Maps Chemistry Ncert

Some Basic Concepts of Chemistry
1
Chapter
1 CLASSIFICATION OF MATTER 3 UNCERTAINTY IN MEASUREMENT
m Matter can exist in three physical states viz solid, liquid and gas m Scientific notation is exponential notation in which any number
m MATTER
represented in N × 10n, where n is exponent having positive or
MIXTURES PURE
SUBSTANCES
negative values and N is number between 1.000 … and 9.999
HETEROGENOUS HOMOGENOUS
.....
MIXTURES MIXTURES
m Significant figures are meaningful digits which are known
ELEMENTS COMPOUNDS with certainity plus one which is estimated or uncertain.
m A mixture contains particles of two or more pure substances in any ratio.
m Rules for determining the number of significant figures.
m Movement of air follow pressure gradient.
m In Homogeneous mixture, components completely mix with each other. m All non zero digits are significant.
m In Heterogeneous mixture, composition is not uniform.
m Zeros preceding to first non-zero digit are non significant.
m Constituent particles of pure substance have fixed composition.
m Compound is formed when two ore more atoms of different elements combine together in definite ratio. m Zeroes between two non-zero digits are significant.
m Zeroes at the end or right of a number are significant

2 PROPERTIES OF MATTER AND THEIR MEASUREMENT
provided they are on the right side of decimal point.
m Properties are of two types viz. physical and chemical properties.
m Physical properties can be measured or observed without changing the identity or the composition of the substance. m Counting numbers have infinite significant figures.
m Chemical properties requires a chemical change to occur. m In a number written in scientific notation, all digits are
m Colour, odour, melting point, density etc are some physical properties.
significant.
m Composition, combustibility, reactivity with acids and bases are examples of chemical properties.
m Quantitative measurement of physical properties represented by a number followed by units. m Precision refers to the closeness of various measurements for
m SI system has seven base units. the same quantity.
m Base physical quantities and their units.
Length (m) Mass (kg) m Accuracy is the agreement of a particular value to the true
Time (s) Electric current (A) value of the result.
Thermodynamic Amount of substance (mol)
m In addition and subtraction of significant figures the result
Temperature (K) Luminous intensity (cd)
cannot have more digits to the right of the decimal point than
SOME PREFIX USED IN SI SYSTEMS ARE
either of the original numbers.
10–12 (pico), 10–9 (nano), 10–6(micro) –3 –2
10 (milli), 10 (centi),
3 6
10 (kilo), 10 (mega) 109(giga) m In multiplication and division of significant figures the result
SOME COMMON UNITS must be reported with no more significant figures as are there
m 1 L = 1000 mL = 1000 cm3 = 1 dm3, °F = 9/5 (°C) + 32, K = °C + 273.15 in the measurement with the fewer significant figures.
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2 Some Basic Concepts of Chemistry NCERT Maps
m Important points for rounding off the numbers.

l If the rightmost digit to be removed is more than 5, the preceding number is increased by one.
l If the rightmost digit is less than 5, the preceding number is not changed.
l If the rightmost digit is 5 then preceding number increased by 1 only if it is an odd number.
m Method used to interconversion of unit is known as dimensional analysis, unit factor method.
4 LAWS OF CHEMICAL COMBINATION

m Law of conservation of mass conclude that in all physical and chemical changes, there is no net change in mass during the change.
m Law of definite proportions/composition stated that a given compound always contains exactly the same proportion of elements by weight.
m Law of multiple proportions stated that, if two elements can combine to form more than one compound, the masses of one element that combine with a fixed mass of other element are in the
ratio of small whole number.
m Gay Lussac's law of gaseous volume : When gases combine or are produced in a chemical reaction they do so in a simple ratio by volume, provided all gases are at same temperature and
pressure.
m Avogadro's law proposed that equal volumes of all gases at same temperature and pressure should contain equal number of molecules.
m Dalton's Atomic Theory proposed to following points
l Matter consists of indivisible atoms.
l All atoms of a given element have indentical properties, including identical mass, atoms of different elements differ in mass
l Compounds are formed when atoms of different elements combine in a fixed ratio
l Chemical reactions involve reorganisation of atoms. These are neither created nor destroyed in a chemical reaction.
5 ATOMIC AND MOLECULAR MASS m Empirical formula represents the simplest whole number ratio of various atoms
m One atomic mass unit (amu) is defined as a mass exactly equal to one-twelfth of the mass of one present in a compound, whereas, the molecular formula shows exact number of
C-12 atom, 1 amu = 1.66056 × 10–24 g. different types of atoms present in a molecule of a compound.
m At present amu has been replaced by unified mass (u)
m Average atomic mass can be computed when we take into account the existence of isotopes 7 STOICHIOMETRY AND STOICHIOMETRIC CALCULATIONS
and their relative abundance. m Stoichiometry deals with calculation of masses (sometime volume) of the
m Molecular mass is the sum of atomic masses of the elements present in a molecule. reactants and products involved in a chemical reaction.
m Formula mass is used instead of molecular mass for ionic solids as in solid state they do not m Reactant, which gets consumed first, limits the amount of product formed is
exist as a single entity. called limiting reagent.
m A majority of reactions are carried out in solutions. The concentration of a solution can
6 MOLE CONCEPT AND MOLAR MASSES be expressed in following ways.
m Mole (Symbol, mol) is seventh base quantity for amount of a substance. m Mass percent = Mass of solute × 100 / (Mass of solution)
m One mole contains exactly 6.02214076 × 1023 elementary entities. This number is the fixed m Mole fraction of solute = No. of moles of solute/No. of moles of solution
numerical value of the Avogadro's constant (NA). m Molarity (M) = No. of moles of solute / Volume of solution in litres
m The mass of one mole of a substance in grams is called its molar mass.
l For dilution of solutions, M1V1 = M2V2
m Mass% of an element = Mass of that element in the compound × 100 / Molar mass of the
m Molality (m) = No. of moles of solute/Mass of solvent in kg.
compound.
2
Structure of Atom Chapter
1 SUBATOMIC PARTICLES Atomic no. (Z) = Number of protons m Photoelectric effect: Ejection of electrons when certain
Name Discovery Charge Mass/kg Mass no. (A) = Number of protons and neutrons metals were exposed to beam of light.
–19 –31
Electron (e) Cathode rays –1.6 × 10 C 9.1 × 10 Isotopes = Same atomic number but different mass Observation of photoelectric effect
–19 –27 12 14
Proton (p) Anode rays +1.6 × 10 C 1.67 × 10 number e.g. 6C, 6C m No time lag between ejection of electrons from metal
–27
Neutron (n) a particles 0 1.67 × 10 Isobars = Atoms with same mass number but different surface and striking of light beam.
bombarded on
14 14
Be thin sheet atomic number e.g. C, N m Number of ejected electrons proportional to the intensity
6 7
or brightness of light.
2 ATOMIC MODELS
3 ELECTROMAGNETIC WAVES m Minimum frequency required to eject electron is known as
m Thomson model (Plum pudding model)
The atom is of spherical shape in which positive charge is m Unlike sound wave, electromagnetic waves do not require threshold frequency (n0).
uniformly distributed and electrons are embedded in it.
medium and can move in vacuum. m Einstein photoelectric equation
m Rutherford's Nuclear Model
Electromagnetic waves are characterised by the properties, 1 m v2
a particle scattering experiment m hn = hn0 +
Gold foil
2 e
frequency (n) and wave length (l) and travel with speed of
8
4 ATOMIC SPECTRA
light i.e., c = 3 × 10 m/s
a m The spectrum of radiation emitted by a substance that has
rays c = nl
absorbed energy is called an emission spectrum.
1 m An absorption spectrum is like photographic negative of

Source of Lead plate Photographic plate
m Wave number (n) = l
alpha particles an emission spectrum.
Observation of experiment dec , inc. Line Spectrum of Hydrogen
n l
(i) Most of a ray passed through gold foil undeflected g X Micro Radio
UV Visible IR n = 109,677 12 12 cm
–1
(ii) A small fraction of the a-particles was deflected by small rays rays wave wave m
angles n1 n1
(iii) A very few a-particles bounced back m Experiment supporting wave nature of electromagnetic where n is the wave number of spectral line in hydrogen spectrum.
m On the basis of Rutherford experiment most of the space in an radiation are interference & diffraction
Series n1 n2 Spectral Region
atom is empty, a centre of atom is occupied by the nucleus in m Experiment supporting particle nature of electromagnetic
which positive charge is concentrated in a very small volume. radiations are photoelectric effect and black body radiations. Lyman 1 2, 3... Ultraviolet
The nucleus is surrounded by electrons that move around the Planck's Quantum Law: Atoms and molecules could emit or Balmer 2 3, 4... Visible
nucleus with a very high speed in circular path called orbits absorb energy only in discrete quantities and not in continous
while electrostatic forces of attraction held nucleus and Paschen 3 4, 5... Infrared
manner known as quantum
electrons together. Brackett 4 5, 6... Infrared
m Draw back of Rutherford model E = hn
It cannot explain the stability of atom. E = energy of quantum Pfund 5 6, 7... Infrared
6 Structure of Atom NCERT Maps
5 BOHR'S MODEL FOR HYDROGEN ATOM 7 QUANTUM MECHANICAL MODEL OF ATOM 9 SHAPES OF ATOMIC ORBITALS
Key points of Bohr's theory m Orbitals and quantum number m Shapes of p-orbital
2px 2py 2pz
m Electron in the hydrogen atom can move in circular path of (1) Principal quantum number 'n' determines the size and z z z
fixed radius and energy known as orbits. energy of orbital.
m The energy of orbit does not change with time. l Number of allowed orbital in a shell = n2
(2) Azimuthal quantum number 'l' defines the three- x x x
m Electron moves from a lower stationary state to higher state
when required amount of energy is absorbed by the electron. dimeinsional shape of orbital y y y
m Electron move from higher energy state to lower energy state l For a given n, possible value of l = 0, 1, 2 ... (n – 1)
leaving the extra energy in the form of electromagnetic l Value of l 0 1 2 3 4 5 m Shapes of d-orbitals
waves.
Notation of s p d f g h dxy dxz dyz
m Angular momentum of electron is quantized. subshell z z z
nh
mvr = (3) Magnetic orbital quantum number 'm l ' gives
2p
information about the spatial orientation of the orbital with
m Frequency of radiation absorbed or emitted respect to standard set of coordinate axis. x x y x
For any subshell, 2l + 1 values of ml are possible. y y
DE E2 – E1 l
n= h = h
l Subshell s p d f g h (a) (b) (c)
2 dx2 – y2 dz2
52.9 (n ) Number of 1 3 5 7 9 11
m rn = pm; radius of nth orbit z z
Z orbitals
2 (4) Two orientations of electrons are distinguished by the
m En = –2.18 × 10
–18 Z
2 J; energy of electron in nth orbit spin quantum numbers (ms) which can take value of
n
1 1 x
+ and – . x
2 2 y y
6 DUAL BEHAVIOUR OF MATTER
m de-Broglie relationship between wavelength (l) and 8 FILLING OF ORBITALS IN ATOM (d) (e)
momentum (P) of the material particle. m Aufbau Principle: In the ground state
of the atoms, the orbitals are filled in 1s
h h Total nodes = n – 1, angular nodes = l, radial nodes
l= = order of their increasing energies. m
P mv
m The maximum number of electrons in 2s 2p =n–1–l
m Heisenberg's Uncertainty Principle 2
a shell = 2n 3d
Energies of Orbitals
It states that it is impossible to determine simultaneously, the 3s 3p
m Hund's Rule of Maximum m 1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f <

exact position and exact momentum (or velocity) of an 4s 4p 4d 4f (for hydrogen)
Multiplicity
electron. m (n + l) rule – the lower the value of (n + l) for an orbital, the
Pairing of electrons in degenerate 5s 5p 5d 5f
h orbitals take place only after each lower is its energy. It two orbitals have the same value of
Dx × Dpx ³ (n + l), the orbital with lower value of n will have the lower
4p degenerate orbitals is singly filled. 6s 6p 6d
energy for multielectron atom.
m Heisenberg uncertainty principle is not valid for macroscopic m Pauli Exclusion Principle 7s 7p m Energies of the orbital in the same subshell decreases
objects. No two electrons in an atom can have
with increase in the atomic number (Zeff)
m Failure of Bohr model: It ignores dual behaviour of matter the same set of four quantum
but also contradicts Heisenberg uncertainty principle. numbers. e.g. E2s(H) > E2s(Li) > E2s(Na) > E2s(K)
Classification of Elements and Periodicity in Properties
Classification of Elements and Periodicity 3

in Properties Chapter
1 GENESIS OF PERIODIC CLASSIFICATION 2 MODERN PERIODIC LAW AND TABLE

m Dobereiner's Triad: Middle element of each of the triads had m Modern Periodic Law: States that the physical and chemical properties of the elements are periodic
an atomic weight about half way between the atomic weights functions of their atomic numbers.
of other two and also the properties of middle element were in
m Modern Periodic table
between other two.
e.g. (Li, Na, K), (Ca, Sr, Ba), (Cl, Br, I)
m Law of Octaves: On arranging the elements increasing
order of their atomic weights, every eighth element had
properties similar to the first element e.g Li, Be, B, C etc
resemble with Na, Mg ,Al and Si respectively.
m Lother Meyer: Plotted the physical properties such as
atomic volume, melting point and boiling point against atomic
weight and obtained a periodically repeated pattern.
m Mendeleev Periodic law: The properties of elements are a
periodic function of their atomic weights.
Mendeleev predicted elements Eka-Aluminium as Gallium
and Eka-Silicon as Germanium.
3 Nomenclature of elements having Z > 100
Atomic Name according Symbol IUPAC IUPAC

Number to IUPAC Official Name Symbol
nomenclature
101 Unnilunium Unu Mendelevium Md

102 Unnilbium Unb Nobelium No
103 Unniltrium Unt Lawrencium Lr
104 Unnilquadium Unq Rutherfordium Rf
105 Unnilpentium Unp Dubnium Db
106 Unnilhexium Unh Seaborgium Sg
107 Unnilseptium Uns Bohrium Bh
108 Unniloctium Uno Hassium Hs
109 Unnilennium Une Meitnerium Mt
110 Un unnillium Uun Darmstadtium Ds
111 Unununnium Uuu Rontgenium Rg 4 ELECTRONIC CONFIGURATION
112 Ununbium Uub Copernicium Cn m 3d series from Z = 21 to Z = 30 m General outer electronic configuration
113 Ununtrium Uut Nihonium Nh 1-2
114 Ununquadium Uuq Flerovium Fl
m 4d series from Z = 39 to Z = 48 s-block = ns
4f-inner transition series from Z = 58 to Z = 71, also 2 1-6
115 Ununpentium Uup Moscovium Mc m
p-block = ns np
116 Ununhexium Uuh Livermorium Lv known as lanthanide series 1-10 0-2
117 Ununseptium Uus Tennessine Ts d-block = (n – 1)d ns
118 Ununoctium Uuo Oganesson Og m 5f-inner transition series from Z = 90 to Z = 103 also 1-14 0-1 2
known as actinoid series f-block = (n – 2)f (n – 1)d ns
NCERT Maps Classification of Elements and Periodicity in Properties 11
5 IMPORTANT TERMINOLOGIES 6 PERIODIC TRENDS IN CHEMICAL PROPERTIES

m The elements of group 1 (alkali metals) and group 2 (alkaline earth metals) are known as m The valence of representative elements is usually equal to valence electrons or
s-block elements. 8-valence electrons.
m The elements of group 13 to 18 are known as p-block elements. m Second period elements show anomalous behaviour due to their small size, large
m s-block and p-block elements together known as Representative elements or Main Group charge/radius ratio, high electronegativity of the elements and only four valence
elements. orbitals.
m All the orbitals in the valence shell of the noble gases are completely filled. m Li and Be is more similar to Mg and Al respectively and this sort of similarity is known as
diagonal relationship.
m Group 17 elements are known as halogens.
m Group 16 elements are known as chalcogens. m The normal oxide formed by the element on extreme left is most basic (e.g. Na2O),
m Elements of group 3 to 12 are known as d-block elements. whereas that formed by the element on extreme right is most acidic (e.g. Cl2O7)
m Transition metals form a bridge between the s-block elements and group 13 elements m Oxides of elements in centre are amphoteric (e.g. Al2O3, As2O3) or neutral (e.g. CO,
m Two rows of elements at the bottom of the periodic table called the Lanthanoid and Actinoids NO, N2O)
and combinely known as Inner-transition elements or (f-block elements) m Amphoteric oxides behaves as acidic with bases and as basic with acids, whereas
m The elements after uranium are called Transuranium elements neutral oxide have no acidic or basic properties.
7 TRENDS IN PHYSICAL PROPERTIES
m Covalent radius is half of the bond distance of valence electron from the nuclecus by
between two similar atoms. intervening core electrons
Electron Gain Enthalpy
m Metallic radius is half the inter nuclear m 2p electron of boron is more shielded from
distance separating the metal cores in the the nucleus than the 2s electron therefore
metallic crystal. ionization energy of boron is slightly less Ionization Enthalpy
m Atomic radius refer to both covalent or than that of beryllium.
metallic radius depending upon the element m In nitrogen atom, three 2p-electrons reside
is a non metal or a metal
Electron Gain Enthalpy

Electronegativity
in different orbitals whereas in oxygen atom,
Atomic Radius
Ionization Enthalpy
Atoms or ions which contains same number two of four 2p-electrons must occupy the
m
er
of electrons are called isoelectronic same 2p-orbital resulting in increased a ract
c Ch
talli
2– – +
species e.g. O , F , Na etc. repulsion therefore ionization enthalpy of N
-me
m Ionic radii can be estimated by measuring
is greater than that of O.
Non er
the distance between cations and anions m Electron Gain enthalpy is the enthalpy
a ract
change when an electron is added to a c Ch
m A cation is always smaller than its parent
gaseous neutral atom to convert it into a Me talli
atom while an anion is always bigger than its
parent atom. negative ion.
m Ionization enthalpy is the energy required m Deg H of O and F is less negative than that of
to remove an electron from an isolated succeeding element due to interelectronic
gaseous atom. repulsion. Atomic Radius
m Third ionization enthalpy is higher than m Electronegativity is a qualitative measure
second and so on. of the ability of an atom in a chemical bond to
m The effective nuclear charge experienced by attract shared electrons. Electronegativity
a valence electron in an atom will be less m F is the most electronegative element while
than the actual charge on the nucleus the electron gain enthalpy of Cl is most
because of the "shielding" or "screening" negative.
Chemical Bonding and Molecular Structure
4
Chapter
1 CHEMICAL BOND 2 LIMITATION OF OCTET RULE 5 RESONANCE STRUCTURES

m The attractive force which holds various constituents m In some compounds, the number of electrons surrounding the m According to the concept of resonance, whenever a single
(atoms, ions etc) together in different chemical species is central atom is less than eight eg. LiCl, BeH2. lewis structure cannot describe a molecule accurately, a
Molecules with an odd number of electron e.g. NO and NO2. number of structures with similar energy, position of nuclie,
called a chemical bond. m
bonding and non-bonding pairs of electrons are taken as the
m In number of compounds there are more than eight valence
m Lewis postulated that atoms achieve the stable octet canonical structures of the hybrid which describes the
electrons around the central atom. eg. PF5, SF6, H2SO4 etc.
when they are linked with chemical bonds. molecule accurately.
m Some noble gases also combine with oxygen and fluorine eg.
m Simple notation to represent valence electrons in an XeF2. O O
· · · O
atom is called Lewis symbols e.g. Li, Be, g Bg m Does not account for the shape of molecules. O O O O
· O O
(Canonical structures) (Resonance hybrid)
m The bond formed, as a result of the electrostatic 3 IONIC BOND OR ELECTROVALENT BOND
attraction between the positive and negative ions was m Misconceptions with resonance
m Ionic bonds will be formed more easily between elements with
termed as the electrovalent bond or ionic bond. m The cannonical forms have no real existence.
comparatively low ionisation enthalpies and elements with
m Octet rule – According to this, atoms can combine either comparatively high negative value of electron gain enthalpy. m The molecule does not exist for a certain fraction of time in
by transfer of valence electrons from one atom to another one cannonical form and for other fractions of time in other
m Lattice enthalpy of an ionic solid is defined as the energy
(gaining or losing) or by sharing of valence electrons in cannonical forms.
required to completely seperate one mole of a solid ionic
order to have an octet in their valence shells. compound into gaseous constituent ions. m There is no such equilibrium between the cannonical forms.
m Covalent bond – When two atoms share electron pair(s) 6 POLARITY OF BONDS
they are said to be joined by covalent bonds. 4 BOND PARAMETERS
m Bond length is defined as the equilibrium distance between m In non-polar covalent bonds electron pair is situated
m It two atoms share one electron pair, the covalent bond the nuclei of two bonded atoms in a molecule. exactly between the two identical nuclei.
between them is called single bond, if two electrons pairs m The Covalent Radius is measured approximately as the m In polar covalent bond electron pair between the two atoms
then double bond e.g. radius of on atom's core which is in contact with the core an gets displaced more towards more electronegative atom.
adjacent atom in a bonded situation.
m The vander Walls Radius represents the overall size of m Dipole moment is the product of the magnitude of the
atoms which included the valence shell in a non-bonded charge and the distance between the centres of positive or
Cl Cl O C O negative charge and denoted by m
, situation.
m Bond Angle is defined as the angle between the orbitals m Dipole moment is a vector quantity and represented by
8e– 8e– 8e– 8e– 8e– containing bonding electron pairs around the central atom in a crossed arrow ( )
Cl – Cl O=C=O molecule/ ion.
eg H —— F
m Bond Enthalpy is defined as the amount of energy required to
break one mole of bonds of a particular type between two m Unit of m is Debye (1D = 3.33564 × 10–30 C m)
Total number of Total number of atoms in a gaseous state. For polyatomic molecules the term m In polyatomic molecules, the dipole moment depend upon
mean or average bond enthalpy is used.
m Formal charge = valence electrons non-bonding individual dipole moments of individual bonds and spatial
m Bond Order is given by the number of bonds between the two arrangement of bonds eg.
in free atom electrons
atoms in a molecule.
m Isoelectronic molecules and ions have identical bond orders H H
Total number of for example F2 and O2– 2 have bond order 1, N2 CO and NO
+
1 O O
- bonding have bond order 3.
2 electrons m With increase in bond order, bond enthalpy increases and H H
bond length decreases. Bond dipole Resultant dipole
NCERT Maps Chemical Bonding and Molecular Structure 15
8 VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY 7 FAJAN'S RULE

m The model used for predicting the geometrical shapes of molecules is based on the m The smaller the size of cation and larger the size of the anion, the greater is the covalent character of an ionic bond.
assumption that electron pairs repel each other therefore try to remain as far apart as possible m Greater the charge on the cation greater is the covalent character.
m The order of electron pair repulsion is lp – lp > lp – bp > bp – bp. m For cations of the same size and charge, the one having d-electrons is more polarising, thus its salts have greater
m Shape (geometry) covalent character.
Number of Number of Arrangement Shape Example

bonding Ione pairs of electron 9 VALENCE BOND THEORY
pairs pairs
m Discusses bond formation in terms of overlap of orbitals
2 0 B–A–B Linear BeF2
m In case of the formation of H2 molecule from two H-atoms involves overlap of s orbitals of two H-atoms which are singly occupied. The
B
potential energy of the systems gets lowered as the two H-atoms come near to each other.
3 0 A Trigonal BF3
B B planar m Types of overlapping.
Sigma (s) bond is formed by the end to end overlap of bonding orbitals along the internuclear axis.
2 1 A Bent SO2
Pi (p) bond is formed in such a way that atomic orbital axes remain parallel to each other and perpendicular to the internuclear axis.
B B
Hybridisation – Atomic orbitals combine to form new set of equivalent orbitals known as hybrid orbitals and this phenomenon is known as
B
hybridisation.
4 0 A Tetrahedral CH4
B B m Number of hybridised orbitals formed is equal to number of atomic orbitals intermixed.
B m Hybridised orbitals only form sigma bond.
2 3 3 2
m Various types of hybridisations are sp, sp , sp , sp d, dsp etc.
3 1 A Pyramidal NH3
B B
B
10 MOLECULAR ORBITAL THEORY

2 2 A Bent H2O
B m LCAO method is used for the formation of molecular orbitals.
B m For two atomic orbitals having wave function yA and yB the molecular orbital (MO) are given as yA ± yB
B
B m MO formed by the addition of atomic orbitals is called Bonding Molecular Orbital (BMO) or s and p while formed by the subtraction of atomic
5 0 A B Trigonal PCl5 orbitals is called anti bonding molecular orbital (ABMO) or s* and p*.
B bipyramidal
B m Increasing order of energies for diatomic molecules upto 14 electrons is
B s1s < s*1s < s2s < s*2s < (p2px = p2py) < s2pz < (p*2px = p*2py) < s*2pz
B Increasing order of energies for diatomic molecules with more than 14 electrons is
4 1 A See saw SF4 m
B
B s1s < s*1s < s2s < s*2s < s2pz < (p2px = p2py) < (p*2px = p*2py) < s*2pz
B 1
m Bond order = (N - NA )
3 2 T-shape ClF3 2 B
B A
1
m Bond order µ Bond strength µ
B Bond length
B
B B m If all the molecular orbitals in a molecule are doubly occupied then the substance is diamagnetic else paramagnetic.
6 0 A Octahedral SF6
B B
B 11 HYDROGEN BONDING
B m Hydrogen bond can be defined as the attractive force which binds hydrogen atom of one molecule with the electronegative atom (F, O or N) of
B B another molecule or within the same molecule.
5 1 A Square BrF5
B B Types of H-bond
pyramid
m Intermolecular hydrogen bond is formed between the atoms of two different molecules e.g. H2O, NH3, HF, C2 H5OH etc.
B B
4 2 A Square XeF4 m Intramolecular hydrogen bond is formed when hydrogen atom is in between the two highly electronegative (F, O, N) atoms present within the
B B same molecule eg. orthonitrophenol.
Planar
5
States of Matter Chapter
1 INTERMOLECULAR FORCES 5 CHARLE'S LAW 7 AVOGADRO LAW

m Gas ® Liquid ® Solid
m Forces of attraction and repulsions (i) Pressure remaining constant, the (i) Equal volumes of all gases under the same
Predominance of intermolecular
between interacting particles force intereactions volume of a fixed mass of a gas is
conditions of temperature and pressure contain
m Types of intermolecular forces directly proportional to its absolute
m Gas ¬ Liquid ¬ Solid temperature. equal number of molecules.
(i) Dispersion forces or London forces
Predominance of thermal energy V V V
(a) Force of attraction between (ii) = k2 or 1 = 2 (ii) V µ n
instantaneous dipole and T T1 T2
t
induced dipole.
(b) Interaction energy proportional m
3 GASEOUS STATE
Gaseous state is characterised by
(iii) Vt = V0 1 + ( 273.15 ( (iii) At standard temperature and pressure (STP),
1 molar volume of ideal gases is 22.7 L mol–1.

to , where r is the distance following physical properties Vt and V0 are volumes of gas at
r6
(i) Highly compressible
between two particles. t°C and 0°C respectively.
(ii) Exert pressure equally in all 8 IDEAL GAS EQUATION
(ii) Dipole-Diple forces act between the
direction
molecules possessing permanent p1<p2<p3<p4 m Boyle's law, Charles' law and Avogadro law can
(iii) M u c h l o w e r d e n s i t y t h a n
p1 be combined together in single equation known
dipole. Dipole-dipole intereaction
Volume
solid /liquid (iv) p2
p3 as ideal gas equation.
energy between stationary (iv) Indefinite shape and volume p4 Ideal gas equation : PV = nRT
molecules is proportional to 13 . (v) Mix evenly and completely in all
m
r
proportions without any ñ
-273.15 m R is universal gas constant and equal to
(iii) Dipole-Induced dipole forces –300 –200 –100 0 100
mechanical aid (i) 8.314JK–1 mol–1
operate between the polar Temperature (°C)
–2 –1 –1
molecules having permanent (ii) 8.20578 × 10 L atm K mol
4 GAS LAWS
dipole and the molecule lacking PM
6 GAY LUSSAC'S LAW m Density of gas = RT
permanent dipole. Interaction m Boyle's law
(i) At constant volume, pressure of a
energy is proportional to 1 . (i) A t c o n s t a n t t e m p e r a t u r e ,
fixed amount of gas varies directly
r6 pressure of a fixed amount of
with temperature 9 DALTON'S LAW OF PARTIAL PRESSURE
(iv) Hydrogen bond is a special case of gas varies inversely with its
dipole-dipole interaction and is volume. (ii) P µ T or P = k3 (i) Total pressure exerted by the mixture of non-
T
found in the molecules in which (ii) P = k1 1 Þ pV = k1 reactive gases is equal to the sum of the partial
highly polar N – H, O – H, or H – F V
V1<V2<V3<V4 pressures of individual gases.
Pressure (bar)
bonds are present. P1V1 = P2V2 V1

V2 Ptotal = P1 + P2 + P3 + ..... (at constant T, V)
V3
2 THERMAL ENERGY T3>T2>T1 V4 (ii) PDry gas= PTotal – Aqueous tension
(iii) P T3
m Energy of a body arising from motion of (iii) P1 = PTotal x1, P2 = PTotal x2 where x1, x2 are the
its atoms or molecules and it is directly T2
T1 0 100 200 300 400
mole fractions of gas 1 and 2 in the mixture.
proportional to the temperature V Temperature (K)
NCERT Maps States of Matter 19
10 KINETIC ENERGY AND 12 BEHAVIOUR OF REAL GASES: 14 LIQUID STATE

