Mesay Solomon Tesema, Digafie Zeleke

Practical Chemistry
Also of Interest
Industrial Inorganic Chemistry
Mark Anthony Benvenuto, 
ISBN ----, e-ISBN ----

Applied Inorganic Chemistry

Volume –
Rainer Pöttgen, Thomas Jüstel and Cristian A. Strassert (Eds.), 
Set-ISBN ----

Inorganic Chemistry.
Some New Facets
Ram Charitra Maurya, 
ISBN ----, e-ISBN ----

Rare Earth Chemistry

Rainer Pöttgen, Thomas Jüstel and Cristian A. Strassert, 
ISBN ----, e-ISBN ----
Mesay Solomon Tesema, Digafie Zeleke

Practical
Chemistry

Transition Metals

Volume 2
Authors
Mesay Solomon Tesema
Department of Chemistry
College of Natural Sciences
Salale University
P.O. Box 245
Oromia, Fiche
Ethiopia
[email protected]

Dr. Digafie Zeleke

Department of Chemistry
College of Natural Sciences
Salale University
P.O. Box 245
Oromia, Fiche
Ethiopia
[email protected]

ISBN 978-3-11-157384-7
e-ISBN (PDF) 978-3-11-157434-9
e-ISBN (EPUB) 978-3-11-157488-2

Library of Congress Control Number: 2024944100

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the internet at http://dnb.dnb.de.

© 2025 Walter de Gruyter GmbH, Berlin/Boston

Cover image: angelp/iStock/Getty Images Plus
Typesetting: Integra Software Services Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck

www.degruyter.com
Preface
This manual has been prepared for CHEM 3033 Inorganic Chemistry Laboratory Man-
ual and includes 12 experiments, which are related to the topics covered in the course
“CHEM 3031 Inorganic Chemistry II.” The main purpose of this laboratory is to provide
the students an appreciation for the occurrence, preparation, reaction, and properties
of transition metals. It is also aimed to provide the students a degree of competence
in the laboratory skills required for accurate and precise chemical analysis. There-
fore, it is expected that the students will demonstrate proficiency in the theory under-
lying analytical techniques and will apply this theory to obtain reliable analytical
results on the preparation of some transition metals.

https://doi.org/10.1515/9783111574349-202
Contents
Preface V

General laboratory safety IX

Laboratory report writing format XIII

1 General aspects of the chemistry of transition elements 1

Experiment 1 14
1.1 Chemistry of titanium 14

Experiment 2 23
2.1 Chemistry of vanadium 23

Experiment 3 35
3.1 Chemistry of chromium 35

Experiment 4 46
4.1 Chemistry of molybdenum 46

Experiment 5 56
5.1 Chemistry of manganese 56

Experiment 6 64
6.1 Chemistry of iron 64

Experiment 7 71
7.1 Chemistry of cobalt 71

Experiment 8 75
8.1 Chemistry of nickel 75

Experiment 9 79
9.1 Chemistry of copper 79

Experiment 10 87
10.1 Chemistry of zinc 87
VIII Contents

Experiment 11 90
11.1 Chemistry of cadmium 90

Experiment 12 93
12.1 Chemistry of mercury 93

References 97

Index 99
General laboratory safety

Introduction

At all times, the instructor and students should observe safety rules. They should al-
ways wear safety glasses in the laboratory and should become familiar with emer-
gency treatment. Laboratories are places of great responsibility. Careful practice and
mature behavior can prevent most mishaps. The following are all very important.
Treating the lab with respect makes it far less dangerous.

Eye protection: Goggles or safety glasses must be worn at all times. Eyeglasses with
shatterproof glass are inadequate without goggles or safety glasses. Side shields are re-
quired for all protective eyewear.

Shoes: Shoes that completely cover the feet are required in the laboratory.

Protective clothing: A protective apron or lab coat is recommended in the laboratory.

If any chemical is spilled on your skin or clothing, it must be washed off immediately.

Food and drink: Food and beverage are strictly prohibited in the laboratory. Do not
taste or smell any chemical.

No unauthorized experiments: Do not perform any unauthorized experiments.

Chemicals, supplies, or equipment must not be removed from the laboratory. All ex-
periments must be approved by the instructor.

Smoking: Smoking is prohibited in the laboratory.

Personal item: No bags, coats, books (except the lab book), or laptop computers should
be brought into the laboratory. Ask your instructor where these items can be stored
while you are in the laboratory. Bring in only the items that are needed during the lab-
oratory period. These items can be damaged by the chemicals in the laboratory.

Use of equipment: Do not use any equipment until the instructor has shown you
how to use it.

Glassware: Do not use any broken, chipped, or cracked glassware. Get replacement
glassware from your instructor.

Bench cleanup: At the end of the laboratory period, put away all equipment, clean
the laboratory bench, and wash your hands.

Use of chemicals: Take only the amount that is needed. Leave all bottles in their proper
places. Place the lids on the bottles after use. Clean up all spilled chemicals immediately.

Careful reading of labels: A material safety data sheet is available for each chemical
in the laboratory. Ask your instructor where the paper copies are located. Material

https://doi.org/10.1515/9783111574349-204
X General laboratory safety

safety data sheets are also available on the web. Many chemical companies have posted
this information. Use web search engines to locate this information. Students are en-
couraged to obtain this information prior to using the chemical in the laboratory.
Safety, health, and fire precautions are the most important information to locate. Spe-
cial instructions for the handling of certain reagents may be posted by the instructor.

Procedures for proper labeling

– Manufacturer chemical labels must never be removed or defaced until the chemi-
cal is completely used.
– All chemical and waste containers must be clearly labeled with the full chemical
name(s) (no abbreviations or formulas) and must contain appropriate hazard
warning information.
– Small containers that are difficult to label such as 1–10 mL vials and test tubes can
be numbered, lettered, or coded as long as an associated log is available that identi-
fies the chemical constituents. Groups of small containers can be labeled as a group
and stored together.
– Unattended beakers, flasks, and other laboratory equipment containing chemicals
used during an experiment must be labeled with the full chemical name(s).
– All chemicals should be labeled with the “date received” and “date opened.”
– All laboratory chemical waste containers must be labeled with the name of the
chemicals contained.

Waste disposal: In recent years, the rules regarding waste disposal have become
more rigidly defined. Reagents are never poured down the sink. Containers for chemi-
cal wastes are provided in the laboratory. Different containers are needed for differ-
ent types of waste chemicals, such as chlorinated hydrocarbons, hazardous materials,
and metals. All reagents in the waste container are listed on the container.

Fume hoods: Most laboratories provide fume hood areas or bench-top fume hoods. Al-
ways use these hoods. If you think the hoods are not turned on, then bring to the atten-
tion of your instructor. Often students are provided with simple methods of testing hood
efficiency, and these should be used periodically. Safety regulations usually prohibit stor-
age of toxic substances in hoods, and fume cupboards for such compounds are normally
available.

Gloves: Most laboratories provide boxes of gloves. Modem gloves are quite manage-
able and allow for handling of equipment with some agility. Gloves have their place
and can certainly protect your hands from obnoxious odors or chemicals that can
cause allergic responses. But they are not a license for sloppy technique. Moreover,
they are often easily penetrated by some compounds. Due care is still required.

Compressed gas cylinders: Compressed gas cylinders, especially those that are nearly
as tall as an adult, can be dangerous if not clamped to the bench top. Gas cylinders con-
 Introduction XI

taining inert gases such as nitrogen or helium may well be around the lab. Cylinders
containing chlorine or more toxic reagents should be stored in a fume cupboard.

Safety equipment: The location of safety equipment should be made known to you.
Moreover, you should know if and when you should use these. Most of the following
items should be readily available in the chemistry laboratory, and items on this list or
their description may vary due to local safety regulations:
– Fire blanket
– Fire extinguisher
– Eye-wash fountain
– Shower and first aid kit washes for acid or base (alkali) bums

Accident reporting: All accidents should be reported. The manner in which they
should be reported will be provided by the instructor. It is also important that some-
one accompany an injured person who is sent out of the laboratory for special care; if
the injured person should faint, the injury could easily become compounded. Medical
treatment, except in the simplest of cases, is usually not the responsibility of the in-
structor. Very simple, superficial wounds can be cleaned and bandaged by the instruc-
tor. But any reasonably serious treatment is the job of a medical professional. The
student should be sent to the college medical center accompanied by someone from
the chemistry department. In all labs, the instructor should provide the students with
instructions that are consistent with local regulations.
XII General laboratory safety

Chemical hazard pictogram

Oxidizers Flammables, Self Reactives, Explosives, Self

Pyrophorics, Self-Heating, Reactives, Organic
Emits Flammable Gas, Peroxides
Organic Peroxides

Acutely Toxic Burns Skin, Damages Gases Under Pressure

(severe) Eyes, Corrosive to Metals

Carcinogen, Respiratory Toxic to aquatic Acutely toxic(harmful),

Sensitizer, Reproductive environment Irritant to skin, eyes or
Toxicity, TargetOrgan respiratory tract, Skin
Toxicity, Mutagenicity sensitizer, Hazardous to
Aspiration Toxicity the Ozone layer.
Laboratory report writing format
1. Cover page
Name of university-----
College-------------------
Department--------------
Practical course name---------
Group -------- subgroup-----
Name of members Id no.
Submission date
2. Body of the report
– Experiment number: ________
– Title: ________
– Objective: (should be clear and short)
– Theory: (not more than half a page)
– Procedure
– List of chemicals and apparatus
– Observation: Compile the possible observation made (solubility, precipitates,
color change, gas evolution, etc.)
– Results: (write the balanced equation of the chemical reaction in ionic form)
– Discussion: To discuss on outcomes the student refer the theoretical parts. Explain
the errors if any.
– Conclusion: Write statements that explain your objective was fulfilled.
– References: Write down your sources except manual.

For example, you can write the observation and result parts as the following sample.

The chemistry of titanium

1 Preparation and properties of titanic acid

1.1 Reaction of titanyl sulfate with aqueous NaOH and ammonia: preparation of
orthotitanic acid

TiO2 + + 2OH − + H2 O ! TiO2 · 2H2 O

Observation: . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Result: With both dilute aqueous NaOH and ammonia, white precipitate of TiO2 · 2H2O,
orthotitanic acid, is best described as hydrated TiO2.

1.2 Reaction of titanyl sulfate with ammonium sulfate

S2 − + H2 O ! HS − + OH − ðprotolysisÞ

https://doi.org/10.1515/9783111574349-205
XIV Laboratory report writing format

TiO2 + + 2OH − + H2 O ! TiO2 · 2H2 O

Observation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Result: White precipitate of orthotitanic acid to protolysis of the sulfide.

1.3 Behavior of orthotitanic acid with respect to sulfuric acid and NaOH:

TiO2 + · 2H2 O + 2H+

! TiO2 + + 3H2 O

Observation. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Result: Freshly prepared orthotitanic acid is dissolved by dilute H2SO4 under the forma-
tion of colorless TiO2+. TiO2 · 2H2O is insoluble in dilute NaOH, although TiO2 · 2H2O has
amphoteric properties that seem to predominate.

1.4 Conversion of orthotitanic acid into metatitanic acid

heat
TiO2 · 2H2 O ! TiO2 · 2H2 O + H2 O
Observation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Result: On boiling, orthotitanic acid (TiO2 · 2H2O) gets converted into metatitanic acid
(TiO2 · 2H2O).
The latter is insoluble in dilute H2SO4 (difference to TiO2 · 2H2O).
1 General aspects of the chemistry of transition
elements

1.1 Position in the periodic table

The periodic table is an arrangement of the entire element in periods and groups ac-
cording to their atomic number and electronic configuration. The latter follows natu-
rally from the Aufbau principle. An important generalization concerning the valence
electronic configuration is that the free atoms of a group in the periodic chart have
the same number of electrons in their outermost shell (valence electron) and usually
also have the same electronic configuration.
Therefore, knowledge of the position of an element in the periodic table (rather
than its atomic number) is for a chemist as essential as the multiplication table for a
mathematician. Depending on the kind of subshell being occupied by the valence elec-
trons, the elements may be classified into three major groups (see figure 1.1):
1. Main group elements (s- and p-block elements) – within the outermost shell only
s- and p-subshells are populated: nsa npb ða = 1, 2; b = 0 − 6Þ
2. Transition elements (d-block elements) – the orbital of the last but one principal
shell are occupied: ðn − 1Þdc ns2 ðc = 0 − 10Þ
3. Lanthanides and actinides; inner transition elements (f-block elements) – The f-levels
of the outermost but two principal shells are filled: ðn − 2Þf d ðn − 1Þd1 ns2 ðd = 1 − 14Þ

Of course, the main group elements can be further subdivided into s-block (all of
them being light metals) and p-block. The latter is composed of the so-called post-
transition metals and nonmetals.

1–2 3 4 5 6 7 8 9 10 11 12 13–18

s-block p-block

Sc Ti V Cr Mn Fe Co Ni Cu Zn

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

La Hf Ta W Re Os Ir Pt Au Hg

Figure 1.1: General sketch of the position of transition metals in the periodic table.

The electronic configuration is the distribution of electrons in the shell. Transition

metals have the scheme that ends with ðn − 1Þdc ns2 ðc = 0 − 10Þ. The division of the first

https://doi.org/10.1515/9783111574349-001
2 1 General aspects of the chemistry of transition elements

transition series into two “sets” is clearly related to the filling of the d-orbitals – at the
dividing element, manganese, the 3d level is half-filled (one electron in each d orbital).
Thereafter the singly occupied d orbitals become double-filled until filling is complete
at copper and zinc. The fact that the configurations 3d5 (half-full) and 3d10 (full) are
obtained at chromium and copper, respectively, in each case (see Table 1.1) (at the
cost of removing an electron from the 4s level) suggests that these configurations 3d5
and 3d10 are particularly “stable.”

Table 1.1: Electronic configuration of the transition elements.

Group          

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

Configuration ds ds ds ds ds ds ds ds ds ds

Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
                 
Configuration d s d s d s d s d s d s d s d s d s ds

Element Lu Hf Ta W Re Os Ir Pt Au Hg
                 
Configuration d s d s d s d s d s d s d s d s d s ds

It is mainly due to the strong interelectronic interaction in the more compact 3d orbi-
tals that the energetically less stable 4s orbital remains doubly occupied in Sc, Ti, and
V. In fact, the 3d orbitals are significantly more stabilized with increasing nuclear
charge across the period than the 4s-level. As a consequence, in the case of chromium,
one electron from 4s orbital drops into the 3d-level giving rise to a 3d5 4s1 configura-
tion. Because of the relatively high spin pairing energy in the compact 3d-orbitals
(compared to the more extended 4s-orbital), the next electron prefers again to stay in
the energetically higher 4s level. Therefore, manganese exhibits the configuration 3d5
4s2. Arriving at copper, a similar anomaly is to be observed. One 4s-electron has fallen
into the now considerably more stable 3d-level despite interelectronic repulsion and
spin pairing. The situation becomes even more complex for the 4d and 5d elements.
Three more characteristics shall be mentioned here:
All transition metal ions involved in chemical bonding possess a dn configuration,
for example, Ti3+ in [Ti(H2O)6]3+ is a 3d1 rather than a 4s1 system. This can be attrib-
uted to the interaction between the central ion and ligands causing a general destabi-
lization of the (n–1)d and ns orbitals, which is, however, greater for large ns than for
the more compressed (n–1)d orbitals. Half and fully occupied subshells represent rela-
tively stable energy states of the electronic system. Recall that spin pairing is an endo-
thermic process. Thus, the addition of a sixth electron to the d5 system requires some
extra energy – the so-called spin pairing energy.
 1.1 Position in the periodic table 3

For example, MnO4 in acidic medium is normally reduced to Mn2+ (d5) rather than
Mn (d6), or that Fe2+ (d6) is readily oxidized to Fe3+ (d5) under various conditions. In
6

case of a fully occupied subshell, it is clear that adding another electron means populat-
ing an energetically higher sub- or principal level.
Due to lanthanide contraction, the 5d elements following lutetium have drasti-
cally reduced the atomic and ionic radii, being quite close to the radii of the corre-
sponding 4d elements. due to the same chemical and physical properties elements are
couples together. for example Y-La, Zr-Hf, Nb-Ta, and Mo-W and, to a smaller extent,
also those of the following 4d–5d element pairs turn out to be rather similar but differ
markedly from the behavior of the 3d elements.

1.1.1 Oxidation states

As a consequence of their electronic configuration, compounds of transition elements

exist in various oxidation states. Thus, stable manganese compounds have been isolated
with Mn in all oxidation states from –III to +VII. Table 1.2 summarizes the most common
and some less frequently encountered positive oxidation numbers (ONs) of the transition
metals.
There are two main trends to be emphasized:
– The stability of the high ONs increases down the group.
– The stability of the highest possible ON decreases across a period from left to
right.

For the elements Ti, V, Cr, and Mn, it is possible to realize the maximum ON in aqueous
solution (TiO2+, VO43–, and MnO4–). However, in the case of iron and the following 3d
elements, the ionization energy required to generate the highest oxidation state is in-
creasing rapidly and can no longer be compensated by exothermic processes such as
hydration, bond formation, and lattice energy.

Table 1.2: Electronic configuration, oxidation number, and color of some transition metal ions.

d transition metal ions Electronic configuration Oxidation number Color

+ 
TiO d +IV Colorless
VO– d V Colorless
CrO– d +VI Yellow
VO–, VO– d V Colorless to yellow
CrO– d +VI Orange
Ti+ d III Violet
VO+ d +IV Blue
V+ d +III Green
V+ d +II Violet
Cr+ d +III Violet (green)
4 1 General aspects of the chemistry of transition elements

Table 1.2 (continued)

d transition metal ions Electronic configuration Oxidation number Color


MnO d +IV Brown solid
Cr+ d +II Blue
Mn+ d +III Violet
Mn+ d +II Pink
Fe+ d +III Yellow
Fe+ d +II Green
Co+ d +III Red
Co+ d +II Pink
Ni+ d +II Green
Cu+ d +II Blue
Cu+ d +I Colorless
Zn+ d +II Colorless

In Table 1.2:
– The colors of M2+ are those of hexaquo derivatives.
– MnO2 is included as it is frequently encountered in redox reactions and is the
only Mn(IV) compound to be dealt with in the experimental part.

1.1.2 Color

Transition metal compounds are very often colored; frequently (but not always) the color
is due to the presence of coordination complexes. When a cation containing d electrons is
surrounded by other ions or polar molecules, either in a complex ion in solution or in a
solid, a splitting of the energy levels of the five d-orbitals (all originally having the same
energy) occurs. When light falls on such a system, electrons can move between these split
levels. The energy absorbed in this process corresponds to the absorption of the light at
certain wavelengths, usually in the visible part of the spectrum; hence, color is observed.
For a given cation, the kind of absorption produced its intensity, and the position in the
spectrum depends very much on the coordination number and the surrounding ligands.
We can illustrate this with reference to the Cu2+ ion. In solid anhydrous copper(II) sulfate,
the Cu2+ ion is surrounded by SO42– ions. In this environment, the d-orbital splitting is
such that the absorption of light by the Cu2+ cation is not in the visible part of the spec-
trum, and the substance appears white. If the solid is now dissolved in water, the Cu2+
ion becomes surrounded by water molecules, and complex species such as Cu(H2O)6+ are
formed. These absorb light in the visible part of the spectrum and appear pale blue. If
this solution of copper(II) sulfate is allowed to crystallize, water molecules remain coordi-
nated around the Cu2+ ion in the solid copper(II) sulfate pentahydrate (CuSO4·5H2O) and
the solid is pale blue. When an excess of ammonia is added to the original solution, some
of the water ligands around the copper(II) ion are replaced by ammonia:
 1.1 Position in the periodic table 5

2+
2+
CuðH2 OÞ6 ðpale blueÞ + 4NH3 ! CuðNH3 Þ4 ðH2 OÞ2 ðdeep blueÞ + 4H2 O

When ligands surround a metal ion, they split its d-orbital energies into two levels. The
color we see comes from the light not absorbed, which depends on the metal, ligands, and
complex geometry. Strong-field ligands often result in blue or green colors, while weak-
field ligands can lead to red or orange hues. (In transition metals, the d-orbitals are essen-
tial because they are commonly utilized in bonding.) If excess chloride ion is added to a
blue solution containing [Cu(H20)6]2+, he-re the new splitting results in a yellow-green color:

th½CuðH2 OÞ6 2+ + 4Cl− ! ½CuCl4 2− + 6H2 O

Distorted Distorted
Octahedral Tetrahedral
Pale blue Yellow

The d-orbital splitting depends on the oxidation state of a given ion; hence, two com-
plex ions with the same shape, ligands, and coordination number can differ in color.

1.1.3 Coordination complexes

Coordination compound is a compound formed when a central metal atom or ion is

surrounded (coordinated) by a number of anions or molecules in such a way that the
number of the coordinated anions or molecules exceeds the normal covalence of the
central atom or ion. It will be recalled that they are defined (and named) in terms of
(a) the central metal atom or ion and its oxidation state, (b) the number of surround-
ing ligands which may be ions, atoms, or polar molecules, and (c) the overall charge
on the complex, determined by the oxidation state of the central atom and the charges
(if any) on the ligands. Some examples are (Table 1.3):

Table 1.3: Oxidation state of central metal.

Oxidation state of Examples Names

central metal ion

 MnO– Permanganate, but better manganite(VII) (strictly,

tetraoxomanganate(VII))

 CrO– Chromate, better chromate(VI) (strictly, tetraoxochromate (VI))

 TiCl Titanium tetrachloride or tetrachlorotitanium(IV)

–
 [Fe(CN)] Hexacyanoferrate(III)
+
 [Ni(NH)] Hexaamminenickel(II)

 Fe(CO) Iron pentacarbonyl or pentacarbonyl iron()

6 1 General aspects of the chemistry of transition elements

Note: Those complexes can have negative, positive, or zero overall charge. MnO4– and
CrO4– are usually considered to be oxo acid anions but there is no essential difference
between these and other complexes. For example, the anion MnO4– can be regarded
formally as a manganese ion in oxidation state +7 surrounded by four oxide ion (O2–)
ligands (in fact of course there is covalent bonding between the oxide ligands and the
MnVII ion, leading to partial transfer of the negative charges of oxide to the manganese).
In general, high oxidation states (e.g., those of manganese +7 and chromium +6) are
 
only found in oxides (e.g., Mn2O7 and CrO3), oxo acid anions MnO4 −, CrO4 2− , Cr2 O7 2− ,
and sometimes fluorides (there is no MnF7 known, but CrF6 is known). Hence, the num-
ber of complexes in high oxidation states is very limited. At lower oxidation states, a
variety of ligands can form complexes, and some common ligands are:

2+
3+
2−
H2 O in FeðH2 OÞ6 , NH3 in CoðNH3 Þ6 , CN− in NiðCNÞ4 , Cl− in ½CuCl4 2−

However, stable complexes where the oxidation state of the central metal atom is 0
are only formed with a very few ligands, notably carbon monoxide (e.g., Ni(CO)4 and
Fe(CO)5) and phosphorus trifluoride, PF3 (e.g., Ni(PF3)4).

1.1.4 Interstitial compounds

The transition metal structures consist of close-packed arrays of relatively large atoms.
Between these atoms, in the “holes,” small atoms, notably those of hydrogen, nitrogen
and carbon, can be inserted, without very much distortion of the original metal struc-
ture, to give interstitial compounds (e.g., hydrides). As the metal structure is “locked” by
these atoms, the resulting compound is often much harder than the original metal, and
some of the compounds are therefore of industrial importance. Since there is a definite
ratio of holes to atoms, filling of all the holes yields compounds with definite small
atom–metal atom ratios; in practice, all the holes are not always filled, and compounds
of less definite composition (nonstoichiometric compounds) are formed.

