UNIVERSITY OF LIMPOPO

Department of Chemistry

SCHB031
Inorganic Chemistry
Practical Manual
2025
Contents
INTRODUCTION ........................................................................................................
SAFETY IN THE LABORATORY .............................................................................................................................. 3
LABORATORY NOTEBOOK ................................................................................................................................... 3
LABORATORY REPORTS ............................................................................................................................... 4
FORMAT ............................................................................................................................................................ 4
Organisation ................................................................................................................................................... 4
Style ................................................................................................................................................................. 4

EXPERIMENT 1................................................................................................................................................... 7
INERT ATMOSPHERE TECHNIQUES AND SEPARATION BY COLUMN CHROMATOGRAPY.
PREPARTION OF FERROCENE AND ITS REACTION WITH ACETIC ANHYDRIDE. ............................. 7
THIS EXPERIMENT IS DONE OVER TWO WEEKS...................................................................................................... 7
LEADING REFERENCES: ................................................................................................................................ 7
PROCEDURE ..................................................................................................................................................... 7
SYNTHESIS OF FERROCENE. ...................................................................................................................... 7
COMPLEMENTARY WORK. ................................................................................................................................... 8
SYNTHESIS AND CHROMATOGRAPHY OF FERROCENE DERIVATIVES. .............................................. 8
CHARACTERIZATION: ........................................................................................................................................... 9

EXPERIMENT 2..........................................................................................................
PREPARATION OF SOME COBALTAMMINE COMPLEXES .................................................................... 10
INTRODUCTION ............................................................................................................................................ 10
EXPERIMENTAL PROCEDURE .................................................................................................................... 11
a) Synthesis of Carbonatotetraamminecobalt(III) Nitrate, [Co(NH 3)4CO3]NO3 ......................................... 11
a) Synthesis of pentaamminechlorocobalt(III) Chloride, [Co(NH 3)5Cl]Cl2 .................................................. 12
CHARACTERIZATION OF THE COMPLEXES............................................................................................ 13
A) U/V-visible spectra .................................................................................................................................. 13
b) Infrared Spectra ........................................................................................................................................ 13
c) Electrical conductivity of solutions of ionic compounds .......................................................................... 14
EXPERIMENTAL PROCEDURE .............................................................................................................................. 15
REPORT ........................................................................................................................................................... 16
QUESTIONS ........................................................................................................................................................ 16

EXPERIMENT3 ..........................................................................................................
KINETICS OF AQUATION OF PENTAAMMINECHLOROCOBALT(III) CHLORIDE [CO(NH3)5Cℓ]2+ ....................... 18
LEADING REFERENCES: .............................................................................................................................. 18
INTRODUCTION: ........................................................................................................................................... 18
EXPERIMENTAL PROCEDURE .................................................................................................................... 21
REPORT ........................................................................................................................................................... 22
QUESTIONS .................................................................................................................................................... 23

EXPERIMENT 4..........................................................................................................
PREPARATION, CHARACTERIZATION AND BONDING MODES OF NICKEL(II) COMPLEXES. ...... 24
LEADING REFERENCES: .............................................................................................................................. 24
INTRODUCTION: ........................................................................................................................................... 24
PROCEDURE: .................................................................................................................................................. 24
Preparation Of Complexes. ........................................................................................................................... 24

EXPERIMENT 5..........................................................................................................
SYNTHESIS AND SPECTRAL STUDY OF COPPER(II) COMPLEXES. ..................................................... 25
PROCEDURE: .................................................................................................................................................. 26
PREPARATION OF cis-bis(GLYCINATO) COPPER(II) MONOHYDRATE: .............................................. 26
PREPARATION OF bis-(ACETYLACETONATO)COPPER(II). .................................................................. 26
SPECTRA OF COPPER(II) COMPLEXES. ................................................................................................. 26

1
REPORT:............................................................................................................................................................. 26

ELECTRONIC SPECTRA OF SOME TRANSITION METAL COMPLEXES .......................................... 27

THE ELECTRONIC SPECTRA OF THE FIRST-ROW TRANSITION METAL IONS ........................................................... 27
SPECTRA OF d3 COMPLEXES .............................................................................................................................. 28
Ion ................................................................................................................................................................. 28

2
 INTRODUCTION
Students are expected to observe Departmental laboratory regulations as well as the safety
outlined below.

SAFETY IN THE LABORATORY

1. Safety glasses MUST be worn when specified for an experiment.

2. There shall be no smoking, eating (including chewing of gum) or drinking in the

laboratory.

3. A laboratory coat MUST be worn at all times, and rubber gloves should be used when
handling corrosive liquids. Open-toed shoes or sandals, shorts and excessive loose or
flowing clothes are forbidden.

4. All chemicals should be assumed to be toxic unless known to be otherwise. Any reaction
which involves or produce toxic fumes should be performed in a fume hood.