MOLECULAR SPEEDS DEVIATION FROM IDEAL GAS BEHAVIOUR
u + u2 + ... un m It is found that real gases do not follow, Boyle's m Volume occupied by the molecules also m Vapour pressure is the pressure
m Average speed (uav) = 1 n law, Charles law and Avogadro law perfectly become significant because instead of at equilibrium between liquid and
where n number of molecules in the sample vapour phase.
under all conditions. moving in volume V, these are now
and u1, u2 .... are their individual speeds. m The temperature at which
restricted to volume V-nb where nb is vapour pressure of liquid is equal
CO
1 CH4 approximately the total volume of to external pressure is called
m KE = mu2rms
2 H2 molecules occupied by themselves. boiling temperature at the
He m van der Waals equation pressure.
m Most probable speed(u m p ) is the speed ideal gas m At 1 atm pressure boiling
pV
2
temperature is called normal
possessed by the maximum number of
molecules (P+
an
V
2 ( (V-nb) = nRT boiling point and at 1 bar then
the boiling point is called
m Root mean square speed(Urns) is the square 0 p standard boiling point of the
a and b are called van der waals constant
root of the mean of the square of speeds. liquid.
and depends on nature of gas.
m Surface Tension is defined as the
m Compressibility factor Z
force acting per unit length
u12 + u 22 .... un2
urms = Real gas
V perpendicular to the line drawn
n
Ideal gas (i) Z = PV , Z = real on the surface of liquid. Denoted
nRT Videal
m ump : uav: urms :: 1 : 1.128:1.224 Pressure by g and SI unit is Nm–1.
(ii) For ideal gas Z = 1 m Viscosity
(i) It is a measure of resistance
11 KINETIC MOLECULAR THEORY OF GASES (iii) At very low pressure Z » 1 for all gases. to flow which arises due to
0 Volume
m Postulates of kinetic molecular theory (iv) At high pressure Z > 1 and at internal friction between
intermediate pressure most gases layers of fluid as they slip
(i) Gases consist of large number of identical past one another while liquid
particles and their actual volume is m Two assumption of kinetic theory do not hold have Z < 1. flows.
negligible in comparison to the empty good for real gases i.e (i) No interparticle (ii) In laminar flow there is a
m Boyle temperature or Boyle point
space between them attraction and (ii) Negligible volume of regular gradation of velocity
The temperature at which a real gas obeys in passing from one layer to
(ii) No force of attraction between particles at molecule of gas in comparison to space
ideal gas law over an appreciable range of next.
ordinary temperature and pressure occupied by the gas.
pressure. du
(iii) Particles of gas are always in constant m Real gases show deviations from ideal gas (iii) F = h A dz where F is force
random motion. of viscosity; A, area of
because molecules of gases intereact with 13 LIQUIFACTION OF GASES
(iv) Particles of gas move in all possible du
each other. This affects the pressure exerted contact; dz velocity gradient;
direction in straight lines and during m Critical temperature (TC) is the highest
by the molecules on the walls of container. h, coefficient of viscosity
motion they collide with each other and temperature at which liquid is observed.
with wall of container elastically. an2 m Critical volume (VC) is the volume of one (iv) SI unit of h is Nsm–2, in cgs
(v) Individual speed of particles are changing Pideal = Preal + mole of the gas at critical temperature
V system unit is poise
but distribution of speeds remains (observed (correction and pressure. 1 poise = 1 gcm–1s–1
pressure) term)
constant at a particular temperature. m For CO2, TC is 30.98°C = 10–1 kgm–1s–1.
Thermodynamics
6
Chapter
1 THERMODYNAMIC TERMS 3 ENTHALPY (H) m Standard enthalpy of sublimation, (DsubH°) is the change
m (i) System - Part of universe under observation. m Thermodynamic function is equal to U + pV in enthalpy when one mole of a solid substance sublimes at
(ii) Surroundings - Include everything other than m It is a state function. constant temperature and under standard pressure (1 bar).
system. m DH = qP, heat absorbed by system at constant pressure. Standard Enthalpy of Formation (DfH°) is the standard
m There are three types of system. m DU = qV at constant volume enthalpy change for the formation of one mole of a compound
(i) Open system - Exchange of energy and matter from its elements in their most stable states of aggregation.
m DH > 0 for endothermic and DH < 0 for exothermic reaction.
between system and surroundings. s
m DH = DU + DngRT where Dng is change in gaseous moles. Standard Molar Enthalpies of Formation (DfH )
(ii) Closed system - No exchange of matter but
at 298 K of a few Selected Substances
exchange of energy is possible.
(iii) Isolated system - There is no exchange of energy 4 EXTENSIVE AND INTENSIVE PROPERTIES Substance Substance
or matter between the system and surroundings. m An extensive property is a property whose value depends
m The state of a thermodynamic system is described by Br2(l) 0 H2O(l) –285.83
on the quantity or size of matter present in the system e.g.
its measurable properties. P, V, T, n etc are called state
mass, volume, enthalpy etc. +30.91 NO(g) +90.25
variables or state functions because their values Br2(g)
depend only on the state of the system and not on how it m Properties which do not depend on the quantity or size of
is reached. matter present are known as intensive properties e.g. C(diamond) +1.89 NO2(g) +33.18
temperature, density, molar heat capacity etc.
2 FIRST LAW OF THERMODYNAMICS Heat Capacity C(graphite) 0 –910.94
m Commonly known as the law of conservation of energy m Molar heat capacity is the quantity of heat required to raise Cl2(g) 0 C(g) +716.68
i.e. energy can neither be created nor be destroyed. the temperature of one unit mole of a substance by 1°C or
m DU = q + w is mathematical statement of the first law of 1 K, q = ncDT H2(g) 0 H(g) +217.97
thermodynamics
m Molar heat capacity at constant pressure is CP and molar –241.82 Cl(g) +121.68
Internal Energy (U) H2O(g)
m Sum of chemical, electrical, mechanical or any other heat capacity at constant volume is CV and CP – CV = R.
type of energy of the system. m Bomb calorimeter is used to find DU. Hess’s Law of Constant Heat Summation
Work (W) m Enthalpy change for a reaction is the same whether it occurs in
m Work is done on an ideal gas when it is compressed one step or in series of steps.
and work is done by an ideal gas when it is expanded 5 REACTION ENTHALPY (DRH)
vf
Standard Enthalpy of Combustion (DCH°) is defined as
W = - ò Pex dV m The standard enthalpy of reaction is the enthalpy change the enthalpy change per mole of a substance, when it
vi for a reaction when all the participating substances are in undergoes combustion and all the reactants and products
m A process or a change is said to be reversible, if a their standard states. being in their standard states at the specified temperature.
change is brought out in such a way that the process Enthalpy Change During Phase Transformation Bond Enthalpy (DbondH°) is energy required to break a bond
could, at any moment, be reversed by an infinitesimal or energy released when a bond is formed.
change. Process other than reversible are known as m The enthalpy change that accompanies melting of one mole
irreversible processes. of solid substance in standard state is called standard Enthalpy of Atomization (DaH°) is the enthalpy change on
For isothermal irreversible change q = –W = Pex(Vf – Vi) breaking one mole of bonds completely to obtain atoms in the
m enthalpy of fusion (DfusH°).
gas phase.
V Amount of heat required to vaporise one mole of liquid at
m For isothermal reversible change q = - W = nRT ln f m
m In case of diatomic molecules, the enthalpy of atomization is
Vi constant temperature and under standard pressure (1 bar)
m For adiabatic change, q = 0 DU = Wad also the bond dissociation enthalpy.
m W = 0 in free expansion is called standard enthalpy of vaporisation DvapH°. m DrH ° = å bond enthalpies reactants - å bond enthalpies products
24 Thermodynamics NCERT Maps
–1 6 SECOND LAW OF THERMODYNAMICS

Some Mean Multiple Bond Enthalpies in kJ mol at Ionization Energy and Electron Affinity
298 K Ionization energy and electron affinity are defined at m It explain the criterion of spontaneity.
absolute zero. At any other temperature, heat Spontaneity
N=N 418 C=C 611 O=O 498
m A spontaneous process is an irreversible process and may only
NºN 946 CºC 837 capacities for the reactants and the products have to be
be reversed by some external agency.
C=N 615 C=O 741 taken into account. Enthalpies of reactions for Entropy S is measure of the degree of randomness or disorder in
CºN 891 CºO 1070 the system.
+ –
M(g) ® M (g) + e (for ionization)
Lattice Enthalpy of an ionic compound is the enthalpy qrev
DS =
change which occurs when one mole of a ionic – –
M(g) + e ® M (g) (for electron gain) T
compound dissociates into its ions in gaseous state. m DStotal = DSsystem + DSsurr > 0 of a spontaneous process.
at temperature, T is
m It is impossible to determine lattice enthalpies directly by m DS = 0 and S in maximum at equilibrium.
experiment therefore we use indirect method Born- T
s s Gibbs Energy (G) and spontaneity
DrH (T) = DrH (0) + ò Dr CPs dT
Haber cycle.
0 m G = H – TS or DG = DH – TDS.
Enthalpy diagram for lattice enthalpy of NaCl
+
m Gibbs function, G is an extensive property and a state function.
Na (g) + Cl(g) The value of CP for each species in the above reaction is
m If DG < 0, process is spontaneous.
–1
5/2 R (CV = 3/2R)

121 kJ mol
s
m If DG > 0, process is non spontaneous.
1/2 DbondH
–1
s
So, DrCP = + 5/2 R (for ionization) DG° = –RT ln K = –2.303 RT log K.
–348.6 kJ mol
s m
DegH
s m DrG° = DrH° – TDrS° = –RT ln K.
+ DrCP = – 5/2 R (for electron gain)
Na (g) + 1/2Cl2(g) s s s
Therefore, DrH DrS DrG Description
s
– + – Reaction spontaneous at all
s DrH (ionization enthalpy)
Di H temperatures
= E0 (ionization energy) + 5/2 RT – – – (at low T) Reaction spontaneous at low

+ – temperature
Na (g) + Cl (g)
s
DrH (electron gain enthalpy) – – + (at high T) Reaction non-spontaneous at
high temperature
Na(g) + 1/2Cl2(g) = –A (electron affinity) – 5/2 RT
+ + + (at low T) Reaction non-spontaneous at
s
–1
D sub H Enthalpy of Solution (DsolH°) is the enthalpy change low temperature

kJ mol
+108.4
when one mole of it dissolves in a specified amount of + + – (at high T) Reaction spontaneous at high
s temperature
DlatticeH solvent.
Na(s) + 1/2Cl2(g) + – + (at all T) Reaction non-spontaneous a
D Hs
sol
AB (S) ¾¾¾¾ ® A + (aq) + B- (aq)
–1
all temperatures
–411.2 kJ mol
Df H
s
DlatticeHs DhydHs
7 ABSOLUTE ENTROPY AND THIRD LAW OF
+ – THERMODYNAMICS
A (g) + B (g)
m The entropy of any pure crystalline substance approaches zero as
m D solH = DlatticeHs + DhydHs
s the temperature approaches absolute zero. This is called third law
NaCl(s) of thermodynamics
Equilibrium
7
Chapter
1 EQUILIBRIUM IN PHYSICAL PROCESSES 2 EQUILIBRIUM IN CHEMICAL PROCESSES 3 APPLICATION OF EQUILIBRIUM CONSTANTS

m When the rates of the forward and reverse reactions m Predicting the Extent of reaction
m Solid-Liquid Equilibrium.
become equal, the concentrations of the reactant and the
(i) During equilibrium, the mass of solid and liquid do not products remain constant. This is the stage of chemical
change with time and temperature remains constant. equilibrium Negligible KC Extremely
large
However equilibrium is not static. The rate of transfer m Chemical reaction reach a state of dynamic equilibrium in Reaction hardly –3 3
of molecules from solid into liquid and liquid into solid proceeds 10 1 10 Reaction proceeds
which the rates of forward and reverse reactions are equal
are equal. Both reactants and products almost to completion
and there is no net change in composition are present at equilibrium
(ii) For any pure substance at atmospheric pressure, the Law of chemical Equilibrium and Equilibrium Constant
temperature at which the solid and liquid phases are at m For a general reversible reaction m Predicting the direction of reaction
equilibrium is called normal melting point or normal
A + B ƒ C + D, QC
freezing point.
Liquid-Vapour Equilibrium [C][D]
m Kc = (K = Equilibrium constant)
(i) At equilibrium, rate of evaproation = rate of [A][B] C
KC QC KC KC
condensation. m At a given Temperature, the product of concentrations of the
(ii) At equilibrium, the pressure exerted by the vapour is reaction products raised to the respective stoichiometric QC
called equilibrium vapour pressure, coefficient in the balanced chemical equation divided by the
(iii) Vapour pressure increases with increase in product of concentrations of the reactants raised to their
temperature and different liquids have different vapour individual stoichiometric coefficient has a constant value.
pressures at same temperature. This is known as the Equilibrium Law or Law of chemical
Reactant Products
(iv) Liquid having higher vapour pressure is more volatile equilibrium Reactants Products Reactant and
products are at equilibrium
and has a lower boiling point. m Equilibrium constants and its multiples
(v) The temperature at which the liquid and vapour is at aA + bB ƒ cC + dD KC Relationship between K, Q and G
equilibrium at one atmospheric pressure is called DG = DGº + RT ln Q
cC + dD ƒ aA + bB KC¢ = 1/KC m
normal boiling point of liquid n
naA + nbB ƒ ncC + ndD KC¢¢ = (KC) m DGº = –RT ln K
m Solid-Vapour Equilibrium - at equilibrium rate of
Sublimation = rate of condensation
m Equilibrium involving dissolution of solid or gases in Homogenous Equilibrium 4 FACTORS AFFECTING EQUILIBRIA
Liquids m When all the reactants and products are in same phase e.g m Le Chatelier’s Principle states that a change in any of
(i) Solids in liquids - In a saturated solution, a dynamic H2(g) + I2(g) ƒ 2HI(g) the factors that determine the equilibrium conditions of a
equilibrium exists between the solute molecules in m Equilibrium constant in terms of partial pressure is KP system will cause the system to change in such a manner
solid state and in the solution i.e. rate of dissolution =
m For the general reaction aA(g) + bB(g) ƒ cD(g) + dD(g) so as to reduce or to counteract the effect of the change.
rate of crystallisation
(ii) Gases in Liquids KP = KC (RT)
Dn
where Dn = (c + d) – (a + b) m Factors which can influence the equilibrium are
(a) There is equilibrium between the molecules in the Hetrogeneous Equilibrium (a) Effect of concentration change
gaseous state and the molecules dissolved in m Equilibrium in a system having more than one phase e.g (b) Effect of pressure change
liquid under pressure. H2O(l) ƒ H2O(g) (c) Effect of inert gas addition
(b) Henry’s Law states that the mass of a gas (d) Effect of temperature change
dissolved in a given mass of solvent at any m Unit of equilibrium constant
–1 Dn Dn
KC = (mol L ) , KP = (atm) or (bar)
Dn (e) Effect of a catalyst
temperature is proportional to the pressure of the
gas above the solvent Where Dn = change in gaseous moles (f) Effect of inert gas addition
28 Equilibrium NCERT Maps
5 IONIC EQUILIBRIUM IN SOLUTION 6 THE pH SCALE 8 SALT HYDROLYSIS

m Substances which conduct electricity in their aqueous m The cations/anions formed on ionization of salts interact
m Negative logarithm to base 10 of the activity (aH+) of with water to reform corresponding acid/bases
solution are called electrolytes while the other are
hydrogen ion depending upon the nature of salt is known as hydrolysis.
called non-electrolytes.
+
pH = – log aH+ = – log [H ] m Salts of strong acid and strong base do not undergo salt
m Strong electrolytes on dissolution in water are ionized
hydrolysis.
almost completely, while the weak electrolytes are only pOH = – log aOH– = – log [OH ]
–
partially dissociated. m The pH of CH3COONa solution in water is more than 7

m Acids and Bases m pKw = pH + pOH = 14 at 298 K m The pH of NH4Cl solution in water is less than 7
(i) Arrhenius concept of Acids and Bases m pH of salt solution of weak acid and weak base
+ –
Acid gives H (aq) and base gives OH (aq) in 1
7 IONIZATION CONSTANTS OF WEAK ACIDS (Ka) pH = 7 + (pK a - pK b )
aqueous solution eg. HCl(Acid), NaOH(Base). 2
m For a weak acid HX,
(ii) The Bronsted-Lowry Acids and Bases + – 2
[H ][X ] Ca
(a) According to this theory, acid is a substance that Ka = = 9 BUFFER SOLUTIONS
[HX] 1–a
+
is capable of donating a hydrogen ion, H and m The solutions which resist change in pH on dilution or with
bases are substances capable of accepting a where C is the initial concentration of acid and a is degree the addition of small amounts of acid or alkali called
+ of dissociation of acid
hydrogen ion, H , Buffer solution
(b) The acid-base pair that differ only by one proton Ionization Constants of Weak Bases (Kb) m Acidic Buffer
–
is called the conjugate acid-base pair eg. OH m For a weak base MOH,
(i) Aqueous solution containing weak acid and its salt
is conjugate base of HOH. + – 2
Kb =
[M ][OH ] Ca
= 1–a with strong base can act as acidic buffer (eg
(c) Strong Bronsted acid has weak conjugate base [MOH]
and vice-versa. CH3COONa + CH3COOH)
m For conjugate acid-base pair [Salt]
– +
e.g. HI ® I + H (ii) pH = pK a + log
Ka.Kb = Kw [Acid]
Strong weak conjugate m Basic Buffer
pKa + pKb = pKw
acid base (i) Aqueous solution of weak base and its salt with
(iii) Lewis Acids and Bases Di-and Polybasic Acids and Di-and Polyacidic Bases strong acid can act as basic buffer (eg NH4Cl +
According to this theory an acid is a species which m Acids having more than one ionizable proton per NH4OH)
accepts electron pair and base which donates an molecule are known as polybasic acids pOH = pK b + log
[Salt]
electron pair. [Base]
m Higher order ionization constant (Ka2, Ka3) are smaller
e.g. AlCl3 [Lewis acid], NH3 (Lewis base) Sparingly Soluble Salts
than the lower order ionization constant (Ka1) of a m Salts having solubility < 0.01 M are considered
Ionization Constant of Water and its Ionic Product
+ –
polyprotic acid. The reason for this is that it is more saparigly soluble salts
m Ionic product of water Kw = [H ] [OH ]
difficult to remove a positively charged proton from a m The equilibrium constant between the undissolved solid
+ – –7
m Concentration of H and OH in pure water at 298 K = 10 negative ion due to electrostatic forces. and the ions in a saturated solution is known as
–14 2
M and Kw = 10 M Common ion effect defined as a shift in equilibrium on Solubility product (Ksp).
+ –
m In acidic solution [H3O ] > [OH ], in neutral solution adding a substance that provides more of ionic species m For sparingly soluble salt MxXy with molar solubility S
+ – + –
[H3O ] = [OH ] and in basic solution [H3O ] < [OH ] already present in the dissociation equilibrium x y
Ksp = x . y (S)
(x+y)
8
Redox Reactions Chapter
1 CLASSICAL IDEA OF REDOX REACTIONS (5) Oxidation number of F is –1, other halide ions is – 1, X + YZ ® XZ + Y
m Oxidation- addition of oxygen/electronegative elements positive oxidation number of halogens (except F) in Types of displacement to reactions.
to a substance or removal of hydrogen/electropositive oxoacids and oxoanions. (1) Metal displacement reaction in which a metal in a
element from a substance. compound can be displaced by another metal in
(6) Algebraic sum of oxidation number of all atoms in a
m Reduction is the removal of oxygen/electronegative uncombined state.
compound is 0. In polyatomic ions, the algebraic sum of
element from a substance or addition of hydrogen/ e.g. CuSO4(aq) + Zn(s) ® Cu(s) + ZnSO4(aq)
oxidation number of all atoms is equal to charge
electropositive element to a substance. (2) Non-metal displacement redox reaction generally
present on the ions. include hydrogen displacement
2 REDOX REACTION IN TERMS OF ELECTRON m Stock notation is expressed by putting a Roman numeral
e.g. 2Na(s) + 2H4O(l) ® 2NaOH(aq) + H2(g)
TRANSFER REACTIONS representing the oxidation number in parenthesis after the
m Disproportionation reactions
m Half reactions that involve loss of electrons are called symbol of metal in the molecular formula eg. Au (III) Cl3 In this type of reaction an element in one oxidation state
oxidation reactions. m Oxidation : An increase in the oxidation number of the is simultaneously oxidised and reduced.
m Half reactions that involve gain of electrons are called element in the given substance. eg: 2H2O2(aq) ¾® 2H2O (l) + O2(g)
reduction reactions.
– m Reduction : A decrease in the oxidation number of the
loss of 2e
element in the given substance. 5 PARADOX OF FRACTIONAL
+ –
2Na (s) + Cl2 (g) ¾® 2Na Cl (s) m Oxidising agent : A reagent which can increase the OXIDATION NUMBER
oxidation number of an element in a given substance
gain of 2e
– In certain compound, the oxidation number of a particular
m Reducing agent : A reagent which can decrease the
m Oxidising agent : Acceptor of electron(s). element in the compound is in fraction. Actually this
oxidation number of an element in a given substance.
m Reducing agent : Donor of electron (s) fractional oxidation state is the average oxidation state of
same element in the compound.
3 OXIDATION NUMBER 4 TYPES OF REDOX REACTIONS
m Combination reactions O O O
m Oxidation number denotes the oxidation state of an +6 +4 +6
element in a compound ascertained according to a set of A + B ¾® C eg: Br3O8 O Br Br Br O,
rules formulated on the basis that electron pair in a (Either A and B or both A and B must be in the elemental
O O O
covalent bond belongs entirely to more electronegative form)
element eg : C(s) + O2(g) ¾® CO2(g) Oxidation no. of Br = 16/3
m Rules of the calculation of oxidation numbers: m Decomposition reactions are the opposite of
(1) In elements in the free state, oxidation number of ¸2 0 +2
combination reaction. eg: C3O2 O C C C O
each atom is zero. D
(2) For ion containing single atom, oxidation number is e.g : 2NaH (s) 2Na (s) + H2 (g) Oxidation no. of C = 4/3
equal to charge on the ion. All decomposition reactions are not redox reactions
(3) Oxidation number of oxygen in oxide = –2, in D O O
e.g : CaCO3 CaO(s) + CO2 (g) +5 0 0 +5 –
peroxide = – 1, in super oxide = –½, in OF2 = + 2, in –
O S S S S O
m Displacement reaction are those in which an ion (or an eg: S4O62–
O2F2 = + 1
O O
(4) Oxidation number of hydrogen is + 1 in binary atom) in a compound is replaced by an ion (or an atom) of
Oxidation of S = 2.5
compound except with metal eg: LiH, CaH2 another element.
32 Redox Reactions NCERT Maps
6 BALANCING OF REDOX REACTIONS Step 3: Balance the atoms other than O and H in For the reaction in a basic medium, first balance the
+
each half reaction individually. Here the oxidation atoms as is done in acidic medium. Then for each H ion,
1. Oxidation Number Method
half reaction is already balanced with respect to –
add an equal number of OH ions to both sides of the
MnO4– (aq) + Br – (aq) ® MnO2 (s) + BrO3– (aq) (in basic medium) Fe atoms. For the reduction half reaction, we + –
3+ equation. Where H and OH appear on the same side
Step 1: The Skeletal ionic equation multiply the Cr by 2 to balance Cr atoms.
of the equation, combine these to give H2O.
MnO4– (aq) + Br – (aq) ® MnO2 (s) + BrO3– (aq) Cr2O72 - (aq) 2Cr 3 + (aq)
Step 4: For reactions occurring in acidic medium, 7 REDOX REACTIONS AND

Step 2: Assign oxidation number for Mn and Br +
+7 –1 +4 +5 add H2O to balance O atoms and H to balance H ELECTRODE PROCESSES
MnO4– (aq) + B r – (aq) ® MnO2 (s) + B rO3– (aq) atoms. Thus, we get :
m A redox couple is defined as having together the
This indicates that permanganate ion is the oxidant and bromide Cr2O72– (aq) + 14H+ (aq) 2 Cr 3+ (aq) + 7H2O(l)
oxidised and reduced forms of a substance taking
ion in the reductant.
Step 5: Add electrons to one side of the half part in an oxidation or reduction half reaction.
Step 3 : Calculate the increase and decrease of oxidation
reaction to balance the charges. If need be, make
number, and make the increase equal to the decrease. m Daniell cell
the number of electrons equal in the two half
–1 Current flow
+7 +4 +5 reactions by multiplying one or both half reactions
Switch
2MnO4– (aq) + Br – (aq) ® 2MnO2 (s) + Br O3– (aq) by appropriate number.
Electron flow
The oxidation half reaction is thus rewritten to Anode Cathode