1.1.5 Acid–base reactions

A simple transition metal salt with x– being the anion of strong acid, for example,
Cl−, NO3 −, or 1=2 SO4 2− , undergoes protolysis when dissolved in water. The solution of
these salts behaves as slightly acidic, due to the partial dissociation of the aqua com-
plexes into hydroxo species and H3O+:

ðn−1Þ+
½MðH2 OÞ6 n+ + H2 OÐ MðH2 OÞ5 ðOHÞ + H3 O +

The extent of protolysis increases with the oxidation state of Mn+. Accordingly simple
aqua cations with the central in a high positive ON are in general unstable with re-
 1.1 Position in the periodic table 7

spect to protolysis in aqueous solution and are immediately converted into the more sta-
ble oxo cations or oxo anions depending on the pH value of the system. Hydrolysis may
also result in the precipitation of insoluble hydroxides or oxides. As an example, the
hexaquotitanium(IV) cation does not exist in the aqueous solutions of Ti(IV) salts. De-
pending on the pH vale, hydroxo complexes or the hydrated TiO2+ ion can be detected:
+2H2 O
2+
½TiðH2 OÞ6 4+ Ð TiðH2 OÞ4 ðOHÞ2 ÐTiO2+ ðaqÞ
−2H3 O+

Other examples for this phenomenon are the various ions of chromium in the oxidation
states +II, +III, and +VI. The hexaquo complexes of Cr2+ and Cr3+ are stable and only
slightly protolyzed.
However, in the oxidation state +VI, it is the oxo anions CrO42– and Cr2O72– that
are exclusively encountered:
h −e− i2+
3+ −3e−
C rðH2 OÞ6 ! CrðH2 OÞ6 ! CrO4 2− + 4H2 O + Cr2 O7 2−

Of great significance for transition metal is the behavior of its oxide with its acids and
bases:

M2 O3 + 6H+ ! 2M3+ + 3H2 O

M2 O3 + 6OH− ! 2MO3 3− + 2H2 O

In the first equation, the oxide is said to be a base anhydride in contrast to the second
one, where it behaves like an acid anhydride. Many transition metal oxides display
amphoteric properties. In principle, the basic character of a transition element in-
creases with decreasing ON. Thus, V(II) and V(III) form simple vanadium salts in acidic
solution. In alkali medium, the sparingly soluble hydroxides that do not dissolve in an
excess of base are precipitated because there is no tendency to form oxo or hydroxo va-
nadates. A similar behavior is found for most of the transition metal M2+ and M3+ ions.
Now, consider vanadium in its highest oxidation state. The oxide V2O5 is amphoteric and
reacts in acidic solution to give VO2+, whereas in basic medium orthovanadates(V) are
obtained:

V2 O5 + 2H+ ! 2VO2 + + H2 O

V2 O5 + 6OH+ ! 2VO4 3− + 3H2 O

Another interesting phenomenon encountered with some transition elements, espe-
cially those of the VB and VIB group, is the tendency to undergo various condensation
reactions, yielding the so-called isopolyanions or isopolyacids. Some such interconver-
sions are depicted in the following equations:
8 1 General aspects of the chemistry of transition elements

2VO4 3− + 2H+ Ð V2 O7 4− + H2 O ðdivanadateÞ

2VO4− 7 + 4H+ Ð V4 O12 4− + 2H2 O ðtetravanadateÞ

5V4 O12 4 + 8H+ Ð 2VO6− + 4HO ðdecavanadateÞ

2VO6− + 6H+ Ð 5VOðaqÞ ðhydrous vanadiumðVÞoxideÞ

With decreasing pH value of the solution, the degree of condensation is enhanced.

The process can be monitored nicely by the characteristic color change from colorless
(VO43–), via yellow (V2O74), and orange (polyvanadates), to orange colored (polymeric
V2O5). In highly acidic medium, the oxide dissolves again, yielding the yellow vanadyl
cation, VO2+.

1.1.6 Redox reactions

The great variety of oxidation states in which transition metals may exist give rise to
numerous redox reactions. It has very often been observed that students are terrified
by balancing such equations along with aqueous solutions, and these are most appro-
priately written as ionic equations. Hence, basic rules and procedures are summa-
rized in this section.
In tackling the problem, three questions have to be considered:
– How does one determine ONs?
– When does one write ions and ionic equations?
– How are redox equations completed and bleached?

1.1.7 Oxidation number

The ON of an element in a molecule or molecular ion is estimated by splitting the latter

hydrolytically into atomic ions according to their relative electronegativities. The ON is
indicated on the top of the element symbol which is a plus or minus sign followed by
the number of charge (Roman or Arabic symbol). Notice that ionic charges are written
in a similar manner but with the number at followed by the ± sign. In order to come up
with correct result, stick to the rules below:
1. In element compounds, the ON is always zero (e.g., graphite, O2, O3, H2, S8, and
metals).
2. The ON of fluorine in compounds must be –1 because it is the most electronegative
element of all.
3. Hydrogen usually gets the ON +1. An exception is hydrides such as NaH or LiAlH4,
where hydrogen is attached to highly electronegative elements. Hydride hydrogen
has the ON –1.
 1.1 Position in the periodic table 9

4. The ON –2 is assigned to oxygen in most of its compounds. The only exception is

peroxo groups with oxygen possessing in ON –1; for example, in H2O2 and Na2O2,
and certain fluoro compounds with +1 or +2 ONs for oxygen.
5. In element compounds, the ON is always zero (e.g., graphite, O2, O3, H2, S8, and metals).
6. The ON of fluorine in compounds must be –1 because it is the most electronegative
element of all.
7. Hydrogen usually gets the ON +1. An exception is hydrides such as NaH or LiAlH4,
where hydrogen is attached to highly electronegative elements. Hydride hydrogen
has the ON –1.
8. The ON –2 is assigned to oxygen in most of its compounds. The only exception is
peroxo groups with oxygen possessing in ON –1, for example, in H2O2 and Na2O2,
and certain fluoro compounds with +1 or +2 ONs for oxygen.
9. The remaining elements are also treated according to their electronegativity, taking
into account that the sum of all ONs must be equal to zero for neutral molecules
and equal to the ionic charge for ions.

The following examples illustrate the above rules:

+ 1 −1 +2−1 + 1 −1 −1 + 1 −2 + 1 +7 −2 + 1 + 6 −2 −1 + 1 −2
Li H , O F2 , H2 O , N H − O H , Mn O4 − , K2 Cr2 O7 , CH3 CH O
2
2−

O O

2−
S2 O 8 = O SH O O S O

O O

The peroxodisulfate anion contains sulfur in ON +6. Six O’s are in the ON –2 but the
remaining two O’s of the peroxo bridge are in the oxidation state −1 (see rule 4).

1.1.8 Ionic equations

If ions are involved in a chemical reaction, ionic equations are the most appropriate to de-
scribe the process taking place. Moreover, ionic equations have the following advantages:
– They take into account that the chemistry in aqueous solution is mainly the chem-
istry of reacting ions.
– Omit all those particles that do not directly take part in the actual reaction.
– The stoichiometry and the balancing of ionic equations are always simpler than for
overall equations.
10 1 General aspects of the chemistry of transition elements

In order to establish an ionic equation one has to distinguish the compounds dissoci-
ating completely in aqueous solutions and those that do not split into ions. Complete
dissociation is found for:
– strong acids and bases, and
– salts.

Overall formulae are necessary for:

– Solids and precipitates that are insoluble in water, for example, BaSO4, Hg2Cl2,
Fe(OH)3, sparingly soluble oxides and sulfides of transition metals, such as MnO2,
TiO2, FeS, and Ag2O.
– Gases that are merely physically dissolved in water or evolved in a reaction, such
as O2, N2, H2, NO, NO2, and Cl2; notice that HCl as a gas is a molecular compound
that, however, dissociates completely into H+ and Cl– after dissolution in water.
– Neutral and ionic complexes, for example, [Fe (CN)6]3/4–, [Mn(H2O)6]2+, [Ni(NH3)6]2+,
and oxo anions such as TiO2+, VO43–, and SO42–.
– Typical covalent compounds, for example, CH3OH, NH2OH, NH3, and H2O.
– In certain cases, one has to decide by means of the pH value of the solution that
either the molecular or ionic formula has to be employed.
– Weak bases, for example, NH3, are protonated in acidic medium (here formation
of NH4+).
– Weak acids are gradually deprotonated in neutral and basic solution, for example,
H2SO3 (HSO3– and SO32–) or H2S (HS– and S2–). Other frequently encountered weak
acids are HNO2, HCN, H3PO4, carbonic acid, and acetic acid.

1.1.9 Redox equations

In a redox process, the ON of one element involved increases (loss of electron; oxidation),
whereas the ON of another participant must be decreased (gain of electrons; reduction).
Both half reactions are coupled with each other because the number of electrons lost in
the oxidation has to be equal to the number of electrons consumed in the reduction. No
electrons are left over.
In establishing a redox equation, the following operation should be strictly followed:
1. Selection of starting material and final products.
2. Determination of the ONs of all elements and selection of those that appear in
different ONs on the left- and right-hand sides of the equation. These elements
are oxidized and reduced, respectively. The ions and the molecules actually react-
ing, as established in this way, are of significance for the next step of the proce-
dure. Set up the partial equations (half equations) for oxidation and reduction in
a completely balanced manner.
3. Count the electron released and consumed, and find the common factor that bal-
ances the electrons.
 1.2 Worked out examples 11

4. Sum up both parallel equations and take care that the electrons are now canceled
out completely.
5. Check the correctness of your equation:
a. The sum of ionic charges must be equal on both sides.
b. Count the element on both sides.
6. Balance the remaining elements beginning with oxygen followed by hydrogen.

Note that mixing the order of operations and mistakes in counting the electrons are
the main reason for failure.

1.2 Worked out examples

1. Dissolution of titanium in dilute sulfuric acid under formation of the violet Ti3+
cation Ti + H+ ! Ti3+ + H2 starting and final products
– Balancing the partial equations and finding the least common factor

Ti ! Ti3+ + 3e− x2

2H+ + 2e− ! H2 x3

– Summing up the completed partial equations and final check

2Ti + 6H+ ! 2Ti3+ + 3H2

Abbreviated procedure:

Ti + 2H+ Ti3+ + H2
- X
3e 2
2e- X
3

2Ti + 6H+ 2Ti3+ + 3H2

2. Oxidation of Fe2+ to Fe3+ by MnO4– in acidic solution

ðH+ Þ
MnO4 − + Fe2+ ! Mn2+ + Fe3+

Fe2+ ! Fe3+ + e− x5

MnO− + 8H+ + 5e− ! Mn2+ + 4H2 O x1

5Fe2+ + MnO4 − + 8H+ ! 5Fe3+ + Mn2+ + 4H2 O

In order to balance oxygen and hydrogen, pay attention to the following:

– If O and H are not directly involved in redox process their ON remains un-
changed (i.e., −2 for O and + for H).
12 1 General aspects of the chemistry of transition elements

– In acidic medium, H+ and H2O can be used for balancing, whereas in alkaline
solution, only H2O and OH– are used.
– The oxide ion O2– itself is unstable in aqueous solution as it would immedi-
ately be converted into H2O (in acidic medium) or OH– (in basic medium):

O2− + 2H+ ! H2 O, O2− + H2 O ! 2OH−

3. Oxidation of sulfurous acid by MnO4- in acidic solution
H2SO3 is extremely unstable and in acidic solution it exists as SO2 or HSO3–. In
alkaline medium, however, the sulfite anion SO32– has to be employed:

SO2 + H2 O Ð HSO3 − + H+ HSO3 − + OH− Ð SO3 2− + H2 O

ðH+ Þ
MnO4 + HSO3 ! Mn2+ + SO4 2−

MnO4− + 8H+ + 5e− ! Mn2+ + 4H2 O x2

HSO3 − + H2 O ! SO4 2− + 3H+ x5

2MnO−4 + 16H+ + 5HSO−3 + 5H2 O ! 2Mn2+ + 8H2 O + 5SO4 2− + 15H+

After canceling H2O and H+, the following equation is obtained:

2MnO4 − + H+ + 5HSO3 − ! 2Mn2+ + 3H2 O + 5SO4 2−

1.2.1 Reduction of MnO4– by H2O2 in acidic solution

H2O2 is known to react in three different ways:

H2 O2 + 2e− ! 2OH− ðoxidizing agentÞ
H2 O2 ! O2 + 2H+ + 2e− ðreducing agentÞ
H2 O2 ! H2 O + 1=2 O2 ðdisproportionationÞ
ðH+ Þ
MnO4 + H2 O2 ! Mn2+ + O2

MnO4 − + 8H+ + 5e− ! Mn2+ + 4H2 O x2

H2 O2 ! O2 + 2H+ + 2e− x5

2MnO4 − + 5H2 O2 + 6H+ ! 2Mn2+ + 5O2 + 8H2 O

1.2.2 Oxidation of Mn2+ by MnO4– in alkaline solution (synproportionation)

In acidic medium, MnO4– is reduced down to Mn2+. Alkaline solutions stop the reduc-
tion, however, at Mn(IV). The only product possible under these conditions proves to
black insoluble MnO2:
 1.2 Worked out examples 13

ðOH− Þ
Mn2+ + MnO4 − ! MnO2

Mn2+ + 4OH− ! MnO2 + 2H2 O + 2e− x3

MnO4 − + 2H2 O + 3e− ! MnO2 + 4OH− x2

3Mn2+ + 2MnO4 − + 4OH− ! 5MnO2 + 2H2 O

1.2.3 Reduction of MnO4– by ethanol in alkaline solution

The determination of ONs in organic compound is necessary in order to count the elec-
trons lost gain in a redox process. Though it is merely a formal matter without any chem-
ical meaning, the procedure is the same as for ionic compounds:

C32 + O24 − ! ðC2 O4 + 2e−Þ ! 2CO42 + + 2e−

1− 1−
3 − CH2 − OH ! CH3 − CHO + 2H ! CH3 − CHO
CH2− 2−
+ 2H + 2e−

CH13 − − CHO1 − + H2 O2− ! CH3 − COOH + 2H ! CH03 − COOH0 + 2H + 2e−

There are similar methods of determining ON yielding different absolute values. Thus, it
is possible either to substitute the nonreacting alkyl chain by hydrogen or to neglect it
completely. Notice that the same procedure is used for reactants and products. Indepen-
dent of the method and the varying absolute ONs, the difference in the ONs, that is, the
number of electrons exchanged in the oxidation or reduction process, is always the same:
ðOHÞ
MnO4 − + C2 H5 OH ! MnO2 + CH3 CHO

MnO4 − + 2H2 O + 3e− ! MnO2 + 4OH− x2

C2 H5 OH + 2OH− ! CH3 CHO + 2H2 O + 2e− x3
2MnO4 − + 3C2 H5 OH ! 2MnO2 + 3CH3 CHO + 2OH− + 2H2 O
Experiment 1

1.1 Chemistry of titanium

1.2 Objective

Students should be able to:

– observe characteristic of Ti3+,
– observe hydrolysis of titanium(III) and titanium(IV),
– observe reducing properties of titanium(III) hydroxide, and
– discuss two methods for the preparation of titanium metal from TiO2.

1.3 Theory

1.3.1 Occurrence

The Earth’s crust contains approx. 0.6% Ti, which is therefore not a rare element. It
occupies the ninth position in the frequency chart of elements and is 5–10 times more
frequent than Cl, S, and P. As its ionic radius proves to be very similar to ions such as
Al3+, Fe3+, and Mg2+, respectively, Ti is found in minor amounts in almost each min-
eral, stone, or soil.
Typical titanium minerals are rutile, anatase, and brookite (three modification of
TiO2), as well as ilmenite (FeTiO3) and perovskite (CaTiO3). Less significant deposits are
ilmenite-containing sands at sea coasts and TiO2 as a constituent of clay. Moon rocks
contain more Ti than earthly minerals.
In nature, titanium occurs only in the form of Ti(IV) compounds. However, lower
ON of the elements such as +3, +2, and even 0 can be obtained synthetically.
Titanium has isotopes such as 46Ti (7.9%), 47Ti (7.3%), 48Ti (73.9%), 49Ti (5.5%), and
50
Ti (5.3%).

1.3.2 Preparation

Unlike the majority of other transition metals, titanium cannot be made by reduction
of the oxide with carbon because of carbide formation. The reduction of TiO2 by base
metals, for example, Na, Ca, Mg, or hydrogen, does also not give the pure metal but
yields lower titanium oxides. That is why most of the procedures go via titanium tet-
rahalides. TiCl4 is prepared from oxide by reductive chlorination:

https://doi.org/10.1515/9783111574349-002
 1.3 Theory 15

TiO2 + 2C + 4Cl2 ! TiCl4 + 2COCl2

The following two equations show some laboratory methods for preparing (extracting)
titanium:

TiO2 + 2CaH2 ! Ti + 2CaO + H2

800 °C
TiCl4 + 4Na 
! Ti + 4NaCl
2,000 °C
TiCl4 + 2H2 ! Ti + 4HCl

Large-scale industrial production of titanium is mainly done by the KROLL procedure:

1,200 °C
TiCl4 + Mg ! Ti + 2MgCl2

High-purity titanium is obtained by the reaction of the crude metal with iodine and sub-
sequent decomposition of the TiI4 vapor at a hot filament according to the Van Arkel
and De Boer process.

1.3.2.1 Physical properties

Metallic titanium occurs in two allotropic (a structurally different form of an element)
forms. Up to 882 °C, the α-modification is stable (hexagonal close-packed structure). At
higher temperature, the latter is converted into the β-form (cubic body-centered struc-
ture). Ore titanium is ductile, silvery-white metal. The mechanical properties have a sub-
tle dependence upon impurities. Thus, the Brinell hardness of pure titanium is twice that
of the Ti containing only 0.003% nitrogen. Titanium is hardly compressible, has a low
density of 4.4–4.5 g/cm, but a high mechanical strength. In particular, its density is lower
than that of iron, its strength is higher than that of aluminum, and its corrosion resistance
is comparable to that of platinum. This makes Ti very attractive for numerous applica-
tions in industry, technology, and science. The limiting factor, however, is its unfortu-
nately difficult and expensive production.

1.3.2.2 Chemical properties

Titanium reacts with air, chlorine, and other gases at relatively low temperatures.
Compact Ti preserves its metallic luster up to 350 °C. With hydrogen it forms a hydride
on heating. As confirmed by the negative standard potential of Ti2+, Ti (Eϴ = −1.63 V),
titanium is a base metal. It is quite resistant to dilute and concentrated acids because of
its passivation. Thus, it is not attacked by mineral acids, concentrated nitric acid, aqua
regia (chloronitrous acid), and aqueous alkali at room temperature. In the presence of
complexing agents, such as HF and oxalic acid, or at higher temperatures, dissolution
takes place. With most nonmetals, titanium tends to form interstitial compounds, for
example, TiN.
16 Experiment 1

1.3.2.3 Applications
Titanium metal is used in chemical apparatus construction (high resistance to corrosion),
centrifuges, rotors, high vacuum technology, and electronic industry.

Titanium(IV) compounds

Halides
Titanium halides are important starting compounds for various syntheses. Their prop-
erties vary considerably with the ON of titanium. The binary TiX4 (X = Cl, Br, I) possesses
a tetrahedral structure with polar covalent Ti–X bonds. TiBr4 and TiI4 are solids, and
TiCl4 is a colorless, fuming liquid. The industrial production of TiCl4 from TiO2, chlorine,
and graphite has already been mentioned in the previous subsection. The following
methods are more suitable for laboratory preparations:
500 °C
TiO2 + 2CHCl3 ! TiCl4 + 2CO + 2HCl
500 °C
TiO2 + CCl4 
! TiCl4 + 2CO2
Ti + 2Cl2 ! TiCl4

TiCl4 and other halides hydrolyze rapidly forming an oxychloride and finally hy-
drated TiO2:

TiCl4 + H2 O ! TiOCl2 + 2HCl

TiOCl2 + 3H2 O ! TiO2 · 2H2 O + 2HCl

In the presence of hydrogen, reduction to purple TiCl3 takes place:

TiCl4 + H2 ! 2TiCl3 + 2HCl

TiCl4 is soluble in various organic solvents, such as CCl4, benzene, and hydrocarbons.
Protic solvents, for example, acids and alcohol, cause protolysis. Numerous complexes
with donor ligands have been described:


TiCl4 + 2CH3 CN ! TiCl4 ðCH3 CNÞ2

Oxides
Titanium(IV) oxide, TiO2, occurs in three modifications: anatase, brookite, and rutile.
Brookite crystallizes in the orthorhombic system, whereas rutile and anatase possess
a tetragonal crystal lattice. In all the three structures, titanium atoms are surrounded
by six oxygen atoms and each O atom is coordinated by three Ti atoms. There are two
industrially significant processes for the synthesis of TiO2.
 1.3 Theory 17

There are two industrially significant processes for the synthesis of TiO2:
1. Sulfate process
H2 SO4
FeTiO3 ðlimoniteÞ ! FeSO4 + Fe2 ðSO4 Þ3 + TiOSO4

TiOSO4 + H2 O ðexcessÞ ! TiO2 · xH2 O + H2 SO4

TiO2 · xH2 O ! TiO2 + xH2 O

2. Vapor phase oxidation of TiCl4

TiCl4 + O2 ! TiO2 + 2Cl2

TiO2 melts at 1,840 °C without decomposition and is inert to H2S, acids, alkali solutions,
and salt solutions. The reactivity of TiO2 varies, however, considerably with the prepa-
ration conditions. At elevated temperatures TiO2 reacts with H2, CO, or carbon to give
low-valent titanium oxides. Rutile is highly demanded for the production of titanium
tetrachloride and organic titanium derivatives. Furthermore, it plays an outstanding
role as white pigment dyestuff.

Titanium(IV) acids and salts

The existence of a stoichiometric Ti(OH)4 has not yet been proved. The precipitate ob-
tained on adding a base to aqueous Ti(IV) solution is suggested to be the hydrated tita-
nium(IV) oxide, TiO2·2H2O, that is also called orthotitanic acid. On boiling, these
hydrogels tend to coagulate under desorption of water eventually yielding metatitanic
acid. The latter has the approximate formula TiO2·H2O or Ti(OH)2, respectively. The
exact composition of these TiO2·xH2O precipitates depends subtly on the pH value of
the solution.
Titanic acids are amphoteric. They display only weakly basic character and are,
therefore, soluble only in strong acids. In conc. acids, some Ti(IV) salts seem to be stable.
In the presence of water, it hydrolyzes to hydroxo and oxo cations. Thus, according to
the following protolysis equilibrium, under acidic conditions, the presence of octahe-
dral hydroxo complex cations has been invoked:

TiðOHÞ4 + 3H2 O ! ½TiðOHÞ3 ðOH2 Þ3 + + OH−

½TiðOHÞ3 ðOH2 Þ3 + + H2 O ! ½TiðOHÞ2 ðOH2 Þ4 2+ + OH

The frequently employed titanyl cation, TiO2+, is of some use to describe the reactions
of Ti(IV) in aqueous solution, though it does not appear to exist either in solution or in
the solid state. The crystalline salt TiOSO4·H2O contains the chain-like (TiO)n2n+ cation
rather than a monomeric TiO2+ species. Anhydrous TiOSO4 can be easily synthesized by
fusing TiO2 with potassium pyrosulfate:
18 Experiment 1

TiO2 + K2 S2 O7 ! TiOðSO4 Þ + K2 SO4

On boiling or at higher pH values, titanyl salts tend to hydrolyze under separation of
TiO2 · H2O or TiO2 · 2H2O.
In accordance with its amphoteric behavior, TiO2 dissolves in concentrated solution of
alkali hydroxides to form hydrated titanates, such as M2ITiO3 · nH2O and M2 I Ti2 O5 · nH2 O:

TiO2 + 2OH− ! TiO3 2− + H2 O

Similar but anhydrous titanates are obtained by fusing the corresponding metal ox-
ides with TiO2.
Several minerals, for example, ilmenite, FeTiO3, and perovskite, CaTiO3, may also be
classified as titanates. In addition to the so-called metatitanates, M2ITiO3 and M2IITiO3,
orthotitanates, M4I TiO4, and M2IITiO4, have also been described. Ti(IV) is capable of
forming rather stable anionic complexes as well. Thus, on dissolving TiCl4 in aqueous
HCl oxo-chloro complex anions and with excess of HCl, the [TiCl6]2– ion may be obtained.
In analytical chemistry, the highly stable [TiF6]2– anion is of some interest.

