Class 11 Chemistry Support Material
Class 11 Chemistry Support Material
Chemistry is the branch of Science that deals with the properties; structure and composition of
matter.There are a large number of branches for Chemistry. Some of them are: The International
System of Units (SI)
Matter: Matter is anything that occupies space, has a definite mass and can be perceived by any of
oursenseorgans.
Classification of matter
Matter can be divided into two categories – pure substances and mixtures.
Pure substances contain only one type of particles. These are further divided into two – elements and
compounds.
Elements are pure substances which contain only one type of particles. These particles may be atoms or
molecules. E.g. Hydrogen, Nitrogen, Oxygen (diatomic), Sodium, Potassium, Lithium, Calcium
(monoatomic), Phosphorus, Sulphur (polyatomic) etc.
Compounds are pure substances which contain more than one type of atoms in a fixed ratio by mass.
E.g. CO2, H2O, NH3, H2SO4 etc.
Mixtures contain more than one type of particles. There are two types of mixtures –Mixtures having
uniform composition throughout are called homogeneous mixtures. E.g. all type of solutions, air etc.
Mixtures having different compositions at different parts are called heterogeneous mixtures. E.g. sea
water, soil etc.
Mass and Weight: Mass is the amount of matter present in a body. It is a constant quantity. Its SI unit is
kilogram (kg). Weight is the gravitational force acting on a body. It is a variable quantity. i.e. it changes
with place. Its SI unit is newton (N).
Temperature (T) It is the degree of hotness or coldness of a body. It is commonly expressed in degree
Celsius (0C). Other units are degree Fahrenheit (0F), Kelvin (K) etc. its SI unit is Kelvin (K).
Degree Celsius and degree Fahrenheit are related as:
0
F = 9/5(0C) + 32
Degree Celsius and Kelvin are related as:
K =0C+273.15
Laws of chemical combination
Law of Conservation of Mass : In a chemical change total mass remains conserved. i.e. mass before
reaction is always equal to mass after reaction.
Law of Definite Proportions: It states that a given compound always contains exactly the same
proportion of elements by weight. All chemical compounds are found to have constant composition
irrespective of their method of preparation or sources
Example: In water (H2O), Hydrogen and Oxygen combine in 2 : 1 molar ratio, this ratio remains constant
whether it is tap water, river water or sea water or produced by any chemical reaction.
Law of Multiple Proportions: States that if two elements can combine to form more than one compound,
the masses of one element that combine with a fixed mass of the other element, are in the ratio of small
whole numbers. For example, hydrogen combines with oxygen to form two compounds, namely, water
and hydrogen peroxide.
Here, the masses of oxygen (i.e. 16 g and 32 g) which combine with a fixed mass of hydrogen (2g) bear a
simple ratio, i.e. 16:32 or 1: 2.
Gay Lussac’s Law of Gaseous Volumes: According to him elements combine in a simple ratio of atoms,
gases combine in a simple ratio of their volumes provided all measurements should be done in the same
temperature and pressure.
Mole: Mole is the unit of amount of substance. It is defined as the amount of substance that contains
asmany particles as there are atoms in exactly 12 g C12 isotope. 1 mole of any substance contains 6.022
x1023 atoms. This number is known as Avogadro numberor Avogadro constant (NAor N0).
Molar mass: The mass of one mole of a substance in gram is called its molar mass (gram molecular
mass).
Molar volume: It is the volume of 1 mole of any substance at STP. Molar volume of any gas = 22.4L
e.g. 22.4 L of hydrogen gas = 1 mole of H2 = 6.022x1023 molecules of hydrogen = 2 g of H2
Percentage composition: It is the percentage of each element present in 100g of a substance. Percentage
of an element =
n=
Stoichiometry and Stoichiometric calculations
The study about the quantitative relationship between the masses or the volumes of reactants and
theproducts
Limiting reagent : The reactant which is consumed first and limits the amount of product formed in the
reaction, and is therefore, called limiting reagent. .
PRACTICE QUESTIONS
Section-A(MCQ TYPE)
01. What is the mass percentage of carbon in carbon dioxide?
(A) 0.034% (B) 27.27% (C) 3.4% (D) 28.7%
02. The empirical formula and molecular mass of a compound are CH2O and 180 g respectively.
What will be the molecular formula of the compound?
(A) C9H18O9 (B) CH2O (C) C6H12O6 (D) C2H4O2
03. The total number of moles of ions present in 111 g of CaCl2 is
(A)One Mole (B) Two Mole (C) Three Mole (D) Four Mole
04. Which one will have maximum numbers of water molecules?
(A)18 molecules of water (B) 1.8 grams of water
(C) 18 grams of water (D) 18 moles of water
05. Which of the following contains the same number of carbon atoms as are in 6.0 g of carbon
(C – 12)?
(A) 6.0 g Ethane (B) 8.0g Methane
(C) 21.0g Propane (D) 28.0 g CO
06. A mixture having 2 g of H2 and 32 g of oxygen occupies a volume of__ at NTP.
(A) 22.4 L (B) 44.8 L (C) 11.2 L (D) 67.2 L
07. In a reaction A + B2→ AB2if 2 moles of A and 3 moles of B2 are used then which one will be a
limiting reagent?
(A) no limiting reagent (B) B2 (C) A (D) Data is insufficient
08. The amount of water produced by the combustion of 32 gram of methane CH4 + 2O2→ CO2
+ 2H2O
(A) 30 g (B) 36 g (C) 72 g (D) 70 g
09. 4.6 x 1022 atoms of an element weigh 13.8 g. The atomic mass of the element is:
(A) 290 (B) 180 (C) 34.4 (D) 10.4
0
10. 35 C in Fahrenheit will be
(A) 90 (B) 91 (C) 95 (D) 99
11. Which of the following statements about a compound is incorrect?
(A) A molecule of a compound has atoms of different elements
(B) A compound cannot be separated into its constituent elements by physical methods of
separation.
(C) A compound retains the physical properties of its constituent elements.
(D) The ratio of atoms of different elements in a compound is fixed.
12. Which of the following statements is correct about the reaction given below:
4Fe(s) + 3O2(g) → 2Fe2O3(g)
(A) Total mass of iron and oxygen in reactants = total mass of iron and oxygen in product
therefore it follows law of conservation of mass.
(B) Total mass of reactants = total mass of product; therefore, law of multiple proportions is
followed.
(C) Amount of Fe2O3 can be increased by taking any one of the reactants (iron or oxygen) in
excess.
(D) Amount of Fe2O3 produced will decrease if the
13. Which of the following statements indicates that law of multiple proportions is being
followed?
(A) Sample of carbon dioxide taken from any source will always have carbon and oxygen in
the ratio 1:2.
(B) Carbon forms two oxides namely CO2 and CO, where masses of oxygen which combine
with fixed mass of carbon are in the simple ratio 2:1.
(C) When magnesium burns in oxygen, the amount of magnesium taken for the reaction is
equal to the amount of magnesium in magnesium oxide formed.
(D) At constant temperature and pressure 200 mL of hydrogen will combine with 100 mL
oxygen to produce 200 mL of water vapour.
14. One of the statements of Dalton’s atomic theory is given below: “Compounds are formed
when atoms of different elements combine in a fixed ratio” Which of the following laws is
not related to this statement?
(A) Law of conservation of mass (B) Law of definite proportions
(C) Law of multiple proportions (D) Avogadro law
15. What is the weight of oxygen required for the complete combustion of 2.8 kg of ethylene?
(a) 2.8kg (b) 6.4kg (c) 9.6kg (d) 96kg
ANSWERS:-
Q.NO. ANS Q.NO. ANS Q.NO. ANS
1 B 6 A 11 C
2 C 7 B 12 A
3 C 8 C 13 B
4 D 9 B 14 D
5 B 10 C 15 C
Reason (R) : Carbon-12 isotope is the most abundant isotope of carbon and has been
chosen as standard.
03. Assertion(A): Combustion of16g of methane gives 28 gm of water.
Reason(R): In the combustion of methane, hydrogen is one of the products.
04. Assertion(A): NaHCO3 has the same empirical and molecular formula.
Reason(R): NaHCO3 evolves CO2 gas on heating.
Answers:-
Q.NO. 1 2 3 4
ANS. B B D B
02. Vitamin C is essential for the prevention of scurvy. Combustion of 0.2000g of vit.C
gives 0.2998g of CO2 and 0.819g of H2O. What is the empirical formula of vitamin C?
03. Find the mass percentage of each component in the calcium phosphate.
04. Write the three points of difference between compound and mixture.
02. Read the given passage and answer the questions that follow:
The mass of one mole of a substance in grams is called its molar mass. The molar
mass in grams is numerically equal to atomic molecular/formula mass in u. An
empirical formula represents the simplest whole number ratio of various atoms
present in a compound, whereas, the molecular formula shows the exact number of
different types of atoms present in a molecule of a compound. If the mass per cent of
various elements present in a compound is known, its empirical formula can be
determined. Molecular formula can further be obtained if the molar mass is known.
Many a time, reactions are carried out with the Amounts of reactants that are
different than The amounts as required by a balanced chemical reaction. In such
situations, one Reactant is in more amount than the amount required by balanced
chemical reaction.
The reactant which is present in the least amount Many a time, reactions are carried
out with the amounts of reactants that are different than the amounts as required by
a balanced chemical reaction. In such situations, one reactant is in more amount than
the amount required by balanced chemical reaction. The reactant which is present in
the least amount gets consumed after sometime and after that further reaction does
not take place whatever be the amount of the other reactant. Hence, the reactant,
which gets consumed first, limits the amount of product formed and is, therefore,
called the limiting reagent.
1) One atomic mass unit (amu) is defined as a mass exactly equal to one-twelfth
of the mass of one …atom.
Ans – carbon – 12
2) The mass of one mole of a substance in grams is called its..
Ans – molar mass
3) … is the sum of atomic masses of the elements present in a molecule.
Ans – Molecular mass
4) One mole contains exactly …elementary entities.
Ans –6.02214076 × 1023
LONG ANSWER TYPE QUESTIONS(5 MARKS)
01. Dinitrogen and dihydrogen react with each other to produce
ammonia according to thefollowingchemical equation:
(i) N2(g)+3H2(g)—–>2NH3(g)
(ii)Willanyofthetworeactantsremain unreacted?
If yes, which one and what would be its mass?
02. What is the difference between empirical and molecular formula? A compound
contains 4.07% hydrogen, 24.27 % carbon and 71.65 % chlorine. Its molar mass is
98.96 g. What are its empirical and molecular formulas?
Ans. An empirical formula represents the simplest whole number ration of various
atoms present in a compound whereas the molecular formula shows the exact
number of different types of atoms present in a molecule of a compound
Relative
Mass Relative
Symbol Mass (amu) Location
Particle (proton Charge
= 1)
inside the
proton p+ 1 1 +1
nucleus
Relative
Mass Relative
Symbol Mass (amu) Location
Particle (proton Charge
= 1)
outside the
electron e− 5.45 × 10−4 0.00055 −1
nucleus
inside the
neutron n0 1 1 0
nucleus
Atomic number (Z): Number of protons in the nucleus of an atom = Number of electrons in the extra
nuclear part of the electrically neutral atom.
Mass number (A) : Number of protons + Number of neutrons in the nucleus of an atom.
01. Isotopes: Atoms of same element having same atomic number but different mass number.
For example, isotopes of Hydrogen are 1 H1, 1H2, 1H3
02. Isobars: Atoms of different elements having the same mass number but different atomic number,
e.g., 18Ar40, 19K40, 20Ca40
03. Isotones: Atoms of different elements which contain the same number of neutrons.
e.g., 6C14, 7N15, 8O16
04. Isoelectronic Species: Atoms or ions containing the same number of electrons+ For example, N3–, O-2 , F2–
, Na+ , Mg2+ , Al 3+ and Ne, having 10 electrons each are isoelectronic
Thomson Model of Atom: An atom possesses a spherical shape (radius approximately 10–10 m) in which
the positive charge is uniformly distributed. The electrons are embedded into it in such a manner as to
give the most stable electrostatic arrangement.
An important feature of this model is that the mass of the atom is assumed to be uniformly distributed
over the atom.
Drawback of Thomson Model of Atom
This model was able to explain the overall neutrality of the atom, it could not satisfactorily, explain the
results of scattering experiments carried out by Rutherford in 1911.
Rutherford’s Model of atom: This model was based upon the results of the famous alpha-rays scattering
experiment. It is also known as ‘Planetary model’ and can be summarized in following points.
(i) Most of the mass and all the positive charge of an atom are present in a very small region called
the nucleus.
(ii) The magnitude of the charge on the nucleus is different in atoms of different elements.
(iii) Electrons revolve in the space around nucleus in different circular orbits and the number of
electrons is equal to the number of units of positive charge in the nucleus.
Drawbacks of Rutherford Model
(iv) Rutherford’s model cannot explain the stability of atom if the motion of electrons is described on
(i) In an atom, the electrons revolve around the nucleus in certain definite circular paths called orbits.
(ii) Each orbit is associated with definite energy and therefore these are known as energy levels or
energy shells.These are numbered as 1, 2, 3, 4……….. Or K, L, M, N………..
(iii) Only those energy orbits are permitted for the electron in which angular momentum of the electron
is a whole number multiple ofh/2π
Angular momentum of electron (mvr) = (n =1, 2, 3, 4 etc).
m= mass of the electron v = tangential velocity of the revolving electron. r=radius of the orbit.
h=Planck’s constant. n is an integer.
(iv) As long as electron is present in a particular orbit, it neither absorbs nor loses energy and its energy,
therefore, remains constant.
(v) When energy is supplied to an electron, it absorbs energy only in fixed amounts as quanta and jumps
to higher energy state away from the nucleus known as excited state. The excited state is unstable, the
electron may jump back to the lower energy state and in doing so, it emits the same amount of
energy.(∆E=E2–E1).
(vi) The radius of orbits can be given by the equation: rn=a0n2wherea0=52.9 pm.
Thus the radius of the first stationary state is 52.9 pm (called the Bohr radius). As n increases, the value
of r will increase.
(vii) It is also possible to calculate the velocities of electrons moving in these orbits. Qualitatively the
magnitude of velocity of electron increases with increase of positive charge on the nucleus and
decreases with increase of principal quantum number.
(viii) The energy of different orbits in an atom in given by the expression
Achievements of Bohr’sTheory
1. Bohr’s theory has explained the stability of an atom.
2. Bohr’s theory has helped in calculating the energy of electron in hydrogen atom and one
electron species.
Limitations of Bohr Atom Model
Bohr atom model could explain the stability and line spectra of hydrogen atom and hydrogen like ions
(e.g.He+, Li2+, Be3+etc).But it has the following limitations:
1. It could not explain the fine spectrum of hydrogen atom.
2. It could not explain the spectrum of atoms other than hydrogen.
3. It was unable to explain the splitting of spectral lines in the presence of electric field (Stark
effect) and in magnetic field (Zeeman Effect).
4. It could not explain the ability of atoms to form molecules by chemical bonds.
5. It did not consider the wave characterof matter and Heisenberg’s uncertainty principle.
Dual Behaviour of Matter (deBroglie Equation)
De Broglie in 1924, proposed that matter, like radiation, should also exhibit dual behaviour i.e., both
particle like and wave like properties. This means that like photons, electrons also have momentum as
well as wavelength.
λ= =
When n =3, Ɩ=0, 1 and 2. i.e. M shell containsthreesubshells– s,p anddsub shells
When n=4,Ɩ=0,1, 2and 3.i.e.Nshellcontainsfoursubshells–s, p,dandf subshells
4. The number ofelectronsthat can beaccommodated in sub-energylevelis equal to2(2l+1).
If l=0 for s orbital then= 2(2*1+1)=2 electrons
If l=1 for p orbital then=2(2*2+1)=6 electrons
If l=2 for d orbital then= 2(2*3+1)=10 electrons
If l =3 for f orbital then=2(2*3+1)=14 electrons
The probability of 1s electron is found to be maximum near the nucleus and decreases with the increase
in the distance from the nucleus. In 2s electron, the probability is also maximum near the nucleus and
decreases to zero probability. The spherical empty shell for 2s electron is called nodal surface or simply
node.
Shapes of p-orbitals
p-orbitals are present in the p-subshell for which l = 1 and m1 can have three possible orientations – 1,
0, +1.
Thus, there are three orbitals in the p-subshell which are designated as px, py and pz orbitals depending
upon the axis along which they are directed. The general shape of a p-orbital is dumb-bell consisting of
two portions known as lobes. Moreover, there is a plane passing through the nucleus along which
finding of the electron density is almost nil. This is known as nodal planeas shown in the fig.
From the dumb-bell pictures, it is quite obvious that unlike s-orbital, a p-orbital is directional in nature
and hence it influences the shapes of the molecules in the formation of which it participates.
Number of radial nodes = n - Ɩ – 1
Number of angular nodes = Ɩ
Total number of nodes = n-1
Shapes of d-orbitals
For d-orbitals, Ɩ = 2 and mƖ = -2, -1, 0, +1 and +2. i.e., there are five possible orientations for
d orbitals. So there are 5types of d-orbitals. They are dxy, dxz, dyz, dx2-y2 and dz2. . The shapes of the
first four d- orbitals are double dumb-bell and that of the fifth one, dz2, is dumb-bell having a circular
collar in the XY- plane. The five d-orbitals have equivalent energies. For d orbitals the number of radial
nodes is 2 and the total number of nodes is n-2. Boundary surface diagrams for d-orbitals areas follows.
orbitals:
For f-orbitals, Ɩ = 3 and mƖ = -3, -2, -1, 0, +1, +2 and +3. i.e., there are seven possible orientations for
f-orbitals. So there are 7 types of f-orbitals. They have diffused shapes.
The principle states: In the ground state of the atoms, the orbitals are filled in order of their increasing
energies.
In other words, electrons first occupy the lowest energy orbital available to them and enter into higher
energy orbitals only after the lower energy orbitals are filled.
This rule has two sub rules:
a) The various orbitals are filled in the increasing order of their (n+l) value.
b) If two orbitals have the same (n+l) values, the orbital with the lower n value is filled first. The
increasing order of orbitals is as follows.
PauliExclusionPrinciple
According to this principle, no two electrons in an atom can have the same set of four quantum
numbers.Only two electrons may exist in the same orbital and these electrons must have opposite
spins.If 2 electrons have same values forn, Ɩ and m, they should have different values for s. i.e.if s = +1/2.
for the first electron,it should be-1/2. For the second electron.
3.Hund’s rule of maximum multiplicity
It states that: pairing of electrons in the orbitals belonging to the same sub-shell (p, d or f) does not take
place until each orbital belonging to that sub-shell has got one electron each with parallel spin. For
example the electronic configuration of N is 1s22s22p1p1p1 and not 1s22s22p2p1
S.N. QUESTIONS
1. Which of the following options does not represent ground state electronic configuration of
an atom?
(A)1s2 2s2 2p63s2 3p6 3d84s2 (B)1s22s22p63s23p63d94s2
(C)1s2 2s2 2p6 3s2 3p6 3d104s1 (D)1s2 2s2 2p6 3s2 3p6 3d5 4s1
2. Numberofangularnodes for4d orbitalis .
(A)4 (B) 3 (C) 2 (D)1
3. The number of radial nodes for 3p orbital is.
(A) 3 (B) 4 (C) 2 (D) 1
4. g subshell is characterised by:
(A)n = 5 (B) m = 3 (C) l = 4 (D)l = 5
The questions given below consist of assertion (A) and reason (R).Use the following key to
select the correct answer.
A. If both assertion and reason are correct and reason is correct explanation for assertion.
B. If both assertion and reason are correct and reason is not correct explanation for assertion.
C. If assertion is correct and reason is incorrect
D. If assertion is incorrect and reason is correct.
01. Assertion (A): An orbital cannot have more than 2 electrons and their spin must be opposite.
Reason (R) : No two electrons in an atom can have same set of all four quantum
numbers
02. Assertion (A): Both position and momentum of an electron cannot be determined simultaneously
with maximum accuracy
Reason (R): This is because of microscopic nature of electron.
03. Assertion (A): The energy of an electron is mainly determined by principal quantum number.
Reason (R): The principal quantum number is the measure of the most probable distance of
finding the electron around the nucleus.
04. Assertion (A): Fe3+ ion is more stable than Fe2+ ion in ground state.
Reason (R): Fe3+ ion has more number of unpaired electrons than Fe2+ ion.
05. Assertion (A): Anorbital cannot have more than two electrons.
Reason (R) : The two electrons in an orbital create opposite magnetic
th
06. Assertion (A): The 19 electron in potassium atom enters 4s-orbital and not 3 d-orbital.
Reason (R) : The energies of the orbitals can be compared with the help of (n+l) rules
07. Assertion (A): All isotopes of a given element show the same type of chemical
behaviour. Reason (R) : The chemical properties of an atom are controlled by the
number of electrons in the atom
ANSWERS:-
Q.NO. 1 2 3 4 5 6 7
ANS. A A A B C A A
04. Heinsberg uncertainty principle has no significance in our everyday life. Explain.
Ans: In our daily life we can see only the moving macro and semi-micro-objects. The mass of
the striking photons of light is too small to cause any shift in their position by the time the
reflected photons form the image of the object. For such particles, there is no problem in
measuring the exact momentum simultaneously. Thus, the principle has no relevance for such
objects.
05. Out of 3d and 4s orbitals which is filled first?
Ans: 4s orbital is filled first because it has lower energy. The energies of the orbitals can be
compared by their n+l values. For 4s orbital n+l(4+0) value is 4 while for 3d orbital, n+l (3+2)
value is 5,Therefore 4s orbital is filled before3d orbital.
06. How many electrons can be filled in all the orbitals with n+l=5?
Ans: (n+l)=5 has 5s,4p and 3d orbitals with two, six and ten electrons respectively. Therefore,
the total number of electrons=18.
SHORT ANSWER TYPE QUESTIONS-II (3 MARKS)
01.
atom of an element contains 29 electrons and 35 neutrons. Deduce
(i) number of protons.
(ii) electronic configuration of the element.
(iii) number of paired electrons.
(iv) number of unpaired electrons.
ANS:
(i) Electrons = 29, Neutrons = 35, Protons = Electrons = 29
(ii) Electronic configuration is
04. Red light has wavelength 750 nm, whereas violet light has wavelength 400 nm. Calculate their
frequency and energy (c = 3 × 108 m s–1, h = 6.63 × 10 –34 J s).
Ans:
05. Calculate the wave number for the longest wavelength transition in the Balmer series of
atomic hydrogen.
Ans:
01. Read the given passage and answer the questions that follow based on passage and related
studied concepts.
Orbitals are region or space where there is maximum probability of finding electrons.
