3complex. Due to the
coordination of CO32- to the central cobalt atom, this CO32- group will exhibit a different IR
spectrum compared to that of Na2CO3. The spectrum of the complex is also expected to
display the absorption band of the NO3- group similar to the absorption band observed in
NaNO3. In contrast, the IR spectrum of

[Co(NH3)5Cl]Cl2will be dominated mainly by

absorptions due to the NH3 group.

In general, M-Cl stretching frequencies (where M represents metal) lies outside the
observable frequencies in an infrared spectrophotometer. The Cl- ion is not attracted strongly
to other atoms in the solid state; hence no absorption due to the Cl is expected to be observed
in the infrared spectrum compound. Other experimental techniques and instrumental methods
will be used to characterize the Cl in this experiment. It must be emphasized the quantitative
elemental analysis is an important step leading to the determination of the composition and
structure of a new compound. This is usually done using a CHN analyzer (or elemental
analyzer). Our school has one such instrument and you should use it when necessary.
Synthesis of the complex compound [Co(NH3)4CO3]NO3 will be carried out
according to the following equation (not balanced):

Commercially available cobalt(II) nitrate has the formula Co(NO3)2.6H2O, and most probably
is a coordination compound with the ionic formula [Co(H2O)6](NO3)2. As Co(II) as well as

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Ni(II) complexes react rapidly via ligand exchange, the first step of the reaction can be
represented by the following equation:

This Co(II) complex is then ionized by the transfer of an electron to H2O2 followed by the
formation of the Co(III) ion which is relatively unreactive as in [Co(NH3)4CO3]+. The
preparation of the [Co(NH3)5Cl]+ complex from the carbonato complex is then completed via
the following series of reaction:

Based on the mechanism studies on the reaction of [Co(NH3)4CO3]+ with acid, the first step
in the series of reactions given above may involve the following mechanism:

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The O-C bond has been proven by

18

O isotope exchange studies on similar carbonato

complexes. The subsequent steps in the synthesis involve the exchange of an external ligand
with one in the coordination sphere4. At a glance one may expect the reaction to take place
via the SN1 or SN2 mechanism5. However, even until the present time, it is debatable as to the
actual mechanism of the reaction.

Electrical Conductivity of Complex Ions in Solution

Introduction

The determination of the number of ions in a particular compound depends firstly on

the measurement of the conductivity of the compound followed by the comparison of this
value with that of unknown compounds. The determination of conductivity starts with the
measurement of resistance because resistance is a quantity that can be measured
experimentally. Resistivity, l(formerly known as specific resistance)is defined as resistance in
ohms, of a solution in a cell with electrodes of surface area 1 cm2 and separated by a distance
1

of 1 cm. The reciprocal of resistivity is called conductivity, L (formerly known as specific

conductance). The resistance, R of a solution in a cell with non-standard dimensions can be

obtained by multiplying with a constant factor k, which depends on the geometry or
dimension of that cell. From experiment, k can be expressed as:
R = lk

(1)

The factor k can be calculated from equation (1) by measuring R for a solution having
resistivity l(measured in a standard cell).
As L=

and =

conductivity, L, that is

1
L

, equation (1) can be expressed in terms of resistance R and

R=L

4
5

(2)

What are coordination sphere? Look it up in an Inorganic chemistry textbook.

Again the students are advised to read up on SN1 and SN2 mechanism. Recall KOT 121/122.

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The constant factor, k, is also known as the cell constant. This constant is often obtained from
equation (1) by measuring resistance (R) of a solution of 0.02 M KCl with conductivity L of
0.002 768 ohm-1 cm-1at 25C. After determining the value of k for a particular cell, the
conductivity of any solution can be calculated from the measured resistance of the solution in
that cell. In conductivity studies of electrolyte solutions, comparisons have to be made under
standard conditions. The molar conductivity, , is defined as the conductivity of a 1 cm3
volume of an electrolyte solution containing 1 mole (or 1 formula weight) of the electrolyte.
As the conductivity L is the conductance of 1 cm3of solution, therefore the conductivity per
mole of solute can be calculated by dividing L with the number of moles contained in 1 cm3
of solution, that is
=

1000

(3)

where M represents the molarity of the solution.

Comparison of the molecular conductivity of a solution of a given ionic compound

with that of known ionic compounds in solution enables the determination of the number of
ions in the given ionic compound, present in the solution.
The range of values at 25C for electrolyte solutions having 2, 3, 4, and 5 ions are
given in the table below:

Number of ions

118-131

235-273

408-435

~ -560

(Taken from M. Sneed & J. Maynard, General Inorganic Chemistry, Van Nostrand, New
York, 1942, page 813)

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Experimental I:

(a)

Preparation of [Co(NH3)4CO3]NO3 and [Co(NH3)5Cl]Cl2

Carbonatotetraaminecobalt(III) nitrate6, [Co(NH3)4CO3]NO3

Dissolve 20g (0.21 mol) ammonium carbonate, (NH4)2CO3 in 60mL of distilled water and
add 60mL of concentrated ammonia solution. While stirring, pour this into a solution
containing 15g (0.052 mol) of hexaaquacobalt(II) nitrate, [Co(H2O)6](NO3)2, in 30mL
distilled water. Add 8.0mL of 30% hydrogen peroxide (H2O2) to the mixture (Reminder:
Use gloves when handling H2O2 solution. H2O2 can cause skin burn; if your skin comes into
contact withH2O2 wash immediately with water). Pour the resulting mixture into the
evaporating basin and concentrate over a hot plate in the fume cupboard until the volume
reaches about 90100mL. Do not allow the solution to boil. During the concentration process,
add 5g (0.05 mol) of powdered ammonium carbonate a little at time. Using the suction
apparatus shown in Figure 1, filter the hot solution and cool the filtrate in an ice bath.
Red crystals of [Co(NH3)4CO3]NO3 forms. Filter the red crystals by suction filtration,
wash with a few milliliters of cold water (this complex is quite soluble in water) followed by
washing with the same amount of cold ethanol.
Dry the compound. Calculate its yield (keep some of your compound for conductivity
measurements). Determine the melting point of the red crystals. Using the KBr technique
obtains the FT-IR spectrum of the compound.

