DEPARTMENT OF CHEMISTRY

CHEMISTRY 211
Inorganic Chemistry

UNIVERSITY of the WESTERN CAPE

PRACTICAL MANUAL
GENERAL INFORMATION

Laboratory requirements:

1. Safety goggles
2. Laboratory coats

Laboratory Safety Guidelines

• Safety goggles and lab coat must be worn at all times while in the laboratory.
• Long hair must be tied back and loose clothing should be secured, to avoid becoming
part of the experiment.
• Shoes must completely cover the foot. No sandals are allowed. Do not eat food, drink
beverages, or chew gum in the laboratory. Report spills and releases without delay
• Close all chemicals containers securely when not in use.

WASTE DISPOSAL

We all have a responsibility towards a clean and safe environment. You will be given specific
instructions on how to dispose of your chemical wastes during each pre-prac briefing. Here
are also some general rules that you must take note of:

1. Place broken glass into the specially marked bins. Do not put anything else (paper
included) in the broken glass bins.
2. Drain all harmless chemicals in solution into the sink followed by plenty of running
water.
3. Pour organic waste solutions into the specially labelled container in the fume cupboard.
4. Pour toxic inorganic waste solutions into the specially labelled container in the fume
cupboard.
5. Discard paper and any other solid waste into the bin at the end of your workbench.
Ensure that matches are extinguished before disposing of them in this way.
6. Shut off all gas and water lines when not in use.

Practical’s

The practical’s are compulsory for all the students. Students who are repeating the course
must apply for exemption from practical’s by emailing the coordinator i.e. Prof Titinchi. All
practicals will take place in the Chemical Sciences building, level 2 and start at 2pm sharp, so
please arrive at least 10minutes prior to allow demonstrators to allow you into the laboratory
and check your work from the previous week. No late comers will be allowed into the lab.

Flow diagram
Students are required to create a flow diagram every week and present it at the start of the
practical in order to access the lab. By creating a flow diagram you will become acquainted
with the practical. You can be creative and use your own style and design, but remember to
keep it simple and include only essential information. An example of a flow diagram is shown
below:
Practical Report Format

Practical reports are due the WEEK AFTER you complete the physical practical. Your report
should have the following subsections and be no longer than 2 pages long in TOTAL. You
can hand in your practical report to your demonstrator or the teaching assistant when you
enter the lab.

Marks Total =
Practical Report Description
100%

You will not be allowed to enter the lab without a

Flow diagram flow diagram of the methods. This should be 5%
stapled to your report when it is submitted

Title e.g Practical 1: The Copper Cycle 5%

A short 1-line description of the purpose of the

Aim 10 %
experiment

Here we require only a half page description in

your own words summarising the underlying
Introduction (what is already known about the topic) and/or 20 %
background information about the topic of the
practical.

Results and Report the findings in the practical and discuss

40 %
discussion the reasons for the results you have gotten

Here the questions/tasks in the manual for each

associated practical needs Iif there are no
Exercise/Questions 15%
questions at the end of each practical, these will
be sent via Ikamva.

Please include max of 2 references (Harvard

References 5%
referencing style)
PRACTICAL 1

COPPER CYCLE
 PRACTICAL 1:

Copper Cycle

_________________________________________________________

CYCLE OF COPPER REACTIONS

The cycle involves the conversion of copper metal through a series of intermediate copper
compounds back to copper metal. By weighing the copper at the start and at the end of the
experiment, the yield (and efficiency of the student) may be calculated. Make notes throughout
the experiment of all colour changes, precipitate formation, and gas evolution, and attempt to
differentiate between significant and insignificant observations.

PROCEDURE

1. In a fume hood, using a 400 cm3 beaker, prepare Cu(NO3)2 by adding 4.0 cm3

concentrated nitric acid to a weighed piece of copper wire (two decimal places). After

the reaction is complete, add distilled water until the beaker is about half full.

2. Add 18 cm3 of 5.0 M NaOH. A precipitate is formed.

3. Add two or three boiling chips (chips should be silicone, not porcelain or marble).

Then, with stirring, heat just to boiling to convert the precipitate formed in 2 to an

insoluble black precipitate. This can be done outside the fume hood.

