Iit Jee
Iit Jee
Iit Jee
ATOMIC STRUCTURE
IIT-JEE Fundamental
Particles
1) The mass of an electron is
1) 0.000549 amu 2) 1.00727amu 3) 1.00867 amu 4) None
Note : Mass of an electron = 9.1x10 -31 Kg
= 5.49 x 10-4 amu
2) The charge on an electron is
1) 9.1 x 10-31 coulombs 2) 1.602 x 10-19 coulombs
3) 4.8 x 10-10 coulombs 4) None
3) The mass of a proton is equal to
1) 1.6726 x 10-24 grams 2) 1.00727 amu
-27
3)1.6726 x 10 Kg 4) All
4) The mass of a neutron is
1) 1.6749 x 10-27Kg 2) 1.00867 amu
3) Both 1 & 2 4) None
5) The charge on a neutron is
1) + 1.6 x 10-19 coulombs 2) -1.6 x 10-19 coulombs
-10
3) 4.8 x 10 e.s.u 4) None
6) 1 amu is equal to
1) 1.6726 x 10-27 Kg 2) 1.6605 x 10-27 Kg 3) 1.6749 x 10-27 Kg 4) None
7) The symbol used to represent a - particle is
1) +1e0 2) -1e0 3) +1p1 4) 2He4
Note : - particle is nothing but an electron
8) The ratio of mass of proton to that of an electron is
1
1) 2) 1836 3) 1839 4) 1
1836
9) The ratio of mass of neutron to that of an electron is
1
1) 1839 2) 3) 2 4) 1836
1836
10) The ratio of specific charge of electron to that of a proton is
1
1) 1836 2) 3) 1839 4) None
1836
Charge e
Note : Specific charge = mass
=
m
11) The equation relating the characteristic frequency ( ) of X-rays emitted by anti-cathode and atomic
number (Z) of the metal used as anti-cathode, given by Moseley is
2
1) a( z b ) 2) a( z b ) 3) z 4) a ( zb )
12) Charge on electron was experimentally determined by
1) Millikan 2) Goldstein 3) Chadwick 4) J.J.Thomson
13) Choose the incorrect statement
1) Nucleus occupies very small fraction of atom and most of the atom is empty, hence most of the
alpha particles passed through the gold foil undeflected during - particle scattering experiment.
2) Entire mass of the atom is concentrated in the nucleus and the mass of electrons is negligible.
3) Nucleus carries positive charge due to presence of protons in it.
2
4) Most of the atom is not empty and hence the -particles are deflected back.
14) The e/m value of cathode rays in a discharge tube is
1) always same irrespective of the gas taken 2) different for different gases
3) same only when noble gases are taken 4) None
15) Neutron was discovered by
1) Thomson 2) Chadwick 3) Goldstein 4) Rutherford
16) The highest value of e/m is observed for anode rays when the discharge tube is filled with
1) N2 2) H2 3) O2 4) He
17) Which of the following pair have identical values of e/m
1) A proton and a neutron 2) A proton and a deuterium nucleus
3) A deuterium nucleus and an -particle 4) An electron and -rays
18) Choose the correct increasing order of e/m values for e,p,n and - particle
1) p < n < < e 2) e < p < < n 3) n < p < e < 4) n < < p < e
19) The e/m value of electron is
1) 9.1 x 10-31 Kg 2) 1.602 x 10-19C 3) 1.759 x 1011C.Kg -1 4) Zero
13 14
20) The relation between 6C and 6C is
1) isobars 2) isotopes 3) isotones 4) None
14
21) The isobar of 6C is
1) 8O16 2) 6C13 3) 7N14 4) 2Be4
22) Isotones contain same number of
1) electrons 2) protons 3) positrons 4) Neutrons
23) The triad of nuclei that is isotonic is
1) 6C14, 7N15, 9F17 2) 6C12, 7N14, 9F19 3) 6C14, 7N14, 9F17 4) 6C14, 7N14, 9F19
24) The radius of atomic nucleus is of the order of
1) 10-10 cm 2) 10-13cm 3) 10-15cm 4) 10-8cm
35 37
25) The natural abundance of 17Cl and 17Cl is approximately 75% and 25% respectively. The molar
atomic mass of chlorine will be
1) 36 g 2) 35.5g 3) 36.5g 4) 37g
26) Which of the following reaction led to the discovery of neutrons.
1) 6 C 16 1 p1 7 N 14 0 n1 2) 4 Be9 2 He 4 6 C 12 0 n1
3) 5 B11 1 D 2 6 C 11 0 n1 4) 4 Be8 2 He 4 6 C11 0 n1
Quantum Theory
1) Quantum theory had suggested
1) Emission of energy is continuouss
2) Energy is emitted discontinuously in the form of quanta
3) Energy of the radiation is quantized.
4) Both 2 & 3
2) The wavelength of a radiation emitted by a sodium lamp is 600 nm. The frequency is
1) 5 Hz 2) 5 x 1014 Hz 3) 500 Hz 4) 5 x 1015 Hz
3) If the light radiation from neon atom has a wavelength of 300 nm, then the energy of the
photon being emitted is
1) 6.626 x 10-19 J 2) 1.1 x 10-10 J 3) 2 x 10-19 J 4) 3.3 x 10-12 J
4) Violet light is able to eject electrons from the surface of potassium metal, whereas red light cannot.It
is because,
1) the intensity of violet light is greater than that of red light.
2) the frequency of red light is lower than that of violet light and its energy is not sufficient to knock out
the electrons.
3) the wavelength of violet light is greater than that of red light
3
4) None
5) Electrons with a kinetic energy of 6.023 x 104 J/mol are evolved from the surface of a
metal, when it is exposed to a radiation of wavelength of 300nm. The minimum amount of
energy required to remove one electron from the metal atom is
1) 5.626 x 10-19J 2) 3 x 10-19J 3) 6.02 x 10-19 4) 6.62 x 10-34J
Formula : E = W + KE
E = Energy of radiation
W = Work function
KE = Kinetic energy.
6) Electrons with kinetic energy of 3.313 x 10-24 J are evolved when a light radiation of 5 x109 s-1 of
frequency falls on a metal surface. The threshold frequency of the metal is
1) 5 Hz 2) 4.5 x 109 Hz 3) 500 Hz 4) 3 x 1024 Hz
Formula : K.E = h ( - 0)
7) When the frequency of light incident on a metalic plate is doubled, the kinetic energy of
emitted photoelectrons will be
1) Doubled 2) Halved 3) More than doubled 4) Unchanged.
Hint : h = W + KE1
2h = W + KE2
2W + 2KE1 = W + KE2
KE2 = 2KE1 + W
8) Photo electrons are ejected from metals A & B when a light beam of wavelength 1 is used to irradiate
them. But electrons are ejected only from metal B, when another radiation of wavelength 2 is used.
Then the false statement among the following is
1) Electrons need more energy to escape from metal A
2) 2 1
3) Threshold frequency of A is higher than that of metal B
4) When irradiated by light beam of wavelength 1 , the electrons ejected out from metal A have
more kinetic energy.
9) Photo-electrons are evolved when a metal is exposed to violet light. But no electrons are evolved
when yellow light is used. If the metal is exposed to red light, the photo-electrons are
1) evolved when the intensity (of red light) is increased
2) not evolved
3) evolved even at low intensities
4) evolved only when a thin sheet of metal is used
10) The value of Plancks constant is
1) 6.625 x 10-34 cal.sec 2) 1.584 x 10-34 cal.sec
3) 6.625 x 10-27J.sec 4) 6.625 x 10-34 erg.sec
Note: 1 calorie = 4.184 Joule
11) The number of photoelectrons emitted during photoelectric effect is proportional to
1) Intensity of incident beam 2) Work function
3) Frequency of incident beam 4) Velocity of incident beam
23) The ratio of energies of electrons in the ground states of H, He+ and Li2+ is
1 1 1 1
1) 9 : 4 : 1 2) : :1 3) 1: : 4) 1 : 4 : 9
9 4 4 9
24) The energy of an electron in the first orbit of hydrogen atom is -y Joule. The kinetic energy of electron
in the second orbit will be
y y y y
1) - Joule 2) Joule 3) Joule 4) Joule
4 2 2 4
25) The potential energy of electron present in the ground state of Li2+ ion is
3e 2 3e 3e 2 3e 2
1) + 2) 4 r 3) 4)
4 0 r 0 4 0 r 4 0 r 2
26) The energy of electron in the first orbit of hydrogen atom is equal to the energy of electron in the
1) 2nd orbit of He+ 2) 3rd orbit of Li2+ 3) 4th orbit of Be3+ 4) All
-18
27) The energy of electron in the ground state of hydrogen atom is -2.18 x 10 J. The potential energy
of electron in the first excited state of He+ ion is
1) - 2.18 x 10-18 J 2) + 2.18 x 1018 J 3) -4.36 x 10-18J 4) - 1.09 x 10-18J
28) The velocity of an electron in Bohrs orbit is expressed as
2 Ze 2 2 Z 2e 4 2 me2 2 Ze
1) 2) 3) 4) 2 2
nh nh nh nh
29) Choose the incorrect statement
1) The energy of electron increases with n value of orbit
2) The kinetic energy of electron decreases with n value of orbit
3) The potential energy of electron increases with n value orbit
4) The velocity of electron increases with n value of orbit
30) The ratio of velocities of electrons in first three orbits of hydrogen atom will be
1 1 1 1
1) 1 : 4 : 9 2) 1: : 3) 1: : 4) 1 : 2 : 3
2 3 4 9
31) The velocity of electron in first orbit of hydrogen atom is
1) 2.188 x 108 cm.sec-1 2) 13.6 cm sec-1 3) 2.188 x 108m.sec-1 4) 0.529 x 10-18 cm sec-1
32) If the velocity of an electron is x cm.sec-1 in the ground state of hydrogen atom, the velocity in the
6
second orbit is
x x x2
1) cm.sec-1 2) x2 cm.sec-1 3) cm.sec-1 4) cm.sec-1
4 2 4
33) Rydbergs constant can be expressed as
2 2 me 4 z 2 2 2 me 4 2 2 me 4 4 2 me4
1) 2) 3) 4)
ch3 n2h2 ch3 ch3
34) The value of Rydbergs constant is
1) 1.096 x 105 cm-1 2) 109677 cm 3) 109.677 m-1 4) 1.096 x 103 m-1
35) An electron jumps from 4th orbit to 2nd orbit. The spectral line corresponding to this transition will be
observed in
1) Lyman series 2) Paschen series 3) Pfund series 4) Balmer series
36) The wave number of limiting line in Lyman series of hydrogen atomic spectrum is
1) 109677 cm-1 2) 27892 cm-1 3) 13142 cm-1 4) 42314 cm-1
37) The ionisation energy of hydrogen atom is
1) 13.6 eV 2) 3.4 eV 3) 1.51 eV 4) 0.85 eV
38) The spectral line corresponding to longer wavelength in hydrogen atomic spectrum is
1) Limiting line in Pfund series 2) First line in Lyman series
3) Limiting line in Lyman series 4) First line in Pfund series
39) A spectral line is observed in the visible region of emission spectrum of hydrogen. The probable
transition corresponding to this line
1) n = 2 n = 5 2) n = 2 n = 3 3) n = 4 n = 2 4) n = 5 n = 3
40) The ratio of energies of first three lines in Lyman series is
1 1 1 3 8 15 4 9 16
1) 1 : 2 : 3 : : 2) 3) : : 4) : :
2 3 4 4 9 16 3 8 15
41) The wave number of a spectral line for a given tranistion is x cm for He+, then its value for Be3+ for
-1
same transition is
x -1
1) x cm-1 2) 4 x cm-1 3) cm 4) 16 x cm-1
4
42) The energy of electron in the infinite orbit is
1) +13.6 eV 2) 1 eV 3) 4) zero
43) A hydrogen atom is supplied with 10.2 eV of energy in its ground state. The highest energy level into
which the electron can be excited is
1) 3rd 2) 4th 3) 2nd 4) 10th
44) The energy required to remove an electron from a hydrogen atom in its 1st excited state is
1) 13.6 eV 2) 3.4 eV 3)1.51 eV 4)0.85 eV
45) The wavelength corresponding to -line in Balmer series is
1) 6564 A0 2) 3282 A0 3) 15232 A0 4) None
46) The number of spectral lines formed when an electron undergoes all possible transitions between
6th orbit and 1st orbit is
1) 6 2) 15 3) 30 4) 21
Use formula :
n n 1
; where n = n 2 n1
2
47) An electron in the ground state of hydrogen atom absorbed 12.75 eV of energy and get excited. The
number of spectral lines formed due to all possible transitions when electron jumps back from highest
possible energy level, during this excitation, to L-Shell of the atom is
1) 15 2) 3 3) 1 4) 10
7
h
48) The difference in angular momentum of two bohrs orbits is 3 . The number of all possible elec-
2
tronic transitions between these two orbits is
1) 3 2) 12 3) 6 4) 1
49) The ratio between Kinetic energy and total energy of electron in atoms according to Bohrs model is
1) 1 : 1 2) 1 : -1 3) 1 : 2 4) -2 : 1
50) The wave number of limiting line of Paschen series of hydrogen atomic spectrum is equal to
RH R R
1) RH 2) 3) H 4) H
25 9 16
51) The lines in Lyman series of hydrogen atomic spectrum are formed in
1) Visible region 2) Far IR region 3) UV region 4) Near IR region
52) Bohrs theory could not explain
1) Zeeman effect 2) Fine atomic spectrum 3) Stark effect 4) All
Quantum Numbers
1) Match the following
A) Principal quantum number (n) 1) Neils Bohr
B) Azimuthal quantum number (l) 2) Uhlenbeck & Goudsmit
C) Magnetic quantum number (m) 3) Lande
D) Spin quantum number (s) 4) Sommerfeld
Choose the correct matching
A B C D
1) 1 2 4 3
2) 1 4 3 2
3) 1 3 2 4
4) 3 1 4 2
2) In order to explain fine hydrogen atomic spectrum, Sommerfeld proposed.
1) Principal quantum number 2) Spin quantum number
3) Azimuthal quantum number 4) Magnetic quantum number
3) Magnetic quantum number (m) is proposed by Lande, in order to explain
1) Low resolution hydrogen atomic spectrum 2) Fine hydrogen atomic spectrum
3) Zeeman effect 4) Spin - Spin coupling
4) The wrong statement about principal quantum number n is
1) It is used to identify the main energy level or shell
2) It is used to determine the size and energy of orbit
3) It is used to calculate the number of orbitals in the nth shell and is given by n2.
4) It is used to determine the orientation of orbital
5) The quantum number which is used to determine the shape of orbital is
1) Principal quantum number (n) 2) Azimuthal quantum number (l)
3) Magnetic quantum number (m) 4) Spin quantum number (ms)
6) The orbital angular momentum of electron is precisely given by
nh h h h
1) 2) l l 1 3) s s 1 4) n n 2
2 2 2 2
7) The number of subshells in a given main shell n is equal to
1) n - 1 2) n2 3) n n 1 4) n
8) The possible subsidiary quantum number values of sublevels in the 3rd shell are
1) l = 1, 2 & 3 2) l = 1 & 2 3) l = 0, l & 2 4) l = 1, 2, 3 & 4
9) Match the following
8
Azimuthal quantum number Shape of orbital
A) l = 0 1) Dumb-bell
B) l = 1 2) Diffused
C) l = 2 3) Spherical
D) l = 3 4) Double dumb-bell
The correct matching is
A B C D
1) 3 2 1 4
2) 3 1 2 4
3) 3 1 4 2
4) 2 3 1 4
10) The n & l values of 4f orbital are
1) 4 & 3 2) 4 & 4 3) 4 & 1 4) 3 & 3
11) The number of orbitals in a given shell n is equal to
1) 2n 2) 2n2 3) n2 4) 2n - 1
12) The number of orbitals in given sub shell l is equal to
1) l + 1 2) l + 2 3) 2l + 2 4) 2l + 1
13) The number of orbitals in l = 2 subshell will be
1) 2 2) 3 3) 5 4) 1
14) The significance of magnetic quantum number (m) is
1) It denotes the size of orbital 2) It represents the shape of orbital
3) It indicate the orientation of orbital 4) It represents angular momentum of orbital
15) The possible values of magnetic quantum numbers of orbitals in a subshell l= 2 are
1) -2, -1, +1, +2 2) -2, -1, 0, +1, +2 3) -1, 0, +1 4) 0, +1, +2, +3
16) The maximum number of electrons that can be accommodated in sub shell l = 2
1) 2 2) 5 3) 4 4) 10
Note : The no.of electrons in subshell l = 4l + 2
17) The maximum number of electrons that can be accommodated in an orbital is
1) 2 2) 1 3) 4 4) 1 / 2
18) The values of spin quantum number can be
1 1 1 1
1) 2) 3) or 4) 0 or 1
2 2 2 2
19) Spin quantum number was proposed by
1) Goudsmidt & Uhlen beck 2) Lande 3) Neils Bohr 4) de Broglie
20) The number of orbitals present in the shell with n = 4 is
1) 4 2) 8 3) 16 4) 32
Note : The number of orbitals in given shell, n is given by n2
21) The maximum number of electrons that can be present in a main energy level n = 3 is
1) 3 2) 18 3) 6 4) 9
22) The quantum number that is not possible for electron in 4d orbital is
1) l = 2 2) s = + 1 / 2 3) m = 0 4) m = + 3
23) 2px and 2py orbitals differ in their
1) energy 2) shape 3) orientation 4) l value
24) The notation of orbital with n = 3 and l = 1 is
1) 3s 2) 3p 3) 3d 4) 2p
25) The incorrect set of quantum numbers for an electron will be
1) n = 3, l = 1, m = 0, s = + 1 / 2 2) n = 2, l = 0, m = 0, s = - 1 / 2
3) n = 4, l = 3, m = -3, s = - 1 / 2 4) n = 3, l = 2, m = +3, s = + 1 / 2
26) The number of p orbitals present in a shell with n = 4 is
1) 4 2) 12 3) 10 4) 3
9
2 2 2 8 m
2) 2 E V 0
x 2 y 2 z 2 h
2 2 2 8 2 m
3) 2 E V 0
x 2 y 2 z 2 h
2 2 2 8 m
4) E V 0
x 2 y 2 z 2 h
2) Choose the incorrect statement
1) is called orbital wave function. It represents the amplitude of electron wave, but has no physical
significance.
2) 2 is called probability density of electron and always has positive values.
3) Schrodingers wave equation is time dependent. 4) None
3) Which of the following is not a boundary condition required to get valid Eigen functions for ?
1) must be finite and continous
2) must be single valued at a given point
3) The probability of finding the electron over the space from + to - must be equal to zero
4) All
4) H in the schrodinger equation, H E ,is known as
1) Kinetic energy operator 2) Heisenberg operator
3) Hamiltonian operator 4) Potential energy operator
Note : The total energy operator also called as Hamiltonian operator is the sum of Kinetic energy operator (T) and potential
energy operator ( V ) . = T + V
i.e., H .
5) The orbital wave function written in terms of polar co-ordinates : r, and can be expressed as
r, , R r
Choose the incorrect statement related to above expression.
11
1) R (r) is called radial wave function which depends on quantum numbers n & l
2) & are the angular wave functions which depend upon quantum numbers l and m
3) R (r) gives dependence of orbital upon radial distance of electron from the nucleus.
4) and are the angular wave functions and depend only on principal quantum number n
Note : The orbital wave functions ( ) can be expressed in terms of spherical polar co-ordinates (r, & ). The relation
between polar co-ordinates and cartesian co-ordinates can be given as
x = r sin cos
y = r sin sin
z = r cos
1 1 1
m mn
e e
Where me = mass of electron
mn = mass of nucleus
2) For hydrogen atom electron energy depends only on n and independent of l and n.
7) The probability of finding an electron at a distance r from the nucleus regardless of direction is called
1) radial wave function 2) radial probability density 3) radial probability function 4) All
Note : R = radial wave function
R2 = radial probability density
2 2
4 r drR radial probability function
8) The correct graph of radial wave function (R) of 2s orbital plotted against radial distance r is
12
12) The space around the nucleus where the 2 > 90% is called
1) atomic orbital 2) nodal region 3) nodal plane 4) All
13) The point at a radial distance from the nucleus where the probability of finding the electron is zero is
called
1) Atomic orbital 2) Nodal point 3) Molecular orbital 4) None
14) The radius of maximum probability for 1s orbital of hydrogen atom is
1) 52.9 pm 2) 105.8 pm 3) 264.5 pm 4) 2.116 pm
15) The radial distance from the nucleus at which the nodal region of 2s orbital of hydrogen atom is
1) 0.529 2) 1.050 3) 2.645 4) 2.116
16) In 2s orbital of hydrogen atom the radial probability function has its maximum value at the radial
distance,
1) 2.645 2) 2.116 3) 0.529 4) 1.058
17) In 2p orbital of hydrogen, the radial probability function has its peak vlaue at the radial distance.
1) 2.645 2) 2.116 3) 0.529 4)1.058
18) Assertion : The energy of 2s orbital will be less than that of 2p orbital even though the radius of
maximum probability for 2s orbital is at 264.5 pm and for 2p orbital is at 211.6 pm.
Reason : There is a small additional maxima at 52.9 pm in case of 2s orbital. Hence the electron in
this orbital penetrates little closer to the nucleus and binds strongly to it than that of 2p orbital.
Choose the correct answer
1) Both A & R are correct ; and R is the correct explanation of A
2) Both A & R are correct ; but R is not the correct explanation of A.
3) A is correct but R is incorrect
4) A is incorrect but R is correct.