Figure 1: Apparatus for vacuum filtration

6

Read up on the nomenclature of coordination compounds

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(b)

Chloropentaaminecobalt(III) chloride, [Co(NH3)5Cl]Cl2

Dissolve 5.0g of carbonatotetraaminecobalt(III) nitrate, [Co(NH3)4CO3]NO3 you synthesized

in (a) in 50.0mL of distilled water. Add concentrated HCl (between 5mL and 10mL) until the
CO2 gas is liberated. Neutralized the solution with concentrated ammonia and add 5.0mL of
excess ammonia solution. Heat the solution for 20 minutes but do not allow it to boil. In this
process, the formation of compound containing the [Co(NH3)5(H2O)]3+ ions takes place. Cool
the solution a little and add 75mL of concentrated HCl. Heat the solution and observe the
colour change. Crystallize the purple red product by allowing the solution to cool to room
temperature upon which the crystals will separate from the solution. Filter the crystals and
wash several times with the cold distilled water followed by a few millilitres of ethanol.
Transfer the product into a clean dry and pre weight beaker (record the mass of the empty
beaker). Dry the compound into the oven at 120C so as to remove the solvent and the
required compound, [Co(NH3)5Cl]Cl2 will then be obtained. After the crystals are dry, allow
it to cool to room temperature. Record the mass of the beaker and its contents (use the same
weighing balance if possible). Calculate the yield of the compound (keep this compound in a
sample bottle for submission together with the report). Determine the melting point of your
product. Use the KBr disc technique to obtain FT-IR spectrum of the compound7.

Experimental II: Determination of Molar Conductivity of[Co(NH3)4CO3]NO3 and

[Co(NH3)5Cl]Cl2
Measure the molar conductivity of the coordination compounds that you have prepared,
[Co(NH3)4CO3]NO3 and [Co(NH3)5Cl]Cl2, by using the given conductivity meter. Read
carefully the instructions given by the manufacturer of the conductivity meter in order to
operate the instrument. When the resistance measurements are carried out, the cell containing
the solution must be thermostatted much earlier at 25C. Use distilled or deionised water for
the preparation of all solutions.

You should learn the art of sample preparation using KBr disc and run the FT-IR spectrum

yourself.

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1.

Prepare an aqueous solution of 0.02M KCl and obtain the cell constant k by
measuring the resistance of the solution.

2.

Prepare both 500mL aqueous solution of 0.002M [Co(NH3)4CO3]NO3 and 0.002 M

[Co(NH3)5Cl]Cl2, respectively. Measure their resistance. The measurements must be
carried out immediately as leaving the solutions overnight will cause
decomposition of the complexes.

In between the measurements, ensure that the cells are thoroughly rinsed with distilled
water. After you have completed, rinse the cell again and soak the cell in a beaker of distilled
water.
Calculate the molar conductivity of both the Co(III) complexes. This measurement is
also a sensitive test for the purity of the ions in your complexes.

Preparation of Experimental Report

The following items must be included in your report:
1. The percentage yields for both coordination compounds that you have been prepared,
namely [Co(NH3)4CO3]NO3 and [Co(NH3)5Cl]Cl2
2. The melting points of both the compounds.
3. The FT-IR spectrum of both compounds. Using the IR spectrum comment on the
similarities and differences in the structural formula of the complexes.
4. The value of molar conductivity, , for both the coordination compounds and your
inference as to the number of ions present in each of the coordination compound.

Questions:
1. Briefly describe a method to analyse the percentage composition of Cl in the coordination
compound [Co(NH3)4CO3]NO3 (Note that the ionic Cl- is more reactive than the Cl in the
coordination sphere of the complex).
2. Briefly describe a method to analyze the percentage composition of NH3 and the
percentage composition of Co in the coordination compound [Co(NH3)4CO3]NO3.
3. Balance the chemical equation (1) for the preparation of [Co(NH3)4CO3]NO3.
4. In the following exchange process,

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How can you determine experimentally if bond cleavage occurs at O-C (a) or Co-O (b)?

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SYNTHESIS OF BIS(TRIPHENYLPHOSPHINE)COPPER(II)
BOROHYDRIDE (Ph3P)CuBH4

Introduction

(Ph3P)CuBH4 is an electron-deficient compound; that is, it process fewer valance

electrons that are required for a localized bonding scheme. However, it does not exhibit the
familiar characteristics of electron deficient compounds i.e. it does not readily react with
oxygen or moisture. It is, therefore, an example of an electron-deficient compound that is
stable under normal atmospheric conditions. The stability is related to the molecular
structure of the compound in which the electron deficiency at the copper atom is overcome
by bridging ligands. In this experiment the FT-IR technique is used to determine how this
bridging technique occurs.

Experimental:

Synthesis of (Ph3P)CuBH4

Carefully crush 1.0g of copper(II) sulphate pentahydrate, CuSO4.5H2O, into powder form and
place the powder in an appropriate size beaker (or Erlenmeyer flask) containing 5.0g of
triphenylphosphine and about 80mL of ethanol. Stir and gradually heat the mixture using a
hot plate to completely dissolve the blue solute. Decant the yellowish solution that results
into another container (preferably a beaker) so as to separate it from any residue or remaining
undissolved salt. To this solution, carefully add (preferably portion wise) about 2.0g of
properly crushed (i.e. powder form) sodium borohydride with continuous stirring of the
mixture until the effervescence (bubbling up) subsides. This suggests the precipitation of
the desired product is completed. Isolate the solid component (comprising the product and
remaining reactant) of the mixture by filtration and transfer it into an Erlenmeyer flask
containing about 50.0mL of chloroform. Separate the chloroform solution (extract) from any
residue (such as the remaining sodium borohydride) by passing it through an appropriate
filter paper and into a clean beaker. Heat the filtrate to almost boiling on a hot plate.
Carefully add ethanol (preferably drop wise) with continuous stirring (and making sure the
content of the beaker remains hot) until the solution appears hazy (i.e. indicating saturation
point) or white precipitate begins to form. Then allow the content of the beaker to slowly cool
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to room temperature before placing the beaker in an ice-bath. Isolate and air-dry the white
solid (crystallized product) by suction filtration. Determine the yield and melting point of the
product. Obtain the FT-IR spectrum of the compound using KBr technique.

Questions:
1. Suggest a plausible reason as to why electron-deficient compounds are generally very
reactive to oxygen or moisture.
2. Draw the molecular structure of (Ph3P)2CuBH4 and briefly describe its bonding scheme.
3. Assign the vibration characteristics (frequencies) of the terminal and bridging hydrogen
atoms of (Ph3P)2CuBH4.
4. How can these vibration frequencies be determined and assigned with certainty to a
particular hydrogen atom in the molecule?
5. Describe the NMR spectra (1H, 13C and/or 31P) of (Ph3P)2CuBH4.