Step 4 : As the reaction occurs in the basic medium, and the ionic
balance the charge: +
–
charges are not equal on both sides, add 2OH . ions on the right 2+ 3+ –
Fe (aq) ® Fe (aq) + e
to make ionic charges equal Now in the reduction half reaction there are net Salt
2M nO 4– (aq) + B r – (aq) ® M nO 2 (s) + B rO 3– (aq) + 2O H – (aq) twelve positive charges on the left hand side and bridge
Step 5 : Finally, count the hydrogen atoms and add appropriate only six positive charges on the right hand side.
Therefore, we add six electrons on the left side.
number of water molecule (i.e. one H2O molecule, on the left + – 3+
Cr2O72– (aq) + 14H (aq) + 6e ® 2Cr (aq) +
side to achieve balanced redox change.)
7H2O (l) Oxidation Reduction
2M nO 4– (aq) + B r – (aq) + H 2 O( l ) ® 2M nO 2 (s) + B rO 3– (aq) + 2O H – (aq)
To equalise the number of electrons in both the
2. Half Reaction Method: half reactions, we multiply the oxidation half
Suppose we have to balance the equation showing the oxidation reaction by 6 and write as : m The potential associated with each electrode is known
2+ 3+ 2– 2+ 3+ – as electrode potential.
of Fe ions to Fe ions by dichromate ions (Cr2O7) in acidic 6Fe (aq) ® 6Fe (aq) + 6e
2– 3+ m If the concentration of each species taking part in the
medium, wherein, Cr2O7 ions are reduced to Cr ions. Step 6: We add the two half reactions to achieve
the overall reaction and cancel the electrons on electrode reaction is unity at 298 K then the potential of
The following steps are involved in this task.
Step 1: Produce unbalanced equation for the reaction in ionic each side. This gives the net ionic equation as : each electrode is said standard electrode potential.
2+ + 3+
form : 6Fe (aq) + Cr2O72– (aq) + 14H (aq) ® 6 Fe (aq) m By convention the standard electrode potential (E°)
3+ of hydrogen electrode is 0 volts.
Fe2+ (aq) + Cr2O72– (aq) Fe3+ (aq) + Cr 3+ (aq) +2Cr (aq) + 7H2O(l)
Step 7: Verify that the equation contains the same m A negative E° means redox couple is a stronger
Step 2: Separate the equation into half reactions:
+2 +3 type and number of atoms and the same charges reducing agent than H+/H2 couple.
Oxidation half : Fe2 + (aq) Fe3 + (aq) on both sides of the equation. This last check
m A positive E° means redox couple is weak reducing
+6 +3 reveals that the equation is fully balanced with
Reduction half : Cr 2 O72– (aq) 3+
Cr (aq) respect to number of atoms and the charges. +
agent than H / H2 couple.
Hydrogen
9
Chapter
1 POSITION OF HYDROGEN IN THE At anode : 2Cl –(aq) ® Cl2(g) + 2e – (v) Reaction with metal ions and metal oxide
PERIODIC TABLE At cathode : 2H 2O(l) + 2e – ® H2(g) + 2OH –(aq) H2(g) + Pd2+(aq) ® Pd(s) + 2H+(aq)
m Hydrogen has electronic configuration 1s1therefore has a Overall reaction : 2Na +(aq) + Cl –(aq) + 2H 2O(l) yH2(g) + MxOy(s) ® xM(s) + yH2O(l)
resemblance to alkali metals which loose one electron to ¯ (vi) Reaction with organic compounds :
form unipositive ions, as well as halogens, which gains Cl2(g) + H2(g) + 2Na +(aq) + 2OH –(aq)
one electron to from uninegative ion; Thus, it is unique in
m Hydrogenation of vegetable oils using nickel as catalyst
(iv) Reaction of steam on hydrocarbon or coke at gives edible fats (margarine or vanaspati ghee)
behaviour and is therefore, best placed seperately in the high temperature with catalyst
periodic table. m Hydroformylation of olefins
1270 K
CnH2n + 2 + nH2O Ni
nCO + (2n + 1)H 2 H2 + CO + RCH = CH2 ®RCH2CH2CHO
2 DIHYDROGEN H2 + RCH2CH2CHO ® RCH2CH2CH2OH
m Occurrence m Mixture of CO and H2 is called water gas or
(i) Dihydrogen is most abundant element in the syngas
universe(70% of the total mass of the universe) 6 USES OF DIHYDROGEN
m The production of H2 can be increased by
(ii) 0.15% by mass in the earth atmosphere and 15.4% reacting CO of syngas with steam in the m For synthesis of NH3 which is used in manufacture of nitric acid
of the earth crust and oceans presence of iron chromate as catalyst & fertilizers
(iii) Occurs in plant and animal tissues, carbohydrate, m It is used in the manufacture of vanaspati ghee, organic
673K
proteins etc. CO(g) + H2O(g) CO2(g) + H chemicals, metal hydride and hydrogen chloride.
Catalyst
3 ISOTOPES
m In metallurgical process
(Water gas shift reaction)
1 m Atomic hydrogen and oxy hydrogen torch, rocket fuel and fuel
(i) Hydrogen has three isotopes: Protium 1H, m Presently 77% of industrial H2 is produced from cell
deuterium, 12 H or D and tritium 13 H or T petrochemicals 18% from coal, 4% from
(ii) The relative abundance of H, D and T are 99.985,
electrolysis 7 HYDRIDES
0.0156 and 10 –15% respectively
(iii) Only tritium is radioactive and emits low energy b
– m Binary compound of hydrogen with other elements called
particles (t 1/2, 12.33 years) 5 PROPERTIES OF DIHYDROGEN hydrides.
m Types of hydrides
m Physical Properties : H2 is a colourless, odourless,
4 PREPARATION OF DIHYDROGEN (i) Ionic or saline hydrides
tasteless and combustible gas, lighter than air and
m Lab method insoluble in water m Stoichiometric compounds of H with most of the s-block
2
(i) Reaction of granulated zinc with dilute hydrochloric m elements.
Chemical Properties :
acid m Significant covalent character is found in lighter metal
Zn + 2H + ® Zn2+ + H2 (i) Reaction with halogens :
hydrides e.g., LiH, BeH2 and MgH2.
(ii) Reaction of zinc with aqueous alkali H2(g)+X2(g) ® 2HX(g)
m Their melts conduct electricity and on electrolysis liberate
Zn + 2NaOH ® Na2ZnO2 + H2 (X = F, Cl, Br, I)
(ii) Reaction with dioxygen : H2 gas at anode which confirms the existence of H– ion.
m Commercial Production m Reacts violently with H O
2
Catalyst or
(i) Electrolysis of acidified water using Pt electrodes 2H2(g) + O2(g) 2H2O(l), DH = –285.9 kJ mol–1 NaH(s) + H2O(aq) ® NaOH(aq) + H2(q)
heating
Electrolysis (ii) Covalent of Molecular Hydride
2H2O(l) 2H2(g) + O2(g) (iii) Reaction with dinitrogen :
Traces of Acid/Base m H2 forms molecular compounds with most of p-block
673K
(ii) High purity (> 99.95%) dihydrogen is obtained by 3H2(g) + N2(g) 2NH3(g), DH = –92.6 kJ mol
–1
elements e.g., CH4, NH3, H2O and HF
electrolysis of warm aqueous Ba(OH) 2 solution with 200atm, Fe
m Hydrogen compounds of non metal considered as hydride.
Ni electrodes. (iv) Reaction with metals : They are volatile in nature.
(iii) Byproduct in the manufacture of sodium hydroxide H2(g) + 2M(g) ® 2MH(s), M = alkali metals
and chlorine by the electrolysis of brine solution m Molecular hydrides are classified further as :
36 Hydrogen NCERT Maps
(iv) Hydrate formation- from aqueous solution many salt 10 HYDROGEN PEROXIDE(H2O2)
(1) Electron deficient hydride has too few electrons for
writing its conventional lewis structure e.g., B2H6.(In can be crystallised as hydrated salt viz., coordinated m Preparation
fact all group 13 hydrides). water (e.g., [Cr(H2O)6]3+3Cl–), interstitial water(e.g., (i) BaO28H2O(s)+H 2SO4(aq)®BaSO4(s)+H2O2(aq) + 8H2O(l)
(2) Electron precise hydrides have the required number BaCl2.2H2O), hydrogen-bonded water (e.g., Electrolysis Hydrolysis
of electrons to write conventional Lewis structure e.g., CuSO4.5H2O). (ii) 2HSO–4(aq) HO3SOOSO3H(aq)
All elements of group 14 form such compounds. 2HSO–4(aq) + 2H +(aq) + H 2O2(aq)
(3) Electron-rich hydrides have excess electrons which 9 HARD & SOFT WATER This method is now used for lab preparation of D 2O2
are present as lone pairs e.g., elements of group m Presence of calcium and magnesium salts in the form K2S2O8(s) + 2D 2O(l) ®2KDSO4(aq) + D 2O2(l)
15 –1 7 form such compounds. of hydrogen carbonate, chlorides and sulphate makes
(iii) (iii) Industrial method O2(air)
Metallic of Non-stoichiometric (or interstials) water ‘hard’, Hard water does not give lather with soap 2-ethylanthraquinol H 2O2 + (Oxidised product)
Water free from soluble salts of calcium and H2/Pd
Hydrides m
m These are formed by many d-block and f-block magnesium is called soft water m Physical properties
elements m Temporary Hardness is due to presence of Mg and (i) H2O2 is an almost colorless liquid
m Metals of group 7, 8 and 9 do not form hydride. Even Ca hydrogen carbonates. It can be removed by
(ii) H2O2 is miscible with water in all proportions and
from group 6, only chromium forms CrH. (i) Boiling During boiling, the soluble Mg(HCO3)2 is forms a hydrate H2O2.H2O. A 30% solution of H2O2
m They are almost always non-stoichiometric and law of converted into insoluble Mg(OH) 2 and Ca(HCO 3)2 is
costant composition does not hold good. changed to insoluble CaCO3. is marketed as 100 volume hydrogen peroxide.
m E.g., LaH2.87, YbH2.55, NiH0.6-0.7 etc. (iii) 100 volume means 1mL of 30% H 2O2 solution will
(ii) Clark’s method : Calculated amount of lime is added.
give 100 mL of O2 at STP.
Ca(HCO 3)2+ Ca(OH) 2 ® 2CaCO3 ¯ + 2H2O
8 WATER Mg(HCO 3)2 + 2Ca(OH) 2®2CaCO3¯ + Mg(OH) 2¯ + 2H2O m Structure
m Physical properties m Permanent Hardness is due to the presence of soluble
(i) It is colourless and tasteless liquid. The unusual sulphates and chlorides of Mg and Ca. It can be
properties of water in the condensed phase are due to removed by
the presence of extensive hydrogen bonding between (i) Treatment with washing soda
water molecule. MCI2 + Na2CO3 ®MCO3¯ + 2NaCl
(ii) Structure of water (M = Mg,Ca)
MSO4 + Na2CO3 ® MCO3¯ + Na2SO4
95.7 pm
104.5º (ii) Calgon’s method - Sodium hexametaphosphate (b) Solid phase
(a) Gas phase
(Na6P6O18) , commercially called ‘calgon’ when added
H H
to hard water following reactions takes place m Chemical properties
(iii) Structure of ice - At atmospheric pressure ice Na6P6O18 ® 2Na++ Na4P6O182–
crystallizes in the hexagonal form but at very low (M = Mg, Ca) (i) Oxidising action in acidic medium
temperature it condenses to cubic form. Density of ice M2++ Na4P6O182– ®[Na2MP6O18]2– + 2Na+ PbS(s) + 4H2O2(aq) ® PbSO4(s) + 4H2O(l)
is less than water due to open type structure with wide
holes. (iii) Ion-exchange method : This method is also called (ii) Reducing action in acidic medium
m Chemical properties zeolite/permutit process. 2MnO–4 + 6H++ 5H2O2® 2Mn2++ 8H2O + 5O2
2NaZ(s) + M2+(aq)®MZ2(s) + 2Na+(aq)
(i) Amphoteric nature -H2O has, the ability to act as an (NaZ is NaAlSiO 4), (M = Mg,Ca) (iii) Oxidising action in basic– medium
acid as well as base Exhausted zeolite regenerated for further use by 2Fe2++ H2O2 ®2Fe3++ 2OH
H2O(l) + H2O(l) H3O+(aq) + OH–(aq) treating with an aqueous sodium chloride solution
acid-1 base-2 acid-2 base-1 (iv) Reducing action in basic medium
MZ2(s) + 2NaCl(aq) ® 2NaZ + MCl2(aq) I2 + H2O2 + 2OH– ® 2I– + 2H2O + O2
(Self ionization of water) (iv) Synthetic resins method
(ii) Hydrolysis reaction - Due to high dielectric constant, it Cation exchange resins contain large organic
has a very strong hydrating tendency. molecule with-SO 3H group and are water insoluble. 11 HEAVY WATER, D2O
P4O10(s) + 6H2O(l) ® 4H3PO4(aq) RSO3H is changed to RNa by treating it NaCl. The resin
(iii) Redox reaction exchanges Na+ ions with Ca2+ and Mg2+ ions present in
m Extensively used as a moderator in nuclear reactors
2H2O(l) + 2Na(s) ® 2NaOH(aq) + H2(g) hard water to make the water soft m It is used to prepare other deuterium compounds
10
The s-Block Elements Chapter
1 GROUP-1 ELEMENTS : ALKALI METALS 2 GENERAL CHARACTERISTICS OF THE COMPOUNDS 2NaHCO3 D Na2CO3 + CO2 + H2O
m Hydration Enthalpy OF ALKALI METALS
(b) NH3 is recovered using Ca(OH)2
(i) Hydration enthalpies decrease with increase in ionic m Oxides and Hydroxides
sizes. (a) On combustion in excess of air, Li forms mainly Li2O 2NH4Cl +Ca(OH)2 ® 2NH3 + CaCl2 + H2O
+
(ii) Li has maximum degree of hydration. (plus some Li2O2), Na forms Na2O2 (plus some NaO2) (c) K2CO3 cannot be prepared by Solvay process because
m Physical Properties whilst K, Rb and Cs form superoxides.
(i) Alkali metals are silvery white, soft and light metals. KHCO3 is too soluble to be precipitated out.
(b) These oxide are easily hydrolysed to form hydroxides.
(ii) Alkali metals have low density which increases down, + –
M2O + H2O ® 2M + 2OH (d) It is white crystalline solid exist as Na2CO3.10H2O. On
from Li to Cs. However potassium is lighter than + –
sodium. M2O2 + 2H2O ® 2M + 2OH + H2O2 heating it forms Na2CO3·H2O and above 373 K forms
+ –
(iii) The melting and boiling point are low due to weak 2MO2 + 2H2O ® 2M + 2OH + H2O2+ O2 Na2CO3, a white powder known as soda ash.
metallic bond. (c) The oxides and peroxides are colourless while m NaCl, Sodium Chloride
(iv) Flame colour: Li(Crimson red), Na (Yellow), K(Violet), superoxides are yellow or orange in colour and
Rb(Red Violet), Cs(Blue) paramagnetic. Most abundant source is sea water and impurities like
m Chemical Properties m Halides CaCl2 and MgCl2 make table salt deliquescent.
(i) Reactivity towards air - Burns vigorously in oxygen. (a) Alkali metal halides are high melting, colourless m Sodium hydroxide (caustic soda), NaOH
Li forms Li2 O, Na forms Na2O2 and K, Rb and Cs form crystalline solids.
In Castner Kellner Cell a brine solution is electrolysed using
superoxides, Li also forms Li3N. (b) DfH° values of fluorides become less negative down the
Hg cathode and carbon anode. (Commercial method)
(ii) Reactivity towards water group while reverse is true for chlorides, bromides and
+ – iodides. Hg
(a) 2M + 2H2O ® 2M + 2OH + H2 : (M = An alkali metal) Cathode : Na + + e - ¾¾¾ ® Na - amalgam
(b) Li has most negative E° but reacts less vigorous (c) For given metal DfH° always become less negative from
1
than Na which has least negative E°. fluoride to iodides. Anode : Cl- ® Cl2 + e -
+ – (d) MP/BP trend: fluoride > chloride > bromide > iodide. 2
(iii) Reactivity towards dihydrogen : 2M + H2 ® 2M H
m Salts of Oxo-Acids 2Na - amalgam + 2H2O ® 2NaOH + 2Hg + H2
(iv) Reactivity towards halogen
(a) Alkali metals react vigorously with halogens to form (a) Alkali metals form salt with all oxoacids NaOH is white crystalline deliquescent solid and readily
+ – (b) Their carbonates and hydrogen carbonates are highly soluble in water to give strong alkaline solutions.
ionic halide M X .
+ stable to heat except that of Li.
(b) Due to high polarisation capability of Li , lithium m Sodium Hydrogencarbonate (Baking Soda) NaHCO3
halides are somewhat covalent. LiI is most
3 ANOMALOUS PROPERTIES OF LITHIUM NaHCO3 is known as baking soda because it decomposes
covalent in nature due to bigger size of I–ion.
(v) Reducing nature m The anomalous behaviour of Li is due to the on heating to generate bubbles of CO2 to make cakes or
(a) Alkali metals are strong reducing agents. (i) Exceptionally small size, and (ii) High polarising power.
pastries fluffy. It is made by saturating a solution of Na2CO3
(b) Li is most and Na is least powerful reducing agent. m Li shows diagonal relationship to Mg.
(c) Dispite of high ionisation enthalpy, E° of Li is most with CO2.
negative due to its high hydration enthalpy. 4 SOME IMPORTANT COMPOUNDS OF SODIUM m Biological importance of sodium and potassium
(vi) Solution in Liquid ammonia m Sodium carbonate, Na2CO3 (washing soda) (i) Sodium ions are found primarily on outside of cells, in
(a) Alkali metals give deep blue solution when blood plasma and in the interstitial fluids which
(i) (a) Prepared by Solvay process
dissolved in liquid ammonia.
+ – 2NH3 + H2O + CO2 ® (NH4)2 CO3 surrounds the cell.
M + (x+y) NH3 ® [M(NH3)x] + [e(NH3)y] (Blue colour)
(b) The solutions are paramagnetic and on standing (NH4)2CO3 + H2O + CO2 ® 2NH4 HCO3 (ii) These ions participate in the transmission of nerve
NH4 HCO3 + NaCl ® NaHCO3 + NH4Cl signal, in regulating flow of water across cell membrane
slowly liberate H2 and form amide.
(c) In concentrated solution, the blue colour of solution NaHCO3 crystal separates out. These are heated to etc.
changes to bronze and becomes diamagnetic. give sodium carbonate. (iii) Potassium ions are most abundant within cell fluids.
40 The s-Block Elements NCERT Maps
5 GROUP 2 ELEMENTS : ALKALINE EARTH METALS 8 GENERAL CHARACTERISTICS OF COMPOUNDS OF m Calcium Hydroxide (Slaked lime), Ca(OH)2
m Except beryllium, group 2 elements are known as alkaline THE ALKALINE EARTH METALS
(i) It is white amorphous powder, sparingly soluble in
earth metals. Oxides and Hydroxides
m water. The aqueous solution is known as lime water and
m Atomic and Ionic Radii
(i) All oxides except BeO (amphoteric) are basic in nature suspension of slaked lime in water is known as milk of
(i) The atomic and ionic radii of group-2 elements are
and react with water to form sparingly soluble lime.
smaller than corresponding alkali metals.
(ii) Within group, atomic and ionic radii increases with hydroxides M(OH)2.
(ii) CO2 turns lime water milky due to the formation of
increase in atomic number. (ii) The solubility, thermal stability and basic character of
m Ionization Enthalpies hydroxides increase down the group however these are CaCO3 and on passing excess CO2, the precipitate
(i) Alkaline earth metals have low ionization enthalpies less basic and less stable than alkali metal hydroxides. dissolves to form Ca(HCO3)2.
due to fairly large size of atoms. (iii) Be(OH)2 is amphoteric.
st (iii) Milk of lime reacts with Cl2 to form hypochlorite.
(ii) The 1 ionization enthalpies of alkaline earth metal are –
nd Be(OH)2 + 2OH ® [Be(OH)4]2– (Beryllate ion)
greater than corresponding group 1 metals. The 2 2Ca(OH)2 + 2Cl2 ® CaCl2 + Ca(OCl)2 + 2H2O
Be(OH)2 + 2HCl + 2H2O ® [Be(OH)4]Cl2
ionization enthalpies of alkaline earth metals are (Bleaching powder)
smaller than corresponding alkali metals. m Halides
(i) Except Be all other halides of alkaline earth metals are 1
m Hydration enthalpies decrease down the group and are m Calcium Sulphate (Plaster of Paris) CaSO4 × HO
ionic. 2 2
larger than those of alkali metals.
(ii) BeCl2 has chain structure in solid state (i) It is a hemihydrate of CaSO4
6 PHYSICAL PROPERTIES Cl Cl (ii) Obtained on heating gypsum, CaSO4·2H2O at 393 K
Cl
(i) BP and MP are higher than alkali metals. Be Be Be
Cl Cl Cl 2(CaSO4·2H2O) D 2(CaSO4) × H2O + 3H2O
(ii) Ca, Sr and Ba give brick red, crimson and apple green
flame colour respectively. (iii) In vapour phase, BeCl2 is a dimer
(iii) Heating above 393 K form CaSO4 known as dead burnt
m Salts of oxo-acids plaster.
7 CHEMICAL PROPERTIES (i) Carbonates m Cement is an important building material
m Reactivity towards air and water (a) All are insoluble and solubility decreases down the
(i) Portland cement composition is
(i) Be and Mg are kinetically inert to oxygen and water group.
because of formation of oxide film on their surface. (b) Thermal stability increases down the group. CaO,50-60%; SiO2, 20-25%; Al2O3, 5-10%;
(ii) Powdered Be readily burns to give BeO and Be3N2 (ii) Sulphates MgO, 2-3%; Fe2O3 1-2% and SO3, 1-2%
(iii) Other elements give oxide and nitride. Solubility decreases down the group.
(ii) The ingredients of portland cement are dicalcium
m Reactivity towards halogens (iii) Nitrates
D All of them decompose on heating silicate (Ca2SiO4)26%, tricalcium silicate (Ca3SiO5)51%
(i) M + X2 ¾¾ ® MX2 : (X = F, Cl, Br, l)
2M(NO3)2 ® 2MO + 4NO2 + O2 and tricalcium aluminate (Ca3Al2O6)11%
D
(ii) (NH4 )2 BeF4 ¾¾ ® 2NH4F + BeF2 (M = Be, Mg, Ca, Sr, Ba) (iii) When cement is mixed with water the setting of cement
600 - 800 K
ˆˆˆˆˆˆˆˆ † takes place to give hard mass. The purpose of adding
(iii) BeO + C + Cl2 ‡ˆˆˆˆˆˆˆ ˆ BeCl2 + CO
9 SOME IMPORTANT COMPOUNDS OF CALCIUM gypsum is only to slow down the process of setting of
m Reactivity towards hydrogen
the cement.
All elements except Be combine with hydrogen to form m Calcium oxide or quicklime, CaO
hydrides, MH2 ; 2 BeCl2 + LiAlH4 ® 2BeH2 + LiCl + AlCl3 (i) Commercial method of preparation - heating limestone
10 BIOLOGICAL IMPORTANCE OF MAGNESIUM
m Reactivity towards Acids : M + 2HCl ® MCl2 + H2 in rotary kiln at 1070-1270 K.
AND CALCIUM
m Reducing nature (ii) It absorbs moisture and CO2 (i) All enzymes that utilize ATP in phosphate transfer require
(i) Be has least negative E° within group.
CaO + H2O ® Ca(OH)2 Mg as the cofactor.
m Solutions in liquid ammonia
(i) Alkaline earth metals give deep blue black colour CaO + CO2 ® CaCO3 (ii) Chlorophyll contains Mg.
solution with ammonia. (iii) Addition of limited amount of water breaks the lump of (iii) Calcium plays important roles in neuro muscular functions,
2+ –
M + (x + 2y)NH3 ® [M(NH3)x] + 2[e(NH3)y] lime. The process is called slaking of lime. blood coagulation etc.
The p-Block Elements
11
Chapter
1 THE p-BLOCK ELEMENTS m Physical Properties (2) Borax give alkaline solution in water
m General valence shell electronic configuration of p-block (i) Boron is hard and black coloured solid, exists in many Na2B4O7 + 7H2O ® 2NaOH + 4H3BO3
2
elements is ns np .
1–6 allotropic forms, high melting point due to strong (3) On heating, borax first loses water molecules
crystalline lattice. and swells up. On further heating turns into a
m Maximum oxidation states = total number of valence
electrons. (ii) Rest members are soft metals transparent liquid with solidifies into glass like
m The occurence of oxidation states two unit less than the (iii) Gallium has low melting point (303 K) and high boiling borax bead.
group oxidation states are sometime attributed to the poin (2676 K) D D
Na2B4O7 .10H2O Na2B4O7 2NaBO2 + B2O3
inert pair effect (iv) Density increases down the group
m The second period elements of p-groups are restricted to m Chemical Properties Metaborates of many transition metals have
a maximum covalence of four (using 2s and there 2p (i) B forms only covalent compounds. characteristic colour therefore borax bead test is
orbitals) (ii) In Ga, ln and Tl, both +1 and +3 oxidation states are used to detect metals.
m Third period elements of p-groups can expand their observed. Relative stability of +1 oxidation state : (ii) Orthoboric acid
covalence above four due to vacant 3d orbitals Al < Ga < ln < Tl (1) White crystalline solid with soapy touch,
m Only first member of group can form pp - pp multiple (iii) For Tl, + 1 is predominant and +3 oxidation state is sparingly soluble in water but highly soluble in
bonds to itself. The heavier elements do form p bonds but oxidising hot water.
this involves d-orbitals (dp - pp or dp – dp). (iv) Reactivity towards air (2) Na2B4O7 + 2HCl + 5H2O ® 2NaCl + 4B(OH)3
4E(s) + 3O2(g) D 2E2O3(s)
(3) Layer structure in which planar BO3 units are
2E(s) + N2(g) D 2EN(s) linked by H-bonds.
2 GROUP 13 ELEMENTS : THE BORON FAMILY
B2O3(Acidic), Al2O3 and Ga2O3 (Amphoteric) (4) H3BO3 monobasic Lewis acid not protonic acid.
m B (non-metal), Al (metal but shows many chemical
similarities to B) Ga, In, Tl, Nh (metal) ln2O3 and Tl2O3(Basic). – +
B(OH)3 + 2HOH ® [B(OH)4] + H3O
(v) Al dissolves in mineral acids and aqueous alkalies thus
m Boron mainly occurs as orthoboric acid (H3BO3), borax
shows amphoteric character
(Na2B4O7.10H2O) and kernite (Na2B4O7. 4H2O) –
(5) D D
10 11
2Al(s) + 6 HCl (aq) ® 2Al3+ (aq) + 6Cl (aq) + 3H2(g) H3BO3 HBO2 B2O3
m Boron has two isotopes B(19%) and B(81%) +
2Al(s) +2NaOH(aq) + 6H2O(l) ® 2Na [Al(OH)4] (aq) +
–
m Aluminium is the most abundant metal, Bauxite (iii) Diborane (B2H6)

3H2(g)
(Al 2 O 3 .2H 2 O) and cryolite (Na 3 AlF 6 ) are important (vi) Reactivity towards halogen (1) Preparation : 4BF3 + 3LiAlH4 ® 2B2H6 + 3LiF +
minerals of aluminium.
2 1 2E(s) + 3X2(g) ® 2EX3(s) (X = F, Cl, Br, I) 3AlF3
m Outer electronic configuration of boron family is ns np m Important Trends and Anomalous Properties of Boron
Atomic Radii (2) Lab method : 2NaBH4 + I2 ® B2H6 + 2NaI + H2
m (i) Tri-chlorides, bromides and iodides of all these
450 K
(i) B < Al > Ga < ln < Tl elements being covalent in nature are hydrolysed in (3) Industrial method : 2BF3 + 6NaH
(ii) Atomic radius of Ga is less than Al due to poor water. B2H6 + 6NaF
screening effect of 10d - electrons of Ga. (ii) Monomeric trihalides are electron deficient and strong
m Ionization Enthalpy Lewis acids. (4) Colourless, highly toxic gas, catches fire
(i) The decrease from B to Al is associated with increase (iii) Halides other than boron are dimerised through spontaneously in air
in size. halogen bridging.
m Some Important Compounds of Boron B2H6 + 3O2 ® B2O3 + 3H2O
(ii) The observed discontinuity between Al and Ga, and (5) Readily hydrolyse to give boric acid
between ln and Tl are due to inablity of d-and f- (i) Borax (Na2B4O7.10H2O) + –
electrons to cause screening effect. 2–
(1) Contains tetranuclear units [B4O5(OH)4] therefore (6) 3B2H6 + 6NH3 ® 3 [BH2(NH3)2] [BH4] D
m Electronegativity – First decreases from B to Al and then the correct formula is Na2[B4O5(OH)4]. 8H2O.
increases marginally. 2B3N3H6 + 12H2 (B3N3H6 inorganic benzene)
44 The p-Block Elements NCERT Maps
(7) m Chemical properties (ii) Carbon Dioxide (CO2)

H (i) Common oxidation states are + 4 and + 2, C also
H H (1) Lab preparation
exhibits negative oxidation states.
B B (ii) +4 oxidation state are generally covalent in nature CaCO3(s) + 2HCl (aq) ® CaCl2(aq) + CO2(g) +
H H Heavier elements show + 2 oxidation state. H2O(l)
H (iii) Halides of group 14 elements except carbon undergo
hydrolysis and have tendency to form complexes by (2) Colourless, odourless gas, low solubility in H2O,
Four terminal B – H are regular two centre-two electron
bonds while the two bridge (B – H – B) bonds are three accepting electron pairs from donor species. with water forms carbonic acid H2CO3(weak
centre-two electron bonds. dibasic acid)
(iv) Reactivity towards oxygen : (1) All members form –
(8) Lithium and sodium tetrahydridoborate also known as mainly two types of oxides MO and MO2. (3) H2CO3/HCO 3 buffer system helps to maintain pH
borohydrides of blood.
(2) CO2, SiO2, GeO2 are acidic and SnO2, PbO2 are
+ –
2 MH + B2H6 ® 2M [BH4] (M = Li or Na) amphoteric (4) C O 2 i s r e m o v e d f r o m a t m o s p h e r e b y
photosynthesis
(v) Reactivity towards water
(iii) Silicon Dioxide (SiO2): It resists the attack of halogens,
3 GROUP 14 ELEMENTS : THE CARBON FAMILY (1) C, Si and Ge are not affected by water, Tin
dihydrogen and most of the acids and metals even at
m
th
C, Si, Ge, Sn, Pb and Fl are 14 group elements. decomposes steam to form SnO2 and H2 elevated temperature. However it is attacked by HF
12 13 . + 2H2O
Sn
D
SnO2 + 2H2 and NaOH.
m C has two stable isotopes : C and C and radioactive
14 SiO2 + 2NaOH ® Na2SiO3 + H2O
isotope C (2) Pb is unaffected by H2O due to protective oxide film
formation SiO2 + 4HF ® SiF4 + 2H2O
m Ge exists only in traces, Sn as cassiterite (SnO2), Pb as
(vi) Reactivity towards halogen (iv) Silicones
galena (PbS)
2 2 (1) Form halides of formula MX2 and MX4. (1) ( R2SiO ) as a repeating unit.
m General valence shell electronic configuration ns np (2) Preparation
(2) Except C all other members react directly with
m Physical Properties Cu Powder
halogen 2CH3Cl + Si (CH3)2SiCl2
C and Si (Non-metals), Ge (metalloid), Sn and Pb (Metals) 570 K
(3) Most MX4 are covalent except SnF4 and PbF4
m Covalent Radius : Considerable increase in covalent
radius from C to Si, small increase thereatfer due to (4) PbI4 does not exist as energy released due to bond +2H2O
2 Polymerisation
completely filled d and f orbitals of heavier members. formation is not sufficient to unpair 6s electrons. Silicone (CH3)2Si(OH)2 – 2HCl
– H2O
m Electronegativity values from Si to Pb are almost same (5) GeX4 is more stable than GeX2 whereas PbX2 is The chain length of polymer can be controlled by
m Ionization Enthalpy: In general decreases down the more stable than PbX4 adding (CH3)3 SiCl
group, small decrease from Si to Ge to Sn and slight m Some Important compound of Carbon and Silicon (v) Silicates :
increase from Sn to Pb. (i) Carbon Monoxide (CO) (1) Silicates mineral like feldspar, Zeolites, mica etc.
m Anomalous Behaviour of Carbon
(1) Preparation exist in nature
(i) Maximum covalence = 4 473-1273 K
C(s) + H2O(g) CO(g) + H2(g) 4–
(ii) Order of catenation C > > Si > Ge » Sn, Pb does not (2) The basic structural unit of silicates is SiO4
(Water gas)
show catenation. (vi) Zeolites
1273 K
m Allotropes of Carbon 2C(s) + O2(g) + 4N2(g) 2CO(g) + 4N2(g)
(1) If aluminium atoms replace few silicon atoms in
3 (Producer gas )
(i) Diamond – sp hybridised, crystalline lattice three-dimensional network of silicondioxide,
(ii) Graphite – Layered structure (held by van der Waals (2) In CO molecule, there is one sigma and two p overall structure known as aluminosilicate
2
forces), sp hybridised, conducts bonds
(2) A type of zeolite ZSM-5 used to convert alcohols
electricity (3) CO is highly poisonous due to its ability to form a
directly into gasoline
complex with haemoglobin
(iii) Fullerenes
Organic Chemistry - Some Basic Principles 12
and Techniques Chapter
1 CLASSIFICATION OF ORGANIC COMPOUNDS (d) For branched alkyl groups, the carbon atom of the O
Organic Compounds branch that attaches to the root alkane is numbered (1) CH3 – C – CH2 – CH2 – CH2 – COOH
such as 6 5 4 3 2 1
4 3 2 1 5-Oxohexanoic acid
CH3 – CH – CH2 – CH – (1, 3-Dimethylbutyl) –
Acyclic or open chain Cyclic or closed chain 5 4 3 2 1 OH
O CH3 CH3 CH2 = CH – CH2 – CH – CH3 1 2
, (e) While writing the names of the substituents in OH Cyclohex-2-en-1-ol
3
alphabetical order, the prefixes iso and neo are Pent-4-en-2-ol
considered to be the part of fundamental name of alkyl NO2
Alicyclic compounds Aromatic compounds m Nomenclature of substituted
group but sec- and tert- are not considered to be the 4
3
part of fundamental name. benzene compounds
(f) If two chains are of equal size then that chain is to be 1 Cl
Homocyclic Heterocyclic Benzenoid Non-benzenoid 2
Cl
selected which contains more number of side chains 1
or carbocyclic compounds compounds compounds
2 4 6 8 10 4 CH3
compounds (non-aromatic) NH 3 5 7 9 O2N 2
NO2
2 3 2-Chloro-1-methyl
1 1-Chloro-2, 4-dinitrobenzene -4-nitrobenzene
, , O OMe NH2
O 1
1
2 Cl 2 CH
3
Heterocyclic aromatic
5-(2-Ethylbutyl)-3, 3-dimethyldecane
compounds 3 3
m Nomenclature of Cyclic Compounds 4 4
, CH3 C 2H 5
O N 1 2 (Alphabetic order of numbering) 2-Chloro-4-methylanisole 4-Ethyl-2-methylaniline
H 1-Methyl-3-propylcyclohexane
3
2 NOMENCLATURE m Nomenclature of organic compounds having functional 3 ISOMERISM
Abbreviation for alkyl groups groups(s)
m (a)Structural Isomerism
CH3 (a) The functional group present in the molecule is identified Compounds having the same molecular formula but
CH3
which determines the choice of appropriate suffix. different structures are classified as structural isomers.
CH3 – CH – CH3 – CH2 – CH – (b) The longest chain of carbon atoms containing the
H3 C CH2 – (i) Chain isomerism: Example, C5H12 represents three
CH3 functional group is numbered in such a way that the
chain isomers
Isopropyl – sec-Butyl – Isobutyl – functional group is attached at the carbon atom
CH3 CH3 possessing lowest possible number in the chain.
(c) The order of decreasing priority for some functional
H 3C – C – CH3 – C – CH2 – groups: Pentane 2-Methylbutane
CH3 CH3 –COOH, –SO3H, –COOR, –COCl, –CONH2, –CN, (2, 2-Dimethylpropane)
tert-Butyl – Neopentyl –
m Nomenclature of Branched Chain Alkanes: (Rules)
(a) Longest carbon chain is identified –HC = O, C = O, –OH, –NH2, C=C , –C º C– (ii) Position isomerism: Example, C3H8O represents
(b) Numbering is done so that branched carbon atoms get two alcohols
the lowest possible numbers O O
OH OH
(c) For two substituents present at equivalent positions, the CH3 – CH2 – C – CH2 – C – CH3
lower number is given to the one coming first in 6 5 4 3 2 1
alphabetical listing Hexane-2, 4-dione Propan-1-ol Propan-2-ol
48 Organic Chemistry - Some Basic Principles and Techniques NCERT Maps
(iii)F u n c t i o n a l g r o u p i s o m e r i s m : E x a m p l e , (ii) Homolytic cleavage: One of the electrons of the (iii) Resonance effect
C3H6O represents an aldehyde and a ketone shared pair in a covalent bond goes with each of m It is a permanent effect
O bonded atoms resulting in formation of free radicals. m It operates through p-bond(s)