4. Allow the black precipitate to settle, then decant the supernatant liquid. Add about

200 cm3 very bot distilled water, settle, and decant once more.

5. Add 35 cm3 2.5 M H2SO4 to convert the black precipitate to CuSO4.

6. In a fume hood, add a few pieces of aluminium foil, about 2 cm square, and several

drops of cone. HCL Soon, copper starts depositing on the surface of the foil as

simultaneously the foil dissolves with evolution of a gas.

 7. Pieces of foil are added until the aqueous NH3 test for Cu2+ (still easily seen in the

presence of Al(OH)3 precipitate) is negative

8. When no gas evolution can be detected visually, filter the product using a scintered,

weighed glass crucible.

9. Wash the product with about 5 cm3 distilled water. Repeat.

10. Wash the product with about 5 cm3 acetone (KEEP AWAY FROM FLAMES!).

11. Put the crucible in the oven at 60°C overnight, to dry the product.

12. After cooling, obtain the product weight to two decimal places.

REPORT

Your report must include balanced equations for all the reactions involved. Account for all
colour changes, precipitate formation, and gas evolution. Account for the discrepancy between
your yield of copper and the theoretical yield of 100%. Explain the use of aluminium in Step 6,
and the aqueous ammonia test in Step 7.

REFERENCE

RJ. Tylkodi, J. Chem. &I., R (1991), Page 106.

This reference is available in the reverse section of the library

 PRACTICAL 2

REACTIONS OF GROUP V
ELEMENTS
 PRACTICAL 2

Reactions of Group V elements

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Figure 1: Structures of some of the oxyacids of phosphorus (a) orthophosphoric (b)

pyrophosphoric (c) bypophosphorus (d) orthophosphorous (e) pyrophosphorous.

II. REACTIONS OF GROUP V ELEMENTS IN +III AND +IV OXIDATION STATES

The reactions to be performed in this practical will illustrate the reactivity and the relative
stabilities of the +Ill and +V oxidation states of these elements. For each of these tests
carefully record observations and interpret the results obtained. Where possible you should
give complete chemical equations to describe the various reactions that you have
performed.
CAUTION: Arsenate salts are very toxic. Wear protective gloves when working with this and
wash your hands thoroughly before leaving the laboratory.

METHOD:

1. To each of the following solutions, 0.1 mol.dm-3 sodium nitrite (1 cm3), 0.1 mol.dm-3
sodium phosphite (1 cm3) and 0.1 mol.dm-3 sodium arsenite (1 cm3), add 2 mol.dm-3 acetic
acid (8 drops) and 2 mol.dm-3 potassium iodide solution (0.5 cm3).

2. Repeat test (1), but instead of adding potassium iodide, add 1 mol.dm-3 potassium
permanganate (4 drops), and if the permanganate is not decolorized gently warm the
solution.

3. To each of the following solutions, 0.1 mol dm-3 sodium nitrite (2 cm3), 0.1 mol dm-3
sodium phosphite (2 cm3) and 0.1 mol dm-3 sodium arsenite (2 cm3) add 2 mol.dm-3
hydrochloric acid (6 drops). Pass hydrogen sulphide through each of these solutions and
through 0.1 mol.dm-3 antimony sulphate (2 cm3) and 0.1 mol.dm-3 bismuth nitrate (2 cm3) in
hydrochloric acid.

4. From the results of tests (1), (2) and (3) place the elements nitrogen, phosphorus, arsenic,
antimony and bismuth in their +3 oxidation states in the order of increasing reducing power.

5. To each of the solutions 0.2 mol.dm-3 sodium nitrate (2 cm3), 0.1 mol.dm-3 sodium
orthophosphate (2 cm3) and 0.1 mol.dm-3 sodium arsenate (2 cm3) add 2 mol.dm-3
hydrochloric acid (8 drops), and pass hydrogen sulphide for approximately 2 min.