Reference:

1. S. J. Lippord and K. M. Melmed, Inorg. Chem.., 6 (1967) p.2223.

2. M. Grace et.al.., Chem. Comm.., (1970), p. 701
3. K. C. Nainan and G. E. Ryschkewitsch, Inorg. Chem. 8(1969) p. 2671.

D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

DETERMINATION OF COMPLEX IONS COMPOSITION USING THE

JOBS METHOD

Introduction
It is often possible to determine the interaction between two molecules in solution
without having to isolate a stable compound. For example, benzene, CH, and iodine, I,
interact in carbon tetrachloride according to the following reaction:

with the formation of an adduct complex with a ratio of 1:1 with respect to the reactants. This
complex is strongly coloured and too unstable to be isolated. The existence or formation of
the adduct is indicated by the strong colour of the solution despite the inability to clearly
determine the presence of one molecule of CH and one molecule of I within this adduct.
Research in coordination chemistry has broadened to the extent of being capable of
identifying complexes in solution without having to isolate them. For example, the reaction
between the Ni2+ ion and ammonia, NH3, in water yields a number of complex ions of these
composition:

[Ni(NH3)4(H2O)5]2+,[Ni(NH3)5(H2O)4]2+,[Ni(NH3)3(H2O)3]2+,

[Ni(NH3)4(H2O)2]2+, [Ni(NH3)5(H2O)2]2+and [Ni(NH3)6]2+. Amongst these, only the

[Ni(NH3)6]2+ ion has been isolated. Nevertheless, investigations through spectrophotometric
methods and potentiometric methods clearly indicate that the other complex ions exist in the
solution. The fact that these complexes cannot be isolated does not indicate weak reactions.
The formation of bonds between the transition metal and the ligand is actually highly
exothermic. However, due to the factors, not all existing species can be crystallised from the
solution. Thus, it is necessary to identify the composition of these species through other
methods.

Crystallisation is one of the methods that can be used to isolate and purify ionic compound.
Non ionic compounds can also be isolated/purified if they existed in crystalline forms.

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In this experiment, you will determine the composition of the complex [Ni2+ethylenediamine] in solution using procedure known as the Constant Variation Method or the
Jobs method. Generally, this method deals with the determination of n for the following
balanced equilibrium:

where, in this experiment, Z is Ni2+ and L, the ligand ethylenediamine (en). The molecular
formula of ethylenediamine is shown below
HNCHCHNH

Both ions, Ni2+ and the product [Ni(en)n]2+ show absorption in the visible region of an
electromagnetic spectrum, although both spectrums are different.
Experimentally, the intensity of absorption for a specific wavelength and for a series
of solution varying in Ni2+ and en content is measured. The absorbance is a function of the
[Ni(en)n]2+concentration in the solution. Solutions are prepared such that the concentration in
Ni2+ and in en is identical for each solution. When the equilibrium constant for reaction (2) is
large, i.e. the equilibrium is shifted to the far right, it is obvious that the absorption intensity
for [Ni(en)n]2+ will have the largest value (the concentration of en in solution is exactly equal
to n times the concentration of Ni2+). As will be observed, this is equally true for cases where
the equilibrium is not shifted to the far right.
Nevertheless, a sufficient level of concentration is required in order to obtain a precise
measurement of the absorbance. Thus, it would be possible to determine n and the
composition in [Ni(en)n]2+ upon knowledge of the en : Ni ratio in the solution which gives
the maximum absorbance for [Ni(en)n]2+
For the Ni2+ - en systems, a series of complex ions, namely [Ni(en)]2+, [Ni(en)2]2+ ,
[Ni(en)3]2+, [Ni(en)4]2+ etc., may exist. The objective of this experiment is to determine which
of these really exists in solution. The following chemical reactions may be possible:

D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

and so forth.
The value of the equilibrium constant will determine which species will exist in excess in the
solution. Thus, if K2 is larger than K1, meaning that [Ni(en)]2+ is nearly inexistent in the
solution, then the Job Method will determine the presence of [Ni(en)2]2+ and will show no
proof of the existence of [Ni(en)]2+. Similarly, the relative comparison in value of K3 with K1
and K2 will determine the species that will be identified. There is however a limitation to this
Method for Continual Variation, that is that, only one equilibrium identical to that in equation
(2) will exist in a solution of Z and L. In other words, this method will lead to a non integer
value for n if apart from Z, L and ZL, another complex, ZLn+1 also exists in the solution.
For the reaction or the Ni2+ -en system, it would imply that only two complexes (Ni2+
and [Ni(en)]2+or [Ni(en)]2+and [Ni(en)2]2+, etc.) can exist in any given solution. This holds
true for determined values of K1, K2 and K3 whereby these values are very different.
Although the Jobs method permits us to determine the composition of a complex within a
system, the results may seem somewhat confusing or false for a system whereby the diverse
values of K for successive reactions remain unknown. Thus, the Continuous Variation
Method or the Jobs method is limited to moderate systems.

Theory
The objective here is to prove that the value of n for ZLn in equation (2) can be determined
from spectrophotometric measures of the absorbance for a series of solutions consisting of
different quantities of Z and L, but with an identical total concentration of Z and L. If the
absorbance for each solution at a given wavelength is plotted against the mole fraction, x, of
the ligand L in the solution, the maximum value for absorbance will occur at a mole fraction
representative of its composition ZLn . Therefore, the value of n can be determined.

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Suppose that the substance Z and the substance, L react according to equation (2). The
equimolar solution for Z and L, each of which have concentration M mol per liter, is then
added in varying quantities such that the total concentration (namely the concentration of Z
and L) is given by M. A series of solution is thus prepared by adding x liters of L to (1- x)
liters of Z, where x < 1. The concentrations of Z,L and ZLn in solution at equilibrium are
represented by c1, c2 and c3, respectively. Thus for any solution , the concentration is given by
the following:

where K is the equilibrium constant for reaction (2). The condition for a maximum for the c3
versus x curve is

Solving equations (5), (4) and (3) for x and combining this with the solution in x for
equations (3), (4) and (6) yields

Thus, n can be calculated from equation (7), from the value of c for which c is a maximum.
Following this, it is necessary to show that the maximum value for absorbance at a given
wavelength, as x varies, will coincide with the maximum value of c3.
According to the Beer Lambert Law,
A = cl

(8)

Where A is the absorbance, is the molar extinction coefficient, c the molar concentration
and lthe path length of light of light or the width of the cell. The molar extinction coefficients
for Z, L and ZLn, at a given wavelength are represented by 1, 2 and 3 respectively. Since
the absorbance of a solution is equivalent to the summation of absorbance at a given
wavelength and for diverse species contained in that solution, thus the measured absorbance,
Ameasured, will be given by :
Ameasured = (1c1 + 2c2 + 3c3) l
D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

(9)

If there is no interaction between Z and L, i.e. c3 = 0, then the absorbance, AZ+L, will be:
AZ+L = [1M (1- x) + 2Mx] l

(10)

where M represents the molar concentration for solution Z and solution L.