m Free radicals : Stability order m It is of two types
CHO · · · ·
+R effect : Halogens, –OH, –OR, –OCOR, –NH2 etc.
propanone propanal CH 3 < CH 3 CH 2 < (CH 3 )2 CH < (CH 3 )3 C
–R effect : –COOH, –CHO, –CN, –NO2 etc.
(iv)Metamerism: (b) Nucleophiles and Electrophiles
(iv) Electromeric effect
It arises due to different alkyl chains on either m Nucleophiles: A reagent that brings an electron pair to
m It is a temporary effect
side of the functional group. the reactive site is called a nucleophile (Nu:)
– – m Organic compounds having multiple bond (a double
Example : CH3OC3H7 and C2H5OC2H5 are metamers. Examples: H2O, NH3, CH3O, SH or triple bond) show this effect in presence of
(b) Stereoisomerism m Electrophile : A reagent that takes away an electron attacking reagent
+
The compounds that have the same constitution pair from reactive site is called electrophile (E ) m It is of two types
+
and sequence of covalent bonds but differ in Example: AlCl3, BF3, NO2 , Cl
+
Positive electromeric effect (+E effect)
relative positions of their atoms or groups in space
are called stereoisomers. They are classified as (c) Electron Displacement Effects in Covalent Bonds + +
(i) Inductive effect C = C + H ¾® C – C
(i) Geometrical isomerism
m When covalent bond is formed between atoms of H
(ii) Optical isomerism
different electronegativity, the electron density is Negative electromeric effect (–E effect)
more towards the more electronegative atom.
4 FUNDAMENTAL CONCEPTS IN ORGANIC – –
m It operates through s-bonds C = C + CN ¾® C – C
REACTION MECHANISM
m The inductive effect is related to the ability of CN
Attacking
reagent substituent(s) to either withdraw or donate electron (v) Hyperconjugation
Organic molecule [Intermediate] ® Byproduct(s)
(Substrate) density to the attached carbon atom.
m It involves delocalisation of s electrons of C – H bond
m It is a permanent effect
Product(s) of an alkyl group directly attached to an atom of
m It is of two types
(a) Fission of Covalent bond unsaturated system or to an atom with an unshared
(i) Heterolytic cleavage and (ii) Homolytic cleavage +I effect : e.g. –CH3, –CH2CH3 etc. p orbital
(i) Heterolytic cleavage –I effect : e.g. –NO2, –CN, –CHO, –COOH etc. H H H
+
H H H H H
In heterolytic cleavage, the bond breaks in such a (ii) Resonance structures +
fashion that the shared pair of electrons remains with H–C–C+«H–C=C«H C=C«H–C=C
m Benzene can be represented by energetically
one of the fragments. H
+
H
m Carbocations:
identical structures (I) and (II) called resonance H H H H H H
l A species having a carbon atom possessing structures. m It is a permanent effect.
sextet of electrons and a positive charge is called 6 6
carbocation. 1 5 1 5
5 METHODS OF PURIFICATION OF
l Alkyl groups directly attached to the positively 2 4 2 4 ORGANIC COMPOUNDS
charged carbon stabilise the carbocations due to 3 3
inductive and hyperconjugation effects. The common techniques used for purification:
(I) (II)
(i) Sublimation (ii) Crystallisation
· Stability order:
+ + + +
m Actual structure is resonance hybrid of (I) and (II) (iii) Distillation : It is used to separate
(CH3 )3C > (CH3 )2CH > CH3CH2 > CH3 m The resonance structures (canonical structures) are (a) Volatile liquids from non-volatile impurities.
m Carbanions: hypothetical and individually do not represent any (b) The liquids having sufficient difference in boiling points
l A carbon species carrying a negative charge on real molecule. e.g. mixture of chloroform (b.p. 334 K) and aniline
carbon atom is called carbanion. (b.p. 457 K) is separated by this method.
m The energy of actual structure of the molecule is
3 (c) Distillation can be achieved by three different ways
l Carbon in carbanion is generally sp hybridised lower than that of any of the canonical structures. m Fractional Distillation: This is applicable if boiling
and its structure is distorted tetrahedral. m The difference in energy between the actual points of two liquids is not much, e.g. this is
· Stability order: structure and the lowest energy resonance structure applicable to separate different fractions of crude oil
CH3 > CH3CH2 > (CH3 )2 CH > (CH3 )3 C is called the resonance energy. in petroleum industry.
NCERT Maps Organic Chemistry - Some Basic Principles and Techniques 49
m Steam Distillation: This technique is applied to (A) Test for nitrogen Let mass of organic compound = m g
separate substances which are steam volatile and – 2+ 4–
Volume of H2SO4 of molarity M needed for neutralisation
6CN + Fe ® [Fe(CN)6]
are immiscible with water. of ammonia produced = V mL
Example: Aniline is separated by this technique 4– 2
3[Fe(CN)6] + 4Fe ¾¾¾¾
3+ xH O
® Fe4 [Fe(CN)6]3 × xH2O
from aniline water mixture. (Prussian blue) V ´ 2M ´ 1.4
m Distillation under reduced pressure: This % of nitrogen =
(B) Test of Sulphur m
method is used to purify liquids having very high 2– 2+
boiling points and those, which decompose at or (i) S + Pb ® PbS (black)
m Kjeldahl’s method is not applicable to compounds
below their boiling points. (ii) S2- + [Fe(CN)5 NO]2 - ® [Fe(CN)5 NOS]4 - containing nitrogen in nitro and azo groups and nitrogen
Example: Glycerol can be separated from spent-lye Nitroprusside Violet present in ring (e.g. pyridine).
in soap industry by using this technique.
In case, nitrogen and sulphur both are present, sodium (B) Halogens
(iv) Differential Extraction:
thiocyanate is formed Carius method:
m When an organic compound is present in an aqueous
Na + C + N + S ® NaSCN
medium, it is separated by shaking it with an organic Fum ing HNO 3
solvent in which it is more soluble than in water. 3+ 2+ Organic compound ¾¾ ¾ ¾ ¾ ¾® AgX ¯
Fe + SCN ® [Fe(SCN)] (Blood red) AgNO D 3
m The organic solvent and the aqueous solution should be

immiscible with each other. (C) Test of Halogen Let mass of compound = m g
– +
m They form distinct layer which can be separated by X + Ag ® AgX
Mass of AgX formed = m1 g
separatory funnel. m A white precipitate, soluble in NH4OH shows presence of
m The compound is obtained by evaporating the organic
chlorine. atom ic m ass of X ´ m 1 ´ 100
solvent. % of halogen = %
m A yellowish precipitate soluble, sparingly soluble in m olecular m ass of Ag X ´ m
(v) Chromatography: It is an important technique extensively
NH4OH shows presence of Br
used to separate mixtures into their components.
A yellow precipitate insoluble in NH4OH shows presence (C) Sulphur
Based on the principle involved it is classified into two main m
categories. of iodine Carius method:

(a) Adsorption chromatography and (D) Test of Phosphorus Organic Na2O2 BaCl2
(b) Partition chromatography Na2O2 HNO3 compound ¾¾¾¾ ® H2SO4 ¾¾¾¾ ® BaSO 4 ¯
(a) Adsorption Chromatography: It is based on the fact Compound Na3PO4 H3PO4
that different compounds are adsorbed on an (NH4)2 MoO4 Let mass of compound = m g
(NH4)3PO4 × 12 MoO3
adsorbent to different degrees. Commonly used
adsorbents are silica gel and alumina. It is of two types
(Yellow ppt) Mass of BaSO4 = m1 g
l Column chromatography
l Thin layer chromatography
7 QUANTITATIVE ANALYSIS 32 ´ m1 ´ 100
% of sulphur = %
(b) Partition Chromatography: It is based on continuous (A) Nitrogen is estimated by Dumas and Kjeldahl's method 233 ´ m
differential partitioning of components of a mixture
(i) Dumas method (D) Phosphorus
between stationary and mobile phases. Paper
chromatography is a type of partition chromatography. Let volume of nitrogen at STP = V mL
Mass of organic compound = m g Organic Fuming (NH4)2MoO4
H3PO4 (NH4)3PO4 × 12MoO3 ¯
compound HNO3
6 QUALITATIVE ANALYSIS OF
ORGANIC COMPOUNDS 28 ´ V ´ 100
Percentage of nitrogen = Let mass of compound = m g
22400 ´ m
Nitrogen, sulphur, halogens and phosphorus present in an
organic compound are detected by Lassaigne's test. The Mass of (NH4)3 PO4 × 12MoO3 = m1 g
(ii) Kjeldahl's Method
elements present in the compound are converted from covalent
Molar mass of (NH4)3PO4 × 12MoO3 = 1877 g
form into the ionic form by fusing compound with sodium metal. Organic compound + H2SO4 ® (NH4)2SO4
D
Na + C + N ¾¾® NaCN NaOH 31 ´ m1 ´ 100
D D H2SO4 % of P = %
2Na + S ¾¾® Na2S ; Na + X ¾¾® NaX (X = Cl, Br or I) (NH4)2SO4 NH3 1877 ´ m
Hydrocarbons
13
Chapter
1 AlKANES m Physical Properties (vii) Pyrolysis Preparation
C6H12+ H2 m
General formula (CnH2n + 2) Isomeric alkanes having more branching 773 K (i) From alkynes
m C6H14 C4H8+ C2H6 R R¢
has lower boiling point.
m Alkanes show structural isomerism C3H6+ C2H2 + CH4 Pd/C
m Chemical properties (a) RC CR¢ C C (cis)
m Conformations: BaSO4
m C6H14 has got five structural isomers (i) Substitution reaction Alkanes show conformational isomerism H H
whereas C7H16 has nine. CH4 + Cl2
hn
CH3Cl + HCl due to C – C bond rotation as is seen in
ethane. H R¢
m Preparation Na
m Rate of reaction of alkanes with halogens is m Ethane molecule (C2H6) contains a carbon- (b) RC CR¢ C C¢ (trans)
(i) Hydrogenation Liq.NH3
F2 > Cl2 > Br2 > I2 carbon single bond.
Pt/Pd/Ni (ii) From alkyl halides R H
CH2 = CH2 + H2 CH3 – CH3 m C – C bond results into infinite number of
m Rate of replacement of hydrogens of alkanes is : spatial arrangements of hydrogen atoms alc./KOH
(ii) From alkyl halides 3º > 2º > 1º CH3 – CH2 – Cl D CH2 = CH2
attached to one carbon atom with respect to
(a) Reduction of alkyl halides (ii) Combustion the hydrogen atoms attached to the other m The reaction is called b-elimination
Zn CH4(g) + 2O2(g) ® CO2(g)+ 2H2O(l) carbon atom. m It is observed that for halogens, the rate
CH3 – Cl + H2 + CH4 m These are called conformational isomers
H is : iodine > bromine > chlorine
(b) Wurtz reaction One such conformation in which hydrogen
CnH2n+2 + 3n + 1 O2 ® nCO2 + (n + 1)H2O
m
dry ether atoms attached to two carbons are as m The rate for alkyl groups is : tert >
2CH3Br + 2Na CH3 – CH3 2 secondary > primary
closed together as possible is called
It is used for the preparation of higher eclipsed conformation. (iii) From vicinal dihalides
alkanes containing even number of (iii) Controlled oxidation
m The conformation in which hydrogens are
carbon atoms. Cu/523 K
as far apart as possible is known as Zn
(a) 2CH4 + O2 2CH3OH CH2 – CH2 CH2 CH2
100 atm
(iii) From carboxylic acids staggered conformation.
Mo2O3
(b) CH4 + O2 CH3OH + H2O m Any other intermediate conformation is Br Br
(a) Decarboxylation D called skew conformation.
CH3COO Na
– + Soda lime
CH4 + Na2CO3 (CH3COO)2Mn H m Chemical Properties
D (c) 2CH3CH3 + 3O2 D H HH H
(b) Kolbe’s electrolytic method H (I) Addition of dihydrogen
H H Pd
RCH CH2 R – CH2 – CH3
– + Electrolysis 2CH3COOH + 2H2O H H H H H2
2CH3COO Na (aq) CH3 – CH3 (i) Eclipsed form (ii) Staggered form
KMnO4 (ii) Addition of halogens
(d) (CH3)3CH (CH3)3COH Br2
m Reaction at anode: 2 AlKENES CH2 = CH2 CCl4
CH2 – CH2
O O (iv) Isomerisation
– –2e
– m General formula (CnH2n ) Br Br
2CH3– C – O 2CH3– C – O m The reddish orange colour of bromine
anhy./AlCl3 m Alkenes show structural isomerism
HCl
+ solution in CCl4 is discharged when Br2
CH2 = CH – CH2 – CH3 CH2 = C – CH3 adds to unsaturation site. this is test for
CH3 – CH3 2CH3 + 2CO2 (i)
(v) Aromatisation CH3 unsaturation.
m Reaction at cathode: CH3 – CH = CH – CH3 (iii) Addition of hydrogen halides
Cr2O3 or V2O5 or Mo2O3 (ii) (iii)
– –
H2O + e OH + H 773 K; 10-20 atm m Alkenes show geometrical isomerism (a) Markovnikov’s reaction
H HBr
2H H2 (vi) Reaction with steam R – CH2 = CH2 R – CH – CH3
cis-But-2-ene & trans-But-2-ene
Ni
m Methane cannot the prepared by this CH4 + H2O CO + 3H2 H H H Br
1273 K
method are geometrical isomers (Major)
54 Hydrocarbons NCERT Maps
(b) Anti Markovnikov addition m Chemical Properties m Chemical Properties

HBr (i) Acidic character m Electrophilic substitution reaction
CH3 – CH = CH2 (C H CO) O CH3CH2CH2Br
CH3 – C º CH + Na ® CH3 – C º C Na + 1 H2
– +
6 5 2 2
(Major) 2 (i) Halogenation (ii) Nitration
Acidity order of some hydrocarbons : Cl NO2
m Peroxide effect is not observed in addition of HCl and HI
HC º CH > CH2 = CH2 > CH3 – CH3 anhyd. Conc. HNO3
(a) + Cl2
(iv) Addition of H2SO4 AlCl3 Conc. H2SO4
HC º CH > CH3 – C º CH >> CH3 – C º C – CH3
(ii) Addition reactions Cl
H2SO4 Cl Cl
CH3 – CH = CH2 CH3 – CH – CH3 (a) Addition of dihydrogen anh.
(b) + 6Cl2 AlCl
dark, cold Cl
3
Cl
(v) Addition of H2O SO3H R – C º CH + 2H2 Pd RCH2CH3 Cl
(b) Addition of halogens
H
+
Br Br (iii) Sulphonation (iv) Friedel-Crafts alkylation
+ H2 O 2-methylpropan-2-ol Br2 SO3H C2H5
OH CH3 – C º CH CH3 – C – CH
(Major) D
+ H2SO4(SO3) + H2O anhyd.
(vi) Oxidation reaction Br Br + C2H5Cl AlCl3
Reddish orange colour of the solution of bromine in fuming D
dil KMnO4
(a) CH2 = CH2 273K CH2 – CH2 CCl4 is decolourised.
(v) Friedel-Crafts acylation COCH3
(c) Addition of hydrogen halides
OH OH anhyd.
Cold, dilute, aqueous solution of KMnO4 is called + CH3COCl
Baeyer’s reagent CH º CH HBr [CH2 = CH – Br] HBr AlCl3
D
CH3 – CHBr2 m Mechanism of electrophilic substitution reaction

Decolorisation of KMnO4 solution is used as a test of Halogenation
(d) Addition of water
unsaturation. Step-I Step-II H Cl
KMnO4 H 2O Tautomerism
(b) CH3CH = CHCH3 + 2CH3COOH CH3C º CH 2+ + CH3–C=CH2 Cl – Cl + AlCl3 Cl + [AlCl4]
–
H Hg /H + Cl ® (s Complex)
(e) Polymerisation O–H CH3 – C – CH3 Step-III
(vii) Ozonolysis
O H Cl Cl
(i) O3 Red hot
O + HCHO 3CH º CH Fe tube 873 K
(ii) Zn/H2O
(vii) Polymerisation
4 AROMATIC HYDROCARBON
High T/P m Addition reactions Cl
nCH2 = CH2
Catalyst
( CH2 – CH2)n m Species which is cyclic, planar having delocalised p
Polythene electrons and follow’s Huckel’s (4n + 2)p rule is 3H2 UV Cl Cl
(i) (ii) + 3Cl2
aromatic. n is an integer (n = 0, 1, 2...) Ni/D 500 K
Cl Cl
3 ALKYNES m Combustion Cl (BHC)
m General formula (CnH2n–2) C6H6 + 15 O2 ® 6CO2+3H2O
2
(i) (ii) (iii) (iv) (v)
Preparation y y
(i) CaC2 + 2H2O ® C2H2 + Ca(OH)2 C xH y + x + O2 ® xCO2+ 4 H2O
are aromatic species 4
(ii) CH2 – CH2 m Preparation of benzene m Directive influence of function group towards EAS reaction:
alc./KOH
D CH2 = CH – Br COONa OH o/p directing groups : – OH, – NH2, – NHR, – NHCOCH3, – OCH3,
Br Br
NaNH2 CaO Zn –CH3, – C2H5 etc.
(i) + NaOH D
(ii) D
CH º CH Meta directing groups : – NO2, – CN, – CHO, – COR, – COOH,
–COOR, – SO3H etc.
Environmental Chemistry
14
Chapter
1 ENVIRONMENTAL POLLUTION 3 GLOBAL WARMING AND GREEN HOUSE EFFECT
m It is effect of undesirable changes in our surroundings that have harmful effects on m About 75% of the solar energy reaching the earth is absorbed by the earth surface, which
plants, animals and human beings. increases its temperature.
m Green house gases: CO2, CH4, O3, CFCs, H2O vapour, N2O, O3.
2 ATMOSPHERIC POLLUTION
m CO2 molecules trap heat as they are transparent to sunlight but not to the heat radiation.
m It is studied as tropospheric and stratospheric pollution.
m CO2 is the major contributor to global warming.
m Troposphere extends to the height of ~10 km from sea level.
m Stratosphere lies between 10 and 50 km above sea level. It contains N2, O2, O3 and 4 ACID RAIN
little H2O vapour. The presence of O3 in it prevents about 99.5% of sun's harmful UV m When the pH of rain water drops below 5.6, it is called acid rain.
radiations from reaching earth's surface.
m Oxide of S, N and C causes acid rain.
m Tropospheric pollution is due to gaseous air pollutants and particulate pollutants.
m The Taj Mahal is being slowly disfigured and marble is getting discoloured and lustreless due to
(i) Gaseous air pollutants
acid rain. The acid rain reacts with marble, CaCO3 of Taj Mahal.
l SO2 which causes respiratory diseases, irritation to eyes resulting in tears and
redness. CaCO3 + H2SO4 ® CaSO4 + H2O + CO2
l Due to burning of fossil fuel in automobile engine, NO and NO2 are produced.
5 SMOG
l The irritant red haze in the traffic and congested places is due to oxides of
nitrogen. m It is mixture of smoke and fog.
m Classical smog is mixture of smoke, fog and SO2, occurs in cool humid climate. It is a reducing
l NO2 is lung irritant.
mixture.
l Hydrocarbons are carcinogenic. m Photochemical smog results from action of sunlight on unsaturated hydrocarbons and
l CO is highly poisonous and produced as a result of incomplete combustion of nitrogen oxides. It occurs in warm, dry and sunny climate. Its main components are O3, NO,
carbon.
acrolein, HCHO and PAN. It is called oxidising smog.
l CO binds to Haemoglobin to form carboxy haemoglobin, which is about 300
times more stable than the oxygen-haemoglobin complex.
l The effect of particulate pollutants are largely dependent on the particle size.
l High level of CO in blood may induce premature birth and deformed babies.
l Lead used to be a major air pollutant emitted by vehicles.
l CO2 is released in atmosphere by respiration, burning of fossil fuel and also
during volcanic eruptions. m Stratospheric pollution is due to the depletion of protective ozone layer. CFCs combine with
ozone and damage ozone layer.
l Increased amount of CO2 in the air is mainly responsible for global warming.
· ·
UV
(ii) Particulate pollutants CF2Cl2 (g) ¾¾¾ ® Cl(g) + CF2Cl(g)
l These are minute solid particles or liquid droplets in air. · ·
l Viable particulates: Bacteria, fungi, moulds, algae etc. Cl(g) + O3 (g) ¾¾® ClO(g) + O2 (g)
l Non-viable particulates: Cigarette smoke, Dust, Sand, Cement, fly ash, · ·
Sulphuric acid mist, fume particles etc. ClO(g) + O(g) ¾¾® Cl(g) + O2 (g)
NCERT Maps Environmental Chemistry 59
6 WATER POLLUTION 8 INDUSTRIAL WASTE
(i) Pathogens: Bacteria and other organisms that l The process in which nutrient enriched water bodies support a m Biodegradable waste: It is generated by cotton mills,
enter water from domestic sewage and animal dense plant population, which kills animal life by depriving it of paper mills and textile factories.
excreta. Human excreta contain bacteria such as oxygen and results in subsequent loss of biodiversity is known as m Non-Biodegradable waste: It is generated by thermal
Escherichia coli and streptococcus faecalis Eutrophication. power plants, iron and steel plants etc.
which cause gastrointestinal diseases. l International standards for drinking water. m Now a days, fly ash and slag from steel industry are
(ii) Organic waste: Leaves, Grass, Trash, Excessive (1) Fluoride: Its deficiency causes tooth decay. It makes utilised by the cement industry.
phytoplankton growth etc. enamel on tooth much harder by converting [3 Ca3(PO4)2 × m Fuel obtained from plastic waste has high octane rating.
l If the concentration of dissolved oxygen (DO) in Ca(OH)2] into [3 Ca3(PO4)2 × CaF2]. It contains no lead and is known as “green fuel”.
water is below 6 ppm, the growth of fish gets –
F ion concentration above 2 ppm causes brown mottling of
inhibited. 9 WASTE MANAGEMENT
teeth.
l The amount of oxygen required by bacteria to The improper disposal of wastes is one of the major
(2) Lead: Upper limit of lead in drinking water is 50 ppb. m
break down the organic matter present in a causes of environmental degradation. Therefore the
(3) Sulphate: Excessive sulphate (>500 ppm) in drinking water
certain volume of a sample of water is called management of wastes is of utmost importance.
causes laxative effect.
Biochemical Oxygen Demand (BOD).
(4) Nitrate: Upper limit of nitrate in drinking water is 50 ppm. m Two programmes are being implemented
l The amount of BOD in the water is a measure of Excess of it causes diseases such as methemoglobinemia
the amount of organic material in the water. Swatchh Bharat Mission - Urban (SBM - U)
(‘blue baby’ syndrome)
Clean water would have BOD value of less than Swatchh Bharat Mission - Gramin (SBM - G)
l (5) Other metals:
5 ppm whereas highly polluted water could have
a BOD value of 17 ppm or more. Metal Fe Mn Al Cu Zn Cd 10 GREEN CHEMISTRY
(iii) Chemical Pollutants:
Maximum m It is a way of thinking and it about utilising the existing
l Water soluble inorganic chemicals such as Cd, Concentration 0.2 0.05 0.2 3.0 5.0 0.005 knowledge and principles of chemistry and other
Hg, Ni etc. These metals can damage kidneys, (ppm) sciences to reduce the adverse impact on environment.
central nervous system, liver etc. m Tetrachloroethene (Cl2C = CCl2), was earlier used as
l NaCl and CaCl2 are used to melt snow and ice in solvent for dry cleaning and is also a suspected
the colder climates. 7 SOIL POLLUTION carcinogen. Now, liquefied CO 2 with a suitable
detergent is used.
l Petroleum products pollute many sources of m Insecticides, pesticides and herbicides cause soil pollution. m Chlorine gas was used earlier for bleaching paper.
water e.g. major oil spills in oceans.
m Prior to World War II, nicotine were used as pest controlling These days, H2O2 with suitable catalyst is used.
l Pesticides that drift down from sprays or runoff substance for major crops. m Ethanal is prepared commercially by one step oxidation
from lands.
m After the World War II, DDT was used in various crop diseases. of ethene.
l Polychlorinated biphenyls (PCBs) which are Catalyst
m Pesticides are basically synthetic toxic chemicals with CH2 = CH2 + O2 ¾¾¾¾¾¾¾¾® CH3CHO (90%)
used as cleansing solvent, detergents and Pd(II)/Cu(II) (in water )
ecological repercussions.
fertilizers. PCBs are suspected to be
m As insect resistance of DDT increased, other organic toxins m Kernel of tamarind seeds has been found to be effective
carcinogenic. to make waste water clean.
such as Aldrin and Dieldrin were introduced.
l Fertilizers contain phosphates. The addition of m Green chemistry is a cost effective approach which
phosphates in water enhances algae growth, m These days herbicides such as NaClO3 and Na3AsO3 have involves reduction in material, energy consumption and
which reduces oxygen concentration in water. more attention. Some herbicides cause birth defects. waste generation.
1
The Solid State Chapter
1 CLASSIFICATION BASED ON CRYSTAL LATTICE
Crystalline Solids 2 CRYSTAL LATTICE AND UNIT CELL Amorphous Solids

m True solids m Pseudo solids or super cooled liquids
m Long range order m Short range order
m Have definite pattern of arrangement of particles m Do not have a definite pattern of arrangement of
Primitive Unit Cells Non-Primitive Unit Cells
m Anisotropic particles
m eg. NaCl, Solid SO2
m Constituent particles are present m Constituent particles are present m Isotropic
m Are categorised according to intermolecular forces, only at the corner of unit cell at corner as well as body-centre or m eg. rubber, glass
into Ionic, Metallic, Molecular and Covalent solids m 7 types of Primitive unit cells with face centre.
14 Bravis lattices
ZM
3 CUBIC SYSTEM Density =
3 5 NON-STOICHIOMETRIC DEFECTS
NA a
m Metal excess defect :
(i) Arises due to anionic vacancies, leaving a hole which is occupied by an electrons thus maintaining
Type Position of Z CN Relation of Packing
electrical neutrality. The anionic sites, occupied by unpaired electrons known as F-centre and impart
atoms r, d, a efficiency
colour to the crystal. eg : NaCl with Na vapour impart yellow colour.
6 d a 52.4% (ii) Arises due to presence of extra cations at interstitial sites. e.g. on heating ZnO loses oxgen and
Simple Corner 1 r= =
8× =1 2 2
8 2+
cubic excess Zn move to interstitial sties.
d m Metal deficiency defect : Arises when metal shows variable valency. The defect occurs due to missing
1 8 3a 68%
BCC Corner and r= =
8× +1=2 4 a cation from its lattice site and the loss of positive charge is made up by the presence of the cation having
Body centre 8 2
higher charge in the adjacent lattice site eg. FeO is found with composition of Fe0.95O
1 1 d a
FCC Corner and 8× +6× =4 12 r= = 74%
8 2 2 2 2 6 IMPURITY DEFECTS
face centre
Na+ Cl– Na+ Cl–
m When molten NaCl containing a little amount of SrCl2 is crystallised,
4 TYPE OF DEFECTS some sites of Na+ are occupied by Sr2+ . Each Sr2+ replaces two Na+ ions. Cl– Sr2+ Cl– Na+
m Another similar example is the solid solution of CaCl2 and AgCl.

Cl– Na+ Cl–
7 STOICHIOMETRIC DEFECTS
(Intrinsic or thermodynamic defect)
9 FRENKEL DEFECT
8 SCHOTTKY DEFECT m Due to dislocation of ions (usually cations) from the lattice sites
+ – + – + – + –
and occupy interstitial sites.
m It is due to equal number of cations and anions are missing from lattice sites. – – + – + –
m Has no effect on density +
m It results in decrease of density of crystal m Found in crystals with large difference in size of ions. + – + –
+ – +
m It is found in crystals having almost similar size of cation and anion eg. NaCl, KCl, AgBr etc. m eg: AgCl, ZnS, AgBr etc.
64 The Solid State NCERT Maps
10 CLOSE PACKING
m In one dimension : Co-ordination number (CN) = 2 m In fcc unit cell, two tetrahedral voids are present on each body diagonal and
m In two dimension : (a) AAA type : Square close packing have CN = 4 octahedral voids are present on body centre and on each edge centres.
(b) ABAB type : hexagonal close packing have CN = 6
Voids in fcc lattice : if N atoms in lattice
m In three dimension :(a) AAA type : simple cubic lattice have CN = 6
(b) ABAB type : hcp lattice have CN = 12 m Tetrahedral voids = N
(c) ABCABC type : fcc lattice have CN = 12 m Octahedral voids = 2N
11 CLASSIFICATION OF SOLIDS
12 Based on Electrical Properties 13 Based on Magnetic Properties
m Conductors : Conductivity 104 – 107 ohm–1 m–1

m Paramagnetic substance : Which are weakly attracted by external magnetic field
m Insulators : Conductivity 10–20 – 10–10 ohm–1 m–1
m Semiconductors : Conductivity 10–6 – 104 ohm–1 m–1 eg.: O2, Cu2+ etc.
m Diamagnetic substances : Which are weakly repelled by external magnetic field :
eg.: NaCl, H2O etc.