6. Acidify the three solutions as in test (5). Add 2 moldm-3 potassium iodide (0.5 cm3) and
chloroform (0.5 cm3) and shake the solutions.
 PRACTICAL 3

COPPER AND COBALT AMINE

COMPLEXES
1. INTRODUCTION

The electronic structures, ionization energies and electronegativities of the Group V elements
are given in Table 1.

Table 1: Electronic configurations, ionization energies and electronegativities (Alldred-

Rochow) of the Group V element

Ionization Energies in kJ.mol-1

Element Electronic Structure 1st 2nd 3rd Electro-negativity

N [He]2s22p3 1404 2858 4577 3.07

P [Ne]3s23p3 1062 1897 2911 2.06

As [Ar]3d104s24p3 1000 2010 2800 2.20

Sb [Kr]4d105s25p3 834 1740 2380 1.82

Bi [Xe]4f145d106s26p3 772 1600 2450 1.67

Here, as in all groups of the periodic table, the electropositive character of the elements
increases on moving down the group. Nitrogen and phosphorus are non-metals, arsenic is a
metalloid whilst antimony and bismuth are metals. Nitrogen and phosphorus usually form
covalent bonds to other elements, whereas arsenic, antimony and bismuth show increasing
ease of cation formation. The ionization energies in Table 1 show that it is very difficult to
remove more than three valence electrons, and the +5 ions do not exist. The cations Bi3+ and
Sb3+ are present in the salts Sb2(SO4)3 and Bi(N03)3.5H20. On moving down the group, the +3
oxidation state becomes more stable and easy to prepare, whereas Bi2O5 is difficult to prepare
in the pure state because it is a powerful oxidizing agent. Some of the general group trends
are reflected in the properties of the oxides. P2O5 and P203 are acidic and easily hydrolysed.
In contrast, Bi2O3 has no acidic properties, and it is basic and soluble in acids to give the
corresponding bismuth salts.

All the Group V elements form hydrides of the type MH3 and their basic character decreases
on moving down the group. Ammonia is inter-molecularly hydrogen-bonded and easily
liquefied. The other hydrides, being weaker bases, which do not form hydrogen bonds, are
more difficult to liquefy. Liquid ammonia is frequently used as a non-aqueous solvent, and
closely resembles water. Nitrogen forms three other hydrides, hydroxylamine, hydrazine and
hydrazoic acid. NH2OH and N2H4. are weaker bases than
 PRACTICAL 3

Copper and Cobalt Ammine Complexes

_________________________________________________________

SYNTHESIS OF AN AMMiNE COMPLEX OF COBALT (III)

UNBALANCED EQUATIONS:

CoCl2.6H2O + H2O2 + NH4Cl + NH3 → [Co(NH3)6]Cl3 + H2O

1. Prepare the complex of Co(III) using the directions supplied.

2. The sample must be thoroughly dried before recording the yield, otherwise the yield
will be artificially high.
3. When the preparation has been completed, the dried product must be placed in a
specimen tube which must be labelled with your name, the name of the complex and
the yield, and handed in with your report.
4. Experiments using noxious reagents (e.g. cone. NH3) must be confined to a fume
cupboard as far as possible.

DISCUSSION

In aqueous solutions containing no complexing agents, the oxidation of Co(II) to Co(III) is very
unfavourable:

[Co(H2O)6]2+ = [Co(H2O)6]3+ + e- Eθ = -1.84

However, in the presence of complexing agents, such as NH3, which form stable complexes
with Co(III), the stability of the higher oxidation state is greatly improved:

[Co(NH3)6]2+ = [Co(NH3)6]3+ + e- Eθ = -0.1 V

Fortunately, the substitution reactions of Co(Ill) are very slow and so these complexes can be
isolated. However, in the presence of base, ammine complexes become more labile and so
some reduction occurs for this reason, recrystallisation is always carried out from acidified hot
water.

Owing to the inert nature of the Co(Ill) ion and the instability of simple Co(Ill) salts, the
preparations of Co(III) complexes invariably involve the preparation of the Co(II) analogue
(Co(II) substitution reactions are rapid) followed by oxidation. Air oxidation usually suffices
but to shorten the preparation time H2O2 is often used.

