CLASS - XII

SUBJECT - CHEMISTRY
GIST OF THE LESSON TAUGHT BETWEEN JULY 1 AND
AUGUST 18, 2023

Alcohols and phenols are classified

CHAPTER –ALCOHOL
PHENOL ETHER (i) On the basis of the number of hydroxyl
groups and

(ii) According to the hybridisation of the carbon atom, sp3 or sp2 to which the –OH
group is attached.
Compounds containing Csp3 − OH bond:

Allylic alcohols:

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Benzylic alcohols:

(ii) Compounds containing C sp2− OH

Vinylic alcohol: CH2 = CH – OH
Phenols:

Ethers are classified on the basis of groups attached to the oxygen atom.
Ethers are classified as simple or symmetrical, and mixed or unsymmetrical.
Diethyl ether, C2H5OC2H5, is a symmetrical ether whereas C2H5OCH3 and C2H5OC6H5
are unsymmetrical ethers.
Structures of functional groups in alcohol, phenol and ether:

Alcohols may be prepared

(1) By hydration of alkenes
(i) In presence of an acid: Alkenes react with water in the presence of acid as catalyst
to form alcohols.

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(ii) By hydroboration-oxidation reaction: Diborane (BH3)2 reacts with alkenes to give
trialkyl boranes as addition product. This is oxidised to alcohol by hydrogen peroxide
in the presence of aqueous sodium hydroxide. The alcohol so formed looks as if it has
been formed by the addition of water to the alkene in a way opposite to the
Markovnikov’s rule.

(2) From carbonyl compounds by

(i) catalytic reduction: Aldehydes and ketones are reduced to the corresponding
alcohols by addition of a) hydrogen in the presence of catalysts
b) By using reducing agents: sodium borohydride (NaBH4) or lithium aluminium
hydride (LiAlH4).
(ii) the action of Grignard reagents:
Alcohols are produced by the reaction of Grignard reagents with aldehydes and
ketones.

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Phenols may be prepared by
(1) Substitution of
(i) halogen atom in haloarenes: Chlorobenzene is fused with NaOH at 623K and 320
atmospheric
pressure. Phenol is obtained by acidification of sodium phenoxide so produced.

(ii) Sulphonic acid group in aryl sulphonic acids, by –OH group

(2) By hydrolysis of diazonium salts:

(3) Industrially from cumene: Phenol is manufactured from the hydrocarbon, cumene.
Cumene (isopropylbenzene) is oxidised in the presence of air to cumene hydroperoxide. It is
converted to phenol and acetone by treating it with dilute acid.

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Alcohols are higher boiling than other classes of compounds, namely hydrocarbons, ethers
and haloalkanes of comparable molecular masses. The ability of alcohols, phenols and ethers
to form intermolecular hydrogen bonding with water makes them soluble in it.
Alcohols and phenols are acidic in nature. Electron withdrawing groups in phenol increase its
acidic strength and electron releasing groups decrease it.
Alcohols undergo nucleophilic substitution with hydrogen halides to yield alkyl halides.
Dehydration of alcohols gives alkenes: Ethanol undergoes dehydration by heating it with
concentrated H2SO4 at 443 K.
Secondary and tertiary alcohols are dehydrated under milder conditions.

On oxidation, primary alcohols yield aldehydes with mild oxidising agents and carboxylic acids
with strong oxidising agents while secondary alcohols yield ketones. Tertiary alcohols are
resistant to oxidation.

The presence of –OH group in phenols activates the aromatic ring towards electrophilic
substitution and directs the incoming group to ortho and para positions due to resonance
effect.
Reimer-Tiemann reaction of phenol yields salicylaldehyde.

In presence of sodium hydroxide, phenol generates phenoxide ion which is even more
reactive than phenol. Thus, in alkaline medium, phenol undergoes Kolbe’s reaction.

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Ethers may be prepared by
(i) Dehydration of alcohols: Ethanol is dehydrated to ethene in the presence of sulphuric acid
at 443 K. At 413 K, ethoxyethane is the main product.

(ii) Williamson synthesis: In this method, an alkyl halide is allowed to react with sodium
alkoxide.

The boiling points of ethers resemble those of alkanes while their solubility is comparable to
those of alcohols having same molecular mass.
The C–O bond in ethers can be cleaved by hydrogen halides: The cleavage of C-O bond in
ethers takes place under drastic conditions with excess of hydrogen halides. The reaction of
dialkyl ether gives two alkylhalide molecules.

In electrophilic substitution, the alkoxy group activates the aromatic ring and directs the
incoming group to ortho and para positions.