5. Volatile solvents should NEVER be used near an open flame. Solvents should NEVER
be heated in a closed system.

6. You WILL be asked to leave the laboratory if any of these rules is violated.

LABORATORY NOTEBOOK

A key requirement for students taking these practical courses is possession of a hard cover
notebook. This will be used to record weights of samples and products in the laboratory, as
well as recording observations as they occur during the experiment. It must be emphasized
that laboratory note-keeping is a valuable part of the training of a scientist. In order to ensure
that good note-keeping is acquired by each student, laboratory notebooks will be inspected,
and signed by the supervisor at the end of each laboratory session. You will lose 5% of the
mark for a laboratory report if your notebook is not signed. It is therefore your responsibility
to ensure that your notebook is signed before you leave the laboratory. No excuses will be
entertained.

3
LABORATORY REPORTS

FORMAT

Reports should be written with a particular emphasis on clarity.

ORGANISATION

1) Repots must contain a front cover which lists the experiment name, the number, etc.

2) The report should not reproduce information from the laboratory manual

3) The report should contain:

a) All results obtained

b) Answers to questions

c) Experimental section

d) Discussion on results

4) Reports will be submitted next Tuesday and Wednesday following the practical on or
before 16H00 in the pigeon boxes next to third year labs – GROUND FLOOR.

STYLE

Most or the entire abstract should be written in past tense because it refers to work done.
Much of the introduction should be written in the present tense, because you will be referring
primarily to established knowledge relating to your work. The experimental section should be
written in past tense. Your results should be presented in past tense but the discussion should
swing back and forth between present and past tense. Established work you refer to should be
in the present tense but your own results should be in the past tense. Use complete sentences,
check spelling, and proofread before you submit your report. Avoid slang such as lab, prep,
rotovapped, pumped dry, etc.

Note well: Strict adherence to the above style and comments will be expected when grading
laboratory reports.

4
 WARNING AGAINST PLAGIARISM

PRACTICAL REPORT SHEETS ARE INDIVIDUAL TASKS AND NOT GROUP

ACTIVITIES. (UNLESS EXPLICITLY INDICATED AS GROUP ACTIVITIES)
Copying of text from other students or from other sources (for instance the study guide,
prescribed material or directly from the internet) is not allowed – only brief quotations are
allowed and then only if indicated as such.
You should reformulate existing text and use your own words to explain what you have
read. It is not acceptable to retype existing text and just acknowledge the source in a footnote
– you should be able to relate the idea or concept, without repeating the original author to the
letter.
The aim of the report sheet is not reproduction of existing material, but to ascertain whether
you have the ability to integrate existing texts, add your own interpretation and/or critique of
the texts and offer a creative solution to existing problems.
Be warned: students who submit copied text will obtain a mark of zero for the report
and disciplinary steps may be taken by the Department. It is also unacceptable to do
somebody else’s work, to lend your work to them or to make your work available to
them to copy – be careful and do not make your work available to anyone!

Practical Session Dates

Name of Experiment Date

Inert atmosphere techniques and separation by TBA

column chromatography. Preparation of ferrocene
and its reaction with acetic anhydride

Inert atmosphere techniques and separation by TBA

column chromatography. Preparation of ferrocene
and it reaction with acetic anhydride

Preparation of Cobaltammine complexes 02-03 / Apr / 2025

Aquation of [Co(NH3)5Cl]2+ 09-10 / Apr / 2025

Preparation ,Characterization and Bonding modes of 16-17 / Apr / 2025

Nickel(II) Complexes
Synthesis and spectral study of Copper (II) 23-24 / Apr / 2025
Complexes
Practical Test Date TBA on the week of 23-24 / Apr / 2025

5
 CONTACT PEOPLE

Position Title & Names Phone & Email Office# &

Building

Senior Dr. BP Moloto 015 268 3710 ([email protected]) Office No. 2022
Laboratory (N-Block)
Assistant

Lecturer Prof MP 015 268 2863 Office No. 2005

Mokhonoana ([email protected]) (N-Block)

Lecturer Mr C 015 268 2336 Office No. 1017

Maswanganyi ([email protected]) (N-Block)

6
 EXPERIMENT 1

INERT ATMOSPHERE TECHNIQUES AND SEPARATION BY COLUMN

CHROMATOGRAPY. PREPARTION OF FERROCENE AND ITS REACTION WITH
ACETIC ANHYDRIDE.

THIS EXPERIMENT IS DONE OVER TWO WEEKS

PART A

LEADING REFERENCES:

1) Wikinson, P.L. Pauson and F.A. Cotton, J. Amer. Chem. Soc. 1974, 76 1970.

2) Jolly, Inorg. Synth., 1968, 11, 120.

3) Bozak, J. Chem. Educ., 1966, 43, 73.

4) Huheey, Inorganic Chemistry, Principles of Structure and Reactivity, Harper and Row, 3 rd
Edition, 1983.