19) The number of radial nodes present in a given orbital is equal to
1) l 2) n - l - 1 3) n - 1 4) n - l - 2
Note : Radial node, also called as nodal region or spherical node, does not pass through the nucleus
20) The number of angular nodes present in a given orbital is equal to
1) l 2) n - l - 1 3) n - l 4) n - l - 2
14
Note : Angular node, also called as nodal plane, passes through the nucleus.
21) The number of radial nodes in 1s orbital is
1) 1 2) 2 3) 3 4) 0
Note: p orbitals have only one angular node perpenducular to the axis of orientation of the orbital. For example, px orbital has
one angular node along yz plane.
25) The number of radial nodes in 4p orbital is
1) 1 2) 2 3) 3 4) 4
26) The number of radial nodes and angular nodes respectively present in 4dxy orbital will be
15
1) 0 & 1 2) 1 & 2 3) 2 & 2 4) 1 & 1
Note: 4d orbital has one radial node. And usually d orbitals have two angular nodes. In case of 4dxy orbital the angular nodes
are present along yz and xz planes.
27) The total number of radial and angular nodes present in a given orbital is equal to
1) n 2) n - l 3) n - l - 1 4) n - 1
28) Which of the following radial distribution graph corresponds to orbital with n = 3, l = 2 ?
29) The orbital with two nodal planes but with no nodal regions is
1) 4d 2) 4s 3) 3d 4) 4f
30) The number of nodal planes in 4f orbital is
1) 1 2) 2 3) 3 4) zero
31) The 2 value is zero along xy and yz planes in a d-orbital. The notation of that d-orbital will be
1) dxy 2) dxz 3) dyz 4) 1 or 3
32) Which of the following orbital belongs to principal quantum level, n = 5?
16
Electronic configuration
1) The orbital with least energy before filling up of electrons is
1) 3d 2) 4s 3) 4p 4) 5s
Note : Orbital with least (n + l) value has least energy and is filled first
2) The orbital which is filled first will be
1) 4f 2) 5d 3) 6p 4) 7s
Note : If the orbitals possess same (n + 1) value, the orbital with least n value has least energys
3) Which of the following electronic configuration violates Hunds rule
1) 1s 2 2s 2 2 p1x p1y p1z 2) 1s 2 2 s 2 2 px2 p1y pzo 3) 1s 2 2 s 2 2 px2 p 2y p1z 4) 1s 2 2 s 2 2 p1x p1y pz0
4) No two electrons in an atom can have same set of quantum numbers. This statement is known as
1) Hunds rule 2) Heisenbergs uncertainty principle 3) Paulis exclusion principle 4) None
5) The correct ground state electronic configuration of chromium is
1) [Ar] 3d4 4s2 2) [Ar] 3d5 4s2 3) [Ar] 3d5 4s0 4) [Ar] 3d5 4s1
6) The set of quantum numbers of valence shell electron in potassium atom is
1) n = 3, l = +1, m = +1, s = + 1 / 2 2) n = 4, l = 0, m = 0, s = + 1 / 2
3) n = 3, l = 0, m = 0, s = + 1 / 2 4) n = 3, l = l, m = 0, s = + 1 / 2
2 3 1
7) [Ne] 3s 3p 3d is the electronic configuration of
1) P in ground state 2) S in 1st existed state
3) P in 1st excited state 4) S in 2nd existed state
8) The number of electrons in the valence shell of calcium is
1) 2 2) 3 3) 1 4) 6
9) In a multi electron atom, which of the following orbitals described by the three quantum numbers will
have the same energy in the absence of magnetic and electric fields ?
a) n = 1, l = 1, m = 0;
17
b) n = 2, l = 0, m = 0;
c) n = 2, l = 1, m = 1;
d) n = 3, l = 2, m = +1;
e) n = 3, l = 2, m = 0
The correct combinations are
1) a & b 2) b & c 3) a & d 4) d & e
10) Which orbital is nearest to the nucleus after filling with electrons ?
1) 5d 2) 6s 3) 6p 4) 4f
2+
11) The number of electrons in 3d - orbital in Zn ion is
1) 8 2) 10 3) 9 4) 0
12) The number of electrons with l = l in the ground state of sulfur atom is
1) 6 2) 10 3) 8 4) 4
13) The number of unpaired electrons in 3d orbital of copper atom is
1) 5 2)10 3) 1 4) None
Note: Copper has anomalous electronic configuration i.e., [Ar] 3d104s1
14) The magnetic moment of Mn2+ ion is
1) 3.87 BM 2) 5.9 BM 3) 7.93 BM 4) 6.92 BM
Formula: magnetic moment( )= n(n+2) BM
where n=no. of unpaired electrons
15) The correct increasing order of energy of 4f, 5p, 6s & 5d orbitals is
1) 4f < 5p < 5d < 6s 2) 4f < 6s < 5d < 5p
3) 5p < 6s < 4f < 5d 4) 5p < 5d < 6s < 4f
16) The number of exchanges possible between parallel electrons in d orbitals of chromium is
1) 6 2) 10 3) 5 4) 4
Note: In [Ar] 3d54s1 configuration, there are five unpaired d electrons. The number of exchanges are calculated by following
formula. These exchanges between degenerate d-electrons lower the energy of the atom and thus by confering more stability to
the atom in this anomalous configuration.
If the configuration is [Ar] 3d44s2 as predicted, then the exchanges possible are only 6. Hence this configuration is less stable.
5 5 1 n!
Formula : 5C = 10 this is the modification of equation
2 2! r ! n r !
ATOMIC STRUCTURE
INTRODUCTION
Atom:- The smallest particle which can take part in a chemical reaction with out losing its identity is known
as atom.
Subatomic particles: Electrons, protons and neutrons are known as subatomic particles.
Electron:- The negatively charged fundamental particle present in an atom with negligible mass is called
electron.
The mass of an electron is 1/1836 of mass of proton or hydrogen atom. In atomic mass units it is equal
to 0.000548 amu or 9.1095 X 10-31kg. Its charge is 1.6022 X 10-19coulomb.
Discovery of Electron : -
Sir William Crookes designed a cathode ray discharge tube in which cathode rays are observed only
at very low pressures and very high voltages. These rays consist of negatively charged particles called
electrons.
To vacuum pump
Cathode - + Anode
High voltage
Charge to mass ratio of Electron (e/me) : - Charge to mass ratio of electron is calculated by J.J.
Thomson as follows.
e
1.75882 x 1011 C kg 1
me
Charge on the Electron :- The charge on the electron was calculated by Millikan in oil drop experiment
as 1.60 x 10-19 coulombs.
The mass of the electron can be derived as follows.
e
me 9.1094 x 10-31 kg
e / me
Atomic structure 2
Proton:- The positively charged fundamental particle present in the atom is called proton.
The mass of a proton is 1.007277 amu or 1.67252 X 10-27 kg. Its charge is same as that of electron.
Discovery of proton : -
Protons are discovered in canal ray experiment. These rays are produced in modified cathode ray
tube.
Neutron:- The neutral fundamental particle present in the atom is called neutron.
The mass of a neutron is 1.00898 amu or 1.67495 X 10-27kg. It has no charge.
Discovery of neutrons: Chadwick discovered neutrons by bombarding a thin layer of Be with par-
ticles.
Relative
Particle Charge Mass in amu Mass in kg
charge
Electron -1.602 x 10-19 -1 0.000542 amu 9.1 x 10-31 kg
Proton +1.602 x 10-19 +1 1.00727 amu 1.672 x 10-27 kg
Neutron 0 0 1.00867 amu 1.674 x 10-27 kg
Atomic number (Z):-The number of protons or the number of electrons in an atom is called atomic
number. It is represented by 'Z'.
Moseley discovered a simple relation between the frequencies of the characteristic X-rays of an
element and its atomic number.
v = a(Z-b)
= frequency of X-rays
Z = atomic number
a,b are constants which are characteristic of elements
Mass number(A):- The total number of protons and neutrons in an atom is called mass number. It is
denoted by 'A'.
A = no. of protons + no. of neutrons
A = Z + no. of neutrons
no. of neutrons = A - Z
Isotope:- Isotopes are the atoms of an element with same atomic number but differ in their mass numbers
i.e., The isotopes of an element have same number of protons but differ in the number of neutrons.
eg., Hydrogen has three isotopes - Hydrogen(1H1), Deuterium (1H2) and Tritium (1H3). They have same
number of protons (one) but the numbers of neutrons are 1,2 and 3 respectively.
Isobars :- The atoms of different elements with same mass number but different atomic numbers are called
Isobars.
Eg., 6C14, 7N14
Atomic structure 3
Atomic weight:- The atomic weight of an element is the average weight of all the isotopes of that element.
Note:- Atomic number is a whole number but Atomic weight may be a fractional number.
ATOMIC MODELS
J.J.Thomsons model:
According to this model, an atom has a spherical shape 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.
Experiment:
A narrow beam of - particles is passed through a thin gold foil which is surrounded by circular
screen made up of fluorescent zinc sulphide. Whenever - particles strike the screen, a tiny flash of
light was produced at that point.
Gold foil
Photographic plate
Observations:
1) Most of the - particles pass through the foil undeflected.
2) A small fraction of the - particles were deflected by small angles.
3) A very few - particles bounced back i.e. were deflected by 180o.
Conclusions:
1. Most of the space in the atom is empty.
2. The positive charge in the atom is concentrated in the small dense portion called the nucleus.
3. Electrons revolve around the nucleus in circular paths called orbits. It resembles the solar
system.
4. Electrons and the nucleus are held together by electrostatic forces of attraction.
Drawbacks:
1) Rutherfords model could not explain the stability of atom. According to electromagnetic theory,
the charged particle under acceleration should continuously emit radiation. Hence the electron moving in
the orbits must lose energy and fall into the nucleus. But this is not happening.
2) This model could not explain the electronic structure and energy of electrons.
3) It could not explain the atomic spectra.
Atomic structure 4
NATURE OF LIGHT
Light is considered as an electromagnetic radiation. An electromagnetic radiation consists of two
components i.e., Electric component and Magnetic component which are perpendicular to each other as
well as to the direction of path of radiation. The electromagnetic radiations are produced by the vibrations
of a charged particle.
wavelength
E amplitude of electric field
M amplitude of magnetic field
The properties of light can be explained by considering it as either wave or particle as follows.
Frequency: The number of vibrations done by a particle in unit time is called frequency. It is denoted by
'.
'
Units: cycles per second = Hertzs = sec-1.
Velocity: Velocity is defined as the distance covered by the wave in unit time. It is denoted by 'c'.
Velocity of light = c = 3.0 x 108 m.sec-1 = 3.0 x 1010 cm.sec-1
Note: For all types of electromagnetic radiations, velocity is a constant value.
The relation between velocity, wavelength and frequency can be given by following equation.
velocity = frequency x wavelength
c
Wave number: The number of waves spread in a length of one centimeter is called wave number. It is
denoted by
1
units: cm , m-1
-1
Amplitude: The distance from the midline to the peak or the trough is called amplitude of the wave. It is
usually denoted by 'A' (a variable).
Amplitude is a measure of the intensity or brightness of light radiation.
Problems
1) The wave length of a radiation emitted by a sodium lamp is 300 nm. Find its frequency.
2) The frequency of an electromagnetic radiation is 300 Hz. Calculate its wave length.
3) The wave number of a radiation is 9000 cm-1. Calculate its frequency.
4) Calculate the wave number of the yellow light of wave length 600 m emitted from sodium lamp.
Atomic structure 5
classical theory
7000 K
intensity
5000 K
wavelength
Where
h = planck's constant
= 6.625 x 10-34 J.sec
= 6.625 x10-27 erg.sec
= frequency of radiation
Atomic structure 6
4. The total energy of radiation is quantized i.e., the total energy is an integral multiple of h . It can only
have the values of 1 h or 2 h or 3 h . It cannot be the fractional multiple of h .
5. Energy is emitted and absorbed in the form of quanta but propagated in the form of waves.
Photoelectric Effect:- The ejection of electrons from the surface of a metal, when the metal is exposed to
light of certain minimum frequency, is called photoelectric effect.
The frequency of light should be equal or greater than a certain minimum value characteristic of the
metal. This is called threshold frequency.
Photoelectric effect cannot be explained by considering the light as wave.
Einstein explained photoelectric effect by applying quantum theory as follows,
1. All electromagnetic radiations consists of small discrete energy packets called photons. These photons
are associated with definite amount of energy given by the equation E=h .
2. Energy is emitted, absorbed as well as propagated in the form of photons only.
3. The electron is ejected from the metal, when a photon of sufficient energy strikes the electron.
When a photon strikes the electron, some part of the energy of photon is used to free the electron
from the attractive forces in the metal and the remaining part is converted into kinetic energy.
h = W + K.E
where
W = energy required to overcome the attractions
K.E = kinetic energy of the electron
Problems
1) Calculate the energy of one photon of radiation whose frequency is 3x1012 Hz.
2) The energy of a electro magnetic radiation is 6.625x10-19 J Calculate The Wavelength of radiation.
SPECTRA
When electromagnetic radiation is passed through a prism or grating it is splitted and forms a collec-
tion of lines representing different wavelengths. This is called spectrum.
Spectra can be divided into two types viz., emission and absorption spectra as given below.
3)These are formed when atoms or molecules are de-These are formed when atoms or molecules are
excited from higher energy level to lower energy excited from lower energy level to higher energy
level. levels.
Spectra can also be divided into line and band spectra as given below.
The wave numbers of spectral lines in each series can be calculated using Rydberg's equation as follows.
1 1
RH Z 2 2 - 2
n1 n2
where
n1and n2 are the principal quantum numbers of orbits corresponding to electronic transition.
RH = Rydberg's constant = 1,09,677 cm-1
Z = atomic number
n=7
n=6
n=5
Pfund
n=4
Brackette
n=3
Paschen
n=2
Balmer
n=1
Lyman
Note: Every element has its own characteristic line spectrum. There is regularity in the line spectrum of each
element. Hydrogen has the simplest line spectrum among all the elements. The line spectra become com-
Atomic structure 8
plex with increase in atomic number of the element.
Problems
1) An electronic transition from n=3 to n=1 shell takes place in a hydrogen atom. Find the wave number
and the wave length of radiation emitted. [Given R=1,09,677 cm-1]
n=3
n=2
n=1
Nucleus
Radius of Orbit
In hydrogen atom, there is one proton in the nucleus, and an electron revolving around the nucleus in
a circular orbit of radius 'r'. Let
the charge on proton = +e
the charge on electron = -e.
Centrifugal force
-e
+e
The attraction between the nucleus and electron acts centripetally towards the nucleus. As per
Coulomb's law,
e 2
force of attraction =
r2
There is also centrifugal force acting away from the nucleus due to the revolving of electron in the
orbit.
mv 2
centrifugal force =
r
where
m = mass of electron,
v = velocity of electron
During the orbiting of electron in a stationary orbit, these two forces must be equal.
e 2 mv 2
i.e., 2 =
r r
e2
or mv 2 --------- 1
r
According to Bohr's theory, Angular momentum of electron in an orbit is given by
nh
mvr
2
nh
or v
2 mr
n2h2
or v2
4 2 m 2 r 2
By substituting the value of v2 in equation-1
Atomic structure 10
e2 mn 2 h 2
2 2 2
r 4 m r
n2h2
or r ------------- 2
4 2 me 2
By substituting the values of
planck's constant = h = 6.625 x 10-27erg.sec
mass of electron = m = 9.1 x 10-28 g
charge on electron = e = 4.802 x 10-10 e.s.u
radius of nth orbit = r = 0.529 x 10-8 x n2 cm
Energy of Electron
The total energy of electron is equal to the sum of Kinetic and Potential energies.
i.e., Total Energy (T.E) = Kinetic Energy (K.E) + Potential Energy (P.E)
1 1 e2 e2
where K.E = mv 2 (since mv 2 from equation 1)
2 2 r r
e2
and P.E =
r
e2 e2
Hence T .E
2r r
e2
T .E
2r
Upon substituting the value of 'r' from equation-2
2 2 me 4
T .E 2 2
nh
By substituting the values of constants, the energy of electron (En) in the nth orbit can be written as
21.7 x10-12
En erg per atom
n2
21.7 x10-19
Joule per atom
n2
21.7 x10-22
kJ per atom
n2
2 2 me 4 1
E2 . 2
h2 n2
2 2 me 4 1 2 2 me 4 1
And E2 E1 . 2 . 2
h2 n2 h2 n1
2 2 me 4 1 1
Therefore E2 E1 2 2 (2)
h2 n1 n2
According to Bohrs postulates,
E2 E1 h
But c
Therefore E2 E1 hc
2 2 me4 1 1
Hence 2 2 2 hc
h n1 n2
1 2 2 me 4 1 1
or 2 2 (3)
ch3 n1 n2
This equation is similar to Rydbergs equation
1 1 1
RH 2 2
n1 n2
2 2 me 4
Where RH is equal to and its value can be determined by substituting the following values.
ch 3
m=9.1 x 10-28 g, e = 4.8 x 10-10 e.s.u.
= 3.14, c = 3 x 1010 cm, h = 6.626 x 10-27 erg. sec
2 2me4
RH = 3
1,09,681cm 1
ch
Above value is almost equal to Rydbergs constant (RH = 1,09,677 cm-1). The frequencies of spectral
lines in hydrogen atomic spectrum can also be determined by using Bohrs theory.
Demerits (defects)
1. Bohr's atomic model is a flat model. But atoms are spherical.
2. This theory could not explain the spectra of atoms containing multi-electrons.
3. It was shown later on that the each spectral line in hydrogen atomic spectrum was actually closely
spaced group of fine lines. These fine lines were revealed when the spectrum was taken on high resolution
spectrometer in later years. Bohr could not explain this fine spectrum.
Atomic structure 12
4. Splitting of spectral lines when the atoms are placed in strong magnetic field is called Zeeman effect.
Splitting of spectral lines when the atoms are placed in strong electric field is called Stark effect.
Bohr could not account for these effects.
5. According to Heisenberg's uncertainty principle, it is not possible to calculate the velocity and position of
an electron accurately and simultaneously. But Bohr calculated them. This is a contradiction.
6. According to De Broglie's wave concept, electron has wave nature. But Bohr's theory considered
electron as a particle.
QUANTUM NUMBERS
Quantum numbers are the numbers used to describe the position and energy of an electron in an
atom. There are four types of quantum numbers.
Problems
1) What is the shape of orbital if the quantum numbers for the electron in it are n = 3, l = 2, m = -1, and
s = +1/2
2) Which of the following set of quantum numbers is not possible?
a) n = 3, l = 2, m = -2, s = +1/2
b) n = 2, l = 2, m = -1, s = +1/2
c) n = 4, l = 3, m = 0, s = +1/2
d) n = 3, l = 1, m = -2, s = +1/2
3) How many electrons in an atom may have the quantum numbers, n = 3 and ms= -1/2 ?
4) How many sub-shells, orbitals and electrons are present in n = 3 main shell?
hc
mc 2
or
h h
(or)
mc p
where
p = momentum of a photon
de Broglie proposed that above equation is applicable to every particle in motion and above equation
can be written as
h h
v
m p
The wavelengths of macro bodies like cricket ball or stones are very small as their masses are large
and hence can be ignored. But for micro particles like electrons, the wavelengths are considerable.
To satisfy this condition, the circumference(2 r) of the orbit must be equal to the integral multiple of
the wavelength( ) of the electron wave.
i.e., n 2 r
Atomic structure 15
2 r
or where 'n' is an integer
n
But according to de Broglie's theory
h
mv
Hence
2 r h
n mv
nh
or mvr
2
This is Bohr's equation. According to Bohr's theory, the angular momentum (mvr) of electron revolv-
h
ing in a stationary orbit is an integral multiple of i.e., angular momentum is quantized.
2
But when the 'n' is not an integer, there is destructive interference and the wave will go out of phase.
This results in loss of energy by the electron wave.
Problems
8) What will be the wavelength of a ball of mass 0.1 Kg moving with a velocity of 10 m/sec.
9) The mass of an electron is 9x10-31 kg and its velocity is 930 m/sec.Calculate its wave length.
10) Calculate the momentum of particle whose de Broglie wavelength is 2A0.
h
or x.v ( p = mv )
4 m
Atomic structure 16
Explanation
Case-1
When the position is calculated accurately, x = 0
then p becomes infinity
i.e., it is not possible to calculate the momentum accurately
Case-2
When the momentum is calculated accurately, p = 0
then x becomes infinity
i.e., it is not possible to calculate the position accurately.
Problems
11) Calculate the uncertainty in the position if the uncertainty in its velocity is 5x105 m/sec for an electron.
12) Calculate the uncertainty in the velocity if the uncertainties in its position is 1A0 for an electron.
13) The uncertainties in the position and velocity of a particle are respectively 1x10-12m and 3x10-24 m/sec.
Calculate the mass of the particle.
When Schrodingers wave equation is solved for hydrogen atom, the solutions give possible energy
levels and corresponding values for the electrons. But the accepted solutions to wave functions, which
are called eigen wave functions, are obtained by applying following boundary conditions.
Boundary conditions
1) must be continuous.
2) must be finite.
3) must be single valued at any point.
4) The probability of finding the electron over the space from + to - must be equal to one.
Atomic structure 17
Important features of quantum mechanical model of atom
1) The energy of an electrons in an atom is quantized.
2) The quantized energy levels of electrons are derived from the accepted solutions of Schrodingers wave
equation by considering electron as a wave.
3. All the information about electron in an atom is contained in its orbital wave function .
4. The path of the electron can never be determined accurately. Therefore we find only the probability of
the electron at different points in space around an atom.
5. The probability of finding an electron at a point within an atom is proportional to the square of the orbital
wave function ( 2 ) at that point. 2 is known as probability density and is always positive.