Qualitatively, these orbitals can be distinguished by their size, shape and orientation. An
orbital of small size means there is more chance of finding the electron near the nucleus.
Shape and orientation means the direction in which probability of finding electron is
maximum. Atomic orbitals can be distinguished by quantum numbers. Each orbital is
designated by three quantum numbers n, l and ml (magnetic quantum number) which define
energy, shape and orientation but these are not sufficient to explain spectra of multi-electrons
atoms. Spin quantum number (ms) determines the spin of electron. Spin angular momentum
of electron has two orientations relative to chosen axis which are distinguished by spin
quantum numbers ms which can take values +1/2 and –1/2
(a) Heat treatment of muscular pain involves radiation of wavelength 900 nm which spectral
line of H-atom is suitable for this purpose.
Ans:
(II)
02. What is the energy in joules required to shift the electron of the hydrogen atom from the
first Bohr orbit to the fifth Bohr orbit and what is the wavelength of light emitted when the
electron returns to the ground state? The ground state electronic energy is – 2.18 × 11-11
ergs.
Ans:
1. Dobereiner's Triads: In 1817 a German chemist Doberneiner identified certain groups of three
elements.
These groups of three elements having similar properties were called triads. When three elements were
arranged in order of their increasing atomic masses, the atomic mass of the middle element was roughly
the mean of the atomic masses of the other two element Examples
Elements Li Na K
At.mass 7 23 39 7 + 39 / 2 = 23
Elements Fe Co Ni
At.mass 55.85 58.93 58.71 nearly same atomic masses It was restricted to few elements, therefore,
discarded.
2. New Lands Law of octaves: When elements were arranged in order of their increasing relative atomic
masses. The properties of every eight elements were similar to the first one, like the eighth note of a
musical scale.This repetition in the properties of elements is just like the repetition of eighth node in an
octave of music.
This arrangement of elements is called as Newland’s law of Octave.
Li Be B C N O F
Na Mg Al Si P S Cl
K Ca
This classification worked quite well for the lighter elements but it failed in case of heavier elements and
therefore, discarded.
3. Mendeleev's Periodic Law: The physical and chemical properties of elements are the periodic function of
their atomic masses.
4. Mendeleev's Periodic Table: When mendeleev started his work, 63 elements were known at that time. He
selected hydrogen and oxygen as they are very reactive and formed compounds with most elements.
Mendeleev's periodic table contains vertical columns called groups and horizontal rows called periods.
There were 7 periods and 8 groups. Noble gases were not known at that time. So there was no group of
noble gases.The elements in each group of the periodic tables are similar to one another in many
properties. The similar properties of the elements are repeated periodically
(a).Merits of mendeleev's classification
Mendeleev's periodic law predicted the existence of some elements that had not been discovered
at that time
Could accommodate noble gases when they were discovered.
Mendeleevs predicted the properties of those missing elements from the known properties of the
other elements in the same group. Eka – aluminium and Eka-silicon names were given for gallium
and germanium (not discovered at the time of Mendeleevs). Properties predicted by Mendeleevs
for these elements and those found experimentally were almost similar.
PROPERTY EKA- GALLIUM EKA-SILICON GERMANIUM
ALUMINIUM (FOUND) (PREDICTED) (FOUND)
(PREDICTED)
Atomic 68 70 72 72.6
Mass
Density / 5.9 5.94 5.5 5.36
(g/cm3)
Melting Low 30.2 High 1231
point (K)
Formula of E2O3 Ga2O3 EO2 GeO2
oxide
Formula of ECl3 GaCl3 ECl4 GeCl4
Chloride
(b) .Limitations of Mendeleev's classification:-
The correct position could not be assigned to the hydrogen in the periodic table.
Wrong order of the atomic masses of some elements could not be explained.
Anomalous position of lanthanides and actinides in periodic table.
The position of isotopes could not be explained.
Order of increasing atomic weights is not strictly followed in the arrangement of elements in the
periodic table. For example Ar(39.94) is placed before K(39.08) and Te (127.6) is placed before I
(126.9)
Similar elements were placed in different groups (Cu lB an Hg llB) and the elements with different
properties were placed in same groups (alkali metals lA and coinage metals lB)
It didn’t explain the cause of periodicity. Uncertainity in prediction of new elements was there.
5. Modern Periodic law (Moseley’s Periodic Law) : Physical and chemical properties of elements are the
periodic functions of their atomic number. If the elements are arranged in order of their increasing
atomic number, after a regular interval, elements with similar properties are repeated.
6. Cause of Periodicty: The periodic repetition of the properties of the elements is due to the reocurrence of
similar valence shell electronic configuration after certain regular intervals. For example, alkali metals
have same electronic configuration ns1, therefore, have similar properties.
7. Modern Periodic Table: The long form of periodic table is the contribution of Range, Werner, Bohr and
Bury.This table is also referred to as Bohr’s table since it follows Bohr’s scheme of the arrangements of
elements into four types based on electronic configuration of elements.
The table consists of 18 vertical columns called groups Elements having similar outer electronic
configurations in their atoms are arranged in vertical columns, referred to as groups.According to the
recommendation of International Union of Pure and Applied Chemistry (IUPAC), the groups are
numbered from 1 to 18 .
The table consists of 7 horizontal rows called periods. Each period starts with an alkali metal having
outermost electronic configuration ns1. Each period ends with a noble gas with outer most electronic
configuration ns2np6 except helium having outermost electronic configuration 1s2. The first period
contains 2 elements. The subsequent periods consists of 8, 8, 18, 18 and 32 elements, respectively.
The seventh period is incomplete and like the sixth period would have a theoretical maximum (on the
basis of quantum numbers) of 32 elements. In this form of the Periodic Table, 14 elements of both
sixth and seventh periods (lanthanoids and actinoids, respectively) are placed in separate panels at
the bottom.
5 pent p
6 hex H
7 sept S
8 oct O
9 enn E
The latin words for various digits of the atomic number are written together in the order of which
makes the atomic number and suffix ‘ium’ is added at the end. In case of bi and tri one ‘i’ is omitted.
We can classify the elements into four blocks viz., s-block, p-block, d-block and f-block depending on the
typeof atomic orbital that are being filled with electrons.
9. s-Block Elements (s-block elements lie on the extreme left of the periodic table.)
Group 1 (alkali metals) & 2 (alkaline earth metals) elements constitute the s-block.
General electronic configuration is [inert gas] ns1-2
19. VAN DER WAALS’ RADIUS: It is one-half of the internuclear distance between two adjacent atoms in two
nearest neighbouring molecules of the substance in solid state.
22. Van der Waals’radius > Metallic radius > Covalent radius, rcovalent < rcrystal <rvander Walls
23. IONIC RADIUS: The effective distance from the centre of the nucleus of an ion upto which it
has aninfluence on its electron cloud is called its ionic radius
24. Variation in Atomic Radius
25. The atomic radii of noble gases are not considered here. Being monoatomic, their (non-bonded radii)
values are very large. In fact radii of noble gases should be compared not with the covalent radii but
with the van der Waals radii of other elements.
26. Ionic radius: The effective distance from the centre of nucleus of the ion up to which it has an influence
in the ionic bond is called ionic radius.
27. A cation is smaller than its parent atom because in a Cation, the number of positive charges on the
nucleus is greater than the number of orbital electrons leading to increased inward pull of remaining
electrons causing contraction in size of the ion. For example the atomic radius of sodium is 186 pm
compared to the ionic radius of 95 pm for Na+.
For example : Na Na+
Number of Electrons : 11 10
Number of Protons : 11 11
28. The size of an anion will be larger than that of the parent atom because the addition of one or more
electrons would result in increased repulsion among the electrons and a decrease in effective nuclear
charge. For example, the ionic radius of fluoride ion (F– ) is 136 pm whereas the atomic radius of
fluorine is only 64 pm.
Cl Cl-
Number of Electrons : 17 18
Number of Protons : 17 17
29. Isoelectronic species: The species containing the same number of electrons but differ in the
magnitude of their nuclear charges are called as isoelectronic species. For example, N3-, O2- , F- , Ne, Na+
, Mg2+ and Al3+ are all isoelectronic species with same number of electrons (i.e. 10) but different
nuclear charges of +7, +8, +9, +10, +11, +12 and +13 respectively
Variation in ionic radii of isoelectronic species Within a series of isoelectronic species as the nuclear charge
increase, the force of attraction by the nucleus on the electrons also increases. As a result, the ionic radii of
isoelectronic species decrease with increase with increases in the magnitude of nuclear charges. For
example,
Al3+ Mg2+ Na+ F- O2- N3-
Ionic radii increase
As effective nuclear charge decrease.
attraction between the nucleus and the remaining electrons increases considerably and hence
subsequent l.E. (s) increase.
The second ionization enthalpy will be higher than the first ionization enthalpy because it is more
difficult to remove an electron from a positively charged ion than from a neutral atom. In the same
way the third ionization enthalpy will be higher than the second and so on. The term “ionization
enthalpy”, if not qualified, is taken as the first ionization enthalpy.
31. Factors Influencing Ionisation energy
Size of the Atom : Ionisation energy decreases with increase in atomic size. As the distance
between the outermost electrons and the nucleus increases, the force of attraction between the
valence shell electrons and the nucleus decreases. As a result, outer most electrons are held less
firmly and lesser amount of energy is required to knock them out. For example, ionisation
energy decreases in a group from top to bottom with increase in atomic size.
Nuclear Charge : The ionisation energy increases with increase in the nuclear charge. The is
due to the fact that with increase in the nuclear charge, the electrons of the outer most shell are
more firmly held by the nucleus and thus greater amount of energy is required to pull out an
electron from the atom. For example, ionisation energy increases as we move from left to right
along a period due to increase in nuclear charge.
Shielding effect : The electrons in the inner shells act as a screen or shield between the nucleus
and the electrons in the outermost shell. This is called shielding effect. The larger the number of
electrons in the inner shells, greater is the screening effect and smaller the force of attraction
and thus (IE) decreases.
Penetration Effect of the Electron : The ionisation energy increases as the penetration effect of the
electrons increases. It is a well known fact that the electrons of the s-orbital has the maximum
probability of being found near the nucleus and this probability goes on decreasing in case of P, d
and f orbitals of the same energy level. Within the same energy level, the penetration effect
decreases in the order S > P > d > f Greater the penetration effect of electrons more firmly the
electron will be held by the nucleus and thus higher will be the ionisation energy of the atom. For
example, ionisation energy of aluminium is comparatively less then magnesium as outer most
electron is to be removed from p-orbital (having less penetration effect) of same energy level.
Electronic Configuration : If an atom has exactly half-filled or completely filled orbitals, then such
an arrangement has extrastability. The removal of an electron from such an atom requires more
energy then expected. For example, Be IE1 > B IE1 Be (Z = 4) 1s2 , 2s2 B(Z 5) 1s2 , 2s2 , 2p1
completaly filled Partially filled
orbital more stable orbital less stable
As noble gases have completely filled electronic configurations, they have highest ionisation
energies in their respective periods.
32. Variation in Ionization Enthalpy
Variation in Ionization Enthalpy in Group Variation in Ionization Enthalpy in Period
As we descend in a group the first ionization The first ionization enthalpy generally
enthalpygenerally decreases increases aswe go across a period.
33. Electron Gain Enthalpy: When an electron is added to a neutral gaseous atom (X) to convert it into a
negative ion, the enthalpy change accompanying the process is defined as the electron gain enthalpy.
Electron gain enthalpy provides a measure of the ease with which an atom adds an electron to form
anion. X (g) + e- X-(g) ; eg H
34. When an electron is added to the atom and the energy is released, the electron gain enthalpy is
negative and when energy is needed to add an electron to the atom, the electron gain enthalpy is
positive.
35. The addition of second electron to an anion is opposed by electrostatic repulsion and hence the energy
has to be supplied for the addition of second electron. For example :
(a)O(g) + e+ O- (g) + energy - - 2-
eg H =-ve (b)O (g) + e + energy O (g) eg H =+ve
36. Group 17 (halogens) have very high negative electron gain enthalpies because they can attain
stablenoble gas electronic configuration by picking up an electron.
37. Noble gases have large positive electron gain enthalpies because the electrons have to enter the
nexthigher energy level leading to a very unstable electronic configuration.
38. Variation in electron gain enthalpies in Group & period:
Variation in electron gain enthalpies in Group Variation in electron gain enthalpies in
Period
We should also expect electron gain enthalpy to As a general rule, electron gain enthalpy
become less negative as we go down a group becomes more negative.
because the size of the atom increases and the Reason: because left to right across a
added electron would be farther from the nucleus. period effective nuclear charge increases
This is generally the case . Exceptions : and consequently it will be easier to add an
Electron gain enthalpy of O or F is less than S or Cl. electronto a small atom.
This is due to the fact that when an electron is added
to O or F, the added electron goes to the smaller n =
2 energy level and experiences significant repulsion
from the other electrons present in this level. In S or
Cl, the electron goes to the larger n = 3 energy level
and consequently occupies a larger region of space
leading to much less electron
repulsion.
1
Factors Influencing electron gain enthalpies (i) Electron gain enthalpy α (ii) Electron gain
Atomic size
enthalpy α Effective nuclear charge (zeff) (iii) Electron gain enthalpy α 1 (iv) stability of
screening effect
half filled and completely filled orbitals of a subshell is comparatively more and the addition of an extra electron to
such an system is difficult and hence the electron affinity value decreases.
40. VALENCE ELECTRONS: The electrons present in outermost shell are called as valence electron. Because
the electrons in the outermost shell determine the valency of an element.
41. VALENCY OF AN ELEMENT: The number of hydrogen or halogen atom or double the number of
oxygen atom, which combin with one atom of the element is taken as its valency. According to the
electronic concept of valency, “ the number of electrons which an atom loses or gains or shares with
other atom to attain the noble gas configuration is termed as its valency.” Periodicity:
In period- The valency first increases then decreases from left to right in a period.
In group- The valency remains constant from top to bottom in a group.
42. ELECTROPOSITIVE OR METALLIC CHARACTER: The tendency of an element to lose electrons and forms
positive ions (cations) is called electropositive or metallic character. The elements having lower
ionisation energies have higher tendency to lose electrons, thus they are electropositive or metallic in
their behaviour. Alkali metals are the most highly electropositive elements.
Periodicity: In period- The electropositive or metallic characters decreases from left to right in a
period.
In group- The electropositive or metallic characters increases from top to bottom in a group.
43. ELECTRO-NEGATIVE OR NON- METALLIC CHARACTERS: the tendency of an element to accept electrons to
form an anion is called its non metallic or electronegative character. The elements having high electro-
negativity have higher tendency to gain electrons and forms anion. So, the elements in the upper right
hand portion of the periodic table are electro-negative or non-metallic in nature. Periodicity:
In period- The electro-negative or non- metallic characters increases from left to right in a
period.
In group- The electro-negative or non-metallic characters decreases from top to bottom in a
group.
44. REACTIVITY OF METALS: Periodicity:
In period- The tendency of an element to lose electrons decreases in a period. So the reactivity
ofmetals decreases from left to right in a period.
In group- The tendency of an element to lose electrons increases in a period. So the reactivity of
metals increases from top to bottom in a group.
45. REACTIVITY OF NON- METALS:
(i) In period- The tendency of an element to gain electrons increases in a period. So the reactivity
of non-metals increases from left to right in a period.
(ii) In group- The tendency of an element to gain electrons decreases in a group. So the reactivity
of non-metals increases from top to bottom in a group.
46. Anomalous Properties of Second Period Elements: The first element of each of the groups 1 (lithium)
and 2 (beryllium) and groups 13-17 (boron to fluorine) differs in many respects from the other members
of their respective group. For example, lithium unlike other alkali metals, and beryllium unlike other
alkaline earth metals, form compounds with pronounced covalent character; the other members of
these groups predominantly form ionic compounds. In fact the behaviour of lithium and beryllium is
more similar with the second element of the Group 1, 2 ,13, 14, 15, 16 ,17. following group i.e.,
magnesium and aluminium, respectively. This sort of similarity is commonly referred to as diagonal
relationship in the periodic properties. The anomalous behaviour is attributed to their small size, large
charge/ radius ratio and high electronegativity of the elements. In addition, the first member of group
has only four valence
orbitals (2s and 2p) available for bonding, whereas the second member of the groups have nine valence
orbitals (3s, 3p, 3d). As a consequence of this, the maximum covalency of the first member of each
group is 4 (e.g., boron can only form [BF4]- , whereas the other members of the groups can expand their
valence shell to accommodate more than four pairs of electrons e.g., aluminium forms [AlF6]3- ).
Furthermore, the first member of p-block elements displays greater ability to form p∏ – p∏ multiple
bonds to itself (e.g.,
subsequent members of the same group.
2. The increasing order of effective nuclear charge in Na, Al, Mg and Si atoms
(A) Na < Mg < Si <Al (B) Na < Mg <Al < Si
(C) Mg < Na <Al< Si (D) Na = Mg =Al = Si ANSWER- B
4. Whenever a list of radii is given, we find that the size of the noble gases is larger than the size of
theiradjacent halogens. The reason is
(A) Noble gases have a complete octet
(B) They have a higher inter electronic repulsion
(C) In halogens it is covalent radii and in noble gases it is Vander walls radii (D) Noble gases
cannot beliquefied ANSWER- B
6. Which one of the following is correct order of the size of iodine species?
(A) I > I– > I+ (B) I > I+ > I– (C) I+ > I– > I (D) I– > I > I+ ANSWER- D
7. Which of the following should be the order of increasing values of second ionisation potential of C6,
N7,O8 and F9.
(A) C > N > F > O (B) C < F < N < O (C) C < F < N < O (D) C < N < F< O ANSWER- D
12. Of the following element of which electronic configuration will have the highest electron
affinity(A) 1s2 2s2 2p3 (B) 1s2 2s2 2p5 (C) 1s2 2s2 2p6 3s2 3p5 (D) 1s2 2s2 2p6 3s2 3p3
ANSWER- C
15. According to the Modern Periodic Law of elements, the Variation in properties of elements is
related tothem?
(A) Nuclear masses (B)Atomic numbers
(C) Nuclear neutron-proton number ratio (D)Atomic masses ANSWER- B
Q.1. Describe the two merits of long form periodic table over the Mendeleev’s periodic table?
Ans- 1. It removed the anomalies about the position of isotopes which existed in the Mendeleev’s
table. 2. It relates the position of an element in the periodic table with its electronic configuration.
Q.2. What is meant by periodicity in properties of elements? What is the reason behind this?
Ans- The repetition of similar properties after regular intervals is called as periodicity. It is due to the
similarity in the outer electronic configurations which gives rise to the periodic properties of the
elements.
Q.4. Name the factors which affect the ionisation enthalpy of an element.
Ans- (i) Size of atom or ion (ii) Nuclear charge (iii) Electronic configuration (iv) Screening effect (v)
Penetration effect of the electrons
Q.5. Noble gases have zero electron gain enthalpy values. Explain.
Ans- Because the outer most shell of noble gases is completely filled and no more electrons can be
added.
Q.1 The first ionisation enthalpy of magnesium is higher than that of sodium. On the other hand, the
second ionisation enthalpy of sodium is very much higher than that of magnesium. Explain.
Ans- The 1st ionisation enthalpy of magnesium is higher than that of Na due to higher nuclear charge
and slightly smaller atomic radius of Mg than Na. After the loss of first electron, Na+ formed has the
electronic configuration of neon (2,8). The higher stability of the completely filled noble gas
configuration leads to very high second ionisation enthalpy for sodium. On the other hand, Mg+
formed after losing first electron still has one more electron in its outermost (3s) orbital. As a result,
the second ionisation enthalpy of magnesium is much smaller than that of sodium.
Q2.Among the elements of the second period Li to Ne pick out the element:
(i) with the highest first ionisation energy
(ii) with the highest electronegativity
(iii) with the largest atomic radius Give the reason for your choice.
Ans- (i) Ne .due to higher nuclear charge.
(ii) F. due to small size
(iii) Li .due to less nuclear charge.
Q4.Explain why are cations smaller and anions larger in size than their parent atoms?
Ans- (a) The cations are smaller than their parent atoms due to the following reasons:
(i) Disappearance of the valence shell.
(ii) Increase of effective nuclear charge
(b) The anions are larger than their parent atoms due to the following reason: An increase in the
number of electrons in the valence shell reduces the effective nuclear charge due to greater mutual
shielding by the electrons. As a result, electron cloud expands, i.e., the ionic radius increases.
Q5.Consider the following species: N3–, O2–, F–, Na+, Mg2+ and Al3+
(a) What is common in them?
(b) Arrange them in the order of increasing ionic radii.
Ans- (a) the same number of electrons (10 electrons)/Iso electronic species. Hence, the given species
are isoelectronic. (b) Al3+ < Mg2+ < Na+ < F– < O2– < N3–
Q.1. What is the cause of the periodicity in the properties of the elements? How do the following
properties vary in (a) a group and (b) in a period
(i) electronegativity
(ii) ionisation enthalpy
(iii) Atomic size
Ans- It is due to the similarity in the outer electronic configurations which gives rise to the periodic
properties of the elements.
(a) In a group:
(i) Electronegativity- It decreases down the group.
(ii) Ionisation enthalpy- It decreases down the group.
(iii) Atomic size- It increases down the group.
(b) In a period:
(i) Electronegativity- Increases
(ii) Ionisation enthalpy- Increases
(iii) Atomic size- Decreases.
Q.2. The first (ΔiH1) and the second (ΔiH) ionization enthalpies (in kJ mol–1) and the (ΔegH) electron
gain enthalpy (in kJ mol–1) of a few elements are given below:
(a) the least reactive element. (b) the most reactive metal.
(c) the most reactive non-metal. (d) the least reactive non-metal.
(e)the metal which can form a stable binary halide of the formula MX2, (X=halogen).
Ans- (a) Element V is likely to be the least reactive element. This is because it has the highest first
ionization enthalpy (ΔiH1) and a positive electron gain enthalpy (ΔegH).
b)Element II is likely to be the most reactive metal as it has the lowest first ionization enthalpy (ΔiH1)
and a low negative electron gain enthalpy (ΔegH).
c)Element III is likely to be the most reactive non–metal as it has a high first ionization enthalpy (ΔiH1)
and the highest negative electron gain enthalpy (ΔegH).
d)Element V is likely to be the least reactive non–metal since it has a very high first ionization enthalpy
(ΔiH2) and a positive electron gain enthalpy (ΔegH).
e)Element VI has a low negative electron gain enthalpy (ΔegH). Thus, it is a metal. Further, it has the
lowest second ionization enthalpy (ΔiH2). Hence, it can form a stable binary halide of the formula
MX2(X=halogen).
1. CHEMICAL BOND- The chemical force which keeps the atoms in any molecule
together is called a chemical bond.