PROCEDURE

SYNTHESIS OF FERROCENE.
A 250 mL three-necked flask, equipped with a magnetic stirring bar and a connection form

one side to a source of nitrogen, is charged with 70 mL of degassed 1,2-dimethoxyethane

(DME) and 25g of KOH powder. While the mixture is stirred slowly and flushed with a

stream of nitrogen, 5.5 mL of freshly cracked cyclopentadiene is added. The other side neck

is stopped and the main neck is fitted with a 100 mL pressure-equalising dropping funnel with

the stop-cock open. After the air has been flushed out, the stop-cock is closed and a solution

of 7.5g of iron(II) chloride tetra hydrate in 25 mL of dimethylsulfoxide (DMSO) is placed in

the dropping funnel. The mixture is stirred vigorously. After five minutes, drop by drop

addition of the iron(II) chloride is begun. The rate of addition is adjusted so that all of the

solution is added in 20 minutes. Stirring is continued for another 15 minutes. The flow of

nitrogen is then stopped and the mixture is added to 90 mL of 6M HCl containing about 100g

7
of ice. After stirring the mixture for 5 minutes the precipitate is isolated by suction filtration

and washed with four 25 mL portions of water. Record the yield of your product.

COMPLEMENTARY WORK.

1. Measure the melting point of the product.

2. Heat a small sample in a test tube and note what happens.

3. Note the solubility of the substance in toluene and in water.

4. Give the overall reaction equation for Part A of this experiment.

5. What is the role of the KOH in the reaction?

6. Record the infrared spectrum of the product and assign the peaks.

7. Add 0.2g of your compound to water (10 mL) in a test tube, followed by conc. HNO3 (10
mL). Shake the tube gently, record and explain your observations.

NOTE: This must be incorporated in your write-up and not as a separate section.

PART B

SYNTHESIS AND CHROMATOGRAPHY OF FERROCENE DERIVATIVES.

Add ferrocene (1.5g, 8.05 mmol) to acetic anhydride (5 mL, 87 mmol) in a 100 mL

Erlenmeyer flask with a ground glass joint and to this mixture carefully add 1 mL of 85%

phosphoric acid with constant swirling. Fit a calcium chloride guard to the flask and heat it

on a steam bath for 10 minutes. Pour the hot mixture on to ice (about 80g) with stirring and

when all the ice has melted, neutralize the mixture by adding solid sodium bicarbonate. Cool

the neutralized solution in ice for about 30 minutes and remove the orange-brown solid that is

deposited by filtration, using a Buchner funnel. Dry the solid by suction. Prepare a column,

using alumina in petroleum ether (b.p. 40-60 °C). Dissolve the orange-brown product in a

minimum quantity of benzene (caution: benzene is a cancer suspecting agent, handle with

extreme care and in a fume hood) and add it to the top of the column with teat pipette. Allow

the solvent to run out of the bottom of the column until the level has fallen to the top of the

8
column material (do not allow it to run dry). Add petroleum ether to the column, allow the

solvent to pass through and collect the yellow band which is eluted. When all of the first

band has been eluted, increase the polarity of the eluent by adding a mixture of ether and

petroleum ether (2:1) to the top of the column. Elute the second red-orange band. Evaporate

the solvent on a rotary evaporator from each fraction to leave red-orange crystals.

Recrystallize the solid from the first band from ether and petroleum ether mixture and the

solid from the second band from petroleum ether.

CHARACTERIZATION:

1. Determine the melting point of each compound.

2. Record the infrared spectrum of each compound.

3. Record the 1H NMR of the two compounds separated by chromatography and the
ferrocene synthesized in part A.

9
 Experiment 2

PREPARATION OF SOME COBALTAMMINE COMPLEXES

INTRODUCTION

The types of complexes to be prepared in this experiment have played a considerable part in

the development of coordination chemistry. Werner, for example, developed his ideas of

coordination number and geometry through studying complexed of Co(III) and Pt(IV) in

particular, with amines, CI-, I-, pyridine, CN-, etc.

Coordination compounds of Co(III) and Cr(III) have been of particular interest because their

complexes undergo ligand exchange very slowly compared with complexes of many other

transition metal ions. For example, [Ni(NH3)6]2+ reacts virtually instantaneously with H2O to

form [Ni(H2O)6]2+. Under the same conditions, the analogous reactions of Co(NH3)63+ and

[Cr(NH3)6]3+ occur very slowly. This difference in behavior of complexes of different metal

ions has been qualitatively accounted for by ligand field theory and molecular orbital theory.

The slow reactivity of Co(III) complex has made the suitable for extensive investigations.

The structures of the octahedral Co(III) complexes which you will prepare are given below.

The synthesis of [Co(NH3)4CO3]NO3 will be carried out according to the unbalanced

equation, Co(NO3)2 + NH3 + (NH4)2CO3 + H2O2 → [Co(NH3)4CO3]NO3 + NH4NO3 + H2O

The Co(NO3)2 that is available commercially has the formula Co(NO3)2.6H2O and very

probably is a coordination compound having the ionic formulation [Co(OH2)6](NO3)2. Since

10
Co(II) complexes, like those of Ni(II), react very rapidly by ligand exchange, the first step in

the reaction might be expected to be

[Co(OH2)6]2+ + 4NH3 + CO32- → [Co(NH3)4CO] + 5H2O

This Co(II) complex could then be oxidised by the transfer of an electron to H2O2 to give the

relatively unreactive Co(III) ion, [Co(NH3)4CO3]+. The preparation of [Co(NH3)5Cl]2+ is

accomplished from the carbonato complex according to the following series of equations:

[Co(NH3)4CO3]+ + 2HCl → [Co(NH3)4(OH2)Cl]2+ + CO2 + Cl-

[Co(NH3)4(OH2)Cl]2+ + NH3(aq) → [Co(NH3)5(OH2)]3+ + Cl-

[Co(NH3)5(OH2)]3+ + 3HCl → [Co(NH3)5Cl]Cl2 + H2O + 3H+

The two complexes will be characterized by infrared and U/V –visible spectroscopy and by

electrical conductance measurements. The first two techniques in particular play a major role

in the modern methods of characterization and study of transition metal complexes and you

must therefore become familiar with them.