Peroxo complexes of titanium(IV)

The substitution of oxo groups by the peroxo anion in transition metal complexes is a
facile reaction, usually yielding characteristically colored peroxo complexes. Thus, the
TiO2+ ion and related Ti(IV) species and H2O2 give the peroxotitanyl cation, Ti(O2)2+, in
slightly acidic solution that has a typically orange color:

TiO2 + + H2 O2 ! TiðO2Þ2+ + H2 O

1.4 Titanium(III) compounds

Binary compounds
Titanium(III) halides are polymeric solids containing chloro-bridges. TiCl3 occurs in
four modifications. The purple α-form is obtained by reducing TiCl4 with hydrogen at
500–1,200 °C. Low-temperature reduction of the tetrachloride with aluminum alkyls
gives a fibrous β-TiCl3, which is of industrial significance for the stereospecific poly-
merization of propylene. TiCl3 forms numerous complexes, [TiCl3Ln] (n = 1–6), with
suitable Lewis basic ligands L. TiCl3 and other Ti(III) derivatives tend to disproportion-
ate into Ti(IV) and Ti(II) on heating:

TiCl3 ! TiCl4 + TiCl2

Ti(III) halides are strong reducing agents and are rapidly oxidized in air.
 1.6 Chemicals and apparatus 19

Oxides and hydroxides

Ti2O3 is obtained from TiO2 at 1,000 °C in a stream of hydrogen. It is quite inert and at-
tacked only by oxidizing acids. Addition of aqueous alkali to Ti(III) salt solution precipi-
tates dark purple Ti(OH)3, which is most appropriately described as hydrous Ti(III) oxide.
Ti(OH)3 is rather sensitive to air and reduces even water under liberation of hydrogen.

Aqueous chemistry of titanium(III)

Reduction of acidic Ti(IV) solutions by base metals, such as Mg or Zn, is the most com-
mon method to prepare Ti(III) compounds. These aqueous solution contains the violet
[Ti(H2O)6]3+ cation. Acidic Ti(III) solutions are also oxidized by air but at a much slower
rate than the basic system. Ti3+ solutions are of use in volumetric analysis as rapid and
mild reducing agent.
The hexaquo ion [Ti(H2O)6]3+ is the predominating constituent of slightly acidic
solutions.
Nevertheless, it hydrolyzes partially but not to such an extent as Ti(IV) due to
lower ON of the central atoms:

3+
2+
TiðH2 OÞ6 ! TiðOHÞðH2 OÞ5 + H+

From aqueous solutions of Ti3+, two isomeric TiCl3·6H2O complex salts, one violet and
the other brown, may be isolated. The type of isomerism encountered here is called
hydrate isomerism.

1.5 Titanium(II) compounds

As Ti(II) has no aqueous chemistry, it is of minor interest for this practical course. For
details, consult a comprehensive textbook of inorganic chemistry.

1.6 Chemicals and apparatus

Chemicals Apparatus

– Concn. sulfuric acid Small flask

– Titanium powder Water bath
– Trivalent titanium sulfate Test tube
– Grain of zinc
– Sodium hydroxide
– Distilled water
– Titanyl sulfate
20 Experiment 1

(continued)

Chemicals Apparatus

– Dilute cupric chloride

– Ferric chloride solution
– Titanium(III) hydroxide

1.7 Procedure

1.7.1 Conversion of Ti metal to Ti3+ by sulfuric acid

Fill the small flask three quarter full with semiconcentrated H2SO4, mix with a small
amount of titanium powder, and heat the mixture for a few minutes in water bath.
The start of the reaction is indicated by vigorous gas evolution. Later on, the solution
turns violet due to the generation of the hexaquo cation [Ti(H2O)6]3+. Save this solu-
tion for further tests:
+
2Ti + 6H+ ! 2Ti3 + 3H2

1.7.2 Reduction of tetravalent titanium with zinc in dilute sulfuric acid

Place 12–15 drops of titanyl sulfate solution into a test tube and add a grain of zinc.
Heat carefully until the solution becomes violet, the characteristic color of the Ti3+
ion. Save the solution for further experiments:

Zn + 2H+ ! Zn2+ + 2H

TiO2+ + H+ ! H + Ti3+ + H2 O

1.7.3 Preparation of titanium(III) hydroxide

Add three to four drops of the Ti3+ solution from Experiment 2.1 into another test tube
and add four drops of 2 N NaOH. Do not shake the test tube in order to avoid side
reactions. Bluish black titanium(III) hydroxide is precipitated:

Ti3+ + 3OH− ! TiðOHÞ3 ðsÞ

 1.7 Procedure 21

1.7.4 Hydrolysis of titanium(III) and titanium(IV) salts

Place three to four drops of a solution of titanyl sulfate into one test tube and the
same volume of the solution of trivalent titanium sulfate into another one (refer to
Experiment 2.1). Add an equal volume of distilled water to both test tubes. Boil the
solution for some minutes. In which case do you observe hydrolysis taking place? Explain
your observation.

1.7.5 Reducing properties of titanium(III) hydroxide

Prepare Ti(OH)3 as in Experiment 2.3. Do not shake the test tube. Observe the contents
of the test tube carefully and you will see gas evolution. Moreover, the mixture slowly
decolorizes and the blue Ti(OH)3 precipitate turns white. This is because Ti(OH)3 and
other titanium(III) compounds are unstable to water in alkaline medium, and the fol-
lowing redox process takes place:

2Ti ðOHÞ3 + 2H2 O ! 2TiO2 · 2H2 O + H2

1.7.6 Reducing properties of Ti(OH)3: reaction with oxygen

Prepare Ti(OH)3 as in Experiment 2.3. Then shake the test tube vigorously. The bluish
precipitate turns white immediately without any gas evolution. This is due to the
rapid oxidation of Ti(OH)3 by atmospheric oxygen yielding TiO2 · 2H2O:

4TiðOHÞ3 + O2 + 2H2 O ! 4TiO2 · 2H2 O

In contrast to the above process, the reaction with water is much slower. Suggest an
explanation.

1.7.7 Reducing properties of trivalent titanium: reduction of copper(II) chloride

Transfer three to four drops of the Ti3+ solution prepared in Experiment 2.1 into another
test tube and add two to three drops of dilute cupric chloride solution. The mixture is
decolorized and a white precipitate of CuCl, which is insoluble in water, settles:

Ti3+ + Cu2+ + Cl− + H2 O ! TiO2+ + 2H+ + CuCl

22 Experiment 1

1.7.8 Reduction properties of trivalent titanium: reduction of ferric chloride

Transfer three to four drops of the Ti3+ solution prepared in Experiment 2.1 into an-
other test tube and add three to four drops of ferric chloride solution. The violet color
of Ti3+ vanishes completely:

Ti3+ + Fe3+ + H2 O ! TiO2+ + Fe2+ + 2H+

The resulting Fe3+ is a pale green color that is barely recognizable when diluted.

1.8 Observation

Color change
Evolution of gas
Sound of reaction

1.9 Results and discussion

1.10 Review problems

1. Discuss two methods for the preparation of titanium metal from TiO2.
2. Explain the ARKEL/De BOER process for the synthesis of pure titanium.
3. Describe the synthesis, structure, and properties of TiCl4.
Experiment 2

2.1 Chemistry of vanadium

2.2 Objective

Students should be able to:

– prepare vanadium pentoxide,
– observe the characteristic of vanadium pentoxide,
– observe the amphoteric property of V2O5,
– synthesize ammonium thiocyanate and vanadium pentasulfide, and
– identify vanadium(V) by the reaction of peroxovanadium(V).

2.3 Theory

Occurrence
Vanadium is widespread in the Earth’s crust (0.016%), but hardly found in great de-
posit. Compared to copper (0.01%) and cobalt (0.012%), vanadium cannot be considered
a rare element. Some of the most frequent minerals are patronite, V2S5·XS, vanadite,
3Pb3(VO4)2·PbCl2, and Carnotite, K2(VO2)2(VO4)2·3H2O. In all these minerals, vanadium
prefers the oxidation state +5. Compounds with vanadium in the +4, +3, and +2 oxida-
tion states have been isolated from aqueous solution but do not occur in nature.
Vanadium has two isotopes: 50V (0.24%) and 51V (99.76%).

Preparation
Most vanadium minerals do not contain more than 0.2% of the element. That is why, in
the first step, they have to be concentrated up to 5% V. For further upgrading, the re-
sulting slag is molten with Na2CO3 at 8,500 °C and, after cooling, extracted with water.
On acidifying the aqueous vanadate extract, V2O5 is precipitated. Vanadium pentoxide
itself or VCl3 as another possible precursor can be reduced by base metals to give pure
vanadium metal. Carbon and hydrogen are not suitable as reducing agents because
they tend to form interstitial compounds with vanadium:
9,000 °C
V2 O5 + 5Ca ! 5CaO + 2V ðVan Arkel=De Boer processÞ
800 °C
VCl3 + 3Mg ! 3MgCl2 + 2V ðVan Arkel=De Boer processÞ
argon

Commercially, vanadium is mainly produced as an iron alloy called ferrovanadium.

https://doi.org/10.1515/9783111574349-003
24 Experiment 2

Properties

Physical properties
Pure vanadium crystallizes in a cubic body-centered lattice with a melting point of
1,700 °C. Addition of carbon (interstitial) raises the melting temperature markedly up
to 2,700 °C (10% carbon content).
The metal resembles titanium in being resistant to corrosion, hard, and steel-
gray. Extremely pure vanadium is, ductile.

Table 1.4: Some physical properties of chromium.

Properties Z Electronic Atomic Density m.p. b.p. χ Atomic

configuration weight radius

Expression  [Ar]ds . . g/c m , °C , °C .  pm

Chemical properties
In the massive state, vanadium is not attacked by air, water, alkalis, or nonoxidizing
acids, except HF. Oxidizing acids such as concentrated sulfuric acid and nitric acid dis-
solve the metal. At elevated temperature, it reacts with many nonmetals, for example,
C, N, H, P, and As, mostly forming interstitial and nonstoichiometric compounds. De-
pending on the reaction temperature, various oxides have been observed, for instance,
V2O3 (brown), VO2 (black), and V2O5 (orange). Vanadium and chlorine react at 200 °C,
yielding VCl4 as a dark brown liquid.

Oxidation state
The simple redox chemistry of vanadium is particularly interesting to inorganic chem-
ists because vanadium readily exists in four different oxidation states: +5, +4, +3, and +2,
corresponding to d0, d1, d2, and d3 electronic configurations.

Application
About 95% of vanadium produced is consumed by steel industry for making hard and
expansible sorts of steel. Vanadium pentoxide, ammonium metavanadate, and silver
vanadate are of importance as catalysts in chemical industry (SO2 oxidation, petrol
cracking, etc.).
 2.3 Theory 25

2.3.1 Vanadium(V) compounds

Halides
The only binary vanadium halide known is VF5, a colorless, viscous liquid with poly-
meric structure. Furthermore, there are some oxyhalides VOX3, (X = F, Cl, Br) and
VO2X (X = F, Cl). All these halides are very sensitive to hydrolysis and not very stable
to reduction.

Oxides
The most important vanadium oxide, V2O5, is usually prepared by thermal decomposi-
tion of ammonium metavanadate:
heat
2NH4 VO3 ! − ! V2 O5 + 2NH3 + H2 O

Another method of preparation is the precipitation from metavanadate solutions by

dilute sulfuric acid:

2VO3 − + 2H+ ! V2 O5 + H2 O

V2O5 is a highly poisonous, brick red powder. It is sparingly soluble in water, yielding
a slightly acidic, pale yellow solution. Although the acidic properties predominate,
V2O5 also dissolves in acids. At higher temperature, V2O5 releases oxygen forming the
dark blue VO2. The latter can be reoxidized by amphoteric oxygen to V2O5. This partic-
ular property makes it an excellent catalyst for many oxidation reactions, for exam-
ple, the contact process for sulfuric acid production and alcohol oxidation:
higher temp
2VO2 + O2 Ð V2 O5
lower temp

Vanadate(V)
Vanadium pentoxide dissolves in aqueous alkali to give the colorless orthovanadate,
VO43–. This anion is stable only at pH 13:

V2 O5 + 6OH− ! 2VO4 3− + 3H2 O

Lowering of the pH value initiates polycondensation processes and the formation of so-
called isopolyanions. Thus, in the pH range 13–3, the yellow V4O74– is encountered. Be-
tween pH 8 and 6 the tetravanadate, V4O124–, and in acidic medium of pH 6–4 the deca-
vanadate, V10O286–, were detected. The latter two anions have a bright orange color. In
addition to various isopolyvanadates, there are also protonated species that may be
considered as derivatives of the corresponding isopolyvanadic acids. At around pH 2,
V2O5 is precipitated with more acids. It is redissolved to give the pale yellow vanadyl
cation,VO2+:
26 Experiment 2

VO4 3− + 2H+ Ð VO3 − + H2 O ðisopoly vanadatesÞ

2VO3 − + 2H+ Ð V2 O5 + H2 O

V2 O5 + 2H Ð 2VO2 + + H2 O

The most common and commercially available vanadate is the tetravanadate, Na4
[H2V4O13], that is conventionally named sodium metavanadate, NaVO3∙H2O. It is only
the mentioned here that vanadium(V) is known to form various coordination com-
pounds, which, in principle, can be regarded as derivatives of the ions VO2+ and VO3+.

Peroxo compounds
In addition to the vanadyl cation, VO2+, acid solutions may also contain the hydrated VO3+
species. The latter has been reported to reacted with hydrogen peroxide to give the
red-brown peroxovanadyl cation, [V(O2)]3+. Excess of H2O2 must be avoided because in
the second step the pale yellow peroxo acid H3[VO2(O2)2] is formed. This compound
has the same color as VO2+:

VO3+ + H2 O2 ! VðO2 Þ3+ + H2 O


½VðO2 Þ3+ + H2 O2 + 2H2 O ! H3 VO2 ðO2 Þ2 + 3H+

Vanadium sulfides
Addition of ammonium sulfide to a neutral vanadium solution turns the color brown
to red-violet due to the formation of thiovanadates, VS43–:

VO2 + + 4S2− + 4NH4 + ! VS4 3− + 4NH3 + 2H2 O

On acidifying this solution, brown V2S5 is separated. Acidic V(V) solutions do not give
a sulfide precipitation after H2S treatment but reduced to blue V(IV):

8VO2 + + H2 S + 14H+ ! 8VO2+ + S4 O2− + 8H2 O

2.3.2 Vanadium(IV) compounds

Halides
Where VI4 has only been detected in the gas phase and VBr4 decomposes already at
−23 °C, the red-brown, monomeric liquid VCl4 is quite stable and boils at 154 °C. Then
latter is conveniently synthesized by chlorination of vanadium or V2O5:
270 °C
V + 2Cl2 ! VCl4
 2.3 Theory 27

red hot 1
V2 O5 + 4CCl4 ! VCl4 + 4COCl2 + O2
2

VCl4 is very sensitive to hydrolysis and reacts violently with water to give a solution
of various oxo-vanadium(IV) chlorides.

Oxo-vanadium(IV) compounds
In case of vanadium oxidation state +4, which seems to be the most stable under nor-
mal condition by simple heating or with mild reducing agents, such as oxalic acid, V2O5
is converted into the dark blue VO2. This oxide is amphoteric and soluble in acids and
bases yielding either the blue VO2+ cation or complex vanadate(IV), VO44–.
The vanadyl cation, VO2+, is actually hydrated and better described as [VO(H2O)5]2+.
Addition of alkali leads to the precipitation of yellow VO(OH)2. The hydroxide is simi-
larly amphoteric as the oxide and dissolves in acids and bases.
The VO2+ cation can also be obtained by the reduction of V2O5 or V2O+ with S2O or
HCl in acid aqueous solution.
The vanadyl(VI) cation has been shown to create an extensive coordination chem-
istry with complexes [VOLn]m± (n = 4 or 5; L = neutral or anionic ligand).

2.3.3 Vanadium(III) compounds

Halides
The trihalides VX3 are shown for X being F, Cl, Br, and I. They are crystalline polymers
with vanadium being octahedrally surrounded by six halogen atoms. The compounds
are sensitive to hydrolysis and oxidized by air. On heating, they tend to disproportion-
ate into VX2 and VX4:

2VX3 ! VX2 + VX4

The red-violet VCl3 can be easily obtained by oxidative chlorination of vanadium, chlo-
rination of vanadium, chlorination of V2O3, or by thermal decomposition of VCl4:

150 °C 1
VCl ! VCl3 + Cl2
2
200 °C
V2 O3 + 3SOCl2 
! 2VCl3 + 3SO2
reflux
2V + 6ICl ! 2VCl3 + 3I2

In water, all the halides hydrolyze to give the green hexaqua cation [V(H2O)6]3+.
28 Experiment 2

Oxide and hydroxide

Vanadium oxide is a black solid prepared by reduction of V2O5 with hydrogen or carbon
monoxide. It tends to form oxygen-deficient forms without structural changes. V2O3 is
purely basic and dissolves in acids under formation of the V3+ cation. Subsequent addi-
tion of alkali gives sparingly soluble, hydrated hydroxide, V(OH)3. The latter is very sensi-
tive to oxidation by air. Notice that oxidation is generally encouraged by a basic reaction
medium.

Vanadium(III) in aqueous solution

The green [V(H2O)6]3+ and related ions can be prepared as mentioned above or by
chemical and electrochemical reduction of vanadium compounds in the +4 and +5 oxi-
dation states. The reduction of VO2+ by iodide in acidic medium is described in detail in
the experiment part. V3+ is also subject to aerial oxidation but considerably more stable
than the hydroxide.
The hexaquo cation, [V(H2O)6]3+, hydrolyzes partially in water to give hydrated
[V(OH)]2+ and VO+ cations. It is, however, stable enough to occur in simple V(III) salts
such as vanadium alums, MIV(SO4)2∙12H2O.

2.3.4 Vanadium(II) compounds

Vanadium(II) forms a black VO, which tends to nonstoichiometry, exhibits metallic

properties, and is basic in nature. Therefore, it dissolves in acids.
Electrolytic or chemical reduction of vanadium compounds in higher oxidation
state in acidic aqueous solution yields the violet, air-sensitive [V(H2O)6]2+. V2+ is a very
powerful reducing agent, and reduces even water to hydrogen:

2V2+ + 2H2 ! 2V3+ + H2 + 2OH −

[V(H2O)6]2+ is the constituent of several V(II) salts, for example, VSO4∙4H2O and M2I[V
(H2O)6](SO4)2 with M = NH4+, K+, and so on. V(II) has a d3 configuration. This is the rea-
son for the kinetic inertness of [V(H2O)6]2+ and related complexes in aqueous solution.
Substitution reactions are evidently relatively slow.
 2.5 Procedure 29

2.4 Chemicals and apparatus

Chemicals Apparatus

– Aqueous solution of sodium metavanadate or with Spatula

solid ammonium metavanadate (NH4VO3) Crucible
– Concentrated H2SO4 Glass rod
– 2 N NaOH Test tubes
– Distilled water
– Sodium metavanadate
– Barium chloride, copper sulfate, silver nitrate
– Sodium or ammonium sulfide solution
– 3% H2O2, oxalic acid, H2C2O4 and V2O5 powder
– Potassium iodide
– Dilute solution of permanganate

2.5 Procedure

1 Preparation and reaction of vanadium compounds

1.1 Preparation of vanadium pentoxide, V2O5

Heat a micro-spatula full of dry ammonium metavanadate, NH4VO3, in crucible with
stirring.
Using glass rod, the white color of NH4VO3 will turn to brick red, which is the
characteristic of V2O5:
Heat
NH4 VO3 + ! V2 O5 + 2NH3 + H2

1.2 Amphoteric property of V2O5

Add very small amount of V2O5 (~0.1 mg) in each of three test tubes. Then add four to
five drops of concentrated H2SO4 into the first test tube, equal amount of 2 N NaOH to
the second test tube, and five to seven drops of distilled water into the third test tube
and heat them in water bath for about 10 min. Observe color changes in each test tube:

V2 O5 + 2H+ ! 2VO2 + + H2 O

V2 O5 + 6 OH− ! 2VO4 3− + 3H2 O

Transfer a few drops from aqua solution of V2O5 into another test tube containing
neutral litmus paper. Observe the change of color in litmus paper and select the possi-
ble equation from the following and explain:
30 Experiment 2

V2 O5 + H2 O ! 2VO3 − + 2 H+

V2 O5 + 3H2 O ! 2VO + 6H+

V2 O5 + H2 O ! 2VO2 + + 2OH

1.3 Conversion of tetravanadate to hexavanadate

Place three to four drops of sodium metavanadate (tetravanadate) into a test tube and
add one drop of concentrated H2SO4. Pale yellow color of tetravanadate turns to yellow-
ish orange, characteristics of hexavanadate, V6O174–, and related species. Write the ionic
equation assuming metavanadate (a) as VO3– and (b) V4O3–

1.4 Preparation of sparingly soluble vanadate

Place three to four drops of sodium metavanadate (tetravanadate) into each of four
test tubes and add the same amount of barium chloride, copper sulfate, silver nitrate,
and lead acetate separately.
Depending on the pH of the medium, metavanadate or orthovanadate can be ob-
tained. Write the color of each precipitate:

Ba2+ + 2VO3 − ! BaðVO3 Þ2

Cu2+ + 2VO3 − ! Cu ðVO3 Þ2

Pb2+ + 2VO3 − + 2H2 O + 4Ac− ! PbðVO4 Þ2 + 4HAc ðAc− = CH3 COO−Þ

Ag2+ + 2VO3 − ! AgðVO3 Þ

1.5 Synthesis of ammonium thiocyanate and vanadium pentasulfide

Place three to four drops of sodium metavanadate (tetravanadate) into a test tube and
add dropwise sodium or ammonium sulfide solution until you observe brown or red-
violet color depending on the sulfur content.
Note: Thiovanadate can be formed in neutral or slightly alkaline (NH4)2S saturate
with H2S to give very good VS43–:

V2 O5 + 4S2− + 3H2 O ! VS4 3− + 6OH−

To the above solution, add 2N, HCl dropwise and you observe brown precipitate that
indicates the formation of V2S5.
Note: Since H2S liberates on the reaction condition, some vanadium (V) reduces to
soluble VO2+ form. As a result, the solution turns to bluish:

VS4 3− + 8H+ ! V2 S5 + 2H2 S

V2 S5 + H2 S + 2H2 O ! VO2+ + S + SH−

 2.5 Procedure 31

1.6 Identification of vanadium (V) by the reaction of peroxovanadium(V)

Place four to five drops of saturated sodium metavanadate into a test tube and add two
to three drops of 2N, H2SO4 followed by one to two drops of 3% H2O2. Observe the color
changes.
Note: A type of per-oxovanadium compound formed depends on the amount of
H2O2, with limited amount of H2O2. [VO(O2)]+ is formed and such species have red-brown
color; however, if excess H2O2 is added, the color will be pale yellow due to formation of
H3[VO2(O2)2]. However, per-oxo compounds are unstable, and H2O2 decomposes due to
the catalytic activity of transition element vanadium so that you will notice vigorous evo-
lution of oxygen, O2.