The difference between Ameasuredand AZ+L is represented by Y. Where Y is given by:

Y = [1c1 + 2c2 + 3c3 1M(1 x) + 2Mx] l

(11)

By differentiating equation (11) with respect to x, it can be shown that Y is a maximum when
c3 is maximum if 3>1 .or Y is a minimum when c3 is a maximum if 3> 1.
In this experiment, Z is Ni2+,and L is ethylenediamineor en. Since en does not show
absorbance in the currently studied region of the spectrum, 2will always be equal to zero.
The cell used for measurements has a width of 1.0 cm. With these conditions, equation (11)
yields:
Y = Ameasured (1 x) AZ

(12)

where AZ is the absorbance fora molar solution M containing Ni2+ only. In order to evaluate n
in [Ni(en)n]2+, it is necessary to plot Y versus x for a given wave length. This plot will show a
maximum for a specific mole fraction. From equation (7) and using the value of x, n can be
calculated. Since more than one composition of a complex is investigated in this experiment,
it is necessary to establish a number of plots for wavelengths corresponding to the different
[Ni(en)n]2+ complexes.

Experimental:

The solutions used are:

a. Nickel(II) sulphate hexahydrate solution, NiSO4.6H2O, with a concentration of 0.4 M and
b. Ethylenediamine (en) solution, with a concentration of 0.4 M.

D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

Using the two solution above, prepare solutions of total volume 10.0mL, for mole fractions of
0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9 in ethtlenediamine. Determine/measure the absorbance for
each of the solutions and also for 0.4 M nickel(II) sulphate, containing no ethylenediamine,
for the following wavelength: 530, 545, 578, 622 and 640 nm.

If a scanning visible spectrophotometer is available, the simplest method to determine the

absorbance at different wavelength would be to record a spectrum for each solution for
wavelength varying from ~ 500 to 650 nm. All spectrums can then be modified on the same
chart. For a spectrophotometer with a fixed wavelength, the absorbance can be measured by
adjusting the spectrophotometer manually such that the wavelength is that required.

Determine the value of Y, from equation (12), for each wavelength through the series
of solutions. For each of the five wavelengths, plot Y versus x. The x value for each of the
five maximums will allow you to calculate the n value for the [Ni(en)n]2+ complex ion from
equation (7).

Preparation of Experimental Report

Include the following in your report:
1.

The spectrum or the absorbance measurements for the different solutions.

2.

The Y versus x plot for each of the five wavelengths used.

3.

The different values of n calculated and the formula for the diverse Ni2+ complexes that
exist in the solution.

Questions:

1.

Draw the structures for each of the [Ni(en)n]2+ complexes in the solution.

2.

From the variations observed I the spectrum, and also determine of the existing
complexes in the solution, comment on the relative ligand field strength for the en and
H2O ligands.

3.

Deduce equation (7), that is

4.

By differentiating equation (11) with respect to x, show that Y is a maximum when

c3is maximum.

D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

THE CHEMISTRY OF VANADIUM

Introduction:
The chemistry of vanadium is described in detail in the given references. Students are
strongly advised to read the chapter before starting this experiment.

Preparation of vanadium(V) standard:

Weight out 1.25g of vanadium(V) oxide into a 200mL beaker. Add 2.0g of NaOH pellets,
followed by 100mL of distilled. Heat the beaker gently until the entire solid dissolved. Add
50.0mL of distilled water. Add sulphuric acid (1M) until the solution just becomes acidic.
The colour of the resulting solution will be yellow. Transfer the solution into a 250.0mL
volumetric flask and add distilled water until the mark. Use the resulting solution for the
following experiment. Duplicate experiments are required for each determination. Record all
experimental data and observations clearly and neatly in your laboratory notebook.

Experimental I:
Use a pipette to transfer 25.0mL of the standard solution above into a conical flask. Add
25.0mL of distilled water and 3.0g of zinc beads and 50.0mL of 1M sulphuric acid. Slowly
heat the solution to boiling. Thecolour will change to blue, then to green and finally
purple/bright lavender. Separate the solution from any un-reacted zinc by slowly pouring out
the solution into a beaker containing 25.0mL of 0.1N potassium permanganate. Perform this
transfer quickly while the solution is still hot. It is advisable to perform this separation by
pouring through a funnel which has been clogged with a bit of glass wool to prevent any zinc
particles from passing through. Quickly wash out the first beaker and add it to the original
filtered solution through the same funnel. Titrate this solution with potassium permanganate
0.1N. The end point of the titration is a very sharp if the titration is carried out at 70-80C.

D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

Experimental II:
Repeat the procedure in (a), but separate the solution from the zinc into an empty conical
flask. Let it cool. Aspirate the solution with air for 65 minutes. Leave it aside for 30 minutes.
The colour of the solution should turn to bright or light green. Heat the solution to 70-80C
and titrate the hot solution with 0.1N potassium permanganate as in (a) above.

Experimental III:
Pipette 25.0mL of the standard vanadium solution into a conical flask. Add approximately
20mL of dilute sulphuric acid and few pieces of sodium sulphite. Heat the solution to boiling
until all the sulphur dioxide gas is evolved. Titrate the hot solution with the 0.1N potassium
permanganate solution.

Questions:
1. In your laboratory report under the heading Introduction, write down a brief description
of the chemistry of vanadium. State all the references you have used in the reference
section.
2. From the above experiments, deduce the valency of the vanadium when the vanadium(V)
species is reduced by
a) Zinc (without air)
b) Zinc
c) Sulphur dioxide
3. Write the equations for all the reactions with the assumption that the permanganate ion
will oxidize all the vanadium species to vanadium(V).
4. Deduce the ionic species responsible for the colour of the solution in each experiment.

References:
1. N. H. Greenwood and A. Earnshaw, Chemistry of the Elements, Pergamon Press, 1994.
QD 466. G74. Pg. 1138 1166.

D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

2. F. A. Cotton, G. Wilkinson, C. A. Murillo and M. Bochman, Advanced Inorganic

Chemistry, 6th Edition, John Wiley & Sons, Inc. 1999. Pg. 714 736.
3. J. D. Lee, Concise Inorganic Chemistry, 4th Edition, Chapman & Hall, 1991. QD
453.2.L45, Pg. 697 712.