2. Lewis dot structures are a shorthand to represent the valence electrons of an atom. The
structures are written as the element symbol surrounded by dots that represent the valence
electrons.
3. Electrovalent bond or Ionic Bond: The chemical bond as result of transfer of electron
from one atom(electropositive) to another atom (electronegative).Ionic bonds will be
formed more easily between elements with comparatively low ionization enthalpies and
elements with comparatively high negative value of electron gain enthalpy. Most ionic
compounds have cations derived from metallic elements and anions from non-metallic
elements.
6. Covalent Bonds- The bond formed between two atoms by mutual sharing of electrons
between them so as to complete their octets or duplets.
7. COVALENCY: The number of electrons which an atom contributes towards mutual
sharing during the formation of a chemical bond called its covalency in that compound.
8. SINGLE COVALENT BOND: A covalent bond formed by the mutual sharing of one
pair of electrons is called a single covalent bond, or simply a single bond. A single covalent
bond is represented by a small line (−) between the two atoms. H2
9. DOUBLE COVALENT BOND: A covalent bond formed by the mutual sharing of two
pair of electrons is called a double covalent bond, or simply a double bond. A double
covalent bond is represented by two small horizontal lines (=) between the two atoms. E.g.
O=O, O=C=O etc.
10. TRIPLE COVALENT BOND: A covalent bond formed by the mutual sharing of three
pair of electrons is called a triple covalent bond, or simply a triple bond. A triple covalent
bond is represented by three small horizontal lines (≡) between the two atoms. E.g. N≡N, H-
C≡C-H etc.
16. Bond length is defined as the equilibrium distance between the nuclei of two bonded
atoms in a molecule.
17. Bond Angle: It is defined as the angle between the orbital containing bonding electron
pairs around the central atom in a molecule/complex ion. It gives some idea regarding the
distribution of orbital around the central atom in a molecule/complex ion and hence it helps
us in determining its shape
18. Bond enthalpy: It is defined as the amount of energy required to break one mole of bonds
of a particular type between two atoms in a gaseous state. The unit of bond enthalpy is kJ
mol–1
19. Bond Order :The Bond Order is given by the number of bonds between the two atoms in
a molecule. E.g.: Bond Order Of O2= 2. With increase in bond order, bond enthalpy
increases and bond length decreases.
20. Covalent character in ionic compounds (Fajan’s rule) :
There is no compound which is 100% ionic.
Covalent character in ionic compound can be explained with the help of Fajan’s rule.
Small size of cation polarisation :
e.g. BeCl2 MgCl2 CaCl2 SrCl2 BaCl2
Size of cation Polarisation Covalent character
- Polarisation
- Covalent character
- Charge on anion
- Polarisation
- Covalent character
Cation which has pseudo inert gas configuration, shows more polarising power
incomparison of cation that has inert gas configuration. CuCl > NaCl (Covalent
character)
Cu+ = [Ne] 3s2p6d10 Na+ = 1s2, 2s2p6
18e- 8e-
Pseudo inert inert gas configuration
gas configuration
21. Resonance: According to the concept of resonance, whenever a single Lewis structure
cannot describe a molecule accurately, a number of structures with similar energy, positions
of nuclei, bonding and the non- bonding pairs of electrons are taken as the canonical
structures of the hybrid which describes the molecule accurately.
22. Polarity of bonds:In case of heteronuclear molecules like HCl, the shared pair of electron
between the two atoms gets displaced more towards chlorine since the electronegativity of chlorine
is far greater than that of hydrogen. The resultant covalent bond is called a polar covalent bond.
23. Dipole moment : As a result of polarization, the molecule possesses the dipole
moment which can be defined as the product of charge and the distance between the centers
of positive and negative charge. It is usually designated by a Greek letter ‘µ’.
Mathematically, it is expressed as follows:
Dipole moment (µ ) = charge (Q) X distance of separation (r)
24. Sigma( ) bond : This type of covalent bond is formed by the end to end (hand-on)
overlap of bonding orbitals along the internuclear axis. This is called as head on overlap or
axial overlap.
25. pi(π ) bond : In the formation of π bond the atomic orbitals overlap in such a way that
their axes remain parallel to each other and perpendicular to the internuclear axis. The
orbitals formed due to sidewise overlapping consists of two saucer type charged clouds
above and below the plane of the participating atoms.
26. In case of sigma bond, the overlapping of orbitals takes place to a larger extent. Hence, it
is stronger as compared to the pi bond where the extent of overlapping occurs to a smaller
extent.
27. VSEPR theory
The shape of a molecule depends upon the number of valence shell electron pairs
(bonded or nonbonded) around the central atom.
Pairs of electrons in the valence shell repel one another since their electron clouds
are negatively charged.
These pairs of electrons tend to occupy such positions in space that minimize
repulsion and thus maximise distance between them.
The valence shell is taken as a sphere with the electron pairs localising on the
spherical surface at maximum distancefrom one another.
A multiple bond is treated as if it is a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.
Where two or more resonance structures can represent a molecule, the VSEPR
model is applicable to any such structure.
The repulsive interaction of electron pairs decrease in the order: Lone pair (lp) –
Lone pair (lp) > Lone pair (lp) – Bond pair (bp) > Bond pair (bp) –Bond pair (bp)
Geometry of Molecules on the basis of VSEPR Theory
Bond pair Lone pair Shape Examples
2 0 Linear BeCl2
3 0 Trigona l BCl3
Planar
2 1 Bent SO2
4 0 Tetrahedral CH4
2 2 V-shape H2 O
5 0 Trigonal PCl5
bipyramidal
3 2 T-shaped CIF3,
2 3 Linear XeF2
6 0 Octahedral SF6
5 1 Square CIF5,
pyramidal IF5
6 1 Distorted XeF6
Octahedral
28. Hybridization: It can be defined as the process of intermixing of the orbitals of slightly
different energies so as to redistribute their energies, resulting in the formations of new set of
orbitals of equivalent energies and shape.
Salient Features of hybridization :
The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridised.
The hybridised orbitals are always equivalent in energy and shape.
The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.
These hybrid orbitals are directed in space in some preferred direction to have
minimum repulsion between electron pairs and thus a stable arrangement.
29. Types of Hybridisation
(a) sp hybridisation: This type of hybridisation involves the mixing of one s and one p
orbital resulting in the formation of two equivalent sp hybrid orbitals. Each sp hybrid
orbitals has 50% s- character and 50% p-character. Such a molecule inwhich the central
atom is sp-hybridised and linked directly to two other central atoms possesses linear
(c) sp3 hybridisation: In this type of hybridisation there is mixing of one s-orbital and
three p- orbitals of the valence shell to form four sp3 hybrid orbital of equivalent energies
and shape. There is 25% s-character and 75% pcharacter in each Sp3 hybrid orbital. The
four Sp3 hybrid orbitals so formed are directed towards the four corners of the tetrahedron
Example CH4 molecule
3
30. sp hybridisation in C2H6 molecule
31. sp2 hybridisation in C2H4 molecule
34. Molecular orbital. It gives electron probability distribution around a group of nuclei in a
molecule. They are filled in the same way as atomic orbitals. Molecular orbitals are formed
bylinear combination of atomic orbitals.
35. Conditions for the Combination of Atomic Orbitals. The linear combination of atomic
orbitals takes place only if the following conditions are satisfied :
(i) The combining atomic orbitals must have same or nearly same energy.
(ii) The combining atomic orbitals must have the same symmetry about the molecular
axis. Byconvention, z-axis is taken as the molecular axis.
(iii) The combining atomic orbitals must overlap to the maximum extent. Greater the
extent of overlapping, the greater will be electron density between the nuclei of a molecular
orbital.
36. Sigma ( ) molecular orbitals. A molecular orbital which is formed from the overlap of
two s atomic orbitlas or head to head overlap of one s and p-atomic orbitals or head to head
overlap of two p-atomic orbitals, is known as sigma molecular orbital.
37. pi ( ) molecular orbitals. A molecular orbital which is formed by lateral overlap of two
parallel p-orbitals is known as pi( ) molecular orbital.
38. Bonding molecular orbital. A molecular orbital that is formed by addition overlap (i.e.,
when the lobes of atomic orbitals overlap with the same sign) of two atomic orbitals is known
as bonding molecular orbital. It is represented as
MO A B Its energy is lower than the atomic orbitals from which it is formed. It
favours bonding.
39. Anti-bonding molecular orbital. A molecular orbital that is obtained by the subtraction overlap
(i.e., when the lobes of atomic orbitals overlap with the opposite sign) of two atomic orbitals is
know as anti-bonding molecular orbital. It is represented as *MO A B Its energy is higher
than the atomic orbitals from which it is formed. It does not favour bonding.
40. Bond order. It is defined as half of the difference between number of electrons in bonding and anti-
bonding orbitals, i.e., B.O. = ½ (Nb – Na) ‘where Nb are number of electrons in bonding
orbitals’ and Na are number of electrons in anti-bonding orbitals. Bond order helps in estimating stability of
atom.
41. Significance of Bond Order
It bond order = 0, it means species does not exist.
Bond order of 1, 2 & 3 corresponds to a single bond, double & triple bondrespectively
Bond order increases stability of molecule increases Bond length decreases
If the molecule has one or more unpaired electron, it will be paramagnetic, while ifall
the electrons are paired it will be diamagnetic.
42. Energy level Diagrams for Molecular Orbitals. The increasing order of energies of various
molecular orbitals for O2 and F2 is given below.
* * * * *
1s 1s 2s 2s 2 pz 2 px 2 p y 2 p x 2 p y 2 p z
However, this sequence of energy levels of molecular orbitals is not correct for remaining molecules
Li2, Be2, B2, C2, N2. For instance, it has been observed experimentally that for molecules such as B 2, C2,
N2 etc., the increasing order of energies of various molecular orbitals is
44. Energy level Diagrams for Molecular Orbitals. B2, C2, N2 is given below
45. Energy level Diagrams for Molecular Orbitals. O2 F2 and Ne2 is given below
46. 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 another molecule. For example, in HF
molecule, the hydrogen bond exists between hydrogen atom of one molecule and fluorine
atom
of another molecule as depicted below :
47. Conditions required for H-bond.
a) Molecule should have more electronegative atom (F, O, N) linked to the H-atom
b) Size of electronegative atom should be smaller.
c) A lone pair should be present on electronegative atom.
48. Types of H-Bonds There are two types of H-bonds (i) Intermolecular hydrogen bond (ii)
Intramolecular hydrogen bond
49. Intermolecular hydrogen bond: It is formed between two different molecules of the same or
different compounds. For example, H-bond in case of HF molecule, alcohol or water
molecules, etc.
50. Intramolecular hydrogen bond : It is formed when hydrogen atom is in between the two
highlyelectronegative (F, O, N) atoms present within the same molecule. For example, in o-
nitrophenol the hydrogen is in between the two oxygen atoms.
(a) 0.6, -0.75 (b) -0.75, 1.25 (c) 1.0, -0.75 (d) 1.25, -3
Answer: (b) -0.75, 1.25
5. Which of the molecules does not have a permanent dipole moment?
(a) SO3 (b) SO2 (c) H2S (d) CS2
Answer: (d) CS2
6. Which one has a pyramidal shape?
(a) SO3 (b) PCl3 (c) CO32- (d) NO3–
Answer: (b) PCl3
7. Polarity in a molecule and hence the dipole moment depends primarily on
electronegativity of the constituent atoms and shape of a molecule. Which of the following has
the highest dipole moment?
(i) CO2 (ii) HI (iii) H2O (iv) SO2
Answer: (iii) H2O
8. Hydrogen bonds are formed in many compounds e.g., H2O, HF, NH3. The boiling point
of such compounds depends to a large extent on the strength of hydrogen bond and the
number of hydrogen bonds. The correct decreasing order of the boiling points of above
compounds is
(i) HF > H2O > NH3 (ii) H2O > HF > NH3
(iii) NH3 > HF > H2O (iv)NH3 > H2O > HF
Answer: (ii) H2O > HF > NH3
9. Which of the following attain the linear structure:
(i) BeCl2 (ii) NCO+ (iii) NO2 (iv) CS2
Answer: (i) BeCl2
10. Which of the following statements are not correct?
(i) NaCl being an ionic compound is a good conductor of electricity in the solid state.
(ii) In canonical structures there is a difference in the arrangement of atoms.
(iii) Hybrid orbitals form stronger bonds than pure orbitals.
(iv) VSEPR Theory can explain the square planar geometry of XeF4.
Answer: (i) NaCl being an ionic compound is a good conductor of electricity in the solid state.
11. The bond length between hybridised carbon atom and other carbon atom is minimum in
(a) Propane (b) Butane (c) Propene (d) Propyne
Answer: (d) Propyne
12. The number of nodal planes present in s × s antibonding orbitals is
(a) 1 (b) 2 (c) 0 (d) 3
Answer: (a) 1
13. Which one of the following does not have sp² hybridised carbon?
(a) Acetone (b) Acetic acid (c) Acetonitrile (d) Acetamide
Answer: (c) Acetonitrile
14. Which of the following will have the lowest boiling point?
(a) 2-MethylButane (b) 2-MethylPropane
(c) 2-Dimethylpropane (d) n-Pentane
Answer: (b) 2-MethylPropane
15. Among the following mixtures, dipole-dipole as the major interaction, is present in
(a) benzene and ethanol (b) acetonitrile and acetone
(c) KCl and water (d) benzene and carbon tetrachloride
Answer: (c) KCl and water
16. Which of the following types of hybridisation leads to three dimensional geometry of
bonds around the carbon atom?
(a) sp (b) sp² (c) sp³ (d) None of these
Answer: (c) sp³
17. The maximum number of hydrogen bonds that a molecule of water can have is
(a) 1 (b) 2 (c) 3 (d) 4
Answer: (d) 4
18. The number of types of bonds between two carbon atoms in calcium carbide is
(a) Two sigma, two pi
1(a) What change in energy takes place when a molecule is formed from its atoms?
Answer: There is a fall in energy.
1(b) Name the shapes of the following molecules: CH4, C2H2, CO2.
Answer: CH4: Tetrahedral; C2H2: Cylindrical; CO2: linear
Arrange the following in order of increasing strengths of hydrogen bonding O, F, S,
2(a) Cl, N.
2(b) Which orbitals can overlap to form a cr-bond and which orbitals can do so to form a
π bond?
Answer: s-s, s-p, p-p form a bond, and only p-p form π bond
3(a)
Which electrons take part in bond formation?
4(a) Name the method generally used for the calculation of lattice energy or
electron affinity.
Answer:
(b) Arrange the following in order of decreasing C-C bond length: C2H6, C2H2, C2H4
Answer: H3C – CH3 > H2C = CH2 > HC ≡ CH.
6
Write down the resonance structures of nitrous oxide.
(a)
Answer:
Answer: The number of electrons that an atom gains or loses or shares with other
atoms to attain noble gas configuration is termed its valency.
(b) Though chlorine has nearly the same electronegativity as nitrogen, yet there is no
hydrogen bonding in HCl. Why?
Answer: The size of the chlorine atom (3 orbits) is bigger than N (2 orbits).
8 On what factors the polarity of the bond depends?
(a)
Answer: Difference of electronegativity of the two atoms.
(b) What type of orbitals can overlap to form a covalent molecule?
Answer: Half-filled atomic orbitals containing electrons with opposite spins.
1 (a) Which out of CH3F and CH3Cl has a higher dipole moment and why?
Answer: The dipole moment of CH3Cl is greater than that of CH3F. The C-F bond length in
CH3F is smaller than the C-Cl bond length in CH3Cl. The charge separation in the C-F bond is
more than in the Cl-C bond- fluoride being more electronegative than chlorine. The bond
length has a greater effect than the charge separation. Hence the dipole moment of CH3C1
is greater than that of CH3F.
(b) Why covalent bonds are called directional bonds whereas ionic bonds are called
non-directional?
Answer: A covalent bond is formed by the overlap of half-filled atomic orbitals which have
definite directions. Hence covalent bond is directional. In ionic compounds, each ion is
surrounded by a number of oppositely charged ions and hence there is no definite
direction.
(c) Account for the following: The experimentally determined N-F bond length in
NF3 is greater than the sum of the single covalent radii of N and F.
Answer: This is because both N and F are small and hence have high-electron
density. So they repel the bond pairs thereby making the N-F bond length larger.
2(a) Why HCl is polar whereas the Cl2 molecule is non-polar?
Answer: In Cl2 both atoms have the same electronegativity. Hence the shared pair of
electrons is attracted equally by both and remains exactly in the center. NO end acquires a
negative or positive charge. In HCl, chlorine is more electronegative than H. Hence shared
pair of electrons is more attracted towards chlorine, which, therefore acquires a
negative charge while H acquires a positive charge.
(b) Out of sigma and pi bonds, which one is stronger and why?
Answer: Sigma (a) bond is stronger This is because a bond is formed by head-on overlapping
of atomic orbitals and such overlapping being on the internuclear axis is large, n bond is
formed by sidewise overlapping which is small and so a Pi bond is weaker.
(c) Out of p-orbital and sp-hybrid orbital which has greater directional character and why?
Answer: sp orbital has a greater directional character than p-orbital. This is because the p-
orbital has equal-sized lobes with equal electron density in both the lobes whereas the sp-
hybrid orbital has greater electron density on one side.
3 (a) Explain giving reasons whether BH4 and H3O+ will have the same/different geometry?
Answer: The central atom in both the ions is surrounded by the same number of pairs of
electrons, that is, 4. Hence they have the same tetrahedral geometry.
(b) Out of peroxide ion (O22- ) and superoxide ion (O2 - ) which has larger bond length and why?
(c) Answer: The bond order of O2– is 1.5 while that of O22- is 1.0.
The lesser the bond order, the greater is the bond length as the bond order is inversely
proportional to bond length. ( Hence O22- has a larger bond length than O22-.
Q2. What is meant by term bond order ? Calculate the bond order of N 2, O2, O2+, O2-
Read the following passage and anshwer the questions given below:
1. The attractive force which holds the two atoms together is called a chemical bond. A covalent bond is
formed by an equal sharing of electrons. A coordinate bond is formed by unequal sharing of electrons. An
ionic bond is formed by the transfer of electrons from one atom to another. Octet rule, although very
useful but is not universally applicable. According to valence bond theory, a covalent bond is formed by
overlapping of half-filled atomic orbitals resulting in a lowering of energy and more stability. Bond order is
the number of bonds between atoms in a molecule. The higher the bond order more will be stability and
bond dissociation enthalpy but the smaller the bond length. The polarity of a covalent bond depends
upon the difference in electronegativity. The covalent character of a bond depends upon polarising
power, smaller cation and bigger anions have higher polarising power. VSEPR theory helps to predict the
shapes of molecules.
(c) Out of CN+, CN–, NO, which has the highest bond order?
Ans (c). CN– (14): σ(1s)2, σ*(1s)2, σ(2s)2, σ*(2s)2, π(2px)2= π(2py)2, σ (2pz)2.
(d) What is the correct order of repulsion bp – bp, lp – lp, and lp – bp?
Ans (d). lp – lp > lp – bp > bp – bp (bp is bond pair, lp is lone pair).
2–
f) Which out of B2, CO, O 2 and NO+ are paramagnetic and why?
Ans (f). B2(10): σ(1s)2, σ*(1s)2, σ(2s)2, σ*(2s)2, π(2px)1= π(2py)1
2. Read the following passage and anshwer the questions given below :
lp – lp>lp –bp>bp – bp
lone pairs are localised on the central atom and each bonded pair is shared between two
atoms. As a result, the lone pair electrons in a molecule occupy more space as compared to the
bonding pairs of electrons. These results in greater repulsion between lone pairs of electrons as
compared to the lone pair – bond pair and bond pair – bond pair repulsions.
Answer: c) 33
4. Hybridisation involves
a) Mixing up of atomic orbitals b) Addition of an electron pair
c) Removal of an electron pair d) Separation of orbitals
Answer: a) Mixing up of atomic orbitals
Answer: b) 1
Reversible process: The process which occurs in infinite number of steps in this Way that the
equilibrium conditions are maintained at each step, and the process can be reversed by infinitesimal
change in the state of functions.
Irreversible process: An irreversible process can be defined as a process in which the system and the
surroundings do not return to their original condition once the process is initiated.
Internal Energy (E or U) :
It is the total energy within the substance. It is the sum of many types of energies like vibrational
energy,translational energy. etc. It is a extensive property and state function.
Its absolute value cannot be determined but experimentally change in internal energy (ΔU)
can be determined by ΔU = U2 – U1 or ΣUP – ΣUR
Modes of energy exchange : These are two ways by which a system can interact or can exchange
energy with its surroundings.
Heat : when the energy transfer takes place because of temperature difference between system &
surroundings. It is known as heat.
Work : Energy transfer which is not heat or which is not because of temperature difference is called
work
First Law of Thermodynamics:
Energy can neither be created nor destroyed although it can be converted from one form to the other.
OR
The energy of an isolated system is constant.
Mathematically, ΔU = q + W
Where, ΔU = internal energy change q = heat added to
systemW = work added to system
Sign convention:
(i) q is + ve = heat is supplied to the system
(ii) q is – ve = heat is lost by the system
(iii) W is + ve = work done on the system
(iv) W is – ve =work done by the system
Enthalpy (H): A thermodynamic quantity equivalent to the total heat content of a system. It is
the sum of internal energy of the system and the product of pressure and volume.
At constant volume ∆V = 0, qv =∆ U
So H = U + p∆V,
qp = H2- H1 = ∆H
∆H = ∆U + P.∆ V.
The enthalpy change accompanying a reaction is called the reaction enthalpy
Exothermic and Endothermic reactions: ∆H = –Ve for exothermic and ∆ H= +Ve for endothermic reaction
i.e. evolution and absorption of heat respectively
HEAT CAPACITY
Heat capacity is the quantity of heat required to raise the temperature by one degree Celsius.(or 1K).
Specific heat capacity (s): It is the quantity of heat required to raise the temperature of one unit mass of a
substance by one degree celsius (or one kelvin). For finding out the heat, q, required to raise the
temperatures of a sample, we multiply the specific heat of the substance, c, by the mass m, and
temperatures change,
ΔT as q=c×m×ΔT =CΔT .
Relation between Cp and Cv and ideal gas Cp -CV=R
Measurement of ∆H and ∆U The process is carried out in a vessel called calorimeter,
immersed in aknown volume of a liquid.
(a) ∆U measurements: The energy changes are measured at constant volume. No work is done
.A bomb calorimeter is used.
(b) ∆H measurements: In exothermic reaction, heat is evolved, so q and H will be negative. In
endothermicp reaction, heat is absorbed, so q and H will be positive
Bond enthalpy: It is amount of energy released when gaseous atoms combines to form one mole of
bondsbetween them or heat absorbed when one mole of bonds between them are broken to give free
gaseous atoms. Further ∆H r = B.E. (Reactants) - B.E. (Products)
Lattice Enthalpy
The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one mole of an
ioniccompound dissociates into its ions in gaseous state.
Spontaneous & Non Spontaneous Processes:
A process which can take place by itself is called spontaneous process.
A process which can neither take place by itself or by initiation is called nonSpontaneous.
Gibbs Energy Change and Work rG0 = -nFE cell ,Here E cell is the standard cell potential.
Gibbs Energy Change and Equilibrium Constant G0 = − 2.303RT log K
Third Law of Thermodynamics: The entropy of perfect crystals of all pure elements & compounds is
zero at the absolute zero of temperature.
PRACTICE QUESTIONS
Section-A(MCQ TYPE)
01. A ...................... in thermodynamics refers to that part of universe in which observations are made
and remaining universe constitutes the……………...
(A) surroundings, system
(B) system, surroundings
(C) system, universe
(D) system, boundary
(D) – 10.3 kJ
07.Amount of heat required to vaporize one mole of a liquid at constant temperature and under
standard pressure (1bar) is called
(A) Standard enthalpy of sublimation
(B) standard enthalpy of fusion
(C) standard enthalpy of vaporization
(D) none of the above
07. The standard enthalpy change for the formation of one mole of a compound from
its elements in their most stable states of aggregation is called:
(A) Standard enthalpy of combustion
(B) standard enthalpy of formation
(C) standard enthalpy of vaporization
(D) standard enthalpy of solution
10.The values of ΔH and ΔS for the reaction C(graphite) + CO2 (g)→ 2 CO (g) are 170 kJ and 170 JK-1
respectively. This reaction will be spontaneous at
(A) 910 K (B) 1110 K
(C) 510 K (D) 710 K
12. If an endothermic reaction occurs spontaneously at constant T and P, then which of the following
is true?
(A) ΔG > 0 (B) ΔH < 0
(C) ΔS > 0 (D) ΔS < 0
13. When 1 mole of crystalline NaCl is obtained from sodium and chlorine gas, 410 kJ of heat is
released. The heat of sublimation of sodium metal is 108 kJ mol-1 and Cl-Cl bond enthalpy is 242
kJ mol–l . If the ionization energy of Na is 493.0 kJ mol–l and the electron affinity of chlorine is 368
kJ mol–l , the lattice energy of NaCl is
(A) 764 kJ mol–l (B) -764 kJ mol–l
(C) 885 kJ mol–l (D) -885 kJ mol–l
14. Under which of the following condition is the relation ΔH = ΔU + pΔV valid for a closed system?
(A) constant pressure
(B) constant temperature
(C) constant temperature and pressure
(D) constant temperature, pressure and composition
15. Which one of the following equations does not correctly represent the first law of
thermodynamics for the given process?
(A) Isothermal process : q = -w (B) Cyclic process : q = -w
(C) Isochoric process : ΔU = q (D) Adiabatic process : ΔU = -w
16 One mole of an ideal gas expands freely and isothermally at 300 K from 10 litres to 100 litres. If
ΔU = 0, the value of ΔH is
(A) 10 kJ (B) 200 kJ
(C) zero (D) 300 Kj
17. An insulated container is divided into two compartments. One compartment contains an ideal
gas at a pressure P and temperature T while in the other compartment there is perfect vacuum. If
a hole is made in the partition wall, which of the following will be true?
(A) ΔU = O (B) w = 0
(C) ΔT = 0 (D) All the three are true
18. Read the following statements carefully and choose the correct option
(i) In case of diatomic molecules, the enthalpy of atomization is also the bond dissociation enthalpy.
(ii) In case polyatomic molecules, bond dissociation enthalpy is different for different bonds within the
same molecule.
(A) Both (i) and (ii) are correct
(B) (i) is correct but (ii) is incorrect
(C) (ii)is correct but (i) is incorrect
(D) Both (i) and (ii) are incorrect19. Enthalpy of sublimation of a substance is equal to
(A) enthalpy of fusion + enthalpy of vaporization
(B) enthalpy of fusion
(C) enthalpy of vaporization
(D) twice the enthalpy of vaporization
20.‘At absolute zero the entropy of perfectly crystalline substance is taken as zero’ is statement of
(A) zeroth law of thermodynamics
(B) 1st law of thermodynamics
(C) 2nd law of thermodynamics
(D) 3rd law of thermodynamics
22. Assertion (A) : A liquid crystallizes into a solid and is accompanied by decrease in entropy.
Reason (R) : In crystals, molecules organize in an ordered manner.
24. Assertion (A) :Molar entropy of vaporization of water is different from ethanol
Reason (R):Water is more polar than ethanol.
25. Assertion: Many endothermic reactions that are not spontaneous at room temperature
become spontaneous at high temperature.
Reason: Entropy of the system increases with increase in temperature
QN 1 2 3 4 5 6 7 8 9 10
ANS B C C A A D B B A B
QN 11 12 13 14 15 16 17 18 19 20
ANS A C B A D C D A A D
QN 21 22 23 24 25
ANS A A D B B
Q1. Given that ∆H = 0 for mixing of two gases. Explain whether the diffusion of these
Gases into each other in a closed container are a spontaneous process or not?
ANS: It is spontaneous process. Although enthalpy change is zero but randomness or disorder (i.e. ∆S)
increases. Therefore, in equation ∆G = ∆H – T∆S, the term T∆S will be negative. Hence, ∆G will be
negative.
Q2. The enthalpy of atomisation for the reaction CH4(g)→ C(g) + 4H (g) is 1665 kJ mol–1. What is the
bond energy of C–H bond?
ANS: 1665/4 kJ mol–1 = 416.2 kJ mol–1
Q3. The standard molar entropy of H2O (l ) is 70 J K–1 mol–1. Will the standard molar entropy of H2O(s)
be more, or less than 70 J K–1 mol–1?
ANS: Less, because ice is more ordered than H2O (l ).
Q4. Identify the state functions and path functions out of the following :
enthalpy, entropy, heat, temperature, work, free energy.
Q6. Calculate the number of kJ of heat necessary to raise the temperature of 60.0 g of aluminium from
35°C to 55°C. Molar heat capacity of Al is 24 J mol–1 K–1.
ANS: Q= n x C X ΔT
= 60/27 x 24 x (55-35)
= 1066.7 J = 1.07 KJ
1. The fH° for CO2(g) CO(g) and H2O(g) are –393.5, – 110.5 and –241.8 kJ/mol
respectively, the standard enthalpy change (in kJ) for the reaction
CO2(g) + H2(g) → CO(g) + H2O(g) is
Ans: H° = [H0f (CO)(g) + H0f (H2O)(g)] – [H0f (CO2 )(g) + H0f (H2 )(g)]
= [– 110.5 + ( – 241.8)]– [– 393.5 + 0]
= 41.2 kJ/mol
2. ) Bond dissociation enthalpy of H2, Cl2 and HCl are 434 , 242 and 431 kJ mol–1 respectively. Enthalpy
of formation of HCl is:
Ans: H2 + Cl2 → 2HCI
Substituting the given values, we get enthalpy of formation of 2 moles of HCl is – ( 862 – 676)
= –186 kJ.so for one mole of HCl is -186/2=-93 kJmol–1
Ans: ∆G =∆ H – T∆S
Assume that the equation is at equilibrium then ΔG = 0
ΔG=ΔH−TΔS=0
Therefore ΔH =TΔS
T= ΔH/ΔS =2000K
At 2000 K ΔG = 0
Reaction to be spontaneous ΔG must be negative. Therefore temperature should be greater than
2000 K
1.We can measure energy changes associated with chemical or physical processes by an
experimental technique called calorimetry. In calorimetry, the process is carried out in a
vessel called calorimeter, whichis immersed in a known volume of a liquid. Knowing the heat
capacity of the liquid in which calorimeter is immersed and the heat capacity of calorimeter,
it is possible to determine the heat evolved in the process by measuring temperature
changes. Measurements are made under two different conditions
i) at constant volume, qV
ii) at constant pressure, qp
(a)The quantity of of heat required to raise the temperature of one unit mass of a
substance by one degreeCelsius is called
(a)Heat capacity (b)Specific heat capacity
(c)Molar heat capacity ( d)Heat content
Answer
b)Specific heat capacity
At constant volume, the heat capacity, C is denoted by CV and at constant pressure, this
is denoted by Cp
We can write equation for heat,
q at constant volume as qV = Cv ΔT= ΔU
at constant pressure as qp= Cp ΔT= ΔH
The difference between Cp and CV can be derived for an ideal gas as:
For a mole of an ideal gas, ΔH = ΔU + Δ(PV ) as PV=RT
ΔH = ΔU + Δ(RT )
ΔH = ΔU + R Δ T
On putting the value of ΔH & ΔU
Cp ΔT = Cv ΔT+ R Δ T
Cp = Cv + R
Cp - Cv = R
2. In a chemical reaction, reactants are converted into products and is represented by,
Reactants Products
The enthalpy change accompanying a reaction is called the reaction enthalpy. The
enthalpy change of a chemical reaction, is given by the symbol rH.
r H = (sum of enthalpies of products) – (sum of enthalpies of reactants)
r H = aiH product - biH reactant
(Here symbol Σ (sigma) is used for summation and ai and bi are the stoichiometric
coefficients of the products and reactants respectively in the balanced chemical equation. For
example, for the reaction
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l)
r H = aiH product - biH reactant
= [Hm (CO2 ,g) + 2Hm (H2O, l)]– [Hm (CH4 , g) + 2Hm (O2, g)]
where Hm is the molar enthalpy’
1. Write the factors affecting enthalpy of reaction.
2.Define Standard Enthalpy of reaction.
3. CaO (s) + CO2 (g) → CaCO3 (s) , f H0 = -178.3 kJmol-1
Can Enthalpy of reaction for above reaction consider as enthalpy of formation of CaCO 3. Explain?
Or
Does entropy increase or decrease when egg is boiled?
Ans.: On boiling egg, entropy decreases as due to denaturation, the helical structure of protein
become more complicated and random coiled structure
SECTION- E (LA-5MARKS)
ANS:
(a)Intensive Properties
Properties of the system which depend only on the nature of matter but not on the quantity of matter
are called Intensive properties, e.g., pressure, temperature, specific heat, etc
Extensive Properties Properties of the system which are dependent on the quantity of matter are
called extensive properties, e.g., internal energy, volume, enthalpy, etc.
(b) CH3OH (l) +3/2 O2(g) → CO2(g) + 2H2O(l) ; ∆rH0 = –726 kJ mol–1
On reversing the above eq.
CO2(g) + 2H2O(l) → CH3OH (l) +3/2 O2(g); ∆rH0 = 726 kJ mol–1 ……….eq. 1
C(graphite) + O2(g) → CO2(g) ; ∆cH0 = –393 kJ mol–1 ………….eq.2
H2(g) +1/2 O2(g) → H2O(l) ; ∆fH0 = –286 kJ mol– ………….eq.3
.
Multiply eq. 3 by 2
2H2(g)+O2(g)→2H2O(l);2ΔfH0=2×−286kJmol−1=−572kJmol−1 ………….eq.4
C(graphite)+2H2(g)+1/2 O2(g)→CH3OH(l)
so
Enthalpy of formation of CH3OH ΔfH0=+726−393−572kJmol−1=−239kJmol−1
CHAPTER --EQUILIBRIUM
KEY NOTES-
Equilibrium is the state of a process in which the properties like temperature, pressure, and
concentration etc of the system do not show any change with passage of time.
In all processes which attain equilibrium, two opposing processes are involved .
Equilibrium is attained when the rates of the two opposing processes become equal.
If the opposing processes involve only physical changes, the equilibrium is called Physical
Equilibrium.
If the opposing processes are chemical reactions, the equilibrium is called Chemical
Equilibrium.
Physical Equilibrium
Solid – liquid Equilibrium: H2 O(s) H2 O(l)
Liquid – Gas Equilibrium: H2 O(l) H2 O(g)
Solid – Solution Equilibrium: Salt(Solid) Salt(in solution)
Gas –Solution equilibrium: CO2(g) CO2(in solution)
Equilibrium in Chemical Process
Reversible reaction: A reaction in which not only the reactants react to form the products
under certain conditions but also the products react to form reactants under the same conditions
Examples: 3Fe(s) + 4H2O(g) Fe3 O4 (s) + 4H 2(g)
Irreversible reaction: A reaction cannot take place in the reverse direction, i.e. the products
formed do not react to give back the reactants under the same condition.
Example: AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO 3(g)
Generally, a chemical equilibrium is represented as
Where A, B are reactants and C, D are products.
Note: The double arrow between the left hand part and right hand part shows that changes are taking
place in both the directions.
On the basis of extent of reaction, before equilibrium is attained chemical reactions may be classified
into three categories.
. Those reactions which proceed to almost completion.
Those reactions which proceed to almost only upto little extent.
Those reactions which proceed to such an extent, that the concentrations of reactants and
products at equilibrium are comparable
The equilibrium state is dynamic and not static in nature.
Homogeneous equilibrium: All the reactants and products of any reaction under equilibrium are
in same physical state. Example: N2 (g) + 3H2 (g) 2NH 3 (g)
Heterogeneous equilibrium? :Physical state of one or more of the reacting species may differ
i.e. all the reactants and products are not in same physical state.Example
2NaHCO 3(s) Na2CO3 (s) + CO2(g) + H2 O(l)?
Characteristics of Equilibrium State
It can be attained only if the reversible reaction is carried out in closed vessel.
It can be attained from either side of the reaction.
A catalyst can hasten the approach of equilibrium but does not alter the state of equilibrium.
It is dynamic in nature i.e. reaction does not stop but both forward and backward reactions
take place at equal rate.
Change of pressure, concentration or temperature favours one of the reactions (forward or
backward) resulting in shift of equilibrium point in one direction.
Law of Mass Action & Equilibrium Constant
“The rate at which a substance reacts is directly proportional to its active mass and rate of a chemical
reaction is directly proportional to product of active masses of reactants each raised to a power equal
to corresponding stoichiometric coefficient appearing in the balanced chemical equation”.
Fore reaction
Rate of reaction ∝ [A]a.[B]b
or rate of reaction = K[A] a[B]b
where K is rate constant or velocity constant of the reaction at that temperature.
Applying Law of mass action for general reversible reaction
aA + bB cC + dD
When the reaction is not at equilibrium this ratio is called ‘Q C ’ i.e., Q C is the general term used for the
above given ratio at any instant of time. And at equilibrium Q C becomes KC .
If the reaction is at equilibrium, Q = K c
A net reaction proceeds from left to right (forward direction) if Q < KC .
A net reaction proceeds from right to left (the reverse direction) if Q >Kc
The Le–Chatelier’s Principle:Statement:
“When a chemical reaction at equilibrium is subjected to any stress, then the equilibrium shifts in that
direction in which the effect of the stress is reduced.”
Effect of Addition of Inert Gases:
Addition of inert gas at constant volume: No effect on equilibrium.
Addition of inert gas at constant pressure: Equilibrium shifts in a direction where there is
increase in number of moles of gases.
Effect of Change in Temperature:
In a system at equilibrium, both exothermic and endothermic reactions take place
simultaneously.
Increase in temperature would shift the equilibrium in the direction of endothermic reaction.
Decrease in temperature would shift the equilibrium in the direction of exothermic reaction.
Effect of Change in Concentration:
When the concentration of reactants increased, equilibrium shifts in forward direction.
When the concentration of the products is increases, equilibrium shifts in backward direction.
Effect of Change in Pressure:
Increase in pressure shifts the equilibrium in the direction of lesser number of gaseous
molecules.
Decrease in pressure shifts the equilibrium in the direction of larger number of gaseous
molecules.
Effect of Catalyst:
Catalyst does not change the equilibrium.
Summary of Le Chatelier’s Principle
Addition of Inert gas at const.pressure where the no. of gaseous moles are more
(A) Shifts in the forward direction (B) Shifts in the reverse direction
(C) Increase the yield of hydrogen (D) No effect.
18. For the chemical reaction3X (g) + Y (g) ⇌ X3Y (g) the amount of X3Y at equilibrium is affected by
(A) Temperature and pressure (B) Pressure only
(C) Temperature only (D) Temperature, pressure and catalyst.
19. When two reactants A and B are mixed to give products C and D, the concentration quotient (Q) at
initial stage of the reaction
(A) Is zero (B) Decreases with time
(C) Is independent of time (D) Increases with time.
20. The following reaction occurs in the blast furnace where iron ore is reduced to iron metal: 3Fe 2O3(s) +
3CO(g) ⇌ 2Fe(l) + 3CO2(g)
Using the Le Chatelier’s principle, predict which one of the following will NOT disturb the equilibrium?
(A) Removal of CO (B) Removal of CO2 (C) Addition of CO2 (D) Addition of Fe2O3
ANSWERS OF MCQ
4 (B) both assertion and reason are true and reason is the not the correct explanation of assertion
VERY SHORT ANSWER TYPE QUESTIONS(2 MARKS)-
1. Identify the type of equilibrium in the following physical processes:
i. Camphor(s) ⇌ Camphor(g)
ii. Ammonium chloride(s) ⇌ Ammonium chloride(g)
iii. Carbon dioxide gas ⇌ Dry ice
iv. Water ⇌ Ice
2. Explain the law of mass action and give its mathematical representation.
3. Write the rate equation for the following reactions:
i. C + O2 → CO2
ii. 2KClO3 → 2KCl + 3O2
4. Explain in short homogeneous equilibrium and heterogeneous equilibrium.
5. What are the characteristics of equilibrium constant?
6. Given the equilibrium reaction, H2O(g) + CH4(g) ⇌ CO(g) + 3H2(g)
Using Le Chatelier’s principle, predict how concentration of CO will change when the equilibrium is
disturbed by
i. adding CH4 ii. adding H2 iii. removing H2O iv. removing H2
ANSWER VERY SHORT ANSWER TYPE QUESTIONS-
ANS 1 :
i. Solid – vapour equilibrium
ii. Solid – vapour equilibrium Solid
iii. Solid – vapour equilibrium
iv. Solid – liquid equilibrium
ANS 2-Statement: The law of mass action states that the rate of a chemical reaction at each instant is
proportional to the product of concentrations of all the reactants.
Explanation: A rate equation can be written for a reaction by applying the law of mass action as follows:
Consider a reaction, A + B → C
Here A and B are the reactants and C is the product. The concentrations of chemical species are expressed
in mol L-1 and denoted by putting the formula in square brackets. On applying the law of mass action to this
reaction, a proportionality expression can be written as: Rate ∝ [A] [B]
This proportionality expression is transformed into an equation by introducing a proportionality constant, k,
as follows: Rate = k [A] [B]
This equation is called the rate equation and the proportionality constant, k, is called the rate constant of
the reaction.
ANS 3- The rate equation is written by applying the law of mass action.
i. The reactants are C and O2
Rate ∝ [C] [O2]
∴ Rate = k [C] [O2]
ii. The reactant is KClO3 and its 2 molecules appear in the balanced equation.
∴ Rate ∝ [KClO3]2
∴ Rate = k [KClO3]2
ANS 4- i. In a homogeneous equilibrium, the reactants and products are in the same phase.
e.g. Dissociation of HI:
2HI(g) ⇌ H2(g) + I2(g)
ii. In a heterogeneous equilibrium, the reactants and products exist in different phases, e.g. Formation of
NH4Cl:
NH3(g) + HCl(g) ⇌ NH4Cl(s)
ANS 5- Characteristics of equilibrium constant:
The value of equilibrium constant is independent of initial concentrations of either the reactants or
products.
Equilibrium constant is temperature dependent. Hence, KC and KP change with change in
temperature.
Equilibrium constant has a characteristic value for a particular reversible reaction represented by a
balanced equation at a given temperature.
Higher value of KC or KP means more concentration of products is formed and the equilibrium point
is more towards right hand side and vice versa.
ANS 6- i. Adding CH4: Adding CH4 will favour the forward reaction and the yield of CO and H2 will increase.
ii. Adding H2: Adding H2 will favour the reverse reaction and the yield of CO and H2 will decrease.
iii. Removing H2O: Removing H2O will favour the reverse reaction and the yield of CO and H2 will decrease.
iv. Removing H2: Removing H2 will favour the forward reaction and the yield of CO and H2 will increase.
SHORT ANSWER TYPE QUESTIONS-(3 MARKS)
1.Determine the concentration of CO2 which will be in equilibrium with 2.5 × 10-2, mol L-1 of CO at 100°C for
the reaction FeO (s) + CO (g) ⇌ Fe (s) + CO2 (g); Kc = 5.0.
2. Prove that the pressure necessary to obtain 50% dissociation of PCl5 at 500 K is numerically equal to the
three times the value of the equilibrium constant, Kp.
3. A solution is found to contain 0.63 g of nitric acid in 100 mL of the solution. What is the pH of the
solution.
4. The ionization constant at 298K is 1.8 x 10 -4 .Calculate the ionization constant of the
correspondingconjugatebase.
ANS 2-
4. The Ksp of AgCl, AgBr, AgI are 1.8 × 10–10, 5.0 × 10–13, 8.3 × 10–17, which will precipitate last if AgNO3
solution is added to NaCl, NaBr, NaI?
Ans. AgI will precipitate because its Ksp is low, ionic product will exceed Ksp.
OR
Write the solubility product expression for:
Ag2CrO4 (s) ⇌ 2Ag+ (aq) + CrO42- (aq)
Answer: Ksp = [Ag+]2[CrO42-].
Read the following passage and answer the questions that follow:
Arrhenius acids give H+ ion in aqueous solution where as bases give OH– in aqueous solution. Bronsted acids
are proton donor where as Bronsted bases are proton acceptors. Acids, on donating proton form conjugate
base where as bases form conjugate acid after accepting proton. Buffer solution is a solution whose pH does
not change by adding small amount of H+ or OH– . The decrease in conc. of one of the ion by adding other
ion as common ion is called common ion effect. Lewis acids are electron deficient or +vely charged. Lewis
bases are electron rich or negatively charged. Ksp (solubility product) is product of molar concentration of
ions raised to power number of ions per formula of the compound in sparingly soluble salt. Precipitation
occurs only if ionic product exceeds solubility product. Solubility of salt decreases in presence of common
ion. Kw is ionic product of water, 1 × 10–14 at 298 K. Kw increases with increase in temperature. pH is –log
[H3O+ ] where [H3O+] = Ca in mono protic acid 'C' is molar conc., 'a' is degree of ionisation. A salt is said to be
hydrolysed if pH of solution changes. KH is hydrolytic constant. pH of salts of strong acid and strong base is
equal to 7. pH of other salts can be 7. pH of buffer solution can be calculated with the help of Henderson
equation.
(1) What will be conjugate base of (i) H2SO4 (ii) HCO3– ?
Ans. (i) HSO4– (ii) CO32–
(2) What are conjugate acids of (i) NH2 – (ii) NH3
Ans. (i) NH3 (ii) NH4+
(3) What is the pH of 0.1 M HCl?
Ans.pH = – log [H+] = – log 10-1 = 1.
(4)What is pOH? What is its value for pure water at 298 K?
Answer:
pOH = – log [OH–]
pH + pOH = 14 for pure water at 298 K
pH = 7
or
pOH of water at 298 = 7.
OR
Calculate the pH of a buffer solution containing 0.1 moles of acetic acid and 0.15 mole of sodium acetate.
The ionization constant for acetic acid is 1.75 × 10-5.
Answer:
(c ) It is due to common ion,Cl- increase, rate of backward reaction increases, solubility of NaCl decreases.
1 Key Notes:
………….. 1
In the above reactions, the elements magnesium and sulphur are oxidised on account of addition of
oxygen to them
……………2
The oxidation of magnesium with fluorine, chlorine is due to addition of electronegative element to
Mg.
………3
oxidation due to the removal of electropositive element potassium from potassium ferrocyanide
before it changes to potassium ferricyanide.
The term “Reduction” is defined as the removal of oxygen/electronegative element from a substance or
addition of hydrogen/ electropositive element to a substance.
…………..4
……..5
………………6
Oxidising agents (Oxidant): Oxidising agents is the substance which supplies oxygen to other elements or
removes hydrogen from other element .It is the substance which itself get reduced in the reaction. For
example O2 in eq.1,Cl2 and F2 in eq.2 and H2O2 in eq.3 are Oxidising agents
Reducing agents (Reductant): Reducing agents is the substance which supplies hydrogen to other
elements or removes oxygen from other element .It is the substance which itself get oxidised in the
reaction. For example H2 in eq.5, SnCl2 in eq.6 are reducing agents agents
2 Redox reactions: oxidation and reduction taking place simultaneously thus these reactions are called
redox reactions.
3 REDOX REACTIONS IN TERMS OF ELECTRON TRANSFER REACTIONS:
Above reaction is a redox reactions because in this reactions sodium is oxidised due to the addition of
more electronegative element (Cl) to sodium. Simultaneously, chlorine is reduced because to it, the
electropositive element sodium has been added.
For convenience, each of the above processes can be considered as two separate steps, one involving
the loss of electrons and the other the gain of electrons.Each of the steps is called a half reaction
The half reactions that involve loss of electrons are called oxidation reactions. Similarly, the half
reactions that involve gain of electrons are called reduction reactions.
Thus from electronic concept:
nitrate for about one hour. You may notice that the strip becomes coated with reddish metallic copper
and the blue colour of the solution disappears. Formation of Zn 2+ ions among the products can easily be
judged when the blue colour of the solution due to Cu2+ has disappeared.
The reaction between metallic zinc and the aqueous solution of copper nitrate is
In above reaction, zinc has lost electrons to form Zn 2+ and, therefore, zinc is oxidised.
Evidently, now if zinc is oxidised, releasing electrons, something must be reduced,
accepting the electrons lost by zinc. Copper ion is reduced by gaining electrons from the
zinc.
Following rules are applied to determine the oxidation of an atom in an ion or a molecule.
1 In elements, in the free or the uncombinedstate, each atom bears an oxidationnumber of zero.
Evidently each atom in H2, O2, Cl2, O3, P4, S8, Na, Mg, Al has theoxidation number zero.
2 For ions composed of only one atom, theoxidation number is equal to the chargeon the ion. Thus Na+
ion has an oxidationnumber of +1, Mg2+ ion, +2, Fe3+ ion, +3, Cl– ion, –1, O2– ion, –2; and so on.
3 The oxidation number of oxygen in mostcompounds is –2. However, we come across
two kinds of exceptions here in peroxides (e.g., H2O2, Na2O2), eachoxygen atom is assigned an
oxidationnumber of –1, in superoxides (e.g., KO2,RbO2) each oxygen atom is assigned anoxidation
number of –(½). When oxygenis bonded to fluorine. In such compounds e.g., oxygen difluoride (OF2)
and dioxygen difluoride (O2F2), the oxygen is assignedan oxidation number of +2 and +1, respectively.
4 The oxidation number of hydrogen is +1, except when it is bonded to metals in binary compounds (that
is compounds containingtwo elements). For example, in LiH, NaH, and CaH2, its oxidation number is –1.
5 In all its compounds, fluorine has anoxidation number of –1. Other halogens (Cl, Br, and I) also have an
oxidation numberof –1, when they occur as halide ions in their compounds. Chlorine, bromine
andiodine when combined with oxygen, for example in oxoacids and oxoanions, havepositive oxidation
numbers
6 The algebraic sum of the oxidation numberof all the atoms in a compound must bezero
7 In polyatomic ion, the algebraic sumof all the oxidation numbers of atoms ofthe ion must equal the
charge on the ion
8 It is clear that the metallic elements have positive oxidation number and nonmetallic elements have
positive or negative oxidation number The highest oxidation number of a representative element is the
group number for the first two groups ( S-Block elements) and the group number minus 10 (following
the long form of periodic table) for the other groups (P-Block elements).Highest negative oxidation state
of P-block elements is equal to 8- no. of valence electrons.
The idea of oxidation number can be apply to define oxidation, reduction, oxidising agent (oxidant),
reducing agent (reductant) and the redox reaction.
we may say that:
Oxidation: An increase in the oxidation number of the element in the given substance.
Reduction: A decrease in the oxidation number of the element in the given substance.
Oxidation number of the Zn is increases from 0 to +2 so Zn is oxidized while Oxidation number of the
Cu is decreases from +2 to0 so Cu is reduced.
Oxidising agent: A reagent which can increase the oxidation number of an element in a given substance.
Or the substance O.N.of whose atom decreases
Reducing agent: A reagent which lowers the oxidation number of an element in a given
Substance Or the substance O.N.of whose atom increases.
Redox reactions: Reactions which involve change in oxidation number of the interacting
Species
Types of Redox Reactions :
1. Combination reactions : A combination reaction may be denoted in the
Either A and B or both A and B must be in the elemental form for such a reaction to be a redox reaction
2. Decomposition reactions:
Decomposition reaction leads to the breakdown of a compound into two or more
components at least one of which must be in the elemental state. Examples of this class of reactions are
Displacement reactions :
In a displacement reaction, an ion (or an atom) in a compound is replaced by an ion (or an atom) of
another element. It may be denotedas:
Y
(b) Non-metal displacement: The non-metal displacement redox reactions include hydrogen
displacement. All alkali metals and some alkaline earth metals (Ca, Sr, and Ba) which are very good
reductants, will displace hydrogen from cold water.
The power of these elements as oxidising agents decreases as we move down from fluorine to
iodine in group 17 of the periodic table. This implies that fluorine is so reactive that it can replace
chloride, bromide and iodide ions in solution. In fact, fluorine is so reactive that it attacks water and
displaces the oxygen of water :
Chlorine can displace bromide and iodide ions in an aqueous solution as shown below:
As Br2 and I2 are coloured and dissolve in CCl4, can easily be identified from the colour of the solution
above reactions form the basis of identifying Br– and I– in the laboratory through the test popularly
known as ‘Layer Test’.
4. Disproportionation reactions:
Disproportionation reactions are a special type of redox reactions. In a disproportionation reaction an
element in one oxidation state is simultaneously oxidised and reduced. One of the reacting substances
in adisproportionation reaction always containsan element that can exist in at least threeoxidation
states. The element in the form ofreacting substance is in the intermediateoxidation state; and both
higher and lower oxidation states of that element are formed inthe reaction.
Phosphorous and chlorine undergo disproportionation in the alkaline medium as shown below :
fluorine that, being the most electronegative element, it cannot exhibit any positive oxidation
state. This means that among halogens, fluorine does not show a disproportionation tendency
(a) Half Reaction Method: In this method, the two half equations are balanced separately and then
added together to give balanced equation.
2. Balance the atoms other than O and H in each half reaction individually
Balance the O atoms in each half reaction individually by adding required of water molecules to the side
deficient in terms of oxygen
Cr2O72– (aq) → 2Cr 3+(aq) + 7H2O (l)
Balance hydrogen atom (a)For reactions occurring in acidic medium, add H+ to balance H atoms to the
side deficient in term of hydrogen.
Cr2O72– (aq) +14H+ → 2Cr 3+(aq) + 7H2O (l)
Balance charge : Add electrons to one side of the half reaction to balance the charges. The oxidation half
reaction is thus rewritten to balance the charge:
Fe 2+ (aq) → Fe 3+ (aq) + e Cr2O72– (aq) +14H+ +6e → 2Cr 3+(aq) + 7H2O (l)
If need be, make the number of electrons equal in the two half reactions by multiplying one or both half
reactions by appropriate coefficients.
6Fe 2+ (aq) →6 Fe 3+ (aq) +6 e Cr2O72– (aq) +14H+ +6e → 2Cr 3+(aq) + 7H2O (l)
We add the two half reactions to achieve the overall reaction and cancel the electrons on each side. This
gives the net ionic equation as :
Cr2O72– (aq)+ 6Fe 2+ (aq) +14H+ → 2Cr 3+(aq) +6 Fe 3+ (aq) + 7H2O (l)
Verify that the equation contains the same type and number of atoms and the same charges on both
sides of the equation. This last check reveals that the equation is fully balanced with respect to number
of atoms and the charges.
For the reaction in a basic medium, first balance the atoms as is done in acidic medium. Then for each H +
ion, add an equal number of OH– ions to both sides of the equation. Where H+ and OH– appear on the
same side of the equation, combine these to give H2O.
(ii) Half Reaction Method in basic medium : In this method, the two half equations are balanced
separately and then added together to give balanced equation.
Step 1: Produce unbalanced equation for the reaction in ionic form :
for eg. Permanganate (VII) ion, MnO4– in basic solution oxidises iodide ion, I– to produce molecular
iodine (I2) and manganese (IV) oxide (MnO2). Write a balanced ionic equation to represent this redox
reaction.
MnO4– (aq) + I– (aq) → MnO2(s) + I2(s)
1.Separate the equation into half reactions:
I– (aq) → I2(s) MnO4– (aq) → MnO2(s)
2. Balance the atoms other than O and H in each half reaction individually
2I– (aq) → I2(s) MnO4– (aq) → MnO2(s)
Balance the O atoms in each half reaction individually by adding required of water molecules to
the side deficient in terms of oxygen
2I– (aq) → I2(s) MnO4– (aq) → MnO2(s) + 2H2O (l)
Balance hydrogen atom (b) For the reaction in a basic medium, first balance the H atoms as is done
in acidic medium. Then for each H+ ion, add an equal number of OH– ions to both sides of the
equation.
Where H+ and OH– appear on the same side of the equation, combine these to give H2O
2I– (aq) → I2(s) MnO4– (aq) ++ 2H2O (l) → MnO2(s) + 4OH-
Balance charge : Add electrons to one side of the half reaction to balance the charges. The
oxidation half reaction is thus rewritten to balance the charge:
2I– (aq) → I2(s) +2e MnO4– (aq) + 2H2O (l) +3e → MnO2(s) + 4OH-
If need be, make the number of electrons equal in the two half reactions by multiplying one or both
half reactions by appropriate coefficients.
[2I– (aq) → I2(s) +2e ]x3 [MnO4– (aq) + 2H2O (l) +3e → MnO2(s) + 4OH- ] x2
6I– (aq) → 3 I2(s) +6e 2MnO4– (aq) + 4H2O (l) +6e → 2MnO2(s) + 8OH-
We add the two half reactions to achieve the overall reaction and cancel the electrons on each
side. This gives the net ionic equation as :
Verify that the equation contains the same type and number of atoms and the same charges on
both sides of the equation. This last check reveals that the equation is fully balanced with respect
to number of atoms and the charges.
Step 2: Identify atoms which undergo change in oxidation number in the reaction by assigning the
oxidation number to all elements in the reaction.
Cr2O72–(aq) + SO32–(aq) → Cr3+(aq) + SO42–(aq)
Step 3: Calculate the increase or decrease in the oxidation number per atom and for the entire
molecule/ion in which it occurs.
This indicates that the dichromate ion is the oxidant and the sulphite ion is the reductant.
Balance hydrogen atom (a)For reactions occurring in acidic medium, add H+ to balance H atoms to
the side deficient in term of hydrogen
Cr2O72–(aq) + 3SO32–(aq) + 8H+ → 2Cr3+(aq) + 3SO42–(aq) +4H2O
Verify that the equation contains the same type and number of atoms and the same charges on
both sides of the equation. This last check reveals that the equation is fully balanced with respect
to number of atoms and the charges.
For the reaction in a basic medium, first balance the atoms as is done in acidic medium. Then for
each H+ ion, add an equal number of OH– ions to both sides of the equation. Where H+ and OH–
appear on the same side of the equation, combine these to give H2O.
2. Which of the following processes does not involve either oxidation or reduction?
(a) Formation of slaked lime from quick lime
(b) Heating Mercuric Oxide
(c) Formation of Manganese Chloride from Manganese oxide
(d) Formation of Zinc from Zinc blende
8.H2O2 changes Cr2O72– ion to CrO5 in an acidic medium, the oxidation state of Cr in CrO5 is
(a) +6 (b) +5 (c) –10 (d) +3
8. Which among the following is the strongest oxidising agent?
(a) H2O2 (b) O3 (c) K2Cr2O7 (d) KMnO4
9. Which among the following compounds is the most reducing compound?
(a) H2S (b) HNO2 (c) SnCl2 (d) H2SO3
11.In which of the following complex, the oxidation number of Fe is +1?
(a) Fe4[Fe(CN)6]3 (b) [Fe(H2O)5NO]SO4 (c) [FeBr4]– (d) [Fe(H2O)6]2–
12. Find the oxidation state of I in H4IO6–
(a) +7 (b) +5 (c) +1 (d) –1
13. H2SO4 acts as a strong oxidising agent. In which of the reaction, is it not acting as an oxidising agent?
(a) C + 2H2SO4 → CO2 + 2SO2 + 2H2O (b) CaF2 + 2H2SO4 → CaSO4 + 2HF
(c) S + 2H2SO4 → 3SO2 + H2O (d) Cu + 2H2SO4 → CuSO4 + SO2 + 2H2O
14. Zn gives H2 gas with H2SO4 and HCl but not with HNO3 because
19 Assertion (A): In Basic medium colour of K2Cr2O7 is changed from orange to yellow.
Reason (R): In basic medium K2Cr2O7 is changed in chromate ion.
(a)Na2S2O8
+2+2X+6(-2)+2(-1) = 0
X = +6
(b) Cr2O7 2-
2X+7(-2)= -2
X = +6
4. Fluorine reacts with ice and results in the change:
H2O(s) + F2(g) → HF(g) + HOF(g)
Justify that this reaction is a redox reaction.
O.N. of fluorine in F2 =0
O.N. of flourine in HF=-1
O.N. of flourine in HOF=+1
So in above reaction F2 is reduced as well as Oxidised so it is a redox reaction more over it is a
disproportionation reaction.
5. Which of the following species, do not show disproportionation reaction and
why ?
ClO–, ClO2–, ClO3– and ClO4–
Also write reaction for each of the species that disproportionate.
Ans: Among the oxoanions of chlorine listed above, ClO4– does not disproportionate because in this
oxoanion chlorine is present in its highest oxidation state that is, +7.so it cannot further increase its
oxidation number.
Section :c (3 marks )
1.Answer the following:
(a) What is the oxidation number of S in S8
(b) Name an indicator which can act as self-indicator.
(c) In the reaction 3Mg + N2 ––→ Mg3N2, Nitrogen is oxidised or reduced.
Ans:
(a)ON of S =0
(b)KMnO4 (Potassium per magnate)
(c) reduced (O.N. decreases from 0 to -3.)
2. Calculate oxidation number of Fe in Fe3O4 and write a suitable justification of your answer.
oxidation number of Fe in Fe3O4 = 3x+(-2x4)=0
3x-8=0
X =8/3
this fractional oxidation state is the average oxidation state of the Fe and the structural parameters
reveal that the element for whom fractional oxidation state is realised is present in different oxidation
states. Here Fe is a mixed oxide
of FeO and Fe2O3 so oxidation state of Fe is +2 and +3 respectively.
3. Split the reaction 2 K (s) + Cl2 (g) ––→ 2 KCl (s) into oxidation and
reduction half reactions and identify oxidising and reducing agents.
Ans:
oxidation half reactions: K (s)→K+ +e-
reduction half reactions : Cl2 +2e- (g) ––→ 2Cl-
oxidising agents : Cl2
reducing agents : K
Section:D (Case based questions -4 marks)
1.Read the given passage and answer the questions.
Redox reactions are reactions in which oxidation and reduction takes place
Simultaneously. Oxidation number is assigned in accordance with the set of rules. Oxidation number
and ion electron methods both are used in balancing ionic equations. Redox reactions are classified as
combination, decomposition, displacement and disproportionation reactions. The concept of redox
couple and electrode processes is basis of electrolysis and electrochemical cells.
(a) What are oxidation number of each individual Br in
Ans. +6
It has peroxide linkage.
2. Oxidation reaction involves loss of electrons; reduction reaction involves gain of electrons. The
reaction in which a species disproportionate in two oxidation states (lower and higher) is called
disproportionation reaction.
(a) Iron turning on addition to CuSO4 solution decolourises.Why
(b) define oxidizing agent in terms of
(c) justify that following reaction is an example of disproportionation reaction.
2H2O2 (aq) → 2H2O(l) + O2(g)
(a) Iron turning on addition to CuSO4 solution decolorizes it as Cu+2 (blue in colour) ions reduced by Fe
in Cu metal
Fe + Cu+2 (blue) → Fe+2 (green) +Cu
(b)oxidizing agent in acceptor of electron(s).
(c)
Ans: Here the oxygen of peroxide, which is present in –1 state, is converted to zero oxidation state
in O2 and decreases to –2 oxidation state inH2O.sooxygensimultaneously oxidised and reduced in this
reaction thus it is disproportionation reaction
SECTION:E (LA-5MARKS)
1. (a) Define oxidation and reduction in terms of oxidation number.
(b) Balance the following redox reactions by ion – electron method:
MnO4– (aq) + SO2 (g) → Mn 2+ (aq) + HSO4– (aq) (in acidic solution)
(a) Oxidation: An increase in the oxidation number of the element in the given substance.
Reduction: A decrease in the oxidation number of the element in the given substance
(b)Balance the following redox reactions by ion – electron method:
MnO4– (aq) + SO2 (g) → Mn 2+ (aq) + HSO4– (aq) (in acidic solution)
2. Balance the atoms other than O and H in each half reaction individually
MnO4– (aq) → Mn 2+ (aq) SO2 (g) → HSO4– (aq)
Balance the O atoms in each half reaction individually by adding required of water molecules to the
side deficient in terms of oxygen
MnO4– (aq) → Mn 2+ (aq) + 4H2O SO2 (g)+ 2H2O → HSO4– (aq)
Balance hydrogen atom (a)For reactions occurring in acidic medium, add H+ to balance H atoms to the
side deficient in term of hydrogen.
MnO4– (aq) +8H+ → Mn 2+ (aq) + 4H2O SO2 (g)+ 2H2O → HSO4– (aq) +3H+
Balance charge : Add electrons to one side of the half reaction to balance the charges. The oxidation
half reaction is thus rewritten to balance the charge:
MnO4– (aq) +8H+ +5e- → Mn 2+ (aq) + 4H2O SO2 (g)+ 2H2O → HSO4– (aq) +3H+ + 2e-
If need be, make the number of electrons equal in the two half reactions by multiplying one or both half
reactions by appropriate coefficients.
2MnO4– (aq) +16H+ +10e- →2 Mn 2+ (aq) + 8H2O 5SO2 (g)+ 10H2O →5 HSO4– (aq) +15H+ + 10e-
We add the two half reactions to achieve the overall reaction and cancel the electrons on each side.
This gives the net ionic equation as :
2MnO4– (aq) +H+ +5SO2 (g)+ 2H2O →2 Mn 2+ (aq) +5 HSO4– (aq)
Verify that the equation contains the same type and number of atoms and the same charges on both
sides of the equation. This last check reveals that the equation is fully balanced with respect to number
of atoms and the charges.
(a)Refer to the periodic table given in your book and now answer the following questions:
(i) Select the possible non metals that can show disproportionation reaction.
(ii) Select metals that can show disproportionation reaction.
(b) Balance the following equations in basic medium by ion-electron method:
Cl2O7 (g) + H2O2(aq) → ClO2 –(aq) + O2(g)
ANSWER:
(a) (i) P4,S8,O2,Cl2.
(b) (ii) Cu,Mn
(b)
1.Separate the equation into half reactions:
2. Balance the atoms other than O and H in each half reaction individually
Cl2O7 (g) →2ClO2 – H2O2(aq) → O2(g)
Balance the O atoms in each half reaction individually by adding required of water molecules to the
side deficient in terms of oxygen
Cl2O7 (g) →2ClO2– + 3 H2O H2O2(aq) → O2(g)
Balance hydrogen atom For the reaction in a basic medium, first balance the atoms as is done in acidic
medium. Then for each H+ ion, add an equal number of OH– ions to both sides of the equation. Where
H+ and OH– appear on the same side of the equation, combine these to give H2O.
Cl2O7 (g)+ 6H++ 6OH- →2ClO2– + 3 H2O+6OH- H2O2(aq) + 2OH- → O2(g)+ 2H++ 2OH-
Cl2O7 (g)+ 3 H2O →2ClO2– +6OH- H2O2(aq) + 2OH- → O2(g)+ 2 H2O
Balance charge : Add electrons to one side of the half reaction to balance the charges. The oxidation
half reaction is thus rewritten to balance the charge:
Cl2O7 (g)+ 3 H2O +8e- →2ClO2– +6OH- H2O2(aq) + 2OH- → O2(g)+ 2 H2O+2e-
If need be, make the number of electrons equal in the two half reactions by multiplying one or both
have reactions by appropriate coefficients.
Cl2O7 (g)+ 3 H2O +8e- →2ClO2– +6OH- 4H2O2(aq) + 8OH- → 4O2(g)+ 8 H2O+8e-
We add the two half reactions to achieve the overall reaction and cancel the electrons on each side.
This gives the net ionic equation as :
Cl2O7 (g)+ 4H2O2(aq) + 2OH- → 2ClO2– +4O2(g)+ 5 H2O
Verify that the equation contains the same type and number of atoms and the same charges on both
sides of the equation. This last check reveals that the equation is fully balanced with respect to
number of atoms and the charges.
Organic compounds are the hydrocarbons and their derivatives and organic chemistry is that
branch ofchemistry that deals with the study of these compounds.
Synthesis of first Organic compounds: Wohler synthesized an organic compound, urea
from an inorganiccompound, ammonium cyanate.
Tetravalency of Carbon :The atomic number of Carbon is 6 and its electronic configuration is 2,4
i.e. it has 4 valence electrons. It can share 4electrons with the other atoms to form 4 covalent
bonds. It is calledtetravalency of carbon.
Catenation- The self-linking property of carbon is known as catenation. This is the main reason
ofexistence of such large number of compound
The Shapes of Carbon Compounds: CH4 is sp3 hybridized and has tetrahedral structure. In
ethene, eachcarbon is sp2hybridized and it has planar structure. In C2H2, carbon is sp hybridized
and it is linear molecule.
Effect of hybridization on bond length and bond enthalpy: The bond length and bond
strength dependsupon hybridization.
sp hybridized: Carbon has 50% s character, and hence it is close to the nucleus and forms
shorter andstronger bond. It is most electronegative
sp2hybridized: Carbon has 33% s- character, and hence it is less close to the nucleus and forms
slightlylonger and less strong bonds than sp hybridized carbon. It is less electronegative than sp
hybridized.
sp3 hybridized: Carbon has 25% s-character and hence it is least close to the nucleus and forms
longer andleast strong bonds. It is bigger in size and is less electronegative than sp2 and sp
hybridized carbon.
Functional group: Atom or group of atoms that largely decide the chemical properties.
Class of organic Name of functional Structure
compounds group
NOMENCLATURE OF ALKANES
Straight chain alkanes: The names of such compounds is based on their chain structure, and
end withsuffix ‘-ane’ and carry a prefix indicating the number of carbon atoms present in the
chain.
Branched chain hydrocarbons:
1) The longest carbon chain in the molecule is identified.
2) The numbering is done in such a way that the branched carbon atoms get the lowest
possible value.
3) The names of the alkyl groups attached as a branch are then prefixed to the
name of the parent alkaneand its position is indicated by numbers.
4) The lower number is given to the first in alphabetical order.
5) The carbon atom of the branch that attaches to the root alkane is numbered
Organic compounds having Functional Groups: The longest chain of carbon atoms containing
the functional groups is numbered in such a way that the functional group attached to the
carbon atom gets thelowest possible number in the chain.
When there are more functional groups then a priority order is followed as:
-COOH, -SO3H, -COOR,- COCl, -CONH2, -CN, -HC=O, =C=O, -OH, -NH2, -C=C-, -CΞ C-.
Aromatic compounds:
Nomenclature of aromatic compounds: Benzene forms only one mono-substituted derivative. It
can formthree di-substituted derivatives; ortho (1,2), meta (1,3), para (1,4).
ISOMERISM
Two or more compounds having the same molecular formula but different physical and
chemical propertiesare called isomers and this phenomenon is called isomerism.
Classification of isomerism: Isomerism is basically classified into 2 types i.e,
1) Structural isomerism
2) Stereo isomerism
Structural isomerism: Compounds having same molecular formula but different structures are
calledStructural isomers..
Chain isomerism: When two or more compounds having same molecular formula but different
carbonskeletons, these are referred to as chain isomers and this phenomenon is called chain
isomerism.
Eg : Butane and isobutane.
Position Isomerism: Compounds which have the same structure of carbon chain but differ in
position ofdouble or triple bonds or functional group are called position isomers and this
phenomenon is called Position Isomerism.
eg :CH3-CH2-CH=CH2 ,CH3-CH = CH – CH3
Functional Isomerism: Compounds which have the same molecular formula but different
functional groupare called functional isomers and this phenomenon is called functional
Isomerism
eg :CH3 – CH2 – OH , CH3 – O – CH3
Metamerism: It is due to the presence of different alkyl groups on either side of functional
group in themolecule eg. C4H10O represents C2H5OC2H5 and CH3OC3H7.
FISSION OF COVALENT BOND
Heterolytic cleavage: In this cleavage the bond breaks in such a way that the shared pair of
electronremains with one of the fragment.
A species having a carbon atom possessing sextet of electrons and a positive charge is
called a carbocation (carbonium ion). The C + H3 ion is known as a methyl cation or
methyl carbonium ion. Carbocations are classified as primary, secondary or tertiary
depending on whether one, two or three carbons are directly attached to the positively
charged carbon.
The observed order of carbocation stability is:
C + H3< CH3C + H2< (CH3)2C + H < (CH3 ) 3C + .
The heterolytic cleavage can also give a species in which carbon gets the shared pair of
electrons. For example, when group Z attached to the carbon leaves without electron pair, the
methyl anion is formed. Such a carbon species carrying a negative charge on carbon atom is
called carbanion. Carbon in carbanionis generally sp3 hybridised . Carbanions are also unstable
Alkyl radicals are classified as primary, secondary, or tertiary. Alkyl radical stability increases
fromprimary to tertiary
Attacking reagents:
Nucleophiles: A reagent that brings an electron pair is called nucleophile eg –OH- ,-CN-
Electrophiles: A reagent that takes away an electron pair is called electrophile eg
Electronic displacements:
Inductive Effect: The permanent electron displacement along a chain due to the presence of a
polar covalent bond that is bond polarity is known as inductive effect. If an atom or group
attracts electron morestrongly than hydrogen, it is said to have –I Effect.
If an atom or group of atom attracts electron less strongly than hydrogen it is said to have +I
Effect.
Resonance Effect: The polarity produced in the molecule by the interaction of two pi bonds or
between api bond and lone pair of electron present on an adjacent atom.
There are two types of resonance effect:
1) Positive resonance effect: In this effect the transfer of electrons is away from an
atom or substituentgroup attached to the conjugated system. The atoms or groups
which shows +R effect are halogens, -OH , -OR,- NH2.
2) Negative resonance effect: In this effect the transfer of electrons is towards the
atom or substituent group attached to the conjugated system. The atoms or groups
which shows -R effect are –COOH , -CHO ,-CN
3) Electrometric effect: It involves the complete transfer of shared pair of electrons to one
of the atomsjoined by a multiple bond at the requirement of the attacking reagent. It is
temporary effect.
Hyperconjugation: Electron release by an alkyl group attached to unsaturated system. There
should be atleast one-H at alpha carbon with respect to sp2 hybrid carbon.
METHODS OF PURIFICATION OF ORGANIC COMPOUNDS:
Sublimation: This method is used to separate the sublimable compounds from non sublimable
compounds.Crystallisation: This method is based on the difference in the solubilities of
compound and impurities in a suitable solvent.
Distillation: This method is used to separate volatile liquids from non-volatile liquids and liquids
havingsufficient difference in their boiling points.
Fractional distillation: If the boiling points of two liquids is not much, they are
separated by this method. Distillation under reduced pressure: This method is used to
purify liquids having high boiling points anddecomposes at or below their boiling points.
Steam distillation: This method is used to separate substances which are steam volatile and are
immisciblewith water
Chromatography:
Adsorption Chromatography: It is based on the fact that different compounds are adsorbed on
anadsorbent to different degrees. Silica gel or alumina is used as adsorbents.
Partition Chromatography: It is based on the continuous differential partitioning of components
of amixture between stationary and mobile phase.
Test for Nitrogen: The sodium fusion extract is boiled with iron II sulphate and then acidified
withConcsulphuric acid, the formation of Prussian blue colour confirms the presence of
nitrogen.
Test for Sulphur: The sodium fusion extract is acidified with acetic acid and lead acetate is
added to it. Ablack precipitate of lead sulphide indicates the presence of sulphur.
Test for halogens: The sodium fusion extract is acidified with nitric acid and then treated with
silver nitrate. A white precipitate, soluble in ammonium hydroxide shows the presence of
chlorine, a yellowish ppt. sparingly soluble in ammonium hydroxide shows the presence of
bromine, a yellowish ppt. insolublein ammonium hydroxide shows the presence of iodine.
QUANTITIVE ANALYSIS
1]Carbon and Hydrogen
Let the mass of organic compound be m g. Mass of water and carbon dioxide produced be m1
and m2 grespectively;
Dumass method: A known mass of organic compound is heated with excess of CuO in an
atmosphere ofcarbon dioxide, when nitrogen of the organic compound is converted into N2 gas
.The volume of N2thus obtained is converted into STP and the percentage of nitrogen is
determined by the following equation:
Kjeldahl’s Method: A known mass of organic compound is heated with concentrated sulphuric
acid in presence of potassium suplhate and little copper sulphate in a Kjeldahl flask when
nitrogen is present in the organic compound is converted into ammonium sulphate. Ammonium
sulphate thus obtained is boiled with excess of NaOH to liberate ammonia gas which is absorbed
in an excess of standard acid such as sulphuric acid or HCl. The volume of the acid unused is
found by titration against a standard alkali solutionfrom the volume of the acid used the
percentage of nitrogen is determined by applying the equation.
Estimation of Halogen:
Carius method: A known mass of an organic compound is heated with fuming nitric acid in the
presenceof silver nitrate contained in a hard glass tube known as Carius tube, in a furnace.
Carbon and hydrogen present in the compound are oxidised to carbon dioxide and water. The
halogen present forms the corresponding silver halide (AgX). It is filtered, washed, dried and
weighed.
Estimation of sulphur:
Estimation of phosphorous:
Estimation of oxygen:
7) The increasing order of electron donating inductive effect of alkyl group is:
(A) −H<−CH3<−C2H5<−C3H7 (B) −H>−CH3>−C2H5>−C3H7
Answer: d) (CH3)3C
11) The correct decreasing order of priority for the functional groups of organic
compounds in the IUPAC system of nomenclature is:
(A) –CHO, –COOH, –SO3H, –CONH2
(B)–SO3H, –COOH, –CONH2, –CHO
(C)–COOH, –SO3H, –CONH2, –CHO
(D)–CONH2, –CHO, –SO3H, –COOH
Answer: C)–COOH, –SO3H, –CONH2, –CHO
12) IUPAC name of compound CH3CH = CH – CHO is
(A) But–2–enal.
(B) Prop–2–enal
(C) But–1–enal
(D) But–2–enol
Answer: A) But–2–enal.
13) The C–H bond distance is longest in
(A) C2H2
(B) C2H4
(C) C2H6
(D) C2H2Br2
Answer: (C) C2H6
14) Which of the following can act as an electrophile?
(A) CN–
B) OH–
(C) H2O
(D) BF3
Answer: (D) BF3
15) The I.U.P.A.C name of the compound is
Answer: (A) Both A and R are correct and R is the correct explanation of A.
4) Assertion: Tertiary carbonations are generally formed more easily than primary
carbocations. Reason: Hyperconjugation as well as inductive effect due to additional
Alkyl groups stabilizetertiary carbocations
Answer: (A) Both A and R are correct and R is the correct explanation of A.
2mark question
2. Explain, why (CH3)3 –C+ is more stable than CH3-CH2+and CH3+ is the least stable cations.
Hyper conjugation interaction in (CH3)3 –C+ is greater than inCH3-CH2+ has (CH3)3 –C+
9 CH bonds. In CH3+, vacant p-orbital is perpendicular to the plane in which C-H- lie; hence
cannotoverlap with it thus C+H3 lacks hyper conjugative stability.
3) Give the number of sigma and pi bond in the following molecules
a) CH3-NO2 b) HCONHCH3
a) 6 sigma and 1πbond
b) 8 sigma and 1πbond
4) It is not advisable to use sulphuric acid in place of acetic acid for acidification while
testing sulphur bylead acetate test. Give reason.
Lead acetate on reacting with sulphuric acid will give a white precipitate of lead sulphate which
interfere n
i the detection of sulphur.
.
a.3,5-Dimethyl-4-propylheptane b. 4-chloro-2,2-dimethylpentane c.) Pent-4-en-2-ol.
b) Sodium fusion extract of the given organic compd. is treated with dilute nitric
acid and then Silver nitrate solution is added. Formation of white ppt indicates the
presence of Chlorine in the givenorganic compound
5 marks questions
Q.No 1
a) What are electrophiles? Give an example.
b) Explain the principle of paper chromatography
c) Write the chemistry of lassaigne’s test for qualitative analysis of nitrogen
a. The species which are positively charged or electron deficient are called
electrophiles(electron seeking agent).example: H+, Cl+,AlCl3 .
b. In paper chromatography, chromatographic paper dipped in solvents act as a
stationary phase whereas mixture of compounds dissolved in suitable solvents forms
the mobile phase. Different compounds have different adsorbing power, therefore they
move with different speeds and gets separated.
c. Lassaigne’s test for qualitative analysis of nitrogen: Fuse the organic compound
with sodium metal. sodium reacts with C and N present in organic compound to form
NaCN.
Add FeSO4 to lassaigne’s extract
Dilute H2SO4 is added to convert Fe2+ to Fe3+ and blue color is formed due to the
formation of ferricferrocyanide.
Q.No 2
a) What are nucleophiles? Give one example of nucleophile.
b) Will CCl4 give white ppt of AgCl on heating with silver Nitrate. Give reason for your
answer.
c) Define hyper conjugation.
d) Draw the condensed formula and bond-line structural formula for
a) 2,2,4-trimethylpentane
b)2-hydroxy-1,2,3-propanetricarboxylic acid.
a. Nucleophiles: Nucleophiles are negatively charged or neutral species with lone
pair of electrons. example: Br- , H2O
b. No, it is because CCl4 is non-polar compound, does not give Cl- in aqueous
solution, therefore itwill not form any precipitate with silver nitrate (aq).
c. Hyperconjugation is a general stabilising interaction. It involves delocalisation of σ
electrons of C—H bond of an alkyl group directly attached to an atom of unsaturated
system or to an atom with an unshared p orbital. The σ electrons of C—H bond of the
alkyl group enter into partial conjugation with the attached unsaturated system or with
the unshared p orbital. Hyperconjugation is a permanent effect.
d.
a) As by the process of sublimation, both will get sublime. We can separate them by
mixing them in hot water and then filtering the solution. Residue will be camphor and
filtrate will be mixture of water & benzoic acid and we can get benzoic acid by
crystallization method.
b) As the difference in their boiling point is sufficiently large, simple distillation
method is used.
c) By distillation under reduced pressure.
d) Steam distillation method because it is steam volatile and immiscible with water.
ii. Name the chain isomers of C5H12 which has a tertiary hydrogen atom.
i. a)
b) C2H5OH , CH3-O-CH3
They are Functional isomers
ii. The chain isomers of C5H12 which has a tertiary hydrogen atom is 2-Methylbutane.
UNIT-XIII HYDROCARBON
Alicyclic Aromatic
Alkanes Alkenes Alkyne
(C-C) (C=C) (C≡C)
Isomerism:
(1) Chain Isomerism: In this isomerism compounds have same molecular formula but different
structure. Ex- Pentane, 2-Methylbutane, 2,2-Dimethylpropane
(2)Position Isomerism: In this isomerism compounds have same molecular formula but position of
substituent group. Ex- 2-Methylpentane, 3-Methylpentane
Type of carbon:
Primary carbon (1°): The carbon atom attached to only one other carbon.
Secondary carbon (2°): The carbon atom attached to only two other carbons.
Tertiary carbon (3°): The carbon atom attached to only three other carbons.
Quaternary carbon (4°): The carbon atom attached to only four other carbons.
Preparation:-
1. From unsaturated hydrocarbons:-
2. From alkyl halides: ( i ) Alkyl halide on reduction with zinc and dil. HCl give alkanes.
(ii) Wurtz reaction : This reaction is used for preparation of higher alkanes.
Useful in preparing an alkane containing even number of carbon atoms
Stepping up reaction
Dry
2CH3CH2Br 2Na
CH3CH2CH2CH3 2NaBr
ether
3. From carboxylic acids- (i) By decarboxylation.-
Physical Properties:-
(1) Nature:- Non-Polar due to covalent nature of C—C bond and C—H bond.
C1—C4 are gases, C5—C17 are colourless odourless liquid and higher are Solids.
(2) Solubility:- Like dissolve like Viz, Polar compounds dissolve in polar solvent and Non-Polar
compound dissolve in non polar solvent.
(3) Boiling point:- Low boiling point due to non polar in nature and weak Van der Waals’ forces.
The boiling point increases with increase the molecular mass as the magnitude of Van der
Waals’ forces is directly proportional to the molecular size.
The boiling points of the branched chain Alkanes are less than the straight chain isomers
because branching of the chain makes the molecule more compact and thereby decreases
the surface area and consequently, the magnitudes of Van der Waals’ forces get decreased.
Ex- n-pentane (309.1K), isopentane(301K), neopentane (282.5 K)
Chemical properties
1. Substitution reactions: Halogenation: Produce Mixture of halo alkanes.
CH4 + Cl2 → 3
Chloromethane
3 → →
2 2 → 3 4
Chloromethane Dichloromethane Trichloromethane TetraChloromethane
CH3- CH3 + Cl2 → 3-CH2-
Chloroethane
Note:- Iodination is a slow and reversible reaction. So it is carried out by heating alkane in the
presence of some oxidizing agent like iodic acid (HIO3) or nitric acid (HNO3) which oxidizes HI
formed during the reaction.
CH4 + I2 3
5HI + HIO3 2 2
Note:- Fluorination of alkane takes place explosively so it is difficult to control.
Features of Halogenations:-
(i) The reactivity of Halogens:- F2 > Cl2 > Br2 > I2.
(ii) The rate of replacement of hydrogen of alkanes is: 3° > 2° > 1°
Mechanism:- halogenations reaction take place by free radical mechanism. The reaction proceeds in
the following steps:
(i) Chain initiation step:-
h
Cl — Cl 2Cl
(ii) Chain Propagation step:-
CH4 Cl CH3 HCl
CH3 Cl2 CH3Cl Cl
(iii) Chain Termination step:-
Conformations
Spatial arrangements which are obtained by rotation around sigma bonds are called conformation or
conformational isomers and this phenomenon is called conformational isomerism.
There are three conformers of ethane.
Eclipsed Staggered Skew
H-atoms H-atoms are Any other
attached to as far apart as intermediate
two carbons possible is conformation
are as closed known as the is called a
together as staggered skew
possible is conformation. conformation.
called
eclipsed
conformation
Dihedral 120° 0- 120°
angle =0°
High torsional Low torsional In between
strain strain
more stable less stable -
ALKENES
Preparation From alkynes: Use of palladised charcoal gives cis-product and Na/NH3 gives trans
product.
2. From alkyl halides: This reaction is also known as dehydrohalogenation i.e., removal of
halogen acid(HX). This is example of β-elimination reaction, since hydrogen atom is
eliminated from the β carbon atom.
Reactivity
R-I >R-Br>R-Cl
tert. >secondary
>primary RX
4. From alcohols by acidic dehydration: HOH molecule is eliminated from alcohol on heating
with con. H2SO4.
Physical Properties
Resembles alkane except their polar nature.
1. Addition of Hydrogen: Produce alkane.
2.Addition of halogens: vicinal dihalides are formed. Discharge of redish brown colour of
bromine is used as test for unsaturation .
Minor product
Markovnikov rule: The major product will be that in which negative part of the addendum
(adding molecule) gets attached to that double bonded carbon which has lesser number of
hydrogen atoms.
Mechanism:
I. Electrophilic attack of H+ :
Since secondary
carbocation is more
stable so it is formed
faster.
Anti Markovnikov addition or peroxide effect or Kharash effect: In the presence of peroxide,
addition of HBr to unsymmetrical alkenes Br- gets attached to double bonded carbon having
more number of hydrogen atoms.
Mechanism:
ALKYNES :
General CnH2n-2
Formula
Hybridisation sp
Bond angle 180°
C≡C bond 120 pm
length
Reactivity Attacked by
electrophiles
Isomerism Chain and
position
Preparation
1.From calcium carbide:
Chemical properties
1.Acidic character of alkyne:
Order of acidity
2.Addition of dihydrogen:
3.Addition of halogens:
5.Addition of water:
6.Cyclic polymerisation:
AROMATIC HYDROCARBON
These hydrocarbons are also known as ‘arenes’.
Position isomerism:
Preparation of Benzene
1.Decarboxylation of aromatic acids:
2. Reduction of phenol:
Chemical properties
Nitration:
Halogenation:
Sulphonation:
Removal of proton:
Addition reactions
Meta directing group: The groups which direct the incoming group to meta position are called
meta directing groups. Some examples of meta directing groups are –NO2, –CN, –CHO, –COR,
–COOH, –COOR, –SO3H, etc.
Activating groups: These groups activates the benzene ring for the attack by an electrophile.
examples–NH2, –NHR, –NHCOCH3, –OCH3, –CH3, –C2H5, etc
Deactivating groups: These groups decrease the overall electron density on benzene ring
making further substitution difficult. Ex: NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H, etc.
CARCINOGENICITY AND TOXICITY-Benzene and polynuclear hydrocarbons containing more
than two benzene rings fused together are toxic and said to possess cancer producing
(carcinogenic) property.
Ex-1,2-Benzanthracene , 1,2-benzpyrene
Practice Questions
MCQ
3. An alkyl bromide [x] reacts with sodium in ether to form 2,3–dimethylbutane, the compound
'x' is .
A. CH3 CH2Br B. (CH3)2 CH Br
C. CH3 CH2CH2Br D. CH3CH2 CH(Br) CH2 CH2CH3
D .
10. Arrange the following hydrogen halides in order of their decreasing reactivity with
propene.
(A) HCl > HBr > HI (B) HBr > HI > HCl (C) HI > HBr > HCl (D) HCl > HI > HBr
11. Some oxidation reactions of methane are given below. Which of them is/are
controlled oxidation reactions?
(A) CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l)
(B) CH4 (g) + 2O2 (g) → C(g) + 2H2O (l)
(C) CH4 (g) + O2 (g) → HCHO + H2O
(D) 2CH4 (g) + O2 (g) → 2CH3OH
12. For an electrophilic substitution reaction, the presence of a halogen atom in the
benzene ring _______.
(A) Deactivates the ring by inductive effect
(B) Deactivates the ring by resonance
(C) Decreases the charge density at ortho and para position relative to meta position by
resonance
(D) Directs the incoming electrophile to meta position by increasing the charge density
relative to ortho and para position
13. Arrange the following in decreasing order of their boiling points.
(A) n–butane (B) 2–methylbutane (C) n-pentane (D) 2,2–dimethylpropane
(i) A > B > C > D (ii) B > C > D > A
(iii) D > C > B > A (iv) C > B > D > A
A. Hydrogenation B. Halogenation
C. Linear Polymerisation D. Cyclic Polymerisation
21.Assertion (A) : Nitration of benzene with nitric acid requires the use of concentrated
sulphuric acid. Reason
(R) : The mixture of concentrated sulphuric acid and concentrated nitric acid produces the
electrophile, NO2 +.
22.Assertion (A): Toluene on Friedal Crafts methylation gives o– and p–xylene.
Reason (R) : CH3-group bonded to benzene ring increases electron density at o– and p–
position.
ANSWER KEY
1.A 2.C 3.B 4.D 5.C
11.C&D 12.A 13.IV 14.C 15.D
21.A 22.A 23.B 24.C
a. b.
Ans. a .Pent-en-3-yne b. 2-methylphenol
3. What effect does branching of an alkane chain has on its boiling point?
Ans. As branching increases, the surface area of the molecule decreases which results in a
small area of contact. As a result, the Van der Waals force also decreases which can be
overcome at a relatively lower temperature. Hence, the boiling point of an alkane chain
decreases with an increase in branching.
5. function of Lewis acids anhydrous aluminium chloride which can be used during alkylation
of benzene. Suggest some other Lewis acids also.
Ans. It is used as catalyst.
anhydrous FeCl3, SnCl4, BF3 etc.
6. Although benzene is highly unsaturated, it does not undergo addition reactions, why?
Ans. Because of extra stability due to delocalization of π-electrons.
1. What is Wurtz reaction? How can it be used to prepare butane? Can pentane be prepared by
this reaction?
Ans- When alkyl halides is treated with metallic Na in presence of dry ether, alkanes are
formed. This reaction is called Wurtz reaction.
Butane is prepared by following reaction
2. An alkene ‘A’ contains three C – C, eight C – H σ bonds and one C – C π bond. ‘A’ on
ozonolysis gives two moles of an aldehyde of molar mass 44 u. Deduce IUPAC name of ‘A’.
Write the chemical reaction.
Ans.. The formation of two moles of an aldehyde indicates the presence of identical structural
units on both sides of the double bond containing carbon atoms. Hence, the structure of ‘A’
can be represented as:
XC = CX
There are eight C–H σ bonds. Hence, there are 8 hydrogen atoms in ‘A’. Also, there are three
C–C bonds. Hence, there are four carbon atoms present in the structure of ‘A’.
Combining the inferences, the structure of ‘A’ can be represented as:
C. CH3CH2I + Na →
Ans: A.CH3—CH(OH)CH2 OH B. Br -CH2—CH2 Br C. CH3CH2 CH2CH3
1. An alkyl halide C5H11Br (A) reacts with ethanolic KOH to give an alkene ‘B’, which reacts
with Br2 to give a compound ‘C’, which on dehydrobromination gives an alkyne ‘D’. On
treatment with sodium metal in liquid ammonia one mole of ‘D’ gives one mole of the sodium
salt of ‘D’ and half a mole of hydrogen gas. Complete hydrogenation of ‘D’ yields a straight
chain alkane. Identify A,B, C and D. Give the reactions invovled.
Ans:
(b)
Or
What is dihedral angle?
ANS: 1. Free rotation of C-C sigma bond.
2.
3. staggered form is more stable due to less torsional strain.
4. Due to restricted rotation
BLUEPRINT
CHEMISTRY SAMPLEPAPER-1
CLASSXI
S.No Name of the chapters MCQ A/R VSAI SAI Case LA Total
based
1 1 2 3 4 5 Weig
Mark Mark Marks Marks Marks Marks htag
e
1. Some basic concepts of 2(2) 2(1) 3(1) 7
chemistry
2. Structure of atom 1(1) 3(1) 5(1) 9
3 Classification of elements 2(2) 1(1) 3(1) 6
And periodicity in properties
4 Chemical bonding and 2(2) 5(1) 7
Molecular structure
5 Chemical thermodynamics 2(2) 4(2) 3(1) 9
6 Equilibrium 1(1) 2(1) 4(1) 7
7 Red-oxreactions 1(1) 3(1) 4
8 Organic chemistry – 2(2) 1(1) 4(2) 4(1) 11
Some basic principles
and Techniques
9 Hydrocarbons 2(2) 1(1) 2(1) 5(1) 10
14 4 14 15 8 15 70
General Instructions:-
Read the following instructions carefully.
a) There are 35 questions in this question paper. All questions are compulsory.
b) Section A: Q. No. 1 to 18 are objective type questions carry 1 mark.
c) Section B: Q. No. 19 to 25 are short answer questions and carry 2 marks each.
d) Section C: Q. No. 26 to 30 are short answer questions and carry 3 marks each.
e) Section D: Q. No. 31 to 32 are case based questions carrying 4 marks each.
f) Section E: Q. No. 33 to 35 long answer questions carrying 5 marks each.
g)There is no overall choice. However, internal choices have been provided.
h) Use of calculators and log tables is not permitted.
Section A(OBJECTIVE TYPE)
A. Hydrogenation B. Halogenation
C. Linear Polymerisation D. Cyclic Polymerisation
14 The position of double bond in alkenes can be located by : 1
(A) Hydrogenation of oil (B) Ozonolysis
(C) Photolysis (D) Hydration
In the following questions (Q. No. 14 - 18) a statement of assertion followed by a statement of
reason is given. Choose the correct answer out of the following choices.
A) Assertion and reason both are correct statements and reason is correct explanation for assertion.
B) Assertion and reason both are correct statements but reason is not correct explanation for
assertion.
C) Assertion is correct statement but reason is wrong statement.
D) Assertion is wrong statement but reason is correct statement.
jumps from n = 4 to n = 2.
21 (a ) Define Zeeman effect. 2
(b) Which equation tell about the dual nature of matter?
22 Using VSEPR theory draw the shape of the SF4 and PCl5.molecules. 2
23 (a)State Hess Law of constant heat summation.. 2
(b)What will be the sign of ΔU if-
(i)q heat is released by the system to surrounding.
(ii)W dork is done on the system.
24 (a)Why the value of second ionisation constant of H2SO4 is lower than first? 2
(b) If value of equilibrium constant (Kc) is 4.0 for a reaction A--->B , calculate the value of
equilibrium constant (Kc’) for the reverse reaction B-->A.
26 50.0 kg of N2 (g) and 10.0 kg of H2 (g) are mixed to produce NH3 (g). Calculate the 3
amount of NH3 (g) formed. Identify the limiting reagent in the production of NH3 in this
situation.
OR
A compound contains 4.07% hydrogen, 24.27% carbon and 71.65% chlorine. Its molar
mass is 98.96 g. What are its empirical and molecular formulas?
27 Table-tennis ball has a mass 10 g and a speed of 90 m/s. If speed can be measured 3
within an accuracy of 4%, what will be the uncertainty in speed and position?
28 Consider the following species: 3
N3-, O2-, F–, Na+, Mg2+, Al3+
(a) What is common in them?
(b) Arrange them in order of increasing ionic radii?
(c)Pridict the group and period of element Z= 53.
29 (i) Calculate the oxidation No. of ClamdMn in HClO3 and in K2MnO4 3
(ii) Balance the following ionic equation by ion electron method or oxidation method.
Cr2O7 2-(aq) + SO32- (aq) Cr3+(aq)+ SO42-(aq) (Acidic medium)
33 (a) Out of 1 mole of H2O(g) and 1 mole of H2O(l) which one will have greater entropy? 5
(b) What will be the value of ΔG° for boiling water?
(c) What is meant by the term state function? Give one example.
(d)Define entropy. And prove that entropy is an extensive property.
OR
(a) State third law of Thermodynamics.
(b) U is a state function but work is not?
(c) Calculate the enthalpy of the reaction:
N204(g) + 3CO(g) N20(g) + 3CO2(g)
Given that; ∆fHº CO (g) = – 110 kj mot-1; ∆fH C02(g) = – 393 kj mol-1
∆fH N20(g) = 81 kj mot-1; ∆fH N2O4(g) = 9.7 kj mol-1
35 5
a. CH ≡ CH red hot iron tube, 873K X CH3COCl, Anhyd.AlCl3 -> Y
Find X and Y in the above sequence of reaction.
b.Explain Markovnikov’s rule with an example .
c. Convert phenol to benzene.
Marking scheme
1B 2B 3D 4A 5A 6A 7D 8A 9D
10 A 11 A 12 C 13 D 14 B 15 C 16 A 17 D 18 A
19. A.Mole Fraction is the ratio of number of moles of one component to the total 1
number of moles (solute and solvents) present in the solution. It is
expressed as 'x'
B. The reactant which gets consumed first or limits the amount of product formed is
known as limiting reagent 1
20 (a) 5f -orbital 1
(b) Balmer Series 1
21 (a) splitting of spectral lines in presence of magnetic field (fine splitting) 1
(b) de Broglie relationship wave length = h/p 1
22
(ii) → ) 1
27 1
1
1
28 (a) All of them are isoelectronic in nature and have 10 electrons each. 1
(b) In isoelectronic species, greater the nuclear charge, lesser will be the atomic or 1
ionic radius. 1
Al3+ < Mg2+ < Na+ < F– < O2- < N3-
(c) group=17 period=5
29 (i)Cl=+5 Mn=+6 ½+½
(ii) Calculation of Oxidation no.
Balance of atoms other than H and O ½X4
Balance of H and O
Complete balanced reaction
30 a) The atom or group of atom attached to carbon chain which is responsible for 1
specific chemical properties of organic compounds. 1
b) –CHO,-NO2 1
c) Sp3 , sp2 ,sp2 ,sp3.
31 1.O2 = σ1s2 σ∗1s2 ,σ2s2,σ∗2s2,σ2pz2,π2px2,π2py 2, π*2px1,π*2py0
+
34 d. The species which are positively charged or electron deficient are called 1
electrophiles (electron seeking agent).example: H+, Cl+,AlCl3 .
to form NaCN.
Add FeSO4 to lassaigne’s extract
Dilute H2SO4 is added to convert Fe2+ to Fe3+ and blue color is formed due to the
formation of ferric ferrocyanide.
a. Nucleophiles: Nucleophiles are negatively charged or neutral species with lone
pair of electrons. example: Br- , H2O
b. No, it is because CCl4 is non-polar compound, does not give Cl- in aqueous
solution, therefore it will not form any precipitate with silver nitrate (aq). 1
c. Hyperconjugation is a general stabilising interaction. It involves delocalisation of σ 1
electrons of C—H bond of an alkyl group directly attached to an atom of unsaturated 1
system or to an atom with an unshared p orbital. The σ electrons of C—H bond of
the alkyl group enter into partial conjugation with the attached unsaturated system
or with the unshared p orbital. Hyperconjugation is a permanent effect. 2
d. Correct structure
35 X= C6H6 Y=C6H5 CO CH3 2
BLUE PRINT
CHEMISTRY SAMPLE PAPER-2
CLASS XI
S.No Name of the chapters MCQ A/R VSA I SA I Case LA Total
based
1 1 2 3 4 5 Weig
Mark Mark Marks Marks Marks Marks htage
1. Some basic concepts of 2 (2) 2(1) 3(1) 7
chemistry
2. Structure of atom 1(1) 3(1) 5(1) 9
3 Classification of elements 2(2) 1(1) 3(1) 6
and periodicity in properties
4 Chemical bonding and 2(2) 5(1) 7
molecular structure
5 Chemical thermodynamics 2(2) 4(2) 3(1) 9
6 Equilibrium 1(1) 2(1) 4(1) 7
7 Red-ox reactions 1(1) 3(1) 4
8 Organic chemistry –Some 2(2) 1(1) 4(2) 4(1) 11
basic principles and
Techniques
9 Hydrocarbons 2(2) 1(1) 2(1) 5(1) 10
14 4 14 15 8 15 70
SECTION A
The following questions are multiple-choice questions with one correct answer. Each question carries 1
mark.There is no internal choice in this section.
Q.2 Equal volume of all gases contain equal no of molecules at constant temperature and 1M
pressure This is stated by
(A) Gay Lussac law (B) Boyle ‘s Law
(C)Avogadro law (D) None of the above
(A) Assertion and reason both are correct statements and reason is correct explanation for assertion.
(B) Assertion and reason both are correct statements but reason is not correct explanation for assertion.
(C) Assertion is correct statement but reason is wrong statement.
(D) Assertion is wrong statement but reason is correct statement
Q.16 Assertion: Noble gas elements have positive electron gain enthalpy. 1M
Reason: Inert gas elements stable octet configuration.
Q.17 Assertion: The reaction between haloalkanes and sodium metal in presence of dry ether 1M
alkanes having even number are produced.
Reason: propane can be prepared by Wurtz reaction
Q.18 Assertion: Resonance hybrid cannot be presented by a single structure 1M
Reason: Energy of resonance hybrid is equal to the average of energiesof all canonical forms.
SECTIONB
This section contains 7 questions with internal choice in two questions. The following
questions are veryshortanswer typeand carry2 marks each.
Q.19 (i) What do you mean by limiting reagent? 2M
(ii)In the reaction 2A +4B --- 3C + 4D, when 5 moles of A react with 6 moles of B, then
which is limiting reagent and also calculate the amount of C formed.
Q.20 (i) Explain the term entropy. 2M
(ii)Write the mathematical form of first law of thermodynamics.
(OR)
Predict whether entropy change is positive or negative
(i)Heating a substance from 0k to 115K
(ii) H2 (g)-----2H (g)
Q.21 Derive the Relation Between Cp and Cv for an Ideal Gas. 2M
Q.22 The concentration of hydrogen ions in a sample of soft drink is 3.8 x 10-3 M. 2M
What is the pH value?
Q.23 Draw the Newman projection formulae of ethane. Which conformation is stable? 2M
(OR)
Explain ozonolysis of alkene and also give reaction.
SECTIONC
This section contains 5 questions with internal choice in two questions. The following questions are short answer
type and carry 3 marks each.
Q.26 A compound contains 4% hydrogen 24% carbon and 71.6% chlorine its molar mass is 3M
98.96g.What is its molecular formula?
Q.29 Balance the following red-ox reaction in acid medium by ion electron method. 3M
Cr2O7+2 + Fe2+ -------- Fe3+ + Cr3+
(OR)
Explain the following reaction with suitable reaction
(I)decomposition reaction
(II) displacement reaction
(III) disproportion reaction
Q.30 Calculate the heat of combustion of ethylene (gas) to from CO2 (gas) and H2O (gas) at 298k 3M
and 1 atmospheric pressure. The heats of formation of CO2, H2O and C2H4are– 393.7,–241.8,
+52.3kJ per mole respectively.
SECTION D
(Case Based Questions)
The following questions are case-based questions. Each question has an internal choice and carries 4 (1, 1, 2)
marks each.
Q.31 Read the passage carefully and answer the questions that follow. 4M
According to Arrhenius concept, acids give H+ ions while bases produce OH˗ ions in their
aqueous solutions. Bronsted-Lowry defined an acid as a proton donor and a base as a proton
acceptor. When a Bronsted – Lowry acid reacts with a base, it produces its conjugate base
and a conjugate acid corresponding to the base with which it reacts. Thus, a conjugate pair
of acid - base differs only by a proton. The strength of acids and bases can be measured in
terms of their dissociation constants Ka (or pKa) and Kb (or pKb). Larger value of Ka or lower
value of pKa corresponds to greater strength of acids. Similarly, larger value of Kb or lower
value of pKb corresponds to stronger base. PH finds vital role in cosmetic formulations and
buffer solution is used in blood bank.
(i) Write the conjugate acid-base pair for the following
(a) NH3(b) HSO4˗
positive charge is called a carbocation (earlier called carbonium ion). The CH3+ion is known as
a methyl cation or methyl carbonium ion. Carbocations are classified as primary, secondary or
tertiary depending on whether one, two or three carbons are directly attached to the
positively charged carbon. Some other examples of carbocations are: CH3CH2+(ethyl cation, a
primary carbocation), (CH3)2CH+ (isopropyl cation, a secondary carbocation), and (CH3)3C+
(tert–butyl cation, a tertiary carbocation).Carbocations are highly unstable and reactive
species. Alkyl radiradicals are classified as primary, secondary, or tertiary. Alkyl radical
stability increases as we proceedfromprimary to tertiary: Organic reactions, which proceed by
homolytic fission are called free radical or homopolaror nonpolar reactions.
(i) Write any two reactive intermediates which are unstable.
(ii) State the hybridation of carbonium ion.
(iii) Explain tertiary carbocation is more stabe than secondary and in turn primary .Explain
(OR)
What are electrophiles and nucleophiles .Give an example each
SECTION E
The following questions are long answer type and carry 5 marks each. Two questions have an internal choice.
Q.34 (i) Write two types of hydrogen bonding with its examples. 2
(ii) Though NH3 involves Sp3hybridisation, the shape is pyramidal .Explain with the help of 2
VSEPR theory.
(iii) Axial bonds in PCl 5 are slightly elongated than equatorial bonds .Give reason. 1
(OR)
(i) Compare the relative stability of O2 , O2 –,O2+, O2 –2 in terms of molecular orbit theory.
3
(ii) Write the resonance structures for NO2 and CO32-.
2
Q.35 Addition of HBr to propene yields 2-bromopropane, while in the presence of benzoyl 5M
peroxide, the same reaction yields 1-bromopropane. Explain and give mechanism
20 a. Measure of degree of 1
disorder b.∆U=q+w 1
(OR)
a. Positive 1
b. Positive 1
21 At constant volume heat capacity = Cv At constant pressure heat capacity = Cp
At constant volume qv= CvΔT =ΔU ½
At constant pressure qp= CpΔT =ΔH For one mole of an ½
idealgasΔH=ΔU+Δ(PV) =ΔU+Δ(RT) ½
ΔH=ΔU+RΔT
On substituting the values of ΔHandΔu, the equation is modified asCp ΔT = ½
CvΔT+RΔT
orCp-Cv =R
22 pH =– log[H+]=– log(3.8 x10-3)=– log3.8+3 =3 – 0.5798 =2.4202=
2.42
23 Staggered conformer is more stable 1+1
(OR)
b. correct structure 1
25 In this cleavage the shared pair of electrons goes with any one of the two bonded 1
atom
CH3- - 1
26 ½
½
1
1
30
.
10 The group number, number of valence electrons, and valency of an element with the atomic number 15,
respectively, are:
(a) 16, 5 and 2 (b) 15, 5 and 3 (c) 16, 6 and 3 (d) 15, 6 and 2
11 The most polar bond is
(a) C – F (b) C – O (c) C – Br (d) C – S
12 The property of self–linkage among identical atoms to form long chain compounds is known as:
(a) Why axial bonds are weaker than equatorial bonds in PCl5
(b) What is the shape of compound undergoing sp3d hybridization?
(c) Explain conditions for Hybridisation (any two )
32 Read the passage given below and answer the following questions.
The Haber process for the synthesis ammonia from molecular hydrogen and nitrogen is represented by the
following thermochemical equations.
N2(g)+3H2(g) → 2NH3(g): ΔH0=-92.6kJ/mol
the reaction is carried out in the presence of a heterogeneous catalyst containing iron the value of Kc for the
reaction is 1.2 at 3750c.
(a)Write the equilibrium constant expression for the reaction taking place during
Haber process.
(b)How does the value of Kc for this reaction change with increase in temperature?
(c)Write the expression which represents the relationship between Kp and Kc for this reaction.
(d)starting with two mol each (N2, H2, NH3) predict the direction of reaction?
SECTION:E
33 (i) What is the criterion for a reaction to be spontaneous?
(ii) Write expression for work done in isothermal reversible process.
(iii) For the reaction, 2 Cl(g) → Cl2 (g), what are the signs of ∆H and ∆S ?
(iv) Consider the following thermochemical equation.
N2 (g) + 3H2 (g) 2 NH3 (g) ; rH° = - 92.4 kJ /mol
and Calculate the standard enthalpy of formation of ammonia.
Or
(a) State third law of Thermodynamics.
(b) U is a state function but work is not?
(c) Calculate the enthalpy of the reaction:
N204(g) + 3CO(g) N20(g) + 3CO2(g)
Given that; ∆fHº CO (g) = – 110 kj mol-1; ∆fH C02(g) = – 393 kj mol-1
∆fH N20(g) = 81 kj mol-1; ∆fH N2O4(g) = 9.7 kj mol-1
34 (a) Complete the following reactions.
(i) CH3COO-Na+ →
(ii) →
(iii) →
(b) State the Huckle Rule.
(c) Show the resonance in phenol.
OR
(a) Explain the following reaction with examples
(i) Friedal-craft alkylation reaction
(ii) Wurtz reaction
(iii) ozonolysis of propene
(c) Draw geometrical isomers of But-2-ene.
(d) arrange the following in increasing order of acidic character.
CH3–CH3 , H2C=CH2 , HC ≡ CH
35 (a)How can ethene be prepared from (i) ethanol (ii) ethyl bromide?
(B)What is Wurtz reaction? How can it be used to prepare butane?
Or
(A) Which alkene upon ozonalysis will give CH3CH2 CHO and CH3 CO CH3
(B) How will you convert ethyne to benzene?
(C) Write chemical reaction to exemplify Friedel-Crafts alkylation of benzene.
(D) Complete the following reactions:
(i) CH3CH2Br + Alc.KOH →
(ii) CH3CH = CHCH3 + O3 →
(ii)
20 (i) Hund’s rule: in degenerated orbitals pairing of does not takes place until each 1
orbital get one e.
21 1
½
(ii)Deactivating groups: these groups deactivate benzene ring towards
electrophilic substitution reaction by decreasing e density on it. Ex- NO2 / X / -CN ½
etc (any other)
22 Law of multiple proportion: when two elements combine to form more than two 1+1
compounds then the ratio of the masses of the second element which combine
with a fixed mass of the first element will be ratio of small whole numbers.
ex - H20
H2O2 (Hydrogen Peroxide)
Here the ratio of oxygen in both compounds= 1 : 2
23 1+1
SECTION C
26 (i)4-Bromo-2-methylpentanoic acid 1
(ii) 4- Methylpentanal 1
(iii) methyl propanoate 1
27 (i)Cl=+7 Mn=+7 ½ +½
(ii) Calculation of Oxidation no.
Balance of atoms other than H and O ½ x 4=2
Balance of H and O
Complete balanced reaction
28 Number of moles of H2 =4.96×103 mol ½
30 a) It is due to small size of fluorine atom. As a result, there are strong inter
electronic repulsions in the relatively small 2p orbitals of fluorine and thus, the 1
incoming electron experience much repulsion. 1
b) Unnilbium ( Unb) 1
c) Fe3+ 1s22s22p63s23p63d5
SECTION:D
31 (a) more repulsions produced by electrone pair of equatorial position 1
( vsepr theory)
(b) trigonal bipyramidal 1
(c)(i) The orbitals present in the valence shell of the atom are hybridised.
(ii) The orbitals undergoing hybridisation should have almost equal energy. 2
OR
i) Friedal-craft alkylation reaction
1X 3
(B)When alkyl halides is treated with metallic Na in presence of dry ether, alkanes
are formed. This reaction is called Wurtz reaction.
Butane is prepared by the reaction of bromoethane with metallic Na in presence
of dry ether
OR 1+1+1+2
(A) CH3-CH2-CH=C (CH3)2
(B)
(C)
Equilibrium
6 1 1 0 1 2 0 1 4 0 7
Redox Reactions
7 1 1 0 0 1 3 0 0 4
Organic
Chemistry: Some
basic Principles
8 and Techniques 2 2 1 1 0 1 3 0 1 5 11
Hydrocarbons
9 2 2 1 1 1 2 0 0 0 1 5 10
1
TOTAL 14 14 4 4 7 14 5 15 2 8 3 5 70
SECTION A
The following questions are multiple-choice questions with one correct answer. Each questioncarries
1 mark. There is no internal choice in this section
1. .Which of the following pairs of gases contains the same number of molecules?
(ii) A compound cannot be separated into its constituent elements by physical method of separation.
4. Which of the following statements concerning the Quantum numbers are correct ?
(i) Angular quantum number determines the three dimensional shape of the orbital.
(ii) The principal quantum number determines the orientation and energy of the orbital.
(iv) Spin quantum number of an electron determines the orientation of the orbital.
5. The elements in which electrons are progressively filled in 5f-orbital are called -
(i) Actinoids
(iii) lanthanoids
(iv) halogens
6. The period number in the long form of the periodic table is equal to
(i) magnetic quantum number of any element of the period.
(ii) NH3
(iii) CH43
(iv) NH4+
(ii) H2O
(iii) HI
(iv) H2S
9.Enthalpy of sublimation of a substance is equal to
(i) enthalpy of fusion + enthalpy of vapourisation
(ii) 0.5
(iii) 1.5
(iv) 2
12. For the reaction H2(g) + I2(g) → 2HI (g), the standard free energy is ∆G0 > 0.
(i) K = 0
(ii) K > 1
(iii) K = 1
(iv) K < 1
(iii) 2K + F2 → 2KF
14. Choose the correct oxidation state of the Underlined atoms of the given molecules –
(i) +5 & +3
(ii) +5 & +6
(iii) +5 & -3
(iv) -5 & -6
15.Assertion (A) : Energy of resonance hybrid is equal to the average of energies of all canonical
forms.
(ii) Both A and R are correct but R is not the correct explanation of A.
16.Assertion (A) : Pent- 1- ene and pent- 2- ene are position isomers.
Reason (R) : Position isomers differ in the position of functional group or a substituent.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
17. Assertion (A) : Toluene on Friedal Crafts methylation gives o– and p–xylene.
Reason (R) : CH3-group bonded to benzene ring increases electron density at o– and p– position.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
18. Assertion (A): Nitration of benzene with nitric acid requires the use of concentrated
sulphuric acid.Reason (R) : The mixture of concentrated sulphuric acid and concentrated
nitric acid produces theelectrophile, NO2+.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
SECTION B
This section contains 7 questions with internal choice in two questions. The following
questionsare very short answer type and carry 2 marks each.
19. The empirical formula and molecular mass of a compound are CH2O and 180 g respectively.What will be
the molecular formula of the compound?
20. Arrange s, p and d sub-shells of a shell in the increasing order of effective nuclear charge (Zeff)
experienced by the electron present in them.
Or
Calculate the total number of angular nodes and radial nodes present in 3p orbital?
21. Explain why the electron gain enthalpy of oxygen is less negative than that of Sulphur.Or
All transition elements are d-block elements, but all d-block elements are not transition
elements.Explain.
22. Calculate the total number of sigma and Pi bonds in Ethene, CH2=CH2 ?
23. Predict the relationship between ΔU and ΔH for the following reactions.
(i) S(s) + O2(g) → SO2(g)
(ii) PCl5(g) → PCl3 (g) + Cl2(g)
24. The following concentrations were obtained for the formation of NH3 from N2 and H2 at
equilibriumat 500K. [N2 ] = 1.5 × 10–2M. [H2 ] = 3.0 ×10–2 M and [NH3 ] = 1.2 ×10–2M. Calculate
equilibrium constant.
SECTION C
This section contains 5 questions with internal choice in 2 questions. The following
questions are short answer type and carry 3 marks each.
26. Name the spectral series which appear in the region of electromagnetic spectrum.
(a) Visible region
(b) UV region
(c) Far IR region.
27. What is meant by hybridisation of atomic orbitals? Describe the shapes of sp, sp2, sp3 hybridorbitals.
29. Write bond line formulas for: Isopropyl alcohol, 2,3-Dimethylbutanal, Heptan-4- one.
OR
Write bond line formulas for: Isobuty alcohol, 2 pentanone, 3-pentene
30. Draw the cis and trans structures of hex-2-ene. Which isomer will have higher b.p. and why?
OR
SECTION D
The following questions are case-based questions. Each question has an internal choice
and carries 4 (1+1+2) marks each. Read the passage carefully and answer the questions
that follow.
molecular orbital (ABMO). Energy of anti bonding orbital is raised above the parent atomic
orbitals that have combined and the energy of the bonding orbital is lowered than the parent
atomic orbitals. Energies of various molecular orbitals for elements hydrogen to nitrogen
increase in the order:
Different atomic orbitals of one atom combine with those atomic orbitals of the second atom
which have comparable energies and proper orientation. Further, if the overlapping is head
on, the molecular orbital is called ‘Sigma’, (σ) and if the overlap is lateral, the molecular orbital
is called ‘pi’, (π). The molecular orbitals are filled with electrons according to the same rules as
followed for filling of atomic orbitals. However, the order for filling is not the same for all
molecules or their ions. Bond order is one of the most important parameters to compare the
strength of bonds.
or
Calculate the bond order and magnetic nature of Nitrogen molecule
Or
Represent the bond line formula of cyclopropane.
33.The first ( iH1) and the second ( iH2) ionization enthalpies (in kJ mol–1)and the ( egH) electrongain
nthalpy (in kJ mol–1) of a few elements aregiven below:Elements
H1 H2 egH
(e) the metal which can form a stable binary halide of the formulaMX2(X=halogen).
Or
Predict the formulas of the stable binary compounds that would be formed by the
combination of thefollowing pairs of elements.
(a) Lithium and oxygen (b) Magnesium and nitrogen
(c) Aluminium and iodine (d) Silicon and oxygen
(e) Phosphorus and fluorine
Or
Give a brief description of the principles of the following techniques taking an example in each case.
(a) Crystallisation (b) Distillation (c) Chromatography
35.a). Write IUPAC names of the products obtained by addition reactions of HBr to hex-1-ene
(i) in the absence of peroxide and (ii) in the presence of peroxide
b). How will you convert ethanoic acid into benzene.
c). Write Friedel craft alkylation and acylation reaction.
SECTION B
19. For correct empirical formula assign 1 mark + 1 mark for molecular formula C6H12O6 (2)
20. d < p < s OR For 3p orbital n = 3, l = 1 (2)
Number of angular nodes = l = 1
Number of radial nodes = n – l – 1 = 3–1–1=1
21. The
added electron in oxygen goes to second quantum level. Due to small lsize of oxygen itexperiences
repulsion from other electrons much more in comparison to that in sulphur because in sulphur, the
electron is added to 3rd quantum level in which larger space is available for movement. (2)
Or
Elements with fully filled d orbitals are not transition elements. (2)
22. 5 sigma bonds and 1 pi bond present in ehene (1+1)
Write kc Substitute and final answer 1.06 x10 3 ( refer TEXT BOOK (1)
29.
(Each correct Answer 1 mark)
Cis- form is more polar than trans-form i.e., cis-form has higher dipole moment than trans-form.
Thus, the boiling point of cis-isomer is greater than that of trans-isomer because of the greater
dipole-dipole interactions between the molecules in it. further more trans-
isomer of hex-2-ene is almost non-polar (1)
OR
Correct explanation with example 2+1
OR
b)The element II which has least first IE and low negative electron gain enthalpy is most
reactive so it must be K
c) The element III which has high first IE and very high negative EG is most reactive non metal so it
must be fluorine
d) The element IV has a high negative electron gain enthalpy but so high first IE .So it the least
reactive non metal ,it is Iodine
e) The element VI has low first IE but higher than that of alkali metal. So It is Alkaline
Earthmetal and forms binary halide. It is Mg
OR
a) Li2O
b) Mg3N2
c) AlI3
d) SiO2
e) PF3 or PF5
34. a) Chain isomers are those compounds with same chemical formula but differ in the name of parent chain
of the compound. (1 )
b) Functional isomerim (1)
c) Position isomerism (1)
d) C2-C3 (1)
e) Refer NCERT text book (1)
OR
(a) Crystallisation Crystallisation is one of the most commonly used techniques for the purification of solid
organic compounds. Principle: It is based on the difference in the solubilities of the compound and the
impurities in a given solvent. The impure compound gets dissolved in the solvent in which it is sparingly
soluble at room temperature but appreciably soluble at higher temperature. The solution is concentrated to
obtain a nearly saturated solution. On cooling the solution, the pure compound crystallises out and is
removed by filtration.
(b) Distillation This method is used to separate volatile liquids from non-volatile impurities or a mixture of
those liquids that have a sufficient difference in their boiling points. Principle: It is based on the fact that
liquids having different boiling points vaporise at different temperatures. The vapours are then cooled and
the liquids so formed are collected separately down
(c) Chromatography It is one of the most useful methods for the separation and purification of organic
compounds. Principle: It is based on the difference in movement of individual components of a mixture
through the stationary phase under the influence of mobile phase. (2+2+1)
6 Equilibrium 2 2 0 1 2 1 3 0 0 7
7 Redox Reactions 1 1 0 0 1 3 0 0 4
Organic Chemistry:
Some basic
Principles and
8 Techniques 2 2 1 1 0 1 3 0 1 5 11
9 Hydrocarbons 2 2 1 1 1 2 0 0 0 1 5 10
TOTAL 14 1 4 4 7 14 5 15 2 8 3 15 70
4
KENDRIYA VIDYALAYA SANGATHAN JAIPUR REGION
SAMPLE PAPER 5 2022-2023
XI- CHEMISTRY Max.marks:70
Max.time:3hrs
Read the following instructions carefully.
There are 35 questions in this question paper with internal choice.
SECTION A consists of 18 multiple choice questions carrying 1 mark each.
SECTION B consists of 7 very short answer questions carrying 2 marks
each.SECTION C consists of 5 short answer questions carrying 3 marks
each.
SECTION D consists of 2 case-based questions carrying 4 marks
each. SECTION E consists of 3 long answer questions carrying 5
marks each. All questions are compulsory.
Use of log tables and calculators is not allowed.
SECTION A
The following questions are multiple-choice questions with one correct answer. Each question carries
1mark. There is no internal choice in this section.
1. What is the mass percentage of carbon in carbon dioxide?
(A) 0.034% (B) 27.27% (C) 3.4% (D) 28.7%
3. Which of the following statements does not form a part of Bohr's model of hydrogen atom?
A. Energy of the electrons in the orbit is quantized.
B. The electron in the orbit nearest to the nucleus has the lowest energy.
C. Electrons revolve in different orbits around the nucleus.
D. The position and velocity of the electrons in the orbit cannot be determined simultaneously.
4. In photoelectric effect, the kinetic energy of photoelectrons increases linearly with the
A.Wavelength of incident light B. Frequency of incident light
C. Velocity of incident light D. Atomic mass of an element
7. When equal volumes of 0.002 M solutions of sodium iodate and cupric chlorate are mixed together (Ksp
(cupric iodate) = 7.4 × 10–8 ), from the following, the correct observation would be
A. Precipitation will occur
B. Precipitation will not occur
C. There are 50 % chances of precipitation
D.Data is not sufficient to make any conclusive observation
11. For the process to occur under adiabatic conditions, the correct condition is
A. T=0 B. p=0 C. q=0 D. w=0
12. The most suitable method used for the separation of 1:1 mixture of ortho and para-nitro phenol is:
A. Chromatography B. Crystallization C. Steam distillation D. Sublimation
14. The reaction of toluene with Cl2 in presence of FeCl3 gives ‘X' and the reaction in presence of light
gives 'Y'. 'X' and 'Y' are respectively-
A. X= Benzal chloride, Y= o-chlorotoluene
B. X= m-chlorotoluene, Y= p-chlorotoluene
C. X= o and p-chlorotoluene, Y= trichloromethyl benzene
D. X= Benzyl chloride, Y= m-chlorotoluene
The questions given below consist of an 'Assertion' (A) and the 'Reason' (R). Use the following keys for
theappropriate answer:
(A) .If both (A) and (R) are correct and (R) is the correct reason for (A).
(B) .If both (A) and (R) are correct but (R) is not the correct explanation
for (A).(C). If (A) is correct but (R) is incorrect.
(D). If(A) is incorrect but (R) is correct.
15. Assertion (A) :In Rutherford's gold foil experiment, very few a-particles are deflected back.
Reason (R) :Nucleus present inside the atom is heavy. (A)
16. Assertion (A) The thermodynamic factor which determines the spontaneityty of a process is the free
energy. For a process to be spontaneous the free energy must be -ve.
Reason (R) The change in free energy is related to the change in enthalpy and change in entropy. Thechange in
entropy for a
17. Assertion (A) : Energy of resonance hybrid is equal to the average of energies of all canonical forms.
Reason (R) : Resonance hybrid cannot be presented by a single structure.
18. Assertion (A) : Nitration of benzene with nitric acid requires the use of concentrated sulphuric acid.
Reason (R) : The mixture of concentrated sulphuric acid and concentrated nitric acid produces the
electrophile,
SECTION B
19) What is the number of photons of light with a wavelength of 4000 pm that provide 1 J of energy?
20) Define the following terms: i. Molarity ii. Limitng reagent
21) Name the factors which affect the ionisation enthalpy of an element.
22. What is mean by bond order? Calculate the bond order of O2
molecule OR
23) Define entropy. predict whether entropy change in the following processes would be positive or
negative.
i. N2O3(g)N2O(g) +O2(g)
ii. NH3(g) +HCl(g) NH4Cl(s)
24) What is meant by the conjugate acid-base pair? Find the conjugate acid and base of NH3
25) What is ozonolysis? Write the names of the products obtained when 2-Methyl propene undergoes
ozonolysis?
OR
SECTION-C
26) An inorganic salt gave the following percentage composition-Na =29.11,S = 40.51 and O =30.38
.Calculate the empirical formula of the salt.(At .mass of Na=23,S=32 and O=16)
28) i) Define the pH of the solution. The pH of a sample of vinegar is 3.76. Calculate the concentration of
hydrogen ion in it.
iii) Write the expression for equilibrium constant, Kc for the
reaction4 NH3(g) + 5 O2(g) ⇌4 NO(g) + 6 H2O(l)
OR
a) State Le-Chatlier’s principle.
b) What is the effect of:
(i) addition of H2 (ii) addition of CH3OH
(iii) removal of CO (iv) removal of CH3OH
30. In the estimation of sulphur by carius method,0.468 gof an organic sulphur compound gave 0.668 g of
barium sulphate.find the percentage of sulphur in the given compound.
OR
0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in carius estimation.calculate
thepercentage of chlorine present in the compound.
SECTION D
31) When anions and cations approach each other, the valence shell of anions are pulled towards
cation nucleus and thus, shape of anion is deformed. The phenomenon of deformation of anion by a
cation is known as polarization and the ability of the cation to polarize the anion is called as polarizing
power of cation. Due to polarization, sharing of electrons occurs between two ions to some extent and
the bond shows some covalent character. The magnitude of polarization depends upon a number of
factors. Thesefactors were suggested by Pajan and are known as Fajan's rules.
i. Greater is the polarization in a molecule, more is covalent character.
ii. As the charge on cation increases, its tendency to polarize the anion increases.
iii. The size of the cation decreases or size of the anion increases, the polarization increases.
iv.The cations with 18 electrons in the outermost shell bring greater polarization of the anion than those
with inert gas configuration even both the cations have same size and same charge.
1. Considering BeCl2 , MgCI2, CaCl2 and BaCl2, predict which of the following statements is true?
A. BeCl2 is least ionic out' of the given chlorides
B. Covalent character increases as the atomic number of the metal atom increases
C. BeCl2 has the highest melting point among the given chlorides
D. All are highly ionic compounds
4. Non-aqueous solvent like ether is added to the mixture of LiCl, NaCl and KCI. Which will be extracted
into ether?
A. NaCI B. LiCI C. KCI D. None
32. Dual nature of matter was proposed by de Broglie in 1923, it was experimentally verified by Davisson
and Germer by diffraction experiment. Wave character of matter has significance only for microscopic
particles. de Broglie wavelength or wavelength of matter wave can be calculated using the following
relation:
A=
where, 'm' and v' are the mass and velocity of the particle. de Broglie hypothesis suggested that
electron.Waves were being diffracted by the target, much as X-rays are. Diffracted by planes of atoms
in the crystals.
Answer the following questions:
1. Planck's constant has same dimension as that of:
A. work B. energy C. power D. angular momentum
4. Which among the following is not used to calculate the de Broglie wavelength?
SECTION –E
33)
i. Give the criteria for spontaneity of a process in terms of free energy change (∆G).
ii. Exothermic reactions associated with a decrease in entropy are spontaneous at lower temperatures.
Justify on the basis of Gibbs equation.
iii. For the reaction 2 A(g) + B(g) → 2D(g) ∆U0 = –10.5 kJ and ∆S0 = –44.1 JK–1 . Calculate ∆G0 for the
reaction, and predict whether the reaction may occur spontaneously.
OR
a. For a reaction both ΔH and ΔS are negative. Under what conditions does the reaction occur
spontaneously?
b. Define- Lattice enthalpy
c.
34. i. Explain the terms Inductive and Electromeric effects. Which electron displacement effect explains the
following correct orders of acidity of the carboxylic acids? Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
ii. Explain why alkyl groups act as electron donors when attached to a π system.
iii. Give condensed and bond line structural formula of 2-Hydroxy-1,2,3-propanetricarboxylic acid
OR
1 B-27.27% 1
2 A-Molarity 1
3 D-The position and velocity of the electrons in the orbitcannot be determined 1
simultaneously.
4 A-Frequency of incident light 1
5 B-BCl3 has no lone pair of electrons whereas NCl3 has a lone pair of electrons 1
6 D- Terbium (Z=65) 1
11 C- q=0 1
12 A-Steam distillation 1
13 A-C6H6+CH3Cl 1
14 C-X= o and p-chlorotoluene, Y= trichloromethyl benzene 1
15 A-If both (A) and (R) are correct and (R) is the correct reason for (A). 1
SiCl4
ClF3
NH3
NH4+ is a conjugate acid of NH3 and NH2- is a conjugate base of acid NH3 1
25 Ozonolysis: Alkenes add ozone to form an ozonide which on hydrolysis in presence of 1
Zn to form carbonyl compounds (Aldehydes or ketones).
OR
OR
SECTION C
26 elements symbol % of At.mass No.of Simplest Simplest
element of moles molar whole
elemets = ratio no.ratio
Sodium Na 29.11 23 2 1
Sulphur S 40.51 32 2 1
oxygen O 30.38 16 3 1
1
OR
OR
a. Le Chatelier's principle states that if a dynamic equilibrium is disturbed by
changing the conditions, the position of equilibrium shifts to counteract the 1
change to reestablish an equilibrium.
b. (i) Equilibrium will be shifted in the forward direction. 2
(ii) Equilibrium will be shifted in the backward direction.
(iii) Equilibrium will be shifted in the backward direction.
(iv) Equilibrium will be shifted in the forward direction.
29 Oxidation half equation:
SO2(g) + 2H2O(l) ————> SO42-(aq) + 4H (aq) + 2 e – …(i)
+
1
Reduction half equation: 1
Cr2O72–(aq) + 14H+(aq) + 6e– ————> 2Cr3+(aq) + 7H 20(l) …(ii)
Multiply Eq. (i) by 3 and add it to Eq. (ii), we have, 1
Cr2O72–(aq) + 3SO2(q) + 2H+(aq) ————> 2Cr3+(aq) + 3SO 42-(aq) + H 20(l)
2
Or
Mass of the compound = 0.3780 g OR
Mass of silver chloride = 0.5740 g
1
SECTION D
31 1. (a) BeCl2 is least ionic out' of the given chlorides 1
2. (D) AlI3 1
3. (B) AlCl3 1
4. (B) LiCI 1
32 1. (D) angular momentum 1
2. (C) diffraction experiment 1
3. (A) Planck's quantum theory 1
(B) Einstein's theory of mass-energy equivalence 1
4. (A) λ=
SECTION E
33 i. For a reaction to be spontaneous ΔG should be negative. 1
ii. if both ΔH and ΔS are negative, ΔG can be negative only if TΔS < ΔH in
1
magnitude.
ΔG = ΔH – TΔS, ΔG = (−) − T(−)
OR
a. Both ΔH and ΔS are positive so ΔG will be negative only if TΔS > ΔH in
magnitude. 1
ΔG = ΔH−TΔS
1
ΔG = (+) − T(+)
OR
Thus either ΔS should be very large so that even if T is low, TΔS is greater
than ΔH, or if ΔS is small, T should be high so that TΔS > ΔH. 1
b. Lattice energy can be defined as the energy required to convert one mole
of an ionic solid into gaseous ionic constituents.
c.
1
v. heptan-4-one
35 a) Decarboxylation:
Sodium salt of carboxylic acids (R-COONa) on heating with soda lime (a mixture of
NaOH and CaO), we get an alkane containing one carbon atom less than that of the 1
carboxylic acid.
e.g. CH3COONa CH4 + Na2CO3
Sodium acetate methane
b) Aromatization:
n-Alkanes having six or more carbon atoms on heating to 773K at 10-20
atmospheric pressure in the presence of oxides of vanadium, molybdenum or
chromium supported over alumina, we get aromatic compounds.
c) Kharash effect:
In the presence of peroxide, addition of HBr to unsymmetrical alkenes takes
place against Markovnikov rule. This is known as peroxide or Kharash effect or anti-
Markovnikov addition reaction.
1
e.g. CH3-CH= CH2 + HBr CH3-CH2-CH2
d) Sulphonation: It is the introduction of sulphonic acid (-SO3H) group to a
benzene ring. It is carried out by heating benzene with fuming sulphuric
acid (H2S2O7 or oleum).
(e) Friedel-Craft’s Acylation reaction: The reaction of benzene with an acyl halide or
acid anhydride in the presence of Lewis acids (AlCl3) yields acylbenzene.
OR
(a) Phenol is reduced to benzene by passing its vapours over heated zinc dust.
OR
(b) Ethyne (acetylene) on passing through red hot iron tube at 873K,
undergoescyclic polymerisation to form benzene (C6H6).
1