It has recently been discovered that suspended activated charcoal exerts a remarkably strong
catalytic influence in forming Co(Ill)-N bonds (but not bonds between this ion and the other
atoms). Thus, in air, oxidation of a mixture of cobalt(ll) chloride, ammonia, and ammonium
chloride in aqueous solution, some 12 hours are required to complete conversion to the
cobalt(Ill) state, and finally a rather tedious separation has to be effected of the two complex
salts, [Co{NH3)6]Cl3 and [CoCl(NH3)5]Cl2. In the presence of charcoal and with the use of
hydrogen peroxide as oxidising agent, a quantitative yield of the pure hexamminecobalt (Ill)
chloride can be obtained in·about 30 minutes.

The preparation carried out in this experiment illustrates the catalytic action of charcoal on the
formation of ammines of cobalt(III).

PREPARATION

HEXAAMMINECOBALT(III) CHLORIDE, [Co(NH3)6]Cl3

REAGENTS REQUIRED

4g NH4Cl; 6g [Co(H2O)6]Cl2; 1g animal charcoal; 14 cm3 conc. ammonia (d. 0.880); 12 cm3 5
percent H2O2; conc. hydrochloric acid; 10 cm3 methanol

METHOD

Weigh 4 g ammonium chloride into a 100 cm3 conical flask. Add 10 cm3 water, bring to boil
Weigh 3 g finely ground [Co(H2O)6]Cl2 and add it to the mixture. Stir to dissolve. Weigh 1 g
finely ground animal charcoal and add this to the hot solution of [Co(H2O)6]Cl2. Cool in an ice-
bath to 10-20°C. Working in a fume cupboard add 14 cm3 concentrated ammonia. Cool in a
salt-ice-bath to 0-10°C. While shaking the flask, slowly and (over a period of about 5 minutes)
12 cm3 of 5 percent H2O2 - maintain the temperature of 0-10°C. Since frothing occurs, heat
the mixture gradually to 60°C on a water bath. Maintain the temperature at 50-60°C for 20
minutes, shaking intermittently until pinkish colour is removed. Crystals may separate. Cool in
an ice bath for at least 10 minutes. Filter off the crude product onto a Hirsch funnel using a
water pump, removing the residual solid from the flask using the filtrate. Without washing the
residue transfer it to a 100 cm3 beaker containing a boiling solution of 2 cm3 conc. HCI in 50
cm3 water. When all the solid except the charcoal bas dissolved (takes approximately 5
minutes), filter the hot liquid through a Buchner funnel using a water pump. Transfer the hot
filtrate to a 100 cm3 beaker. If precipitation occurs during transfer, reheat solution until it
redissolves. Add 6 cm3 conc. HCl and cool in an ice bath for approximately 20 minutes.

Collect the precipitated product on a Buchner funnel and wash with 10 cm3 methanol Transfer
to a watch-glass, dry in the oven at 60°C for 15 minutes, place in a weighed specimen tube,
label and record yield. The sample is pale orange.in colour.

PREPARATION OF [Cu(NH3)4)SO4. H2O

UNBALANCED EQUATION

CuSO4.5H2O + NH3 → [Cu(NH3)4]SO4.H2O +H2O

Weigh out 3.5 g of CuSO4.5H2O on a top-pan balance. Weigh the solid either on piece of paper
or in a small beaker and not directly on the balance pan. Transfer the solid copper sulfate to
a 125 ml Erlenmeyer flask and add 10ml of water. Heat the flask to dissolve the solid, then
cool to room temperature.

Carry out the remaining steps under the hood. Add 13 ml of concentrated NH3 solution, a few
ml at a time, swirling the flask to mix the reagents, until the first precipitate has completely
dissolved. All the copper should now he present in solution as the complex ion Cu(NH3)42+.