D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

ELECTRONIC SPECTRA OF COORDINATION COMPOUNDS

Introduction
One of the characteristics of transition metal is its colour. The existence of colour is
due to the absorption and emission of light in the visible region of the electromagnetic
radiation. The quantum of light in the electromagnetic radiation region (or spectral region)
results in the rising of excitation of d electrons from a low energy level to the level with
higher energy. The spectrum obtained from this electronic transition is normally called the
electronic spectrum.
The electronic transition between d orbitals can also be caused by the ultraviolet light.
The electronic transition for a molecule leading to both vibrational as well as rotational
changes involves the energy of quantum of light. In general, the band in the electronic
absorption spectrum is broader than that in the infrared spectrum. Therefore, electronic
absorption spectrum is not often used for identifying the molecular structure.
The Crystal Field Theory related to the bonding of transition metal complexes has
been very helpful in explaining various physical characteristic of metal-containing
complexes. The simplest example is the one which contains only one d electron such as the
complex ion [Ti(H2O)6]3+. The interpretation of the spectra for the ion complexes containing
more than one or slightly greater than nine d electrons is found to be complicated and it
requires the energy-level diagrams. For a field free ion as depicted by Russell-Saunders, the
energy of this ion will be split into different energy level when it is placed in the crystal field.
The energy-level diagrams show how the splitting magnitude is affected by the crystal field
splitting, 0 or t of which the respective value is relevant to the ligand (the subscript o and t
refers to octahedral and tetrahedral geometry, respectively). Since the crystal field splitting
changes with the type of ligand in the complex, therefore the energy level diagram can be
referred to the changes of field free ion of Russel-Saunders with respect to the type of ligand
in the complex.
Crystal field state is normally denoted with a Mulliken symbol. This symbol
originates from the Group Theory and it can be regarded as an easy-to-be uses symbol.
Besides, it is the most precise description of energy state or level.

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The intensities of the electronic absorption band observable in the spectra of different
compounds or different bands ascribes to the same compound could vary remarkably. The
value of molar absorptivity (formerly known as molar extinction coefficient), max, ranges
from 1 x 104 or 1 x 105 for a strong band to 1 x 10-1 or 1 x 10-2 for that which is very weak in
intensity.
We can make a few correlations between the electronic transitions with the
magnitudes of absorption intensity. This correlation is generally shown by the selection rule
which predicts whether the transition is allowed or forbidden leading to the appearance of
absorption band of which the intensity is either strong or weak.

Selection Rule
(a)

Spin transition rule

As for the allowed electronic transition, the number of unpaired electron at the initial

stated should be about the same with that number in the final state wherein the spin-allowed
transition occurs between the states of same spin multiplicities. The spin multiplicity of
Russell-Saunders is given by 2S + 1, where S represents the combination of spin quantum
number for related ions; and the figure relevant to 2S+1 is written as superscript at the top left
side of the term symbol. Although the electronic transition between the states of different
spin multiplicities is supposed to be forbidden but the very weak absorption band resulting
from the spin-forbidden transition can also be observed in the spectra of some coordination
compounds. The presence of spin-forbidden absorption band results from the coupling of spin
with orbit.
In the Russell-Saunders procedures on the interaction of ion, the emphasis is focused
on both the coupling of orbital angular momentum for unpaired electrons, resulting in the
combined orbital angular momentum for unpaired electrons resulting in the combined orbital
angular momentum (its symbol of quantum number is L) and also on the coupling of the
same spin angular momentum (its symbol of quantum number is S). It has been assumed that
there is no coupling occurring between these two combinations.
As for the energy level of atoms with atomic number up to 30 (Zn), the coupling
between these two combinations resulting in the coupling of spin-orbit is considered not
important but it becomes significant for those with electronic configurations of 4d and 5d.
D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

In the absence of spin-orbit coupling, the quantum number S of combined spin angular
momentum is the most accurate and no absorption bands resulting from spin-forbidden
transition will be observed. However, this spin-orbit coupling will somehow be mixed up
with different states wherein S=1 and this mixing depends on the magnitude of spin-orbit
coupling. As a result, the spin-forbidden absorption bands for the first series of transition
metals are low in intensity in comparison with the third series which are of high intensity and
reaches the intensities of absorption band for spin-allowed electronic transition.

(b)

Laporte selection rule.

This rule as summarized by Laporte can be described in several ways. One of its

definitions is that the electronic transition is not allowed if it merely involves the
rearrangement of electrons in the same orbitals and in the same quantum shells. In other
words, only transition with the changes of azimuthal quantum number by +1 or -1 will lead to
the optical spectrum1. this criterion means that the electronic transition between the orbital of
similar symmetry is forbidden, for example, the d-d transition (g g, geradegerade) or p-p
transition (u u, ungeradeungerade) are not allowed. If this rule followed, than the
absorption spectrum originating from the electronic transitions in the same d orbitals will not
be observed.
All states resulting from the dn electronic configuration of the complex with a centre
of symmetry possess g character (gerade character); which is the property of d orbital. As for
octahedral complex, it has some general or normal vibration modes wherein some of them are
of u types (ungerade type) with antisymmetrical vibration mode in relation to its inversion
centre. The related molecule occupies the transient nucleus position upon vibration will be
losing its inversion centre. As a result, the d-d transition becomes partially allowed and is
regarded as vibronic transition owing to the mixing between the vibrational wave function
and the electronic wave function. For all molecules of any symmetry, there is a vibration
mode that fulfils the requirement whereby the forbidden electronic transition as derived from
Laporte rule will become allowed vibronic transition. As such, the leniency of the mechanism
in this symmetry selection rule can be very wide.
When a complex, for instance, a tetrahedral complex which lacks a symmetry center
in its equilibrium configuration, the d-d electronic transition becomes allowed due to the mild

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variation in its electronic wave function. The way in which the non-centrosymmetric ligand
field changes the d electronic wave function so that the state of d configuration will no longer
possesses acute g character could probably be due to the mixing of d and p orbitals. As such,
supposing there are two different electronic states of d configuration of a metal ion possess
very much different in p character, then the transition from one electronic state to another will
likely be the d-d (g u) or p-d (u g) transitions of which they are allowed in term of their
symmetries.