EXPERIMENTAL PROCEDURE

No precautions are necessary to protect the reaction mixtures from the atmosphere. (This is

required for preparations that involve reactants or products that reacts with moisture or

oxygen in the air). Operations that necessitate heating of the solutions should be carried out

in fume cupboard.

A) SYNTHESIS OF CARBONATOTETRAAMMINECOBALT(III) NITRATE,

[Co(NH3)4CO3]NO3
Dissolve 20 g (0.21 mole) of (NH4)2CO3 in 60 ml of H2O and add 60 mL of concentrated

aqueous NH3. While stirring, pour this solution into a solution containing 15 g (0.05 mole) of

[Co(OH2)6](NO3)2 in 30 ml H2O. Then slowly add 8 mL of 30 % H2O2 solution. (Handle

H2O2 with rubber gloves. If the affected area is not washed immediately with water,

11
hydrogen peroxide can cause severe skin burns). Pour the solution into an evaporating dish

and concentrate over a gas burner in a hood 90-100 ml. Do not allow the solution to boil (use

thermometer, temperature ~900C). During the evaporation time add, in small portions, 5g

(0,05mol) of (NH4)2CO3. Suction filter (with water aspirator; for better control of the

vacuum, use a pinch clamp on the rubber tubing between the trap and the filtration flask; see

Figure 1) the hot solution and cool the filtrate in an ice water bath. Under suction, filter off

the red product crystals. Wash the [Co(NH3)4CO3](NO3) in the filtration apparatus first with a

few millitres of water (the compound is somewhat soluble) and then with a similar amount of

ethanol. Calculate the yield. (Save a portion of your product for the conductance

determination).

A) SYNTHESIS OF PENTAAMMINECHLOROCOBALT(III) CHLORIDE,

[Co(NH3)5Cl]Cl2
Dissolve 5.0g of [Co(NH3)4CO3]NO3 in 50 ml of H2O and add concentrated HCl (5 to 10 ml)

until all the CO2 is expelled. Neutralize with concentrated aqueous NH3 and then add about

5ml in excess.

Heat for 20 minutes, again avoiding boiling; [Co(NH3)5(OH2)]3+ is formed. Cool the solution

slightly and add 75 ml of concentrated HCl. Reheat for 20 to 30 minutes and observe the

change in colour. Purple-red crystals of the product separate on cooling to room temperature.

Wash the compound several times, by decantation, with small amounts of ice-cold distilled

water, then filter under a water aspirator vacuum with a glass fritted funnel (medium

porosity). Wash with several millilitres of ethanol. Drying in an oven at 1200C to remove

solvent yields [Co(NH3)5Cl]Cl2. Calculate the yield. (Do not discard the product because

part of it will be needed for the kinetics experiment, Experiment 3).

12
CHARACTERIZATION OF THE COMPLEXES

A) U/V-VISIBLE SPECTRA
Before you attempt to run the spectra of your complexes read the notes on “Electronic spectra

of Some Transition Metal complexes” at the back of this manual.

Make up 5 x 10-3M solutions of the two complexes in water and run the spectra in the range

350 nm to 750 nm using 1 cm path length cells. The spectrum of [Co(NH3)5Cl]Cl2 may

change slowly with time, so the spectrum should be run as quickly as possible after making

up the solutions. If you are unsure how to use the instrument ask a demonstrator to help you.

Record the band positions and the absorbance at the band maxima and work out the extinction

coefficients of each peak using the formula:

 = (M x A)/(g x 1) in L.M. cm-1

Where M = molecular weight

g = concentration in g/dm3

1 = path length in cm

A = measured absorbance

 = molar extinction coefficient

Compare your spectra with those given in Table 3 of the notes on “Electronic Spectra of

Some Transition Metal Complexes” and comment on the results (see below).

B) INFRARED SPECTRA
The infrared spectra of your two samples must be run as nujol mulls between sodium chloride

plates. If you do no know how to run a nujol mull ask the demonstrator to show you. Two

very important points:

(a) The NaCl plates are expensive and require care in handling. Do not drop them, wash

13
 with water or aqueous organic solvent mixtures, touch the flat surfaces with your fingers

or scratch with a spatula. Clean with a little CHCl3, wipe with a tissue, and store them in

the desiccator after use.

(b) Run a spectrum of nujol by placing a small drop between two NaCl plates. Subtract

these peaks from your spectrum to get the spectrum of your sample.