Semiconductors : When the energy gap between the valence band
and conduction band is small eg.: Si, Ge m Ferromagnetic substances : substance which show permanent magnetism even
in the absence of external magnetic field. eg Ni, Fe, Co, CrO2 etc.
n-type semiconductor : When Si is dopped with P or As.

m Antiferromagnetic substances, which have zero net dipole moment even
though they have large number of unpaired electrons eg. MnO

p-type semiconductors : When Si is dopped B or Al.
m Ferrimagnetic substances : Which posses very small net magnetic moment even
l Diode is a combination of n-type and p-type semicoductors
through they have very large number of unpaired electrons eg. Fe3O4, MgFe2O4.
and used as a rectifier.
These substance lose ferrimagnetism on heating and become paramagnetic.
l VO, VO2, VO3 and TiO3 show metallic or insulating properties
depending on temperature.
2
Solutions Chapter
1 EXPRESSING CONCENTRATION OF SOLUTIONS 4 RAOULT'S LAW 6 COLLIGATIVE PROPERTIES
Mass of a component For non-volatile solute in volatile solvent o
m Mass percentage (w/w) = × 100 m p 1 – p1
o Relative lowering of vapour pressure :
Mass of solution psolution = p solvent xsolvent m o = xsolute
p1
Volume of a component m For volatile liquids: 0
m Volume percentage (v/v) = × 100 o o o o o m Elevation in boiling point: DTb = Tb – Tb = Kbm
Total volume of solution ptotal = p1 + p2 = p1 x1 + p2 x2 = p 1 + (p 2 – p 1 )x2
2
m Mole fraction of any component in vapour phase: R × M1 × Tb
Mass of solute Where, Kb =
m Mass by volume percentage (w/v) = × 100 y1 = p1/ptotal 1000 × DvapH
Volume of solution
0
5 TYPE OF SOLUTIONS m Depression in freezing point: DTf = Tf – Tf = Kfm
Mass of solute 6 2
m Parts per million (ppm) = × 10 m Ideal solutions: A – B interactions are of same R × M1 × Tf
Mass of solution Where, Kf =
magnitude as A – A and B – B interactions. DVmix = 0 and 1000 × DfusH
Mole of a component
m Mole fraction (X) = DHmix = 0 n
Total moles of all components m Osmotic pressure:p = CRT = RT
eg.: n-hexane and n-heptane, bromoethane and v
Moles of solute chloroethane. m Osmotic pressure method is widely used to determine
m Molarity (M) =
Volume of solution (l) m Non-ideal solutions: A – B interactions are of different molar mass of proteins, polymers.
magnitude than A – A and B – B interactions. DVmix ¹ 0 m Isotonic solution have same osmotic pressure.
Mass of solute
m Molality (m) = m Osmotic pressure associated with the fluid inside the
Mass of solvent (kg) and DHmix ¹ 0.
blood cell is equivalent to 0.9% (mass/vol) of NaCl solution.
m (+)ve deviations: A – B interactions are weaker than
m Solubility of a substance is its maximum amount that can be
dissolved in a specified amount of solvent at a specified A – A and B – B interactions. 7 van't Hoff FACTOR AND ITS SIGNIFICANCE
temperature. Observed value of colligative property
l DHmix > 0, DVmix > 0, Pobs > Pcal i=
Calculated value of colligative property
2 SOLUBILITY OF A SOLID IN A LIQUID l eg: acetone + ethanol, Normal molar mass
Significantly affected by temperature change. m (–)ve deviations: A – B interactions are stronger than =
m Abnormal molar mass
m Pressure does not have any significant effect. A – A and B – B interactions. m For normal solute (i = 1)
m For association, i < 1

l DHmix < 0, DVmix < 0, Pobs < Pcal
3 SOLUBILITY OF A GAS IN A LIQUID m For dissociation, i > 1
l eg: nitric acid + water, chloroform + acetone
m Henry's law: p = KHx m Azeotropes: constant boiling mixtures whose 8 MODIFIED COLLIGATIVE PROPERTIES
o
m Decreases with increase in temperature. composition does not change on distillation. p – p1
1 in2
Increases with increase in pressure.
m
o =
m
p1 n1
m Minimum boiling azeotrope: 95% C2H5OH and 5%
m The air tanks of scuba divers are diluted with He to avoid
H2O by volume m DTb = iKbm
bends.
m To increase the solubility of CO2 in soft drinks and soda water, m Maximum boiling azeotrope: 68% HNO3 and 32% H2O m DTf = iKfm
the bottle is sealed under high pressure. by mass
m p = iCRT
Electrochemistry
3
Chapter
1 TYPE OF CELLS 4 NERNST EQUATION 6 ELECTROCHEMICAL SERIES

m Electrochemical cell : Device used to convert chemical m
n+
For the reaction : M + ne ¾® M– m A negative E° means that the redox couple is stronger
energy of a redox reaction into electrical energy. It is also reducing agent than the H+/H2 couple.
RT [M]
known as galvanic cell. E = E° - ln m A positive E° means that the redox couple is a weaker
nF [Mn + ]
reducing agent than the H+/H2 couple.
m Electrolytic cell : Device which uses electricity to bring 0.0591 1 Oxidised form Reduced form E°/V
about a non-spontaneous redox reaction. E = E° - log n +
n [M ] F2(g) + 2e– ® 2F– 2.87
ne - Co3+ + e– ® Co2+ 1.81
2 DANIELL CELL
m For the reaction : aA + bB ¾¾¾ ® cC + dD Cl2(g) + 2e– ® 2Cl– 1.36
2+ 2+
RT [C]c [D]d O2(g)+ 4H+ + 4e– ® 2H2O 1.23
Increasing Strength of Oxidising Agent

m Cell reaction : Zn(s) + Cu (aq.) ¾® Zn (aq.) + Cu(s) Ecell = E°cell - ln
nF [A]a [B]b Br2 + 2e– ® 2Br– 1.09
m When external opposite potential is applied to the cell in Ag+ + e– ® Ag(s) 0.80
standard state m For a reaction at equilibrium, Ecell = 0. Fe3+ + e– ® Fe2+ 0.77
(a) Eext = 1.1 V, no flow of electrons. 2.303 RT 0.0591 O2(g) + 2H+ + 2e– ® H2O2 0.68
m E°cell = log K C = log K C I2 + 2e– ® 2I
–
0.54
(b) Eext > 1.1 V, electrons flow from Cu rod to Zn rod. nF n
Cu2+ + 2e– ® Cu(s) 0.34
(c) Eext < 1.1 V, electrons flow from Zn rod to Cu rod. 5 GIBBS ENERGY 2H+ + 2e– ® H2(g) 0.00
m It is the reversible work done by the galvanic cell. Pb2+ + 2e– ® Pb(s) –0.13
3 CELL POTENTIAL m DrG = –nF Ecell Sn2+ + 2e– ® Sn(s) –0.14
m Electrode potential : It is the potential difference developed m DrG° = –nF E°cell Cr3+ + 3e– ® Cr(s) –0.74
between the electrode and the electrolyte. When the m DrG° = –RT ln K = –2.303 RT log K Zn2+ + 2e– ® Zn(s) –0.76
concentration of all the species involved is unity it is known 2H2O + 2e– ® H2(g) + 2OH–(aq) –0.83
as standard electrode potential. 7 CONDUCTANCE OF ELECTROLYTIC SOLUTIONS Na+ + e– ® Na(s) –2.71
m Cell potential : The difference between the electrode Ca2+ + 2e– ® Ca(s) –2.87
potentials (reduction potentials) of the cathode and anode. m Resistance : R = rl , unit = ohm K+ + e – ® K(s) –2.93
A
m EMF of cell : The cell potential when no current is drawn RA Li+ + e– ® Li(s) –3.05
through the cell. m Resistivity : r = , unit = ohm - cm
l
m Ecell = Eright – Eleft 8 DILUTION EFFECT ON CONDUCTANCE
m Conductance : G = 1 = k A , unit = ohm -1 or S m Conductivity always decreases with decrease in
m E°cell = E°R – E°L R l
concentration (means on dilution) both for weak and strong
m In a galvanic cell : l
m Cell constant : G* = , unit = cm –1 electrolytes.
(a) Anode has negative potential w.r.t solution. A m For weak electrolytes, molar conductivity increases steeply
(b) Cathode has positive potential w.r.t solution. Gl on dilution.
-1 -1
m Standard hydrogen electrode :
m Conductivity : k = , unit = ohm cm
A m For strong electrolytes, molar conductivity increases slowly
1 with dilution.
H+ (aq.) + e - ¾® H2 (g), E° = 0 Volt (Assumed)
2 m Molar conductivity : L = k ´ 1000 , unit = S cm2 mol-1
(1M)
(1bar ) m
M
m For strong electrolyte : L m = L °m - A C .
NCERT Maps Electrochemistry 73
9 KOHLRAUSCH LAW OF INDEPENDENT 12 BATTERIES m Secondary batteries : Which can be recharged

MIGRATION OF IONS (1) Lead storage battery :
m Primary Batteries : Which cannot be reused.
m Limiting molar conductivity of an electrolyte can be
(1) Dry cell : (Leclanche cell) discharging
represented as the sum of the individual contributions of the ˆˆˆˆˆˆˆ
Pb(s) + PbO 2 (s) + 2H2SO 4 (aq.) ‡ˆˆˆˆˆˆ †
ˆ
2+ – charging
anion and cation of the electrolyte at infinite dilution. Anode : Zn(s) ¾® Zn + 2e
+
2PbSO 4 (s) + 2H2O( l )
m If an electrolyte on dissociation given v+ cations and v– anions Cathode : MnO2 + NH + e– ¾® MnO(OH) + NH3
4
(2) Nickel cadmium cell : It has longer life than lead
then L °m = v + l °+ + v - l °-
storage cell :
l l°m : H+ > Ca2+ > Mg2+ > K+ > Na+ Carbon rod
(cathode) Cd(s) + 2Ni(OH)3(s) ® CdO(s) + 2Ni(OH)2(s) + H2O(l)
l l°m : OH– > SO42 – > Br– > Cl– > CH3 COO– m Fuel cells : Galvanic cell that converts the energy produced
during combustion of fuel directly into electrical energy
l For a weak electrolyte : a = Lm/L°m
2 e.g: H2 — O2 fuel cell
Ca 2 CL m
l For acetic acid : K a = = –
1 - a L° ( L° - L ) Anode : H2(g) + 2OH (aq.) ¾® 2H2O(l) + 2e–
m m m
–
Cathode : O2(g) + 2H2O(l) + 4e– ¾® 4OH (aq.)
10 FARADAY’S LAW OF ELECTROLYSIS
The cell was used in Apollo space programme
E H 2O
m First law : w = ZQ = ZIt = ´ It + Cathode
96500 Anode –
w1 E1 Zinc cup MnO2 +
m Second law : = (anode) carbon black Aqueous electrolyte
w2 E2
+ NH4Cl paste NaOH
m 1F = Charge on 1 mol electron = 96487 C ; 96500 C
Fig. A commercial dry cell consists of
a graphite (carbon) cathode in a zinc
H2 O2
11 PRODUCTS OF ELECTROLYSIS container; the latter acts as the anode.
m Molten NaCl : Anode : Cl2, Cathode : Na (2) Mercury cell : Cell potential (; 1.35 V) remains constant
m Aqueous NaCl : Anode : Cl2, Cathode : H2 during its life
–
m Dilute H2SO4 : Anode : O2, Cathode : H2 Anode : Zn(Hg) + 2OH ¾® ZnO(s) + H2O + 2e–
–
m
2–
Concentrated H2SO4 : Anode : S2O8 , Cathode : H2 Cathode : HgO + H2O + 2e– ¾® Hg(l) + 2OH Fig. Fuel cell using H2 and O2 produces electricity
13 CORROSION
O2 + Fe2+ 4H+(aq) + O2
m It slowly coats the surfaces of metallic objects with oxides or other salts of metal.
Fe2+ Fe2+ 2H2O
m Corrosion of iron is called rusting. It is an electrochemical phenomenon. Fe2O3
Fe Fe
m Rust is Fe2O3 · xH2O.
4e–
m Prevention of rusting can be done by 2e– 2e–
(i) Covering the surface with paint or by chemicals (e.g. bisphenol) Oxidation : Fe(s) ® Fe2+(aq) + 2e–
(ii) Cover the surface by other metals (Sn, Zn etc.) Reduction : O2(g) + 4H+(aq) + 4e– ® 2H2O(l)
Atmospheric oxidation : 2Fe2+(aq) + 2H2O(l) + 1/2O2(g) ® Fe2O3 + 4H+
(iii) Provide a sacrificial electrode of other metal (Mg, Zn etc.) Fig. Corrosion of iron in atmosphere
4
Chemical Kinetics Chapter
1 RATE OF REACTION 5 INTEGRATED RATE EQUATION AND HALF LIFE 8 TEMPERATURE DEPENDENCE OF THE RATE OF
For a reaction, aA + bB ® xX + yY REACTION
m Zero order reaction:
-1 d[A] -1 d[B] 1 d[X] 1 d[Y] -d[R] m For a chemical reaction with rise in temperature by 10°,
rate = = = = Rate = = k[R]°
dt the rate of reaction is nearly doubled
a dt b dt x dt y dt -Ea
[R] = [R]0 – kt m Arrhenius equation : k = Ae RT
m Unit of rate of reaction : [R0]
–1 –1 [R]0 slope= – k Intercept = InA
[R]
(i) mol L s t1 =
2
2k
–1
Ink
(ii) atm s –Ea
[R]0 slope =
t100% = R
-D[R] - ([R2 ] - [R1] ) k
m Average rate = = 0 t
Dt t 2 - t1 First order reaction:
-d[R] 0 1/T
d[R] d[P]
m Instantaneous rate = - = Rate = = k[R]1
dt dt dt
æk ö Ea é T2 - T1 ù
In [R] = ln [R]0 – kt m log ç 2 ÷ = ê ú
2 ORDER è k1 ø 2.303 R ë T1T2 û
x y 2.303 [R]
log 0
log([R]0/[R])
m For a rate law equation : rate = k[A] [B] order of k= m The energy required to form the reaction intermediate,
t [R]
reaction = x + y slope = k called activated complex, is known as activation energy (Ea)
2.303 [R] 2.303
m Order of reaction can be 0, 1, 2, 3 and even a fraction. k= log 1 m Threshold energy = Activation energy
(t 2 - t1) [R]2
m Order of reaction is an experimental quantity. 0 t + energy possessed by
m Order is applicable to elementary as well as complex 0.693
t1 = reacting species.
reaction. k
2
-Ea
m For complex reaction, order is given by slowest step. th For biomolecular reaction. Rate = PZ e RT
m For n order reaction, t 1 µ [R0 ]1-n m
AB
3 MOLECULARITY 2
where, P is steric factor and ZAB is Collision frequency.
m It is the number of atoms, ions are molecules that must
6 PSEUDO FIRST ORDER REACTIONS
collide simultaneously with one another to result into a 9 EFFECT OF CATALYST
m Hydrolysis of ethyl acetate in acidic medium
chemical reaction
m Inversion of cane sugar in acidic medium m Catalyst increases the rate of reaction by reducing the
m It cannot be zero or a non-integer activation energy of reaction.
7 ORDER OF SOME REACTIONS
m It is applicable only for elementary reactions
m A small amount of the catalyst can catalyse a large amount
Reaction Order
1130 K
of reactants
4 Reaction order Unit of rate constant 2NH3(g) Pt catalyst
N2(g) + 3H2(g) Zero
–1 –1 Gold surface
m A catalyst does not alter Gibbs energy, DG of a reaction.
Zero mol L s 2HI(g) D
H2(g) + I2(g) Zero
m Catalyst does not change the equilibrium constant of a
–1 Radioactive decay
First s First reaction
–1 –1 D 1
Second mol L s N2O5(g) 2NO2 + O2 First m A catalyst can catalyse the spontaneous reactions only.
2
Surface Chemistry
5
Chapter
1 ADSORPTION 3 CATALYSIS
m The accumulation of molecular species at the surface rather than in the bulk of a solid or liquid is termed adsorption. m Substance, which accelerate the rate of a chemical reaction and
m The molecular species or substance, which concentrates or accumulates at the surface is termed adsorbate and the themselves remain chemically and quantitatively unchanged after the
material on the surface of which the adsorption takes place is called adsorbent reaction, are known as catalyst
m In adsorbtion the concentration of the adsorbate increases only at the surface of the adsorbent, while in absorbtion m Promoters are substance that enhances the activity of catalyst
the concentration is uniform throughout the bulk of solid. m Poisons decrease the activity of a catalyst
Mechanism of adsorption m When the reactants, products and the catalyst are in same phase, the
m The extent of adsorption increases with the increase of surface area per unit mass of the adsorbent at a given process is said to be homogeneous catalysis
temperature and pressure. m The catalytic process in which the reactants and the catalyst are in
m Another important factor featuring adsorption is the heat of adsorption during adsorption, there is decrease in surface different phases is known as heterogeneous catalysis
energy which appears as heat therefore adsorption is an exothermic process. In other words, DH of adsorption is
always negative. When a gas is adsorbed, the freedom of movement of its molecules become restricted. This Adsorption of
reacting molecules A
amounts to decrease in the entropy of the gas after adsorption i.e., DS is negative for a process to be spontaneous, +A+B
DG must be negative at constant pressure and temperature. B
Reacting
m As the adsorption proceeds DH becomes less and less negative ultimately DH becomes equal to TDS and DG
molecules
becomes zero. At this state equilibrium is attained
Catalyst surface having Adsorption
Types of adsorption free valencies of reacting
molecules
Physisorption Chemisorption
1. It arises because of van der Waals’ forces. 1. It is caused by chemical bond formation. Desorption of
product molecules A
2. It is not specific in nature. 2. It is highly specific in nature. +A–B
3. It is reversible in nature. 3. It is irreversible. Product B
4. It depends on the nature of gas. More easily 4. It also depends on the nature of gas. Gases which
liquefiable gases are adsorbed readily. can react with the adsorbent show chemisorption.
–1 –1 Catalyst
5. Enthalpy of adsorption is low (20-40 kJ mol ) 5. Enthalpy of adsorption is high (80-240 kJ mol ).
6. Low temperature is favourable for adsorption. It 6. High temperature is favourable for adsorption. m The activity of a catalyst depends upon the strength of chemisorption to
decreases with increase of temperature. It increases with the increase of temperature. a large extent
7. No appreciable activation energy is needed. 7. High activation energy is sometimes needed. m The selectivity of a catalyst is its ability to direct a reaction to yield a
8. It depends on the surface area. It increases with 8. It also depends on the surface area. It too increases particular product selectively, when under the same reaction conditions
an increase of surface area. with an increase of surface area. many products are possible
9. It results into multimolecular layers on adsorbent 9. It results into unimolecular layer.
surface under high pressure. m The catalytic reaction that depends upon the pore structure of the
catalyst and the size of the reactant and product is called shape-
selective catalysis e.g. zeolites.
2 ADSORPTION ISOTHERMS (FREUNDLICH ADSORPTION ISOTHERM) m Numerous reactions that occur in bodies of animals and plants are
x catalysed by enzymes termed as biochemical catalyst
m
= kp1/n (n > 1) y
m m Characteristics of enzyme catalysis
1
x = mass of gas adsorbed, m = mass of adsorbent Slope = (i) Most highly efficient
p = pressure of gas, K, n = constants depend on nature of adsorbent and gas n
x (ii) Highly specific nature
at a particular temperature log
m (iii) Highly active under optimum temperature
m
x 1
log = log K + log P logk = intercept (iv) Highly active under optimum pH
m n
1 x (v) Increasing activity in presence of activators and co-enzymes.
lies between 0 to 1 (probable range 0.1 to 0.5) O log P
n (vi) Influence of inhibitors and poisons
82 Surface Chemistry NCERT Maps
SOME ENZYMATIC REACTION (iii) Classification based on type of particles of dispersed phase
(a) Multimolecular colloids contains a large number of atoms or smaller molecules of a
Enzyme Source Enzymatic reaction substance aggregate together to form species having size in the colloidal range. e.g., Gold
Invertase Yeast Sucrose ® Glucose and fructose sol, sulphur sol
(b) Macromolecular colloids - Macromolecules in suitable solvents form solutions in which
Zymase Yeast Glucose ® Ethyl alcohol and carbon dioxide
the size of the macromolecule may be in colloidal range e.g., starch, protein etc.
Diastase Malt Starch ® Maltose (c) Associated colloids (Micelles) : At low concentrations behave as normal strong
electrolyte, but at higher concentrations exhibit colloidal behaviour due to formation of
Maltase Yeast Maltose ® Glucose
aggregates (micelles) Micelles formation takes place above a particular temperature called
Urease Soyabean Urea ® Ammonia and carbon dioxide Kraft temperature (TK) and above a particular concentration called critical micelle
Pepsin Stomach Proteins ® Amino acids concentration (CMC) e.g. soaps and synthetic detergents
5 PREPARATION OF COLLOIDS
4 COLLOIDS
m Chemical methods
m A colloid is a Heterogeneous system in which one substance is dispersed Double decomposition
(dispersed phase) as very fine particles in another substance called dispersion As2O3 + 3H2S As2S3 (sol) + 3H2O
medium
Oxidation
m The range of diameters of colloidal particles is between 1 to 1000 nm SO2 + 2H2S 3S(sol) + 2H2O
m Classification of colloids
Reduction
(i) Classification based on physical state of dispersed phase and dispersion 2AuCl3 + 3HCHO + 3H2O 2Au(Sol) + 3HCOOH + 6HCl
medium
Hydrolysis
Dispersed Dispersion Type of FeCl3 + 3H2O Fe(OH)3 (sol) + 3HCl
Examples
phase medium colloid
m Electrical disintegration or Bredig’s Arc method - In this method, electric arc is struck between
Solid Solid Solid sol Some coloured glasses and gem stones electrodes of metal immersed in dispersion medium. The intense heat produced vapourises the
Solid Liquid Sol Paints, cell fluids metal, which then condenses to form particles of colloidal size. Colloidal sols of metals such as gold,
Solid Gas Aerosol Smoke, dust silver, platinum etc. can be prepared by this method.
Liquid Solid Gel Cheese, jellies
m Peptization - Process of converting a precipitate into colloidal sol by shaking it with dispersion
Liquid Liquid Emulsion Milk, hair cream, butter
medium in the presence of a small amount of electrolyte. The electrolyte used for this purpose is
Liquid Gas Aerosol Fog, mist, cloud, insecticide sprays
called peptizing agent
Gas Solid Solid sol Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather
6 PURIFICATION OF COLLOIDAL SOLUTIONS
(ii) Classification based on nature of interaction between dispersed phase The process used for reducing the amount of impurities to a requisite minimum is known as purification
and dispersion medium of colloidal solution.
(a) Lyophilic colloids directly formed by mixing substances like gum, m Dialysis : Process of removing a dissolved substance from a colloidal solution by means of
gelatin, starch, rubber etc with a suitable liquid. These sols are diffusion through a suitable membrane.
reversible in nature m Electro-dialysis : Ordinarily, the process of dialysis is quite slow. It can be made faster by applying
(b) Lyophobic colloids can be prepared only by special methods. These an electric field if the dissolved substance in the impure colloidal solution is only an electrolyte.
sols are readily coagulated on addition of small amount of electrolyte by m Ultrafiltration is the process of separating the colloidal particles from the solvent and soluble.
heating or by shaking and hence are not stable. These sols are solutes present in the colloidal solution by specially prepared filters which are permeable to all
irreversible in nature. substance except the colloidal particles.
NCERT Maps Surface Chemistry 83
7 PROPERTIES OF COLLOIDAL SOLUTIONS

HARDY-SCHULZE RULE
m Colligative properties : Colloidal particles being bigger aggregates, the number of particles in a
Greater the valence of the flocculating ion added, greater is its power to
colloidal solution is comparatively small as compared to the true solution hence colligative
cause precipitation.
properties are of small order as compared to true solutions.
3+ 2+ +
m Tyndall effect is due to the fact that colloidal particles scatter light in all directions in space which For –ve colloids flocculating power is in the order : Al > Ba > Na
4–
illuminates the path of beam. The bright cone of light is known as Tyndall cone. For +ve colloids flocculating power is in the order : [Fe(CN)6] >
3– 2– –
m Colour : Depends on the wavelength of light scattered. The wavelength depends on size and PO4 > SO4 > Cl
nature of the particles. The colour of colloidal solution also changes with the manner in which the
observer receives the light m Coagulating value : The minimum concentration of an electrolyte in
m Brownian movement : Zig-zag continuous motion of colloidal particles and depends on the size of millimoles per litre required to cause precipitation of a sol in two hours. The
particles and viscosity of solution. smaller the quantity needed, the higher will be the coagulating power of an
m Charge on colloidal particles: ion.
Positively charged sols Negatively charged sols
Hydrated metallic oxides, e.g., Al2O3.xH2O, Metals, e.g., copper, silver, gold sols. 8 EMULSIONS
CrO3.xH2O and Fe2O3.xH2O. etc. Metallic sulphides, e.g., As2S3, Sb2S3, CdS sols. These are liquid-liquid colloidal systems. These are of two types
Basic dye stuffs. e.g., methylene blue sol. Acid dye stuffs, e.g., eosin. congo red sols. m Oil dispersed in water (O/W type) e.g., : milk and vanishing cream.
Haemoglobin (blood) Sols of starch, gum, gelatin, clay, charcoal, etc. m Water dispersed in oil (W/O type) e.g., butter and cream
Oxides, e.g., TiO2 sol.
9 COLLOIDS AROUND US
m Zeta potential : The potential difference between the fixed layer and diffused layer of opposite
charges is called electrokinetic potential or zeta potential. m The styptic action of alum and ferric chloride solution is due to the coagulation of
m Electrophoresis : Movement of colloidal particles under an applied electric potential. blood forming a clot which stops further bleeding
m When electrophoresis i.e., movement of particles is prevented by some suitable means, it is m When river water meets the sea water, the electrolyte present in sea water
observed that the dispersion medium begins to move in an electric field. This phenomenon is coagulate the colloidal solution of day resulting in the deposition with the
termed electroosmosis. formation of delta.
m Coagulation or precipitation m Argyrol is a silver sol used as eye lotion.
The process of settling of colloidal particles. The coagulation of lyophobic sols can be carried out
m Colloidal antimony is used in curing kalaazar.
by
m Colloidal gold is used for intramuscular injection.
(a) Electrophoresis
(b) By mixing two oppositely charged sols m Milk of magnesia is used for stomach disorders.
(c) By boiling m Animal hides are colloidal in nature when soaked in tannin results in hardening of
(d) By persistent dialysis lather. This process is known as tanning. Chromium salts are also used in place of
(e) By addition of electrolytes tannin.
General Principles and Processes of Isolation of Elements
General Principles and Processes 6