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 Aldehydes, ketones and carboxylic acids are
CHAPTER –ALDEHYDES some of the important classes of organic
AND KETONES compounds containing carbonyl group which
contains a carbon atom connected to an
oxygen atom by a double bond. The trigonal
2
planar carbon (sp hybridised) in the carbonyl group can attach to two other substituents leading
to several subfamilies (aldehydes, ketones, carboxylic acids and esters).
These are highly polar molecules. Therefore, they boil at higher temperatures than the
hydrocarbons and weakly polar compounds such as ethers of comparable molecular masses. The
lower members are more soluble in water because they form hydrogen bonds with water. The
higher members, because of large size of hydrophobic chain of carbon atoms, are insoluble in
water but soluble in common organic solvents.

Hydrogen bonds
with water

Aldehydes are prepared by dehydrogenation or controlled oxidation of primary alcohols and

controlled or selective reduction of acyl halides.
Aromatic aldehydes may also be prepared by oxidation of (i) methylbenzene with chromyl
chloride or CrO3 in the presence of acetic anhydride, (ii) formylation of arenes with carbon
monoxide and hydrochloric acid in the presence of anhydrous aluminium chloride, and (iii)
cuprous chloride or by hydrolysis of benzal chloride.
Ketones are prepared by oxidation of secondary alcohols and hydration of alkynes. Ketones
are also prepared by reaction of acyl chloride with dialkylcadmium. A good method for the
preparation of aromatic ketones is the Friedel-Crafts acylation of aromatic hydrocarbons with
acyl chlorides or anhydrides.
Both aldehydes and ketones can be prepared by ozonolysis of alkenes.

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 Aldehydes and ketones undergo
nucleophilic addition reactions onto
the carbonyl group with a number of
nucleophiles such as, HCN, NaHSO3,
alcohols (or diols), ammonia derivatives,
and Grignard reagents. Aldehydes are
generally more reactive than ketones in
nucleophilic addition reactions due to
steric and electronic reasons.

The α-hydrogens in
aldehydes and ketones
are acidic. Therefore,
aldehydes and ketones
having at least one α-
hydrogen, undergo Aldol
condensation in the
presence of a base to give
α-hydroxyaldehydes
(aldol) and α-
hydroxyketones(ketol)
respectively.

Aldehydes having no α-hydrogen undergo Cannizzaro reaction in the presence of

concentrated alkali.
Aldehydes and ketones are reduced to alcohols with NaBH4, LiAlH4, or by catalytic
hydrogenation.

The carbonyl
group of
aldehydes and
ketones can be
reduced to a
methylene
group.

Aldehydes are easily oxidised to carboxylic acids by mild oxidising reagents such as Tollens’
reagent and Fehling’s reagent. These oxidation reactions are used to distinguish aldehydes
from ketones.

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CHAPTER –THE d AND f BLOCK ELEMENTS

(v) Trends in the M2+/ M standard electrode potentials: EoM2+/M is governed by three
factors. Enthalpy of sublimation, enthalpy of ionisation and enthalpy of hydration. The
irregular trend in 3d series is due to irregular variation in ionisation enthalpy and heat of
sublimation.

(vi) Density d-block elements have high density because of their small atomic size and strong
metallic bonding. Osmium has slightly lower density (22.52 g cm-3) as compared to iridium
(22.61 g cm-3). Thus, iridium has the highest density among transition metals.

(vii) Reactivity d-block elements are less reactive due to high ionisation energies.

(viii) Complex formation: They are well known to form a large number of complex compounds
mainly due to (a) small atomic size and high nuclear charge (b) presence of partly filled or
vacant d-orbitals, e.g., K4[Fe (CN)6]

(ix) Coloured ions Colour exhibited by transition metal ions is due to the presence of unpaired
electrons in d-orbitals and is due to the d-d transitions of electrons, when invisible light is
incident on the ion. Colour of a complex depends on the metal, its oxidation state and its
ligands, e.g., [Cu(H2O)4]2+ is pale blue while [Cu(NH3)4]2+ is dark blue.

(x) Magnetic properties Paramagnetic nature is due to the presence of unpaired electrons in
d-orbitals. Magnetic moment is given by μ = √n (n + 2) BM, Where, n = number of unpaired
electrons and BM = Bohr magneton (unit of magnetic moment).

(xi) Catalytic properties the transition metals and their compounds behave like catalyst due
to

➢ the presence of partly filled d-orbitals resulting in variable oxidation states.

➢ formation of intermediate complex with reactants by lowering the energy of
activation.
➢ their rough surface area which provides active sites for adsorption of reactant
molecules.
Iron in the preparation of NH3 (Haber‘s process).

(xii) Formation of alloys d-block elements have a strong tendency to form alloys.

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(xiii) Interstitial compounds: The vacant space present in a crystal lattice is known as
interstitial site or void. The non-metal atoms (e.g., H, N, C, etc.) due to their small size when
occupy such place, the resulting compound is known as interstitial compound.