The major peaks in the spectrum must be assigned. Help with your assignments can be

obtained from K. Nakamoto, “Infrared and Raman Spectra of Inorganic and Coordination

Compounds”, 3rd edition (see also; CRC Handbook).

C) ELECTRICAL CONDUCTIVITY OF SOLUTIONS OF IONIC COMPOUNDS

The determination of the number of ions constituting a given substance is largely a matter of

defining conductance and then comparing conductance of known ionic substances with those

of unknown compounds. The definitions usually begin with resistance, since this is the

quality that is experimentally measured. The specific resistance, p, is defined as the resistance

in Siemens of a solution in a cell that has 1 cm2 electrodes that are separated from each other

by a distance of 1 cm. The reciprocal of p is the specific conductance, L. The resistance, R,

of the same solution in a cell of nonstandard dimensions is obtained by multiplying by a

correction factor k, which depends upon the geometry of the cell. Experimentally, k is

evaluated:

R = kp (1)

By measuring R for a given solution whose p has been measured in a standard cell and then

calculating k from the preceding expression:

R = k/L (2)

The cell constant, k, is frequently obtained from (2) by measuring the resistance, R, of a 0.02

M KCl solution whose specific conductance at 250C is 0.02768 ohm-1. Having evaluated k

for the cell used in the study, the measurement of R will allow the calculation of the specific

14
conductance of any solution. In determining the conductance of a solution of an electrolyte, it

is desirable to compare conductance of a 1 cm3 cube of solution that contains one mole (or

formula weight) of solute. Thus the molar conductance, M, is defined as the conductance of a

1cm3 cube of solution that contains one mole of solute. Since the specific conductance, L, is

the conductance of a 1 cm3 cube of solution, the conductance per mole of solute may be

calculated by dividing L by the number of moles present in 1 cm3 solution:

M= 1000L/M

where M = the molarity of the solution.

Comparisons of the molar conductance’s with those of known ionic substances allow one to

determination the number of ions present in a given salt. General ranges of M for 2,3,4, and

5 ion conductors at 250C in water solvent are tabulated as follows:

Number of ions M

2 118 – 131

3 235 – 273

4 408 – 435

5 ~560

EPERIMENTAL PROCEDURE

You will be provided with a conductance cell, conductivity bridge and a standard 0.02 M

solution. Read carefully the instruction provided by the manufacturer for the operation of the

conductivity bridge. If you need help, ask the instructor. In making all resistance

measurements, thermostat the cell containing the solution at 250C for approximately 10

minutes before making a reading. Use distilled water in all solution preparations.

1. Prepare a 0.02 M KCl aqueous solution and obtain the cell constant, k, from the resistance

measured for the solution.

15
2. Prepare 500ml of 0.001 M aqueous solutions of [Co(NH3)4CO3] and [Co(NH3)5Cl]Cl2 and

measure their resistances. Make the measurements immediately after the solutions are

prepared, since significant decomposition occurs on standing overnight.

Be certain to rinse the cell well with distilled water between measurements and when you

have completed the experiment rinse it thoroughly and leave it filled with water.

Calculate the molar conductance’s of the two Co(III) complexes. These measurements are

fairly sensitive tests for the ionic purity of your compounds.

REPORT
Include the following:

1. Percentage yields of [Co(NH3)4CO3]and [Co(NH3)5Cl]Cl2.

2. Values of M for the preceding complexes and your conclusions as to the number of ions

in each compound.

3. IR spectra of [Co(NH3)4CO3]NO3 and [Co(NH3)5Cl]Cl2, indicating the absorptions

characteristic of NH2-, CO32-, and NO3-. What are the spectral similarities and differences

between these two complexes?

4. Visible spectra of the two complexes and comment on the results.

QUESTIONS
1. Outline methods for analysing [Co(NH3)5Cl]Cl2 for the ionic chloride and for the total

chloride content.

2. The conductance of a solution of [Co(NH3)5Cl]Cl2 changes overnight. Give a reason for

this observation. Would you expect the conductance to decrease or increase?

3. How do [Co(NH3)4CO3]NO3 and [Co(NH3)5Cl]Cl2 differ structurally? How would

You distinguish between these complexes experimentally?

4. Cobalt(III) complexes are relatively inert and react very slowly whereas the corresponding

cobalt(II) complexes are very labile (react very rapidly). Explain this observation.

16
N.B. Cotton and Wilkinson, Advanced Inorganic Chemistry should be consulted).

Reference: The above experiment has been adapted from Angelici, “Synthesis and Technique

in Inorganic Chemistry”, pp13 – 25.

17
 EXPERIMENT3

KINETICS OF AQUATION OF PENTAAMMINECHLOROCOBALT(III) CHLORIDE

[Co(NH3)5Cl]2+

LEADING REFERENCES:
1) R.J. Angelici, Synthesis and Technique in Inorganic Chemistry, Saunders, 1977.

INTRODUCTION:

The reactions of cobalt(III) and chromium(III) complexes are normally slow enough that they

can be followed by simple spectrophotometric techniques. Very labile complexes, e.g. those

of nickel(II) usually react so rapidly that special techniques are required. Such techniques are

Stopped Flow Spectrophotometry which can follow reactions with half-lives of the order of a

few micorseconds.