of Isolation of Elements Chapter
1 OCCURRENCE OF METALS 3 CONCENTRATION OF ORES l Ores of Ag and Au are treated with aqueous
m The most abundant metal in the earth's crust is aluminium. The removal of impurities from the ores is known as dilution solution of NaCN in presence of oxygen.
concentration or dressing or benefaction of ore. The The Ag and Au particles get dissolved forming
m Gem 'ruby' (impure Al2O3) has Cr impurity
concentration is done in number of ways depending upon the complex cyanides. Ag or Au recovered from
m Gem 'sapphire' (impure Al2O3) has Co impurity solution by adding Zn.
nature of impurities.
m The second most abundant metal on earth crust is iron. –
4M(s) + 8CN (aq.) + 2H2O(aq.) + O2(g)
m Minerals: These are naturally occuring chemical substances (i) Hydraulic Washing: The process of removing of lighter
– –
containing metal in the earth's crust and are obtain through particles of sand, clay etc. by washing with water using ® 4[M(CN)2] (aq.) + 4OH (aq.) (M = Ag or Au)
mining. hydraulic classifer. Separation is based on difference – 2–
2[M(CN)2] (aq.) + Zn(s) ® [Zn(CN)4] (aq.) + 2M(s)
m Ores: Minerals which are viable to be used as source of the between specific gravity of the ore and gangue particles. It
metal are called ores. is type of a gravity separation. 4 EXTRACTION OF CRUDE METAL FROM
m Gangue: The undesired impurities such as sand, clay (ii) Magnetic Separation: This is used when either the ore or CONCENTRATED ORE
associated with the ore are called gangue or matrix. the gangue is attracted towards magnetic field. Wolframite Extraction involves following two steps
m Principal ores of some important metals: (FeWO4), a magnetic ore is separated from non-magnetic (i) Conversion of ore into metallic oxide
Metal Ore Composition ore, cassiterite (SnO2) by this method. (ii) Reduction of metallic oxide
Aluminium Bauxite AlOx(OH)3-2x (iii) Froth Floatation Method: This method is used for the (i) Two methods ore used for conversion into oxide
where, 0 < x < 1 concentration of sulphides ore. This process is based on the (a) Calcination: It involves heating of ore below its
Iron Haematite Fe2O3 preferential wetting of ore particles by pine oil and gangue fusion temperature in the absence of air
particles by water. D
Magnetite Fe3O4 Fe2O3 × xH2O(s) Fe2O3(s) + xH2O(g)
l Pine oil, fatty acids and xanthates are used as collectors. D
Siderite FeCO3 ZnCO3(s) ZnO(s) + CO2(g)
l Cresols, aniline are used as froth stabilizer.
Iron pyrite FeS2
l In case of ore containing ZnS and PbS, the depressant
(b) Roasting: It involves heating of ore below its
Copper Copper pyrite CuFeS2 fusion temperature in regular supply of air.
NaCN is used which prevents ZnS from coming to the
Malachite CuCO3 . Cu(OH)2 froth. 2ZnS + 3O2 ® 2ZnO + 2SO2
Cuprite Cu2O (iv) Leaching: It involves the treatment of the ore with a suitable
2Cu2S + 3O2 ® 2Cu2O + 2SO2
Copper glance Cu2S reagent to make it soluble while impurities remain insoluble.
l The sulphide ores of copper are heated in
Zinc Zinc blende or sphalerite ZnS The ore or the metal is recovered from the solution by a
reverberatory furnace. If the ore contains iron,
suitable chemical method. examples
Calamine ZnCO3 silica is added before heating. Iron oxide 'slags of'
l Leaching of Alumina from bauxite: Bauxite is digested
Zincite ZnO as iron silicate and copper is produced in the form
with aqueous solution of NaOH, where Al2O3 dissolves
of copper matte which contains Cu2S and FeS
forming sodium aluminate while impurities such as Fe2O3
2 METALLURGY FeO + SiO2 ® FeSiO3 (slag)
and TiO2 remain insoluble
The entire scientific and technological process used for isolation (ii) Reduction of the oxide ore into free metal is done by a
of the metal from its ore is known as metallurgy. It involves Al2O3(s) + 2NaOH(aq.) + 3H2O(l) ® 2Na[Al(OH)4](aq.) suitable reducing agent.
following main operations The pure alumina is recovered from filtrate. l Smelting: When C or CO or other metal are used
(i) Concentration or dressing of ore 2Na[Al(OH)4](aq.) + CO2(g) ® Al2O3.xH2O(s) + as reducing agent at high temperature. The
(ii) Isolation of crude metal 2NaHCO3(aq.) process in general known as pyrometallurgy
(iii) Purification or refining of metal 1470 K
Al2O3 . xH2O(s) Al2O3(s) + xH2O(g) MxOy + yC ® xM + yCO
NCERT Maps General Principles and Processes of Isolation of Elements 87
5 THERMODYNAMIC PRINCIPLES OF METALLURY 7 EXTRACTION OF COPPER FROM CUPROUS OXIDE 8 HALL-HEROULT PROCESS
m For considering the choice of reducing agent in reduction of m The sulphide ores containing iron are roasted/smelted to Purified Al2O3 is mixed with Na3AlF6 (Cryolite) and CaF2
oxide, Elligham Diagram is used. give oxide (fluorspar) to lower the melting point of the mixture and to
m Ellingham diagram consists of plots of DfG° vs T for the 2Cu2S + 3O2 ® 2Cu2O + 2SO2 increase conductivity
formation of oxides of metals and reducing agents. m The oxide is reduced to copper using coke 2Al2O3 + 3C ® 4Al + 3CO2
eg: 2x M(s) + O2(g) ® 2MxO(s) Cu2O + C ® 2Cu + CO m Steel vessel with lining of carbon acts as cathode and
m The ore is heated in a reverberatory furnace after mixing graphite is acts as anode.
m The difference in the two DrG° values determines whether
reduction of the oxide of the element of the upper line is with silica, where iron oxide "slags of" as iron silicate
feasible by the element of which oxide formation is FeO + SiO2 ® FeSiO3(slag) 9 REFINING
represented by the lower line. If the difference is large, the The process of purifying impure metals is called refining.
m Copper is produced as copper matte containing Cu2S and
reduction is easier. (i) Distillation: It is used for those metals which are
FeS, which is then charged into silica lined convertor in
presence of hot air blast. volatile. The impure metal is heated and the vapours are
2O 2 SiO separately condensed in receiver. It is used for
FeS ¾¾¾ ® FeO ¾¾¾
® FeSiO3
–SO 2 purification of Zn, Hg etc.
Cu2S ¾¾¾
O
2
® Cu2O ¾¾¾2 Cu O
® Cu(blister copper) (ii) Liquation: When impurities are less fusible than the
–SO –SO
2 2 metal itself then this process is used. The impure metal
such as Sn is purified by liquation.
BLAST (iii) Electrolytic refining: Metal like Cu are purified by this
FURNACE
method. The impure metal is made the anode and a strip
of a pure metal is made as cathode while the electrolytic
solution consists of solution of a suitable salt of metal.
(iv) Zone refining: It is based on the concept that impurities
are more soluble in melt than in the solid state of the
metal. This method is useful for Ge, Si, B for obtaining
highly pure metals.
(vi) Vapour phase refining:
330 - 350 K
(a) Mond process: Ni + 4CO ¾¾¾¾¾
® Ni(CO)4 ()
6 EXTRACTION OF IRON FROM ITS OXIDE 450 - 470 K
Ni(CO)4 ¾¾¾¾¾
® Ni + 4CO
Reduction of oxides of iron (Fe2O3, Fe3O4) is done in blast
(b) Van Arkel method: (for Zr/Ti)
furnace.
1800 K
m Iron obtained from blast furnace contains 4% carbon, Zr + 2I2 ® ZrI4 ¾¾¾® Zr + 2I2
(volatile)
known as pig iron.
(vii) Chromatographic Methods: Column chromatography
m Cast iron is obtained by melting pig iron with scrap iron and
is used for purification of elements which are available in
coke using hot air blast. It contains about 3% carbon.
minute quantities and impurities are not very different in
m Wrought iron is the purest form of commercial iron and
prepared in a reverberatory furnace lined with haematite. the chemical properties from the element to be purified.
USES OF m Zn is used for galvanising iron. m Al is used in extraction of Cr and Mn from their oxides. m Wrought iron is used making anchors, wires, bolts.
10
METALS m Zn in Alloys (Brass : Cu + Zn, german silver: Cu + Zn + Ni). m Cu is used for making wires used in electrical industry m Chrome steel is used for cutting tools.
The p-Block Elements
7
Chapter
1 GROUP 15 ELEMENTS 13. All oxidation states +1 to +4 for nitrogen tend to 21. Preparation of ammonia
disproportionate in acid solution. (i) NH2CONH2 + 2H2O (NH4 )2 CO3 ƒ 2NH3 + H2O + CO2
+3 +5 +2
1. Pnictogens: N, P, As, Sb, Bi, Uup (ii) 2NH4Cl + Ca(OH)2 2NH3 + 2H2O + CaCl2
3H N O2 HNO3 + H2O + 2NO
non-metals Metalloids metals 14. Anomalous behaviour of nitrogen is due to its (iii) Haber’s process: N2(g) + 3H2(g) ƒ 2NH3(g), DH < 0
2. Physical properties: (i) small size 22. NH3 behave as a lewis base
(ii) High electronegativity 2+ 2+
l Covalent radii : N < P < As < Sb < Bi Cu (aq) + 4NH3 (aq) ¾® [Cu(NH3)4 ] (aq)
(iii) High ionization enthalpy (blue) (deep blue)
l Ionisation enthalpy : N > P > As > Sb > Bi (iv) Non-availability of d-orbitals
AgCl(s) + 2NH3 (aq) ¾® [Ag(NH3)2 ] Cl (aq)
l Electronegativity: N > P > As > Sb = Bi 15. All elements of this group form hydrides of type MH3 (white ppt) (colourless)
3. Nitrogen is a gas, which all remaining elements are (i) Melting point: NH3 > SbH3 > AsH3 > PH3 23. Oxides of nitrogen:
solids. (ii) Boiling Point: BiH3 > SbH3 > NH3 > AsH3 > PH3 N 2O
D
Neutral NH4NO3 N2O + 2H2O
4. Nitrogen is a diatomic molecule with very large bond (iii) Bond angle: NH3 > PH3 > AsH3 > SbH3
–1 (iv) Bond enthalpy: NH3 > PH3 > AsH3 > SbH3 NO Neutral 2NaNO2 + 2FeSO 4 + 3H2SO 4
enthalpy (941.4 kJ mol )
(v) Basicity: NH3 > PH3 > AsH3 > SbH3 ³ BiH3 Fe2 (SO 4 )3 + 2NaHSO 4 + 2H2O + 2NO
5. The boiling points, in general increase from top to
16. All elements of this group form two types of oxides:
bottom in the group but melting points increases upto 250 K
N2O3 Acidic 2NO + N2O4 2N2O3
E2O3 and E2O5
arsenic and then decreases upto bismuth.
N2O3, P2O3, As2O3, Sb2O3, Bi2O3 NO2 Acidic 2Pb(NO3 )2 673 K 4NO2 + 2PbO + O2
6. Only nitrogen in this group is capable of forming
pp–pp multiple bonds within itself and with carbon, Acidic Amphoteric Basic Cool
N2O4 Acidic 2NO 2 N2O4
oxygen etc, due to small size. Phosphorus and other 17. Except nitrogen, the rest of the elements form two type of Heat
elements do not form pp–pp multiple bonds. halides : EX3 and EX5. Nitrogen does not form pentahalide N2O5 Acidic 4HNO3 + P4O10 4HPO3 + 2N2O5
due to absence of d-orbitals. Among trihalides of nitrogen
Phosphorous and arsenic can form dp–dp bond. 24. Preparation of nitric acid on large scale is done by
7. Except nitrogen, all elements show allotropy only NF3 is stable. Ostwald’s process.
18. Preparation of Dinitrogen Pt/Rh gauge catalyst
8. Single N–N bond is weaker than single P-P bond. 4NH3 (g) + 5O2 (g) 4NO(g) + 6H2O(g)
500 K, 9 bar
9. Maximum covalency of N and P are 4 and 6 (i) NH4Cl(aq) + NaNO2 (aq) N2 (g) + 2H2O(l ) + NaCl(aq) (from air )
respectively. D 2NO(g) + O2 (g) 2NO2 (g)

(ii) (NH4 )2 Cr2O7 N2 + Cr2O3 + 4H2O
10. Common oxidation state: –3, +3 and + 5 3NO2 (g) + H2O(l ) 2HNO3 (aq) + NO(g)
11. Due to inert pair effect, stability of +5 oxidation state (iii) Ba(N3 )2 D Ba + 3N2 (very pure) 25. Concentrated nitric acid attacks most metals except
deceases and stability of + 3 state increases on noble metals such as Pt and Au.
19. Nitrogen combines with CaC2 to form nitrolim (CaCN2 + C) at
dil. HNO3
moving down the group. 100°C, which is used as a fertilizer. Cu Cu(NO3)2 + NO
5+ 20. Liquid dinitrogen is used as a refrigerant to preserve
12. The only well characterised Bi compound is BiF5 conc. HNO3
biological materials and in cryosurgery. Cu Cu(NO3)2 + NO2
92 The p-Block Elements NCERT Maps
26. Brown ring test: 31. Oxoacids of phosphorus: 6. Anomalous behaviour of oxygen is due to its
NO3– + 3Fe2 + + 4H+ NO + 3Fe3 + + 2H2O Characteristic (i) Small size
2+ 2+ Name Formula bonds and (ii) High electronegativity
[Fe(H2O) 6 ] + NO [Fe(H2O)5 (NO)] + H2O
(brown ring)
their number
(iii) Absence of d-orbitals
27. Phosphorus exists in a number of allotropic forms. Hypophosphorous H3PO2 One P – OH
(i) White phosphorus : It is less stable and therefore (Phosphinic) Two P – H 7. All the elements of group-16 form hydrides of type H2E
more reactive than the other solid phases under normal One P = O (i) Melting point : H2O > H2Te > H2Se > H2S
Orthophosphorous H3PO3 Two P – OH
conditions (bond angle 60°), poisonous, soluble in CS2 (Phosphonic) (ii) Boiling point : H2O > H2Te > H2Se > H2S
One P – H
and glows in dark (Chemiluminescence). One P = O (iii) Acidic nature : H2Te > H2Se > H2S > H2O
Pyrophosphorous H4P2O5 Two P – OH
P 8. S, Se, Te and Po form oxides of type EO2 and EO3, all are
Two P – H
60°
Two P = O acidic in nature.
P P
Hypophosphoric H4P2O6 Four P – OH 9. These elements form halides of type EX6, EX4 and EX2.
P
Two P = O – – – –
Fig. White phosphorus One P – P (i) Stability order of halides : F > CI > Br > I
(ii) Red phosphorus : Non-poisonous and insoluble in Orthophosphoric H3PO4 Three P – OH (ii) SF6 is exceptionally stable
CS2. It is polymeric and less reactive than white One P = O
(iii) All elements except oxygen form dichlorides and
phosphorous. Pyrophosphoric H4P2O7 Four P – OH
dibromides
Two P = O
One P – O – P (iv) Dimeric halides undergo disproportionation
P P P
Cyclotrimetaphosphoric (HPO3)3 Three P – OH 2Se2Cl2 ¾® SeCl4 + 3Se
P P P P P P Three P = O 10. Preparation of dioxygen
Three P – O – P
P P P D
D (i) 2KClO3 2KCl + 3O2
Fig. Red phosphorus 32. (i) 4H3PO3 3H3PO4 + PH3 MnO2
(iii) Black phosphorus : It has two forms a and b-
(ii) 4AgNO3 + 2H2O + H3PO2 ® 4 Ag + 4HNO3 + H3PO4 D
phosphorus. (ii) 2Ag2O 4Ag + O2
28. Preparation of phosphine: 2 GROUP 16 ELEMENTS 11. Hydrazines with liquid oxygen is used as fuel in rockets.
(i) Ca3P2 + 6H2O 3Ca(OH)2 + 2PH3
1. Chalcogens : O, S, Se, Te, Po, Lv 12. (i) Mixed oxide : Pb3O4, Fe3O4, Mn3O4
(ii) P4 + 3NaOH + 3H2O PH3 + 3NaH2PO2 (ii) Simple oxides:
non-metals metalloid Metal
29. PH3 becomes inflammable due to presence of P2H4 and (a) Acidic oxide : SO2, Cl2O7, N2O5
2. (–DegH) : S > Se > Te > Po > O.
P4 vapours. Spontaneous combustion of phosphine is (b) Basic oxide : CaO, Na2O
3. Oxygen (O2) is a gas whereas sulphur (S8) exist as solid.
technically used in Holme’s Signals. (c) Amphoteric oxide : Al2O3
4. Oxygen shows generally negative oxidation state - 2.
30. Preparation of PCl5:
5. The stability of +6 oxidation state decreases down the (d) Neutral oxide :CO, NO, N2O
(i) P4 + 10Cl2 4PCl5 group and stability of +4 oxidation state increases due to 13. Ozone is allotropic form of oxygen and prepared by
(ii) P4 + 10SO2Cl2 4PCl5 + 10SO2 inert pair effect. passing silent electric discharge through dry oxygen.
NCERT Maps The p-Block Elements 93
14. Ozone is powerful oxidising agent 3. Chemical properties 4 GROUP 18 ELEMENTS

O3 (i) Oxidising power : F2 > Cl2 > Br2 > I2 1. Noble gas : He, Ne, Ar, Kr, Xe, Rn, Og
PbS (s) PbSO4 (s)
(ii) Reaction with H2 O :
2. DHeg : Ne > Ar ; Kr >Xe > Rn > He
y O3 l 2F2 (g) + 2H2O(l) ¾® 4HF + O2
2I (aq) I2 (s) st
l Cl2 (g) + H2O(l) ¾® HCl + HOCl 3. 1 compound of noble gas element is formed by Neil
15. Sulphur exists in several allotropic forms (i) Rhombic 4. All the halogens react with hydrogen to form volatile Bartlett on the concept of similar IP of O2 and Xe
sulphur (a-sulphur), (ii) Monoclinic sulphur (b-sulphur). covalent hydrides of type HX. + –
S (i) Acidic nature : HI > HBr > HCl > HF Xe + Pt F6 ¾® Xe [Pt F6]
20
4p S S
S m (ii) Boiling point : HF > HI > HBr > HCl
107° S 205.7 pm S 4. Xenon-fluorine compounds preparation :
S S (iii) Melting point : HI > HF > HBr > HCl
S 673 K, 1 bar
102.2° 5. Halogen formed many oxide with oxygen. (i) Xe + F2 XeF2(s)
S S S
(excess)
(i) F formed two oxides OF2 and O2F2
(a) (b) (ii) Stability order of oxides form by halogen : I > Cl > Br 873 K, 1 bar
S (ii) Xe + F2 XeF4(s)
6. Preparation of Cl2 1:5
Fig. The structures of (a) S8 ring in
(i) MnO2 + 4HCl ¾® MnCl2 + 2H2O + Cl2 573 K, 60-70 bar
(iii) Xe + 3F2 XeF6(s)
rhombic sulphur and (b) S6 form
(ii) 2KMnO4 + 16HCl ¾® 2KCl + 2MnCl 2 + 8H2O + 5Cl2 1 : 20
16. Rhombic sulphur transform into monoclinic sulphur
(iii) Deacon’s process :
above 369 K. At elevated temperature (~ 1000 K), S2 is (iv) XeF4 + O2F2 143 K XeF6 + O2
CuCl2
dominant species and is paramagnetic like O2 4HCl + O2 2Cl2 + 2H2O
5. Hydrolysis reactions
17. All oxoacids of sulphur are dibasic acid.
7. Reactions of Cl2
H2SO3 : sulphurous acid, H2SO4 : Sulphuric acid, H2S2O8 : (i) 2XeF2 + 2H2O ¾® 2 Xe + 4HF + O2
Peroxodisulphuric acid, H2S2O7 : Pyrosulphuric acid (i) 2NaOH + Cl2 ¾® NaCl + NaOCl + H2O
(Cold and dil.) (ii) 6XeF4 + 12H2O ¾® 4 Xe + 2XeO3 + 24HF + 3O2
(Oleum), H2S2O6 : Dithionic acid
(ii) 6NaOH + 3Cl2 ¾® 5NaCl + NaClO3 + 3H2O
18. H2SO4 is manufactured by contact process (Hot and conc) (iii) XeF6 + 3H2O ¾® XeO3 + 6HF
O2 V2O5 H2SO4 (explosive)
S SO2 SO3 H2S2O7 (iii) 2Ca(OH)2 + 2Cl2 ¾® Ca (OCl)2 + CaCl2 + 2H2O
Catalyst (Bleaching powder) –
6. Xenon fluoride reaction with F donors and acceptors:
Oleum
8. Aqua regia (3HCl + HNO3) is used for dissolving noble
+ –
metals. (i) XeF2 + PF5 ¾® [XeF] [PF6]
3
GROUP 17 ELEMENTS – –
Au ¾® AuCl4 , Pt ¾® Pt Cl62 (ii) XeF4 + SbF5 ¾® [XeF3] [SbF6]
+ –
1. Halogens : F, Cl, Br, I, At
9. Fluorine forms only one oxoacid (HOF), other Halogen-
2. Atomic and physical properties of halogens (iii) XeF6 + NaF ¾® Na [XeF7]
+ –
forms several oxoacids.
(i) Bond energy : Cl2 > Br2 > F2 > I2 HOX HOXO HOXO2 HOXO3 7. He is used in filling balloons for meteorological
(ii) Electron affinity : Cl > F > Br > I Hypohalous Halous Halic Perhalic
observations
acid acid acid acid
(iii) Electronegativity : F > Cl > Br > I 8. Liquid He is used as cryogenic agent
10. Interhalogen compound : XX¢, XX¢3, XX¢5, XX¢7
(iv) Physical state : F2 , Cl2 , Br2 , I2
(gas) (liq.) (Solid) (i) All the solid or liquid at 298 K except CIF 9. Ne is used in discharge tubes and fluorescent bulbs for
(v) Colour : F2 , Cl2 , Br2 , I2 (ii) These are more reactive than Halogen except F2 advertisement display
Yellow Greenish Re d Violet
yellow (iii) CIF + H2O ¾® HF + HOCl 10. Ar is used to provide an inert atmosphere in arc welding.
8
The d- and f-Block Elements Chapter
st
1 d-BLOCK ELEMENTS 12. The 1 ionisation enthalpy in any d-series generally 25. Many Cu(I) compounds are unstable in aqueous solution
1. The d-block of the periodic table contains the elements of increases but the magnitude of increase in 2nd and 3rd and undergo disproportionation.
+ 2+
the group 3-12. ionisation enthalpies for the successive elements, is 2Cu ¾® Cu + Cu
2. Transition metals : Metals which have incomplete much higher along a series. 2+
26. The stability of Cu (aq) rather than Cu (aq.) is due to the
+
nd rd
d-subshell either in neutral atom or in their ions. 13. The trend of steady increase in 2 and 3 ionisation much more negative DHydH° of Cu (aq.) than Cu (aq),
2+ +
st
3. General electronic configurations energies for 1 transition series breaks for the formation which more than compensates for the second ionisation
1–10 1–2 2+ 3+ 5
(n –1)d ns , but this has several exceptions due to of Mn and Fe respectively as both ions have d enthalpy of Cu.
2–
very little energy difference between (n – 1)d and ns configuration. 27. Ferrates (FeO4) are formed in alkaline media but they
orbitals. 14. The three terms responsible for the value of ionisation readily decompose to Fe2O3 and O2.
4. There are mainly four series of the transition metals : 3d enthalpy are attraction of each electron towards nucleus,
28. The highest Mn fluoride is MnF4 whereas highest oxide is
series (Sc to Zn), 4d series (Y to Cd), 5d series (La and Hf repulsion between the electrons and the exchange
to Hg), and 6d series (Ac and Rf to Cn) energy. Mn2O7
+ +
5. Zn, Cd and Hg are not regarded as transition metals. 15. Ionisation energy of Mn is lower than Cr as there is no 29. Mn 2 O 7 is a covalent oxide in which each Mn is
6. With the exceptions of Zn, Cd, Hg and Mn, these have one 6
loss of exchange energy at d configuration. tetrahedrally surrounded by O’s including Mn–O–Mn
or more typical metallic structures at normal bridge.
16. Mn exhibits all the oxidation states from +2 to +7.
temperatures. 30. Order of oxidising power : VO2+ < Cr2O72– < MnO4–
17. Sc(II) virtually unknown.
7. With the exception of Zn, Cd, and Hg, these metals are 31. Ti & V, in practise, are passive to dilute non-oxidising acids
18. The only oxidation state of Zn is +2.
very hard and have low volatility. at room temperature.
19. In group-6, Mo(VI) and W(VI) are found to be more stable 3+ 2+ 3+ 3+
8. These elements have high melting and boiling point. In any 32. E°(M /M ) values shows that Mn and Co ions are
than Cr(VI)
row the melting points of these metals rise to a maximum at 2+ strongest oxidising agents in aqueous solutions among
5 20. Among 3d series elements, E°(M /M) is positive only for 3d series.
d except for anomalous values of Mn and Tc.
copper because high energy to transform Cu(s) to 2+ 2+ 2+
9. These metals have high enthalpy of atomisation due to 2+ 33. The ions Ti , V and Cu are strong reducing agents
nd rd Cu (aq.) is not balanced by its hydration enthalpy. Only
strong interatomic interactions. Metals of 2 and 3 oxidising acids (nitric and hot concentrated sulphuric) among 3d series and will liberate H2 from dilute acids.
series have more enthalpies of atomisation than the reacts with Cu. 34. Each unpaired electron has a magnetic moment
st
corresponding elements of 1 series due to much more 2+ associated with its spin angular momentum and orbital
21. Among 3d series, the value of E°(M /M) for Mn, Ni and Zn
frequent metal-metal bonding. angular momentum.
are more negative than excepted from the trend.
10. Tungsten (W) has highest melting point among d-block 35. For the compounds of first transition series metals,
22. In halides of 3d series, the highest oxidation numbers are
elements. magnetic moment is determined by 'spin only' formula :
achieved in TiX4, VF5 and CrF6.
11. The filling of 4f before 5d orbitals results in a regular m = n(n + 2) BM
+5
decrease in atomic radii called lanthanoid contraction. 23. V halide is represented only by VF5, the other Halides 36. The colour of some aquated transition metal ions :
nd rd 3+ 4+ 2+ 3+ 2+ 2+ 3+
The net result of it is that the 2 and 3 d-series exhibits undergo hydrolysis to give oxohalides VOX3. Sc , Ti , Zn : Colourless, V , Fe , Ni : Green , Fe :
similar radii (e.g. Zr and Hf). 24. Cu(II) halides are known except the iodide. Yellow, Mn : pink.
2+
NCERT Maps The d- and f-Block Elements 97
37. These metals form a large number of complex 48. In acidic solution, K2Cr2O7 is used as oxidising agent as l The overall decrease in atomic and ionic radii from La
compounds due to comparatively smaller sizes of the 2– + – 3+ to Lu due to poor shielding to 4f is known as
Cr2O + 14H + 6e ¾® 2Cr + 7H2O (E° = 1.33 V)
metal ions, their high ionic charges and the availability of 7
lanthanoid contractions
d-orbitals for the bond formation. 49. Preparation of KMnO4 l Most common oxidation state is +3
38. These metals and their compounds are used as a catalyst +
KOH H – l Pr, Nd, Tb and Dy also exhibit +4 oxidation state but
due to their ability to adopt multiple oxidation states and to (i) MnO2 K2MnO4 MnO + MnO2
4
O2
(Green) (Pink) only in oxides, MO2
form complexes.
2+ –
39. When small atoms like H, C or N are trapped inside the (ii) Lab method : 2Mn + 5S2O8 + 8H2O ® 2MnO 2–
4 l Eu and Yb also exhibit +2 oxidation states.
crystal lattice of these metals, the combination are called 2– +
+ 10 SO 4 + 16 H l Their melting point range between 1000 to 1200 K but
interstitial compounds which are usually non-
Sm melts at 1623 K
stoichiometric. 50. KMnO4 decomposes at 513 K as :
3+
40. Due to similar radii, transition metals form alloy. D l Ln ions may be coloured due to presence of
2KMnO4 K2MnO4 + MnO2 + O2
eg. : Brass (Cu – Zn), Bronze (Cu – Sn). f-electrons
51. KMnO4 behaves as oxidising agent as :
41. Manganese (VI) becomes unstable relative to
l Lanthanoids form Ln(OH)3 which are basic like
– 2–
manganese (VII) and manganese (IV) in acidic solution l Basic medium : MnO4 + e– ¾® MnO4 alkaline earth metal hydroxides.
2– + –
3MnO4 + 4H ® 2MnO4 + MnO2 + 2H2O l Neutral/faintly alkaline medium : l Mischmetal is an alloy which consists lanthanoids
42. All 3d metals forms MO oxides except scandium. – + –
MnO + 4H + 3e ¾® MnO2 + 2H2O (~95%) and Iron (~5%)
4
43. Mn2O7 is acidic, Cr2O3 is amphoteric and CrO is basic in
l Acidic medium : 4. Actinoids
nature
0–14 0–1 2
– +
MnO + 8H + 5e ¾® Mn + 4H2O
– 2+ l Outer electronic configuration : 5f 6d 7s
44. Preparation of K2Cr2O7 : 4
– – l All actinoids are radioactive elements

Na2CO3 H2SO4 52. KMnO4 oxidises I into I2 and IO3 respectively in acidic
FeCr2O4 Fe2O3 + CO2 + Na2CrO4 Na2Cr2O7 There is gradual decrease in the size of atoms or M
3+
O2 and faintly alkaline medium. l
Chromite (Yellow) (Orange)
ore 53. Permangnate titrations in presence of HCl are ions across the series known as actinoid contraction,
KCl
K2Cr2O7 which is greater than lanthanoid contraction.
unsatisfactory since HCl is oxidised to Cl2.
45. Na2Cr2O7 is more soluble than K2Cr2O7 l Their general oxidation state is +3 but these element
46. Chromate and dichromate are interconvertible in can show variety of oxidation states.
2 f-BLOCK ELEMENTS
aqueous solution depending upon pH of the solution.
1. The f-block consists of elements in which 4f and 5f
2– + 2– 3 APPLICATION OF d- AND f-BLOCK ELEMENTS
2CrO4 + 2H ¾® Cr2O7 + H2O orbitals are progressively field and known as inner-
2– – 2– transition elements. 1. TiO is used in pigment industry
CrO7 + 2OH ¾® 2CrO4 + H2O
2. The two series of inner transition elements : 4f (Ce to Lu) 2. MnO2 is used in dry battery cells
47. 2– m m
O 9p 3 pO 2–
and 5f (Th to Lr) are known as lanthanoids and actinoids
O 17 O 16
respectively. 3. TiCl4 and Al(CH3)3, Ziegler catalyst is used to
CrO4 :
2– 2– Cr Cr
Cr Cr2O7 : 126°
O O manufacture polyethene
O O 3. Lanthanoids (Ln) :
O O O
l Outer electronic configuration : 4. PdCl2 is used as catalyst in Wacker process.
(tetrahedral) (dichromate ion)
1–14 0–1 2
(Chromate ion) 4f 5d 6s 5. AgBr is used in photographic industry.
Coordination Compounds
9
Chapter
1 WERNER'S THEORY 4 STRUCTURAL ISOMERISM

m In coordination compounds metals posses two type of valences: primary m Ionisation isomerism : Isomers give different ion in solution eg. [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4.
and secondary
m The primary valences are normally ionisable and are satisfied by m Solvate isomerism : Different number of solvent molecule bonded to metal eg. [Cr(H2O)6]Cl3 and
negative ions. [Cr(H2O)5Cl]Cl2 × H2O
m Secondary valences are non-ionisable and satisfied by neutral m Coordination Isomerism : The ligands are interchanged in both the cationic and anionic ions. eg. [Co(NH3)6]
molecules or negative ions. [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
m Linkage isomerism : It is due to presence of ambidentate ligand eg. [Co(NH3)5ONO]Cl2 and
2 SOME IMPORTANT TERMS [Co(NH3)5NO2]Cl2.
m Double salts : Which are stable in solid state but broken down into
individual constituents when dissolved in water eg. Mohr's salt, [FeSO4 × 5 STEREOISOMERISM
(NH4)2SO4 × 6H2O] and potash alum [KAl(SO4)2 × 12H2O]
m Geometrical isomers : Common in heteroleptic m Optical isomers : These are mirror images that
m Coordination compounds : Which retain their identity in solid state as complexes with in CN = 4 (square planar) and CN = 6. cannot be superimposed on one another.
well as in solution eg K4 [Fe(CN)6] (i) Square planar complex : [MX2L2] (2 isomers), (i) [Co(en)3]3+ have d and l isomer
m Ligands : Species which are directly linked with the central metal in [MABXL] (3 isomers) show cis-trans isomerism. 3+ 3+
complex. These are Lewis base. (ii) Octahedral complex : [MX2(L – L)2], [Ma3b3] (fac-
– en en
(a) Unidentate ligand : Cl , H2O, NH3 mer isomers).
(b) Didentate ligand : NH2CH2CH2NH2, C2O24 - NH3 NH3
en Co Co en
O2N NH3 H3N NO2
(c) Hexadentate ligand : EDTA4– Co Co
(d) Ambidentate ligand : NO2– , SCN– O2N NH3 O2N NO2 en en
NO2 NH3 dextro Mirror laevo
m Coordination number : The number of atoms of the ligands that are
directly bound to the central metal Fac Mer (ii) Cis-[PtCl2(en)2]2+ show optical activity
3– 2+
eg. [Fe(C2O4)3] , here CN = 6, [Ni(NH3)4] , here, CN = 4
m Homoleptic complex : Only one kind of ligands are present eg. 6 IMPORTANT COMPLEXES
[Co(NH3)6]3+ Complex Coordination number Hybridisation Shape Nature Unpaired electrons
m Heteroleptic complex : More than one kind of ligands are present eg. [Co(NH3)6]3+ 6 d2sp3 Octahedral Diamagnetic Zero
[Co(NH3)4Cl2]+ [CoF6]3– 6 sp3d2 Octahedral Paramagnetic Four
[NiCl4]2– 4 sp3 Tetrahedral Paramagnetic Two
3 NAMING OF COORDINATION COMPOUNDS [Ni(CO)4] 4 sp3 Tetrahedral Diamagnetic Zero
m [Cr(NH3)3(H2O)3]Cl3 : Triamminetriaquachromium(III) chloride [Ni(CN)4]2– 4 dsp2 Sequare planar Diamagnetic Zero