2 Preparation and reaction of vanadium(IV) compounds

2.1 Preparation of vanadium dioxide, VO2

Mix equal amounts of oxalic acid, H2C2O4, and V2O5 powder in a test tube. Fix the tube
with an iron stand and heat. You will observe the dark blue color because of the for-
mation of VO2:
heat
V2 O5 + ðCOOHÞ2 ! VO2 + CO2 + H2 O

2.2 Amphoteric property of VO2

From Experiment 2.1, place small amount of VO2 into two test tubes and add four to
five drops of 2N, NaOH into one of the tubes and equal amount of 2N, H2SO4 into the
other. Heat both test tubes gently to dissolve the solid and observe the color of the
resulting solution:
 
VO2 + 2OH−VO3 2− + H2 O or VO4 4− and V4 O9 2−

VO2 + 2H+ VO2+ + H2 O ðmore precisely written as penta hydratedÞ

2.3 Reduction of vanadium(V) by sodium sulfite, Na2SO3, in aqueous solution

Place five to eight drops of saturated sodium metavanadate into a test tube and add two
to three drops of 2N, H2SO4 followed by two to three crystals of Na2SO3. Heat with stir-
ring using glass rod until evolution of SO2 gas stops. You will observe blue colored solu-
tion that contains VO2+ and keep it for the next experiments:
+
VO3 − + SO2 + 4H+ ! VO2 + SO4 2− + 2H2 O

Write another possible equation using VO+ and HSO3– as starting reactants.
32 Experiment 2

2.4 Hydroxides of tetravalent vanadium

To the solution of Experiment 2.3, add 2N, NaOH dropwise and you will observe yel-
low precipitate due to the formation of VO(OH)2:

VO2+ + 2OH− ! VOðOHÞ2

The hydroxide VO(OH)2 is expected to be amphoteric so check it using 2N, NaOH and
2N, H2SO4 and write the equations.

2.5 Reduction property of tetravalent vanadium: reduction of MnO4-

in acidic media
Place three to five drops of dilute solution of permanganate, MnO4–, and add one to
two drops of 2N, H2SO4 followed by two to three drops of vanadyl, VO2+, solution. The
solution decolorizes due to the reduction of permanganate:

VO2+ + MnO4 − + H2 O ! 5VO2+ + Mn2+ + 2H+

2.6 Identification of vanadium by reduction with hydrochloric acid, HCl,

and reoxidation with iron(III) chloride
Place three to four drops of saturated sodium metavanadate into a test tube and add
two to three drops of concentrated HCl. Boil it until the appearance of blue color, which
indicates VO2+. Then add two to three drops of ferric chloride, FeCl3, and the blue color
turns to slightly yellow color. This confirms reoxidation of VO2+ to VO2+:

VO2+ + 2Cl− + 4H + VO2+ + Cl2+ 2H2 O

VO2+ + Fe3+ + H2 O ! VO2+ + Fe2+ + 2H+

3 Compounds of tetravalent vanadium

3.1 Reduction of pentavalent vanadium to tetravalent

Mix 5–10 drops of saturated sodium metavanadate and one to two drops of 2N, H2SO4
into a test tube.
Then add five to six drops of potassium iodide (KI) solution and heat the mixture
until you observe green color of [V(H2O)6]3+.
Note: Green color does not appear unless all iodine has been evaporated through
boiling. In order to check the presence of iodine, transfer a drop of sample solution in a
test tube containing 8–10 drops of starch solution. Iodine forms the dark blue color. To
remove iodine, put the remaining solution in an evaporating dish and heat gently on a
lower flame by adding some drops of water if the volume of the solution becomes too
small.
 2.6 Observation 33

When all iodine evaporates, the solution turns to green:

3
VO2+ + 3I− + 4H+ ! V3+ + I2 + 2H2 O
2

3.2 Preparation and properties of vanadium(III) hydroxides

Place two to three drops of V3+ from Experiment 3.1 into two test tubes and add two to
three drops of 2N, NaOH.
Notice the formation of precipitate, V(OH)3. This hydroxide is purely basic; prove
that by testing its behavior toward 2N, H2SO4 and NaOH. Write the chemical equations
of precipitate and dissolution.

4 Compounds of divalent vanadium

4.1 Successive reduction V5+ to V2+

Acidify 12–15 drops of saturated sodium metavanadate with 4–5 drops of concentrated
HCl into a test tube and add 2–3 zinc grains.
Note: The test tube should not be too small as H2 evolves. Gradual color changes
from yellow (VO2+) to green due to the mixture of VO2+/VO2+ to blue (VO2+), eventually
green (V3+) to violet (V2+):

VO2+ + Zn + 4H+ ! VO2+ + Zn2+ + 2H2 O

VO2+ + Zn + 4H+ ! V3+ + Zn2+ + 2H2 O

V3+ + Zn ! V2+ + Zn2+

4.2 Preparation and properties of vanadium(II)hydroxides

Place two to three drops of V3+ from procedure 4.1 into two test tubes and both test
tubes add three to four drops of 2N, NaOH until the formation of precipitate, V(OH)2.
This hydroxide is purely basic; prove by testing its behavior toward 2N, H2SO4 and
NaOH. Write the chemical equations of precipitate and dissolution.
Note: In the test tube, Zn2+ also exists and can form Zn(OH)2; however, it has am-
photeric property so that it dissolves in excess NaOH through forming [Zn(OH)3]–. The
remaining nonsoluble part of the precipitate is expected to be V(OH)2.

2.6 Observation

Color change
Evolution of gas
Sound of reaction
34 Experiment 2

2.7 Results and discussion

2.8 Review problems

1. In which types of chemical compound does vanadium occur in nature?

2. How do you prepare elemental vanadium from V2O5?
3. Vanadium tetrachloride is a brown oily liquid and may be synthesized from V/Cl2
or V2O5/SOCl2. Write the correct equations.
4. Discuss the acid–base properties of V oxides you do know.
Experiment 3

3.1 Chemistry of chromium

3.2 Objective

Students should be able to:

– understand the most important oxidation states of chromium,
– describe the preparation of ferrochromium and pure chromium,
– prepare chromium trioxide, and
– understand hydrolysis of Cr(III) salts in the presence of carbonate and ammo-
nium sulfide.

3.3 Theory

The element
Chromium is named after Greek word chrōma, meaning color, because many of its
compounds are intensely colored. Chromium is a steely-gray, lustrous, hard, and brit-
tle metal found in Group 6 in the periodic table.

Table 1.5: Some physical properties of chromium.

Properties Z Electronic Atomic Density m.p. b.p. χ Atomic

configuration weight radius

Expression  [Ar]ds . . g/c , °C , °C .  pm

Occurrence
In nature, chromium occurs as chromite (chrome iron ore), FeCr2O4, and crocoites (red
lead ore), PbCrO4. Chromium is a trace element. Its content in the Earth’s crust amounts
to 200 g/t. The chromium content in the plant has been estimated to be 5 g/t. The most
stable oxidation state of chromium is +3 although +7 is also quite common. Compounds
with chromium in all the other positive ON have been synthesized as well.

Preparation
If chromium is needed as an additive for iron alloys, chromite is directly reduced by car-
bon to give a carbon-containing ferroalloy called ferrochromate (about 60% chromium):

FeCr2 O4 + 4C ! Fe=2Cr + 4CO

https://doi.org/10.1515/9783111574349-004
36 Experiment 3

Pure chromium can be obtained by fusing chromite and alkali hydroxide in the pres-
ence of oxygen. Chromium is oxidized yielding soluble chromate(IV), whereas iron re-
mains as insoluble Fe(OH)3. Chromate is then transferred into sodium dichromate
followed by reduction with carbon to give chromium(III) oxide. Further reduction of
Cr2O3 to metallic chromium is accomplished using aluminum as the reducing agent:

4FeCr2 O4 + 7O2 + 16NaOH ! 8Na2 CrO4 + 4FeðOHÞ3 + 2H2 O

Na2 Cr2 O7 + 2C ! Cr2 O3 + Na2 CO3 + CO

Cr2 O3 + 2Al ! Al2 O3 + 2Cr

Properties

Physical properties
Chromium is white shiny hard and brittle metal with the melting point of 1,903 ± 10 °C.

Chemical properties
Chromium is insoluble in aqua regia (chloronitrous acid) and dilute or concentrated ni-
tric acid because of its passivation . Nonoxidized mineral acids, such as HCl and H2SO4,
dissolve the metal readily. At higher temperatures, chromium reacts with B, N2, P, O2,
and some other nonmetals.
Especially Cr(VI) components but, to some extent, also other chromium-containing
substances are highly carcinogenic.

Application
Chromium is used in the industry for the production of steel. With Cr content higher
than 12% steel becomes extraordinarily resistant to corrosion and heat because of passiv-
ating influence of particular elements. Chromium may serve as protective for other met-
als (chromium plating), and is also used for several alloys, as well as dying and tanning.

3.3.1 Chromium(II) compounds

Binary chromium(II) compounds

Anhydrous Cr(II) halides, Crx2 (x = Cl, B, I), are obtained by the action of HF, HCl, HBr,
or iodine on the metal at 600–700 °C, or by reduction of the trihalides CrX3 with hydro-
gen at 500–600 °C. Most important is the white, crystalline CrCl2. All chromous halides
dissolve readily in water to give the sky-blue hexaquo cation [Cr(H2O)6]2+. In general,
chromium(II) compounds are highly sensitive to oxygen.
 3.3 Theory 37

The chromous cation and chromium(II) compounds

In aqueous medium, chromium(II) compounds may be synthesized either by reduc-
tion of Cr(III) precursor zinc amalgam or electrolytically as well as by dissociation of
the metal in mineral acid under exclusion of air:

2Cr3+ + Zn ! 2Cr2+ + Zn2+

Cr + 2H+ ! Cr2+ + H2

Chromium(II) represents a d4 system and forms many octahedral complexes. Most char-
acteristic is a blue chromous cation [Cr(H2O)6]2+. It possesses a high-spin electronic con-
figuration (t2g) 3(eg)1. As the eg electron is easily slightly antibonding, it is readily split
off under oxidation to Cr(III). Thus, Cr2+ acts as a strong reducing agent:

4Cr2+ + O2 + 4H+ ! 4Cr3+ + 2H2 O

In the absence of suitable oxidizing agent, Cr(II) salts may even reduce water:

2CrCl2 + 2H2 O ! 2CrðOHÞCl2 + H2

On addition of alkali hydroxide to an aqueous Cr(II) solution, the very air-sensitive, yel-
low Cr(OH)2 is precipitated. This hydroxide is purely basic in nature.

3.3.2 Chromium(III) compounds

Of all common oxidation states of chromium, Cr(III) is assumed to be the most stable one.

Halides, CrX3
CrCl3 is a common starting material for synthetic purpose and can be prepared by:
a) Chlorination of the metal

3
Cr + Cl2 ! CrCl3
2

b) Dehydration of the hydrated chloride

CrCl3 · 3H2 O + 3SOCl2 ! CrCl3 + 3SO2 + 6HCl

c) De-oxygenation of the oxide

Cr2 O3 + 3CCl4 ! 2CrCl3 + 3COCl2

Due to kinetic hindrance, CrCl3 dissolves in water at an extremely low rate. Interestingly,
the rate of dissolution can be enormously increased by catalytic quantities of Cr2+. The
latter is formed by adding traces of reducing agents such as Zn and Mg.
38 Experiment 3

Chromium(III) is considered the most stable state of this element. In basic medium,
especially to hexavalent, chromate occurs with oxidizing agents such as hydrogen perox-
ide and bromine. In acidic solution, such a powerful oxidant as peroxodisulfate is re-
quired for the preparation of dichromate, Cr2O72–, from chromium(III) compounds (of
next subsection and experimental part).

3.3.3 Chromium(VI) compounds

CrO2 + 2HCl ! Cr2 O2 Cl2

K2 Cr2 O7 + 4KCl + 3H2 SO4 ! 2CrO2 Cl2 + 3K2 SO4 + 3H2 O

The only oxohalide that is much important to be mentioned here is chromyl chloride,
CrO2Cl2, a deep-red liquid with b.p. 117 °C. The compound is obtained either from
chromium(VI) oxide with concentrated HCl or by concentrating with dichromate in al-
kali chloride and concentrated sulfuric acid.
The latter reaction is of analytical use as it proves to be the way of separating even
small amount of chromium from a sample by converting it into chromyl chloride and
subsequent distillation of volatile product.
CrO2Cl2 is a strong oxidizing agent and hydrolyzes immediately in water.

Other oxo-chromium(VI) compounds

Chromium(VI) oxide, CrO3, an orange, crystalline substance of m.p. 170 °C, precipitates
on adding concentrated sulfuric acid to a saturated solution of alkali dichromate:

Cr2 O7 2− + 2H+ ! 2CrO3 + H2

As CrO3 and related Cr(VI) compounds are very efficient oxidizing agents, a solution of
K2CrO7 in concentrated H2SO4, called chrome sulfuric acid, is frequently used for de-
greasing and cleaning laboratory glassware. The red-brown solution forms needles of
CrO3 on standing. A brown precipitate, casually settling in the same mixture, is chromyl
sulfate, CrO2SO4:

CrO3 + H2 O4 ! CrO2 SO4 + H2 O

CrO3 behaves like a typical acid anhydride, is soluble in water, and is very poisonous.
Above its melting point, CrO3 loses oxygen under formation of dark green Cr2O3. Chro-
mite(VI), M2ICrO4 (yellow), and dichromate(VI), M2ICr2O7 (orange), are usually synthe-
sized by the oxidation of Cr(III) compounds in basic or acidic medium. Sparingly soluble
chromates precipitate with Ba2+, Pb2+, and Ag+.
On acidifying a chromate solution, its color turns from yellow to orange due to the
formation of dichromate. This condensation reaction is initiated by protonation of the
chromate followed by losing water:
 3.3 Theory 39

CrO4 2− + H+ ! CrO3 ðOHÞ−2CrO3 ðOHÞ− ! Cr2 O7 2− + H2 O

These equilibria are extremely pH dependent. Further addition of acid leads to isopoly
anions, such as Cr3O102–, Cr4O132–, and, finally, solid CrO3. Whereas some oxygen acids
tend to form simple hydrogen salts in acidified aqueous solution:

PO4 3 + H+ Ð HPO4 2−

Co3 2− + H+ Ð HCO3 −

Elements like Cr, Mo, W, V, Nb, Ta, Si, and Sn are capable of condensing to polynu-
clear anions, that is, isopolyanion.
In contrast to basic chromate solutions, dichromate in acidic medium represents
a strong oxidizing agent:

CrO4 2− + 4H2 O + 3e− ! CrðOHÞ3 + 5OH− Eθ = − 0.13 V

CrO2− + 14HO+ + 6e− ! 2Cr3+ + 21HO Eθ = + 1.33 V

Examples of oxidation with dichromate are given in the experimental part (e.g., H2S,
I–, Cl–, and Fe2+). The following reaction is employed to detect alcohol in the breath of
drunken car drivers:

CrO2− + 3CHOH + 8H+ ! 2Cr3+ + 3CH CHO + 7HO

ðOrangeÞ ðGreenÞ

Peroxo compounds of chromium(VI)

In similarity with other transitional metals in higher oxidation state (e.g., Ti, V, Nb, Ta,
Mo, and W), chromates form comparatively unstable but characteristically colored per-
oxo compounds. Thus, on treating acidic dichromate solutions with H2O2 at room tem-
perature, deep blue CrO5 is generated. The peroxide decomposes rapidly yielding green
Cr3+ and O2. CrO5 may, however, be extracted into ether and is then more stable:

CrO2− + 4HO + 2H+ ! 2CrOðOÞ + 5HO

4CrOðO2 Þ2 + 12H+ ! 4Cr3+ + 6H2 O + 7O2

At temperature below 0 °C, green cationic peroxo species, such as [Cr2(O2)]4+ and [Cr3
(O2)2]5+, have been detected. From neutral or slightly acidic solutions of dichromate
and H2O2, blue violet peroxo salts believed to contain the ion [Cr(O2)2(OH)]– could be
separated.
Alkaline chromate solutions and 30% H2O2 give, under certain conditions, red-
brown peroxochromates, M3ICrO8. All solid peroxo salts are highly explosive.
40 Experiment 3

3.4 Chemicals and apparatus

Chemicals Apparatus

Ammonium dichromate (NH)CrO Test tube

Aqueous solution of KrCr(SO)·HO Iron stand
Chromium sulfate Bunsen burner
N, NaOH and N, HSO Water bath
NaCO, (NH)SO,CrO
Potassium dichromate
CrCl·HO solid
% HO
N nitric acid
Potassium chromate (KCrO), CrO

3.5 Procedure

1 Preparation and reaction of Cr(III) compounds

1.1 Preparation of Cr(III) oxide, Cr2O3

Put (NH4)2Cr2O7 powder in a test tube and clam it vertically with iron stand and heat
until the color of ammonium dichromate disappears. The appearance of dark green
tells you the formation of chromium(III) oxide:

ðNH4 Þ2 Cr2 O7 ! Cr2 O3 + N2 + 4H2 O

1.2 Preparation of Cr(III) hydroxide, Cr(OH)3

In two test tubes, place three to four drops of aqueous KrCr(SO4)2·12H2O or chromium
sulfate, Cr2(SO2)3, and add one to two drops of 2N, NaOH into both tubes until you
observe grayish green, gel-like precipitate, which confirms the formation of Cr(OH)3.

Note:
1. Both KrCr(SO4)2·12H2O and Cr2(SO4)3 contain [Cr(H2O)6]3+ complex ion
2. Addition of excess hydroxides leads to the disappearance of precipitate, which
may be due to the formation of [Cr(OH)6]3–.

1.3 Amphoteric property of Cr(OH)3

In one of the test tubes, refer Experiment 1.2, add dropwise 2N, H2SO4 and 2N, NaOH
into the other and observe the color of the resulting solution:
 3.5 Procedure 41

dropwise
CrðOHÞ3 + 2 N 3H2 SO4 ! Cr3+ + 3H2 O
dropwise
CrðOHÞ3 + 2 N NaOH ! ½CrðOHÞ6 3−

1.4 Hydrolysis of sodium hexahydroxochromate(III): refer 1.3. above

Heat hexahydroxochromate(III), [Cr(OH)6]3–, in a test tube in water bath until grayish
color appears, which tells you the formation of Cr(III) hydroxide, Cr(OH)3:
Δ
½CrðOHÞ6 3− ! CrðOHÞ3 + 3OH−

The equilibrium will be shifted to the right due to heat.

1.5 Hydrolysis of Cr(III) salts

In five drops of litmus solution in a test tube, add two drops of chromium(III) sulfate or
chromicōsulfate, Cr2(SO4)3 · 12(H2O) and observe the color change and write the chemi-
cal equation. If violet-blue color appears, then that indicates the presence of Cr3+:

Litmus ð5dÞ + Cr2 ðSO4 Þ3 ð2dÞ ! ½CrðH2 OÞ6 OH3+ + H3 O+

1.6 Hydrolysis of Cr(III) salts in the presence of carbonate and ammonium sulfide
Place three to four drops of aqueous solution chromic salt in each of two test tubes
and add dropwise Na2CO3 solution in one of the tubes and (NH4)2S into the other. You
will observe greenish precipitate due to the formation of Cr(OH)3:

Cr3+ ð3dÞ + Na2 CO3 ðdwÞ ! CrðOHÞ3 + Na2 SO4 + CO2

Cr3+ ð3dÞ + NH4 Þ2 S ðdwÞ ! CrðOHÞ3 + Na2 SO4 + H2 S ðdw = dropwiseÞ

Note: Carbonates and sulfides in water undergo protolysis, releasing gaseous CO2 and
H2S as byproducts.

CO3 2− + H2 O ! HCO3− + OH−

HCO3− + OH− ! CO2 + OH−

S2− + H2 O ! HS− + OH−

HS− + H2 O ! H2 S + OH−

Cr3+ + 3OH− ! CrðOHÞ3

1.7 Aqua complexes of Cr(III)

In two separate test tubes, pour five to six drops of water and add some CrCl3·6H2O
solid. Heat one of the test tubes in boiling water bath for not less than 10 min until the
42 Experiment 3

color of the solution changes. Compare the color with the test tube that has been kept
at room temperature:

CrCl3 · 6H2 O ð0.01 gÞ + H2 O ð6dÞ + heat ! ½CrðH2 OÞ4 Cl2 + green

CrCl3 · 6H2 O ð0.01 gÞ + H2 O ð6dÞ ! CrCl3 · 6H2 O

Note: Chromic chloride has violet-blue color due to [Cr(H2O)6]+; however, green color
may arise from the formation of [Cr(H2O)5Cl]+ (pale-green) or [Cr(H2O)4Cl2]+ (dark green).

2 Preparation and reaction of Cr(VI) compounds

2.1 Preparation of chromium trioxide, CrO3

Dissolve 5 g of potassium dichromate in 10 mL of boiling water. Cool the solution to room
temperature and very slowly add 7 mL of concentrated sulfuric acid. Allow it to settle
down for 2 h, and then filter off the liquid potassium hydrogen sulfate from the crystals.
Heat the filtrate to 85 °C and add 5 mL of dilute sulfuric acid.
Evaporate the liquid on a water bath until crystals form on this surface, then set it
aside to crystallize. Filter through glass wool, preferably with suction, and evaporate the
filtrate to produce more crystals. To remove traces of sulfuric acid, wash the crystals
while still in the filter with concentrated nitric acid. Chromium trioxide is not soluble in
nitric acid. Transfer the crystals to a dry evaporating basin and heat in an air oven at
130 °C:

K2 Cr2 O7 + 2H2 SO4 ! 2KHSO4 + 2CrO3 ðsÞ + H2 O

2.2 Decomposition of chromic anhydride (chromium trioxide, CrO3)

Place 0.05 g of chromium trioxide in a crucible and heat it with a Bunsen burner on
asbestos wire gauze. The color changes from brown to dark green, which is the char-
acteristic color of Cr2O3:
3
CrO3 ð0.05 gÞ + heat ! Cr2 O3 + O2
2

2.3 Oxidation of trivalent Cr to chromate, Cr(VI), by hydrogen peroxide

in alkaline media
Note: Cr(III) can be oxidized to Cr(VI) in an acidic media but it needs extremely pow-
erful oxidizing agents. Refer Experiment 1.3.
Place [Cr(OH)6]3– in a test tube and add one to two drops of NaOH followed by
addition of three to five drops of 3% H2O2. Then heat the mixture in a water bath until
green color changes into yellow, which indicates the formation of chromate:
 3.5 Procedure 43

½CrðOHÞ6 3− + NaOH + 3% H2 O2 ! CrO4 2− + H2 O + 2OH−

2.4 Oxidation of trivalent to Cr to chromate, Cr(VI), by peroxodisulfate, K2S2O8

Place three to four drops of aqueous solution of chromium(III) salt in a test tube and
add the same volume of 2N, H2SO4 followed by a few crystals of potassium peroxodi-
sulfate and boil the mixture for a minute. The color of the mixture would change,
which indicates the formation of Cr2O72–:

+
Cr3 + ð3dÞ + H2 SO4 ð3dÞ + S2 O2−
8 ð1 gÞ ! Cr2 O7 + SO4 + 14H
2− 2−

2.5 Interconversion of chromate and dichromate

2K2 CrO4 + H2 SO4 ! K2 SO4 + K2 Cr2 O7 + H2 O

+
4 ð3dÞ + 2H ðdwÞ ! 2CrO4 + H2 O
2 CrO2− 2−

To three to four drops of potassium dichromate solution, add sodium hydroxide solution
dropwise until its orange color changes to yellow, which conforms the formation of the
chromate ion:

−
7 ð3dÞ + 2OH ðdwÞ ! 2CrO4 + H2 O
Cr2 O2− 2−

2.6 Preparation of sparingly soluble chromates

Place three drops of potassium chromate solution into three separate test tubes. Then
add equal volume of BaCl2 into the first test tube, lead acetate into the second test tube,
and silver nitrate into the third test tube. Note the color changes and write the ionic
equation:

4 ð3dÞ + M ð3dÞ ! M2 ðCrO4 Þ

2CrO2− n+
ðM = Ba2+ , Pb2+ , Ag+ Þ

2.7 Oxidation property of hexavalent chromium

2.7.1 Oxidation of hydrogen sulfide, H2S

Place five drops of potassium dichromate solution in a test tube and acidify it with
three drops of 2N, H2SO4. Then add freshly prepared H2S dropwise until the color
changes to green, which indicates the formation Cr3+:
+ +
7 ð5dÞ + H2 S ðdwÞ + 8H ð3dÞ ! 2Cr + 3S 7H2 O
Cr2 O2− 3+
44 Experiment 3

2.7.2 Oxidation of Iodide by dichromate in acidic media

Place five drops of potassium dichromate solution in a test tube and acidify it with
three drops of 2N, H2SO4. Then add five drops of potassium iodide solution. Observe the
color changes but if green color does not appear, heat the tube to avoid iodide ion:
+
7 ð5dÞ + KI ð4dÞ + 14H ð4dÞ ! 2Cr + 3I2 + 7H2 O
Cr2 O2− 3+

2.7.3 Oxidation of hydrochloric acid by dichromate

Place three drops of potassium dichromate solution, and add five drops of concentrated
hydrochloric acid until orange color changes to green, which is characteristic for Cr3+:
− +
7 ð3dÞ + 6 Cl ð4dÞ + 14H ð5dÞ 2Cr + 3Cl2 + 7H2 O
Cr2 O2− 3+

2.8 Peroxo compounds of chromium(VI) – blue chromium peroxide

Place five drops of potassium dichromate solution, and add drops of 2N, nitric acid until
orange color changes to green, which is the characteristic for Cr3+. Then add 0.5 mL di-
ethyl ether and three drops of 3% H2O2. Formation of blue color is the pointer for the
formation of chromium peroxide:

7 ð3dÞ + 2 N 6HNO3 ð1dÞ + H2 O2 ð3dÞ ! 2HCrO5 + 2KNO3 + 7H2 O

Cr2 O2−
+
7 ð3dÞ + 2H + 5H2 O2 ð3dÞ ! 2CrO5 + 7H2 O
Cr2 O2−

2CrO5 ! Cr2 O3 + O2

3.6 Observation

Color change
Evolution of gas
Sound of reaction

3.7 Results and discussion

3.8 Review questions

1. Describe the preparation of ferrochromium and pure chromium.

2. Cr2O3 exhibits amphoteric properties. Find chemical reactions to confirm this.
3. Write the equation for the following reactions:
a. Addition of NaOH to Cr(III) salt solutions
b. Chromium(III) chloride with sodium sulfide in water
 3.8 Review questions 45

4. Write the Lewis formulae of:

a. CrO−2 ; b. CrO−4 ; c. Cr2 O2− 7
5. CrCl3 exists in the form of three differently colored hydrate isomers. Write down
their exact formulae.
6. Complete the following reaction equations:
+
a. Cr3+ + S2 O2−
8 + H !
− +
b. Cr2 O7 + I + H !
2−
+
7 + SO3 + H !
c. Cr2 O2− 2−
+
d. CrðOHÞ3 + H !
e. CrðOHÞ3 + OH− !
f. Cr3+ + H2 !
g. Cr2+ + H2 O !
+
h. CrO2−4 + H !
Experiment 4

4.1 Chemistry of molybdenum

4.2 Objective

Students should be able to:

– describe the preparation and properties of MoCl5,
– identify Mo(V) in aqueous solution by means of two precipitation and two redox
reactions, and
– understand which one is the most common oxidation states of molybdenum.