The large excess of water in aqueous solution (55 M) means that the potential ligand, H2O,

can often displace ligands already coordinated to the metal ion. In this experiment, you will

investigate the kinetics of a reaction involving the substitution of Cl- by H2O in acidic

solution:

[Co(NH3)5Cl]2+ + H2O → [CoNH3)5(OH2)]3+ + Cl-

Substitution reactions may proceed by a variety of mechanism. One possibility in an S N1

mechanism in which the rate determining step is the breaking of the Co-Cl bond. The

resulting open coordination site in the complex is then rapidly filled by a molecule of H 2O.

An SN2 mechanism involves the attack of an H2O molecule on the Co(III) complex to form a

very short-lived seven-coordinated intermediate, which rapidly loses Cl- to generate the

product. While these two mechanisms are very different, experimentally it is impossible to

differentiate between them if the reaction is conducted in H2O solvent. The SN1 mechanism

predicts the first-order rate law,

18
 Rate of reaction of [Co(NH3)5Cl]2+ = k1[Co(NH3)5Cl]2+

Where k1 is the first-order constant expressed in units of sec-1. Although the SN2 mechanism

requires the overall second-order rate law,

Rate of reaction of [Co(NH3)5Cl2+][H2O],

in the case where H2O is the solvent, it is possible to change its concentration. Hence in this

experimental situation it is impossible to determine whether the rate of reaction depends on

the H2O concentration or not. Because the nucleophile, H2O, is in such large excess

compared with the [Co(NH3)5Cl]2+ concentration, and so little of the H2O is consumed in the

actual reaction, the H2O concentration, [H2O], remains essentially constant during the

progress of the reaction. Thus one would predict the experimentally observed rate law to be

Rate = Kobs[Co(NH3)5Cl]2+

Where k0bs = k2[H2O].

Experimentally the reaction would appear to obey the first-order rate law, whereas in fact the

reaction may be proceeding by an SN2 mechanism. The problem of distinguishing SN1 and

SN2 mechanisms for aquation reactions in water solvent has not been satisfactorily solved;

hence the literature contains numerous kinetic studies of aquation reactions for which the

mechanisms are not well established.

A third possible mechanism is the acid catalysed aquation reaction. An example of this

mechanism is found in the following:

[Co(NH3)5F2+] + H2O  [Co(NH3)5(OH2)]3+ + F-

The experimentally determined rate law is

Rate of reaction of [Co(NH3)5F2+] = k[Co(NH3)5F2+][H+]

The acid catalysis apparently results from the addition of H+ to the coordinated F-

19
 [(NH3)5Co-F2+] + H+  [(NH3)Co-FH3+]

The protonation of the coordinated F- would be expected to weaken the Co-FH bond. One

might visualize the proton as pulling off the F- as HF, leaving an open coordination position

that is quickly occupied by a H2O molecule.

[(NH3)5Co-FH3+] + H2O → [(NH3)5Co(OH2)3+] + HF

If this last step is rate-determining, this mechanism predicts the rate law

Rate of reaction of [Co(NH3)5F2+] = k3K[Co(NH3)5F2+][H+]

This is the same expression that is observed experimentally. The only difference is that the

experimental rate constant, k, is, in terms of this mechanism, equal to the product of the

equilibrium constant, K, and the rate constant for the rate-determining step, k3:

k = k3K

If one wishes to evaluate the rate constant k3, some other experimental means of measuring

the equilibrium constant, K, must be devised, so that k3 may be calculated from the preceding

expression. In this experiment you will measure the rate of aquation of [Co(NH3)5Cl]2+ at

different H+ concentrations and express your rate data in the form of a rate law. You will then

postulate a mechanism, which is consistent with your rate law, for the reaction. Since the

starting complex and the product, [Co(NH3)5(OH2)] 3+ have different extinction coefficients at

550 nm in their visible spectra, noting the change in the intensity of the absorption at that

wavelength as a function of time provides a convenient means for determining the rate of the

reaction. It should be recalled that the colours and associated absorption spectra of transition

metal complexes usually result from electronic transitions between d orbitals of different

energies on the metal.

20
EXPERIMENTAL PROCEDURE

Although some reactions are catalysed by light and oxygen, this reaction is not, and

precautions eliminate them need not be taken. Scale down the quantities by a factor of 5.

In a bath set at 600C, thermostat for at least 15 minutes two 100 ml volumetric flask, one

containing 0.10 M HNO3 and the other 0.30 M HNO3 solution (concentrated HNO3 is

approximately 15.9 M). To each solution add sufficient [Co(NH3)5Cl]Cl2 (prepared in

experiment 2) give a 1.2 x 10-2 M complex concentration. Shake the flasks until all the

complex has dissolved, and then return the flasks to the thermostatted bath. When the

solution has again reached a temperature of 600C (approximately 15 minutes), begin

withdrawing samples with a pipette (use a rubber bulb, not your mouth). At approximately 15

minutes intervals withdraw 10 ml samples from each reaction mixture. Measure the visible

spectrum of each sample immediately after removing it from the thermostatted solution and

record the time of withdrawal. Take 8 aliquots from each reaction solution during the course

of the rate study.