The sulfate salt of this complex cation can be precipitated by the addition of a liquid. such as
ethyl alcohol, in which Cu(NH3)4SO4.H2O is insoluble. Add 5 ml of 96% ethyl alcohol to the
solution; this should result in the formation of a deep blue precipitate of Cu(NH3)4SO4.H2O.
Filter the solution through a Buchner funnel using suction. Wash the solid in the funnnel by
adding two 3 ml portions of 95% ethanol Dry the solid by pressing it between two pieces of
filter paper. When the solid is thoroughly dry, weigh it to 0.1 g.
RELATIVE LABILITY OF COMPLEX IONS (The ease with which ligands are replaced in
coordination complexes)

Dissolve a small portion (about 0.5 g) of the complex [Cu(NH3)4SO4].H2O in a few ml of water.
Note the colour and observe the effect of the addition of a few drops of 10 M HCl Now repeat
the experiment using [Co(NH3)6]Cl3.

CAUTION: In these experiments you will be using 15 M NH3, 10 M HCl and a 5% solution of
H2O2. These are caustic reagents, so use them carefully. Avoid getting them on your skin or
clothing, and don't breathe the vapours of NH3 or HCl If you do come into contact with any of
these reagents, wash them off thoroughly with water.

ASSIGNMENT

1. Name the following compounds:

(a) [Cr(NH3)6]Cl3
(b) K[Co(EDTA)]
(c) trans-Ni(en)2Cl2
(d) [Pt(py)4][PtCl4]
(e) [CoCl(NH3)5]Cl2

2. Give the formula of Diamminetriaquahydroxochromium(III) nitrate.

3. Why is [Co(NH3)6]3+ more stable with respect to reduction than [Co(H2O)6]3+?

 PRACTICAL 4

OXALATO COMPLEXES of IRON

 PRACTICAL 4

Oxalato Complexes of Iron

_________________________________________________________

INTRODUCTION

Oxalic acid is a dibasic acid, in other words it contains two ionisable hydrogen atoms. It is

a dicarboxylic acid.

The dianion of oxalic acid Ox2- c.an act as a bidentate chelating ligand to several metal ions
including those of iron.

Iron has two common oxidation states, II and lll. Both iron (II) and iron (Ill) form oxalato
complexes. The iron (II) compound formed in this experiment has the formula Fe(Ox).2H2O.
The Fe2+ is octahedrally coordinated with two water molecules in the axial positions. The
overall structure is a chain polymer with each Ox2 bridging between two Fe2+ ions. The
negative changes are delocalised over the carboxylate group.

The Fe3+ complexes contain an octahedral complex anion with three chelating Ox2- groups,
such octahedral complexes exhibit optical isomerise
EXPERIMENTAL

Preparation of Iron (II) Oxalate and Potassium Trisoxalatoferrate(Ill) Trihydrate

Materials Required: Ferrous ammonium sulphate

Oxalic acid dihydrate
Potassium oxalate monohydrate
Hydrogen peroxide (20 vol)
Ethanol

(a) Iron(ll) Oxalate Dihydrate

Dissolve ferrous ammonium sulphate (8 g) in warm water (30 cm3), which has been acidified
with 2 mol.dm-3 sulphuric acid (1 cm3). Add a solution of (5 g) oxalic acid in 30 cm3 of water)
with rapid stirring. Gently heat the mixture to the boiling point and then allow the yellow
precipitate of ferrous oxalate to settle. Remove the precipitate by filtration on a Bucher funnel

(b) Potassium Trisoxalatoferrate(lll)trihydrate

Suspend one portion of ferrous oxalate in a warm solution of potassium oxalate (5 g in 15 cm3
water). Add 20 volume hydrogen peroxide (12.5 cm3) from a burette whilst the solution is
stirred continuously and maintained at about 40°C. The solution now contains a precipitate of
ferric hydroxide. Remove this by heating the solution to boiling, add 10 per cent oxalic acid
(10 cm3) and then a further small amount of oxalic acid (about 3 cm3) dropwise from a burette
until the precipitate just dissolves. During the addition of oxalic acid the solution should be
maintained near the boiling point. Filter the hot solution. Add ethanol (15 cm3) to the filtrate
redissolve any crystals formed by gentle heating and put the solution in a dark cupboard to
crystallize. Remove the crystals by filtration on a Buchner funnel Wash them with an
equivolume mixture of ethanol and water and finally with acetone. The complex is
photosensitive, but it is quite stable if it is stored in the dark. .
ASSIGNMENTS