(xiv) Non-stoichiometric compounds can be formed due to the variability of Oxidation state
in the transition metal. These elements form such compound by trapping H, B, C and N etc.

(xv) Oxides and Oxoanions of Metals: The transition metals react with a number of non-
metals like oxygen, nitrogen, sulphur and halogens to form binary compounds. The first series
transition metal oxides are generally formed from the reaction of metals with oxygen at high
temperatures. These oxides dissolve in acids and bases to form oxometallic salts. Potassium
dichromate and potassium permanganate are common examples. Potassium dichromate is
prepared from the chromite ore by fusion with alkali in presence of air and acidifying the
extract. Pyrolusite ore(MnO2) is used for the preparation of potassium permanganate. Both
the dichromate and the permanganate ions are strong oxidising agents.

Preparation of potassium dichromate:

Structure of Chromate and Dichromate ion:

Chromates and dichromates are interconvertible depending upon the pH of the solution:

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Potassium dichromate is used as a primary standard in volumetric analysis. In acidic solution,
its oxidising action can be represented as follows:

Preparation of potassium dichromate:

A few important oxidising reactions of KMnO4 are given below:

1. In acid solutions:

Fe2+ ion (green) is converted to Fe3+ (yellow):

2. In neutral or faintly alkaline solutions: A notable reaction is the oxidation of iodide to

iodate:

Inner-Transition ElementsThe elements in which the filling of atomic orbitals by electrons

take place in antepenultimate shell, two levels inside the outer subshell, are known as inner-
transition elements. They are also known as f-block elements.

They have been classified into two series.

(a) 4f-series (first inner-transition series) The last electron enters in 4f-orbital. The elements
belonging to this series are also known as lanthanoids.
(b) 5f-series (second inner-transition series) The last electron enters in 5f-orbital. The
elements belonging to this series are also known as actinoids.
Lanthanides The fifteen elements from lanthanum (at. no. 57) to lutetium (at. no. 71) are
known as lanthanides or rare earths. Their properties are as follows:
1. Electronic configuration: The general electronic configuration of these elements is
[Xe]4f0–14 5d0-1 6s2.

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2. Oxidation state: The most common and most stable oxidation state of lanthanides is +3
but some elements also exhibit +2 and +4 oxidation states.
3. Chemical reactions of the lanthanoids

Lanthanoid contraction
Steady decrease in the atomic and ionic (Ln3+) radii as the atomic number of the lanthanide
elements increases is called lanthanide contraction. This is because the additional electron
goes to 4f-subshell and 4f-orbitals being large and diffuse, have poor shielding effect. The
effective nuclear charge increases whichcauses the contraction in the size of electron charge
cloud. This contraction in size is quite regular and is known as lanthanoid contraction.
Consequences of lanthanoid contraction

(i) Covalent character of cations increases.

(ii) The electronegativity of trivalent ions increases slightly.

(iii) There is decrease in basic strength of oxides and hydroxides from La to Lu.

(iv) There is small increase in standard electrode potential values.

(v) Sizes of Zr and Hf; Nb and Ta are similar, so they are called chemical twins.

Actinoids: The actinoids include the fourteen elements from Th to Lr. The chemistry of the
actinoids is more complex in view of their ability to exist in different oxidation states.
Furthermore, many of the actinoid elements are radioactive which make the study of these
elements rather difficult.
Their properties are as follows:
1. Electronic configuration: The general electronic configuration of these elements is
[Rn]865f1-146d0-17s2.

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2. Oxidation state: Actinoids exhibit a greater range of oxidation states. This is because the
5f, 6d, and 7s levels are of comparable energies. Again, (+3) is the principal oxidation state for
actinoids.
3. Atomic and ionic sizes: Both lanthanoids and actinoids show decrease in size of their atoms
or ions in +3 oxidation state. In lanthanoids, the decrease is called lanthanoid contraction
whereas in actinoids, it is called actinoid contraction.
4. Chemical reactivity: Actinoids are highly reactive metals, especially when they are finely
divided. When they are added to boiling water, they give a mixture of oxide and hydride.
Actinoids combine with most of the non-metals at moderate temperatures. Alkalies have no
action on these actinoids. In case of acids, they are slightly affected by nitric acid (because of
the formation of a protective oxide layer).
There are many useful applications of the d- and f-block elements and their compounds,
notable among them being in varieties of steels, catalysts, complexes, organic syntheses, etc.
highly useful compounds in industry.