3–
[Mn(CN)6] 6 d2sp3 Octahedral Paramagnetic Two
m K2[Zn(OH)4] : Potassium tetrahydroxidozincate(II)
[MnCl6]3– 6 sp3d2 Octahedral Paramagnetic Four
m [Ni(CO)4] : Tetracarbonyl nickel(0) [Fe(CN)6]3– 6 d2sp3 Octahedral Paramagnetic One
m [CoCl2(en)2]+ : Dichloridobis(ethane-1,2-diamine)cobalt(III) ion. [FeF6]3– 6 sp3d2 Octahedral Paramagnetic Five
3–
m [Pt(NH3)2Cl(NO2)] : Diamminechloridonitrito-N-Platinum(II) [Co(C2O4)3] 6 d2sp3 Octahedral Diamagnetic Zero
102 Coordination Compounds NCERT Maps
7 CRYSTAL FIELD THEORY (CFT)

According to CFT, under the influence of ligand field, degeneracy of d-orbitals is destroyed and they split into two or more energy levels. The extent of spilliting depends upon the strength of ligand.
TETRAHEDRAL COMPLEXES OCTAHEDRAL COMPLEXES
dxy, dyz, dxz
t2 eg
d ,d
x2 - y 2 z2
2 3
D z D
5 t 5 0
Barycentre
Dt y D0
Energy
3 x
2
D D
5 t 5 0
dxy, dyz, dxz
e Metal d orbitals t2g
d ,d
x2 - y 2 z2
d orbitals free ion Average energy of the Splitting of d orbitals d ,d dxy, dyz, dxz Average energy of the Splitting of d orbitals
x2 - y2 z2
d orbitals in spherical in tetrahedral crystal d orbitals in spherical in octahedral crystal
crystal field field Free metal ion crystal field field
8 SPECTROCHEMICAL SERIES 9 COLOUR OF COMPLEXES 10 METAL CARBONYLS

Arrangement of ligands in order of increasing field strength. m Colour of complex can be explained by d-d transition m The metal-carbon bond in metal carbonyls possess both s and
I- < Br - < SCN- < Cl- < S2- < F- < OH- < C2O24- < H2O 0 10 p character.
< NCS- < edta4- < NH3 < en < CN- < CO m Metal atom/ion of d or d configuration do not show d-
m The M – C s bond is formed by the donation of lone pair of
m If D0 < P, complex is high spin and ligand is weak field ligand d transition. electrons on the carbonyl carbon into a vacant orbital of the
m The colour of the complex is complementry to that metal.
m If D0 > P, complex is low spin and ligand is strong field ligand
which is absorbed. m The M – C p bond is formed by the donation of a pair of
m Dt = (4/9)D0 electrons from a filled d orbital of metal into the vacant
Complex Colour
antibonding p* orbital of carbon monoxide.
11 APPLICATIONS OF COORDINATION COMPOUINDS [Ti(H2O)6]3+ Violet m Metal to ligand bonding is known as synergic effect.
m Hardness of water is estimated by titration with Na2EDTA [Cu(H2O)4]2+ Blue p*
p p
[Co(NH3)6]3+ Yellow orange
m [(Ph 3 P) 3 RhCl], Wilkinson catalyst is used for the s
M C O
hydrogenation of alkenes. [CoCl(NH3)5]2+ Violet
p
m Excess of Cu and Fe are removed by the chelating ligands D- CuSO4 × 5H2O Blue
Synergic bonding
penicillamine and desferrioxime B. [Co(CN)6]3– Pale yellow O
eg : CO CO eg :
[Ni(H2O)6]2+ Green CO CO OC C CO
m EDTA is used in the treatment of lead poisoning
2+ OC Mn Mn CO OC Co Co CO
[Ni(H2O)4(en)] Pale blue
m Cis-platin effictively inhibit the growth of tumors. OC OC OC C CO
2+
CO CO
[Ni(H2O)2(en)2] Blue/Purple O
m In photography, hypo (Na2S2O3) solution on reaction with
[Mn2(CO)10] [Co2(CO)8]
3–
AgBr form (Ag(S2O3)2) ion. [Ni(en)3]2+ Violet Decacarbonyldimanganese(0) Octacarbonyldicobalt(0)
10
Haloalkanes and Haloarenes Chapter
1 CLASSIFICATION (ii) By electrophilic substitution CH3

4 CHEMICAL REACTIONS
REACTION OF HALOALKANE
CH3 CH3
(a) On the basis of number of halogen atoms X2
+ (A) Nucleophilic substitution reaction
C2H5X CH2 — CH2 CH2 — CH — CH2 Fe/dark
X – d+ d– –
Monohaloalkanes Nu + C X C Nu + X
X X X X X X
Dihaloalkane Trihaloalkane
l Fluoro compounds are not prepared by this method Mechanism : This reaction has been found to
due to high reactivity of fluorine. process by two different mechanism.
(b) Compounds containing sp3 C– X bond:
(i) Alkyl halides or haloalkanes (R – X) (iii) Sandmeyer’s reaction X (i) Substitution nucleophilic bimolecular (SN2) :
+ – l The reaction between CH3Cl and OH ion to yield
Primary (1°) Secondary (2°) Tertiary (3°) NH2 N2X
NaNO2 + HX Cu2X2 methanol follows a second order kinetics, i.e. the rate
+ N2
(ii) Allylic halides (iii) Benzylic halides
273 – 378 K [X = Cl, Br] depends upon the concentration of both reactants.
X –
X H H
– H H –
(iv) From alkenes OH + H HO Cl + Cl
Cl H H HO H
(c) Compounds containing sp2 C – X bond: l Addition of halogen halides : H (T.S.)
(i) Vinylic halides : (ii) Aryl halides : I
l Transition state (T.S.) is formed
X X + I
+H–I l Reaction is generally carried out in acetone or
X Major Minor
polar aprotic solvents
l Addition of halogen:
Addition of Br 2 in CCl 4 to an alkene results in (ii) Substitution nucleophilic unimolecular (SN1) :
2 METHOD OF PREPARATION l It occurs in two steps
discharge of reddish brown colour of Br 2
(a) From alcohols
ZnCl 2
Br2 HO – + (CH3 )3 C — Br (CH3 )3 C — OH + Br –
l R – OH + HCl R – Cl + H 2O CCl4 Br
H 2SO 4
Br Step-I + + Br–
R – Br + NaHSO 4 + H 2O vic-dibromide (CH3 )3 CBr
l R – OH + NaBr
(c) Halogen Exchange Slow
l 3R – OH + PX 3 3R – X + H 3PO 3 (X = Cl, Br) – Step-II
l Finkelstein reaction : + + OH (CH3 )3 COH
l R – OH + PCl 5 R – Cl + POCl 3 + HCl Fast
R – X + NaI ¾® R – I + NaX [X, Cl, Br]
Red P/X 2 l Swarts reaction : l Greater the stability of carbocation greater is the
l R – OH R–X
X 2 = Br 2, I 2 CH3 – Br + AgF ¾® CH3 – F + AgBr¯ rate of reaction
l R – OH + SOCl 2 R – Cl + SO 2 + HCl
l S N1 and S N2 order can be generalised as
3 PHYSICAL PROPERTIES
(b) From Hydrocarbons For S N2 reaction
(i) Free radical halogenation l Boiling point of alkyl halide decrease in the order:
Tertiary halide, secondary halide, primary halide, CH3X
Cl2/UV light RI > RBr > RCI > RCI > RF
+ l Boiling point of isomeric haloalkanes decrease with
or heat Cl For S N1 reaction
Cl increase in branching
NCERT Maps Haloalkanes and Haloarenes 107
l For a given alkyl group reactivity of halide follows Replacement by hydroxyl group
(d) Inversion, retention and recemisation l
same order in both the mechanisms
C2H5 C2H5 C2H5 Cl OH
R – I > R – Br > R — Cl >> R – F Y Y
H H H
Y (i) NaOH, 623K, 300 atm
(iii) Stereochemical aspects of nucleophilic (inversion) X Y (retention)
+
H3C CH3 CH3 (ii) H
substitution reaction :
B A
Some important concepts Y Presence of an electron with drawing group at o/p
(a) Optical activity : positions increases the reactivity of haloarenes
A + B
The compounds which rotate plane polarised 50% 50% Cl OH
(racemisation)
light are optically active (I) NaOH, 443 K
l If a compound rotates plane polarised light in (B) Elimination reactions +
(ii) H
clockwise direction. It is called dextrorotatory Br
Alc. Alc. NO2 NO2
and if it rotates in anti clock wise direction it is Hofmann
KOH/D KOH/D Minor
Major product (B) Electrophilic substitution reactions :
called laevorotatory.
(b) Molecular asymmetry, Chirality and enantiomers: Saytzeff product Haloarenes undergo electrophilic reactions of the
l If the spatial arrangment of four different groups benzene ring such as halogenation, nitration,
(C) Reaction with metal
around the central carbon is tetrahedral then the l Preparation sulphonation and friedel crafts reaction.
carbon is called asymmetric carbon dry MgBr
Br + Mg
ether Reaction with metals
l The compounds which are non-superimposable on
Grignard reagent (i) Wurtz-Fittig reaction
their mirror images are Chiral and are called
(Organometallic compound) X
enantiomers R
RMgX + H2O RH + Mg (OH)X Ether
l The stereoisomers having no mirror image + Na + RX
Hydrocarbon
relationship are called diastereomers.
Reaction of Haloarenes (ii) Fittig reaction
l A mixture containing two enantiomers in equal
(A) Nucleophilic substitution : Aryl halides are extremely X
proportions will have zero optical rotation. Such
less reactive towards nucleophilic substitution reactions Ether
mixture is known as racemic mixture. 2 + 2 Na
due to following reasons :
(c) Retention : In general, if during a reaction, no (i) Resonance effect : Lone pair of chlorine is in Diphenyl
bond to the stereocentre is broken, the reaction is conjugation with benzene resulting in double bond Polyhalogen Compounds
said to proceed with retention of configuration hn
character of C — Cl bond. As a result bond cleavage 2CHCl3 + O2 2COCl2 + 2HCl
CH3 in haloarene is difficult. Phosgene
CH3
D
H CH2 — OH + HCl H CH2 — Cl + H2O (ii) Difference in hybridization of carbon atom in C– X bond
CH2 CH2 (iii) Instability of phenyl cation
CH3 CH3 (iv) Repulsion between haloarene and approaching
(–)-2-methylbutan-1-ol (+)-1-chloro-2-methylbutane nucleophile
Alcohols, Phenols and Ethers
11
Chapter
1 PREPARATION OF ALCOHOLS 2 PREPARATION OF PHENOLS Acidity of alcohols : Acidic strength order
(i) From alkenes
(a) By acid catalysed hydration : (a) From haloarenes R R
– + CHOH > R COH
Cl ONa OH R–CH2OH >
+ R R
CH3CH=CH2+H2O H CH3–CH–CH3(Major)
623 K HCl Acidity of phenols : Phenols are more acidic than alcohol because
+ NaOH
(b) By hydroboration - oxidation OH 300 atm conjugate base of phenol (phenoxide ion) is resonance stabilised.
–
CH3–CH=CH2+ (H–BH2)2 ® CH3–CH2–CH2–BH2 (b) From benzene sulphonic acid O O O O O–
CH3CH=CH2 SO3H OH – –
CH3CH=CH2
(CH3CH2CH2)3B (CH3CH2CH2)2BH Oleum (i) NaOH
– (ii) H
+ –
H2O 3H2O2/OH
(c) From diazonium salts + (ii) Esterification : H+
3CH3CH2CH2OH + B(OH)3 NH2 N2Cl
–
OH Ar/R–O–H + R¢COOH Ar/ROCOR¢ + H2O
Ester
The alcohol formed looks as if it has been formed
by the addition of water to alkene in a way opposite NaNO2 H2O COOH COOH
to Markovnikov’s rule. HCl Warm OH + OCOCH3
273-278 K H
(ii) From carbonyl compounds + (CH3CO)2O + CH3COOH
(d) From cumene
(a) By reduction of aldehydes and ketones : H 3C
CH(CH3)2 C–O–OH OH Salicylic acid (Aspirin)
H 3C
RCHO + H2 Pd RCH2OH +
(b) Reactions involving cleavage of C-O bond in alcohols
NaBH4 O2 H (i) Reaction with hydrogen halides : (Lucas test)
R–CH–R¢ + CH3COCH3
RCOR¢ H2O ROH + HX ® R–X + H2O
OH Cumene Lucas reagent (Conc. HCl and ZnCl2)
Cumene Tertiary alcohol produce turbidity with Lucas reagent immediately
(b) By reduction of carboxylic acids and esters : hydroperoxide
Primary alcohols do not produce turbidity at room temperature.
(i) LiAlH4 3 PHYSICAL PROPERTIES
RCOOH RCH2OH (ii) Reaction with phosphorus trihalides :
(ii) H2O High boiling points of alcohols are mainly due to the 3R–OH + PX3 ® 3R–X + H3PO3 (X = Cl, Br)
R¢OH H2 presence of intermolecular hydrogen bonding in them. H SO
RCOOH RCOOR¢ RCH2OH (iii) Dehydration : C2H5OH 2 4 CH2 = CH2 + H2O
H+ Pd Solubility of alcohols and phenols in water is due to their 443 K
(iii) From Grignard reagent + R¢OH
ability to form hydrogen bonds with water. Relative ease of dehydration : Tertiary > Secondary > Primary
H 2O (iv) Oxidation
HCHO + RMgX ® RCH2OMgX RCH2OH
4 CHEMICAL REACTIONS : CrO3
1° alcohol RCH2OH RCHO
H 2O [A] Reaction of alcohols PCC
RCHO + R¢MgX ® R – CH – OMgX CH3–CH=CH–CH2OH CH3–CH=CH–CHO
(a) Reactions involving cleavage of O-H bond
(i) Acidity of alcohols and phenols CrO 3
R¢ R – CH – OH R–CH–R¢ R–C–R¢
Reaction with metals
– + OH O
R¢ 2° alcohol 2R–O–H + 2Na ® 2RONa + H2
R Cu Cu
Phenol reacts with aqueous NaOH RCH2OH RCHO R–CH–R¢ R–C–R¢
H2O 573 K 573 K
RCOR + R¢MgX ® R – C – OMgX OH ONa
CH3 OH O
R¢ R
Cu
R – C – OH + NaOH + H2O CH3–C–OH CH3–C=CH2
573 K
CH3 CH3
3° alcohol R¢
112 Alcohols, Phenols and Ethers NCERT Maps
[B] Reaction of phenols : 5 PREPARATION OF COMMERCIALLY IMPORTANT ALCOHOLS Mechanism :

(a) Electrophilic aromatic substitution ZnO–Cr2O3 CH3
(i) Nitration : Methanol : CO + 2H2 CH3OH + Slow +
200-300 atm CH3–C—O–CH3 (CH3)3C + CH3OH
OH OH OH H
573-673 K CH3 Stable carbonium ion
NO2 Invertase
Dilute + Ethanol : C12H22O11 + H2O C6H12O6 + C6H12O6 + – Fast
Glucose Fructose (CH3)3C + I (CH3)3C – I
HNO3
Zymase (ii) Electrophilic substitution
C6H12O6 2C2H5OH + 2CO2
OH OH NO2 (a) Halogenation
Ethanol is made unfit for drinking by mixing in it some copper
O2N NO2 sulphate and pyridine. It is known as denaturation of alcohol. OCH3 OCH3 OCH3
Conc. (Picric acid) Br
HNO3 6 ETHERS Br2 in
+
(Poor yield) Preparation of ethers Ethanoic acid
NO2 H2SO4
OH OH (a) Dehydration of alcohols : CH3CH2OH C2H5OC2H5
OH 413 K Br Minor
SO3H O2N NO2 – + SN2 Major
Conc. (b) Williamson synthesis : R–X + R¢ – ONa R–O–R¢ + NaX
Conc. (b) Friedel-Crafts reaction :
H2SO4 l Alkyl halide is primary l Alkylation
HNO3
l Alkoxide ion can be primary, secondary or tertiary. OCH3
OCH3
SO3H NO2 CH3 CH3
(ii) Halogenation – + anhyd. AlCl3
OH OH OH CH3–C–ONa + CH3—Br CH3–C–O–CH3 + CH3Cl
CS2
Br CH3 CH3
Br2 in CS2 + l If tertiary alkyl halide is used, then only alkene is formed. CH3
273 K CH3 Major
– + +
Br (Minor) CH3–C–Br + CH3–ONa CH3–C=CH2 OCH3
(Major)
OH CH3 CH3 CH3
OH Chemical reactions :
Br Br (i) Cleavage of C–O bond in ether : R–O–R + HX ® RX + R–OH
Br2
(White ppt) l The order of reactivity of halogen halides HI > HBr > HCl Minor
H 2O l Acylation
l Cleavage of ether takes place with concentrated HI or HBr OCH3 OCH3
Br at high temperature.
(b) Kolbe’s reaction : 2, 4, 6-Tribromophenol anhyd.
Example 1 : Excess
OH ONa OH + CH3COCl
CH3–O–C2H5 CH3–I + C2H5–I AlCl3
COOH HI
NaOH (i) CO2 O CH3
+
H –
(ii) H Step-1: CH3–O–CH2CH3 + H—I CH3–O–CH2CH3 + I Major
+
(Salicylic acid) H SN2 +
(c) Reimer-Tiemann reaction –
Step-2: I + CH3—O–CH2CH3 CH3–I + CH3CH2OH OCH3 O
– + – + +
OH ONa ONa OH
CHCl2 CHO CH3
CHO
CHCl3 NaOH H
+
+ –
Step-3:CH3CH2–O–H + H—I CH3CH2–OH2 + I
aq. NaOH
(c) Nitration : Minor
(d) Reaction with Zinc dust and chromic acid Salicylaldehyde Step-4: – + SN2 OCH3 OCH3 OCH3
O OH I + CH2—OH2 CH3CH2–I + H2O
NO2
CH3 H2SO4
Na2Cr2O7 Zn CH3 +
+ ZnO HNO3
H2SO4 SN1
Example 2 : CH3–C–O–CH3 + HI CH3OH + (CH3)3C–I Minor
NO2
O CH3 Major
(Benzoquinone)
Aldehydes, Ketones and Carboxylic Acids
12
Chapter
ALDEHYDES AND KETONES

(ii) From nitriles
1 PREPARATION OF ALDEHYDES NMgBr R R
PhMgBr
OH HCl gas O
(i) From acyl chlorides (Rosenmund reduction) CH3CH2C º N Ether CH3CH2 – C – Ph O+ + H2O
CHO O OH dil HCl O
O Cl + R R
H3 O Ketone Ketal
H2 CH3CH2 – C – Ph
(iii) From aromatic hydrocarbons O R
Pd-BaSO4
O OH
(ii) From Nitriles and Esters anhyd. O+H2N=Z C C=N–Z+H2O
+ R – C – Cl NHZ
m Stephen reaction AlCl3
+
H3 O (d) Addition of ammonia and its derivative
RCN + SnCl2 + HCl RCH = NH RCHO
3 CHEMICAL REACTIONS
(Reduction by DIBAL-H Z = alkyl, aryl, – OH, – NH2, C6H5NH etc
(i) Nucleophilic addition reactions
(i) DlBAL-H Reagent Carbonyl derivative Product name
CN CHO (a) Addition of hydrogen cyanide (HCN)
(ii) H2O –
O H
+ OH
OC2H5 (i) DlBAL-H H C = O + CN C C Ammonia NH Imine
(ii) H2O CN CN
O O Schiff’s base
Cyanohydrin Amine
(iii) From Hydrocarbons (b) Addition of NaHSO3 NR
m Etard reaction SO3H
CHO O + NaHSO3 Hydroxylamine N – OH Oxime
CH3
CH(OCrOHCl2)2 H O+ ONa
CS2 3
+ CrO2Cl2 SO3Na Hydrazine N – NH2 Hydrazone
Proton
(Chromium
Complex) transfer
OH NO2
m Gatterman-Koch reaction (Crystalline)
CHO m Bisulphite addition product is crystalline 2,4-DNP N – NH NO2 2, 4- Dinitrophenyl-
CO, HCl hydrazone
m It is water soluble and converted back to original carbonyl
Anhyd.AlCl3/CuCl
O
compound by treating it with acid or alkali
Semicarbazide N–NH –C–NH2 Semicarbazone
m It is useful for separation and purification of aldehydes.
2 PREPARATION OF KETONES (c) Addition of alcohols :
(ii) Reduction
(i) From acyl chlorides
OR¢ OR¢ (a) Reduction to alcohols : Aldehydes and ketones are
R¢OH R¢OH
2R – Mg – X + CdCl2 R2Cd + 2 Mg(X)Cl RCHO R – CH + R – CH reduced to primary and secondary alcohols respectively
HCl gas H
O O OH OH by NaBH4 or LiAlH4
Aldehyde Hemiacetal Acetal
2R¢ – C – Cl + R2Cd 2R¢ – C – R + CdCl2 (b) Reduction to hydrocarbons
118 Aldehydes, Ketones and Carboxylic Acids NCERT Maps
Zn – Hg (ii) Cross aldol condenstation (c) From nitriles and amides

O HCl + H2O (Clemmensen reduction)
O
CHO O +
H or O H
– +
H or O H
–
NH2 – NH2 KOH/ OH OH O R – CN H 2O

R – C – NH2 D
RCOOH
O HCl N – NH2 + N2 –
D OH
+ D CH = CH – C
(Wolff-Kishner reduction) CONH2 COOH
(iii) Oxidation H 3O
+
Other reactions + NH3
m Aldehydes are oxidised to carboxylic acids on treatment (v) Cannizzaro reaction
D
O
with common oxidising agents like HNO3, KMnO4, Conc. KOH – + (d) From Grignard reagents
2HCHO D CH3OH + H – C – O K
K2Cr2O7 etc. O
Dry – +
m M i l d o x i d i s i n g a g e n t s ( Te s t s o f a l d e h y d e s ) CHO CH2OH COO Na
– + R – Mg – X + O = C = O Ether
R – C – O Mgx
Tollen’s test : Silver mirror is formed on warming +
H 3O
aldehyde with freshly prepared ammoniacal Conc. NaOH R – COOH
2 D +
AgNO3 solution (Tollen’s reagent) (e) From acyl halides and anhydrides
+ – – (vi) Electrophilic substitution reaction H 2O –
RCHO + 2 [Ag(NH3)2] + 3OH ® RCOO + 2Ag RCOCl R – COOH + Cl
CHO CHO H 2O
2H2O + 4NH3 (C6H5CO)2O 2C6O5COOH
HNO3/H2SO4
Fehling’s Test : 273 – 283 K
NO2 (f) From esters
m On heating aldehyde with Fehling’s reagent, a reddish
COC2H5 COOH
brown precipitate is obtained.
2+ – –
R – CHO + 2Cu + 5OH®RCOO + Cu2O ¯+ 3H2O
+
H 3O
4 CARBOXYLIC ACIDS + C2H5OH
(red-brown ppt)
m Methods of Preparation
m Aromatic aldehydes do not respond to this test O
(a) From primary alcohols NaOH
Haloform reaction : O CH3CH2CH2COO Na + C2H6OH
–
Oxidation of methyl ketones (i) alkaline KMnO4

RCH2OH + RCOOH Ethyl butanoate +
O O (ii) H3O H 3O
X2 – + CrO3 – H2SO4
R – C – CH3 R – C – O Na + CH3(CH2)8CH2OH CH3(CH2)8COOH CH3CH2CH2COOH
NaOH Jones reagent
CHX3(X = Cl, Br, I) Butanoic acid
m Iodoform reaction with I2/NaOH is used for detection of (b) From alkylbenzenes
5 PHYSICAL PROPERTIES
CH 3 CO or CH 3 CH(OH) groups which produces CH3 COOK COOH
CH3CHO group on oxidation. m Due to extensive association by intermolecular
+
KMnO4– KOH H3O
D
H-bonding carboxylic acids have higher boiling point than
(iv) Reaction due to a-hydrogen
aldehydes, ketones and alcohols of comparable
(i) Aldol condensation reaction :
dil. NaOH
COOK COOH molecular mass.
2CH3 – CHO CH3 – CH – CH2 – CHO +
KMnO4– KOH H3O m In vapour phase or in aprotic solvent most carboxylic
OH D
D
CH3 – CH = CH – CHO acids exist as dimer
– H 2O
NCERT Maps Aldehydes, Ketones and Carboxylic Acids 119
6 CHEMICAL REACTIONS (b) Reaction involving cleavage of C – OH bond (c) Reactions involving – COOH group
(a) Reactions involving cleavage of O – H bond (i) Formation of anhydrides (i) Reduction
(Acidity) (i) LiAlH4/ether or B2H6
RCOOH + RCH2OH
(ii) H3O
– + O O
2RCOOH + 2Na ® 2RCOO Na + H2 + OO
H /D
CH3 – C + C – CH3 or
– + (ii) Decarboxylation
RCOOH + NaOH ® RCOO Na + H2O P2O5/D O
OH HO Ethanoic anhydride
NaOH & CaO
– + RCOONa D
R – H + Na2CO3
RCOOH + NaHCO3 ® RCOO Na + H2O + CO2
(ii) Esterification
m Carboxylic acids evolve CO2 gas on reaction with NaHCO3. +
(d) Substitution reactions in the hydrocarbon part
H
This is used to detect the presence of carboxyl group in an RCOOH + R¢OH RCOOR¢ + H2O (i) Halogenation (Hell - Volhard-Zelinsky reaction)
organic compound. (iii) Reaction with PCl5, and SOCl2 X

(i) X2/Red P
Carboxylic acids dissociate in water to give resonance RCH2 – COOH R – CH – COOH
(ii) H2O
stabilised carboxylate anions and hydronium ion RCOOH + PCl5 ® RCOCl + POCl3 + HCl X = Cl, Br
RCOOH + SOCl2 ® RCOCl + SO2 + HCl (ii) Ring substitution

O O O
+ (iv) Reaction with ammonia Aromatic carboxylic acids undergo electrophilic
R – COOH + H2O ƒ H3O + R – C R–C ºR–C – m
O O O –+ CONH2 substitution reaction

COOH COONH4
+ NH3 ƒ D m They do not undergo Friedel-Crafts reaction because
–H2O
m Effect of substituents on the acidity of carboxylic acids : the carboxyl group is deactivating and catalyst
Ammonium Benzamide
O Electron withdrawing group (EWG) benzoate aluminum chloride gets bonded to carboxyl group
EWG stabilises carboxylate anion and increases + m Nitration
O acidic stength COOH COONH4
(Phthalic acid) + NH3 +
COOH COONH4 COOH COOH
O Electron donating group (EDG) destablises
Ammonium Conc. HNO3
EDG the carboxylate anion and decreases phthalate
Conc. H2SO4
O acidic strength NO2
D (–2H2O) m-nirtobenzoic acid
m Acidic strength order of some carboxylic acid m Bromination
CF 3 COOH > CCl 3 COOH > CHCl 2 COOH > NO 2 CH 2 COOH> O
NCCH2COOH > FCH2COOH > ClCH2COOH > BrCH2 COOH > – NH3 CONH2 COOH COOH
(Phthalimide) NH Strong
HCOOH > ClCH2CH2COOH > C6H5COOH> C6H5CH2COOH > heating CONH2 Br2/FeBr3
O Phthalamide
CH3COOH > CH3CH2COOH Br
Direct attachment of groups such as phenyl or vinyl to the carboxylic m-bromobenzoic acid
acid increases the acidity of corresponding carboxylic acid,
Contrary to the decrease expected due to resonance effect.
13
Amines Chapter
1 CLASSIFICATION (iii) Reduction of Nitrites 5 CHEMICAL REACTIONS