Charge Transfer
Since the central metal atom and the ligand are adjacent to each other and also there is
bonding between them, therefore, the electron transfer from the orbital within the metal to that of

ligand and vice-versa is likely to occur. That electron transfer is known as charge transfer.
The electronic transition will be symmetry allowed if the orbital involved are d and p
orbital for metal and ligand, respectively. Thus, it leads to strong absorption band. Besides,
the absorptions are observable in the electromagnetic spectrum in the ultraviolet region close
to the visible region owing to the large magnitude of the energy difference between the
orbitals.

Spectrochemical Series
The splitting magnitude of f orbital for metal ion changes with the nature of
coordinating ligand around the metal ion. The vast study on the selected spectra of different
complexes especially Cr(III) and Co(III) complexes of high kinetic stability showed that
various ligands could be arranged in an order depending on its ability to cause splitting of the
d orbital. For some of the ligands, in general, the order will be as follows:
I-<Br-<C1-<F-<OH-<C2O42- ~ H2O <NCS-<NH3<en<NO2-<CN-<CO
(Where en = H2NCH2CH2NH2)

Take note that whilst the ligands lie at the lower positions in this spectrochemical
series possess p orbital which can donate its electron density to d orbital of the
D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

metalviabonding, the ligands at higher positions in the same series can accept the electron
density from d orbital of the metal through bonding.
Experimental:

Determination of octfor some ligands and arrangement of partial

spectrochemical series

The coordination compounds to be studied include:

(i)

potassium tris(oxalate)chromate(III) trihydrate, K3[Cr(C2O2)3].3H2O

(Refer to the following section A for preparative method)

(ii)

potassium hexathiocyanatochromate(II) tetrahydrate, K3[Cr(SCN4)6]4H2O

(Refer to the following section B for preparative method)

(iii)

potassium chromium(III)sulphate (chrom alum) dehydrate, KCr(SO4)2.2H2O and

chromium chloride, trans-[CrCI2(H2O)4]CI

Section A:

Preparation of potassium tris(oxalato)chromate(III) trihydrate

Add slowly 3.0 g potassium dichromate to a solution containing 9.0 g oxalic acid in 20.0 mL
warm water. A vigorous reaction will be observed. Heat the solution until it reaches the
boiling pointand then add 3.5 g potassium oxalate while stirring until it dissolves. Cool the
solution to room temperature before adding 3-4 mL ethanol and subsequently cool it in an
ice-bath. The solution will be left for a while whereupon green blue crystals precipitate out
from the dark solution. Filter off the product and wash with ethanol and water mixture
(ethanol:water in ratio of 1:1) and finally with pure ethanol. Dry the product and record the
weight. Recrystallise the product from hot water before cooling it in ice-bath.

Section B:

Preparation of potassium hexathiocyanatochromate(II) tetrahydrate

Heat an aqueous solution of moderate concentration containing 12.0 g KSCN and 10.0 g
chrom alum for 2 hours in a steam bath. Concentrate the solution in a petri dish until reddish
crystals form upon cooling. The crystals are extracted with absolute alcohol in which they
dissolve easily leaving behind the K2SO4 residue. Slowly evaporate the alcohol until
crystalline K3[Cr(SCN4)6] are obtained. Filter the crystals before being recrystallized from
alcohol.
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Section C:

Spectrum

Use a glass cell or a silica cell with a 1.0 cm path length. Glass cells will absorb light of
wavelength 300 nm and below. All spectra should be obtained by setting the absorbance
range from 0-1 that is 1 absorbance range setting.
Compound
1) K3[Cr(C2O2)3].3H2O

Spectrum range

Concentration of solution

Cell

0.30 g in 10 mL (A solution)

Glass

750-650

Dilute 1 mL A solution to 10 mL
(B solution)

Glass

750-370

Dilute 1 mL B solution to 250

mL

Silica

370-190

(nm)

Work out for the molar absorptivity, s, for each of the above solution at the maximum
absorption, respectively. From the max thus obtained, assign the type of electronic transition
which is responsible for each of the absorption band.
Compound

Concentration of solution

Cell

Spectrum range
(nm)

0.10 g in 25 cm3 (C solution)

Glass

750-400

Dilute 0.5 cm3 C solution to

250 cm3

Silica

370-190

3) KCr(SO4)2.2H2O

0.25 g in 10 cm3

Glass

750-230

4) trans-[CrCI2(H2O)4]CI

0.10 g in 10 cm3

Glass

750-370

2) K3[Cr(SCN4)6].4H2O

Keep all the solutions for one week and then re-record all the spectra again. Comment on the
variation of the spectra obtained.

Question 1:

From some of the spectra obtained, determine the wavelength (in unit of nm)

of maximum absorption for each of the absorption bands and from the energy level diagram,
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determine the oct value for some of the ligands ranging from water (chrom alum),
ethylenediamine or en, oxalate and cyanide, when these ligands are coordinated to a d3ion,
that is Cr(III) ion.
octvalues for the ligands can also be obtained in term of energy (in unit of cm-1) from the
lowest energy of d-d electronic transition, because this conforms with the electronic transition
processes from

Question 2:

Qualitatively analyze the spectra 3 and 4 determine which one of these two

ligands, i.e. water or chloride ion yields the bigger splitting of the d orbital. A simple
spectrochemical series can now be arranged for the five ligands in this experiment.

References
1.

Cotton, F.A. & Wilkinson,G., Advance Inorganic Chemistry. Wiley-Interscience,

2nd ed. pp.826-827 (1996). 3rd ed.pp.838-839 (1972).

2.

Cotton,F.A., Chemical Applications of Group Theory. Wiley-Interscience, 1st ed.

p.231-238 (1963). 2nd ed. p.280-287 (1971).

3.

Sutton,D., Electronic Spectra of Transition Metal Complexes. McGraw Hill, p.8-17

and p.180-184 (1968).

D/NAK/BUKUPANDUANAMALI2015/KUT203/OGOS2015

PREPARATION AND REACTION OF

TRIS(ETHYLENEDIAMMINE)COBALT(III) INTO ITS OPTICAL
ANTIPODE

Experimental I:

Preparation of barium d-tartarate

20.0 g d-tartaric acid is dissolved in 100.0 mL distilled water. Slowly add 25.0 g of barium
carbonate into the solution while stirring. To ensure the solution is neutralized, heat and stir
the solution and the precipitate for another half hour. Filter the solution and wash the
precipitate with cold water. The precipitate is dried at 100 C.
37.0 mL of 24% ethylenediammine is added into a 250 conical flask. Subsequently
add into the solution, 15 mL concentrated HCl, aqueous solution of cobalt(II) sulphate (14 g
of CoSO4.7H2O in 25 mL water) and 2 g of charcoal. The solution is then aerated for at least
four hours in order that Co(II) is then oxidized to Co(III). Using either dilute HCl for
ethylenediammine, the pH of the Co(III) solution is then adjusted to between 7.0-7.5. In order
to ensure that the reaction goes to completion, the solution is heated over the steam bath for
another hour. Cooling the solution to room temperature. Filter to remove the charcoal.
Into the resultant tris(ethylenediammine)cobalt(III) chloride solution, add 14.0 g of
barium d-tartrate. Stir the solution while heating it on a steam bath for 30.0 minutes. Filter
out the barium sulphate precipitate; wash the precipitate with warm distilled water and add
the wash solution to the filtrate. The filtrate is then slowly evaporated to half its volume over
slow heat. The solution is slowly cool to room temperature. On cooling the diastereomer, Dtris(ethylenediammine)cobalt(III) chloride crystallizes out. The D-isomer is filtered and the
filtrate is set-aside for its L-isomer.
Recrystallisation of the D-isomer is carried out with approximately 15.0 mL warm
water and ethanol. The crystals obtained are then allowed to dry in air.

The iodide salt of the D-isomer can be prepared by the following procedure:
Dissolve the D-isomer into 15.0 mL hot water and add to it 0.5 mL concentrated ammonia
and sodium iodide solution (18.0 g Nal in 8.0 mL hot water) while carefully stirring the
solution. Using ice, cool down the solution and upon formation of the crystals filter out the
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D-isomer of tris(ethylenediammine)cobalt(III) iodide. Wash the crystals with 20.0 mL of

30% sodium iodide, ethanol and a final wash with acetone. The crystals are left to dry in air
and record the weight of dried crystals obtained.
The solution of L-tris(ethylenediammine)cobalt(III) chloride d-tartrate is added to 0.5
mL conc. ammonia solution and heat it to 80 C, then add 19 g sodium iodide. The solution is
then cooled using ice cubes. Filter out the impure L-isomer, wash it first with 10.0 mL of
30% sodium iodide, then a final wash with ethanol. The crystals are then allowed to dry. The
resultant crystals may contain its racemate. The racemate can be separated by adding 30.0 mL
water and heating the solution 50 C. The undissolved racemate is then isolated by filtration.
Add 5.0 g sodium iodide into the filtrate, heat to 50 C, and slowly cool it with ice cubes.
Filter and wash the crystals with ethanol and acetone then allow it to dry in air. The weight of
the crystals is recorded.

Experimental II:

Molecular Rotation Determination for the Two Diastereomers

Weight out accurately 0.5 g (accurate to 0.1 mg) of each isomer and transfer it quantitatively
into two separate 25.0 mL volumetric flasks. Distilled water is added to the 25.0 mL mark in
each of the volumetric flasks. Determine the optical rotation for both the solutions using the
2.0-decimeter polarimeter. Make sure the solutions do not contain any undissolved particles,
since these particles will cause light scattering. Fill the polatimeter tube with the prepared
solution. Make sure there are no bubbles present in the polarimeter tube.
Specific rotation [] is defined as the rotation (in degree unit) of a solution containing
1 g of substance in 1 cm3 solvent and when the solution is placed in a polarimeter of 1 dm
long.

Since the optical rotation is usually measured using the sodium F emission line at a
particular temperature, therefore for specific rotation must be stated asand []D .Where is
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the temperature in C. Hence the molecular rotation, [M] D , is given by the following
equation,

Experimental III:

Determination of Percent Composition of Iodide in Complex

Prepare 250 mL 0.01 M standard1 potassium iodide solution. Use this standard solution to
standardise2 the sodium thiosulphate solution of approx. 0.05 M. To prepare the sodium
thiosulphate solution, weigh approximately 3.0 g of the salt and dissolve it in 250 mL
distilled water.
Weigh out accurately (in the range of 0.20 0.25 g) the Co(III) complex and transfer
quantitatively into the 250.0 mL iodine flask. After dissolving the sample in about 35.0 mL
water, add 1.0 g of urea and stir. Then add 5.0 mL of 0.5 M sodium nitrite followed by 3.0
mL of 1.0 M sulphuric acid. Iodine gas is liberated as soon as the acid is added. Quickly
stopper the conical flask to prevent the iodine gas from escaping. Grease the stopper lightly
and add some water on the top of the stopper. Occasionally shake the conical flask for 15
minutes, and then cool it with ice. Observe that a gas is been liberated. Do not cover the
conical flask too tightly excessive pressure builds up in the container. The water on the
stopper will ensure that any of the iodine gas which escapes will be dissolved. After the
solution is cooled (as indicated by the absence of iodine gas), add 2.0 g of sodium acetate and
then 1.0 g of potassium iodide. Shake and swirl the solution until all the iodine gas is
dissolved. The solution is then titrated with the standardized sodium thiosulphate solution
(~0.05 M), add starch solution as the indicator as it approaches the end-point.

What are standard solutions? How do you prepare standard solutions? Refer to 1st year lab
work or any analytical textbook.
2
Standardise means to determine the exact concentration (molarity), usually to 4 decimal
places.

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(Caution:The Co(III) ion complex which is yellowish-orange maybe mistaken for residual
iodine in the solution. Hence the colour changes that occur in the solution must be carefully
observed such that the starch indicator is only added before all of the iodine is been liberated
in the reaction). At the end-point the colour changes from blue to yellow. Carry out the
analysis in duplicates. Calculate the percent iodine in the complex and compare with the
theoretical value. The crystallized complex from water with the analytical formula of
[Co(C2H8N2)3]I3.H2O.

Question:

What are the gases evolved during the analysis?

Tridentate metal complexes are complexes which will exhibit optical isomer because the
mirror image of the diastereomers are non-super imposible.

In the diagram above, the shaded area represents planes which is formed by the
backbone of the bidentate ligands of a tris(bidentate) complex. In fact it is only possible to
isolate the optical isomer for only these types of compounds from a number of metal ions
3

only, example Cr(III) with t2 configuration, Co(III) with t2 configuration and Rh(III) with
6

t2 configuration due to the kinetic stability of the complexes from these metal ions. In most

other cases, these types of complexes from other metal ions are found to be kinetically more
labile. Hence isolation of its optical isomer is so easily done since it is more prone to
racemisation.

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Question:
Do complexes types [MB2A2], [MBA4] and [MBA2C2], with M = metal ion, B = bidentate
ligand and A, C = monodentate ligands exhibit optical isomerism? Explain your answers by
drawing all the possible structures of these six coordinated complexes.
Note: All the charges on the above complexes have been removed since these charges will
depend on the charges of M, A, B and C.

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CHARACTERIZATION OF THE LINKAGE ISOMERS:

NITROPENTAAMINECOBALT(III) CHLORIDE, [CO(NH3)5NO2]CI2, AND
NITRITOPENTAAMINECOBALT(III) CHLORIDE, [CO(NH3)5ONO]CI2

Introduction
An ambidentate ligand is a ligand that contains two or more different atoms that can
be bonded to a metal centre. However, at any one time, only one atom-donating site will be
bonded to the metal centre. One example of an ambidentate ligand is the nitrite ion. The
nitrite ion can form a bond either through its nitrogen atom to give the nitro complex or
through its oxygen atom to give the nitrito complex. The nitrite ion attracts the researchers
from its historical point of view because it is the first example of such ion to display linkage
isomers such as [Co(NH3)5NO2]2+ and [Co(NH3)5ONO]2+. Jrgensen first identified these
compounds as linkage isomers, which was obtained from its complex ion in 1884.
The nitrite ion is a versatile species and is known to exist in various linkages. For
example the nitrite ion can be N bonded (I), O bonded (II), bidentate O and O bonded (III),
bridging with N and O bonded to different metals (IV) and bridging two different metals with
a single O atom (V).

The nitrite ion is a C2v symmetry and therefore has three basic vibrations, which are all
infrared active. Therefore, the number of bands will not be changed after coordinated. The

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use of infrared spectrum gives information regarding the structure of a compound, based on
the shifting of the frequency between coordinated and non-coordinated form of the ionic
ligand. The active vibrations are N-O symmetry stretching, N-O asymmetry stretching and ON-O bending. These three modes of vibrations will be seen at 1335 cm-1, 1250 cm-1 and 830
cm-1 in the FT-IR spectrum. The nitro complex displays absorption bands for the NO
symmetry and asymmetry stretching modes in the range of 1300-1340 cm-1 (for symmetric) and
1360-1430 cm-1 for the (asymmetric). The same frequency values obtained will indicate the
equivalence of the bond order in the N-O for the nitro complex. The nitro complex has a very
different bond as shown in (II) above. The absorption bands due to the NO stretching modes
are seen for the nitrito complex at 1400-1500 cm-1 for the N = O vibration and at 1000 1100
cm-1 for the N-O vibration.

Objective of the experiment

The objective of this experiment is to prepare the two linkage isomers of
[Co(NH3)5(NO2)]CI2. The spectra of these linkage isomers will be compared to those of
sodium nitrite (NaNO2) and chloropentaaminecobalt(III) chloride, [Co(NH3)5CI]. The
information from these spectra will determine whether the isomer contains the nitro group,
which is N bonded or it contains the nitrito group that is O bonded.

Experimental
The synthesis of the nitrite complex can be done from the chloropentaaminecobalt(III). The
schemes of the reactions are given below.

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Section A: Preparation of chloropentaaminecobalt(III) chloride, [Co(NH3)5CI]C12

In a 30.0 mL aqueous concentrated ammonia solution, add ammonium chloride (5.0 g). With
stirring, add cobalt(II) chloride 6-hydrate (10.0 g) in successive small portions. Do not add
the next portion until the added portion has dissolved in the solution. A yellow precipitate
will form easily.
To the slurry above, with stirring, slowly add hydrogen peroxide solution (8.0 mL,
30% v/v) from a burette. A strong reaction will occur. After the reaction has stopped add
slowly concentrated HClsolution (30.0 mL) to the red aquapentaamine solution. This will
produce a purple precipitate together with a greenish blue solution. Heat this product on a
steam bath for 20 min. Cool and collect the product by vacuum filtration. Wash it with icecold water (30.0 mL, 0-10 C), followed by HCI solution (30.0 mL, 6.0 M). Wash the
product with a small amount of ethanol, then acetone, so that the drying process will be
faster. Dry the product in the oven at 110 C for one hour. Report your yield and percentage
yield. Determine the melting point of your product. This product is pure enough to be used in
the next preparations.
Section B:

Preparation of the X isomer

Prepare an aqueous ammonia solution by adding 10 mL of concentrated ammonia solution to

30 mL of water. Dissolve chloropentaaminecobalt(III) chloride (1.5 g) into the aqueous
ammonia solution. If necessary, warm the solution to dissolve the salt completely. Then
neutralise the solution by adding dilute HCI solution (4.0 M). Add 1.5 g sodium nitrite to the
solution mixture and cool it in an ice bath for 1-2 hours. Filter off the red product and wash it
with cool water (0 10 C). Dry the product at room temperature.
Section C:

Preparation of the Y isomer

In 20.0 mL aqueous ammonia solution (2.0 M), add chloropentaaminecobalt(III) chloride (1.5
g). Heat the solution in a water bath until the compound dissolved completely. Cool the
resulting solution and add slowly HCI (4.0 M) solution until pH 4.0 is obtained, followed by
sodium nitrite (2.0 g). Heat the product slowly until a red precipitate appears again. Cool the
resulting product and add concentrated HCI solution (20.0 mL). Cool the solution again and
then filter off the yellowish crystals. Wash the product with ethanol before drying in the
oven. Record the melting points of the X and Y isomers.

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Section D:

Determination of the infrared spectrum

Obtain the infrared spectra of the two X and Y isomers (use KBr sample preparation
technique). Explain the differences in colour between the two isomers that you have prepared
and relate it to the FT-IR spectrum. Label your samples and spectra clearly.

References
1.

Nakamoto, K., Infrared Spectra of Inorganic and Coordination Compounds. Wileyinterscience, 2nd ed., p. 160 (1970)

2.

Cotton, F.A. & Wilkinson, G.,Advanced Inorganic Chemistry. Wiley-Interscience,

3rd ed., p. 639, (1972).

3.

Huheey, J. E., Inorganic Chemistry. Harpers Row, 2nd ed., p. 468 (1978), or 1st ed.,
p. 406, (1972)

4.

Nakamoto, K., Fujita, J. and Murata, H., J. Amer. Chem. Soc., 80(1959), 4817.

5.

Faust, J. P. and Quagliano, J. V., J. Amer. Chem. Soc., 76(1954), 5346.

6.

Penland, R. B., Lane, T. J. and Quagliano, J. V., J. Amer, Chem. Soc., 78(1956), 887.

7.

Beattie, I. R., and Satchell, D. P. N., Trans. Faraday Soc., 52(1956), 1590.

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