The absorbance of each solution should be measured using the UV SP1800 or an SP 8 100

spectrometer at 550 nm. Set the spectrometer at 0 using distilled water in the cell. After each

measurement wash the cell thoroughly with water, then acetone and then dry using

compressed air. The full spectra of initial and final samples in the range 350 nm to 750 nm

can be run using the U/V-visible spectrometer if so desired.

In the kinetic studies of substitution reactions, it is usually valid to assume that the rate law

will exhibit a first-order dependence on the complex concentration. Since both SN1 and SN2

mechanisms predict the rate law

Rate = kobs[complex],

the evaluation of the measured rate constant, kobs, can be made from first-order kinetic plot of

your data. If the reaction is acid catalysed, the rate law, Rate = [complex][H+]n where n =

21
1,2,3 etc., will hold. Since H+ is not consumed during the reaction, the [H+]n term is a

constant in the rate law, which reduces the expression to Rate = kobs[complex], where kobs =

k[H+]n. Thus kobs can be obtained from a first-order kinetic plot of your data, and kobs may

depend upon the concentration of H+.

From your absorbance and time data you will determine a first-order rate that will either be or

not be dependent upon H+ concentration. In order to calculate the rate constant you will need

to determine the A value. This can be calculated from the known extinction coefficient of

[Co(NH3)5(OH2)]3+, which is 2.10 m2 mol-1 at 550 nm. Plot a graph of ln(At-A) versus time

and determine the first-order rate constant as the slope of this plot. At is the absorbance of the

solution at any given time, t.

Tabulate your results as follows:

Time/min Absorbance (At) (At-A) ln(At-A)

REPORT
Include the following:

1. Absorbance measurements or spectra taken during the kinetic run.

2. Kinetic plots of data used to determine the rate constants

3. Justification for using the plot of ln (At – A) vs time (t) to obtain the first-order rate

constants

4. Rate constants and rate law.

22
5. Proposed mechanism.

QUESTIONS
1. Account for the fact that trans-[Co(NH3)4Cl2]+ undergoes substitution of one Cl- by

water at a rate that is 1000 times faster than that of [Co(NH3)5Cl]2+. Both react by the

same mechanism.

2. The equation of [Co(NH3)5Cl]2+ is accelerated by Ag+. Propose the mechanism for

this reaction.

3. Consider the reaction:

[Co(NH3)5Cl]2+ + NH3 → [Co(NH3)6]3+ + Cl-

The rate law for this reaction may be written in the general form Rate = k

[Co(NH3)5Cl2+]x[NH3]y where the orders x and y are to be determined. Carry out the rate

studies with [Co(NH3)5Cl2+] = 0.001 M and several different NH3 concentrations, e.g., [NH3]

= 0.2, 0.3, 0.4, and 0.6 M. From the results of these runs, how would you determine x and y?

4. Why was HNO3, not HCl, used in this study?

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 Experiment 4

PREPARATION, CHARACTERIZATION AND BONDING MODES OF NICKEL(II)

COMPLEXES.

LEADING REFERENCES:

1. C.T. Eagle and F. Wamsley, J. Chem. Educ., 1991, 68, 336 and references therein.

2. L.M. Venanzi, J. Chem. Soc., 1958, 719.

3. K. Nakamoto, Infrared and Raman spectra of Inorganic and Coordination compounds, 2nd
Edition, Wiley Interscience, 1969.

INTRODUCTION:

Multi-atom ligands can coordinate to metal atoms in complexes through different atoms.

They can also be bonded to the metal through more than one atom. For instance, it is possible

for NO3- to coordinate as a monodentate or bidentate ligand. The coordination mode in turn

affects the geometry around the metal atom. Nickel(II) commonly forms complexes with

three different geometries; namely octahedral, tetrahedral and square planar. The bonding

mode of a ligand in a complex and the structure of the complex can be determined by the

indirect means of infrared spectroscopy, magnetic susceptibility and to a limited degree of

success by visible spectroscopy. In this experiment a combination of the above physical

methods will be used to determine:

a) the bonding modes of SCN- in Ni(SCN)2(PPh3)2, and

b) the geometries of Ni(SCN)2(PPh3)2 and Ni(NO3)2(PPh3)2.

PROCEDURE:

PREPARATION OF COMPLEXES.
i) Ni(SCN)2(PP3)2: Reflux a solution containing 2.91 g (0.01 mole) of nickel nitrate
hexahydrate in butanol (150c.c) with finely powdered potassium thiocyanate (2.92 g, 0.03
mole) for 2 hours. Cool the mixture, filter, and add the filtrate to a boiling solution of

24
 triphenylphosphine (5.25 g, 0.02 mole) in butanol (50cm3). The product is obtained on
slow cooling of the resulting solution. Scale down the quantities by a factor of ten.

ii) Ni(NO3)2(PPh3)2: All operations should be performed in a fumehood. Dissolve 1.0 g of

NiCl2.6H2O in 2 mL of H2O and dilute the solution with 25 mL of glacial acetic acid. To
the above solution, add 2 equivalents of PPh3 in glacial acetic acid and stir the mixture for
15 minutes. Filter to isolate the product and wash thoroughly with glacial acetic aicd.