It is possible to predict the region around the nucleus in this region 2 has maximum values. Which is
called atomic orbital, from the 2 values.
Radial Probability Function (D-function):- The function which denotes the probability of finding an
electron in small volume at a radial distance from the nucleus, without any reference to its direction, is
known as radial probability function or D-function.
D 4 r 2 dr. 2
Nodal Plane:- The plane where the probability of finding the electron is zero ( 2 = 0) is known as nodal
plane.
The nodal plane passes through the nucleus and hence is also known as angular node.
The number of nodal planes for a given orbital = l (azimuthal quantum number)
The number of nodal planes for different orbitals are as follows,
s 0 0
p 1 1
d 2 2
f 3 3
Nodal region:- The region around the nucleus where the probability of finding the electron is zero
( 2 = 0) is known as nodal region.
The nodal region does not pass through the nucleus and hence known as radial node.
The number of nodal regions for a given orbital = n - l - 1
For example, the number of nodal regions
for 1s orbital = 1-0-1 = 0
for 2s orbital = 2-0-1 = 1
for 2p orbital = 2-1-1 = 0
Note:-The total of no. of nodal planes and regions for a given orbital = n - l
Radial Probability Distribution curves:- The graphs plotted between the D-function and the radial
Atomic structure 18
distance from the nucleus are known as radial probability distribution curves. These curves give an idea
about the variation of electron density with radial distance around the nucleus for a given orbital.
s-orbital
s-orbitals are spherical in shape with spherical symmetry.
There are no nodal planes for s-orbitals.
The nodal regions for s-orbitals are given as follows
orbital no. of nodal regions
1s 0
2s 1
3s 2
The radial probability curves and shapes of 1s and 2s orbitals are given as follows.
radial distance
Radial probability distribution curve and shape of 1s orbital
radial node
radial distance
Radial probability distribution curve and shape of 2s orbital
p-orbitals
The p-orbitals are double dumbbell in shape.
Each p-orbital contains a nodal plane.
The shapes and orientations of p-orbitals in a given sub level along with the nodal planes are shown as
follows.
The lobes of d-orbitals in t2g group are oriented in between the axes by making 450 of angle with
them. There are three t2g orbitals i.e., dxy, dxzand dyz.
Where as the lobes of d-orbitals in eg group are oriented along the axes. There are two such eg
orbitals i.e., d x 2 y2 and d z 2 .
In case of d z 2 orbital, there are only two lobes oriented along the z axis and there is a concentric ring
called torus along the xy axes.
x-axis x-axis
z-axis
y-axis y-axis
dxy d x2 y2 d z2
nlx method
'n' is principal quantum number
'l' is azimuthal quantum number, indicated by letters s,p,d,f....
'x' is the number of electrons in the orbital
For example, the electronic configuration of 'He' atom can be represented as 1s2.
Here, 'l' is principal quantum number, 's' represents azimuthal quantum number, l = 0 and the super-
script 2 represents the number of electrons present.
Box method
In this method, the orbitals are represented by boxes and the electrons are denoted by upward and
downward arrows in the boxes.
For example, the electronic configuration of 'He' can be represented as follows.
1s2
Principles and rules: The following principles and rules are used in writing the electronic configurations.
Atomic structure 20
Pauli's Exclusion Principle: No two electrons in an atom can have same set of quantum numbers.
For example, the electronic configuration of 'He' is 1s2
The set of quantum numbers of two electrons in 'He' atom are
For first electron, n = 1, l = 0, m = 0, s = +1/2
For second electron, n = 1, l = 0, m = 0, s = -1/2
Aufbau Rules
The electrons in an atom are arranged according to aufbau rules. According to these rules, the differ-
entiating electron in an atom enters into the orbital with lowest energy. The relative energy of an orbital can
be decided from following rules.
1. The orbital with least (n + l) value possesses lowest energy.
For example, the (n + l) values of 1s and 2s orbitals are
for 1s, n + l = 1 + 0 = 1
for 2s, n + l = 2 + 0 = 2
Hence 1s orbital has lower energy than 2s, as it has low n + l value, and the electron will first enter into
1s orbital.
2. If two are more orbitals possess same (n + l) value, the orbital with lower 'n' value has low energy.
For example, the (n + l) values of 2p and 3s orbitals are same
for 2p, n + l = 2 + 1 = 3
for 3s, n + l = 3 + 0 = 3
But 2p orbital with lower 'n' value (=2) possesses lower energy and hence the electron enters first into
this orbital.
Hund's Rule of Maximum Multiplicity: No pairing of electrons occur until all the degenerate orbitals in
an atom are filled with one electron each.
For example, the electronic configuration of carbon is 1s2 2s2 2px1 2py1
In above case, the differentiating electron is entering into the 2py orbital instead of 2px because both 2px and
2py orbitals are degenerate orbitals. Hence no pairing occured.
Cr (Z =24) has [Ar] 3d5 4s1 configuration instead of [Ar] 3d4 4s2 as the half filled d-sub level is more
stable.
Cu (Z =29) has [Ar] 3d10 4s1 configuration instead of [Ar] 3d9 4s2 as the full filled d-sub level is more
stable.
Problems
1) Arrange the electrons, for which the quantum numbers are given below, in their increasing order of
energy.
a) n = 3, l = 1, m = -1, s = +1/2
b) n = 4, l = 0, m = 0, s = -1/2
c) n = 3, l = 2, m = -2, s = -1/2
d) n = 5, l = 3, m = +2, s = +1/2
Prepared by Aneesh Damodaran
KEY
1) 1 2) 2 3) 2 4) 1 5) 2 6) 3
CHEMICAL KINETICS
Rates of reaction
Change in concentration of any of the reactants or products in unit time.
Change in conc. of any reactant or product
Rate of reaction =
Time interval
Expression of average rate of reaction
For a reaction A + B C + D
A B C D
The rate of reaction =
t t t t
For the reaction xA + yB mC + nD
To rationalize the rate of reaction each expression is divided by number of molecules of that substance in equation.
A B C D
So rate of reaction =
xt yt mt nt
Unit of rate of reaction moles L1 S1 or moles L1 min1 or atm S1 or atm min1.
But O is not the actual reactant, so its concentration is taken in terms of O2 from step I.
Applying law of chemical equilibrium to step-I
K= 2
O O
O3
So [O] = K
O3
O2
Substituting the value of [O] in eq. (i)
Rate of reaction 3
O O3
O2
Rate of reaction = K [O3]2 [O2]-1
Step II A + B2 AB + B (slow)
Applying law of mass action to slow step
Rate of reaction [A] [B2](i)
As A is not the reactant, so its concentration is taken in terms of A2 from step-I.
Applying law of chemical equilibrium to step-I
A2
K=
A2
Or [A] = K [ A2 ] (ii)
Applying the value of [A] from eq (ii) in eq (i)
Rate of reaction A2 B2
Order of reaction
Rate of reaction = K [C]a [B]b
So order of reaction = a + b
Molicularity of a reaction:
Units of rate constant or Specific reaction rate for different order reactions.
For a reaction of nth order
2
dx
Rate, = K [conc.]n.
dt
Or K =
dx
1
1 conc. = 1
dt conc. conc. time time conc.n1
n n
Relation between half life period & initial conc. of reactants for nth order reaction.
1
t1/2
[ R ] 0n 1
where [R]0 = initial conc. of reactant and n = order of reaction.
Amount of a substance left after nth half life periods for a 1 st order reaction.
initial amount
Amount of reactant left = , where n = number of half-lives.
2n
3
CH3COOC2H5 + H2O H
CH3COOH + C2H5OH
2.303 V V0
K= log
t V Vt
(5) Inversion of canesugar
C12H22O11 + H2O C6H12O6 + C6H12O6
H
4
Ea Ea
2.303 log K = 2.303logA - or log K = log A -
RT 2.303RT
If the values of rate constants at temp T 1 and T2 are K1 and K2.
K Ea T2 T1
log 2 =
K1 2.303R T1 T2
This equation is equation of straight line so if we plot log verses 1/T we get a
straight line.
Ea
The slope of line =
2.303R
(c) 105mm (d) 17.5 min. and Ea =2.0x 10- kJmol-1 . When T
2. If in the fermentation of sugar in an enzymatic (a) A = 2.0x 102 kJmol-1
solution that is 0.12 M, the concentration of the (b) A = l.2x 103 mol-1 Ls-1
sugar is reduced to 0.06 M in 10 h and to 0.03 M in (c) A = 1.2x 103 mol-1 L-1s-1
20 h. What is the order of the reaction? (d) A = 2.4x 103 kJmol-1 s-1
(a) 1 (b) 2 (c) 3 (d) 0 8. The rate of a chemical reaction generally increases
3. For the reaction rapidly even for small temperature increase because
2NO+Br2 > 2NOBr, of rapid increase in the
the following mechanism has been given (a) collision frequency |
NO Br2 NOBr2
fast (b) fraction of molecules with energies in excess of
the activation energy'
NO NOBr2 2 NOBr
slow
(c) activation energy
Hence, rate law is: (d) average kinetic energy of molecules
(a) k NO2 Br2 (b) k NO Br2 9. Rate constant of a reaction is 0.0693 min-1. Starting
with 10 mole, rate of the reaction after 10 min is:
(c) k NOBr NO (d) k NOBr2 2 (a) 0.693 mol min-1
4. At a certain temperature, the first-order rate (b) 0.06932 mol min-1
constant k1 is found to be smaller than the second- (c) 0.0693 5 mol min-1
order rate constant k2 . If the Ea (l) of the first order (d) 0.0693 (5)2molmin-1
reaction is greater than Ea (2) of the second-order
reaction, then as temperature is raised: 10. The reaction H2(g)+2ICl(g)> I2(g)+ 2HCl(g)
(a) k2 will increase faster than k1 has a second-order rate law, rate = k[H2 ] [ICI].
(b) k1 will increase faster than k2 but will always Hence, rate-determining step is:
remain less than k2 (a) H2(g)+ICl(g)> HCl(g)+ HI(g)
(c) k1 will increase faster than k2 and become equal (b) HI(g)+ICl(g)> HCl(g)+ I2(g)
to k2| (c) both (a) and (b)
(d) k1 will increase faster than k2 and become (d) none of these
greater than k2 11. For the reaction:
5. A > B, H =-10kJmol-1, Ea=50 kJ mol-1 then A2 +2B > 2AB
Ea of B > A will be:
(a) 40 kJ mol-1 (b) 50 kJ mol-1 A 2 B dA 2
-1
(c) -50 kJ mol (d) 60 kJ mol-1 dt
6. Rate of formation of S03 in the following reaction 0.1 M 0.2 M 1x 10-2 Ms-1
5
0.2 M 0.2 M 2 x l0-2 Ms-1 NO2 + CO NO + CO2
0.2 M 0.4M 8 x l0-2 Ms-1 Step I NO2 + NO2 k NO3 +NO
1 , slow
(a) 1, 2 (b) 2, 1 dx
Hence, for the given reaction is:
(c) 1, 1 (d) 2, 2 dt
12. A > B kA =1015 e-2000/T (a) k1[NO2 ]2 k2[NO3] [CO]
C > D kC =1014 e-1000/T (b) k1[NO2 ]2 + k2[NO3] [CO]
Temperature T/K at which (kA = kC ) is; (c) k1[NO2]2
(a) 1000K (b) 2000 K (d) k1[NO2] + k2[CO]
2000 1000 18. For the following reaction
(c) K (d) K
2.303 2.303 A B + l0 kcaI
increase in temperature:
(a) increases rate of the forward as well as
backward reaction
13. (b) increases rate of the forward reaction but
Half-life is independent of concentration of A. decreases that of backward reaction
After 10 minutes volume of N2 gas is 10 L and after (c) decreases rate of the forward reaction but
complete reaction 50 L. Hence rate constant is : increases that of the backward reaction
2.303 2.303 (d) decreases rate of forward as well as backward
(a) log 5 min 1 (b) log 1.25 min 1
10 10 reaction.
19. for the second order reaction:
2A Product
2.303 2.303
(c) log 2 min 1 (d) log 4 min 1 the initial concentration of A is 0.1 M and rate
10 10 constant is 2x 10-3 dm3 mol-1 s-1. The half-life
14. 2N2O5 > 4NO2 + O2 period of the reaction is:
N 2 O5 NO2
If k1 N 2 O5 , k 2 N 2 O5 , (a) 5 sec (b) 50 sec
t t (c) 500 sec (d) 5000 sec
O2 20. The activation energy of a reaction is zero. At 280
k 3 N 2 O5 K rate constant is 1.6 10-6 s -1. The rate constant at
t
300 K is
then: (a) zero (b) 3.2 l0-6s-l
(a) k1 = k2 = k3 (b) 2 k1 = k2 = 4k3 -5 -1
(c) l.6 l0 s (d) 1.6 l0-6s-1
(c) 2k1 = 4k2 = k3 (d) none of these
21. For the reaction
2H2 (g) + 2NO (g) N2 (g) + 2H2O (g)
15. The rate law for the dimerisation of NO2 into N2O4 rate law is: rate = k[NO]2 [H2O2 ], Mechanism is
is given by:
d NO2
k NO2 2 Step I: 2NO N2O2
dt Step II: N2O2 + H2 > N2O + H2O
Step III: N2O + H2 N2 + H2O
Which of the following changes will change the
Rate law is true if:
value of the specific rate constant k7?
(a) step I is the slow step
(a) doubling the total pressure
(b) step II is the slow step
(b) decreasing the pressure
(c) step III is the slow step
(c) changing the volume of the flask
(d) steps I and II are slow steps
(d) changing the temperature
22. Rate constant k of a reaction is dependent on
16. When temperature of a reaction is changed from T1
temperature:
and T2 half-life is found to decrease. Thus:
K = Ae-Ea/RT
(a) T1 > T2 and reaction is endothermic
k has the least value at:
(b) T2 > T1 and reaction is exothermic
(a) high T and high Ea
(c) T1 > T2 and reaction is exothermic
(b) high T and small Ea
(d) T2 > T1 and reaction can be exothermic or
(c) low T and low Ea
endothermic
(d) low T and high Ea
17. Following reaction takes place by mechanism
6
23. Which of the these factors affect the value of the
specific rate constant for the reaction?
2A (g) B (g)
(a) temperature only
(b) temperature and concentration
(c) pressure only
(d) pressure and concentration
24. The radioisotope N-13, which has a half-life of 10
minutes, is used to image organs in the body. If the
injected sample has an activity of 40 Ci
The enthalpy change and activation energy for the
(microcurie), what is the activity after 30 minutes? reverse) reaction C + D > A + B are
(a) 10 Ci (b) 20 Ci respectively:
(c) 5 Ci (d) 2.5 Ci (a) x, y (b) x, x + y
25. A particular reaction increases by a factor of 2 (c) y, x + y (d) y, y + z
when the temperature is increased from 27C to 30. The rate of a first order reaction is 1.5x 10 2 mol l1
37C. Hence activation energy of the reaction is min1 at 0.5 M conc. of reactants. the half life of
(a) 12.9 kcal (b) 0.14 kcal the reaction
(c) 1.1 kcal (d) none is correct (a) 23.1 min (b) 8.73 min
26. What function of [X], plotted against time, will give (c) 7.53 min (d) 0.383 min
a 31. In a first order reaction conc. of reactants decreases
straight line for a second-order reaction? from 0.8 M to 0.4 M in 15 minutes . Time taken
(a) [X] (b) [X]2 for the conc. to change from 0.1 M to 0.025 M is
1 (a) 30 min (b) 60 min
(c) log[X] (d) (c) 7.5 min (d) 15 min
[X} 32. The rate equation for the reaction 2A + B
27. Two reaction with different activation energies C is found to be rate = k[A][B]. The correct
have the same rate at room temperature. Which statement in relation to this reaction is that the
statement correctly describes the rates of these two (a)the unit of k be s1
reactions at the same higher temperature? (b) value of k is independent of initial conc of A
(a) the reaction with the greater activation energy and B
will be faster (c)rate of formation of C is twice the rate of
(b) the reaction will the smaller activation energy disappearance of A
will be faster 1
(d) t 2 is constant
(c) the two reactions will have the same rate
33. The temperature dependence of rate constant (k) of
(d) temperature range is also required a chemical reaction is written in terms of
Arrhenius equation, k = A. e-Ea / RT . Activation
28. The rates of many chemical reactions double for a
energy (Ea)of the reaction can he calculated by
ten degree rise in temperature. Which of these
ploting :
factors does not contribute to this change in the rate
with increaser temperature? 1
(a) log k vs (b) k vs T
(a) the average kinetic energy of the reactant log T
species 1 1
(b) the number of collisions in a given time (c) k vs (d) log k vs
log T T
(c) the number of very eneretic spector
(d) the activation energy
34. The rate of reaction is equal to the rate constant .
29. Given the following diagram for the reaction
the order of reaction is
A+B > C+D
(a) 3 (b) 0 (c) 1 (d) 2
35. The activation energy for a simple chemical
reaction A B Ea in forward direction. The
activation energy for reverse reaction is
(a) Always double of Ea
(b) is negative of Ea
(c) is always less than Ea
(d) Can be less that or more than Ea
7
36. The reaction A B follows first order kinetics. the NO (g) + Br2(g) NOBr2(g)
time taken for 0.8 mole of A to produce 0.6 moles
of B is one hour. What is the time taken for the NOBr2 (g) + NO (g) 2NOBr(g)
conversion of 0.9 mole of A to produce 0.675 If second step is rate determining step , the order of
mole of B ? reaction with respect to NO (g) is
(a) 2 hr (b) 1 hr (a) 3 (b) 2 (c) 1 (d) 0
(c) 0.5 hr (d) 0.25 hr 43. For the reaction 2A + B 3C + D Which of the
37. For the reaction system following doesnot express the reaction rate
2NO(g) + O2(g) 2NO2 (g) ,the volume is
d ( D) dA
suddenly reduced to half its value by increasing the (a) (b)
pressure . If the reaction is of first order w.r.t. O 2 dt 2dt
and 2nd order w.r.t. NO. the rate of reaction will dC d[B]
(c) (d)
(a) diminishes to of its value 3dt dt
(b) diminishes to 1/8 of its value 44. A reaction involving two different reactants can
(c) increases to 8 times of its initial value never be
(d) increase to 4 times of its initial value (a) 2nd order (b) Bimolecular
38. In respect of equation k = A. e-Ea / RT in chemical (c) Unimolecular (d) first order
kinetics which of the following statement is 45. Consider the reaction
correct? N2 (g) + 3H2(g) 2NH3 (g)
(a) k is equilibrium constant d[ NH 3 ] d[H 2 ]
(b) A is adsorption factor the rection between and
(c) Ea energy of activation dt dt
(d) R is Rydbergs constant d[ NH 3 ] 3 d[H 2 ]
39. Select the law that corresponds to data shown ofr (a) + =
dt 2 dt
the following reaction
d[ NH 3 ] d[H 2 ]
A + B C, (b) =
Exp. [A]0 [B]0 Initial rate dt dt
1 0.012 0.035 0.10 d[ NH 3 ] 1 d[H 2 ]
2 0.024 0.070 0.80 (c) =
3 0.024 0.035 0.10
dt 3 dt
4 0.012 0.070 0.80 d[ NH 3 ] 2 d[H 2 ]
(d) =
The rate law corresponds lo the above data is: dt 3 dt
(a) rate = k[B]3 (b) rate = k[B]4 46. Rate of reaction between two reactants decreases by
3
(c) rate = k[A][B] (d) rate = [A]2[B]2 a factor of 4 if conc. of B is doubled . the order of
40. A reaction was found to be of 2nd order with reaction with respect to reactant B is :-
respect to the conc. of carbon monoxide. If conc. (a) 2 (b) 1 (c) 1 (d) 2
of carnon monoxide is doubled with everything 47. For a first order reaction
else kept the same , the rate of reaction will A B the reaction rate at a conc of 0.01 m is
(a) decrease by a factor of 4 found to be 2.0 x 105 moll1s1 . the half life
(b) double period of reaction is :-
(a) 300 s (b) 30 s
(c) remains unchanged (c) 220 s (d) 347 s
(d) Triple
41. Rate of reaction can be expressed by Arrhenius
equation k = A. e-Ea / RT . In the reaction e 48. Rate constant of a chemical reaction has unit L
represents mol1 s1 order of reaction is :
(a) total energy of reacting molecules at a temp T. (a) 0 (b) 1 (c) 2 (d) 3
(b)fraction of molecule with energy greater than 49. For a reaction xA yP [A] = 2.2 mM
activation energy of reactants . rate was found to be 2.4 mMs1 on reducing the
(c) Energy above which all the colliding molecules conc of A to half . the rate changes to 0.6 m M s 1
will react . Order of reaction is :-
(d) Energy below which colliding molecules will (a) 1.5 (b) 2.0
not react (c) 2.5 (d) 3.0
42. The following mechanism has been proposed for 50. Consider a reaction aG + bH Products
the of NO with Br2 to form NOBr
8
When concentration of both reactants G and H is
doubled, the rate increases by 8 tomes. However
when the conc. of G is doubled keeping the conc. of
H fixed . the rate is doubled. Over all order of
reaction is
(a) 0 (b) 1 (c) 2 (d) 3
9
Chemical Bonding 1
CHEMICAL BONDING
Chemical Bond : The attraction between two atoms or ions is called a chemical bond. Chemical bond
is formed either due to sharing or transfer of electrons between atoms.
A chemical bond is formed by an atom inorder to get stability by lowering its potential energy.
Atoms (noble gases) with octet configuration in outer shell are stable. Hence every atom tries to get
octet configuration either by losing or gaining or sharing electrons.
1) Ionic bond :The electrostatic force of attraction between two oppositely charged ions is called ionic
bond.
* An ionic bond is formed due to transfer of electrons from one atom to another.
* The atom which loses electrons will form a cation and the atom which gains electrons will form an
anion. These oppositely charged ions come closer to each other due to electrostatic force of attraction
and thus form an ionic bond.
* An ionic bond is formed between two atoms when their electronegativity difference is greater
than 1.7.
* Usually an ionic bond is formed between a metal and a nonmetal.
E.g., NaCl, LiF, MgCl2 etc.,
2) Covalent Bond : The attraction between two atoms formed due to the sharing of electron pair(s) is
called covalent bond.
* It is formed when electronegativity difference between two atoms is less than 1.7.
* Usually two nonmetals form a covalent bond.
E.g., H2, F2, HCl, H2O etc.,
3) Metallic bond: It is the attraction between metal atoms in a metallic crystal. It is formed between
electropositive metal atoms.
Electrovalency: The number of valence electrons either lost or gained by an atom during the ionic
Chemical Bonding 2
bond formation is called electrovalency.
2) F + 1e -
F-
z=9
He 2s 2 2p5 He 2s2 2p6
3) Li F
LiF
2) 2 x ( Cl + 1e -
Cl- )
z=17
Ne 3s 2 3p5 Ne 3s2 3p6
3) Mg 2+ 2Cl
MgCl2
2) 3 x( F + 1e -
F- )
z=9
2s 2 2p5
He He 2s2 2p6
3) Al3+ + 3F -
AlF3
2)
O + 2e
O 2
z 8
1s 2 2s 2 2p 4 1s 2 2s 2 2p 6
3) 2Na + + O 2-
Na 2O
4) Octet electronic configuration : The cations with 8 electrons in the outer shell (octet configura-
tion) are highly stable and hence formed readily. Whereas cations with 18 electrons in outer shell
(Pseudo inert gas configuration) are comparatively less stable and hence are not formed easily.
Chemical Bonding 4
FAJAN'S RULES
These rules are used to predict the nature of the bond formed by atoms based on their polarizing
power and polarizability.
1) Greater the size of cation, greater is the ionic nature.
E.g. In IA group elements ionic nature increases with increase in the size of cation from Li+ - Cs+.
i.e, Increasing order of ionic nature : Li+ < Na+ < K+ < Rb+ < Cs+
less more
ionic ionic
2) Greater the size of anion, greater is the covalent nature.
E.g. Among the halides of the calcium the covalent nature increases from CaF2 to CaI2 with in-
crease in the size of anion.
Increasing order of covalent nature : CaF2 < CaCl2 < CaI2
3) Greater the charge on cation, greater is the covalent nature.
E.g. In case of Na+, Mg+2 and Al+3 , the covalent nature of cations increases with increase in the
charge as follows.
Na+ < Mg+2 < Al+3
i.e., The compounds of Al3+ are more covalent.
4) The cations with octet configuration in the valence shell exhibit more ionic nature whereas cation with
pseudo inert gas configuration exhibit more covalent nature in their compounds.
E.g. CaCl2 is more ionic [ Ca2+ has octet configuration]
Whereas CuCl, AgCl, ZnCl2 are more covalent. [ Cu+, Ag+, Zn2+ have Psuedo inert gas configu-
ration].
BORN-HABER CYCLE : The principle involved in Born-Haber cylcle is Hess's law of constant
heat summation which can be stated as follows.
Hess's Law : The total energy change in a reaction remains same whether the reaction takes
place in one step or in several steps.
Direct step : NaCl crystals are formed by combining Na metal with chlorine gas in one step. The
energy evolved during this reaction is called heat of formation
Hf .
1
Na s Cl2 g
NaCls ; H f = -410.5 kJ/mol
2
Indirect method : The formation of NaCl crystals may occur in several steps as follows.
i) Sublimation of sodium : Solid sodium is first converted gaseous sodium by absorbing 108.7 kJ/
mole of energy. This is called sublimation energy H s or + S .
Na s
Na g ; Hs = + S = +108.7 kJ/mol
ii) Ionization of sodium : Gaseous sodium atoms are ionized by absorbing 492.82 kJ / mole of
energy. It is called ionization energy H i or + I .
Na +g + 1e-
Na g ; H i = + I = + 492.82 kJ/mol
iii) Dissociation of chlorine molecule : One mole of gaseous chlorine molecules are dissociated into
two moles of chlorine atoms by absorbing energy equal to 239.1 kJ/mole. This is called dissociation
energy H d or D .
Cl 2g
2Cl g ; H d = +D = 239.1 kJ/mol
But the energy required to get one mole of chlorine atoms is equal to
+D 139.2
= = +119.55 kJ/mol
2 2
1 1 +D
Cl 2 g
Cl g ; H d = = +119.55 kJ/mol
2 2 2
Chloride ion formation : The gaseous chlorine atoms are added with electrons to get gaseous chlo-
ride ions. The energy liberated in this process is called electron affinity (H e or E) .
Cl 2 g + e-
Cl-g ; H e = - E = -361.6 kJ/mol
Formation of NaCl Crystals : The gaseous Na+ and Cl- ions unite to form one mole of NaCl crys-
tals. The energy liberated during this process is called lattice energy H u or -U . This value can be
calculated by using Hess's law as follows.
Na +g + Cl- g
NaCl s ; H u = -U
Chemical Bonding 6
According to Hess's law the energy change in the steps involved in indirect method.
1
i.e. H f H s H f H d H e H u
2
(or)
D
H f S I E U
2
H d
i.e., U H f H S H i H e
2
U 410.5 108.7 492.82 119.55 (361.6) 769.97 kJ .mol 1
1 Hf
Na(s) + /2Cl2(g) NaCl(s)
H d
Hs= +S
2
Na(g) Cl(g)
-U
Hi= +I He= +E
+ -
Na (g) + Cl (g)
Born-Haber cycle
AZ .Z Be 2
U N o No n
r r
attractive repulsive
force force
Where A = Madelung constant (which depends on geometry of the crystal)
AZ .Z e 2 r n 1
B = Repulsion coefficient
n
(This depends on the structure and approximately proportional to the number of nearest
neighbours)
No = Avogadro's number
Z+ & Z- = Charges on the positive and negative ions respectively.
e = Charge of an electron.
r = Distance between the oppositely charged ions
n = Born exponent (a constant which is usually taken as 9)
AZ .Z e 2 N o 1
U 1 n
ro
CRYSTAL STRUCTURES
Unit cell : The smallest part of the crystal which produces entire crystal upon repeating three dimen-
sionally is called unit cell.
Coordination number : Maximum number of nearest oppositely charged ions surrounding any par-
ticular ion in ionic crystal is called the coordination number of that ion.
r
Limiting radius ratio ( ): The ratio of radius of positive ion to that of negative ion is called limiting
r
radius ratio.
The coordination number and crystal structure of an ionic crystal can be predicted from the limiting
radius ratio value.
r
Limiting radius ratio ( Coordination
r ) number
Structure
Cl- Cl-
Cs+ 1
Number of Cl- ions = 8 x =1
8
Cl- Cl- Number of Cs+ ions = 1
Cl- Cl-
Formula weight: Ionic compounds contain only ions and there are no molecules in it. Hence their
molar mass is expressed as formula weight instead of molecular weight.
Examples
1) H2 molecule
* Electronic configuration of hydrogen is 1s1.
* Each hydrogen atom contribute one electron to form a pair of electrons, which is shared in between
the two atoms. Thus a covalent bond is formed.
* Thus in H2 molecule, each hydrogen atom gets its nearest inert gas - Helium's configuration.
* Covalency of hydrogen is 1.
H. .H .
+ H H
or
H H
2) Cl2 molecule
2 2 6 2 5
* The electronic configuration of Cl is 1s 2s sp 3s 3p .
7
* In order to get the nearest inert gas- Argon's configuration, each chlorine contributes one electron for
the bond formation.
* Covalency of chlorine is 1.
.. .. .. ..
. + . Cl .
..
..
..
..
Cl
.. .. . . Cl
Cl ..
or
.. ..
..
. . Cl
..
Cl ..
.. ..
H X . Cl
..
..
.. or H Cl
..
4) Methane (CH4)
2 2 2
* The electronic configuration of carbon is 1s 2s 2p .
4
1
* The electronic configuration of hydrogen is 1s .
* The carbon atom forms four covalent bonds by contributing four of its valence electrons for the bond
formation. It forms 4 bonds with four hydrogen atoms. Thus it gets octet configuration.
* Covalency of carbon is 4.
H H
.x
.
H x C. . x H or H C H
x
H H
5) Ammonia (NH3) :
* The electronic configuration of nitrogen is 1s2 2s 2 2p3 .
5
1
* The electronic configuration of hydrogen is 1s ,
* In the formation of Ammonia molecule, nitrogen atom contributes 3 of its electrons to form three
bond pairs which are shared with hydrogen atoms. Thus nitrogen forms 3 single bonds with three
hydrogen atoms and gets the configuration of Neon.
* Covalency of nitrogen is 3.
.. ..
H x .N. x H or H N H
.
x
H H
5) H2O molecule
* Electronic configuration of oxygen is 1s2 2s 2 2p 4 .
6
1
* Electronic configuration of Hydrogen is 1s .
* In the formation of water molecule, oxygen atom contributes two electrons to form two bond pairs
which are shared with hydrogen atoms. Thus two bonds are formed by oxygen atom to get the configu-
ration of neon. There are also two lone pairs on oxygen atom.
* Covalency of oxygen is 2.
.. ..
H .O.
x x H or H O H
.. ..
6) Oxygen molecule (O2)
2 2 4
* The electronic configuration of oxygen is 1s 2s 2p .
6
* In the formation of oxygen molecule, each oxygen atom contributes 2 electrons to form 2 bond pairs.
Chemical Bonding 11
Thus a double bond is formed between oxygen atoms. Thus each oxygen atom gets Neon's configura
tion.
.. .. .. ..
.. .
O .O
.. or O
.. O
..
7) Nitrogen molecule (N2)
* The Electronic configuration of nitrogen is 1s2 2s 2 2p3 .
5
* In the formation of Nitrogen molecule, each nitrogen atom contributes 3 electrons to form 3 bond
pairs. Thus a triple bond between nitrogen atoms is formed. Each nitrogen atom gets Neon's configura-
tion.
or
...
...
.. N N N N
..
..
..
8) Carbon dioxide (CO2)
2 2 2
* Electronic configuration of carbon is 1s 2s 2p .
4
2 2 4
* Electronic configuration of oxygen is 1s 2s 2p .
6
* In carbon dioxide, carbon atom forms double bond with each oxygen. Thus both oxygen and carbon
..
..
.. .. .. ..
or O C O
..
O
..
O C
..
..
..
.. .. .. ..
Cl . . Cl or Cl Be Cl
..
..
Be
..
..
x x
.. .. .. ..
BCl3 (Boron trichloride)
2 2 1
* Electronic configuration of Boron is 1s 2s 2p .
3
2 2 6 2 5
* Electronic configuration of chlorine is 1s 2s sp 3s 3p .
7
* In BCl3 molecule, boron contributes 3 of its valence electrons and forms three bond pairs with
chlorine atoms. There are only six electrons in the valence shell of boron atom in BCl3. But still it is
stable. It is an electron deficient compound. It is also the violation of octet rule.
* Covalency of boron is 3.
.. ..
Cl
..
..
Cl
..
..
.
.. x .. .. ..
. . Cl or Cl
..
B Cl B
..
Cl
..
..
x x
.. .. .. ..
.. ..
Cl
..
..
.. Cl
..
..
..
. .. ..
Cl . Cl
..
x
.
..
Cl
..
.. x Cl
..
x .. or ..
P .. P
x x
. .. .. ..
.. .
Cl Cl
..
..
Cl Cl
..
..
.. .. .. ..
F F
F * F F F
* * or
S
* *
S
F * F F F
F F
Conclusion: Lewi's electronic theory could not explain the shapes and bond angles of molecules. It
also could not explain why some molecules are stable eventhough they violate octet rule.
_ _
x x
O O
.. .. x
C xx O C O
H .S. x x H or H S H x or
.. .. Ox O
x _
Hydrogen sulphide _
Carbonate ion
3) SiCl4 4) HCOOH
.. ..
Cl O O
..
..
Cl ..
..
..
.. .x .. ..
x.
Si . x Cl Cl Si Cl H C OR H C
..
Cl
..
or
..
..
.. .x .. ................
Cl O H O H
..
..
Cl
..
..
..
..
Silicon tetrachloride Formic acid
5) NF3 6) HNO3
.. xx .. xx + +
. N . F F N F O N O H O N O H
..
F x
..
x
.. . .. or
x
` O O
F F - -
Nitrogen trifluoride Nitric acid
7) CO 8) O3
Chemical Bonding 14
:
:
::: : : O :O
: :
O:
: :
C O or C O or :
: :
:
:
:
O O
: O
:
:
Carbon monoxide molecule Ozone molecule
-1 +
8) NO2 9) NH4
+ +
- H
- H
O N O or O N O ..
H x .N. x H or H N H
.
x
Nitrite ion
H H
Examples:
1) PH3 molecule
Lewi's dot structure:
.. ..
H x .P. x H H P H
.
x or
H H
1 6
Formal charge on 'P' = N A - N LP - N BP 5 2 0
2 2
1 2
N BP 1 0 0
Formal charge on 'H' = N A - N LP -
2 2
2) N2O molecule: It exists in following two resonance forms.
For the following first resonance form:
- + - +
:
:
:
:N N O
: or : N : :N : :O :
(1 ) (2 ) (1 ) (2 )
1 4
Formal charge on first nitrogen 'N(1) ' = N A - N LP - N BP 5 4 1
2 2
1 8
Formal charge on second nitrogen 'N(2) ' = N A - N LP - N BP 5 0 1
2 2
Chemical Bonding 15
1 4
Formal charge on 'O' = N A - N LP - N BP 6 4 0
2 2
:
:N N O
:
or :N : ::
N
:
O
:
(1 ) (2)
:
(1 ) (2 )
1 6
Formal charge on first nitrogen 'N (1)' = N A - N LP - N BP 5 2 0
2 2
1 8
Formal charge on second nitrogen 'N (2) ' = N A - N LP - N BP 5 0 1
2 2
1 2
Formal charge on 'O' = N A - N LP - N BP 6 6 1
2 2
Hence the formal charges vary with structural environment.
THE GEOMETRY OF MOLECULES CONTAINING ONLY BOND PAIRS IN THE CENTRAL ATOM
Number of
Formula Molecular geometry Examples
bond pairs
2 AB2 Linear B A B BeCl2, BeF2
B
Trigonal
3 AB3 BF3, BCl3
planar A
B B
4 AB4 Tetrahedral A
B
CH4, CCl4
B
B
B
Trigonal
5 AB5 B A PCl5, PF5
bipyramidal
B
B
B B
6 AB6 Octahedral A SF6
B B
B
Chemical Bonding 17
Explanatory examples:
1) BeCl2: The valence shell of central atom, beryllium contains only two bond pairs. Hence it is linear
in shape with 180o bond angle.
180o
Cl Be Cl
Linear molecule
2) BF3: The valence shell of the central atom - boron contains only three bond pairs. Hence it's shape
is trigonal planar with 120o bond angle.
Cl
Cl
120o Cl
3) CH4: The valence shell of the central atom - carbon contains only four bond pairs. Hence it is
tetrahadral in shape with 109o28' bond angle.
The bond pairs are arranged tetrahedral symmetry so as to minimize repulsions. If the bond pairs
Chemical Bonding 18
are arranged in square plane, the angles between them will be only 90o and the repulsions will be more
than in case of tetrahedral arrangement. Hence tetrahedral structure is more favorable than square
planar structure.
109o28'
C
H
H
H
Tetrahedral structure of methane
4) NH3: There are three bond pairs and one lone pair in the central atom, nitrogen. The bond angle is
decreased from 109o28' to 107o48' due to repulsion caused by lone pair.
N
H H
107o48'
H
5) H2O: There are two bond pairs and two lone pairs in the central atom, oxygen. The bond angle is
decreased from 109o28' to 104o28' due to repulsion caused by two lone pairs.
O
H
o
104 28'
H
Angular shape of water molecule
Note: The 's' orbitals can only form bonds, whereas the p, d & f orbitals can form both and
bonds.
Examples
1) H2 molecule
* Electronic configuration of hydrogen is 1s1.
* In the formation of hydrogen molecule, two half filled 1s orbitals of hydrogen atoms overlap along the
internuclear axis and thus form a s-s bond.
H + H H H
Cl + Cl Cl Cl
3) HCl molecule
* Electronic configuration of hydrogen is 1s1.
* Electronic configuration of Cl is 1s2 2s2 2p6 3s2 3px2 3py2 3pz1
* The half filled 1s orbital of hydrogen overlap with the half filled 3pz atomic orbital of chlorine atom
along the internuclear axis to form a s p bond.
H + Cl H Cl
4) O2 molecule
* Electronic configuration of O is 1s2 2s2 2px2 2py1 2pz1
* The half filled 2px orbitals of two oxygen atoms overlap along the internuclear axis and form
p-p bond. The remaining half filled 2pz orbitals overlap laterally to form a p-p bond. Thus a double
bond (one and one ) is formed between two oxygen atoms.
p p bond
p p bond
O + O O O
5) N2 molecule
* Electronic configuration of N is1s2 2s2 2px1 2py1 2pz1
* p-pbond is formed between two nitrogen atoms due to overlapping of half filled 2px atomic
Chemical Bonding 20
orbitals axially. The remaining half filled 2py and 2pz orbitals form two p-p bonds due to lateral
overlapping. Thus a triple bond (one and two )is formed between two nitrogen atoms.
p p
p p
p p
N N
Valence bond theory could not explain the structures and bond angles of molecules with more than
three atoms. E.g. It could not explain the structures and bond angles of H2O, NH3 etc.,
Inorder to explain the structures and bond angles of molecules, Linus Pauling modified the valence
bond theory by proposing hybridization concept.
HYBRIDIZATION
The intermixing of atomic orbitals of almost equal energies of an atom to give an equal
number of identical and degenerate hybrid orbitals is called hybridization.
Characteristics of hybridization :
1) Pure atomic orbitals of same atom should participate in the hybridization.
2) The energies of atomic orbitals participating in hybridization must be nearly same.
3) The number of hybrid orbitals formed is equal to the number of atomic orbitals participating in the
hybridization.
4) The hybrid orbitals formed are identical in shape and degenerate.
5) These hybrid orbitals are symmetrically arranged around the nucleus so as to minimize the repulsion
between them and thus get maximum stability.
6) The filling of electrons into hybrid orbitals follows Pauli's exclusion principle and Hund's rule of
maximum multiplicity.
7) A hybrid orbital may be empty or half-filled or full filled.
8) Usually hybrid orbitals form sigma bonds only.
TYPES OF HYBRIDIZATION
1) 'sp' hybridization
* Intermixing of one 's' and one 'p' orbitals of almost equal energy to give two identical and degen-
erate hybrid orbitals is called 'sp' hybridization.
* These sp-hybrid orbitals are arranged linearly at 180o of angle.
* They possess 50% 's' and 50% 'p' character.
Examples:
1) BeCl2
* Electronic configuration of 'Be' in ground state is 1s2 2s2
Chemical Bonding 21
sp
hybridization
(2 bonds)
* In the excited state, beryllium undergoes 'sp' hybridization by using a 2s and a 2p orbitals. Thus two
half filled 'sp' hybrid orbitals are formed. These are arranged linearly.
* These half filled sp-orbitals form two sp p bonds with two 'Cl' atoms.
* Thus BeCl2 is linear in shape with the bond angle of 180o.
sp p sp p
Cl Be Cl
BeCl2
Hybridization - sp
180o Shape - linear
Cl Be Cl Bond angle - 180o
Linear molecule
2) Acetylene (C2H2)
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3
sp
hybridization
(2 bonds) pure
orbitals
form
2 bonds
* Each carbon atom undergoes 'sp' hybridization by using one 2s and one 2p orbitals in the excited
state. Thus two half filled 'sp' orbitals are formed. These are arranged linearly.
The two carbon atoms form one sp sp bond with each other by using sp-orbitals. They also form
two p p bonds by overlapping half filled pure p-orbitals ( 2py and 2pz). Thus a triple bond (1 & 2 )
is formed between carbon atoms.
Each carbon also forms a sp s bond with the hydrogen atom.
Thus acetylene molecule is linear with 180o bond angle.
Chemical Bonding 22
p p
p p
sp s sp sp
H C C H
C2 H 2 - Acetylene
Hybridization - sp
Shape - linear
180o
Bond angle - 180o
H C C H
sp2 hybridization :
* Intermixing of one 's' and two 'p' orbitals of almost equal energy to give three identical and degener-
ate hybrid orbitals is known as sp2 hybridization.
* The three sp2 hybrid orbitals are oriented in trigonal planar symmetry at angles of 1200 to each other.
* sp2 hybrid orbitals have 33.3% 's' character and 66.6% 'p' character.
+ +
Examples:
1) BCl3
* Electronic configuration of 'B' in ground state is 1s2 2s2 2p1
* Electronic configuration of 'B' in excited state is 1s2 2s12px12py1
sp2
hybridization
(3 bonds)
In the excited state, Boron undergoes sp2 hybridization by using a 2s and two 2p orbitals. Thus
three half filled sp2 hybrid orbitals which are oriented in trigonal planar symmetry are obtained.
Boron forms three sp2 -p bonds by using sp2 hybrid orbitals with three chlorine atoms. Each
chlorine atom uses it's half filled p-orbital for the bond formation.
Thus the shape of BCl3 is trigonal planar with Cl-B-Cl bond angles equal to 120o.
Chemical Bonding 23
Cl
Cl
B
B
Cl
120o Cl
Cl Cl
2) Ethylene (C2H4).
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3
sp2
hybridization
(3 bonds)
pure
orbital
forms
one bond
* In the excited state, each carbon in ethylene undergoes sp2 hybridization by mixing 2s and two 2p
orbitals. Thus three half filled sp2 hybrid orbitals are formed in trigonal planar symmetry. There is also a
half filled 2pz orbital on each carbon.
* The carbon atoms form a sp2 -sp 2 bond with each other by using hybrid orbitals.
The remaining pure atomic orbitals overlap laterally and form a p-p bond.
* There is a double bond (1 & 1 ) between two carbon atoms.
* Each carbon atom also forms two sp 2 -s bonds with two hydrogen atoms.
* Thus ethylene molecule is planar with H-C-H & C-C-H bond angles equal to 120o.
* All the atoms are present in one plane.
Chemical Bonding 24
p p
H H
sp 2 sp 2 H H C2 H 2 - Ethylene
o
C C 120
C C sp 2 s Hybridization - sp 2
H H
Shape - planar
H H
Bond angle - 120o
Planar structure of ethylene molecule
sp3 hybridization:-
* Intermixing of one 's' and three 'p' orbitals of almost equal energy to give four identical and degener-
ate hybrid orbitals is called sp3 hybridization.
* Thus formed four sp3 hybrid orbitals are oriented in tetrahedral symmetry with 109028' angle with
each other.
* In these orbital the s character is 25% and p character is 75%.
+ + +
Examples:
Methane (CH4)
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3
sp3
hybridization
(4 bonds)
* In the excited state, the carbon atom undergoes sp3 hybridization by mixing one 2s and three 2p
orbitals. Thus four half filled sp3 hybrid orbitals are formed in tetrahedral symmetry.
* Each of these form sp3 - s bond with hydrogen atom. Thus carbon forms four bonds with four
hydrogen atoms.
* Methane molecule is tetrahedral in shape with 109028' bond angle.
Chemical Bonding 25
H H
sp3 s
109o28'
CH 4 - Methane
C C
H H Hybridization - sp3
H H Shape - Tetrahedral
H H Bond angle - 109o 28 '
Tetrahedral structure of methane
2) Ethane (C2H6)
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3
sp3
hybridization
(4 bonds)
* In the excited state, each carbon atom undergoes sp3 hybridization by using one 2s and three 2p
orbitals. Thus four half filled sp3 hybrid orbitals are formed in tetrahedral symmetry around each car-
bon.
* The two carbon atoms form a sp3 - sp3 bond with each other by overlapping sp3 hybrid orbitals
axially.
Each carbon atom also forms three sp3 -s bonds with hydrogen atoms.
* Thus there is tetrahedral symmetry around each carbon with HCH and HCC bond angles equal
to 1090 28' .
H H
sp3 sp 3 H 109o28' H
sp3 s 109o28'
C C C
C H H H
H
H H
H H
Structure of Ethane molecule
C 2 H 6 - Ethane
Hybridization - sp3
Bond angle - 109o 28 '
3) Ammonia (NH3)
* Electronic configuration of nitrogen is 1s2 2s2 2px1 2py1 2pz1
Chemical Bonding 26
sp3
hybridization
(3 bonds)
* Nitrogen undergoes sp3 hybridization by using one 2s and three 2p orbitals. Thus formed four sp3
orbitals are arranged in tetrahedral symmetry. Among them three are half filled and one is full filled.
* Nitrogen forms 3 sp3 -s bonds with three hydrogen atoms by using three half filled hybrid orbitals.
The bond angle is decreased from 1090 28'to 1070 48' due to the repulsion caused by lone pair.
Thus ammonia acquires trigonal pyramidal shape.
N sp3 s N NH 3 - Ammonia
H H H Hybridization - sp3
H 107o48' Shape - Trigonal pyramidal
H
H Bond angle - 107o 48'
Trigonal pyramidal structure of ammonia molecule
sp3
hybridization
(2 bonds)
* Oxygen atom undergoes sp3 hybridization by mixing a 2s and three 2p orbitals and forms four sp3
hybrid orbitals arranged in tetrahedra symmetry. Among thenm two are half filled and the remaining two
are completely filled.
Oxygen forms two sp3 -s bonds with hydrogen atoms by using half filled hybrid orbitals.
The bond angle is decreased from 1099 28' to 1040 28' due to repulsions caused by two lone
pairs. Thus water molecule gets angular shape (V shape).
sp 3 s O water - H 2 O
O
H Hybridization - sp3
H o
104 28' shape - Angular
H
H Bond angle - 104o 28'
Angular shape of water molecule
sp3d Hybridization
* The intermixing of one 's', three 'p' and one 'd' orbitals to give five identical and degenerate hybrid
Chemical Bonding 27
3
orbitals is called sp d hybridization.
* Thus formed sp3d orbitals are arranged in trigonal bipyramidal symmetry. Among them, three are
arranged in trigonal plane and the remaining two orbitals are present perpendicularly above and below
the trigonal plane.
Examples:
1) PCl5 (phosphorus pentachloride)
* E.configuration of 'P' in ground state is 1s2 2s2 2p6 3s2 3p3
* E.configuration of 'P' in excited state is 1s2 2s2 2p6 3s1 3p3 3d1
3s 3p 3d
sp3d
hybridization
(5 bonds)
* In the excited state, phosphorus undergoes sp3d hybridization by using a 3s, three 3p and one 3d
orbitals which are arranged in trigonal bipyramidal symmetry.
* By using these half filled sp3d orbitals, phosphorous forms five sp3d - p bonds with chlorine atoms.
Each chlorine atom makes use of half filled 3pz orbital for the bond formation.
* The shape of PCl5 molecule is trigonal bipyramidal with 1200 and 900 of Cl - P - Cl bond angles.
Cl
Cl PCl5 (Phosphorous pentachloride)
90o
Cl P 120o Hybridization - sp3d
Shape - Trigonal bipyramidal
Cl Bond angles - 120o & 90o
Cl
sp3d2 hybridization
* Intermixing of one 's', three 'p' and two 'd' orbitals of almost same energy by giving six identical and
degenerate hybrid orbitals is called sp3d2 hybridization.
* These six sp3d2 orbitals are arranged in octahedral symmetry by making 900 angles to each other.
Chemical Bonding 28
Examples:
1) Sulfur hexa flouride (SF6)
* E.configuration of 'S' in ground state is 1s2 2s2 2p6 3s2 3p4
* E.configuration of 'S' in 2nd excited state is 1s2 2s2 2p6 3s1 3p3 3d2
3s 3p 3d
sp3d2
hybridization
(6 bonds)
* In the second excited state, sulfur under goes sp3d2 hyrbidization by mixing a 3s, three 3p and two 3d
orbitals. Thus formed six half filled sp3d2 hybrid orbitals are arranged in octahedral symmetry.
Sulfur atom forms six sp3d 2 - p bonds with 6 fluorine atoms by using these sp3d2 orbitals. Each
flourine uses is half-filled 2pz orbitals for the bond formation.
SF6 is octahedral in shape with F -S- F bond angles equal to 90o.
F
F F SF6 - Sulfur hexafluoride
Hybridization - sp3d 2
S
shape - Octahedral
F F Bond angle - 90o
F
* The atom which donates the electron pair is called as donor, whereas the atom which accepts that
pair is called as acceptor.
* Both donor and acceptor will share the electron pair.
* Coordinate bond is also known as dative bond.
* It is represented by an arrow pointing towards the acceptor.
Examples:
1) Formation of Ammonium ion (NH4+)
* Ammonium ion is formed when ammonia reacts with hydrogen ion. In the formation of ammonium
ion, the sp3 orbital with a lone pair on nitrogen overlaps with the empty 1s orbital of hydrogen ion to
form a coordinate covalent bond.
* Ammonium ion contains 4 bond pairs in the valence shell of nitrogen atom and hence it is tetrahedral
in shape with 109o28' bond angles. The hybridization of nitrogen will remain sp3 only.
+
H
109o28'
N
H
H
H
Note: In NH4Cl, there are three covalent bonds, one coordinate covalent bond and an ionic bond.
Ionic bond is present between NH4+ and Cl- ions.
* The hybridization in boron is changed from sp2 to sp3 during the formation of coordinate covalent
bond. Hence the geometry around boron in the complex formed will be tetrahedral.
Chemical Bonding 30
H H
H H
N B
H H
3) Formation of Hydronium ion
* The sp3 orbital containing lone pair on oxygen in water molecule overlaps with the empty 1s orbital on
hydrogen ion to form a coordinate covalent bond.
:
:
H2O: + H+ [H2O H]+ or H3O+
Donor Acceptor Hydronium ion
2) Formation of [AlCl4]-
* The chloride ion (Cl-) donates a lone pair of electrons to the empty 'p' orbital of aluminium in AlCl3.
Thus a coordinate bond is formed. During the bond formation, the 'p' orbital containing the lone pair on
chloride ion overlaps the empty 'p' orbital of aluminium.
_
Cl
Cl _ :
Cl
:
Cl Al + : Cl : Al Cl :
:
:
Cl Cl
* The hybridization in aluminium is changed from sp2 to sp3 during the formation of coordinate covalent
bond. Hence the geometry around aluminium in AlCl4- will be tetrahedral.
More examples:
SO2 and SO3 also considered to have coordinate covalent bonds according to octet rule as shown
below.
O
:
S S
O O O O
Bonding orbitals
10) The bond order of the molecule can be calculated by using the following formula.
number of bonding electrons - number of antibonding electrons
Bond order (B.O) =
2
Chemical Bonding 32
+ + + + +
+ +
s s s
bonding orbital
Chemical Bonding 33
+ - + - + -
+
s s
s *
anti bonding
orbital
+ + +
+ + - + -
+
-
p s p
s
bonding orbital
- -
+ + - + - - + -
p s p *
s
bonding orbital
+
- + + + - - ++ - -
+
-
p p p
bonding orbital
- + + - + - +- + - + - +
p p p*
anti bonding
orbital
-Molecular orbitals
-Molecular orbitals are formed due to sidewise overlapping of atomic orbitals on either sides of
the internuclear axis of bonded atoms. The electron density is concentrated on either side of the axis.
Bonding orbital is designated as , whereas antibonding orbital is designated as * .
Illustrations:
Chemical Bonding 34
Combination of two 'p' orbitals above and below the internuclear axis
+
+
+
+
+
- -
- - - -
p
bonding orbital
- -
+
+
-
+
+
-
+
- -
+
+
p*
anti bonding
orbital
But for elements heavier than nitrogen i.e., from oxygen onwards, the order will be as follows:
Chemical Bonding 35
2 p y *2 p y
1s *1s 2 s *2 s 2 px *2 px
2 p z *2 p z
1) MOED of H2
*1s
Energy H H
1s 1s
1s
H2
2) MOED of N2
Chemical Bonding 36
*2 p x
*2 p y *2 pz
2 px
2 p y 2 pz
*2 s
Energy
2s 2s
2s
*1s
1s 1s
1s
N atom N2 molecule N atom
10 - 4
* Bond order (B.O) = 3
2
* Hence there is a triple bond in N2 molecule.
2) MOED of O2
Chemical Bonding 37
*2 p x
*2 p y *2 pz
2 p y 2 pz
2 px
*2 s
Energy
2s 2s
2s
*1s
1s 1s
1s
O atom O2 molecule O atom
10 - 6
* Bond order (B.O) = 2
2
* Hence there is a double bond in O2 molecule.
* It is paramagnetic due to presence of two unpaired electrons.
HYDROGEN BONDING
The electrostatic force of attraction between partially positively charged hydrogen in a polar
molecule and an electronegative atom is called hydrogen bond.
It is represented by dotted line.
CHEMICAL EQUILIBRIUM
Reversible reaction : A reaction which proceeds through forward and backward directions is called
reversible reaction. In a reversible reaction, reactants are converted into products and vice versa.
Eg.,
Irreversible reaction: A reaction that occur only in direction is called irreversible reaction i.e., only
reactants are converted to products and conversion of products to reactants is not possible.
Eg.,
Chemical equilibrium: The state at which the rate of forward reaction becomes equal to the rate of
backward reaction.
state of equilibrium
i) For dilute solutions, the molar concentrations are taken as active masses.
ii) For gases at low pressures, the partial pressures are taken as active masses.
iii) The active mass of a solid is taken as unity.
where [A], [B], [C] and [D] are the equilibrium concentrations of A,B,C and D respectively.
Kf and Kb are the rate constants of forward and backward reactions respectively.
But at equilibrium,
rate of forward reaction (vf) = rate of backward reaction (vb)
i.e., K f [A]a [B]b K b [C]c [D]d
CHEMICAL EQUILIBRIUM 3
K f [C]c [D]d
or =
K b [A]a [B]b
[C]c [D]d
or Kc =
[A]a [B]b
Kf
where K c = and is known as equilibrium constant.
Kb
product of concentrations of products at equilibrium
In general, Kc =
product of concentrations of reactants at equilibrium
Units of K c (mole.L-1 ) n
Where n = (c+d)-(a+b) = no. of moles of products - no. of moles of reactants
or K P =K c [RT]n
where n=(c+d)-(a+b) = no. of moles of gaseous products - no.of moles of gaseous reactants
If n=0 then K p =K c
and if n>0 then K p >K c
and if n<0 then K p <K c
Illustrations
[HI]2
Kc =
[H 2 ] [I2 ]
PHI2
Kp =
PH . PI 2
2
K P =K c [RT]n
CHEMICAL EQUILIBRIUM 4
n=(2)-(1+1)=0
Kp = Kc
[PCl3 ][Cl 2 ]
Kc =
[PCl5 ]
PPCl3 .PCl2
Kp =
PPCl 5
n = (1+1)-(1) = +1
Kp > Kc
[NH 3 ]2
Kc =
[N 2 ][H 2 ]3
PNH3 2
Kp =
PN2 .PH2 3
K P =K c [RT]n
n = (2) - (1+3) = -2
K p <K c
[N 2 ][H 2 ]3
Kc =
[NH3 ]2
PN2 .PH2 3
Kp =
PNH3 2
n = (1+3) - (2) = +1
Kp > Kc
K c =[CO 2 ]
K p =PCO2
n=(1)-(0)=+1
Kp > Kc
Problems :
1) The molar concentrations of A, B & C at equilibrium for the reaction 2A + B 3C are 1,2
& 3 moles / litre respectively calculate Kc
CHEMICAL EQUILIBRIUM 5
2) Kc value of the following reaction is 0.4
H 2(g) + I2(g) 2HI(g)
if the equilibrium concentrations of H2 & HI are 0.2 and 0.8 moles/litre respectively. What is the
concentration of I2 at equilibrium.
3) The Kc of a reversible reaction is 5. if the rate constant of forward reaction is 2.5 what is the rate
constant for backward reaction.
4) Give the relations between Kc and Kp for the following reactions .
(i) CH 3COOC 2 H 5(aq) + NaOH (aq)
CH 3COONa (aq) + C 2 H 5OH (aq)
(ii) NH 4 HS(s)
NH 3(g) + H 2S(g)
5) For the following reversible reaction Kc is 0.5 L2/m2
N 2(g) +3H 2(g) 2NH 3 (g)
Calculate the Kp value at 270C.
Le Chatelier's principle
When external stress is applied on a system at equilibrium, the system shifts the position of
equilibrium so as to nullify the effect of stress.
Stress can be applied by changing the concentration or pressure or temperature. The effects of
these factors are discussed below.
Effect of concentration:
1) The forward reaction is favored when the concentration of reactants is increased.
2) The backward reaction is favored when the concentration of products is increased.
Effect of pressure:
1) When pressure is increased, the system tries to decrease the pressure by favoring the reaction in
which the number of moles of gaseous substances are decreased.
2) When pressure is decreased, the system tries to increase the pressure by favoring the reaction in
which the number of moles of gaseous substances are increased.
Effect of temperature:
1) When the temperature is increased, the endothermic reaction is favored.
2) When the temperature is decreased, the exothermic reaction is favored.
Industrial applications
Effect of temperature: Forward reaction is exothermic. Hence increase in temperature favors the
dissociation of ammonia. But at low temperatures the reaction does not occur. Hence the reaction is
carried out at moderate temperatures (725 - 775 K).
To increase the rate of reaction, finely powdered iron is used as catalyst and Mo is used as promoter.
CHEMICAL EQUILIBRIUM 6
Favourable conditions:
Pressure 200 atm
Temperature 725 to 775 K
Catalyst Fe
Promoter Mo
Effect of temperature: Forward reaction is exothermic. Hence low temperatures favor the synthesis of
sulfur trioxide. But at low temperatures the reaction does not occur. Hence the reaction is carried out at
moderate temperatures (673 K).
To increase the rate of reaction, platinized asbestos or V2O5 are used as catalysts.
Favorable conditions
Pressure 10 atm
Temperature 673 K
Catalyst Pt or V2O5
CHEMICAL KINETICS
Chemical kinetics deals with
1) Study of rates of reactions
2) Factors affecting rate of reaction
3) Study of mechanisms of reactions
Rate of reaction : The rate of reaction is defined as the change in molar concentration of either
reactants or products in unit time.
change in concentration
rate r =
time interval
Let dc is the decrease in concentration of reactants in a small interval of time dt then
dc
r=- ( negative sign indicates decrease in concentration )
dt
If dx is the increase in concentration of products in a small interval of time dt then
dx
r= ( positive sign indicates increase in concentration )
dt
E.g., For a reaction, A
B
d A d B
rate r
dt dt
In general for a reaction, pP + qQ rR + sS
the relations between rates of reaction with respect to P,Q,R and S can be written as
1 d P 1 d Q 1 d R 1 d S
- =- =+ =+
p dt q dt r dt s dt
d N2 1 d H2 1 d NH 3
- -
dt 3 dt 2 dt
concentration of reactants
Time
3) Temperature : The average kinetic energy and hence the number of collisions increase with abso-
lute temperature. Hence rate of reaction increases with increase in temperature.
Usually the rate of a reaction is doubled when the temperature is increased by 10oC.
Temperature Coefficient : The ratio of rate constants of a reaction at two different temperatures
which differ by 10oC is called temperature coefficient.
k t +10o C
Temperature coefficient = 2 to3
k t oC
The relation between rate constant and temperature can be shown by Arrhenius equation.
k = A.e-Ea/RT
Where k = specific rate constant
A = Frequency factor
Ea = Activation energy
R = Universal Gas constant
T = Absolute Temperature
Multiplying by 'ln' (natural logarithm) on both sides,
Ea
ln k = ln A-
RT
Ea
or 2.303 log k = 2.303 log A-
RT
Ea
or log k = log A-
2.303 RT
When a graph is plotted by taking log k on y - axis and 1/T on x-axis, a straight line with negative slope
is obtained.
Ea E
slope = - =- a where R = 1.987 cal / K / mole
2.303 R 4.576
3
log A
Ea
slope = -
2.303 R
log k
1
T
Relation between two rate constants at two different temperatures can be given as
k2 Ea 1 1
log = -
k1 2.303R T1 T2
k2 E a T2 -T1
or log =
k1 2.303R T1T2
4) Catalyst: Catalyst is a substance which alters the rate of reaction without being consumed or without
undergoing any chemical change during the reaction.
A catalyst increases the rate of reaction by providing a new path with lower activation energy for the
reaction. In case of reversible reactions, catalyst lowers the activation energies of both forward and
backward reaction to the same extent and helps in attaining the equilibrium quickly.
without catalyst
Potential energy
in presence of catalyst
Reaction coordinate
Problems :
1) Write the relations between the rates with respect to reactants & products in the following reaction.
2N2O 2N2 + O2
Rate Equation or Rate Expression or Rate Law: Equation that describes mathematical dependance
of rate of reaction on the concentration terms of the reactants is called Rate Equation.
Order of reaction :Sum of the powers of the concentration terms in the rate equation is called order
of reaction.
For a general reaction, xA + yB + zC products.
4
x y z
if the rate expression is r = k A B C
Then the order of this reaction is equal to x + y + z
Note: Order of a reaction is to be determined experimentally. It may have positive or negative or zero
or a fractional values.
In case of simple reactions, the order of reaction and hence the rate equation can be written
according to stoichiometric equation. But the actual rate law should be written by conducting experi-
ments.
Depending on the order of reaction, chemical reactions can be divided into zero, first, second &
third order reactions as follows.
Rate constant (k): The rate of a reaction at the unit concentrations of all the reactants of the reaction is
called specific rate (or) rate constant.
rate = k when [reactants] = 1
mole / litre 1
Units of k = x n
sec mole / litre
1-n
=
mole / litre
sec
= Ln-1 .mole
- n-1
.sec-1
For 1st order reaction sec
-1
-1 -1
For zero order reaction mole .L sec
Molecularity
Elementary reactions: The chemical reactions which occur in one single step are called elementary
reactions.
But most of the reactions occur in more than one step. The sequence of elementary steps that occur
during a reaction is referred to as mechanism of that reaction.
Rate determining step: The elementary step or reaction with slowest rate is called rate determining step
or rate limiting step. The rate of overall reaction depends on this step.
Molecularity: Total number of atoms or molecules or ions taking part in an elementary reaction is called
molecularity of that elementary reaction (or step).
It is only possible to define the molecularity of an elementary step. But the molecularity of the overall
reaction which involves more than one step cannot be defined.
Molecularity is an integer. It cannot be zero or fractional. The maximum value observed is 3. It can be
deduced theoretically from the proposed mechanism
6
Differences between Order and Molecularity
Order Molecularity
1) Sum of the powers of concentration terms 1) Total number of atoms or molecules or
in rate expression is called order. ions taking part in an elementary reaction is
called molecularity
2) It may have zero or positive or negative or 2) It can only have integral values (1,2 or 3).
integer or fractional values. Its value cannot be zero or fractional.
3) It is determined experimentally 3) It is deduced theoretically from the
mechanism of the reaction.
Half life (t1/2) of a reaction :The time required for initial concentration of reactants to become half is
called half life.
0.693
or t1/2
k
a
For a first order reaction, the graph of log versus 't' should be a straight line with positive slope
a-x
and should pass through the origin
a
log
a-x
x
For a second order reaction, the graph of a a-x vs 't' must be a straight line passing through the
x OR b(a-x)
a(a-x) log
a(b-x)
t t
is inversely proportional to a
Half life t 1
2
n-1
9
1
t1
2 a n -1
where a = initial concentration
n = order
The order 'n' of a reaction can be calculated by comparing two half lives - t 1 & t 1 with initial
2 2
dc dc
log - 1 - log - 2
n dt dt
log c1 logc2
For two different initial concentrations c1 and c2, the rates are determined at any given time from c-t graph.
These are substituted in the above equation and 'n' is calculated.
concentration of reactants
concentration of reactants
c1
c2
2 8 kT
Z AB .n A .n B
where AB = Collision diameter
= reduced mass
n A & n B are number of molecules of A & B
8) The relation between specific rate (k), temperature (T) and activation energy Ea can be given as follows
k = A.e -Ea /RT
or
k = p.Z.e-Ea /RT
where p = probability factor
The concept of activation energies of both forward and backward reactions (Ea and Ea') can be
shown graphically as follows.
11
Energy barrier
ET
Ea E1a
ET
ER
H
Ep
Problems :
1) The rate constant of a first order reaction is 1.386 sec-1. What is it's half life.
2) The initial concentration of A is 0.5 moles/litre. If the concentration becomes 0.25 mole/litre in 5 sec.
What is the value of rate constant.
1) The rate of a reaction increases with time as the concentration of reactants decreases.
2) The order of a reaction is always determined experimentally.
3) The units of rate constants for the following reaction are (L / mol /sec).
2NO(g) + Cl2 (g) 2NOCl (g)
4) The half life of zero order reaction is proportional to the initial concentration.
5) The rate of consumption of hydrogen gas is thrice of formation of Ammonia in the following reaction.
N2 (g) + 3H2 (g) 2 NH3 (g)
6) In Ostwald isolation method, the reactant for which the order is going to be determined is taken in
excess when compared to the concentrations of other reactants.
7) A positive catalyst increases the activation energy of both forward and backward reactions.
8) In exothermic reaction the activation energy of forward reaction is always greater than that of back
ward reaction.
a
9) For a second order reaction, a straight line is obtained when log is plotted against time (t)
ax
10) Rate of reaction increases with increasing temperature as the threshold energy increases.
Electrochemistry 1
ELECTROCHEMISTRY
* Electrochemistry deals with
1) The processes in which electrical energy is converted to chemical energy.
2) The processes in which chemical energy is converted to electrical energy.
3) Preparation of metals and alloys using electricity.
The electrical conductors are again divided into two types as follows;
i) Metallic or electronic conductors:- The conductors which conduct the electricity through the elec-
trons.
e.g. All metals, Graphite etc...
* No chemical reaction occurs during the conduction of electricity.
* Conductivity decreases with increase in temperature due to vibrational disturbances.
ii) Electrolytes :- The substances which furnish oppositely charged ions for the conduction of electricity.
e.g :- NaCl, KCl, CH3COOH, HCl etc.......
* There is flow of ions towards the oppositely charged electrodes.
* During conduction of electricity through electrolytes, oxidation occurs at anode whereas reduction
occurs at cathode i.e., a chemical reaction occurs.
* The conductivity increases with increase in temperature as the extent of ionization increases.
Non electrolytes :- The substances which do not furnish ions for electrical conduction are called non -
electrolytes.
e.g : urea, glucose, sucrose etc. ...
Strong electrolytes : undergo complete ionization in water
e.g. NaCl, KCl, K2SO4, HCl, H2SO4,NaOH, NaNO3 etc....
Weak electrolytes : under go partial ionization in water
e.g. HF, CH3COOH, NH4OH, HCOOH etc....
Resistance and ohm's law :- According to Ohm's law, resistance (R) offered by an electrolyte in a
solution is proportional to length (l) and inversely proportional to the cross sectional area (a) of electrodes.
length (l )
Resistance (R) area (a)
l
i.e., R
a
l
or R=s.
a
Where s = specific resistance (resistivity)
Electrochemistry 2
a
s = R. l
When a = 1 cm2 and l = 1 cm
Then s=R
Specific resistance (s) : The resistance shown by a material of 1 cm length and 1 cm2 of cross sectional
area is called specific resistance (or) resistivity.
Units of 's'
a
s=R.
l
cm 2
ohm .
cm
ohm . cm. (in CGS)
or ohm . m (in SI)
Conductance ratio ( ) : The ratio of the equivalent conductance ( c ) at given concentration to that at
infinite dilution ( o ) is called conductance ratio ( )
c
o
For weak electrolytes, ' ' is called degree of ionization.
c
i.e.,
Problems:-
1) At 250C, the specific conductance of acetic acid of 0.01N concentration is 0.000163 ohm-1 cm-1. What
is c at this concentration ?
2) At 250C, the equivalent conductances of CH3COONa, HCl and NaCl at infinite dilution respectively
are 91.0, 426.16 & 126.45 ohm-1. cm2. eq-1. What is o of CH3COOH ?
3) c of acetic acid at 250C is 16.3 ohm-1 cm2 eq-1. The ionic conductances of H+ and CH3COO - are
349.83 & 40.89 ohm-1 cm2 eq-1. What is of CH3COOH ?
ELECTROLYSIS
The decomposition of chemical compound in the molten state or in solution state into it's constituent
elements under the influence of an applied E.M.F is called electrolysis.
Electrolysis is carried out in an electrolytic cell, provided with two electrodes. The electrode con-
nected to negative end of a battery is called cathode and which is connected to positive end is called
anode.
An electrolyte either in molten state or in solution state is taken into this cell and electrolyzed by
applying E.M.F. The cations are reduced at cathode and anions are oxidized at anode.
Battery
+ e-
e-
Anode + - cathode
electrolyte
Examples:
Electrolysis of molten KCl
Following reactions will occur at electrodes when molten KCl is electrolyzed using platinum elec-
trodes.
KCl K + + Cl-
molten
At cathode
K + +1e-
K Reduction
At anode
2Cl-
Cl 2 2e - oxidation
Electrochemistry 6
Complete redox reaction
2KCl
2K + Cl 2
At cathode: Ag + (aq) 1e -
Ag
At anode: 2H 2 O 4H + + O 2 + 4e -
4) Electrodes which do not participate in the electrochemical reaction are called inert or passived
electrodes. Usually platinum and graphite electrodes are used as inert electrodes.
But some electrodes may participate in the electrochemical reaction. These are said to be active
electrodes.
e.g. When aqueous solution of AgNO3 is electrolysed by using copper electrodes, silver is deposited
at cathode and dissolved at anode.
Electrochemistry 7
+ -
At cathode: Ag (aq)
1e
Ag Deposition of silver on cathode
Faraday :- The amount of charge transported during the migration of 1 mole of electrons is called
Faraday.
Faraday (F) = 1.602 x 10-19C x 6.022 x 1023
= 96,500 coulombs
Equivalent weight (E) :- The amount of substance formed at electrodes when one Faraday of electricity
is passed through the electrolyte.
Hence E=Fxe
E
or e=
F
Ect Eq
m or m
F F
Atomic weight
Where E=
Valency
Faraday's Second law :- If the same quantity of electricity is passed through different electrolytic cells
Electrochemistry 8
connected in series containing different electrolytic solutions or melts, the amounts of substances deposited
or liberated or dissolved are directly proportional to their equivalent weights.
mE
m1 E
or 1
m2 E2
Illustration :- When three electrolytic cells containing different electrolytes i.e., CuSO4 , AgNO3 and
H2SO4 in aqueous solutions are connected in series and same quantity of electricity is passed through
them, then from Faraday's second law the ratio of amounts of Cu, Ag, H2 and O2 formed at different
electrodes can be given as follows.
m Cu : m Ag : m H 2 : m O 2 = E Cu : E Ag : E H2 : E O2
mCu E
or Cu
mAg E Ag
mH2 EH2
or
mO2 EO 2
mCu E
or = Cu etc. .....
m O2 E O2
Battery
+ - + - + -
Problems :
1) A current of 10 amperes is passed through molted AlCl3 for 96.5 sec. Calculate the mass of
aluminium deposited at cathode.
2) What is the ratio of weights of Ag and Al deposited at respective cathodes when the same current
is passed for same period through aqueous AgNO3 and Al2(SO4)3 solutions.
Construction of a galvanic cell : A galvanic cell consists of two half cells called single electrodes which
are connected to each other.
Single electrode: A single electrode consists of a metal or a non metal in contact with their ions.
While representing a single electrode, the metal or non metal and its ion are written by separating with
a vertical line.
e.g: Metal electrodes
Zn2+ / Zn
Cu2+ / Cu
Electrochemistry 9
Ag+ / Ag
Note: In galvanic cell, anode is indicated by negative sign whereas cathode is indicated by positive sign.
Reactive resistance
Ammiter
e-
e- e-
Anode Cathode
Zn rod Cu rod
Zn-2 Cu+2
CuSO4 solution
ions ions
ZnSO4 solution
Porous diaphragm
Voltaic cell :
Daniel cell is modified by connecting two half cells internally by a salt bridge. One half cell contains a
zinc rod immersed in ZnSO4 solution and another half cell consist of a copper rod immersed in CuSO4
solution.
These two half cells are connected externally by a metallic wire whereas a salt bridge is used to
connect them internally.
Salt bridge is a U-shaped tube filled with Agar - Agar solution of KCl or NH4NO3. This is used to
avoid junction potential.
Following reactions occur in this cell.
In Zn half cell (anode) Zn Zn+2 + 2e- oxidation
In Cu half cell (cathode) Cu2+ + 2e- Cu Reduction
Ammeter
e- Reactive resistance
e-
e-
e-
Anode cathode
salt bridge
Electrolyte - I Electrolyte - II
Representation of galvanic cell :- According to IUPAC convention the oxidation half cell is written on
the left hand side and reduction half cell is written on the right hand side. Two vertical lines are used to
indicate the salt bridge. Negative sign is used to indicate the oxidation half cell (anode) and a positive sign
is used to indicate the reduction half cell (cathode).
e.g : Above galvanic cell can be represented as follows.
Zn / Zn2+ // Cu2+ / Cu
Where Zn / Zn2+ = Zn half cell
2+
Cu / Cu = Cu half cell
// = salt bridge
Note: 1) Oxidation occurs at anode and reduction occurs at cathode in both the cells.
2) The flow of electrons is always from anode to cathode in both the cells.
Single electrode potential (E) :- The potential difference existing at the surface of contact between
metal (or) non metal and its ionic solution is called single electrode potential.
Standard electrode potential (E0) :- The potential difference at the surface of contact between metal
(or) non metal and its ionic solution at unit concentration and at 250C is called standard electrode potential
(E0).
Single electrode potential can be written for oxidation half cell or reduction half cell. Both oxidation
electrode potential and reduction electrode potential have same magnitude but have opposite signs.
e.g : Zn / Zn2+ is oxidation half cell and its E0 value is + 0.762V.
Zn2+ / Zn is reduction half cell and its E0 value is - 0.762V.
H2 (1 Atm)
Pt rod
hole
1M HCl
Black Pt foil
EMF of galvanic cell : The potential difference between two different electrodes in the galvanic cell is
called EMF of that cell.
E Cell = E Reduction - E Oxidation
half cell half cell
E Cell = ER - EL
According to IUPAC convention, EMF of a galvanic cell is calculated by substraction of the reduc-
tion electrode potential of left hand cell from that of right hand cell.
E Cell = E Right - E Left
Electrochemical series :- The standard reduction electrode potentials of various electrodes are deter-
mined relative to that of SHE.
These electrodes are arranged in their increasing order of standard reduction potentials in a series
called as electrochemical series.
In this series, the electrodes with negative Eo values are placed above hydrogen electrode whereas
the electrodes with positive Eo values are placed below hydrogen electrode.
Problems
1) Construct a galvanic cell containing two electrodes Ag+ / Ag and Zn2+ / Zn calculate the EMF of cell.
Write the cell reactions.
Eo for Ag+ / Ag = + 0 .799 volts
Eo for Zn2+ / Zn = - 0 .762 volts
NERNST EQUATION
The electrical energy (nFE cell ) produced in a reversible galvanic cell is equal to the decrease in Gibbs
free energy ( G)
Hence G = - nFEcell
Where n = no. of electrons transferred in redox reaction
F = Faraday
E = EMF of the cell
Under standard conditions
Go = - nFEocell
Consider the following equilibrium for a redox reaction occurring in a Galvanic cell;
aA + bB
cC + dD
For above reaction, the equilibrium constant from law of mass action can be written as
c d
C D
(Kc) = a b
A B
From laws of thermodynamics, the relation between Gibbs free energy and equilibrium constant (Kc)
is given as
G = G o + RTlnK c
nFE nFE o + RTlnK c
RT
-E = -E o + ln K c
nF
RT
E Eo ln K c
nF
2.303RT
E Eo log K c
nF
c d
EE
2.303RT
o
. log
C D
a b
nF A B
2.303RT product of equilibrium conc. of products
E Eo . log
nF product of equilibrium conc. of reactants
Electrochemistry 13
This equation is also applicable to single electrodes.
Battery or cell : It is a galvanic cell which is used as source of electrical energy. These are of two types
viz., 1) Primary cells, 2) Secondary cells
1) Primary cell
It is an electrochemical cell which acts as a source of electrical energy without being previously
charged up by an electric current from an external source.
In this cell, the reaction occurs only once and it becomes dead after using over a period of time. This
cell cannot be reused again as the reaction cannot be reversed.
E.g.,
1) LACLANCHE CELL
It consists of a carbon rod placed in a porous pot containing a mixture of MnO2 and carbon powder.
It acts as cathode whereas an amalgamated zinc acts as anode. The porous pot and zinc rod are placed in
20% NH4Cl solution.
Electrochemistry 14
Following reaction occur in this cell
At cathode :
2MnO 2 2H 2O 2e
2MnO OH 2OH
MnO 2 NH 4 e
MnO OH NH3
At anode :
Zn 2 2e
Zn
Zn 2 2OH + 2MnO OH
Zn 2MnO2 2H 2 O
Some secondary reactions are
2NH 4 Cl 2OH
2NH 3 2Cl 2H 2O
- +
C
Amalgamated Zn
porous pot
Glass Jar
C+MnO 2
mixture
20% NH4Cl
solution
2) DRY CELL
It is a modified Laclanche cell. It consists of a cylindrical zinc vessel acting as anode (negative elec-
trode). It is covered with a cardboard and sealed with pitch. A carbon rod acting as cathode (positive
electrode) is introduced at the centre of Zn vessel. It is surrounded by a paste of (C+MnO2). The remain-
ing empty space is filled with NH4Cl + ZnCl2 paste. These two pastes are separated by a porous sheet.
Following reaction occur in this cell
At cathode :
2MnO 2 2H 2O 2e
2MnO OH 2OH
MnO 2 NH 4 e
MnO OH NH3
At anode :
Zn 2 2e
Zn
Zn 2 2OH + 2MnO OH
Zn 2MnO2 2H 2 O
Some secondary reactions are
2NH 4 Cl 2OH
2NH 3 2Cl 2H 2O
Carbon rod
(cathode)
MnO2+
Zinc cup carbon black
(anode) +NH4 Cl paste
SECONDARY CELL
The cell in which electrical energy from an external source is first converted to chemical energy and
then made to operate in opposite direction by removing the external source.
In this cell, the reaction can be reversed practically. It can be recharged after its discharging.
E.g., 1) Acid storage cell (lead accumulator)
2) Alkali storage cell ( Edison battery)
LEAD ACCUMULATOR
Lead accumulator is an acid storage secondary cell which can be charged and discharged for several
times.
It consists of two lead electrodes
Anode ------- made by sponge lead
Cathode ----- Lead coated with PbO2
It can be represented as
Pb H2SO4 PbO2
or
Pb 2+ + SO 2-4
PbSO 4 s
Pb 4+ + 2e
Pb 2+ reduction
Pb 2+ + SO 24
PbSO 4 s
Electrochemistry 16
- +
4OH + 4H
4H 2O
Net Reaction PbO 2 + 4H + + SO 2-4 + 2e
PbSO 4 s + 2H 2 O
FUEL CELLS
A fuel cell is a galvanic cell in which the chemical energy of fuel-oxidant system is converted
directly into electrical energy.
In fuel cells, the fuel and oxidant are supplied continuously on to the two different electrodes. The fuel
is oxidized at the anode and the oxidant is reduced at cathode. Theoretical efficiency of fuel cells is 100%.
Fuels used may be gases or liquids. E.g., H2, alkanes, carbon monoxide, Methanol, Ethanol, hydra-
zine, formaldehyde etc.,
Oxygen, air, hydrogen peroxide, nitric acid etc., are used as oxidants.
Platinum, porous PVC or PTFE (Teflon) coated with silver, nickel boride, raney nickel etc., can be
used as electrodes.
Examples
H2 - O2 Fuel cell
In this fuel cell, hydrogen and oxygen gases are continuously bubbled over porous carbon electrodes
suspended in concentrated NaOH solution. These electrodes are embedded with finely divided Pt or Pd
catalysts.
Electricity is produced due to the following reactions occurring at electrodes.
- -
At cathode: O 2 (g) + 2H 2O (l) + 4e 4OH
- -
At anode: 2 x [ H2 (g) + 2OH (aq) 2H2O (aq) + 2e ]
Prevention of corrosion
1) By avoiding the contact with surroundings by painting the surface of metal.
2) By adding another metal which is more anodic than the metal to prevent corrosion.
e.g. Zinc is more anodic than iron. Hence zinc is added to iron to prevent corrosion. This is
called galvanization.
3) By avoiding the contact of metal with other materials which are good electical conductors.
PASSIVITY
The state of non reactivity reached after an initial state of reactivity is called passivity.
Passivity of metals can be classified into
1) Chemical passivity
Electrochemistry 18
2) Mechanical passivity
3) Electrochemical passivity
2) Mechanical passivity: An invisible thin film of oxide formed over metal surface prevent it from reacting
with acids. This is called mechanical passivity.
E.g. An invisible layer of PbO2 formed over the surface of Pb makes it passive and hence Pb is not
soluble in acids. This type of passivity is also shown by Fe, Co, Ni, Mn etc.,
3) Electrochemical passivity: During electrochemical processes, the dissolution of metal at anode is stopped
after some time. This is called electrochemical passivity.
E.g. Zn, Fe, Ni metals acting as anodes dissolve in the solution due to oxidation as follows.
Zn --------> Zn2+ + 2e-
Ni --------> Ni2+ + 2e-
But they stop dissolving after some time during electrochemical processes.
Theory of passivity
A metal becomes passive due to the formation of invisible thin film of its oxide over the surface which
prevents further reaction. Usually a thick layer of oxide is also formed beneath the thin film.
IIT-JEE Review Questions
Halogens and their compounds
Level-1(Following Questions have only one correct response)
(A) They are strong oxidizing agent and oxidizing power decreases down the group.
(B) They all disproportionate in aqueous alkali.
(C) Upper halogen in the group displaces lower halides from aqueous solution.
(D) Their boiling points increases from top to bottom in the group.
Q2. The wrong statement regarding hydrohalic acid is: (B)
(A) They are all strongly acidic and acid strength increases from HF to HI.
(B) They are all strong reducing agent and reducing power increases from HF to HI.
(C) HF is most soluble in water.
(D) HF attack glass.
Q3. Which of the following reaction/product is wrongly matched? (C)
(A) Cl2 + HgO Cl2O + HgCl2.HgO (B) NaClO3 + H2C2O4 ClO2 + CO2 + Na2C2O4
(C) ClO2 + NaOH NaClO3 + H2O (D) Cl2O6 + NaOH NaClO3 + NaClO4 + H2O
Q4. Which of the following statement regarding oxides of chlorine is not correct? (D)
(A) They are all acidic in aqueous solution. (B) They are all oxidizing agent.
(C) They are all pure anhydride. (D) Lower oxides are both oxidizing and reducing agent.
Q6. Which of the following is the correct order of acidic strength? A
(A) Cl2O7 > SO2 > P4O10 (B) CO2 > N2O5 > SO3
(C) Na2O > MgO > Al2O3 (D) K2O > CaO > MgO
(a) Only HCl (b) only HClO (c) HCl and HClO2 (d) HCl and HClO
Q8. Which of the following is called Euchlorine? (A)
(a) Cl2 + ClO2 (b) Cl2 + CO (c) CO2 + ClO2 (d) CO + ClO2
Q9. Chlorine can not be obtained by action of HCl on (C)
1
Q11. Chlorine acts as a bleaching agent only in presence of (B)
(a) Dry air (b) Moisture (c) Sunlight (d) Pure oxygen
Q12. Which of the following can not act as a reducing agent under any conditions? (D)
(a) KCl(aq) and KF(aq) (b) KCl(aq) and F2(g) (c) No reaction
(d) C/F and KCl /aq (e) K2 Cl2(s) and KCl(aq)
Q15. Bleaching powder on treatment with excess of HCl gives (D)
(a) CaO (b) CaO and Cl2 (c) CaCl2 (d) CaCl2 and Cl2
Q16. HI on reaction with H2SO4 yields (B)
(a) H2O2 & I2 (b) SO2 & I2 (c) HIO3 (d) No reaction
Q17. The least stable halogen acid is (D)
(a) NaNO3 + NaIO3 (b) NaIO3 (c) NaNO2 + NaIO3 (d) NaNO3 + I2
Q23. Which of the following is least soluble in water (C)
(a) HF > HCl > HBr > HI (b) HF > HI > HBr > HCl
(c) HCl > HBr > HF > HI (d) HF > HI > HCl > HBr
Q28. The decreasing order of acid strength for the hydrogen halides is (A)
(a) HI > HBr > HCl > HF (b) HF > HCl > HI > HBr
(c) HCl > HBr > HI > HF (d) HBr > HI > HCl > HF
2
Q29. Strongest reducing agent is (D)
(a) HClO4 > HClO3 > HClO2 > HClO (b) HClO4 > HClO2 > HClO3 > HClO
(c) HClO > HClO2 > HClO3 > HClO4 (d) HClO > HClO3 >HClO2 > HClO4
Q34. The thermal stability of oxy-acid of chlorine is (A)
(a) HClO4 > HClO3 > HClO2 > HClO (b) HClO4 > HClO2 > HClO3 > HClO
(c) HClO > HClO2 > HClO3 > HClO4 (d) HClO > HClO3 >HClO2 > HClO4
Q35. The strongest acidic oxyacid among the following is (D)
(a) 2KBr + H2SO4 (conc) K2SO2 + 2HBr (b) NaCl + H2SO4(conc) NaHSO4 + HCl
(c) NaHSO4 + NaCl Na2SO4 + HCl (d) CaF2 + H2SO4 CaSO4 + 2HF
Q42. Which one of the following chlorides is not hydrolysed in water at room temperature to give hydrogen chloride? (B)
(a) aluminium chloride (b) calcium chloride (c) silicon tetrachloride (d) sulphur dichloride
Q43. In which of the following glass is soluble (D)
3
Q46. In the preparation of chlorine from HCl, MnO2 acts as (C)
(a) oxidizing agent (b) reduction agent (c) catalystic agent (d) dehydrating agent
Q47. Which of the following will displace the halogen from the solution of halide? (C)
(a) Cl2 added to NaF (b) Cl2 added to KCl (c) Br2 added to NaCl (d) Br2 added to NaI
Q48. Which of the following non-metal brings about highest oxidation state of metals? (C)
(a) HI > HBr > HCl (b) HI > HCl > HBr (c) HCl > HBr > HI (d) HBr > HCl > HI
Q51. The purification of iodine is done by (C)
(a) Distillation (b) fractional crystallization (c) sublimation (d) steam distillation
Q52. Conc. H2SO4 cannot be used to prepare HBr from NaBr because it B
(A) reacts slowly with NaBr (B) oxidises HBr (C) reduces HBr (D) disproportionates HBr
Q53. An inorganic white crystalline compound (A) has a rock salt structure. (A) on reaction with cone. H2SO4 and MnO2, A
evolves a pungent smelling, greenish-yellow gas (B). Compound (A) gives white ppt. of (C) with AgNO3 solution.
Compounds (A), (B) and (C) will be respectively
(A) NaCl, Cl2, AgCl (B) NaBr, Br2, NaBr
(C) NaCl, Cl2, Ag2SO4 (D) Na2CO3, CO2, Ag2CO3
Q55. When chlorine gas is passed through an aqueous solution of a potassium halide in the presence of chloroform, a violet D
colouration is obtained. On passing more of chlorine water, the violet colour is disappeared and solution becomes
colourless. This test confirms the presence of ........... in aqueous solution.
(A) chlorine (B) fluorine (C) bromine (D) iodine
(a) dry air (b) sunlight (c) moisture (d) pure oxygen
Q59. Br2 vapour turns, starch + KI paper (B)
4
Q61. The element which can displace three other halogens form their compounds is (D)
5
Answers
1. (B) 21. (D) 41. (A) 61. (D)
2. (B) 22. (A) 42. (B) 62. (A)
3. (C) 23. (C) 43. (D) 63. (C)
4. (D) 24. (C) 44. (C) 64. (B)
5. (C) 25. (A) 45. (A) 65. (C)
6. (A) 26. (D) 46. (C) 66. (D)
7. (D 27. (D) 47. (C) 67. (B)
8. (A) 28. (A) 48. (C) 68. (D)
9. (C) 29. (D) 49. (C)
10. (C) 30. (D) 50. (A)
11. (B) 31. (A) 51. (C)
12. (D) 32. (B) 52. (B)
13. (A) 33. (C) 53. (A)
14. (C) 34. (A) 54. (A)
15. (D) 35. (D) 55. (D)
16. (B) 36. (D) 56. (D)
17. (D) 37. (B) 57. (B)
18. (D) 38. (C) 58. (C)
19. (C) 39. (D) 59. (B)
20. (B) 40. (A) 60. (D)
6
IIT JEE-2008 (PAPER-2)
C. Question paper format:
14. The question paper consists of 3 parts (Part-I : Mathematics, Part-II : Physics, Part-III : Chemistry).
Each part has 4 sections.
15. Section I contains 9 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D), out
of which only one is correct.
16. Section II contains 4 Reasoning type questions. Each question contains STATEMENT-1 and
STATEMENT-2.
Bubble (A) if both the statements are TRUE and STATEMENT-2 is the correct explanation of
STATEMENT-1.
Bubble (B) if both the statements are TRUE but STATEMENT-2 is NOT the correct explanation of
STATEMENT-1.
Bubble (C) if STATEMENT-1 is TRUE and STATEMENT-2 is FALSE
Bubble (D) if STATEMENT-1 is FALSE and STATEMENT-2 is TRUE
17. Section III contains 2 paragraphs. Based upon each paragraph, 3 multiple choice question have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which only one is correct.
18. Section IV contains 3 questions. Each question contains statements given in 2 columns. Statements in
the first column have to be matched with statements in the second column. The answers to these questions
have to be appropriately bubbled in the ORS as per the instructions given at the beginning of the section.
D. Marking Scheme:
19. For each question in Section I, you will be awarded 3 marks if you have darkened only the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (1) mark will be awarded.
20. For each question in Section II, you will be awarded 3 marks if you have darkened all the bubble(s)
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (1) mark will be awarded.
21. For each question in Section III, you will be awarded 4 marks if you darken only the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (1) mark will be awarded.
22. For each question in Section IV, you will be awarded 6 marks if you darken ALL the bubbles
corresponding ONLY to the correct answer or awarded 1 mark each for correct bubbling of answer
in any row. No negative mark will be awarded for an incorrectly bubbled answer.
[1]
IIT JEE-2008 PAPER-2
MATHEMATICS
PART I
SECTION - I
Straight Objective Type
This section contains 9 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.
There is NEGATIVE marking. 1 mark will be deducted for wrong answer.
Q.1 Let
ex
e4x e2x 1 e 4x e 2x 1 dx
ex
I= dx , J =
1 e 4 x e 2 x 1 e2x ex 1
(B) 2 log 2 x +C
1
(A) 2 log 4 x +C
e e 1
2x x
e e 1
e2x ex 1 1 e 4 x e 2 x 1
(C) 2 log 2 x +C
1
(D) 2 log 4 x 2 x +C
e e 1
x
e e 1
Ans. [C]
Q.2 Let g (x) = log f (x) where f (x) is a twice differentiable positive function on (0, ) such that
f (x + 1) = x f (x). Then for N = 1, 2, 3
1 1
g' ' N g' ' =
2 2
1 1 1 1
(A) 41 ..... 4 1 .....
1 1
2 (B) 2
9 25 (2 N 1) 9 25 (2 N 1)
1 1 1 1
(C) 41 ..... (D) 41 .....
1 1
9 25 (2 N 1) 2 9 25 (2 N 1) 2
Ans. [A]
Q.3 Let two non-collinear unit vector a and b form an acute angle. A point P moves so that at any time t the
position vector O P (where O is the origin) is given by a cos t b sin t . When P is farthest from origin
a b a b
1 1
a b a b
1 1
1 1
2 3 2 3
(A) 1 (B) (C) 1 (D)
3 2 3 2
Ans. [B]
Q.6 A particle P starts from the point z0 = 1 + 2i, where i = 1 . It moves first horizontally away from origin
by 5 units and then vertically away from origin by 3 units to reach a point z1. From z1 the particle moves
2 units in the direction of the vector i j and then it moves through an angle 2 in anticlockwise
direction on a circle with centre at origin, to reach a point z2. The point z2 is given by
(A) 6 + 7i (B) 7 + 6i (C) 7 + 6i (D) 6 + 7i
Ans. [D]
1 sin x 1 sin x
Q.7 The area of the region between the curves y = and y = bounded by the lines
cos x cos x
x = 0 and x = is
4
2 1 2 1
t 4t
(A) dt (B) dt
0 (1 t ) 1 t
2 2
0 (1 t ) 1 t
2 2
2 1 2 1
4t t
(C) dt (D) dt
0 (1 t 2 ) 1 t 2 0 (1 t 2 ) 1 t 2
Ans. [B]
Q.8 An experiment has 10 equally likely outcomes. Let A and B be two non-empty events of the experiment.
If A consists of 4 outcomes, the number of outcomes that B must have so that A and B are independent,
is
(A) 2, 4 or 8 (B) 3, 6, or 9 (C) 4 or 8 (D) 5 or 10
Ans. [D]
[3]
Q.9 Consider three points P = sin( ), cos , Q = cos( ), sin and
R = cos( ), sin( ) , where 0 < , , < /4
(A) P lies on the line segment RQ (B) Q lies on the line segment PR
(C) R lies on the line segment QP (D) P, Q, R are non collinear
Ans. [D]
SECTION-II
Reasoning Type
This section contains 4 reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.
There is NEGATIVE marking. 1 mark will be deducted for wrong answer.
Q.10 Suppose four distinct positive numbers a1, a2, a3, a4 are in G.P. Let b1 = a1, b2 = b1 + a2, b3 = b2 + a3
and b4 = b3 + a4.
STATEMENT-1 : The number b1, b2, b3, b4 are neither in A.P. nor in G.P.
and
STATEMENT-2 : The number b1, b2, b3, b4 are in H.P.
(A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [C]
Q.11 Consider
L1 : 2x + 3y + p 3 = 0
L2 : 2x + 3y + P + 3 = 0,
where p is a real number, and C : x2 + y2 + 6x 10y + 30 = 0.
STATEMENT-1 : If line L1 is a diameter of circle C, then line L2 is not always a diameter of circle C.
and
STATEMENT-2 : If line L1 is a diameter of circle C, then line L2 is not a chord of circle C.
(A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [C]
[4]
Q.12 Let a solution y = y (x) of the differential equation
x x 2 1 dy y y 2 1 dx 0
2
satisfy y (2) = .
3
1
STATEMENT-1 : y (x) = sec sec x
6
and
1 2
1 2 3 1
STATEMENT-2 : y (x) is given by
y x x
(A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [C]
1
Let a, b, c, p, q be real numbers. Suppose , are the roots of the equation x2 + 2px + q = 0 and a,
Q.13
are the roots of the equation ax2 + 2bx + c = 0, where 2 {1, 0, 1}
STATEMENT-1 : (p2 q)(b2 ac) 0
and
STATEMENT-2 : b pa or c qa
(A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [A]
[5]
SECTION - III
Linked Comprehension Type
This section contains 3 paragraphs. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.
1 t 2 dt
f ' (t )
Q.16 Let g (x) =
0
Which of the following is true?
(A) g ' (x) is positive on ( , 0) and negative on (0, )
(B) g ' (x) is negative on ( , 0) and positive on (0, )
(C) g ' (x) changes sign on both ( , 0) and (0, )
(D) g ' (x) does not change sign on ( , 0) and (0, )
Ans. [B]
[6]
Q.18 The shortest distance between L1 and L2 is
17 41 17
(A) 0 (B) (C) (D)
3 5 3 5 3
Ans. [D]
Q.19 The distance of the point (1, 1, 1) from the plane passing through the point (1, 2, 1) and whose
normal is perpendicular to both the lines L1 and L2 is
2 7 13 23
(A) (B) (C) (D)
75 75 75 75
Ans. [C]
SECTION - IV
MatrixMatch Type
This section contains 3 questions. Each question contains statements given in two columns which have to
be matched. Statements in Column I are labelled as A, B, C and D whereas
statements in Column II are labelled as P, Q, R and S. The answers to these questions have to be
appropriately bubbled as illustrated in the following example.
If the correct matches are A-P, A-S, B-Q, B-R, C-P, C-Q and D-S, then the correctly bubbled
4 4 matrix should be as follows: [6 Marks for correct (No Negative)]
Column-I Column-II
6
(B) One of L1, L2, L3 is parallel to at least one of the other two, if (Q) k=
5
5
(C) L1, L2, L3 form a triangle, if (R) k=
6
[7]
Q.21 Consider all possible permutations of the letters of the word ENDEANOEL
Match the statements / Expression in Column-I with the statements / Expressions in Column-II and
indicate your answer by darkening the appropriate bubbles in the 4 4 matrix given in OMR.
Column-I Column-II
(B) The number of permutations in which the letter E occurs in the (Q) 2 5!
first and the last position is
Q.22 Match the statements / Expression in Column-I with the statements / Expressions in Column-II and
indicate your answer by darkening the appropriate bubbles in the 4 4 matrix given in OMR.
Column-I Column-II
x 2 2x 4
x2
(A) The minimum value of is (P) 0
a
(C) Let a = log3 log32. An integer k satisfying 1 < 2 ( k 3 )
< 2, must be (R) 2
less than
1
are
2
(D) If sin q = cos y, then the possible values of (S) 3
[8]
PHYSICS
PART - II
SECTION - I
Straight Objective Type
This section contains 9 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.
Q.23 A parallel plate capacitor C with plates of unit area and separation d is filled with a liquid of dielectric
d
constant K = 2. The level of liquid is initially. Suppose the liquid level decreases at a constant speed
3
V, the time constant as a function of time t is
Figure :
d d R
3
6 0 R (15d 9Vt ) 0 R
5d 3Vt 2d 2 3dVt 9V 2 t 2
(A) (B)
6 0 R (15d 9Vt ) 0 R
5d 3Vt 2d 2 3dVt 9V 2 t 2
(C) (D)
Ans. [A]
Q.24 A light beam is traveling from Region I to Region IV (Refer Figure). The refractive index in Regions I, II,
n0 n0 n0
III and IV are n0, , and , respectively. The angle of incidence for which the beam just
2 6 8
misses entering Region IV is
Figure :
n0 n0 n0
n0 6 8
2
0 0.2 m 0.6 m
3 1 1 1
(A) sin1 (B) sin1 (C) sin1 (D) sin1
4 8 4 3
Ans. [B]
[9]
Q.25 A vibrating string of certain length under a tension T resonates with a mode corresponding to the first
overtone (third harmonic) of an air column of length 75 cm inside a tube closed at one end. The string
also generates 4 beats per second when excited along with a tuning fork of frequency n. Now when the
tension of the string is slightly increased the number of beats reduces to 2 per second. Assuming the
velocity of sound in air to be 340 m/s, the frequency n of the tuning fork in Hz is :
(A) 344 (B) 336 (C) 117.3 (D) 109.3
Ans. [A]
Q.26 A radioactive sample S1 having an activity of 5Ci has twice the number of nuclei as another sample S2
which has an activity of 10Ci. The half lives of S1 and S2 can be :
(A) 20 years and 5 years, respectively (B) 20 years and 10 years, respectively
(C) 10 years each (D) 5 years each
Ans. [A]
Q.27 A transverse sinusoidal wave moves along a string in the positive x-direction at a speed of 10 cm/s. The
wavelength of the wave is 0.5 m and its amplitude is 10 cm. At a particular time t, the snap-shot of the
wave is shown in figure. The velocity of point P when its displacement is 5 cm is :
Figure :
y
3 3
(A) j m/s (B) j m/s
50 50
(D)
3 3
(C) i m/s i m/s
50 50
Ans. [A]
[10]
q q 2q
Q.28 Consider a system of three charges , and placed at points A, B and C, respectively, as
3 3 3
shown in the figure. Take O to be the centre of the circle of radius R and angle CAB = 60
Figure :
y
C x
O
60
q
(A) The electric field at point O is 8 R 2 directed along the negative x-axis
0
q
(D) The potential at point O is 12 R
0
Ans. [C]
Q.29 A block (B) is attached to two unstretched springs S1 and S2 with spring constants k and 4k, respectively
(see figure I). The other ends are attached to identical supports M1 and M2 not attached to the walls.
The springs and supports have negligible mass. There is no friction anywhere. The block B is displaced
towards wall 1 by a small distance x (figure II) and released. The block returns and moves a maximum
distance y towards wall 2. Displacements x and y are measured with respect to the equilibrium position
y
of the block B. The ratio is
x
Figure :
2 1
M2 S2 S1 M1 I
B
2 x 1
M2 S2 S1 M1 II
B
x
1 1
(A) 4 (B) 2 (C) (D)
2 4
Ans. [C]
[11]
Q.30 A glass tube of uniform internal radius (r) has a valve separating the two identical ends. Initially, the valve
is in a tightly closed position. End 1 has a hemispherical soap bubble of radius r. End 2 has sub-
hemispherical soap bubble as shown in figure. Just after opening the valve,
Figure :
2 1
(A) air from end 1 flows towards end 2. No change in the volume of the soap bubbles
(B) air from end 1 flows towards end 2. Volume of the soap bubble at end 1 decreases
(C) no change occurs
(D) air from end 2 flows towards end 1. Volume of the soap bubble at end 1 increases
Ans. [B]
Q.31 A bob of mass M is suspended by a massless string of length L. The horizontal velocity V at position A
is just sufficient to make it reach the point B. The angle at which the speed of the bob is half of that at
A, satisfies
Figure :
B
V
A
3 3
(A) = (B) << (C) << (D) <<
4 4 2 2 4 4
Ans. [D]
[12]
SECTION - III
Reasoning Type
This section contains 4 reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.
Q.32 STATEMENT-1 : For an observer looking out through the window of a fast moving train, the nearby
objects appear to move in the opposite direction to the train, while the distant objects appear to be
stationary.
and
STATEMENT-2 : If the observer and the object are moving at velocities V1 and V2 respectively with
reference to a laboratory frame, the velocity of the object with respect to the observer is V2 V1 .
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [B]
Q.33 STATEMENT-1 : For practical, the earth is used as a reference at zero potential in electrical circuits.
and
STATEMENT-2 : The electrical potential of a sphere of radius R with charge Q uniformly distributed
Q
on the surface is given by 4 R .
0
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [B]
Q.34 STATEMENT-1 : The sensitivity of a moving coil galvanometer is increased by placing a suitable
magnetic material as a core inside the coil.
and
STATEMENT-2 : Soft iron has a high magnetic permeability and cannot be easily magnetized or
demagnetized.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [C]
[13]
Q.35 STATEMENT-1 : It is easier to pull a heavy object that to push it on a level ground.
and
STATEMENT-2 : The magnitude of frictional force depends on the nature of the two surfaces in
contact.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [B]
SECTION - III
Linked Comprehension Type
This section contains 2 paragraphs. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.
The nuclear charge (Ze) is non-uniformly distributed within a nucleus of radius R. The charge density (r)
[charge per unit volume] is dependent only on the radial distance r from the centre of the nucleus as
shown in figure. The electric field is only along the radial direction.
Figure :
(r)
a r
R
Q.38 The electric field within the nucleus is generally observed to be linearly dependent on r. This implies
R 2R
(A) a = 0 (B) a = (C) a = R (D) a =
2 3
Ans. [C]
[14]
Paragraph for Question Nos. 39 to 41
A uniform thin cylindrical disk of mass M and radius R is attached to two identical massless springs of
spring constant k which are fixed to the wall as shown in the figure. The springs are attached to the axle
of the disk symmetrically on either side at a distance d from its centre. The axle is massless and both the
springs and the axle are in a horizontal plane. The unstretched length of each spring is L. The disk is
initially at its equilibrium position with its centre of mass (CM) at a distance L from the wall. The disk rolls
without slipping with velocity V0 V0 i . The coefficient of friction is .
Figure :
2d
d d
R V0
Q.39 The net external force acting on the disk when its centre of mass is at displacement x with respect to its
equilibrium position is :
2kx 4kx
(A) kx (B) 2kx (C) (D)
3 3
Ans. [D]
Q.40 The centre of mass of the disk undergoes simple harmonic motion with angular frequency equal to :
k 2k 2k 4k
(A) (B) (C) (D)
M M 3M 3M
Ans. [D]
Q.41 The maximum value of V0 for which the disk will roll without slipping is :
M M 3M 5M
(A) g (B) g (C) g (D) g
k 2k k 2k
Ans. [C]
[15]
SECTION - IV
MatrixMatch Type
This section contains 3 questions. Each question contains statements given in two columns which have to
be matched. Statements in Column I are labelled as A, B, C and D whereas statements in Column II.
are labelled as p, q, r and s. The answers to these questions have to be appropriately bubbled as
illustrated in the following example.
If the correct matches are A-q, A-r, B-p, B-s, C-r, and D-q, then the correctly bubbled
4 4 matrix should be as follows:
p q r s
A p q r s
B p q r s
C p q r s
D p q r s
Q.42. Column I gives a list of possible set of parameters measured in some experiments. The variations of the
parameters in the form of graphs are shown in Column II. Match the set of parameters given in Column
I with the graphs given in Column II. Indicate your answer by darkening the appropriate bubbles of the
4 4 matrix given in the ORS.
Column I Column II
y
x
O
y
[16]
Q.43. Column I contains a list of processes involving expansion of an ideal gas. Match this with Column II.
describing the thermodynamic change during this process. Indicate your answer by darkening the
appropriate bubbles of the 4 4 matrix given in the ORS.
Column I Column II
(A) An insulated container has two chambers (p) The temperature of the gas
separated by a valve. Chamber I contains an decreases
ideal gas and the chamber II has vacuum. The
valve.
I II
(B) An ideal monoatomic gas expands to twice its (q) The temperature of the gas
original volume such that its original volume such increases or remains constant
1
that its pressure P , where V is the
V2
volume of the gas.
(C) An ideal monoatomic gas expands to twice its (r) The gas loses heat
1
original volume such that its pressure P ,
V4 / 3
where V is its volume.
(D) An ideal monoatomic gas expands such that its (s) The gas gains heat
pressure P and volume V follows the behaviour
shown in the graph.
V
V1 2V1
[17]
Q.44. An optical component and an object S placed along its optic axis are given in Column I. The distance
between the object and the component can be varied. The properties of images are given in Column II.
Match all the properties of images from Column II with the appropriate components given in Column
I Indicate your answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.
Column I Column II
S
(A) (p) Real image
S
(B) (q) Virtual image
S
(C) (r) Magnified image
S
(D) (s) Image at infinite
[18]
CHEMISTRY
PART-III
SECTION-I
Straight Objective Type
This section contains 9 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.
Q.45 Among the following, the surfactant that will from micelles in aqueous solution at the lowest molar
concentration at ambient conditions is
(A) CH3(CH2)15N+(CH3)3Br (B) CH3(CH2)11OSO3Na+
(C) CH3(CH2)6COONa+ (D) CH3(CH2)11N+(CH3)3Br
Ans. [A]
Q.46 Solubility product constants (Ksp) of salts of types MX, MX2 and M3X at temperature T are
4.0 108, 3.2 1014 and 2.7 1015, respectively. Solubilities (mol dm3) of the salts at temperature
T are in the order
(A) MX > MX2 > M3X (B) M3X > MX2 > MX
(C) MX2 > M3X > MX (D) MX > M3X > MX2
Ans. [D]
Q.47 Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milli ampere current. The time
required to liberate 0.01 mol of H2 gas at the cathode is (1 Faraday = 96500 C mol1)
(A) 9.65 104 sec (B) 19.3 104 sec (C) 28.95 104 sec (D) 38.6 104 sec
Ans. [B]
Q.48 Cellulose upon acetylation with excess acetic anhydride / H2SO4 (catalytic) gives cellulose triacetate
whose structure is
AcO
H O O
AcO H
(A) OAc H
H O O H
AcO H
OAc H H OAc
O O
H H H
OAc H H OAc
O H
H OAc
AcO
H O O
AcO H
OH H
H O O H
AcO H
OH H H OH
O O
(B) H H H
OH H H OH
O H
H OH
[19]
AcO AcO AcO
O H O H
(C) H H H
H
H O O
H
OAc H OAc H
O O O
OAc H
H
H OAc H OAc H OAc
Q.49 In the following reaction sequence, the correct structures of E, F and G are
O O
|| || I2
Heat [E] [F] + [G]
Ph * OH NaOH
(* implies 13C labelled carbon)
O O
|| ||
(A) E = * F= - + G = CHI3
Ph CH3 Ph * O Na
O O
|| ||
(B) E = * F= - + G = CHI3
Ph CH 3
Ph O Na
O O
|| || *
(C) E = * F= - + G = CHI
Ph CH 3
Ph O Na
3
O O
|| || *
(D) E = * F= - + G = CH 3I
Ph CH 3
Ph O Na
Ans. [C]
O O +
[20]
Q.51 Among the following, the coloured compound is
(A) CuCl (B) K3 [Cu (CN)4] (C) CuF2 (D) [Cu(CH3CN)4] BF4
Ans. [C]
Q.53 Both [Ni(CO)4] and [Ni(CN)4]2 are diamagnetic. The hybridisations of nickel in these complexes,
respectively, are
(A) sp3, sp3 (B) sp3, dsp2 (C) dsp2, sp3 (D) dsp2, dsp2
Ans. [B]
SECTION-II
Reasoning Type
This section contains 4 reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.
Q.54 STATEMENT-1 : Aniline on reaction with NaNO2 / HCl at 0C followed by coupling with -naphthol
gives a dark blue coloured precipitate.
and
STATEMENT-2 : The colour of the compound formed in the reaction of aniline with NaNO2 / HCl at 0
followed by coupling with -naphthol is due to the extended conjugation.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [D]
Q.55 STATEMENT-1 : The geometrical isomers of the complex [M(NH3)4Cl2] are optically inactive.
and
STATEMENT-2 : Both geometrical isomers of the complex [M(NH3)4Cl2] possess axis of symmetry.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [A]
[21]
Q.56 STATEMENT-1 : There is a natural asymmetry between converting work to heat and converting heat to
work.
and
STATEMENT-2 : No process is possible in which the sole result is the absorption of heat from a
reservoir and its complete conversion into work.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [A]
SECTION-III
Linked Comprehension Type
O O Me
(C) || + PhCH2MgBr (D) || +
Ph H Ph H Ph MgBr
Ans. [B]
[22]
Q.59 The structure of compound I is
Ph CH3 H3C Ph CH3 H3C CH3
Ph
(A) (B) (C) (D)
H Ph H Ph H CH2Ph Ph H
Ans. [A]
[23]
SECTION-IV
Matrix Match Type
This section contains 3 questions. Each question contains statements given in two columns which have to
be matched. Statements in Column I are labelled as A, B, C and D whereas statements in Column II
are labelled as p, q, r and s. The answers to these questions have to be appropriately bubbled as
illustrated in the following example.
If the correct matches are A-q, A-r, B-p, B-s, C-r, C-s and D-q, then the correctly bubbled
matrix will look like the following :
p q r s
A p q r s
B p q r s
C p q r s
D p q r s
Q.64 Match the compounds in Column I with their characteristic test(s)/reaction(s) given in Column II.
Indicate your answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.
Column I Column II
-
(A) H2N NH3Cl
+
(p) sodium fusion extract of the compound gives
Prussian blue colour with FeSO4
+ -
NH3I
(B) HO (q) gives positive FeCl3 test
COOH
+ -
(C) HO NH3Cl (r) gives white precipitate with AgNO3
-
NH NH3Br
+
(D) O2N (s) reacts with aldehydes to form the corresponding
hydrazone derivative
NO2
[24]
Q.65 Match the entries in Column I with the correctly related quantum number(s) in Column II. Indicate
your answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.
Column I Column II
(A) Orbital angular momentum of the (p) Principal quantum number
electron in a hydrogen-like atomic orbital
(C) Shape, size and orientation of hydrogen (r) Magnetic quantum number
like atomic orbitals
(D) Probability density of electron at the nucleus (s) Electron spin quantum number
in hydrogen-like atom
Q.66 Match the conversions in Column I with the type(s) of reaction(s) given in Column II. Indicate your
answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.
Column I Column II
[25]
IITJEE2004 Mains Paper
Chemistry
Time: 2 hours
Note: Question number 1 to 10 carries 2 marks each and 11 to 20 carries 4 marks each.
2. 100 ml of a liquid contained in an isolated container at a pressure of 1 bar. The pressure is steeply increased
to 100 bar. The volume of the liquid is decreased by 1 ml at this constant pressure. Find the H & U.
3. Draw the shape of XeF4 and OSF4according to VSEPR theory. Show the lone pair of electrons on the
central atom
Sol. F
F F O
Xe
(square planar) F S (Trigonal bipyramidal)
F F (sp3d2) (sp3d)
F
F
1
IIT-JEE 2004-M-2
HO H
H OH
H OH
HO
Sol. -
O O
CHO
H OH H OH
HO H +
HO H
Ag( NH3 )2
H OH H OH
HO H HO H
(L glu cos e)
HO HO
5. a) Draw New mann`s projection for the less stable staggered form of butane.
b) Relatively less stability of the staggered form is due to
i) Torsional strain.
ii) Vander Waals strain.
iii) Combination of the above two.
Sol. a) CH3
H CH3
. .
. H
H
H
b) Less stability is due to Vander Waals strain
7. AlF3 is insoluble in anhydrous HF but when little KF is added to the compound it becomes soluble. On
addition of BF3 ,AlF3 is precipitated. Write the balanced chemical equations.
8. The crystal AB (rock salt structure) has molecular weight 6.023 y amu. where y is an arbitrary number in
amu.. If the minimum distance between cation & anion is y1/ 3 nm and the observed density is 20 Kg / m3 .
Find the
a) density in Kg / m3 and
b) type of defect
2
IIT-JEE 2004-M-3
4 6.023 y
Sol. a) Density = [Since a = 2y1/3]
6.023 1023 8 y 1027
= 5 103 g / m 3
= 5Kg / m 3
b) Since the (density) calculated < density observed, it means the defect is metal excess defect.
Sol. Br
Ag aq.
Aromatic Ion
(highly stable)
Ag
Br Antiaromatic Ion
(highly unstable)
3
IIT-JEE 2004-M-4
2
1 1 1
3
r r / a
=0= 2 e 0
2
4 2 a 0 a0
r r
2 = 0 2 = 2a0 = r
a0 a0
h 6.626 1034
b) = =
mv 100 103 100
= 6.62610-35 m = 6.62610-25 A
c) Yis 84Po206
12. On the basis of ground state electronic configuration arrange the following molecules in increasing O-O
bond length order.
KO2, O2, O2[AsF6].
2p y 2p y
2 1
Sol. O 2 = 1s 2 , 1s 2 , 2s 2 , 2s 2 , 2p 2x
2p z 2p z
2 1
10 6
bond order = =2
2
2P 2 2Py
* 2
O +2
2P 2
= 1s2 , * 1s2 , 2s2 , * 2s2 , 2Px2 2Pzy2 * 2p y1
{ }
in [O 2 (AsF6 )]
10 5 5
bond order =
2 2
Bond length order is O2+ < O2 < O2
G reaction = 2G f ( NO 2 ) G f ( N 2 O 4 )
0 = 100 100
G = G + RT lnk
G = RT ln Q
= 2.303 .082 298 log 9.9 = 56.0304 Lit atm. = Positive
4
IIT-JEE 2004-M-5
14. a) 1.22 g C6H5 COOH is added into two solvent and data of Tb and Kb are given as:-
i) In 100 g CH3COCH3 Tb= 0.17
Kb = 1.7 Kg Kelvin /mol
ii) In 100 g benzene, Tb = 0.13 and Kb = 2.6 Kg Kelvin/mol
Find out the molecular weight of C6H5COOH in both the cases and interpret the result.
b) 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at end point. Given Ka(HA)=510-6 and
<< 1
Sol. a) In first case
i) Tb = Kbm
1.22
0.17 = 1.7 M = 122
M 100 10 3
ii) In second case
Tb = Kbm
1.22
0.13 = 2.6
M 100 103
M = 244
Benzoic acid dimerises in benzene
0.1
b) Since at end point molarity of salt = = M
2
pH of salt of weak acid and strong base
( pK w + pK a + logc ) 1
pH = = [14 + 5.3010 + [-1.3010] pH = 9.
2 2
15. NO2 NO2
in not more than four steps. Also mention the temp and reaction
Convert
to
condition.
OH
Conc.H 2 SO 4
NH 4 HS
NaNO2 / HCl
H2 O
0 C 5 C
NO2 NH2 + OH
N
NCl
Cl
16.
+
KCN
DMF
(A)
C2 H5 ONa / C 2 H 5 OH
C6 H5 CHO /
(B)
H3 O
(C)
SOCl2
CH3 NH 2
(D)
Identify A to D.
5
IIT-JEE 2004-M-6
CN
Sol. NC Ph
H
A= B=
O NH
COOH CH3
Ph Ph
C= D=
17. A1 & A2 are two ores of metal M. A1 on calcination gives black precipitate, CO2 & water.
n Black solid + CO2 + H2O
atio
l ci n
Ca
A1 dil HCl
KI I 2 + ppt
A 2
roasting
Metal + gas
K 2 Cr2 O7 + H 2SO4
green colour
Sol. A1 = Cu(OH) 2 CuCO3
A 2 = Cu 2S
Cu(OH) 2 CuCO 3
Calcination
2CuO + CO 2 + H 2 O
(A1) (Black Solid)
Ni
C C
N
H3C N CH3
OH O
Oxidation state of nickel is +2 and hybridization is dsp2
s = n(n + 2) B.M
n=0
s = 0
6
IIT-JEE 2004-M-7
20. An organic compound P having the molecular formula C5H10O treated with dil H2SO4 gives two
compounds, Q & R both gives positive iodoform test. The reaction of C5H10O with dil H2SO4 gives
reaction 1015 times faster then ethylene. Identify organic compound of Q & R. Give the reason for the extra
stability of P.
Sol. CH3
C5 H10 O is
H2C O CH3
7
ANEESH DAMODARAN
ANSWER: C
ANSWER: B
ANSWER: D
ANSWER: A
ANSWER: D
ANSWER: A
ANSWER: B
ANSWER: C
ANSWER: B
ANSWER: A and C
ANSWER: B and D
ANSWER: A and B
ANSWER: C and D
ANSWER: A
ANSWER: D
ANSWER: C
ANSWER: B
ANSWER: C
ANSWER: 2
ANSWER: 5
ANSWER: 1
ANSWER: 4
ANSWER: 3
ANSWER: either 0 or 8
ANSWER: 3
ANSWER: 3
ANSWER: 0
ANSWER: 4
ANSWER: D
ANSWER: C
ANSWER: C
ANSWER: A
ANSWER: A
ANSWER: B
ANSWER: B
ANSWER: D
ANSWER: C and D
ANSWER: B
ANSWER: A
ANSWER: D
ANSWER: C
ANSWER: D
ANSWER: B
ANSWER: A
ANSWER: 3
ANSWER: 2
ANSWER: 5
ANSWER: 2
ANSWER: 6
ANSWER: 4
ANSWER: 1
ANSWER: 3
ANSWER: 3
ANSWER: 9
ANSWER: C
ANSWER: D
ANSWER: D
ANSWER: C
ANSWER: B
ANSWER: C
ANSWER: A
ANSWER: A
ANSWER: A and D
ANSWER: A and C
.
ANSWER: A and C
ANSWER: B
ANSWER: D
ANSWER: A
ANSWER: B
ANSWER: 6
ANSWER: 3
ANSWER: 4
ANSWER: 9
ANSWER: 5
ANSWER: 4
ANSWER: 6
ANSWER: 3
ANSWER: 8
ANSWER: 7
********************************************
FIITJEE Solutions to
IITJEE-2007
(Paper-I, Code-7)
Time: 3 hours M. Marks: 243
Note: (i) The question paper consists of 3 parts (Physics, Chemistry and Mathematics). Each part has 4 sections.
(ii) Section I contains 9 multiple choice questions which have only one correct answer. Each question carries +3 marks
each for correct answer and 1 mark for each wrong answer.
(iii) Section II contains 4 questions. Each question contains STATEMENT-1 (Assertion) and STATEMENT-2 (Reason).
Bubble (A) if both the statements are TRUE and STATEMENT-2 is the correct explanation of STATEMENT-1
Bubble (B) if both the statements are TRUE but STATEMENT-2 is NOT the correct explanation of STATEMENT- 1
Bubble (C) if STATEMENT-1 is TRUE and STATEMENT-2 is FALSE.
Bubble (D) if STATEMENT-1 is FALSE and STATEMENT-2 is TRUE.
carries +3 marks each for correct answer and 1 mark for each wrong answer.
(iv) Section III contains 2 paragraphs. Based upon each paragraph, 3 multiple choice questions have to be answered. Each
question has only one correct answer and carries +4 marks for correct answer and 1 mark for wrong answer.
(v) Section IV contains 3 questions. Each question contains statements given in 2 columns. Statements in the first column
have to be matched with statements in the second column and each question carries +6 marks and marks will be awarded if
all the four parts are correctly matched. No marks will be given for any wrong match in any question. There is no negative
marking.
PART- I (PHYSICS)
SECTION I
This section contains 9 multiple choice questions numbered 1 to 9. Each question has 4 choices (A), (B), (C) and (D), out of
which only one is correct.
1. A circuit is connected as shown in the figure with the switch S open. When the 3F X 6F
switch is closed the total amount of charge that flows from Y to X is
(A) 0 (B) 54C
(C) 27 C (D) 81 C S
3 6
Y
9V
Sol. (C)
27 C
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3F X 6F 3F 6F
+9C X +18C
+18C +18C +9C +36C
S
S
3 6
1A +27C
Y
3 Y 6
9V
9V
Initial charge distribution (when switch S is open) Final charge distribution (when switch S is closed)
2. A long, hollow conducting cylinder is kept coaxially inside another long, hollow conducting cylinder of larger radius.
Both the cylinders are initially electrically neutral.
(A) A potential difference appears between the two cylinders when a charge density is given to the inner cylinder.
(B) A potential difference appears between the two cylinders when a charge density is given to the outer cylinder.
(C) No potential difference appears between the two cylinders when a uniform line charge is kept along the axis of the
cylinders.
(D) No potential difference appears between the two cylinders when same charge density is given to both the
cylinders.
Sol. (A)
dV = E dr
and E =
2 0 r
where r is distance from the axis of cylindrical charge distribution (r is equal to or greater than radius of cylindrical
charge distribution).
3. In the options given below, let E denote the rest mass energy of a nucleus and n a neutron. The correct option is
(A) E ( 236
92 U ) > E ( 137
53 I ) + E ( 39 Y ) + 2E(n)
97
(B) E ( 236
92 U ) < E ( 137
53 I ) + E ( 39 Y ) + 2E(n)
97
(C) E ( 236
92 U ) < E ( 140
56 Ba ) + E ( 36 Kr ) + 2E(n)
94
(D) E ( 236
92 U ) = E ( 140
56 Ba ) + E ( 36 Kr ) + 2E(n)
94
3. (A)
Rest mass energy of U will be greater than the rest mass energy of the nucleus in which it breaks (as conservation of
momentum is always followed)
4. In an experiment to determine the focal length (f) of a concave mirror by the uv method, a student places the object
pin A on the principal axis at a distance x from the pole P. The student looks at the pin and its inverted image from a
distance keeping his/her eye in line with PA. When the student shifts his/her eye towards left, the image appears to the
right of the object pin. Then,
(A) x < f (B) f < x < 2f
(C) x = 2f (D) x > 2f
Sol. (B)
Due to parallax
5. The largest wavelength in the ultraviolet region of the hydrogen spectrum is 122 nm. The smallest wavelength in the
infrared region of the hydrogen spectrum (to the nearest integer) is
(A) 802 nm (B) 823 nm
(C) 1882 nm (D) 1648 nm
Sol. (B)
Transition from to n = 3 will produce smallest wavelength in infrared region.
6. A resistance of 2 is connected across one gap of a metre-bridge (the length of the wire is 100 cm) and an unknown
resistance, greater than 2, is connected across the other gap. When these resistance are interchanged, the balance point
shifts by 20 cm. Neglecting any corrections, the unknown resistance is
(A) 3 (B) 4
(C) 5 (D) 6
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Sol. (A) 2 x
2
= (i) G
x 100
x + 20
= (ii) 100
2 80
Solving (i) and (ii) x = 3
7. A ray of light travelling in water is incident on its surface open to air. The angle of incidence is , which is less than the
critical angle. Then there will be
(A) only a reflected ray and no refracted ray
(B) only a refracted ray and no reflected ray
(C) a reflected ray and a refracted ray and the angle between them would be less than 180 2
(D) a reflected ray and a refracted ray and the angle between them would be greater than 180 2
Sol. (C)
Refracted ray
air
water
Reflected ray
Incident ray
8. Two particle of mass m each are tied at the ends of a light string of length 2a. The F
whole system is kept on a frictionless horizontal surface with the string held tight so
that each mass is at a distance a from the center P (as shown in the figure). Now, the
mid-point of the string is pulled vertically upwards with a small but constant force F. As
m m
a result, the particles move towards each other on the surface. The magnitude of P
acceleration, when the separation between them becomes 2x is a a
F a F x
(A) (B)
2m a x 2
2 2m a x 2
2
F x F a2 x2
(C) (D)
2m a 2m x
Sol. (B)
2T sin = F F
T cos = mA
F a T
2 tan = N T
mA m
P
F x x
A= 2
2m a x 2
mg
9. Consider a neutral conducting sphere. A positive point charge is placed outside the sphere. The net charge on the
sphere is then,
(A) negative and distributed uniformly over the surface of the sphere
(B) negative and appears only at the point on the sphere closest to the point charge
(C) negative and distributed non-uniformly over the entire surface of the sphere
(D) zero
Sol. (D)
SECTION II
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IIT-JEE2007-PAPER-I-4
10. STATEMENT-1
The formula connecting u, v and f for a spherical mirror is valid only for mirrors whose sizes are very small compared
to their radii of curvature.
because
STATEMENT-2
Laws of reflection are strictly valid for plane surfaces, but not for large spherical surfaces.
(A) Statement-1 is True, Statement-2 is True; Statement -2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement -2 is NOT a correct explanation for Statement-1.
(C) Statement -1 is True, Statement-2 is False.
(D) Statement -1 is False, Statement-2 is True.
Sol. (C)
11. STATEMENT-1
If the accelerating potential in an X-ray tube is increased, the wavelengths of the characteristic X-rays do not change.
because
STATEMENT -2
When an electron beam strikes the target in an X-ray tube, part of the kinetic energy is converted into X-ray energy.
(A) