UNIT 1

KNOWLEDGE TRADITION OF INDIAN CHEMISTRY

CONTENTS-

PART A

1. Ancient Indian chemists and their works-

NAGARJUNA, VAGBHATA, GOVINDACHARYA, YASHODHARA, RAMCHANDRA, SOMDEVA, ETC.
2. Introductory Idea about rasas
Main RASA- MAHARAS, UPARAS, COMMON RAS, RATNA, DHATU, POISON, ALKALI, ACID,
SALT, LOHABHASMA.
3. MAHARAS- ABRAM, VAIKRANT, BHASIK, VIMALA, SHILAJATU, SASAK, CHAPALA, RASAK
4. UPARAS- GANDHAK, GARIK, KASHIS, SUVARI, LALAK, MANAH, SHILA, ANJANA, KANKUSHTHA
5. COMMON RASA- KOYLA, GOURIPASHAN, NAVASARA, VARATAKA, AGNIJAR, LAJAVARTA, GIRI
SINDOOR, HINGUL, MURDAD SHRANGAKAM.

PART B

CHEMISTRY OF d AND f BLOCK ELEMENTS-

1. Chemistry of transition elements.

2. Chemistry of Inner transition elements.
3. Transuranic elements.

Chemistry in India: A Survey

Chemistry, it took shape in 18th-century Europe, as an alchemical tradition, which was partly borrowed
from the Arabs. “Alchemy was a practice whose main aim was to turn metals into gold and discover an
‘elixir of life’ that would grant immortality”. Other cultures — especially the Chinese and the Indian —
had alchemical traditions of their own, which included much knowledge of chemical processes and
techniques.

In India, we can trace such techniques all the way to the Indus valley civilization (3rd millennium BCE)
and its antecedents. The Harappans used metallurgical, pottery making, bead making and many such
skills that involved control of processes such as heating, fusion, evaporation, complex treatment of
minerals, including bleaching a bead with a solution of calcium carbonate and heating it in kiln (furnace
or oven) to leave permanent white designs on it (fig 1).

Harappans also experimented with various mortars and cements made of burnt limestone and gypsum,
coated with silica (fused with soda) to which copper oxide was added to give it a shiny turquoise glaze
(peacock green/blue flowing low fire) which was then shaped into various ornaments or figurines. The
addition of iron oxide gave a greenish blue tint to glazed pottery, while manganese oxide resulted in a
maroon color (fig 2).

Figure 1
 Figure 2

Such techniques survived the end of the Indus civilization and found their way to the later Ganges
civilization (1st millennium BCE), often with innovations such as glass manufacture, for instance:
numerous glass beads and other artefacts have been unearthed from Taxila in the Northwest to Nalanda
in the East and Arikamedu in the South.

Pigments were another area for skilled chemical practices and were required for painting (witness the
famous Ajanta murals) as well as dyeing of cotton and other textiles. The sources of pigments were not
limited to organic materials (such as extracts of specific flowers or fruits) but included mineral sources,
from carbon (lamp black) to arsenic sulfide (yellow ochre) or copper acetate (verdigris, greenish blue in
color).

Also, Atomism, or the concept that matter is ultimately made of indivisible building blocks, appeared
in India a few centuries BCE as part of philosophical speculations, in the Vaiśeṣika, one of the six
philosophical systems of ancient India. The author of the Vaiśeṣika Sutras came to be known as Kaṇāda
(literally ‘eater of particles’) and may have lived any time after 500 BCE.

In the system of Vaisesika , all substances were seen as an aggregated form of smaller units called atoms
(aṇu or paramāṇu), which were eternal, indestructible, spherical, supra-sensible and in motion. they
could form pairs or triplets, among other combinations, and unseen forces caused interactions between
them. The Vaiśeṣika system identified nine types of substance (dravya): (1 to 5) the five elements (earth
or prithvi, water or ap, fire or tejas, wind or vāyu, ether or ākāśa), (6) time (kāla), (7) space or direction
(dik), (8) the mind (manas), and (9) the spirit or knower (ātman). Besides, these nine substances it also
mentioned the twenty-four different qualities (guṇas) of matter, including fluidity, viscosity, elasticity,
and gravity. While fluidity was related to water, earth and fire, viscosity was unique to water, and
gravity to earth. Distinctive characteristics of sound, heat and light were also mentioned, which often
came close to later discoveries of physics, although, lacking a mathematical apparatus, they did not
evolve into any scientific theories.

Chemistry in Early Literature

We find plentiful evidence of knowledge of chemical practices in some of India’s early literature.

 Kauṭilya’s Arthaśāstra is a well-known text of governance and administration authored

probably in the 3rd or 4th century BCE, during the Mauryan era. It has much data on prevailing
chemical practices, in particular a long section on mines and minerals (including metal ores of
gold, silver, copper, lead, tin, and iron). It has also discussed about the various characteristics of
precious stones (pearl, ruby, beryl, etc.), details of fermented juices (from sugarcane, jaggery,
honey, jackfruit, mango, etc.), and oil extraction.
 The fundamental two texts of Ayurveda are the Charaka Saṃhitā and the Suśruta Saṃhitā,
both dated a few centuries CE. They discussed about the wide range of chemicals for medical
 use, metals, minerals, salts, juices, etc., but they also discussed about the preparation of various
alkalis (kṣāra), which is regarded as one of the ‘ten arts’ (kalā). Alkalis are described as mild,
caustic, and are prepared from specific plants as follows-
 After the plants have been burnt together with some limestone, their ashes are stirred
in water, filtered, and the resulting solution is concentrated by boiling, to which burnt
limestone and conch shells are added.
 Such alkalis were used to treat surgical instruments as well as thin sheets of metals like
iron, gold or silver intended for the preparation of drugs.

 Varāhamihira’s Bṛhat Saṃhitā, an encyclopedia- composed in the 6th century CE, has a chapter
on the preparation of numerous perfumes out of sixteen fundamental substances mixed in
different proportions. Indeed, perfumery and cosmetics formed a major branch of chemical
practices in classical and medieval India. It also includes various recipes, for instance for the
preparation of a glutinous material to be applied on the roofs and walls of houses and temples;
it was prepared entirely from extracts from various plants, fruits, seeds, and barks which, after
being boiled and concentrated, were then treated with various resins.

The Classical Age

 Alchemy in India emerged around the mid-first millennium CE, during the Gupta empire. Its
origins remain hard to trace, and scholars have proposed that it received inputs from China,
where the discipline is well attested as early as in the 2nd century CE. It was variously called
rasaśāstra, rasavidyā or dhātuvāda; the word rasa has many meanings, such as essence, taste,
sap, juice. Mercury was identified with the male principle (Shiva), while sulfur (gandhaka) was
associated with the female principle (Shakti), and most alchemical texts were presented as a
dialogue between Shiva and Shakti.
 There is a vast alchemical literature, authored by savants such as Nāgārjuna, Govinda Bhāgavat,
Vāgbhata, Somadeva, Yaśodhara, among many others.
 The Rasa sastra texts discusses many chemical substances and their interactions. They were
categorized as follows (with some variations):
 Mahārasas or eight major substances: mica, tourmaline, copper pyrite, iron
pyrite, bitumen, copper sulphate, zinc carbonate, and mercury (sometimes lapis
lazuli and magnetite or lodestone are included).
 Uparasas or eight minor substances: sulfur, red ochre, iron sulphate, alum,
orpiment (arsenic trisulfide), realgar (arsenic sulfide), collyrium (compounds of
antimony), and tint stone or cassiterite (tin dioxide).
 Navaratnas or nine gems, including pearl, topaz, emerald, ruby, sapphire, and
diamond.
  Dhātus or seven metals: gold, silver, copper, iron, lead, tin, zinc; a few alloys
(such as brass, bronze and combinations of five metals) were also included.
 Poisons (viṣa or garala)

In the quest for the elixir of life, mercurial preparations were supposed to bestow long life and youthful
vigor; mercury was sometimes called amṛtadhātu or ‘immortal metal’. In practice, some Ayurvedic and
Siddha medicines were derived from various metals and minerals, but only after those had undergone
complex purificatory processes to remove their toxic effects and make them fit for internal use.

For instance, although mercury compounds are regarded as poisonous, cinnabar Figure 3 (mercuric
sulfide, HgS) went through eighteen complex processes (saṃskāras), including rubbing with various
medicinally efficacious plant juices and extracts, incorporation of sulfur, mica, alkaline substances, etc.
The resulting mercury compound was then declared fit for consumption and believed to be as the
body’s rejuvenation. Similar processes existed in Tamil alchemy and the Siddha system of medicine,
which in addition, developed special techniques in connection with naturally occurring salts.

 Transmuting base metals, such as lead, tin, or copper, into gold was another pursuit of alchemy,
and involved five operations: smearing, throwing, pouring, fumigating, and impact. Here again,
mercury, sometimes called svarṇakāraka or ‘maker of gold’, often played a major role.
 Rasavidyā was regarded as essential for the rasavādin to achieve success, but the actual
practices were kept secret, as people believed that the goal would fail to be reached if they
were divulged to the uninitiated.

In the alchemical tradition, the transmutation of metals for the elixir of life, which was the ultimate
objective of Indian alchemists was not a success …but this quest for this elixir or the transmutation
of base metals lead to actual and valuable chemical techniques, in the medical field, and eventually
contributed to the Ayurvedic and Siddha pharmacopeias.
 Figure 3

Laboratory and Apparatus

The layout of the laboratory had doors such as, Rasaliṅga in the east, furnaces in the southeast,
instruments in the northwest. These included mortars (of stone or iron) and pestles, bellows (to heat
the furnaces), sieves, pans, tongs, scissors and earthen or glass vessels, the apparatus included
specialized instruments ingeniously developed for heating, steaming, distilling, extracting substances.
Few of them are-

 The mūsa yantra or crucible, usually made of white clay mixed with rice husk, iron dust, chalk,
etc.; such crucibles would have various shapes and sizes, depending on their application.
 The koṣṭhi yantra- for the extraction of ‘essence’ of metals, consisting of two rimmed vessels,
with fire urged from above and a side blower.
 The svedanī yantra- a big earthen vessel used for steaming.
 The dolā yantra- in which a pot is half-filled with a liquid and a suspended substance absorbs
the liquid’s vapors.
 The pātana yantra- for sublimation or distillation.
 The dhūpa yantra, used for fumigation of gold leaves or silver foils with fumes of sulfur or other
substances.
Altogether, India’s chemical traditions were rich and varied, and fused elaborate techniques with a
spiritual component. Although not have directly contributed to the birth of modern chemistry, but
resulted in considerable practical applications, especially in fields like metallurgy, gemology, and
medicine.

Ancient Indian chemists and their works-

1. NAGARJUNA-

Sir Nagarjuna was a great Indian scientist who was born in Gujarat (931 A.D.). He was a reputed chemist,
an alchemist, and a metallurgist. The main aim of his experiments was to transform base elements into
gold, like the alchemists in the western world. Even though he was not successful in his goal, he
succeeded in making an element with gold-like shine. Till date, this technology is used in making
imitation jewelry. In his treatise, Rasaratnakara, he has discussed methods for the extraction of metals
like gold, silver, tin, and copper.

He did a lot of research work in the field of Chemistry and metallurgy. He wrote many books on
chemistry in which ‘Ras Ratnakar’ and ‘Rasendra Mangal’ are very famous. He had prepared many
medicines for many uncurable diseases. His famous books in the field of medical sciences are ‘Arogya
Manjari’, ‘Yoga Saar’ and ‘Yogashtak.’ The method of distillation is described in Nagarjuna’s Ras
Ratnakar to obtain mercury from ore Cinnabar. The methods of obtaining many types of acids and bases
from plants are also described in Ras Ratanakar.
 2. Acharya Vagbhata –

Maharishi Vagbhata, the Indian physician was born in Sindh, Pakistan in 600 AD. He was a Vedic
Brahmin. Buddhism influenced him as in his childhood he was taught by a Buddhist teacher
Avalokita. He was the author of the Astanga-sangraha also known as Astanga Hrdaya which is
known as the best book in the field of research and acts as most important guide in Ayurvedic
medicine. Thus, he was a Scientist, Writer, and a doctor.

In the book “Ashtanga Hridaya Sahinata”-

The first part of the book included all about the Ayurvedic medicines of ancient India. All the
required instruction for the students, origin and treating all the diseases, daily and periodic
observations, keeping hygiene and personal cleanliness around, all medicines their
departments and all about their benefits, etc.

The second part of the book included and described the structure of the human body,
humankind nature, all the major parts of the body, human practices, and different forms of
human beings.