1. Draw the structure of Fe(OX).2H20.

2. Draw the possible structures of [Fe(OX)3]3- and explain why the complexes drawn are
optically active.
3. Explain how you would analyse Fe(OX).2H20 for iron and oxalate if you were provided
with a standardised solution of potassium permanganate, dilute sulphuric acid and zinc
dust.
4. Explain how you would analyse K3[Fe(OX)3]3H2O for iron and oxalate if you were
provided the same reagents as in 3 above.
 PRACTICAL 5

ETHYLENEDIAMINE COMPLEXES
of

CHROMIUM (III)
 PRACTICAL 5

Ethyelendiamine Complexes of Chromium(III)

_________________________________________________________________________

INTRODUCTION

Chromium (IlI) forms many different hexa-coordinate octahedral complexes. However, in

aqueous solution simple salts of chromium (Ill) tend to form the ion [Cr(H2O)6]3+. This ion is
very kinetically inert, it only exchanges water ligands very slowly with other available ligands
in solution. Thus, preparations using simple salts in aqueous solution are very slow often
taking several days of refluxing to obtain measurable yields.

The use of non-aqueous solvents such and catalysts speed up the reactions. Zinc metal is a
good catalyst since it reduces Cr3+ to Cr2+. The Cr2+ complexes are kinetically labile and rapidly
exchange ligands. Using methanol instead of water also prevents the formation of [Cr
(H2O)6]3+ and helps speed up the reaction.

In these experiments the above methods and used to prepare this-ethylenediamme

complexes of chromium (IlI).

(N.B.: The correct nomenclature is 1,2-diaminoethane not the old name of ethylenediamine,
however ethylenediamine is still used in many text books).

The complex formed is [Cr(en)3]Cl3.3H2O which when heated forms cis-dichlorobis

(ethylenediamine)chromium(Ill) chloride. The above complexes exhibit optical activity.

PREPARATION [Cr(en)3]Cl3.3H2O

A single piece (ca. 1 g) of granulated zinc is added to a solution of green chromium(Ill) chloride
(CrCl3.6H2O, 9 g) in methanol (25 ml) and the mixture heated under reflux on a steam bath.
Anhydrous ethylenediamine (13.4 ml) is added (this addition should be made very slowly to
avoid frothing and may cause loss of product) and the heating continued for one hour. After
cooling, the solid product is collected on a Buchner or fritted-glass funnel and the piece of zinc
removed. The yellow product is washed with 10% solution (25 ml) of ethylenediamine in
methanol (until the washings are colorless) and then with ether and air-dried.
PREPARATION of cis-[CrCl2(en)2]CI

The cis-dichlorobis(ethylenediamine)chromium(ill) chloride is obtained by heating 3 g of

Co(en)3Cl3.3H2O. Carry out the pyrolysis in an oven, the temperature of which has been
previously adjusted within the range 210° - 215°C. Below 210°C reaction is slow whereas
above 215°C more extensive decomposition occurs. Spread the complex out in a thin layer
on a watch glass or petri dish and place it in the oven. Decomposition soon begins and within
one or two hours the colour changes to red-violet., The course of the reaction can be followed
by observing the weight loss. Decomposition beyond 85% of the theoretical value is very slow
and hardly practicable.

The purity of the product cis-dichlorobis(ethylenediamine) chromium (III) chloride is improved

by washing with cold concentrated hydrochloric acid. Dry in an oven.

ASSIGNMENTS

1. Draw the structure of [Cr(en)3]3+ and its optical isomer.

2. Draw the structure of cis[CrCl3(en)2]+ an dits optical isomer.
3. Draw energy level diagrams to indicate the relative sizes of Δo for the following
[Cr(H2O)6]3+, [CrF6]3-, [Cr(en)3]3+.