4.3 Theory

4.3.1 The element

Molybdenum is named molybdenum in Neo-Latin and molybdos in ancient Greek,

meaning lead, since its ores were confused with lead ores. Silvery metal with a gray
cast has the sixth highest melting point.

Occurrence
Molybdenum does not occur naturally as a free metal on the Earth, instead being found
only in various oxidation states in minerals. Molybdenum is most frequently found in
molybdenite, MoS2, and to some extent in wulfenite, PbMoO4. It is a trace element like
that of chromium.

Preparation
Initially, sulfidic molybdenum ores are concentrated by froth floatation followed by
roasting to give MoO3. The oxide has to be further upgraded by dissolution in ammonia
and calcination of the resulting ammonium molybdate. The MoO3 thus purified can be
reduced by hydrogen yielding elemental molybdenum:

MoS2 + 3.5O2 ! MoO3

MoO3 + 3H2 ! Mo + 3H2 O

Ferromolybdenum, an alloy of iron and molybdenum, is manufactured electrother-

mally from a mixture of iron oxide, MoO3, and coal.

https://doi.org/10.1515/9783111574349-005
 4.3 Theory 47

Properties

Physical properties
In the powder form, Mo is dull gray. After fusion in the massive state, the metal has a
lustrous, silver-white appearance. Its electrical conductance is about 30% that of sil-
ver. The metal melts at 2,610 °C.

Table 1.6: Some physical properties of molybdenum.

Properties Z Electronic Atomic Density m.p. b.p. χ Atomic

configuration weight radius

Expression  [Ar]ds . . g/c m , °C , °C .  pm

Chemical properties
Molybdenum is inert to oxygen at room temperature but reacts to give MoO3 at red
heat. The metal is dissolved by concentrated nitric acid, boiling concentrated sulfuric
acid, and chloronitric acid. Dilute and nonoxidizing acids do not attack the element.

Application
Molybdenum is largely used for the production of various steel alloys to increase their
hardness and toughness. Molybdenum filaments are needed for electrical bulbs. A great
many industrial catalysts are based on MoO3 and MoS2 (e.g., petrol cracking, oxidation of
benzene to phthalic anhydride, and metathesis of propene into ethane and butane). The
sheet-like MoS2 is very common grease-free lubricating agent. Molybdenum-containing
enzymes play a significant role in the biological nitrogen fixation.

4.3.2 Molybdenum(VI) compounds

Halide and oxyhalides

All molybdenum(VI) halide and oxyhalides are highly sensitive to moisture and they
hydrolyze rapidly. The following list gives a brief impression of the chloro and fluoro
derivatives:

MoFMo + 3F2 MoF6 ! colorless, volatile, m.p. 17.5 °C, b.p. 35 °C

MoOF4 Mo + 2F2 + O ! MoOF2 colorless, volatile, m.p. 975 °C

MoOCl4 + 4HF MoOF4 + 4HCl ! b.p. 180 °C

MoO2 F2 MoF6 + 2H2 O ! MoO2 F2 + 4HF White solid sublimes at 270 °C
48 Experiment 4

MoO2 Cl2 + 2HF ! MoO2 F2 + 2HCl ð1.013 barÞ

MoCl6 not existent

1 1
MoOCl4 MoCl5 + O2 ! MoOCl4 + Cl2 Dark green crystals
2 2
MoO3 + 2SOCl2 ! MoOCl4 + 2SO2 m.p. 102 °C
MoO2 Cl2 MoO2 + Cl2 ! MoO2 Cl2 White crystals, m.p. 175 °C

On acidifying aqueous molybdate solution by an excess of HCl, various chloro complexes


are formed: 2N HCl: MoO2 Cl2 ðH2 OÞ2 and ½MoO2 Cl3 ðH2 OÞ− 12N HCl:cis − ½MoO2 Cl4 2−

Oxide
Molybdenum trioxide, MoO3, is a white solid turning yellow on heating (m.p. 795 °C).
It crystallizes in a rare layer lattice with each molybdenum coordinated by six oxygen
atoms in distorted octahedral manner.
The hydrate, MoO3·XH2O (X = 1,2), may be obtained as white precipitate on acidify-
ing aqueous molybdate solutions:

+
4 + H2 O + 2H ! MoO3 · 2H2 O ðor MoO3 · H2 OÞ
MoO2−

NMR spectroscopy has shown that these compounds are molybdenum(VI) oxide hy-
drate rather than molybdic acid.

The molybdenyl cation and simple molybdates

Molybdenum oxide has amphoteric properties. Freshly prepared MoO3 hydrates dis-
solve in strong acid to give the molybdenyl cation, MoO22+:

MoO3 + 2H+ ! MoO2+

2 + H2 O

An analytically interesting reaction is the precipitation of red-brown (MoO2)2[Fe(CN)6]

from HCl-acidic Mo(VI) solution and ferrocyanide.
In alkali solutions, MoO3 hydrates are dissolved under the formation of mono-
meric, colorless orthomolybdates, MoO42–:

MoO3 + 2OH − ! MoO2− + HO

Only alkali, ammonium, and thallium(I) molybdates are soluble in water.

Isopoly and heteropoly anions and acids

On acidifying a slightly basic molybdate solution, polycondensation under abstrac-
tion of water takes place, yielding a great variety of oligomeric and polymeric, color-
 4.3 Theory 49

less molybdate called isopolymolybdates. Finally, polymeric, hydrated molybdenum

oxide, MoO3·xH2O, is precipitated. The stability of different anions and the extent of
polycondensation depend heavily on the pH value of the system:

2MoO + 2H+ Ð Mo2 O2−

7 + H2 O

3Mo2 O7 + 2H+ Ð 2Mo3 O2−

10 + H2 O

+ 6−
4 + 8H Ð Mo6 O21 + 2H2 O
6MoO2−

Mo6 O621− + 6H+ Ð MoO3 + 3H2 O

Isopoly acids and salts are readily formed with B, Si, Sn, P,V, Nb, Ta, Cr, Mo, and W. They
are generated either by acidifying an aqueous solution of the monomeric precursor (the
ortho anion) or by heating of a suitable solid salts. The polyanions may be linear or cy-
clic structures. If such polyanions involves two or more different central atoms, it is
called a heteropoly anion or acid, respectively. These species are normally prepared by
combining solutions of both a weak metal acid (H2WO4, H6Mo6O21, etc.) or its anion and
weak or moderate strong nonmetal acid or its anion. The latter can be H3BO3, H3PO4,
H4SiO4, and so on. Many salts of these heteropoly acids are sparingly soluble and, there-
fore, of analytical interest. One of the most representative examples is the slightly solu-
ble, yellow ammonium dodecylmolybdatophosphate hexahydrate:

2MoO6− + 11H+ + HPO2− + 3NH+ ! ðNHÞ½PðMoOÞ · 6H2 O

This precipitation reaction is usually employed for the qualitative and quantitative
determination of molybdenum and phosphorus.

Sulfide and thiomolybdate

Black-brown MoS3 is formed from molybdate and H2S in aqueous solution:
−
4 + 3H2 S ! MoS3 + 2H2 O + 2OH
MoO2−

The reaction proceeds very slowly and, incidentally, has to be carried out under H2S
pressure. MoS3 is sparingly soluble in concentrated HCl, but readily soluble in chloro-
nitric acid, and yellow ammonium sulfide (ammonium polysulfide, (NH4)2SX) solution.
Molybdate and (NH4)2SX give red thiomolybdate, MoS42–, which on acidifying is con-
verted into insoluble MoS3

4.3.3 Molybdenum(V) compounds

On heating stoichiometric amounts of MoO3 and Mo or MoO2, respectively, in evacuated

quartz tube, some oxides with molybdenum in formal oxidation state between +5 and
50 Experiment 4

+6 are formed. These oxides are nonstoichiometric substances with formulae such as
Mo9O26 and Mo18O52.
They are closely related to the so-called molybdenum blue compounds. The latter are
frequently described with formulae such as Mo4O10(OH)2 or Mo3O8(=MoO3, Mo2O5), and
Mo2O5. Molybdenum blue can be obtained by partial reduction of MoO3 or molybdate(VI)
with Zn/HCl, SnCl2/HCl, concentrated H2SO4, and other reducing agents (see experimental
part). The reaction is a convenient confirmatory test for traces of molybdenum. Tungsten
gives similarly blue oxides.
Molybdenum(V) hydroxide, MoO(OH)3, precipitates on adding ammonia to an
aqueous solution of a Mo(V) compound. A higher temperature of it dehydrates to give
blue Mo2O5.
Molybdenum(V) chloride, MoCl5, is another Mo(V) compound of great interest. The
black, crystalline solid (m.p. 194 °C, b.p. 628 °C) proves to be extremely sensitive to hy-
drolysis. MoCl5 is commercially available and readily obtained by heating molybdenum
powder in a stream of chloride at 300–400 °C:

Mo + 25Cl2 ! MoCl5

The chloride has high affinity to oxygen. Its dissolution in water or other oxygen-
containing solvents usually results in the generation of green MoOCl5 derivatives. A
large variety of complexes with the moiety MoOCl3 and related compounds have been
described.

4.3.4 Molybdenum(VI) compounds

MoO2 is generated by synproportionation from MoO3 and Mo or by reduction of MoO3

with hydrogen:
1,000 °C
2MoO3 + Mo ! 3MoO2
MoO3 + H2 ! MoO2 + H2 O

MoCl4 can be obtained as a blackish brown powder by refluxing MoCl5 in benzene or

other organic solvents:

2MoCl5 + C6 H6 ! MoCl4 + C6 H5 Cl + HCl

With various O–, N–, and p-donor ligands, complexes of composition MoCl4L2 may be
synthesized.
 4.5 Procedure 51

4.3.5 Molybdenum(III) compounds

Mo2O3 is formed on reducing MoO3 with potassium in liquid ammonia:

MoO3 + 6K ! 3Mo2 O3 + 3K2 O

MoCl3 was prepared from MoCl5 and SnCl2 at 300 °C:

300 °C
2MoCl5 + SnCl2 ! MoCl3 + SnC

Aqueous Mo(III) solution is synthesized by chemical or electrochemical reduction of

molybdenum(VI) compounds. The common reducing agents for this purpose are SnCl2,
Zn, and Na2S2O3 in acidic medium. In the presence of thiocyanate, SCN–, the characteris-
tic, red [Mo(SCN)6]3– complex anion is formed. The latter can be used to identify molyb-
denum even in the presence of tungsten. Tungsten(VI) is only reduced to tungsten blue
by these reducing agents.

4.4 Chemicals and apparatus

Chemicals Apparatus

Ammonium molybdate(VI), (NH)MoO (aq) Dropper

HCl, HSO, or HNO Test tube
N, NaOH and N, HCl Water bath
Potassium hexacyanoferrate(II) (aq) Bunsen burner
Calcium chloride and lead acetate
Hydrogen phosphate (aq)
Ammonium sulfide
Ammonium molybdate (solid)
% HO and concentrated ammonia
Stannous chloride and grains of zinc
Potassium thiocyanate

4.5 Procedure

1 Preparation and reaction of Mo(VI) compounds

1.1 Preparation and properties of molybdic acid, MoO3·H2O or H2MoO4

Place three to four drops of saturated ammonium molybdate into each of two test
tubes and add concentrated hydrochloric acid dropwise until a white crystalline solid:
molybdic acid precipitates. Let the solution settle, remove the supernatant liquid from
both test tubes using a pipette, and save the product for the next experiment:
52 Experiment 4

ðNH4 Þ2 MoO4 ð4dÞ + Conc. H+ ðdwÞ ! MoO3 · H2 O

Molybdic acid, H2MoO4, is most appropriately described as hydrated molybdenum tri-
oxide, MoO3·H2O. Under certain conditions, a dihydrate can also be isolated.
Note: Semiconcentrated HCl, H2SO4, or HNO3 can be used in the preparation of
molybdic acid.

1.2 Amphoteric property of molybdic acid

Take two test tubes containing molybdic acid prepared at Experiment 1.1, then add
dropwise 2N, NaOH into one of the test tubes and 2N, H2SO4 into the other and notice
the color change. Save molybdyl sulfate solution to the next experiment:
a) MoO3 · H2 O + 2H+ ! MoO2 2+ ðmolybdenylÞ + 2H2 O
b) MoO3 · H2 O + 2OH− ! MoO4 2+ · 2H2 O

1.3 Preparation of molybdenyl hexacyanoferrate(II)

In the molybdyl sulfate solution prepared at Experiment 1.2, add solution of potas-
sium hexacyanoferrate(II), K4[Fe(CN)6], dropwise. You will observe red-brown precipi-
tate that confirms the formation of molybdenyl hexacyanoferrate(II):



MoO2 2+ ð4dÞ + K4 FeðCNÞ6 ðdwÞ ! ðMoO2 Þ2 FeðCNÞ6 − red brown

1.4 Preparation of sparingly soluble molybdates

Pour three to four drops of saturated ammonium molybdate solution into each of two
test tubes and add the same volume of calcium chloride into the first and lead acetate
into the other. Note the color of the corresponding molybdate precipitate:

Ca2+ + MoO4 2− ! CaMoO4

Pb2+ + MoO4 2− ! PbMoO4

1.5 Specific precipitation reaction for molybdate ion: identification as ammonium

molybdatophosphate
Pour five to six drops of saturated ammonium molybdate solution into a test tube fol-
lowed by addition of one to two drops of concentrated HNO3. Add a drop of hydrogen
phosphate solution and heat gently in water bath until you observe a yellow precipi-
tate, which is characteristic of ammonium molybdatophosphate:

ðNH4 Þ2 MoO4 ð6dÞ + Na2 HPO4 ð1dÞ + conc. HNO3 ð2d Þ


! ðNH4 Þ3 PðMo3 O10 Þ4 · 6H2 O + 6H2 O − yellow
 4.5 Procedure 53

1.6 Preparation of thiomolybdate and Mo(VI) sulfide, MoS3

Pour five to six drops of saturated ammonium molybdate solution into a test tube and
then add ammonium sulfide dropwise. The mixture turns to red due to the formation
of ammonium thiomolybdate.
Note: Ammonium sulfide has yellow color in solution due to the presence of am-
monium polysulfide, (NH4)2Sx:

ðNH4 Þ2 MoO4 ð4dÞ + ðNH4 Þ2 S ðdwÞ ! MoS4 2− + 8NH3 + 4H2 O

NB: The red color is due to the presence of MoS42–.

Now add dropwise 2N, HCl into the red precipitate or solution till it changes to
black, which indicates the formation of molybdenum trisulfide:

MoS4 2− + 2 N, HCl ðdwÞ ! MoS3 + H2 S

1.7 Peroxomolybdate
Place a few crystals of ammonium molybdate in a test tube and then add two to three
drops of concentrated ammonia followed by two to three drops of 3% H2O2. Note the
color change due to the formation of ammonium permolybdate, MoOx2–. (X may vary
from 5 to 8 depending on the concentration of H2O2 and the reaction temperature.)
The equation for MoO52– and MoO62– are given below:

ðNH4 Þ2 MoO4 ð1 gÞ + Conc. NH3 ð3dÞ + 3 % H2 O2 ð3dÞ ! MoO3 ðO2 Þ2− + H2 O

ðNH4 Þ2 MoO4 ð1 gÞ + Conc. NH3 ð3dÞ + 3% 2H2 O2 ð3dÞ ! MoO2 ðO2 Þ2 2− + H2 O

2 Preparation of lower valent molybdenum

2.1 Preparation of molybdenum blue, Mo2O5

Add three to four drops of saturated ammonium molybdate solution into a test tube
and acidify it with two to three drops of 2N, HCl and then add stannous chloride solu-
tion in dropwise manner until the mixture turns blue and blue precipitate begins to
settle:

ðNH4 Þ2 MoO4 ð4dÞ + 2 N, HCl ð3dÞ + SnCl2 ðdwÞ ! Mo2 O5 + Sn4+ + 3H2 O

MoS4 2− + Sn2+ + 6H+ ! Mo2 O5 + Sn4+ + 3H2 O

2.2 Reduction of Mo(VI) to Mo(III)

Pour five to eight drops of saturated ammonium molybdate solution into a test tube
and add one to two grains of zinc followed by three to four drops of concentrated HCl.
54 Experiment 4

Note gradual the color change from blue to green and finally to brown, which is the
characteristic property of Mo(III):

ðNH4 Þ2 MoO4 ð4dÞ + Conc. HCl ð4dÞ + Zn ð2 csÞ ! brown

MoS4 2− + 3Zn + 16H+ ! Mo3+ + 3Zn2+ + 8H2 O

2.3 Identification of molybdenum by its hexathiocyanato Mo(III) complex

Add three drops of saturated ammonium molybdate solution into a test tube and two
drops of 2N, HCl followed by potassium thiocyanate, KSCN, and two drops of stannous
chloride solution. You will observe red color due to the formation of hexathiocyanato
molybdenum(III) ion, [Mo(SCN)6]3-. Then add 5–10 drops of diethyl or petroleum ether
and shake. After a minute, you will observe red ether layer. Thiocyanato complex is
soluble in organic solvents:

3−
ðNH4 Þ2 MoO4 ð3dÞ + 2 N HCl ð2dÞ + KSCNð3dÞ + SnCl2 ð2dÞ ! MoðSCNÞ6 + Sn4+ + 8H2 O

3−
MoðSCNÞ6 + ether => red ether layer

3−
2MoS4 2− + 12SCN− + Sn2+ + 16H+ ! 2 MoðSCNÞ6 + 3Sn4+ + 8H2 O

4.6 Observation

Color change
Evolution of gas
Sound of reaction

4.7 Result and discussion

Result: Write the balanced equation of the chemical reaction in ionic form.

Discussion: Discuss the outcomes of the experimental part and theoretical parts. Ex-
plain the errors if any.
 4.8 Post lab questions 55

4.8 Post lab questions

1. Describe the preparation and properties of MoCl5.

2. Identify Mo(V) in aqueous solution by means of two precipitation and two redox
reactions.
3. Complete the following equations:

MoO3 + H2 !

MoO4 2− + S2− + NH4 + !

Experiment 5

5.1 Chemistry of manganese

5.2 Objective

Students should be able to:

– prepare manganese(II) hydroxide and its oxidation by atmospheric oxygen,
– describe the preparation of metallic manganese (equations),
– understand the most common positive oxidation states of manganese in its com-
pounds, and
– write down the equations for reactions in which MnO2 acts as a reductant and an
oxidant.

5.3 Theory

The element
After iron, manganese is the most frequent heavy metal and occurs up to 0.1% in the
Earth’s crust. An important manganese ore is manganese dioxide, MnO2, and others
are rhodochrosite, MnCo3, braunite, Mn(OH), and sulfides, MnS and MnS2. A consider-
able amount of manganese is involved in certain iron, zinc, and cadmium minerals. It
has one isotope: 55Mn (100%).

Preparation
Manganese-containing ores are roasted to Mn3O4 followed by reduction with aluminum:

3Mn3 O4 + 8Al ! 9Mn + 4Al2 O3

Pure metallic manganese is manufactured by electrolysis of Mn(II) salts, such as

MnSO4. Most of the manganese produced is processed as ferromanganese. This alloy
can be obtained by the reduction of mixtures of Fe- and Mn-containing ores.

5.4 Chemicals and apparatus

Chemicals Apparatus

Solutions of MnSO and KMnO Crucible

Solid of KMnO and MnO Test tube
N, NaOH Water bath

https://doi.org/10.1515/9783111574349-006
 5.5 Procedure 57

(continued)

Chemicals Apparatus

N solution of ammonia Bunsen burner

Distilled water Test tube clamp
NHCl solution and concentrated HCl
Sodium sulfide solution
Bromine-water and potassium iodide solution
% CuSO
N nitric acid

5.5 Procedure

Preparation and reactions of manganese compounds

1 Manganese(II) compounds

1.1 Preparation of manganese(II) hydroxide and its oxidation by atmospheric

oxygen
Add three to four drops of manganese(II) salt solution to the test tube followed by two
to three drops of 2N, NaOH. Pink Mn(OH)2 is precipitated. Stir the mixture with a glass
rod and note the color change to brown due to the oxidation of divalent manganese
to the tetravalent state:

Mn2+ + 2OH− ! MnðOHÞ2

2MnðOHÞ2 + O2 ! 2MnOðOHÞ2

Remember that the formation of higher positive oxidation state is, in general, facili-
tated under basic conditions.