CHAPTER – COORDINATION
COMPOUNDS

❖ A coordination compound contains a central metal atom or ion surrounded by

number of oppositely charged ions or neutral molecules. These ions or molecules re
bonded to the metal atom or ion by a coordinate bond. Example: [Cr (NH3)6] Cl3
❖ They do not dissociate into simple ions when dissolved in water.
❖ Double salt When two salts in stoichiometric ratio are crystallized together from their
saturated solution, they are called double salts. Example: FeSO4.(NH4)2SO4.6H2O
(Mohr‘s salt). They dissociate into simple ions when dissolved in water.
❖ Coordination entity: A coordination entity constitutes a central metal atom or ion
bonded to a fixed number of ions or molecules.
In [Cr (NH3)6]Cl3, [Cr(NH3)6]3+ – represents coordination entity.
❖ Ligands: A molecule, ion or group that is bonded to the metal atom or ion in a complex
or coordination compound by a coordinate bond is called ligand. It may be neutral,
positively or negatively charged. Examples: NH3, H2O, NO+, CN-etc.
❖ Coordination number: The coordination number of a metal ion in a complex can be
defined as the number of ligand donor atoms to which the metal is directly bonded.
Example: In the complex [Cr(NH3)6]Cl3, the coordination number of Cr is 6.

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 ❖ Coordination polyhedron: The spatial arrangement of the ligand atoms which are
directly attached to the central atom/ ion defines a coordination polyhedron about
the central atom. The most common coordination polyhedra are octahedral, square
planar and tetrahedral. Examples: [Cu(CN)4]2- is square planar, [Ni(CO)4 ]is tetrahedral
while [Co(NH3)6]3+ is octahedral.
❖ Denticity: The number of ligating (linking) atoms present in ligand is called denticity.
Unidentate ligands: The ligands whose only one donor atom is bonded to metal atom
are called unidentate ligands. Examples: NH3, H2O etc.
❖ Bidentate ligands: The ligands which contain two donor atoms or ions through which
they are bonded to the metal ion. Examples: Ethylene diamine (H2NCH2CH2NH2) i.e
(en) has two nitrogen atoms, which can bind with the metal atom.
❖ Polydentate ligand: When several donor atoms are present in a single ligand, the
ligand is called polydentate ligand. Examples: (EDTA)4- Ethylenediaminetetraacetate
ion is an important hexadentate ligand. It can bind through two nitrogen and four
oxygen atoms to a central metal ion.
❖ Chelate: An inorganic metal complex in which there is a close ring of atoms caused by
attachment of a ligand to a metal atom at two points. An example is the complex ion
formed between ethylene diamine and cupric ion, [Cu(en)2]2+.
❖ Ambidentate ligand: Ligands which can ligate (link) through two different atoms
present in it are called ambidentate ligand. In CN-, Here CN-, can link through N as well
as C.
❖ Werner’s Theory: The first systematic attempt at explaining the formation, reactions,
structure and bonding of a coordination compound was made by A. Werner. His
theory postulated the use of two types of linkages (primary and secondary) by a metal
atom/ion in a coordination compound. In the modern language of chemistry these
linkages are recognised as the ionisable (ionic) and non-ionisable (covalent) bonds,
respectively. Using the property of isomerism, Werner predicted the geometrical
shapes of a large number of coordination entities.

Types of isomerism:

a. Structural isomerism

i. Linkage isomerism ii. Solvate isomerism or hydrate isomerism

iii. lonisation isomerism iv. Coordination isomerism

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b. Stereoisomerism

I. Geometrical isomerism II. Optical isomerism

Structural isomerism: This type of isomerism arises due to the difference in structures of
coordination compounds. Structural isomerism, or constitutional isomerism, is a form of
isomerism in which molecules with the same molecular formula have atoms bonded together
in different orders.

a. Ionisation isomerism: This form of isomerism arises when the counter ion in a complex salt
is itself a potential ligand and can displace a ligand which can then become the counter ion.

Example: [Co(NH3)5Br]SO4 and [Co(NH3)5 SO4] Br

b. Solvate isomerism: It is isomerism in which solvent is involved as ligand. If solvent is water

it is called hydrate isomerism.

e.g. [Cr(H2O)3Cl3] and [CrCl2(H2O)4Cl2.2H2O

c. Linkage isomerism: Linkage isomerism arises in a coordination compound containing

ambidentate ligand. In this isomerism, a ligand can form linkage with metal through different
atoms.

Example: [Co(NH3)5ONO]Cl2 and [Co(NH3)5NO2]Cl2

d. Coordination isomerism: This type of isomerism arises from the interchange of ligands
between cationic and anionic entities of different metal ions present in a complex.

Example: [Co(NH3)6][Cr(C2O4)3] and [Cr(NH3)6][Co(C2O4)3]

Stereoisomerism: This type of isomerism arises because of different spatial arrangement.

a. Geometrical isomerism: It arises in heteroleptic complexes due to different possible

geometrical arrangements of ligands.

b. Optical isomerism: Optical isomers are non-superimposable mirror images of each other.
Optical isomerism is common in octahedral complexes involving didentate ligands.

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