CHARACTERIZATION

INFRARED AND VISIBLE SPECTRA:

i) Run the infrared spectra of all the complexes above and determine the bonding mode
of SCN in these complexes.

ii) Run the visible spectra of Ni(SCN)2(PPh3)2 and Ni(NO3)2(PPh3)2. For

Ni(SCN)2(PPh3)2 use acetonitrile as solvent and a concentration of 1 x 10-3 M and for
Ni(NO3)2(PPh3)2 use nitromethane as solvent and a concentration of 5 x 10-3M.
Determine the geometries of these two compounds from this information.

EXPERIMENT 5

SYNTHESIS AND SPECTRAL STUDY OF COPPER(II) COMPLEXES.

25
PROCEDURE:

PREPARATION OF CIS-BIS(GLYCINATO) COPPER(II) MONOHYDRATE:

A 3.0g sample (12.0 mmole) of Copper(II) sulfate pentahydrate is dissolved in 17 mL of 1M

hydrochloric acid. To this solution 1.5g (20.0 mmole) of glycine is added and then warmed

for about 1 hr. Sodium hydrogen carbonate is added until precipitation is complete (avoid a

large excess). The precipitate is suction-filtered, recrystallized from hot water, and dried in an

oven.

PREPARATION OF BIS(ACETYLACETONATO)COPPER(II).
A solution of acetylacetone is prepared by adding 2.5g (25.0 mmole) of acetylacetone to 100
mL of 0.25M NaOH solution (25.0 mmole). This solution is added to a solution of 3.1g (12.5
mmole) of copper(II) sulfate pentahydrate in 100 mL of water. The precipitate is suction
filtered, recrystallized from dioxane, and air dried.

SPECTRA OF COPPER(II) COMPLEXES.

Prepare the following stock solutions:

i) 0.10M NH3

ii) 0.01M Cu(NO3)2

Run the spectra of the following four solution:

Cu2+ - glycine complex 0.01M in CH2Cl2 and Cu2+ - acetylacetone complex 0.01M in CH2Cl2.

REPORT:

i) Your report should include an interpretation of the spectra in terms of ligand field
strength, using crystal field theory. Assume that all complexes have octahedral
geometries.

ii) Comment on these shifts in max obtained and construct a spectrochemical series.

iii) Identify all the absorbing species responsible for each spectrum.

26
 ELECTRONIC SPECTRA OF SOME TRANSITION METAL

COMPLEXES

INTRODUCTION

One of the most important techniques for the study of compounds of the transition elements is
electronic spectroscopy. A definition of a transition element is “an element which has partly
filled d or f orbitals in some or all of its compounds” and it is these partially filled orbitals
which lead to the electronic spectrum and, if the absorption is in the visible region of the
spectrum, to coloured compounds.

In inorganic chemistry we can use electronic spectroscopy to

(i) Determine the structure, geometry and even the absolute configuration of a
compound.

(ii) Study equilibria in solution.

(iii) Study the kinetics of formation or decomposition of compounds,and

(iv) Determine the purity of our products.

In this practical class you are required to run an electronic spectrum of your products to
ensure that you have a pure sample, in the same way as any inorganic researcher would. In
these practicals the spectra that are important are those of Co(III) (expts. I and II), and Cr(III)
(expt.III), and in these notes we will discuss the spectra of these ions.

THE ELECTRONIC SPECTRA OF THE FIRST-ROW TRANSITION METAL IONS

A full discussion of the spectra is outside the scope of the third year and, in fact, is only

discussed at this University at the fourth year honours level.

27
SPECTRA OF D3 COMPLEXES
TABLE 1
1() 2()
ION

Cr(H2O)63+ 406(15) 574(13)

Cr(H2O)5Cl2+ 428(21) 607(16.4)
cis-Cr(H2O)4Cl2+ 450(26) 635(18)
trans Cr(H2O)4Cl2 450(22) 635(24)
Cr(NH3)63+ 350(32) 462(392)
Cren33+ 350(52.5) 458(68.5)
Cr(NH3)5H2O3+ 360(29) 479(34)
Cr(NH3)5(OH)2+ 399(41) 507(43)
Cr(NH3)5Cl2+ 376(43.6) 515(38)452(sh)
cis-Cr(NH3)4(H2O)23+ 364(26) 493(36)
trans-Cr(NH3)4(H2O)23+ 368(30) 476(20.6)
1,2,3 Cr(NH3)3(H2O)33+ 375(22) 518(34.5)
1,2,6 Cr(NH3)3(H2O)33+ 373(25.6) 503(25.6)
trans Cr(NH3)2(H2O)43+ 382(18.5) 521(21)

As can be seen from this table accurate measurement of band position and intensity can be a

valuable method for the identification of your products.

Note that the relative intensity of 1 and 2 can distinguish between the cis and trans isomers

of Cr(H2O)4Cl2+ even though the band positions in the two ions are identical.

28