1.2 Action of ammonia on divalent manganese salts in the absence and presence
of ammonium salts
In each of the test tubes, add three drops of 2N solution of ammonia. Add three drops
of distilled water into one and the same volume of saturated NH4Cl solution into the
other test tube. Now add three drops of MnSO4 to each of the test tubes and note the
occurrence of pink precipitate of Mn(OH)2 in one of them. Write down the relevant
equations to explain these results.
58 Experiment 5

1.3 Preparation of manganese(II) sulfide and its oxidation by atmospheric oxygen

Place three to four drops of manganese(II) salt solution into the test tube and add two
to four drops of ammonium or sodium sulfide solution. Note the precipitation of
creamy pink MnS. Stir the mixture with glass rod and observe the color change to
brown attributed to the formation of MnO(OH)2:

Mn2+ + S2− ! MnS

MnS + O2 + H2 O ! MnOðOHÞ2 + S

Pay attention to the last equation. It is an overall equation. Manganese(II) as well as

sulfide are simultaneously oxidized by oxygen.

1.4 Oxidation of manganese(II) to its tetravalent state by bromine

in alkaline medium
Add two drops of MnSO4 solution to a test tube followed by three drops of 2N, NaOH.
Manganese hydroxide is precipitated. Then add six drops of bromine water. The pink
hydroxide turns immediately brown due to the formation of MnO(OH)2:

MnOðOHÞ2 + Br2 + OH− ! MnOðOHÞ2 + H2 O + 2Br −

Note that Br2 in aqueous alkali forms hypobromite, OBr–, which is the actual oxidizing
agent.

1.5 Oxidation of Mn(II) to heptavalent manganese by bromine in alkaline solution

with Cu(II) as a catalyst
Mn(II) is oxidized to Mn(VII) by hypobromite in the presence of Cu(II) salt acting as a
catalyst. For the experiment, take two to three drops of MnSO4 solution and add five
drops of 1% CuSO4 solution. In another test tube, prepare hypobromite by mixing five
drops of bromine water with such an amount of 2N, NaOH as is necessary to decolorize
the solution. Now add the hypobromite reagent to the Mn(II)/Cu(II) sample and boil for a
minute. Let the precipitate settle and observe the violet color of the supernatant solution:

2Mn2+ + 5BrO− + 6OH ! 2MnO4 − + 5Br− + 3H2 O

1.6 Oxidation of Mn(II) to heptavalent manganese by lead dioxide in acidic solution

Add a small quantity of lead dioxide to a test tube followed by six to eight drops of 2N
nitric acid and then one drop of Mn(II) salt solution. Boil carefully. Then let the excess
PbO2 to settle and observe the color of the supernatant solution:

2Mn2+ + 5PbO2 + 4H+ ! 2MnO4 − + 5Pb2+ + 2H2 O

 5.5 Procedure 59

2 Manganese(IV) compounds

2.1 Oxidizing properties of manganese dioxide

Place a micro-spatula full of manganese dioxide into a test tube and add two to three
drops of concentrated HCl. Yellow chlorine gas evolves. If the reaction is not intense,
heat the test tube gently over a small flame:

MnO2 + 4HCl ! MnCl2 + Cl2 + 2H2 O

2.2 Reducing properties of manganese dioxide: identification of manganese

by oxidative fusion
Place a small pellet of NaOH and the same amount of crystalline potassium nitrate into a
crucible and heat in a clay triangle (or asbestos wire gauze) over a burner and melt the
mixture. Continue heating and add a very small quantity of manganese dioxide. A green
melt is obtained due to the formation of manganate(VI), MnO42–. A shade of the blue
may be attributed to manganate(V), MnO43–, a side product of the reaction. Cool the melt
and continue immediately with the following experiment:

3MnO2 + 3MINO3 + 4HIOH ! 3MI2 MnO4 + 2NO + 2H2 O

3 Manganese(VI) compounds

3.1 Disproportionation of manganate(VI)

Add water to the melt prepared in the previous experiment (as soon as it is cold) and
stir the crucible content with the glass rod. Transfer five to six drops of the resulting
green solution into each of the two test tubes. Add two to three drops of 2N acetic acid
in one test tube. The solution turns violet immediately and the brown precipitation set-
tles. The solution in the other test tube is, however, fairly stable. Only after a longer
time, it turns slowly violet with concomitant precipitation of brown solid.
The disproportionation of manganese(VI) in water can be described by the follow-
ing equation:

3MnO4 2− + 2H2 O ! 2MnO4 − + MnO2 + 4OH−

Thus, valence disproportionation may be defined as a redox process with a species in a
medium oxidation state being transferred into two other species, one in a higher and
another in a lower oxidation state. Manganate(VI) in neutral or acidic solution under-
goes such a reaction.
60 Experiment 5

3.2 Oxidizing properties of manganate(VI): reaction with sodium sulfite

Place small quantities of crystalline sodium sulfite into test tube containing 5–10
drops of green manganate(VI) solution. The solution decolorizes and a brown precipi-
tate settles. The latter is MnO2:

MnO4 2− + SO3 2− + 2H2 O ! MnO2 + SO4 2− + 2OH−

4 Manganese(VI) compounds

4.1 Preparation and properties of permanganic hydride

This experiment is to be performed only by the instructor. Permanganic hydride is
extremely explosive. Manganese(VII) oxide, Mn2O7, is a very powerful oxidizing agent.
Oxidation of organic matter usually proceeds under ignition or explosion. Mn2O7
proves to be thermodynamically unstable with respect to decomposition into MnO2
and O2. Therefore, it explodes on heating. For the instructor: Drop a few crystals of
potassium permanganate into a test tube and add some drops of concentrated sulfuric
acid. The mixture warms up and attains a greenish dark brown color. Manganese hep-
taoxide, a dark brown liquid, has been formed. Now take a piece of filter paper and
fold it into a paper cone. Put it on an asbestos wire gauze in a hood. Then add a few
drops of the Mn2O7-containing liquid onto the top of the paper cone. The strong oxi-
dizing agent turns the paper black. The heat of reaction will ignite the paper finally:

2KMnO4 + H2 SO4 ! Mn2 O7 + K2 SO4 + H2 O

4.2 Thermal decomposition of potassium permanganate

Place three to four crystals of potassium permanganate into a test tube, clamp it on a
stand in the horizontal position, and heat over a low flame to decompose the substance
completely to K2MnO4, MnO2, and O2. Cool the test tube and add five to six drops of
distilled water to the dry residue. Observe a blue solution and a brown precipitate:

2KMnO4 + H2 SO4 ! K2 MnO4 + MnO2 + O2

The evolution of oxygen and the completeness of the decomposition should be checked
with a glowing splint. If the oxygen test fails, try it again with some more KMnO4.

4.3 pH dependence of the oxidizing properties of potassium permanganate:

reaction with sodium sulfite in acidic, neutral, and alkaline mediaum
The oxidation potential of permanganate in aqueous solution depends on the pH value.
In acidic medium, MnO4– is reduced to Mn2+, in neutral and slightly alkaline systems
MnO2 precipitates, and in strongly basic solution green manganate(VI) is formed.
 5.5 Procedure 61

Place three to four drops of potassium permanganate solution into each of three
test tubes. Add two drops of 2N sulfuric acid into one test tube, two drops of water
into the second test tube, and two to three drops of 2N aqueous NaOH into the third
one. Take a concentrated solution of sodium sulfite and add it dropwise to the three
samples. Record carefully your observations:
acidic
2MnO4 − + 5HSO3 3− + 5H+ 
! 2Mn2+ + 5SO4 2− + 3H2 O
sl − alkali
2MnO4 − + 3SO3 2− + H2 O 
! 2MnO2 + 3SO4 2− + 2OH −
str − alkali
2MnO4 − + SO3 2− + 2OH − ! 2MnO4 2− + SO4 2− + H2 O

4.4 Reaction of potassium permanganate with potassium iodide in acidic, neutral,

and alkaline media
Add three to four drops of potassium permanganate solution into each of three test
tubes. Add two drops of 2N sulfuric acid into one test tube, two drops of water into
the second test tube, and three to four drops of 2N aqueous NaOH into the third one.
In acidic solution, dropwise addition of potassium iodide solution first decolorizes the
system under precipitation of black solid iodide. With excess of iodide, the iodine is
redissolved to give a brown solution containing the triiodide anion, I3–:

MnO4 − + 10I− + 16H+ ! 2Mn2+ + 5I2 + 8H2 O

In neutral MnO4– solution, KI forms the brown MnO2 precipitate, whereas in alkaline
medium the color of the solution changes to green. Interpret the result and write ionic
equations. Note that in the presence of alkali, iodate (IO3–) is formed rather than iodine.

4.5 Oxidation of ferrous sulfate by potassium permanganate

Add three to four drops of potassium permanganate to a test tube. Then add three to
four drops of 2N sulfuric acid and few crystals of Mohr’s salt (NH4)2Fe(SO4)2. The color
of MnO4– will disappear and pale yellow color will form due to the formation of Fe3+:

MnO4 − + 5Fe2+ + 8H+ ! 2Mn2+ + 5Fe3+ + 4H2 O

4.6 Oxidation of hydrogen peroxide by potassium permanganate

Add three to five drops of potassium permanganate into a test tube followed by two
to three drops of 2N sulfuric acid, and then add three to four drops of 10% hydrogen
peroxide. The color of MnO4– will disappear and oxygen is formed:

MnO4 − + 5H2 O2 + 6H+ ! 2Mn2+ + 5O2 + 8H2 O

62 Experiment 5

4.7 Oxidation of alcohol by potassium permanganate

Add three to four drops of potassium permanganate to two test tubes followed by two
drops of 2N sulfuric acid in one of the test tubes and equal amount of 2N, NaOH into
the other. Then add three drops of alcohol in both test tubes. Heat gently the acidic
solution over the small flame, and the alcohol reduces from MnO4– to Mn2+. However,
in an alkaline medium, the color changes to green and eventually to brown, which is
the characteristic color of MnO2:

MnO4 − + 5C2 H5 OH + 6H+ ! 2Mn2+ + 5CH3 CHO + 8H2 O

MnO4 − + 5C2 H5 OH + 2OH− ! 2MnO4 2− + 5CH3 CHO + 8H2 O

2MnO4 − + 5C2 H5 OH ! MnO2 + 5CH3 CHO + 2OH−

4.8 Synproportionation of manganese(II) and manganese(VII)

Place three to four drops of potassium permanganate into two test tubes and equal
amount of manganese(II) sulfate. The color of MnO4– disappears and brown precipitate
is formed, which indicates the formation of MnO2. Check the pH of the solution using
the litmus paper:

MnO4 − + Mn2+ + 2H2 O ! MnO2 + 4H

5.6 Observation

Color change
Evolution of gas
Sound of reaction

5.7 Results and discussion

5.8 Post lab questions

1. Compile all the oxides and hydroxides or acids of manganese in various oxidation
states and discuss their acidic and basic behavior.
2. The following substances are added to manganese(II) sulfate dissolved in water in
open air:
a. Potassium hydroxide
b. Ammonium sulfide
c. Potassium permanganate. Write the equations.
 5.8 Post lab questions 63

3. How can the following substances be prepared from MnSO4?

A. Mn (OH)2; B. MnO2; C. KMnO4. Write down the equations.
4. Write the equations for reactions in which MnO2 acts as
a. reductant and b. an oxidant
Experiment 6

6.1 Chemistry of iron

6.2 Objective

Students should be able to:

– describe the preparation of metallic iron in industry and laboratory scales,
– characterize the solubility of iron in acids,
– characterize the main types of ions and compounds in these oxidation states, and
– know how a ferrous salt can be converted into ferric salt and how this process
can be reversed.

6.3 Theory

Occurrence
In the frequency chart of elements, iron holds the fourth position by 5.1%. After alu-
minum, it is the most frequently occurring metal. Metallic iron is the main constituent
of many meteorites.
Iron is a heavy metal and occurs in various ores (magnetite, Fe3O4, hematite, Fe2O3,
brown iron stone, Fe2O3·XH2O), sulfidic ores (pyrite, FeS2; magnetic pyrites, Fe1–xSx), and
spathic iron ore, FeCO3.
Iron exists as the following isotopes: 54Fe(5.84%), 56Fe(91.66%), 57Fe(2.17%), and
58
Fe(0.33%).

Preparation
The enormous cultural importance of iron originates from its great strength and the
ability of forming alloys with carbon and many metals. All various iron ores are first of
all upgraded to iron oxide. The latter is reduced in blast furnace by means of carbon
and CO. In addition, coke serves as a heating medium and forms compounds with iron
that modifies the properties of the final product. Mineral impurities are converted
into slag.
The reaction taking place in the blast furnace is of complex nature. At higher tem-
peratures, the Boudouard equilibrium is of importance:

CO2 + C ! 2CO

In the upper part of the furnace, CO acts as a reducing agent because below 7,000 °C,
CO proves to have a higher reducing power than carbon. In the lower part of the
oven, elementary carbon comes directly into action as a reducing agent:

https://doi.org/10.1515/9783111574349-007
 6.5 Procedure 65

FeO + CO ! Fe + CO2
FeO + C ! Fe + CO

Above 10,000 °C, carbon may react with iron to give Fe3C.
Chemically pure iron is obtained by thermolysis of Fe(CO)5:
250 °C
FeðCOÞ5 ! Fe + 5CO 250 °C

Other methods are the reduction of iron oxide prepared from iron(II) oxalate, carbon-
ate, or nitrate by hydrogen at 7,000 °C. Iron powder prepared in this way is usually
pyrophoric.

6.4 Chemicals and apparatus

Chemicals Apparatus

Iron fillings Test tube

Aqueous solutions of Mohr’s salts (NH)Fe(SO)·HO Spatula
Iron(III) chloride, FeCl·HO Bunsen burner
Iron(II) oxalate (Fe(CO))
N, HCl, HSO, HNO
Conc. HSO
Potassium or ammonium thiocyanate
N, NaOH and % HO
Tin(II) chloride, mercuric nitrate
Copper(II) sulfate
Ferric chloride salt solution
NaCO solution

6.5 Procedure

1 Preparation and properties of pyrophoric iron

1.1 Preparation and properties of pyrophoric iron

Place one spatula full of iron(II) oxalate, Fe(C2O4)2. Clamp the tube in a horizontal po-
sition with an iron stand and heat it on the Bunsen burner gently until the yellow
color turns to black and gas evolution stops. Remove the tube from the burner and
stopper it immediately. After cooling, pour the product on a paper from the height of
25–30 cm above the paper. You will observe the spark of burning iron:
heat
FeðC2 O4 Þ2 ! FeO + CO + CO2
66 Experiment 6

heat
FeO 
! Fe + Fe3 O4

Iron oxidizes by air to Fe3O4:

Fe + 2O2 ! Fe3 O4

1.2 Reaction of Fe with acids

Add five drops of 2N, HCl, H2SO4, HNO3 and three drops of conc. H2SO4 to four test
tubes separately. Add one micro-spatula full of iron filling to each test tube and ob-
serve the reaction. Then add a drop of potassium or ammonium thiocyanate tubes
containing dilute acids, and the appearance of red color indicates the presence of iron
(III). Note that iron(III) thiocyanate is unstable so the red color persists only for 1 or
2 min. Heat the tube containing conc. H2SO4 and iron filling. After heating, transfer
two to three drops to another test tube and dilute with 1 mL distilled water. Then add
thiocyanate reagent and observe the reaction. Write the equation.

1.3 Displacement of some metals from their salts by iron

Add 10 drops of tin(II) chloride, mercuric nitrate, and copper(II) sulfate to three test
tubes separately. Then put cleaned iron nails into each test tube and interpret your
observation.

2 Iron(II) compounds
Due to the partial oxidation in air, ferrous salts always contains traces of Fe(III). The
most stable crystalline Fe(II) is Mohr’s salt (NH4)2Fe(SO4)2·6H2O; a double salt dissoci-
ates completely in water.

2.1 Preparation of ferrous hydroxide and it oxidation by atmospheric oxygen

Place three to four drops of Mohr’s salt into a test tube and add 2N, NaOH until white
flakes of Fe(OH)2 are precipitate.
Note: If the solution contains trace of Fe3+, the color of the precipitate becomes
pale green:

Fe2+ + 2OH− ! FeðOHÞ2

4FeðOHÞ2 + O2 + 2H2 O4 ! FeðOHÞ3

2.2 Basic character of ferrous hydroxide

Place ferrous hydroxide, Fe(OH)2, into two test tubes and add several drops of 2N, H2SO4
in one of the tubes and 2N, NaOH into the other. Fe(OH)2 dissolves in acid:
 6.5 Procedure 67

4FeðOHÞ2 + 2H+ ! 4Fe2+ + 2H2 O

2.3 Preparation of sparingly soluble ferrous carbonate

Add five drops of distilled water to a test tube and boil it to remove dissolved oxygen.
Dissolve a few crystals of Mohr’s salt in this oxygen-free water and add three to five
drops of Na2CO3 solution.
You will observe white precipitate that indicates ferrous carbonate:

Fe2+ + 2CO3 2− ! FeCO3

2.4 Preparation of ferrous sulfide

Add five to six drops of Mohr’s salt to each of two test tubes followed by a drop of
freshly prepared H2S to one test tube and (NH4)2S to the other tube. Black FeS precip-
itates only in slightly alkaline medium. Explain the influence on the solubility and
check the solubility of FeS in dilute HCl.

2.5 Reaction of iron(II) with potassium hexacyanoferrate(III) – Turnbull’s blue

Add two to three drops of Mohr’s salt to a test tube and then a drop of potassium hex-
acyanoferrate(III), K3[Fe(CN)6]. A deep blue precipitate of Turnbull’s blue will appear:

3−
2
Fe2+ + 2 FeðCNÞ6 ! K3 FeðCNÞ6

Note: This test is sensitive to Fe2+.

2.6 Reducing property of divalent iron

2.6.1 Reduction of nitric acid, HNO3

Add five drops of fresh Mohr’s salt to each of two test tubes, then a drop of concen-
trated HNO3 to one test tube and heat until gas evolution stops, finally cool it down.
The color turns from green to yellow. The intermediate brown color is due to the for-
mation of unstable [Fe(NO)(H2O)5]2+. This is the identification of nitrate (ring test) and
nitrite:

Fe2+ + NO3 − + 4H+ ! Fe3+ + NO + 2H2 O

2.6.2 Reduction of potassium permanganate, MnO4–

Add five to six drops of MnO4– to a test tube followed by two drops of concentrated
H3SO4. Then add Mohr’s salt solution dropwise until you observe decolorization of the
mixture, which infers the reduction of MnO4– to Mn2+. Write the equation.
68 Experiment 6

2.6.3 Reduction of H2O2

Add five to six drops of Mohr’s salt to each of two test tubes and to one sample add
two to three drops of 2N, H2SO4 followed by the same volume of 3% H2O2. Observe the
color change from green to yellow. Check for Fe3+ in both test tubes using ammonium
thiocyanate reagents:

Fe2+ + H2 O2 + 2H+ ! Fe3+ + 2H2 O

The evolution of oxygen is the side product from disproportionation reaction of H2O2
because of the transition metal catalyst.

3 Iron(III) compounds

3.1 Detection of iron(III) as a constituent of the decomposition products of the

iron oxalate thermolysis
Take 1 g of iron(II) oxalate in a crucible fixed in clay triangle and heat over a burner
until the color change occurs. Cool the resulting residue and dissolve a small quantity
of sample in a test tube with 2N, HCl. Test for Fe3+. Write the equation for the reaction.

3.2 Preparation and properties of ferric hydroxide

Take five to six drops of ferric chloride salt solution in two test tubes and add three to
four drops of 2N, NaOH, you will observe brown precipitate due to the formation of
Fe(OH)3.
Note: If the solution contains traces of Fe3+, the color of the precipitate becomes
pale green:

Fe3+ + 3OH− ! FeðOHÞ3

Then add 2N, H2SO4 into one of the tubes containing Fe(OH)3 and 2N, NaOH into the
other and observe changes. Compare Fe(OH)3 with Cr(OH)3, Mn(OH)2, and Fe(OH)2
using table.
Note: Fe(OH)3 is insoluble in NaOH.

3.3 Specific reactions of Fe3+

3.3.1 Reaction with potassium thiocyanate

Take five to six drops of ferric chloride salt solution in a test tube and add a drop of po-
tassium thiocyanate, KSCN, you will observe red which is the characteristic of Fe(SCN)3:

Fe3+ + 3SCN− ! FeðSCNÞ3

Repeat the experiment using freshly prepared Mohr’s salt.

 6.6 Observation 69

3.3.2 Reaction with potassium hexacyanoferrate(II), K4[Fe(CN)6]

Take five to six drops of ferric chloride salt solution in a test tube and add a drop of
K4[Fe(CN)6], you will observe deep blue precipitate. Prussian blue indicates the pres-
ence of Fe(III):

4−
3
Fe3+ + 3 FeðCNÞ6 ! Fe4 FeðCNÞ6

Note: This test is extremely sensitive to Fe3+.

3.4 Oxidizing properties of iron(III)

3.4.1 Oxidation of sodium sulfite, Na2SO3

Take five to six drops of ferric chloride salt solution in a test tube and add a few crys-
tals of Na2SO3. At first you will observe red color due to the formation of Fe(III) sulfite
complex but fades quickly and change to pale green, indicating the presence of Fe2+.
Check it by adding K3[Fe(CN)6].

3.4.2 Oxidation of hydrogen sulfide, H2S

Take three to four drops of ferric chloride salt solution in a test tube and add two to
three drops of freshly prepared hydrogen sulfide solution. The color of Fe3+ fades and
the colloidal precipitate of sulfur turns the mixture white and turbid:

Fe3+ + H2 S ! Fe2+ + S + 2H+

3.5 Preparation of ferric sulfide

Take three to four drops of ferric chloride salt solution in a test tube and add two to
three drops of ammonium sulfide solution. Black precipitate forms but fades soon due
to its instability and decomposes to black FeS and white S:

Fe3+ + 3S2 − ! Fe2 S3

Fe2 S2 ! 2FeS + S

To check the presence of S, add 2N, H2SO4; the acid dissolves FeS but leaves S.

6.6 Observation

Color change
Evolution of gas
Sound of reaction
70 Experiment 6

6.7 Results and discussion

6.8 Review problems

1. Characterize the solubility of iron in acids.

2. What is understood by the term “rusting”? How can it be prevented?
Experiment 7

7.1 Chemistry of cobalt

7.2 Objective
Students should be able to:
– discuss the preparation of metallic cobalt,
– describe the reaction of cobalt compound with alkali, with ammonia and carbonates,
– observe the oxidation of Co(OH)2 with hydrogen peroxide, and
– identify Co(II) as hexanitrocobaltate(III).

7.3 Theory

Occurrence
The content of cobalt in the Earth’s crust amounts to 0.001%. Cobalt is closely associ-
ated with nickel, mainly in the form of arsenic and sulfur compounds. The most im-
portant minerals are skutterudite, (Co,Ni)As3, cobaltite, CoAsS, and smalite, CoAs2. The
metallic element is itself found in meteorites with 0.5–2.5% cobalt.

Preparation
The combination of chemical, thermal, and electrolytic methods of preparation for co-
balt depends on the nature of the minerals available. Initially, all Ni–Co–Cu ores are
roasted and upgraded to give oxides, sulfates, and arsenates. The latter are then dis-
solved in sulfuric acid and chemically separated. Cu, Pb, Bi, and others are precipi-
tated by H2S, As, and Fe by means of limestone, and Co by chlorinated lime as Co(OH)3.
Nickel remains in solution. Co(OH)3 is calcined followed by reduction with charcoal or
hydrogen:

2CoðOHÞ3 ! Co2 O3 + H2 O

Co2 O3 + 3H2 ! 2Co + 3H2 O

Co2 O3 + 3C ! 2Co + 3CO

Pure cobalt may be obtained by H2 reduction of recrystallized cobalt complexes for


example, CoðNH3 Þ5 Cl Cl2 .

https://doi.org/10.1515/9783111574349-008
72 Experiment 7

7.4 Chemicals and apparatus

Chemicals Apparatus

– Solution of Co(NO3)2.6H2O or CoCl2· 6H2O Test tube

– Concentrated aqueous solution of NaOH Water bath
– 2N, H2SO4 and 2N, NaOH Bunsen burner
– Dilute ammonia solution
– NH4Cl and 6% H2O2
– Sodium carbonate
– NH4S, bromine water, and KCN

7.5 Procedure

1 Preparation and reactions of cobalt compounds

1.1 Reaction of Co(II) with alkali hydroxide

Take five drops of Co(II) salt solution in two test tubes and slowly add two to three
drops of concentrated aqueous solution of NaOH to it. Blue precipitate will be ob-
served and the precipitate will turn to pink through heating:

Co2+ + 2OH− ! CoðOHÞ2

1.2 Solubility of Co(II) hydroxide, Co(OH)2

Take seven to eight drops of Co(OH)2 in each of two test tubes and two to three drops
of 2N, H2SO4 in one test tube and equal volume of 2N, NaOH in the other. Co(OH)2 dis-
solves readily in acid but partly in NaOH by forming a deep blue complex, [Co(OH)4]2–.
Write the equations.

1.3 Reaction of Co(II) with ammonia

Take five drops of Co(II) salt solution in two test tubes and add dilute ammonia solu-
tion to it in a dropwise manner. Blue precipitate is formed but turns to pink in air
due to oxidation and forms Co(III) ammine complexes:

3+
Co2+ + O2 + 6H2 O + 20 NH3 ! CoðNH3 Þ5 ðH2 OÞ + 4 OH−

Repeat the above experiment in the presence of NH4Cl; no precipitate will be formed
but yellowish solution changes to pink.
 7.5 Procedure 73

1.4 Reaction of Co(II) with carbonate, CO32–

Take five drops of Co(II) salt solution in a test tube and add an excess of sodium car-
bonate solution. Depending on the concentration, bluish or reddish precipitate of
basic carbonate is formed.

1.5 Reaction of Co(II) with ammonium sulfide, NH4S

Take five drops of Co(II) salt solution in a test tube and add a few drops of NH4S to
form black CoS precipitate. Repeat the experiment using gaseous H2S or H2S–water.
CoS is soluble in HNO3 but hardly soluble in HCl:

Co2+ + S2 − ! CoS

3CoS + HNO3 + 6H+ ! Co2+ + 3S + 2NO + 4H2 O

1.6 Oxidation of Co(OH)2 with hydrogen peroxide

Add seven to eight drops of Co(OH)2 to a test tube followed by three drops of 6% H2O2
and boil. Observe the formation of black solid, Co(OH)3:

CoðOHÞ2 + H2 O2 ! CoðOHÞ3

1.7 Oxidation of Co(OH)2 with bromine water

Add seven to eight drops of Co(OH)2 to a test tube followed by two to three drops of
bromine water and observe the formation of black precipitate, Co(OH)3. Write the
equation.

1.8 Reaction of Co(II) with potassium cyanide, KCN

Take five drops of Co(II) salt solution in a test tube and add KCN in a dropwise man-
ner. Red brown Co(CN)2 precipitate is formed. In excess KCN, Co(CN)2 dissolves and
forms [Co(CN)6]4–. Then add two to three drops of 6% H2O2 color of the solution that
turns to blue due to the formation of complex anion, [Co(CN)6]3–:

4−
3−
CoðCNÞ6 + H2 O2 ! CoðCNÞ6 + 2OH−

1.9 Reaction of Co(II) with thiocyanate

Take five drops of Co(II) salt solution in a test tube and add the same volume of con-
centrated ammonium or potassium thiocyanate solution. Then cover the mixture with
l mL of ether. In neutral solution, blue Co(SCN)2 is formed, which is soluble in organic
solvent.
74 Experiment 7

Repeat the experiment by adding two drops of dilute acetic acid, and the same
observation will appear even if the result is a complex acid, H2[Co(SCN)4]. It dissolves
in ether layer:

Co2+ + 2 SCN− ! CoðSCNÞ2


Co2+ + 4SCN− + 2H+ ! H2 CoðSCNÞ4

7.6 Observation

Color change
Evolution of gas and sound of reaction

7.7 Review questions

1. Name important cobalt-containing minerals. To which class of compounds do

they belong?
2. Discuss the preparation of metallic cobalt.
3. Which are the most common ONs of cobalt in its compounds? Discuss their
stability.
4. Co(NO3)2 is stable in aqueous solution but Co(NO3)3 is not. However, Co(NO3)2 is
rapidly oxidized in the presence of cyanide. Explain these phenomena.
5. Describe the oxides and hydroxides of cobalt and account for their behavior with
respect to acids and bases, respectively.
6. Compile analytically significant precipitation, redox, and complex formation reac-
tions of cobalt.
Experiment 8

8.1 Chemistry of nickel

8.2 Objective

Students should be able to:

– discuss the methods of preparation for crude and pure nickel,
– describe the so-called Mond process,
– understand how nickel reacts with aqueous HCl and HNO3, and
– discuss the reaction of Ni(II) with cyanide, thiocyanate, and dimethylglyoxime.

8.3 Theory

Occurrence
With 0.016% nickel contained in the Earth’s crust, this element occurs with a higher
frequency than Cu, Zn, and Pb all together. However, its industrial preparation is
much more difficult because nickel is widely spread in nature and larger deposits
are rare.
Nickel ores occur as sulfides, oxides, silicates, and amides. Elementary nickel has
been found in meteorites (e.g., 91% Fe, 8% Ni, and 0.6% Co).
Nickel’s isotopes are 58Ni(67.76%), 60Ni(26.26%), 61Ni(1.25%), 62Ni(3.66%), and 64Ni(1.16%).

Preparation
The metallurgy of nickel is rather complicated. In principle, the ores are upgraded,
concentrated, transferred into nickel sulfide, oxidized to NiO by roasting with hot air,
and eventually reduced by charcoal to give crude nickel.
Pure nickel is prepared by the Mond process. The crude metal reacts at 50 °C with
carbon monoxide yielding tetracarbonyl nickel(0), Ni(CO)4, a poisonous, colorless liquid
with b.p. 43 °C. Ni(CO)4 decomposes again at 2,000 °C to give very pure nickel (99.99%):

50 °C
Ni + 4CO ! NiðCOÞ4

Other methods of purification are electrolytic refining and zone melting.

https://doi.org/10.1515/9783111574349-009
76 Experiment 8

8.4 Chemicals and apparatus

Chemicals Apparatus

– Solution of NiCl2·6H2O Test tube

– 2N, NaOH Bunsen burner
– Crystal of K2S2O8 Water bath
– Chlorine water and KI solution
– 2N, HCl and ammonia
– Saturated Na2CO3
– Ammonium sulfide
– Dilute sodium cyanide

8.5 Procedure

1 Reaction of Ni(II) with alkali hydroxide

Take five drops of Ni(II) salt solution in a test tube and add dropwise 2N, NaOH. You
will observe green precipitate of Ni(OH)2, which is insoluble in excess NaOH. Save the
precipitate for the following experiments:

Ni2+ + 2OH− ! NiðOHÞ2

2 Oxidation of Ni(II) hydroxide by potassium peroxodisulfate, K2S2O8

Take Ni(OH)2 (from Experiment 1) in a test tube and add crystals of K2S2O8, then you
will observe blue hydrous Ni(II) oxide:

NiðOHÞ2 + S2 O8 2− + H2 O ! NiOðOHÞ + 2SO4 2− + 2OH

Note: Ni(OH)2 is not oxidized by H2O2.

3 Oxidation of Ni(II) hydroxide by chlorine

To Ni(OH)2 precipitate, add two to three drops of chlorine water and you will observe
black precipitate, which indicates the oxidation of Ni(OH)2 to NiO(OH). Write the
equation. When the black precipitate settles, decant the supernatant solution and add
three to four drops of KI solution followed by two drops of 2N, HCl. The black precipi-
tate dissolves and Ni(III) reduces to Ni(II) eventually turns to brown due to the forma-
tion of triiodide ion:
1
NiOðOHÞ + I− + 3H+ ! Ni2+ + I2 + 2H2 O
2
 8.5 Procedure 77

4 Reaction of Ni(II) with aqueous ammonia

Take 0.5 mL of Ni(II) salt solution in a test tube and add ammonia dropwise. At first,
green Ni(OH)2 precipitates but it dissolves in excess ammonia through forming blue
hexamine complex [Ni(NH3)6]2+. Write down the equation.

5 Reaction of Ni(II) with sodium carbonate

Take five drops of Ni(II) salt solution in a test tube and add several drops of saturated
Na2CO3. The green precipitate confirms the formation of basic carbonate.
Note: The protolysis reaction of carbonate with water increases pH and initiates
partial precipitation of Ni(OH)2 mixed with NiCO3. Write the equation.

6 Reaction of Ni(II) with sulfide

Take five drops of Ni(II) salt solution in a test tube and add several drops of ammo-
nium sulfide. Black NiS will be precipitated:

Ni2+ + S2− ! NiS

Note:
– NiS is formed only in neutral or slightly alkaline medium.
– NiS is soluble in mineral acids, immediately oxidizes to Ni(OH)S and Ni2S3 like
CoS, and dissolves in HNO3 and HAc/H2O2.

7 Reaction of Ni(II) with sodium cyanide

Take five drops of Ni(II) salt solution in a test tube and add dilute sodium cyanide
solution in dropwise manner. The light green precipitate indicates the formation of
Ni(CN)2, which dissolves in excess CN– yielding [Ni(CN)4]2– yellow solution:

Ni2+ + 2CN− ! NiðCNÞ2

2−
NiðCNÞ2 + 2CN− ! NiðCNÞ4

8 Reaction of tetracyanonickelate(II) [ Ni(CN)4]2– with NaOH/Br2

Attention!!! do this experiment in a hood

Dissolve Ni(CN)2 in a limited amount of CN– and add three drops of 2N, NaOH fol-
lowed by three to four drops of bromine water. You will observe the black color:

2−
NiðCNÞ4 + 6OH− + 9Br2 ! 2NiOðOHÞ + 10Br− + 8BrCN + 2H2 O
78 Experiment 8

NB: Avoid excess CN– because it reacts first with Br2:

CN− + Br2 ! BrCN + Br−

9 Complex formation of Ni(II) with pyridine

To 1 mL of Ni(II) salt solution, add 1 mL of aqueous potassium thiocyanate and a few
drops of pyridine. A pale green, sparingly soluble complex salt [Ni(py)6](SCN)2 is pre-
cipitated. Write down the equation.

8.6 Observation

Color change
Evolution of gas
Sound of reaction

8.7 Results and discussion

8.8 Post lab questions

1. Discuss the methods of preparation for crude and pure nickel.

2. Describe the so-called Mond process.
3. How does nickel react with aqueous HCl and HNO3?
4. Discuss the reaction of Ni(II) with cyanide, thiocyanate, and dimethylglyoxime.
5. Find some simple reactions to distinguish between Ni(II), Co(II), Fe(II), and Mn(II).
6. How is it possible to stabilize high and low oxidation states of an element? Take
nickel as an example.
Experiment 9

9.1 Chemistry of copper

9.2 Objective

Students should be able to:

– prepare copper from copper(II) oxide,
– understand why it is possible to use anhydrous CuSO4 as an indicator for traces
of moisture,
– observe the reaction of copper(II) oxide with dilute acids,
– understand the reducing properties of metallic copper,
– distinguish between Cu(I) and Cu(II) compounds by making uses of their magnetic
properties, and
– propose at least three confirmatory tests for Cu(II) in aqueous solution.

9.3 Theory

Occurrence
The Earth’s crust contains about 100 g/t copper. This element occupies the 26th position
in the frequency list and is, therefore, a rather common metal. Most copper ores are
sulfides (more than 90%) with chalcopyrite, CuFeS2, at the top. However, there are also
some oxidic copper ores formed by weathering of sulfide ones (ores). Well known are
cuprite, Cu2O, and malachite, Cu2(OH)2CO3. Occasionally, copper has been found in ele-
mentary form. Copper has two isotopes; namely, 63Cu (69.1%) and 65Cu (30.9%).

Preparation
More than 80% of the processed copper ores have a copper content of less than 2%.
Therefore, the ore must first be concentrated by floatation. Sulfide ores are then
roasted with sulfur being partially converted into SO2. At the same time, ingredients
such as As, Sb, and Se are removed. The remainder mixture of mainly oxides and sul-
fides of Fe and Cu is molten under addition of SiO2 and air. Iron sulfide is thus trans-
ferred into iron oxide, which is finally separated as slag. Copper sulfide is more
resistant to air than FeS:
3
FeS + O2 + SiO2 ! FeSiO3 + SO2
2

https://doi.org/10.1515/9783111574349-010
80 Experiment 9

Now part of the copper sulfide is also converted into the oxide. The latter reacts with
excess CuS under exclusion of air, yielding crude copper with a copper content of
98–99%:
3
Cu2 S + O2 ! Cu2 O + SO2
2
Cu2 S + 2Cu2 O ! 6Cu + SO2

Further refining is accomplished in two different ways. Dry refining starts with mol-
ten copper being treated with wood. Copper oxides are hereby reduced to the metal
(99.95% copper content). About 80% of the crude copper is upgraded and purified
electrolytically. In doing so, copper is made to operate as anode in an aqueous solu-
tion of CuSO4 and sulfuric acid. At a voltage of 0.2–0.3 V, the anodically dissolved cop-
per is separated as pure copper at the cathode. All the less noble impurities remain is
solution, whereas the nobler metal settles as anode slime at the bottom of electrolysis
cell. Due to the high cost of electric power consumed by electrolysis, it is only the
noble metals in the anode mud which make the process economical one.
As the copper prices are rapidly increasing, the upgrading of poor copper ores
becomes more and more interesting. Thus, extraction processes (hydrometallurgy)
are about to gain industrial significance nowadays.

Physical properties
Copper is ductile and relatively hard. It exhibits the highest thermal and electrical
conductivity next to silver. Impurities decrease the conductivity but in turn increase
the hardness of the metal. Volatile copper compounds, for example, the halides cause
the green flame (Beilstein test for halides in organic compounds using a copper wire).
The metal itself has a reddish color.

Table 1.7: Some physical properties of copper.

Properties Z Electronic Atomic Density m.p. b.p χ Atomic

configuration weight radius

Expression  [Ar]ds . . g/cm , °C , °C .  pm

Chemical properties
Copper is relatively resistant to corrosion but attacked by air, giving a thin layer of
oxide. In CO2- or SO2-containing wet atmosphere, green hydrocarbonates and hydroxo-
sulfates are formed. At red heat, copper reacts with O2 to give CuO, which is again de-
composed to Cu2O at higher temperatures. Copper and sulfur form Cu2S or other
nonstoichiometric sulfides. With halogens, the corresponding copper(II) halides are ob-
 9.3 Theory 81

tained. As copper is nobler than hydrogen, it cannot be dissolved by nonoxidizing acids.

However, if oxygen is present, even these acids attack copper. Nitric and hot concen-
trated sulfuric acid dissolve copper under evolution of NO and SO2, respectively:

3Cu + 2HNO3 + 6H+ ! 3Cu + 2NO + 4H2 O

Copper has some physiological significance as a trace element. It is the constituent of

certain oxidizing enzymes. Unlike other heavy metals, copper is only slightly toxic to
human beings but causes vomiting after consumption of several hundred milligrams.

Application
At present, copper is the most frequently used metal after iron and aluminum. Due to
its excellent electrical conductivity, it is essential for the electroindustry but nowa-
days it is being gradually displaced by aluminum. Its high thermal conductivity and
resistance to corrosion make it valuable for containers, heat engineering purposes,
and so on. Finely dispersed copper, prepared by reduction of CuO with hydrogen,
may be used for catalytic purposes (e.g., dehydrogenation of aldehydes) and for re-
moval of oxygen traces from nitrogen.

Copper(I) compounds
In general, copper(II) seems to be more stable than copper(I). However, the stability
depends greatly on the reaction conditions (solubility, complex formation, etc.). The
following equilibrium has an equilibrium constant of 106 in aqueous solution:

2Cu2+ ðaqÞ Ð Cu2+ ðaqÞ + CuðsÞ

The formation of sparingly soluble cuprous compounds or very stable complexes of

Cu(I) may, however, shift it to left-hand side. Cu+ shows a tendency for covalent bond-
ing and, therefore, reacts preferably with polarizable anions or ligands. Copper(I) fa-
vors low coordination numbers in its compounds. Tetrahedral and linear ligand
arrangements are commonly encountered. This is in contrast to Cu2+, which prefers
ionic bonding as well as square planar and distorted octahedral structures.

Halides
Copper(I) has a d10 configuration and its compounds are usually white or pale yellow.
Cu(I) halides may be synthesized either by synproportionation of Cu(II) compounds
and elementary copper, or by reduction of Cu(II) halides with sulfite or other suitable
reducing agents.
Cu2O is the most stable copper oxide at high temperatures, and is generated from
CuO above 1,200 °C. The sparingly soluble compound which is semiconductor can also
be obtained by reduction of alkaline Cu(II) solutions. A modification of this reaction is
82 Experiment 9

used as a very sensitive test for organic reducing agents (aldehydes, aldehyde-containing
sugars, etc.). Fehling’s solution, which is recommended for this test, contains CuSO4,
NaOH, and sodium ammonium tartrate as a strong complexing ligand. The latter is nec-
essary in order to avoid precipitation of Cu(H2O). In this way, it is possible to detect 1 μg
of sugar (e.g., in human blood):

4Cu2+ + HCHO 4OH− ! 4Cu+ + CO2 + 5H2 O

The unstable, yellow CuOH is immediately converted into red Cu2O. Cu2S is a black
solid formed from the elements at higher temperatures.

Other copper(I) compounds and complexes

Cu2+ reacts with cyanide in a similar manner as with iodide. Reduction takes place
under precipitation of yellow CuCN and also evolution of gaseous dicyane (CN)2. The
white CuCN can also be obtained:

2CuðCNÞ2 ! 2CuCN + ðCNÞ2

9.4 Chemical and apparatus

Chemicals Apparatus

Copper metal and grain of zinc Test tube

CuSO Bunsen burner
Iron nail
AgNO solution and copper wire
N, HCl
N, HSO
N, HNO
Copper(II) oxide
NaOH and NaCO solution
Aldehyde solution and KI solution

9.5 Procedure

1.1 Preparation of copper from copper(II) oxide

On a sheet of paper thoroughly mix two to three micro-spatulas of Cu and an equal
amount of powdered charcoal. Transfer the mixture to a test tube and heat strongly
for 5 min. Observe the reduction to brown, metallic copper:
 9.5 Procedure 83

2CuO + C ! Cu + CO2

If it proves to be difficult to clean the test tube, use some drops of concentrated nitric
acid. This acid dissolves the remaining copper completely.

1.2 Preparation of copper by displacement from copper(II) salt solution with zinc
and iron
Take five to six drops of CuSO4 in a test tube and add grain of zinc. Shake gently and
observe the appearance of a red color deposit on the surface of zinc. Repeat the exper-
iment using iron nail in place of zinc:

Cu2+ + Zn ! Cu + Zn2+

1.3 Reducing properties of metallic copper: displacement of silver from Ag(I)

solution by copper
Add five to six drops of AgNO3 solution to a test tube and dip end of a cleaned copper
wire. You will observe grayish spongy deposition of white substance together with
some lustrous crystal of silver on the surface of the copper wire:

Cu + 2Ag+ ! Cu2+ + 2Ag

1.4 Action of dilute and concentrated acids on copper

Add a small piece of copper to each of three test tubes and then five to six drops of
2N, HCl to one test tube, 2N, H2SO4 to the second test tube, and 2N, HNO3 to the third
one. The color of the solution in the third test tube changes to green, which indicates
the formation of Cu2+ and brown gas involved implies NO2 formed from NO and air.
Note: Only 2N, HNO3 dissolves copper:

Cu + HNO3 + 6H+ ! 3Cu2+ + NO + 4H2 O

Repeat this experiment with concentrate HCl, H2SO4, and HNO3. Note that Cu dissolves
both in concentrated H2SO4 and HNO3:

Cu + H2 SO4 ! CuSO4 + SO2 + 2H2 O

84 Experiment 9

2 Copper(II) compounds

2.1 Reaction of copper(II) oxide with dilute acids

Add two to three micro-spatula of copper(II) oxide to each of two test tubes, then add five
to six drops of 2N, HCl to one test tube and equal amounts of 2N, H2SO4 to the other test
tube. What can be concluded from the color of the resulting solution? Write the equation.

2.2 Preparation of copper(II) hydroxide and its reaction with acids and bases,
and thermal decomposition
Add five to six drops of CuSO4 solution to three test tubes and then three to four
drops of NaOH to all three test tubes. Blue Cu(OH)2 precipitates will be observed.
Then heat one of the test tubes until black color appears. Take the remaining two
tubes, add 2N, NaOH to one test tube and equal amount of 2N, H2SO4 to the other.
The acid completely dissolves Cu(OH)2 to give blue solution of Cu2+ while the base
dissolves only partially by forming dark blue tetrahydroxocuprate.
Reactions:
heat
Cu2+ + 2OH− ! CuðOHÞ2 ! CuO + H2 O

CuðOHÞ2 + 2H+ ! Cu2+ + 2 H2 O

2−
CuðOHÞ2 + 2OH−! CuðOHÞ4

2.3 Hydrolysis of copper(II) salts

Place two drops of CuSO4 solution and the same volume of CuCl2 on a blue litmus
paper. The litmus paper turns to red:

2+

CuðH2 OÞ6 + H2 O ! CuðH2 OÞ5 ðOHÞ + H3 O+

2.4 Sparingly soluble Cu(II) salts: CuS

Add two to three drops of CuSO4 solution to a test tube and the same amount of fresh
H2S water. Black CuS mixed with Cu2S is precipitated:

Cu2+ + S2 − ! CuS

2.5 Preparation of copper(II)carbonate (CuCO3)

Add two to three drops of CuSO4 solution to a test tube and the same amount of soda
NaCO3 solution. Observe the precipitation of blue basic copper carbonate, Cu(OH)2·CaCO3:

Cu2+ + CO3 2− + H2 O ! CuðOHÞ2 · CuCO3

 9.5 Procedure 85

2.6 Complex formation of copper(II): reaction with ammonia

Place two to three drops of CuSO4 solution into a test tube and add dropwise ammonia
solution. At first, blue Cu(OH)2 precipitates but dissolves in excess ammonia under the
formation of deep blue tetrammine complex, [Cu(NH3)4]2+. This reaction is overly sen-
sitive and specific for Cu(II):

Cu2+ + 2OH− ! CuðOHÞ2

2+
CuðOHÞ2 + 4NH3 ! CuðNH3 Þ4 + 2OH−

3 Copper(I) compounds

3.1 Preparation of Cu(I) hydroxide and its thermal decomposition

Take two to three drops of CuSO4 solution and add five to six drops of 10% aldehyde
solution. Heat the mixture to boiling and treat with four to five drops of 2N, NaOH.
Note: The precipitation of yellow CuOH. Continue heating until the color of the
solid turns to red, which indicates the presence of Cu2O:

CuðOHÞ2 + 4HCOH ! CuOH + CO2 + 3H2 O

Note: Similarly CuOH is thermally unstable and decomposes to Cu2O + H2O:

CuOH ! CU2 O + H2 O

3.2 Preparation of cuprous iodide, CuI

Add two drops of CuSO4 solution and the same amount of KI solution to a test tube.
White CuI precipitates and the mixture turns to yellow to brown due to the formation
of iodine (as I3–). Use starch solution to prove the presence of iodine; touch the sample
with a glass rod and dip it into another test tube containing some drops of starch solu-
tion. The latter will turn blue.
To observe the white color of CuI, add several drops of Na2SO3 solution. Na2SO3
removes iodine and white color appears, hence, keep it for further experiments:
1
Cu2+ + 2I− ! CuI + I2 I2 + I− ! I3 −
2
I2 + SO3 2− + H2 O ! 2I− + SO4 2− + 2H+
86 Experiment 9

9.6 Observation

Color change
Evolution of gas
Sound of reaction when reaction takes place

9.7 Results and discussion

9.8 Review questions

1. Indicate the position of copper in the periodic table and work out its electronic
configuration.
2. The electronic configuration of group IB elements is quite similar to that of alkali
elements (ns1). Compare the properties of both groups of elements and find the
similarities in their behavior.
3. Why copper and silver are poorer reducing agents than the alkali metals?
4. Which are the most common oxidation states of copper in its compounds?
5. How can you distinguish between Cu(I) and Cu(II) compounds by making uses of
their magnetic properties?
6. What reaction, if any, takes place on treating copper with:
a) dilute sulfuric acid and b) hot conc. H2SO4?
7. Dry copper chloride is yellow-brown. A conc. aqueous solution of the halide has
green color. On adding conc. H2SO4 or HCl, the color changes to yellow-brown.
Dilution with water creates a blue color. Explain these color changes.
8. Why is it possible to use anhydrous CuSO4 as an indicator for traces of moisture?
Experiment 10

10.1 Chemistry of zinc

10.2 Objective

Students should be able to:

1. understand how you will prepare metallic zinc from ZnS and ZnCO3,
2. write the equation for the reaction of zinc with
a. hydrochloric acid,
b. dilute and concentrated sulfuric acid,
c. dilute and concentrated nitric acid, and
d. alkali hydroxide, and
3. characterize the behavior of Zn(OH)2 with respect to its solubility in acids and
bases (NaOH and NH3).

10.3 Theory

Occurrence
Zinc is widespread in nature with a portion of 120 g/t in the Earth’s crust (similar to cop-
per). Zinc occurs most frequently in the form of sulfides (sphalerite, ZnS), carbonates
(galmei, ZnCO3), and also as silicates and oxides. Most of zinc ores contain about 0.3%
Cd. Zinc is known with isotopes 64Zn (48.9%), 66Zn (27.8%), 67Zn (4.1%), 68Zn (18.6%), and
70
Zn (0.6%).

Preparation
As brass alloy (Cu/Zn), zinc has been known since antiquity. The preparation of the
pure metal, however, proved to be difficult because of its considerable volatility. Zinc
ores are normally concentrated by floatation followed by roasting to give the oxide:

3
ZnS + O2 ! ZnO + SO2
2
ZnCO3 ! ZnO + CO2

The preparation of the metal is brought about thermally or electrolytically:

ZnO + C ! Zn + CO
ZnO + CO ! Zn + CO2

https://doi.org/10.1515/9783111574349-011
88 Experiment 10

The electrolytic method starts with ZnO being dissolved in sulfuric acid followed by
electrolysis to give the metal.

10.4 Chemical and apparatus

Chemicals Apparatus

– Zinc dust Test tube

– Solution of zinc sulfate or chloride. Bunsen burner
– 2N, H2SO4
– Concentrated H2SO4
– 2N, NaOH
– 0.5 N KNO2
– 2N, NH3
– Acetic acid and sodium acetate

10.5 Procedure

1.1 Dissolution of zinc in H2SO4

Add a micro-spatula of zinc dust to four to five drops of 2N, H2SO4 in a test tube and
heat the mixture gently in a water bath until you note the evolution of hydrogen gas,
which leads to the formation of colorless Zn2+ solution:

Zn + 2H+ ! Zn2+ + H2

Repeat the above experiment using concentrated H2SO4.

Note: Zinc does not dissolve readily in concentrated H2SO4 and only reacts slowly
on heating to form ZnSO4 and SO2:

Zn + 2H2 SO4 ! ZnSO4 + SO2 + H2

1.2 Dissolution of zinc in alkali hydroxide

Add a micro-spatula of zinc dust to four to five drops of 2N, NaOH in a test tube and
heat the mixture gently in a water bath. Zinc dissolves by giving colorless solution,
[Zn(OH)3]–, liberating hydrogen gas:

−
Zn + 2H2 O + 2OH− ! ZnðOHÞ3 + H2
 10.6 Observation 89

1.3 Reducing property of zinc: reduction of nitrite to ammonia

In a porcelain crucible containing a micro-spatula of zinc dust, add four drops of
0.5 N KNO2 followed by four to five drops of concentrated NaOH. Heat the mixture
gently to boil on asbestos wire gauze. You will feel the smell of pungent odor due to
the formation of ammonia. Check using the red litmus paper:

−
Zn + NO2 − + 5H2 O + 2OH− ! ZnðOHÞ3 + NH3

1.4 Reaction of Zn(II) with ammonia: formation of tetrammine zinc(II)

Add three drops of Zn(II) solution in a test tube, and then 2N NH3 in dropwise manner.
White Zn(OH)2 precipitates in the first instance but dissolves in excess amount of NH3:

2−
ZnðOHÞ2 + NH3 ! ZnðNH3 Þ4 + 2OH−

1.5 Sparingly soluble zinc salts: zinc carbonate

Add equal amount of sodium carbonate to three to four drops of zinc salt solution in
a porcelain crucible. White zinc carbonate precipitates and heat gently; carbonate
and hydroxides of Zn decompose well. Write the equation.

1.6 Preparation of zinc sulfide

Add a drop of acetic acid and sodium acetate into a test tube containing three to four
drops of zinc salt solution and treat with a few drops of freshly prepared H2S solution.
Note the white precipitate of zinc sulfide:

Zn2+ + H2 S ! ZnS + 2H+

Repeat the above experiment using two to three drops of H2SO4 in place of acetic acid
and sodium acetate. No precipitate is formed, but what is the reason behind? Explain.

10.6 Observation

Color change
Evolution of gas
Sound of reaction when reaction takes place
Experiment 11

11.1 Chemistry of cadmium

11.2 Objective

Students should be able to:

1. observe the reaction of cadmium(II) with aqueous sodium hydroxide,
2. characterize the behavior of Cd(OH)2, and
3. understand the precipitation of cadmium sulfide.

11.3 Theory

11.3.1 The element

Cadmium is always associated with zinc. Zinc ores normally contain 0.2–0.4% cad-
mium. The element is used for protective layers on other metals. Its production ap-
pears to be quite complex and starts with the oxide or the sulfate. Cadmium oxide can
be reduced by carbon, and CdSO4 is processed electrolytically. The latter is soluble in
dilute nitric acid but only slowly dissolved by HCl and H2SO4.
Additionally cadmium has eight isotopes: 106Cd (1.2%), 108Cd (0.9%), 110Cd (12.4%),
111
Cd (12.7%), 112Cd (12.4%), 113Cd (12.3%), 114Cd (28.9%), and 116Cd (7.6%).

11.3.2 Cadmium compounds

The only stable oxidation state of cadmium in its compounds under normal condition
is +II. In all, its reaction cadmium is quite similar to zinc.
Cadmium hydroxide is obtained as white precipitate on adding NaOH or ammo-
nia to an aqueous Cd(II) salt solution. In contrast to zinc hydroxide, Cd(OH)2 is not
soluble in an excess of alkali hydroxide. It dissolves, however, in aqueous ammonia
under formation of the ammine complex.
The oxide, CdO, can be prepared from Cd(OH)2 by heating above 150 °C. Its brown
color is a result of lattice defects.
Cyanide and Cd2+ give a white precipitate of Cd(CN)2, which reacts with excess
cyanide yielding the soluble complex anion, [Cd(CN)4]2–.
Brown yellow CdS is precipitated from slightly acidic (mineral acid) aqueous solu-
tions of Cd(II) salts with H2S.

https://doi.org/10.1515/9783111574349-012
 11.5 Procedure 91

Notice that ZnS has a slightly higher solubility and its precipitation requires acetic
acid medium. CdS seems to be rather inert to complexing agents and is not attacked
by cyanide (difference to CuS).

11.4 Chemicals and apparatus

Chemicals Apparatus

– A solution of cadmium sulfate or chloride Test tube

– NaOH Bunsen burner
– 2N ammonia
– 2N sulfuric
– H2S

11.5 Procedure

1 Reaction of cadmium(II) with aqueous sodium hydroxide

Add three to four drops of Cd(II) salt solution to a test tube and then add NaOH in a
dropwise manner. Observe the white precipitate of Cd(OH)2. In contrast to Zn, Cd(OH)2
is not soluble in excess NaOH:

Cd2+ + 2OH− ! CdðOHÞ2

Find an explanation for the different behavior of Zn(OH)2 and Cd(OH)2.

2 Reaction of cadmium(II) with ammonia: formation of a hexammine complex

Repeat the previous experiment but use 2N ammonia instead of aqueous alkali hy-
droxide. Initially, white precipitate of Cd(OH)2 appears, which is, however, dissolved
in excess ammonia. The colorless hexammine complex [Cd(NH3)6]2+ is formed. Zinc
exhibits the same behavior. Write down the equations.

3 Preparation of basic cadmium carbonate

Add three to four drops of Cd salt solution into a porcelain crucible followed by an
equal volume of sodium carbonate solution. Observe the white precipitate of basic
cadmium carbonate. The compound has variable compositions. After evaporating the
solvent and heating residue, a color change from white to brown will occur. This is
attributed to lattice defects in CdO, which has been formed by thermal decomposition
of the basic cadmium carbonate.
Write down the equations.
92 Experiment 11

4 Precipitation of cadmium sulfide

Add three to four drops of Cd(II) salt solution to the test tube, and then one drop of 2N
sulfuric acid followed by two to three drops of freshly prepared H2S water. Observe
the brownish yellow precipitate of CdS. The latter is soluble in semiconcentrated min-
eral acids.

11.6 Observation

– Color change
– Evolution of gas
– Sound of reaction when reaction takes place

11.7 Review problems

1. Describe the position of cadmium in the periodic table and find out its electronic
configuration.
2. Which hydroxide is more basic, Zn(OH)2, or Cd(OH)2? Give a reason for your
choice.
3. What happens to a solution containing Zn2+ and Cd2+ ions on adding excess NaOH
or ammonia? Is it possible to distinguish between the two ions?
Experiment 12

12.1 Chemistry of mercury

12.2 Objective
Students should be able to:
– understand the reaction of mercurous salts with sodium hydroxide and
– observe the reaction of mercury with hydrochloric acid.

12.3 Theory

Occurrence
Mercury occurs only 0.5 g/t in the Earth’s crust and, therefore, represents a rare ele-
ment. Nevertheless, some relatively high deposits are known, which contain mercury
in the form of red cinnabar, HgS. This is occasionally mixed with small droplets of
mercury.

Preparation
After flotative concentration of the mercury ore, the sulfide is roasted in a stream of
air followed by condensation of the mercury vapor passing over:

HgS + O2 ! Hg + SO2

The crude mercury is washed with dilute HNO3, filtered, and distilled in vacuum.

Physical properties
Mercury is a white-lustrous metal and liquid at room temperature. As metal, it proves
to be comparatively volatile with a vapor pressure of 0.0016 mbar at 200 °C (for Cd only
10–10 mbar). Mercury and bismuth exhibit the highest specific resistance of all metals.
Furthermore, Hg has a remarkably high surface tension compared to other liquids.

Chemical properties
With respect to its chemical behavior, Hg differs considerably from its homologs Zn
and Cd. As a noble one, it is resistant to O2, water, CO2, SO2, HCl, HF, and ammonia at
room temperature although it reacts with halogens and sulfur under these conditions.
Nonoxidizing acids do not attack mercury, but HNO3 and conc. sulfuric acid dissolve
the metal. Due to its liquid state, mercury alloys with many other metals even at room
temperature to form an amalgam. Very good precursors of amalgams are alkali and

https://doi.org/10.1515/9783111574349-013
94 Experiment 12

alkaline earth metals, whereas 3d elements (except Mn and Cu) are nearly insoluble
in liquid mercury. Mercury and all its soluble and volatile compounds are highly
toxic as it reacts with human proteins to form Hg–S bond, which blocks the protein
functions completely.

12.4 Chemicals and apparatus

Chemicals Apparatus

Aqueous solutions of Hg(NO) and Hg(NO) Dropper

Ammonia solution Porcelain crucible
Hydrochloric acid Test tube

12.5 Procedure

12.5.1 Displacement of mercury from its salts

Clean a copper plate with abrasive paper, place a drop of mercuric nitrate solution on
it, and let it rest for 5 min. Rub the gray spot with filter paper to make it lustrous:

Hg2+ + Cu ! Hg + Cu2+

12.5.2 Reaction of mercurous salts with sodium hydroxide

Take three drops of the mercurous salt solution in a test tube and add dropwise 2N,
NaOH. The black precipitate consists of a mixture of Hg and HgO. It is soluble in nitric
acid but insoluble in excess NaOH:

Hg2 2+ + 2OH− ! Hg + HgO + H2 O

12.5.3 Reaction with hydrochloric acid

Add three drops of the mercurous nitrate solution to a test tube followed by a few
drops of HCl. A white precipitate of Hg2Cl2 is obtained. The compound is not soluble
in dilute mineral acids:

2Hg2 2+ + 2Cl− ! Hg2 Cl2

Addition of some drops of ammonia to thus

 12.6 Review problems 95

12.6 Review problems

1. Compile some of the characteristic group properties of Zn, Cd, and Hg. In which
way does mercury differ from the other two elements?
2. How do you prepare metallic zinc from ZnS and ZnCO3?
3. Write down the equation for the reaction of zinc with:
a. hydrochloric acid,
b. dilute and concentrated sulfuric acid,
c. dilute and concentrated nitric acid, and
d. alkali hydroxide.
4. Characterize the behavior of Zn(OH)2 with respect to its solubility in acids and
bases (NaOH, NH3).
5. Zinc reduces nitrate and nitrite to ammonia in alkaline aqueous solution. Write
down the equations.
6. Which solution, H2S or (NH4)2S, would more completely precipitate ZnS from a
solution of its salt?
7. A solution of ZnSO4 in water is acidic. Why?
8. Which salt, ZnCl2 or [Zn(NH3)4]Cl2, is hydrolyzed more strongly? Prove your
answer.
9. Write down the various types of salts that can be formed from Zn(OH)2.
References
[1] Cotton, F. A. and Wilkinson, G. (1972). Advanced Inorganic Chemistry (3rd ed.). Inter science
Publishers, a division of John Wiley and Sons, New York.
[2] Chambers, C. and Holliday, A. K. (1975). Modern Inorganic Chemistry (1st ed.). R. I. Acford Ltd.,
Industrial Estate, Chichester, Sussex.
[3] Housecroft, C. E. and Sharpe, A. G. (2005). Inorganic Chemistry (2nd ed.). Pearson Education
Limited, England.

https://doi.org/10.1515/9783111574349-014
Index
accidents should be reported IX coal 46
acidic medium 3, 8, 10, 12, 25, 28, 38–39, 51, 60 completely cover the feet VII
acid–base reactions 6 complex 2, 4–5, 17–19, 27, 40, 51, 54, 64, 69, 72–74,
alkali medium 7 77–78, 81, 85, 90–91
alkaline chromate solutions 39 complex formation of Ni(II) with pyridine 78
alkaline solutions 12 complexing agents 15, 91
allotropic 15 compressed gas cylinders VIII
alloys 35–36, 47, 64, 94 concentrated ammonia 51, 53
amalgams 94 concentrated by floatation 79
amphoteric XII, 7, 17–18, 23, 25, 27, 32–33, 44, 48 Concentrated by floatation 87
amphoteric properties XII, 7, 44, 48 concentrated nitric acid 15, 36, 42, 47, 83, 87, 95
analytical techniques V concentrated solution 18, 61
anionic ligand 27 concentrated sulfuric acid 24, 38, 47, 60, 81, 95
antibonding 37 condensation reactions 7
aqueous chemistry of titanium(III) 19 converted into slag 64
aqueous solutions 7–8, 10, 19, 90 coordination compound 5
atomic number 1 coordination number 4–5
Aufbau principle 1 copper is ductile 80
covalent compounds 10
basic medium 7, 12, 38 crucible 29, 42, 59, 68, 89, 91, 94
biological nitrogen fixation 47 crystallize 4, 42
blast furnace 64 crystals 31, 42–43, 48, 60–61, 67, 69
blocks the protein functions completely 94 cubic body – centered structure 15
Boudouard equilibrium 64
brass alloy 87 dangerous VII, VIII
Brinell hardness 15 De Boer process 15
Bunsen burner 40, 42, 51, 57, 65, 72, 76, 82, 88, 91 decolorizes 21, 32, 60–61
decomposition 15, 17, 25, 27, 60, 68, 84–85, 91
cadmium 90–92 dehydrates 50
catalyst 25, 58, 68 disproportionation 12, 59, 68
catalysts in chemical industry 24 distorted octahedral 48, 81
cation 4, 7–8, 17–20, 25–28, 36–37, 48 d-orbitals 2, 4
central metal atom 5 dropwise 30, 32, 40–41, 43, 51–53, 61, 67, 72–73,
characteristic of Ti3+ 14 76–77, 85, 89
charcoal 71, 75, 82
chemical analysis V Earth‘s crust 35, 56
chemical hazard IX Earth‘s crust contains approx. 0.6% Ti 14
chemical properties 15, 80, 94 Earth’s crust 14, 71, 75, 79, 87, 93
chemical reaction XI, 9, 54 electrical conductivity 80–81
chemicals and apparatus 19, 29, 40, 51, 56, 65, electrolytic 28
72, 76 electrolytic refining and zone melting 75
chromite is directly reduced by carbon 35 electronegative element 8–9
chromium 35–38, 40, 42, 44 electronic configuration 1, 3, 37, 86, 92
chromium containing substances are highly electronic industry 16
carcinogenic 36 electrothermally 46
chromium plating 36 equilibrium 17, 41, 81
clay triangle 59, 68 evaporating 32, 42, 91

https://doi.org/10.1515/9783111574349-015
100 Index

exothermic processes 3 laboratory V

experiments V, VII, 20, 31, 76, 85 lanthanides and actinides 1
extremely explosive 60 lattice energy 3
extremely low rate 37 Lewis basic 18
eye-wash fountain IX ligands 2, 4–6, 16, 18, 50, 81
liquid at room temperature 93
ferric chloride salt solution 68–69 litmus paper 29, 62, 84, 89
fire blanket IX loss of electron 10
fire extinguisher IX
food and beverage are strictly prohibited VII magnetic properties 79, 86
fume hood VIII main group elements 1
fusing chromite 36 manganese 2–3, 6, 56–59, 62
Manganese 57
gain of electrons 10 manual V, XI
gloves VIII material safety data sheet VII
goggles or safety glasses VII maximum oxidation number in aqueous 3
green flame 80 mercury 93–94
metallic cobalt 71, 74
half-filled 2 metallic copper 79, 82–83
halide and oxyhalides 47 metallurgy 75
heavy metal 56, 64 metals VIII, 1, 3, 8–10, 14–15, 19, 23, 36, 39, 64, 66,
hexagonal 15 80–81, 86, 90, 93–94
high resistance to corrosion 16 microgram 82
high surface tension 93 mineral acids 15, 92
high vacuum technology 16 minerals 14, 18, 23, 46, 56, 71, 74
higher pH values 18 Mohr’s salt 61, 66–68
hydrolysis 7, 14, 17, 21, 25, 27, 35, 38, 41, 50, 84 molybdenum 46–54
hydrolysis of titanium(III) 21 molybdenum does not occur naturally 46
hydrometallurgy 80 molybdenum filaments needed for electrical
bulbs 47
identification of vanadium 31–32 Mond process 75, 78
impurities 15, 64, 80 most frequently occurring metal 64
in nature chromium occurs as chromite 35
indicator 67, 79, 86 neutral and basic solution 10
inorganic chemistry V neutral and ionic complexes 10
insoluble in water 10, 21 nickel 71, 75, 78
instructor VII, IX60 NMR spectroscopy 48
interstitial compounds 6, 15, 23 nonstoichiometric compounds 6, 24
ionic equations 8–10, 61
ionization energy 3 occurrence 14, 23, 35, 46, 64, 71, 75, 79,
iron 3, 5, 15, 23, 31–32, 35–36, 40, 46, 56, 64–68, 87, 93
70, 79, 81, 83 ores 46, 56, 64, 71, 75, 79–80, 87, 90
Iron 46, 65, 83 organic solvents 50, 54
isotopes 14, 23, 64, 75, 79, 87, 90 orthorhombic system 16
orthotitanic XII, 17
kinetic hindrance 37 overall charge 5–6
KROLL procedure 15 overall equations 9
 Index 101

oxidation 3–10, 13, 21, 23–25, 27–28, 32, 35, 37–39, reducing properties of titanium(III) hydroxide 21
46, 49, 56–57, 59–60, 62, 64, 66, 71–72, 76, 78, reduction 10, 12–14, 16, 18, 25, 27–28, 32, 36–37,
86, 90 50–51, 56, 65, 67, 71, 81–82
oxidation number 3–4, 6–8, 13–14, 16, 19, 35 resistant to corrosion 24, 36, 80
oxidation state 3, 5–7, 9, 23, 27–28, 35, 39, 49, 57, roasted 56, 71, 79, 93
59, 90
oxidation states 3 safety equipment IX
oxidative chlorination 27 safety rules VII
oxidizing acids saturated ammonium molybdate 51–54
– concentrated sulfuric acid 24 semiconcentrated 52
oxidizing agent 12, 37–39, 58, 60 separation 18
oxidizing enzymes 81 shatterproof glass VII
shoes VII
periodic table 1, 35, 86 shower and first aid kit washes IX
peroxide decomposes rapidly 39 slightly toxic to human 81
pH value 7–8, 10, 17, 49, 60 smoking is prohibited VII
physical properties 15, 47, 80 solubility XI, 64, 67, 70, 81, 87, 91, 95
pictogram IX soluble in various organic solvents 16
polar covalent 16 sparingly soluble 7, 10, 25, 28, 30, 43, 49, 52, 67,
polycondensation processes 25 78, 81
polymerization of propylene 18 stable complexes 6, 81
potassium dichromate solution 43–44 strong acids and bases 10
precipitate XII, 17, 21, 30, 32–33, 38, 40–41, 48, strong inter-electronic interaction 2
52–53, 57–58, 60–62, 66–69, 72–73, 76–77, supernatant solution 58, 76
89–92, 94–95 syntheses 16
precipitates XI, 10, 17, 19, 50–51, 60, 67, 77, 85, 89
preparation XI, 14, 20, 23, 29–31, 33, 35, 40, 42–43, test tube 19–22, 29–33, 40–43, 52–54, 57–61,
46, 51–53, 56–58, 60, 64–69, 71–72, 75, 79, 66–69, 73, 76–77, 82–85, 88–89, 91–92,
82–85, 87, 89, 91, 93 94–95
procedures 8, 14 tetrahedral structure 16
proper labeling VIII thermodynamically 60
properties of transition metals V titanium 5, 7, 14–22, 24
protective apron VII titanium halides 16
protective eyewear VII titanium(III) compounds 18
protic solvents 16 titanium(IV) oxide 16
protolysis XII, 6–7, 16–17, 41 transition elements 1
transition metal compounds are very often
qualitative and quantitative 49 colored 4

rare element 14, 23, 93 unauthorized VII

rather common metal 79 under basic conditions 57
reaction of Co(II) with ammonia 72 unstable to water 21
reaction of Fe with acids 66
reaction of Ni(II) with aqueous ammonia 77 V2O5 is a highly poisonous, brick red powder 25
recrystallized 71 valence electron 1
redox process 10–11, 13, 21, 59 Van Arkel 15, 23
redox reactions 4, 8, 46, 55 vanadium 7–8, 23–34
reducing agent 12, 19, 28, 36–37, 64 vanadium is widespread in the earth‘s crust 23
102 Index

vanadium oxide is a black solid 28 wear safety glasses VII

vertically with iron stand 40 white, crystalline CrCl2 36
visible part of the spectrum 4 white shiny hard and brittle metal 36
wire gauze 42, 59–60, 89
waste disposal VIII with human proteins to form Hg – S bond 94
water bath 19–20, 29, 40–42, 51–52, 72, 76, 88
wavelengths 4 zinc 2, 19–20, 33, 37, 51, 53, 56, 82–83, 87–90, 95