LiAlH 4 (i) Basic character of amines
R R R–CN R–CH 2 –NH 2
RNH2 or H 2 /Ni or Na(Hg)/C 2 H 5 OH
N–H N – R" m Order of bascity of amines in gaseous phase:
R¢ R¢ (iv) Reduction of amides
Primary Secondary Tertiary tertiary amine > secondary amine > primary amine > NH3
O
(1°) (2°) (3°) (i) LiAlH4 m Basic nature of amines in aqueous medium:
m Amines are said to be simple when all the alkyl groups are R – C – NH2 (ii) H2O
R – CH2 – NH2
(a) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
same and mixed when they are different. (v) Gabriel phthalimide Synthesis
(b) (CH3)2NH > CH3NH2 > (CH3)3N > NH3
O O O
2 NOMENCLATURE m Aryl amines are less basic than alkylamines because in
KOH – + R–X
NH2 NH NK N–R arylamine the lone pair on nitrogen is involved in
resonance.
CH3 – NH – CH2CH3
Propan-2-amine N-methylethanamine O O O
(ii) Alkylation
N(CH3)3 –
COO R–NH2
NaOH(aq) R – NH2 + CH3 – Br RNH – CH3 + HBr
+
– (1°-amine)
COO
NH2 (iii) Acylation
m This method is useful in the preparation of aliphatic O
Propan-2-en-1-amine N,N-Dimethylbenzenamine C2H5NH2 + CH3 – C – Cl
Base
C2H5 – NH – C – CH3 + HCl
primary amine
NH2 O
3 PREPARATION OF AMINES m Aromatic primary amine is not prepared by (iv) Carbylamine reaction (chemical test)
(i) Reduction of nitro compounds D
this method because arylhalide donot undergo R – NH2+ CHCl3 +3KOH R – NC + 3KCl + 3H2O
H2/Pd
a. PhNO2 PhNH2 nucleophilic substitution reaction. It is used as a test for primary amines
Ethanol
(vi) Hoffmann bromamide degradation reaction (v) Reaction with nitrous acid (With primary aliphatic amine)
Sn/HCl
b. PhNO2 PhNH2 O +
or Fe + HCl NaNO2 – H 2O
R – C – NH2 + Br2 + 4NaOH R – NH2 + Na2CO3 R – NH2+ HNO2 [R – N2Cl ] ROH + N2+ HCl
HCl
(ii) Ammonolysis of Alkyl Halides
+ 2NaBr + 2H2O (vi) Reaction with arylsulphonyl chloride
+ NaOH
NH3 + R – X RNH3X RNH2 m Primary amine formed contains one carbon less than that (Hinsberg's reagent)
+ present in the amide.
R4NX m Reaction with primary amine
RNH2 RX R2NH RX R3N RX
Quaternary 4 PHYSICAL PROPERTIES PhSO2Cl+ C2H5NH2 PhSO2NHC2H5
(1°) (2°) (3°)
ammonium salt (Soluble in alkali)
m Aniline and other arylamines are usually colourless but
m Ammonolysis has disadvantage of yielding a mixture of get colour on storage due to atmospheric oxidation m Reaction with secondary amine
primary, secondary, tertiary amines and also quaternary Lower aliphatic amines are soluble in water because they
m PhSO2Cl+ (C2H5)2NH PhSO2N(C2H5)2
ammonium salt form hydrogen bonds with water molecules. (insoluble in alkali)
m Primary amine is obtained as major product by taking large m Order of boiling points of isomeric amines: Primary > m Tertiary amines do not react with benzensulphonyl
excess of NH3. Secondary > Tertiary chlorides.
NCERT Maps Amines 125
(vii) Electrophilic substitution reaction: 6 DIAZONIUM SALTS (b) Replacement by iodide ion
(a) Bromination + –
m Primary aliphatic amines form highly unstable Ar N2Cl +KI ArI + KCl + N2
NH2 NH2
alkyldiazonium salts. (c) Replacement by fluoride ion
Br2 Br Br
(White precipitate)
m Primary aromatic amines form arenediazonium salts + – + – D
H 2O Ar N2Cl + HBF4 Ar N2BF4 Ar – F + BF3+ N2
(2, 4, 6-tribromoaniline) which are stable for a short time in solution at low
temperature (273-278 K) due to resonance (d) Replacement by Hydrogen
Br
+
O O –
Ar N2Cl + H3PO2 + H2O ArH + N2 + H3PO3 + HCl
N N N=N N=N N=N N N + –
NH2 NH NH NH2 Ar N2Cl + CH3CH2OH ArH + N2 + CH3CHO + HCl
–
(CH3CO)2O Br2 OH
+
(e) Replacement by hydroxyl group
Pyridine CH3COOH or H
+ – 283 K
Ar N2Cl + H2O ArOH + N2 + HCl
Br Br
(Major) (i) Method of preparation of C6H5N2Cl
(f) Replacement by –NO2 group
273- 278 K + +
(b) Nitration C6H5NH2 + NaNO2 + 2HCl C6H5N2Cl – –
N2Cl N2BF4 NO2
NH2 NH2 NH2 NH2
(ii) Physical properties NaNO2
HNO3,H2SO4 NO2 + HBF4
+ + m Benzenediazonium chloride is colourless crystalline Cu, D
288 K
NO2 solid and readily soluble in water.
m It is stable in cold but reacts with water when warmed. B. Reactions involving retenation of diazo group
NO2 (47%) (2%) (Coupling reaction)
m Benzenediazonium Fluoroborate is water insoluble
(51%) and stable at room temperature.
–
m Controlled nitration reaction Cl
(iii) Chemical reactions N
NH2 NHCOCH3 NHCOCH3 NH2 +
A. Reactions involving displacement of nitrogen N OH
–
(CH3CO)2O HNO3×H2SO4 OH
pyridine +
(a) Replacement by halide or cyanide ion –
OH
288 K or H + N=N OH
Sandmeyer reaction
NO2 NO2 phenol (Orange dye)
(Major) Cu2Cl2/HCl p-hydroxyazobenzene
ArCl + N2
–
(c) Sulphonation Cu2Br2/HBr Cl
+ –
+ – + Ar N2X ArBr + N2 N
NH2 NH3HSO4 NH2 NH3
CuCN/KCN N
+
NH2
ArCN + N2
H2SO4 453-473 K
Gatterman reaction H
+
+ N=N NH2
Anilinium Cu/HCl
SO3H SO
–
+
ArCl + N2 + CuX
hydrogen 3 – (Yellow dye)
Ar N2X aniline
sulphate Sulphanilic Zwitter Cu/HBr
acid ion ArBr + N2 + CuX p-aminoazobenzene
14
Biomolecules Chapter
1 CARBOHYDRATES m Carbonyl group present is an aldehyde is confirmed by O

the given reaction H– C
1
Classification of Carbohydrates: H OH HO H
CHO COOH 2
A. Monosaccharides: A carbohydrate that cannot be Br2 H OH H OH H OH
(CHOH)4 (CHOH)4 (Gluconic acid) O 3 O
hydrolysed further to give simpler unit of polyhydroxy H2O HO H HO H HO H
4
aldehyde or ketone. Examples: Glucose, fructose, CH2OH CH2OH H OH H OH H OH
5
arabinose etc. H H OH H
m Acetylation of glucose gives glucose pentaacetate which
B. Oligosaccharides: These carbohydrates yield two to ten confirms presence of five OH groups CH2OH 6 CH2OH CH2OH
monosaccharide units on hydrolysis. They are further CHO CHO O a-D-(+)-glucose b-D-(+)-glucose
classified as disaccharides, trisaccharides etc. Acetic
(CHOH)4 (CHO – C – CH3)4 m a and b forms of glucose are called anomers. Six
C. Polysaccharides: They yield a large number of anhydride O
CH2OH membered cyclic structure of glucose is called pyranose
monosaccharide units on hydrolysis. CH2O – C – CH3 structure
Example : Starch, Cellulose etc. m Glucose and gluconic acid is oxidised to saccharic acid
CH2OH CH2OH
Monosaccharides: by nitric acid. This indicates presence of primary –OH
group H O H H O OH
m If a monosaccharide contains an aldehyde group, it is
CHO COOH COOH H H
known as an aldose and if contains a keto group, it is
called ketose (CHOH)4
Oxidation
(CHOH)4
Oxidation
(CHOH)4
OH H OH H
HO OH HO H
(a) Glucose: It is an aldohexose CH2OH COOH CH2OH
Saccharic acid H OH H OH
Structure of glucose Gluconic
acid a-D-(+) -Glucopyranose b-D-(+) -Glucopyranose
Glucose has been assigned the structure
CHO m Fischer suggested following configuration of D(+) (b) Fructose
glucose CHO m Fructose is a ketohexose
(CHOH)4 on the basis of following evidences:
H HO m Following structures have been assigned to this molecule
CH2OH
HO H 1
CH2OH 6 1 6
m Its molecular formula is found to be C6H12O6. H OH HOH2C CH2OH HOH2C OH
2C =O O O
H OH 5 2 5 2
m On prolonged heating with HI, it forms n-hexane, HO
3
H
CH2OH H HO H HO
suggesting carbons are linked in straight chain. H
4
OH H OH H CH2OH
4
5 3 3 1
m Presence of carbonyl group is confirmed by the following Cyclic Structure of Glucose H OH 4
reactions. m The given observations could not explain chain structure CH2OH OH H OH H
6
CN of glucose D-(–)-fructose a-D-(–)-Fructofuranose b-D-(–)-Fructofuranose

CH (i) It does not react with NaHSO3 or Schiff's reagent
OH CHO CH = N – OH Tests of Glucose and Fructose
HCN NH2OH (ii) Pentaacetate of glucose does not react with NH2OH.
(CHOH)4 (CHOH)4 (CHOH)4 (iii) Glucose exist in two different crystalline forms, a and b Both glucose and fructose reduce Tollen's reagent and
CH2OH CH2OH CH2OH forms. Fehling's solution. They are also called reducing sugars.
NCERT Maps Biomolecules 131
2 DISACCHARIDES 3 POLYSACCHARIDES 5 VITAMINS

m Two monosaccharides are joined together by an oxide Amylose (15-20% of starch) (i) Fat soluble vitamins: vitamins are soluble in fat. These are
linkage formed by loss of water molecule forming a (i) Starch
Amylopectin (80-85% of starch) vitamins A, D, E and K.
disaccharide. Such a linkage between two monosaccharide (ii) Water soluble vitamins: B group vitamins and vitamin C
units through oxygen atom is called glycosidic linkage. m Amylose is water soluble component. It is long are water soluble vitamins.
(i) Sucrose unbranched chain with 200-1000 a-D-(+) glucose units.
Name of Vitamin Deficiency Diseases
CH2OH m Amylopectin is water insoluble component. It is branched
6 1
HOH2C chain polymer of a-D-glucose units. 1. Vitamin A Xerophthalmia
H 5 O H O H
(ii) Cellulose 2. Vitamin B1 (Thiamine) Beri beri
H 5
4 1 2 m It is a straight chain polysaccharide 3. Vitamin B2 (Riboflavin) Cheilosis
OH H O H HO
HO m It is composed of b-D-glucose units
3 2
CH2OH 4. Vitamin B12 Pernicious anaemia
Glycosidic 3 4
6 (iii) Glycogen 5. Vitamin C (Ascorbic acid) Scurvy
H OH linkage m It is called animal starch.
OH H 6. Vitamin D Rickets (in children)
m Its structure is similar to amylopectin and is rather more
a-D-glucose b-D-fructose osteomalacia (in adults)
highly branched. 7. Vitamin K Increased blood clotting time
m It is dextrorotatory
m It is non reducing sugar 4 PROTEINS 6 NUCLEIC ACIDS
(ii) Maltose m All proteins are polymers of a-amino acid m Complete hydrolysis of DNA (or RNA) yields a pentose
6 6 m The amino acids which can be synthesised in the body, sugar, phosphoric acid and nitrogen containing
CH2OH CH2OH
are known as non-essential amino acids. heterocyclic compound (called bases)
H 5 O H H 5 O The amino acids which cannot be synthesised in the body
H m m In DNA molecule, the sugar moiety is b-D-2-deoxyribose
H H and must be obtained through diet are known as essential
4 1 4 1 whereas in RNA molecules, it is b-D-ribose
OH H O OH H amino acids. 5
HO OH HOH2C5 O OH HOH2C O OH
3 2 3 2 m In aqueous solution, the carboxyl group can lose a proton
4 1 4 1
H OH H OH and amino group can accept a proton, giving rise to a
H H H H
a-D-glucose b-D-glucose dipolar ion known as zwitter ion H H H H
3
m It is dextrorotatory O O 3 2 2
–
m It is reducing sugar R – CH – C – OH R – CH – C – O OH OH OH H
It gives positive test with Tollen's reagent and Fehling's (Zwitter ion)
m NH2 NH 3 b-D-ribose b-D-2-deoxyribose
solution
m Bases in DNA: Adenine (A), guanine (G), Cytosine (C)
(iii) Lactose Structure of Proteins
6
and thymine (T)
6
CH2OH CH2OH m Proteins can be classified into two types on the basis of
m Bases in RNA: Adenine (A), guanine (G), cytosine (C) and
their molecular shape O
5 O 5 O uracil (U)
HO H OH (a) Fibrous proteins: 5' –
5'
H H m The polypeptide chains run parallel and held together by HO – H2C Base O – P – O – H2C O Base
4 1 O 4 1 O
OH H OH H hydrogen and disulphides bonds giving fibre like structure O
–
4' 1'
4' 1'
H 3 H 3 H
2 2 m They are insoluble in water e.g. keratin, myosin H H H H
H H H H
H OH H OH (b) Globular proteins: 3' 2'
3' 2'
a-D-galactose b-D-glucose m In this case polypeptide chains coil around to give a
m It is dextrorotatory and is a reducing sugar spherical shape HO OH HO OH
m It reduces Tollen's reagent and Fehling's solution m They are soluble in water e.g. insulin, globulin nucleoside nucleotide
Polymers
15
Chapter
1 CLASSIFICATION OF POLYMERS Uses: It is used in making sheets, bristles for brushes and in
m Classification based on source textile industry
a. Natural polymers : These polymers are found in plants and animals. Examples are proteins, starch, rubber etc. m Nylon 6:
b. Semi-synthetic polymers : Cellulose derivatives as cellulose acetate and cellulose nitrate are semi-synthetic polymers. H
N O
c. Synthetic polymers : These are man made polymers examples are Buna-S, nylon 6,6, polythene etc. O 533-543 K H
H2O
–[C–(CH2–)5N–]n
2 TYPE OF POLYMERISATION REACTION Nylon 6
Caprolactam
A. A d d i t i o n p o l y m e r i s a t i o n o r c h a i n g r o w t h l High density polythene:
polymerisation TiCl4,(C2H5)3Al Use: It is used in manufacture of tyre cords, fabrics and ropes.
nCH2 = CH2 –(CH2 – CH2–)n
l The molecules of the same monomer or different (333-343) K (6-7) atm ii. Polyesters: These are condensation products of
High density polythene
monomers add together on a large scale to form a dicarboxylic acids and diols.
polymer. l Catalyst TiCl4, (C2H5)3Al is called Ziegler-Natta catalyst
COOH
l The polymer obtained has high density due to close C C
l Monomers used are unsaturated compounds, e.g.
alkenes, alkadienes and their dirivatives packing.
nHOCH2 – CH2OH + –[OCH2 – CH2 – O – C C–]n
l Chain growth can take place through the formation of l These are also called linear polymers.
either free radicals or ionic species. l It is also chemically inert, more tough and hard. (Ethylene glycol) Terylene (dacron)
COOH
l The addition polymers formed by the polymerisation ii. Polytetrafluoroethene (Teflon) (Terephthalic acid)
of a single monomeric species are known as Catalyst Use: It is used in blending with cotton and wool fibres.
homopolymers. nCF2 =CF2 –[CF2 – CF2–]n
high pressure
Teflon iii. Phenol formaldehyde polymer (Bakelite)
Example : Polythene Uses: It is used in making oil seals, gaskets and non-stick OH OH OH OH
l The polymers made by addition polymerisation from surface coated utensils.
two different monomers are termed as copolymers. + CH2O
H+ or
–
OH + OH + HO OH
iii. Polyacrylonitrile: OH
Example : Buna-S CN
Polymerization OH OH
n CH2 = CH – CH = CH2 + n C6H5CH = CH2 nCH2 = CHCN [–CH2 – CH–]n
1,3-Butadiene Styrene Peroxide catalyst
OH OH OH OH
Uses: It is used as a substitute for wool in making H2C CH2
commercial fibers as orlon or acrilan. n OH +
C6H5 H
B. Condensation polymerisation or step growth

–(CH2 – CH = CH – CH2 – CH – CH2– )n polymerisation Novolac
Butadiene-styrene copolymer (Buna-S)
l It generally involves a repetitive condensation reaction l Novolac on heating with formaldehyde undergoes cross
l Preparation and uses of important addition polymers between two bi-functional or tri-functional monomeric linking to form bakelite
i. Polythene: There are two types of polythene units. l Bakelite is thermosetting polymer which can not be reused or
Low density polythene: l This is also called step growth polymerisation. remoulded
l It is obtained by the polymerisation of ethene under
OH OH OH
Preparation and uses of some polymers obtained by H2 C
high pressure of 1000 to 2000 atmospheres at a condensation polymerisation. CH2
temperature of 350 K to 570 K in presence of a
peroxide initiator. i. Polyamides: These polymers possess amide
(Bakelite)
linkages and are called nylons. H2 C
l It is obtained through free radical addition and H-
l Nylon 6,6:
CH2
atom abstraction. n COOH(CH 2)4COOH + n NH 2(CH2)6NH2
l It has highly branched structure. OH OH OH
553 K High Pressure O
l They are chemically inert, tough but flexible and
O
Uses: It is used for making combs, electrical switches and
poor conductor of electricity –[NH – (CH 2–)6NH – C(CH 2)–4 C–]n + nH2O handles of various utensils.
136 Polymers NCERT Maps
iv. Melamine-formaldehyde polymer 3 BIODEGRADABLE POLYMERS

m Poly b-hydroxybutyrate – co – b-hydroxy valerate (PHBV)
H2N N NH2 H2N N NHCH2OH N
HN NH OH
Polymerisation
+ HCHO CH2 COOH + O–CH – CH2 – C – O – CH – CH2 – C
N N N N n COOH
formaldehyde N N 3-Hydroxybutanoic acid OH CH3 O CH2 O n
NH2 NH2 3-Hydroxypentanoic acid

Melamine Resin intermediate
NH2 CH3
PHBV
Melamine polymer
Uses: It is used in orthopaedic devices and in controlled release of drugs.
Use: It is used in the manufacture of unbreakable crockery m Nylon 2-nylon 6
m Copolymerization:
O O
l Here a mixture of more than one monomeric species are allowed to polymerise and form a
nH2N – CH2 – COOH + nH2N(CH2)5COOH NH – CH2 – C – NH(CH2)5 – C n
copolymer
Glycine Caproic acid nylon 2-nylon 6
l The copolymer can be made both by chain growth and by step growth polymerisation.
4 POLYMERS OF COMMERCIAL IMPORTANCE
n CH2 = CH – CH = CH 2 + n –[CH2 – CH = CH – CH 2 – CH – CH 2–]n m Some commercially important polymers along with their structures and uses are given below in
table.
1,3-butadiene styrene Butadiene-styrene copolymer
Name of polymer Monomer Structure Uses

Uses: It is used in manufacture of autotyres, floortiles, cable insulation etc.
CH3
m Rubber (Elastomer) Polypropene Propene Manufacture of ropes,
–(CH2 – CH–)n toys, pipes, fibres, etc.
i. Natural rubber: It is a linear polymer of isoprene (2. methyl - 1, 3 - butadiene) and is also
called as cis-1, 4- polyisoprene Polystyrene Styrene C6H5 As insulator, wrapping
material, manufacture
H3C H CH2 CH2 H3C H –(CH2 – CH–)n
C=C C=C C=C of toys, radio and
H2C CH2 H3C H CH2 CH2
television cabinets.
Vulcanisation of rubber: This process consists of heating a mixture of raw rubber with
sulphur and appropriate additive at 273 K to 415 K. Polyvinyl chloride Vinyl chloride Cl Manufacture of rain
(PVC) coats, hand bags,
l Sulphur forms cross links at the reactive sites of double bond. –(CH2 – CH–)n
vinyl flooring, water
l Due to valucanisation rubber gets stiffened pipes.
ii. Synthetic rubbers Urea-formaldehyde (a) Urea For making
–(NH – CO – NH – CH2–)n
l Neoprene Resin (b) Formaldehyde unbreakable cups and
Cl Cl laminated sheets.
Polymerisation
n –[CH2 – C = CH – CH 2–]n Glyptal (a) Ethylene glycol –(OCH2–CH2OOC )n Manufacture of paints
CO–
Chloroprene Neoprene (b) Phthalic acid and lacquers.
Uses: It is used for the manufacture of conveyor belts, gaskets and hoses.
m Buna-N CN Bakelite (a) Phenol O–H O–H For making combs,
Copolymerisation (b) Formaldehyde CH2 electrical switches,
n CH2 = CH – CH = CH 2 + n CN –[CH2 – CH = CH – CH 2 – CH2 – CH–]n CH2
n handles of utensils
1,3-Butadiene acrylonitrile Buna-N
and computer discs.
Uses: It is used in making oil seals, tank lining etc.
Chemistry in Everyday Life
16
Chapter
1 SOME IMPORTANT TERMS (a) Tranquilizers :

l These drugs are used for the treatment of stress, and mild or even severe mental
m Drugs : Drugs are chemicals of low molecular masses (100-500u). These interact with diseases.
macromolecular targets and produce a biological response. When the biological response is l These relieve anxiety, stress, irritability or excitement by inducing a sense of well
therapeutic and useful, these are called medicines. being.
m Enzymes : Proteins which perform the role of biological catalysts in the body are called enzymes. l They form an essential component of sleeping pills.
m Receptors : Proteins which are crucial to communication system in the body are called receptors. l Examples are : Iproniazid, phenelzine (Nardil), Meprobamate, Chlordiazepoxide,
Equanil
m Enzyme inhibitors: Drugs can block the binding site of the enzyme and prevent the binding of
l Derivatives of barbituric acids also constitute important class of tranquilizers.
substrate, or can inhibit the catalytic activity of enzyme. Such drugs are called enzyme inhibitors
Examples: Veronal, amytal, nembutal, luminal and seconal
m Competitive inhibitors : Drugs compete with natural substrate for their attachment on the active (b) Analgesics : These drugs reduce or abolish pain. These are of two types
sites of enzymes. Such drugs are called competitive inhibitors. (i) Non-narcotic analgesics : These drugs inhibit synthesis of prostaglandins which
m Allosteric site : Some drugs do not bind to the enzyme’s active site. These bind to a different site stimulate inflammation in the tissue and cause pain.
of enzyme which is called allosteric site. Examples: Aspirin and paracetamol
m Chemical messengers : In human body, message between two neurons and that between (ii) Narcotic analgesics:
l Morphine when administered in medicinal dose, relieve pain and produce sleep.
neurons to muscles is communicated through certain chemicals. These are called chemical
messengers. (iv) Antimicrobials :
l An antimicrobial destroy/prevent development or inhibit the pathogenic action of
m Antagonists : Drugs that bind to the receptor site and inhibit its natural function are called microbes such as bacteria, fungi, virus, parasites selectively
antagonists. l Antibiotics, antiseptics and disinfectants are antimicrobial drugs
m Agonists : Drugs that mimic the natural messenger by switching on the receptor are called (A) Antibiotics : Antibiotics are used as drugs to treat infections because of their low
agonists. toxicity for humans and animals.
l Arsphenamine also known as salvarsan was used to treat syphilis caused by
2 THERAPEUTIC ACTION OF DIFFERENT CLASSES OF DRUGS bacteria spirochete.

l Antibiotics are of two types :
(i) Antacids : (a) Bactericidal : These antibiotics have killing effect on microbes
Examples: Penicillin, Aminoglycosides, Ofloxacin
l Over production of acid in the stomach causes irritation and pain
(b) Bacteriostatic : These antibiotics have inhibitory effect on microbes.
l Histamine stimulates the secretion of pepsin and HCl in the stomach Examples : Erythromycin, Tetracycline, chloramphenicol
l Antacids prevent the interaction of histamine with receptors present in the stomach wall. This l Antibiotics which kill or inhibit a wide range of Gram-positive and Gram-negative
results in the release of lesser amount of acid. bacteria are said to be broad spectrum antibiotics.
Examples: Ampicillin, Amoxycillin, Chloramphenicol, vancomycin, ofloxacin.
Examples of antacids :
l Antibiotics effective mainly against Gram-positive or Gram-negative bacteria are
Cimetidine (Tegamet), ranitidine (Zantac) narrow spectrum antibiotics.
(ii) Antihistamines : Example: Penicillin G
l Histamine is a potent vasodilator (B) Antiseptics and disinfectants
(a) Antiseptics: These are applied to the living tissues such as wounds, cuts, ulcers
l Histamine is also responsible for the nasal congestion associated with common cold and
and diseased skin surfaces.
allergic response to pollen Examples: Furacine, soframicine
l Synthetic drugs, brompheniramine (Dimetapp) and terfenadine (Seldane), act as l Dettol is a mixture of chloroxylenol and terpineol.
l Bithional is added to soaps to impart antiseptic properties.
antihistamines
l 2-3 per cent solution in alcohol-water mixture is known tincture of iodine. It is
(iii) Neuologically active drugs :
applied on wounds.
Tranquilizers and analgesics are neurologically active drugs. These affect the message l Boric acid in dilute aqueous solution is weak antiseptic for eyes.
transfer mechanism from nerve to receptor. l 0.2 per cent solution of phenol is an antiseptic.
NCERT Maps Chemistry in Everyday Life 141
(b) Disinfectants : 3 CHEMICALS IN FOOD

l These are applied to inanimate objects such as floors, drainage system, (i) Artificial sweetening agents : Natural sweeteners, e.g., sucrose add to calorie intake
instruments etc. and therefore many people prefer to use artificial sweeteners.
l 1% solution of phenol is used as disinfectant Artificial sweetener Sweetness value in
l Chlorine in the concentration of 0.2 to 0.4 ppm in aqueous solution and SO2 in comparison to cane sugar
very low concentrations, are disinfectants. (a) Aspartame 100
(v) Antifertility drugs : (b) Saccharin 550
l Antifertility drugs are used to control birth in human beings.
(c) Sucralose 600
l Birth control pills essentially contain a mixture of synthetic estrogen and
(d) Alitame 2000
progesterone derivatives.
l Aspartame is limited to cold foods and soft drinks because it is unstable at cooking
l Norethindrone and novestrol are used as antifertility drugs.
temperature.
4 CLEANSING AGENTS l Alitame is high potency sweetener. It is more stable than aspartame.
Two types of detergents are used as cleansing agents. l Sucralose is trichloro derivative of sucrose. It is stable at cooking temperature.
(i) Soaps : (ii) Food preservatives:
l Soaps are sodium or potassium salts of long chain fatty acids. l Food preservatives prevent spoilage of food due to microbial growth.
l Soaps containing sodium salts are formed by heating fat with aqueous NaOH. This Examples : Table salt, sugar, vegetable oils, C6H5COONa etc.
reaction is called saponification (iii) Antioxidants in Food
O l These help in food preservation by retarding the action of oxygen on food.
CH2 – O – C – C17H35 CH2 – OH l These are more reactive towards oxygen than food materials which they are
O
protecting.
CH – O – C – C17H35 + 3 NaOH 3C17H35COONa + CH – OH
l Butylated hydroxytoluene (BHT) and butylated hydroxy anisole (BHA) are most
O Sodium familiar antioxidants.
stearate CH2 – OH
CH2 – O – C – C17H35 SO2 and sulphite are useful antioxidants for wine and beer, sugar syrups and cut,
Glycerol l
Glyceryl ester of peeled or dried fruits and vegetables.
stearic acid(Fat)
(ii) Synthetic Detergents : These are cleansing agents which have all the properties of CH3 +
–
soaps, but can be used both in soft and hard water. CH3(CH2)15 – N – CH3 Br
l These are of three types CH3
(a) Anionic detergents : Anionic detergents are sodium salts of sulphonated long (c) Non-ionic detergents : Non-ionic detergents do not contain any ion in their constitution.
chain alcohols or hydrocarbons. Examples : Detergent formed when stearic acid reacts with polyethylene glycol.
Examples : Sodium laurylsulphate (CH3 (CH2 )10 CH2OSO3-Na+ ), CH3(CH2)16COOH + HO(CH2CH2O)nCH2CH2OH

– +
Stearic acid Polyethylene glycol
Sodium dodecylbenzene sulphonate CH3(CH2)11 SO3Na –H2O
(b) Cationic detergents : Cationic detergents are quaternary ammonium salts of CH3(CH2)16COO(CH2CH2O)nCH2CH2OH
amines with acetates, chlorides or bromides as anions.
l Liquid dishwashing detergents are non-ionic type
Example : Cetyltrimethyl ammonium bromide l Detergents and soap remove grease and oil by micelle formation

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Some Basic Concepts of Chemistry

m Zeroes at the end or right of a number are significant

m Important points for rounding off the numbers.

4 LAWS OF CHEMICAL COMBINATION

1 m An absorption spectrum is like photographic negative of

m Hund's Rule of Maximum m 1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f <

Classification of Elements and Periodicity 3

1 GENESIS OF PERIODIC CLASSIFICATION 2 MODERN PERIODIC LAW AND TABLE

3 Nomenclature of elements having Z > 100

Atomic Name according Symbol IUPAC IUPAC

101 Unnilunium Unu Mendelevium Md

5 IMPORTANT TERMINOLOGIES 6 PERIODIC TRENDS IN CHEMICAL PROPERTIES

7 TRENDS IN PHYSICAL PROPERTIES

Electron Gain Enthalpy

1 CHEMICAL BOND 2 LIMITATION OF OCTET RULE 5 RESONANCE STRUCTURES

8 VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY 7 FAJAN'S RULE

Number of Number of Arrangement Shape Example

10 MOLECULAR ORBITAL THEORY

1 INTERMOLECULAR FORCES 5 CHARLE'S LAW 7 AVOGADRO LAW

1 molar volume of ideal gases is 22.7 L mol–1.

bonds are present. P1V1 = P2V2 V1

10 KINETIC ENERGY AND 12 BEHAVIOUR OF REAL GASES: 14 LIQUID STATE

–1 6 SECOND LAW OF THERMODYNAMICS

5/2 R (CV = 3/2R)

= E0 (ionization energy) + 5/2 RT – – – (at low T) Reaction spontaneous at low

D sub H Enthalpy of Solution (DsolH°) is the enthalpy change low temperature

1 EQUILIBRIUM IN PHYSICAL PROCESSES 2 EQUILIBRIUM IN CHEMICAL PROCESSES 3 APPLICATION OF EQUILIBRIUM CONSTANTS

5 IONIC EQUILIBRIUM IN SOLUTION 6 THE pH SCALE 8 SALT HYDROLYSIS

partially dissociated. m The pH of CH3COONa solution in water is more than 7

Step 4: For reactions occurring in acidic medium, 7 REDOX REACTIONS AND

The oxidation half reaction is thus rewritten to Anode Cathode

m Aluminium is the most abundant metal, Bauxite (iii) Diborane (B2H6)

(7) m Chemical properties (ii) Carbon Dioxide (CO2)

O bonded atoms resulting in formation of free radicals. m It operates through p-bond(s)

m The organic solvent and the aqueous solution should be

categories. of iodine Carius method:

(b) Anti Markovnikov addition m Chemical Properties m Chemical Properties

CH3 – CHBr2 m Mechanism of electrophilic substitution reaction

6 WATER POLLUTION 8 INDUSTRIAL WASTE

1 CLASSIFICATION BASED ON CRYSTAL LATTICE

Crystalline Solids 2 CRYSTAL LATTICE AND UNIT CELL Amorphous Solids

m Long range order m Short range order

m Another similar example is the solid solution of CaCl2 and AgCl.

12 Based on Electrical Properties 13 Based on Magnetic Properties

m Conductors : Conductivity 104 – 107 ohm–1 m–1

m Diamagnetic substances : Which are weakly repelled by external magnetic field :

eg.: NaCl, H2O etc.

n-type semiconductor : When Si is dopped with P or As.

though they have large number of unpaired electrons eg. MnO

m For association, i < 1

1 TYPE OF CELLS 4 NERNST EQUATION 6 ELECTROCHEMICAL SERIES

Increasing Strength of Oxidising Agent

9 KOHLRAUSCH LAW OF INDEPENDENT 12 BATTERIES m Secondary batteries : Which can be recharged

7 PROPERTIES OF COLLOIDAL SOLUTIONS

Positively charged sols Negatively charged sols

General Principles and Processes 6

respectively. D 2NO(g) + O2 (g) 2NO2 (g)

14. Ozone is powerful oxidising agent 3. Chemical properties 4 GROUP 18 ELEMENTS

– – l All actinoids are radioactive elements

1 WERNER'S THEORY 4 STRUCTURAL ISOMERISM

m [Cr(NH3)3(H2O)3]Cl3 : Triamminetriaquachromium(III) chloride [Ni(CN)4]2– 4 dsp2 Sequare planar Diamagnetic Zero

7 CRYSTAL FIELD THEORY (CFT)

8 SPECTROCHEMICAL SERIES 9 COLOUR OF COMPLEXES 10 METAL CARBONYLS

1 CLASSIFICATION (ii) By electrophilic substitution CH3