The third part of the book describes the causes and how treatment of the disease can be cured
of fever, skin diseases, asthma, vomiting, epilepsy, etc.

In the fourth part of the book, he explained all about the cleanliness and vomiting and in the
fifth part which was the last part he included all about the diseases related to children, treating
diseases, insanity, eyes, ears, wounds of mouth and nose, treatment of insect and animal bites
all of it has been explained.
 PART B
Chemistry of d and f block elements
The d-block elements-

1. The elements in which last electron enters the ‘d’ orbital of the
penultimate shell i.e. (n-1) d orbital are d-block elements.
2. The d –block elements are called transition elements and consist of
elements lying between s and p –blocks starting from fourth period
onwards. These elements have properties which are transitional between
those of s and p block elements.
3. All these elements are metal.
4. The transition elements may be defined as elements whose atoms or simple
ions in their common oxidation have their electron in d orbitals. Thus,
elements whose atoms have partially filled d orbital of (n-1) that is
penultimate shell are termed as d- block elements. Based on this Zn, Cd, and
Hg which have filled d orbitals should not be included in this category. Also,
these elements do not resemble d-block elements in number of properties
even then these elements have been included and are termed as non-typical
transition elements.
5. The general electronic configuration of these metals is (n-1) d1-10ns1-2
where n is the number of last orbit.
Classification of d –block elements:

These are divided into four transition series-

i. The first transition series- (3d-series) involves the filling of 3d- orbitals
and has 10 elements from Scandium (Z = 21) to Zinc (Z = 30) in the
fourth period.
ii. The second transition series (4d-series)-involves the filling of 4d orbitals
and has 10 elements from Yttrium (Z= 39) to Cadmium (Z= 48) in the
fifth period.
iii. The third transition series (5d-series)-involves the filling of 5d-orbitals
and has 10 elements. The first element of this series is Lanthanum (Z= 57).
it is followed by 14 elements (lanthanides or lanthanons involving filling of
4f- orbitals). The next nine elements are from Hafnium (Z =72) to
mercury (Z = 80).
iv. The fourth transition series (6d-series) involves the filling of 6d- orbitals
and is incomplete starting from Actinium (Z= 89) and extended up to
element with atomic number Copernicium 112 (Cn). All the elements other
than Actinium in this series are synthesized.
1. Electronic configuration-
 2. General Characteristics of Transition Elements:
1. Metallic Character: d- Block elements have low ionization energy and
hence easily lose electrons to form cations. Furthermore, these elements
have only one or two electrons in their outermost energy shell i.e., they have
many vacant orbitals in the outermost shell which make them form
metallic bond and due to this all the transition elements are metal. They
are generally-
a. Malleable and ductile
b. Form alloys with several other metals.
c. They are good conductors of heat and electricity.
d. They are usually solids (Mercury has an exceptional behavior. It is a
liquid at room temperature).
e. In a particular series the hardness increases up to the middle with
increasing number of unpaired d- electrons. Cr, Mn and W having
maximum number of unpaired d- electrons are very hard metals, while
Zn, Cd and Hg are not hard metals due to the absence of unpaired
electrons.

2. Melting and Boiling Points: The melting and boiling points of the
transition elements are generally very high. This is probably due to two
reasons-
a. The presence of covalent bonding by the unpaired d- orbital electrons.
b. Strong metallic bonding due to overlapping of (n-1) d-orbitals.

Also, in moving along the period from left to right the melting point of these
metals first increases to maximum and decreases regularly towards the end of the
period.
 3. Atomic Radii:

Following overall trends in the variation of atomic radii across the period, are
observed as follows-

a) The atomic radii of the d-block elements of a given series generally

decrease with increase in the atomic number. This is since with an
increase in atomic number the nuclear charge increases which in turn tends
to attract the electron cloud inward resulting in decrease in size. However,
the decrease in the radii across a period is not uniform. The decrease in
radii of transition metals is small as compared to the decrease in the radii of
s and p block elements for the same periods. For ex. The radii of the
elements from Cr to Cu are very close to one another. This may be
explained based on screening effect. In d- block elements electrons are
added to an (n-1) d- subshell which adds to the primary screening effect
the additional electrons effectively screen the outer ns- electrons from
the inward pull of the nucleus. As a result, the size of the atom does not
change much from Cr to Cu.
b) In each series the atomic radius decreases from group 3 elements up to the
group 10 elements and then increases again towards the end of the series.
This anomalous increase in atomic radius towards the end of the series is
because of the increased force of repulsion among the added electrons.

c) Atomic radius increases on descending down the groups although the

increase is not as significant as in case of s and p block elements. The very
 close similarity between the radii of the elements of second and third
transition series, (Ex. Zr and Hf, Nb and Ta, Mo and W, Tc and Re etc.)
is the consequence of the filling of 4f subshell.

4. Atomic Volume and Densities:

i. The atomic volume of the transition elements is much lower than those of
their neighboring s and p block elements.
ii. Due to the decrease in atomic volume, the density of these elements’
increases. Therefore, the transition elements have quite high density.
Following trends are observed among the densities of the transition
elements.
a. In each transition series, the density increases across the series and
reaches a maximum value at the middle of the series.
b. The density increases down the group because the atomic size of the
elements of second and third transition series is nearly the same, their
atomic masses increase nearly two-fold and the densities of the
elements of the third series are generally twice those of the
corresponding elements of the second transition series.

5. Ionization potential:
 The ionization potentials of most of the d-block elements lie in between
those of s and p –block elements. These are higher than those of s- block
elements and are lower than those of p – block elements. This indicates that
the d- block elements are less electropositive than the s- block elements.
(Alkali and alkaline earth metals).
 The ionization potential of d- block elements increases as we move
across the series from left to right. However, the increase in the value is
not as pronounced as in case of s and p – block elements of the same period.
This is because in the transition elements, the effect of increasing nuclear
charge is almost compensated by the extra screening effect provided by the
increasing number of (n-1) d electrons.
 6. Variable oxidation state- All transition elements, except the first and the
last members of each series exhibit variable oxidation state. The cause of
showing different oxidation states is since there is only a small
difference between the energies of the electrons in the ns orbitals and (n-
1) d –orbitals with the result that both ns as well as (n-1) d –electron may
be used for compound formation. Therefore, the variable oxidation state of
transition elements is related to their electronic configuration.

7. Complex Formation-

The cations of transition metals have a great tendency to form complexes with
several molecules or ions called ligands. The bond involved in the formation of
complexes are coordinate hence the complexes are termed as coordinate
complexes. The tendency of formation of complexes is due to the following two
factors-

a. The cations of these metals are very small in size and have a high
effective nuclear charge. Thus, they have a very high positive charge
density which facilitates the acceptance of lone pairs of electrons
from other molecules or ions.
b. The transition metal cations have vacant inner d-orbitals which are
of appropriate energy to accept lone pair of electrons from the ligands.
 8. Formation of Colored Compound:

The transition metal ions have unpaired d-electrons, which on absorbing visible
light can excite from one d-orbital to another i.e., intra d-d transition takes place.
Thus, when light falls certain visible wavelength are absorbed. The transmitted
(unabsorbed) or reflected light (or color) appears colored and gives the color of
compounds.

For example- consider complex [Ti (H2O)6] 3+, In this case, Titanium is in +3
oxidation state. The electronic configuration of Ti+3: [Ar]3d1.

During the formation of complex, as the six water molecules approach Ti+3 ion
from different side these develop a negative field around it, as they donate lone
pair present on oxygen to metal ion. There occurs repulsion between electrons of
metal ion and ligand and energy of degenerate orbitals of metal ions increase and
they split into two set of orbitals. The electron in Ti+3, prefers lower set of d
orbitals. The energy gap between two set of d orbitals is very less and the energy
available in the visible light is sufficient to cause excitation of electron from lower
set of d - orbitals to higher set of d –orbitals, called a d-d transitions. Ti+3 absorbs
greenish yellow component of white light during excitation of electron; hence
its aqueous solution appears as purple. This is because purple is the
complimentary color of greenish yellow in white light.
Note- The ions having no d-d transition are colorless.

9. Magnetic Properties:

Mostly the transition elements show Para-magnetism. Para-magnetism arises due

to the presence of unpaired electrons in atoms, ions, or molecules.

The magnetic character is comparable in terms of magnetic moment given by the

expression-

𝜇 = √𝑛 (𝑛 + 2) Bohr Magneton

Where, n= the number of unpaired electrons.

In general, greater the number of unpaired electrons, greater is the magnetic

character. The maximum Para-magnetism is in d5 case which has maximum
number of unpaired electrons.
 10.Formation of alloys: Since, the transition metals have almost equal atomic
sizes, they can mutually substitute one another in the crystal lattice to form
alloys. For example- Brass (copper, zinc, manganese), Nickel hydride
(hydrogen) Stainless steel (chromium, molybdenum, carbon, manganese,
Sulphur, phosphorus, silicon) Coin silver (nickel).

11.Formation of non-stoichiometric compounds and interstitial

compounds-

Transition metal can trap some small size atoms like hydrogen, boron, carbon,
nitrogen etc., in the vacant spaces between the crystal lattice forming inter-orbital
compounds.

For example, FeC, Fe8N, TiH2.

This property of these elements differentiates these metals from non-transition

elements. The products obtained are hard and rigid.

Non – stoichiometric compounds like i.e., Fe0.98O, Fe0.86S, VH0.56, TiH1.7 etc.,

12.Catalytic properties:

Some of the transition metals and their compounds show catalytic properties, the
most common being Fe, Pt, Ni, V2O5 etc. This property may be due to their-
  variable valency (incomplete d- orbitals) which enables them to form
unstable intermediate compounds.
 They can also provide a suitable reaction surface.

13.Reactivity-

The d- block elements are less reactive due to the following factors:

a. Small size of their atoms.

b. High heat of sublimation: Due to presence of covalent bonding, these
have high heat of sublimation.

The tendency to remain less reactive is more pronounced in Platinum and Gold in
the third transition series.

14.Standard Electrode Potential:

The standard reduction potential of all the transition elements (except Cu and Hg in
3d-series etc) is lower (negative) than that of hydrogen (taken as Zero).

Thus, all the transition elements, with negative reduction potential, liberate
hydrogen from dilute acids

𝑀 + 2𝐻 + ⟶ 𝑀2+ + 𝐻2 ↑

However, some, metals evolve hydrogen very slowly because they are protected
from the attack of acids by the formation of an impervious layer of an inert oxide.
For example, Chromium is so unreactive that it can be used as a protective
non-oxidizing metal.

15.Reducing Properties:

Transition metals with sufficiently negative standard reduction potential should be

good reducing agents i.e., they can be oxidized easily to their ions.

M → M2+ + 2e

However, they are not good reducing agents as compared to elements of Groups 1,
2, and 13. this is because transition metals have less tendency to form ions due to
their low reactivity.
 Complexes- K2Cr2O7 and KMnO4

PREPARATION, PROPERTIES, AND USES

1. Potassium dichromate, K2Cr2O7:

Preparation:

It is prepared from chromite ore or Ferro chromes (FeCr2O4 or FeOCr2O3) by

following steps-

a. Fusion of the ore with molten alkali in presence of air-

4FeCr2O4 + 16 NaOH + 7O2→ 8Na2CrO4 + 2Fe2O3 + 8H2O

The fused mass is extracted with water and filtered.

b. Conversion of sodium chromate into sodium dichromate by treating the

filtrate with dilute H2SO4 –

2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O

Na2SO4 being less soluble is separated as Na2SO4.10H2O by fractional

crystallization.
c. Conversion of sodium dichromate into potassium dichromate by heating
with KCl.

Na2Cr2O7 + 2KCl →K2Cr2O7 + 2NaCl

Potassium dichromate being less soluble is obtained by fractional crystallization.

a. Properties:
i. Physical state: Potassium dichromate forms orange-red crystals
which melt at 669 K. It is moderately soluble in cold water but freely
soluble in hot water.
ii. Action of heat: When heated strongly, it decomposes with the
evolution of oxygen.

4K2Cr2O7 + heat → 4K2CrO4 + 2Cr2O3+ 3O2

Pot. Dichromate Pot. Chromate chromic oxide

iii. Action of alkalis: When an alkali is added to an orange red solution

containing dichromate ions, a yellow solution is obtained due to the
formation of chromate ions.

K2Cr2O7+ 2KOH → 2K2CrO4 + H2O

Pot. Dichromate Pot. Chromate (Yellow solution)

On acidifying the above yellow solution containing chromate ions, it again

changes to orange red due to the formation of dichromate ions.

2K2CrO4 + H2SO4 →K2Cr2O7+ K2SO4 + H2O

Pot. Chromate Pot. Dichromate

In fact, in any given solution, dichromate ions and chromate ions exist in
equilibrium and are interconvertible by altering the pH of the solution.

2CrO4 2- + 2H+⇌ 2HCrO4 -⇌ Cr2O7 2- + H2O

iv. Action of concentrated H2SO4:

red crystals of chromic anhydride (CrO3) are formed

K2Cr2O7 + 2H2SO4(conc) → 2CrO3 + 2KHSO4 + H2O

v. Oxidizing properties: Potassium dichromate is a powerful oxidizing

agent.

In acidic solution, its oxidizing action can be represented as follows-

Ionic equation: CrO7 2- + 14H+ + 6e-→ 2Cr3+ +7 H2O [ E0 = +1.31V]

 It oxidizes iodides to iodine-

Cr2O7 2- + 14H+ + 6I-→ 2Cr3+ + 7H2O + 3I2 (Ionic Equation)
 This reaction is used in the estimation of iodide ions in the volumetric
analysis.
 It oxidizes ferrous salts of ferric salts:

Cr2O7 2- + 14H+ + 6Fe2+→ 2Cr3+ + 7H2O + 6Fe3+

This reaction is used in the estimation of ferrous ions in the volumetric

analysis.

 In oxidizes H2S to S:

Cr2O7 2- + 8H+ + 3H2S → 2Cr3+ + 7H2O + 3S

 It oxidizes sulfur dioxide to sulfuric acid:

Cr2O7 2- + 2H+ + 3SO2→ 2Cr3+ + H2O + 3SO42-

vi. With hydrogen peroxide:

Acidified potassium dichromate forms a deep blue color with hydrogen

peroxide due to the formation of CrO5.

K2Cr2O7 + H2SO4 + 4H2O2→ 2CrO5 + K2SO4 + 5H2O

The blue color fades away gradually due to decomposition of CrO5 into Cr3+
ions and oxygen.

vii. Uses-
 In volumetric estimation of reducing agents e.g., ferrous salts, iodides,
and sulphites. This is since K2Cr2O7 is obtained in a much higher
degree of purity than Na2Cr2O7.
 In the preparation of chromium compounds e.g., chrome alum.
 In photography for hardening of gelatin.
 Chromic acid mixture (K2Cr2O7 + conc. H2SO4) is used for cleaning
glassware in the laboratory.
 As an oxidizing agent.
 2. Potassium permanganate, KMnO4:
1. Preparation:

It is prepared by fusing pyrolusite ore (MnO2) with KOH in the presence of

atmospheric oxygen or an oxidizing agent like KNO3 or KClO3 to get potassium
manganate, K2MnO4 (green).

This is then extracted with water and is oxidized to potassium permanganate, either
electrolytically or by-passing chlorine or ozone into the solution.

The purple solution so obtained is concentrated by evaporation which on cooling

deposits crystals of KMnO4.

2MnO2 + 4KOH + O2 + 𝑒𝑎𝑡 → 2K2MnO4 + 2H2O

K2MnO4 ⇌ 2K+ + MnO4 2-

MnO4 2- 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠 → MnO4- (purple)

2. Properties:
i. Potassium permanganate exists as dark purple black prismatic crystals
having a greenish metallic luster.
ii. It melts at 523 K.
iii. It is moderately soluble in water at room temperature giving a purple
solution. However, its solubility in water increases with temperature.

iv. Effect of heat-

Liberates oxygen on heating

2KMnO4 →K2MnO4 + MnO2 + O2

v. Oxidizing properties-
a. In acidic medium: it dissociates as follows-
2KMnO4 + 3H2SO4 →K2SO4 + 2MnSO4 + 3H2O + 5[O]
[Equivalent weight of KMnO4 in acidic medium =𝑀𝑜𝑙.𝑀𝑎𝑠𝑠 5 =
158 5 = 31.6].
b. In neutral medium:
 2KMnO4 + H2O→2KOH + 2MnO2 + 3[O] [Equivalent weight of
KMnO4 in neutral medium =𝑀𝑜𝑙. 𝑀𝑎𝑠𝑠 3 = 158 3 = 52.6].

c. In basic medium:
2KMnO4 + 2KOH→2K2MnO4 + H2O + [O] [Equivalent weight of
KMnO4 in basic medium =𝑀𝑜𝑙. 𝑀𝑎𝑠𝑠 1 = 158 1 = 158]
In basic medium, MnO4 - (manganate ions) is further reduced to
MnO2 in the presence of reducing agent.

In acidic medium Potassium Permanganate (KMnO4) oxidizes as -

i. Ferrous to ferric salt-

MnO4 - + 5Fe2+ + 8H+→ Mn2+ + 5Fe3+ + 4H2O

ii. Oxalates to carbon dioxide

2MnO4 - + 5C2O4 2- + 16H+→ 2Mn2+ + 10CO2 + 8H2O

iii. Iodides to iodine-

10I - + 2MnO4 - + 16H+→ 2Mn2+ + 5I2 + 8H2O

iv. Sulphites to sulphates

5SO3 2- + 2MnO4 - + 6H+→2Mn2+ + 5SO42- +3H2O

In alkaline solution-

i. Iodides to iodates-

I - + 2MnO4 - + H2O→ IO3 - + 2MnO2 + 2OH -

Uses-

a. As oxidizing agent in laboratory and industry. Potassium permanganate is a

powerful and versatile oxidizing agent and is widely used for titration against
reducing agents like oxalic acid and Mohr’s salt. During the titration, the
reduction of potassium permanganate by a reducing agent e.g., oxalic acid or
Mohr’s salt, produces manganous ions which are colorless. As the titration
proceeds and when the whole of the reducing agent is consumed up, then the
addition of an excess drop of potassium permanganate solution gives its own
color (pink) to the solution. Therefore, at the end point the color changes from
colorless to pink. Thus, potassium permanganate acts as a self-indicator.

MnO4 - + 8H+ + 5e-→ Mn2+ + 4H2O

b. In volumetric estimation of ferrous salts, oxalates, and other reducing agents in

redox titration.
c. As disinfectant in water.
d. For qualitative detection of halides, oxalates, tartrates.
 Chemistry of elements of Second and Third Transition Series-

 General Group trends with Electronic Configuration

 Oxidation states
 Color
 Spectral and Magnetic Properties
 Lanthanide Contraction
 Separation of Lanthanides (Ion exchange method only)

1. In second transition (4d series) series there are 10 elements from

Yttrium (39) to Cadmium (48).
2. General electronic configuration- 4d1-10, 5s0-2.
3. In third transition series there are 10 elements from Lanthanum (57) to
Mercury (80) except Lanthanides. It is also called 5d series and have the
electronic configuration- 4f0-14, 5d1-10, 6s1-2.
 Chemistry of Lanthanides and Actinides-

1. Lanthanides-
1. Initially lanthanides were called rare earths because they were extracted
from oxide which were rare.
2. It is a group of 14 elements from atomic number 58-71.
3. On increasing the atomic number electron enters f subshell this f sub shell
is (n-2) shell also termed as anti-penultimate shell. Hence these elements
are called f- block elements or inner transition elements.
4. Lanthanides are also termed as Lanthanon’s/ 4f block elements or first inner
transition series.
1. Electronic configuration-
 2. Oxidation states-
 All Lanthanides exhibit +3 oxidation state.
 Some elements show +2 and +4 oxidation states also.

3. Ionic radii
 The atomic radii of lanthanides decrease with increase in atomic
number.
 Decrease in atomic radii or ionic radii of lanthanides with increasing
atomic number is called Lanthanide contraction.
Lanthanide contraction-
 Chemistry of ACTINIDE Elements

1. Elements after actinium from atomic number 89 to 103 are called

Actinides or Actinons.
2. The last electron enters anti-penultimate 5f shell.
3. Actinides form second inner transition series while lanthanides form
first inner transition series.
4. All actinides are assumed to be the elements of third group in the
periodic table and are placed below lanthanides.

General Electronic configuration-

The general electronic configuration of valance shell of actinides is written as-

5f 0-14 6d 0-2 7s2.

Oxidation states-

1. Except Nobelium (No i.e., No+2), from Americium (Am) to Lawrencium

(Lr) all elements in solution exhibit maximum stability in +3 oxidation
state.
2. Thorium (Th) and Plutonium (Pu) are stable in +4 oxidation states.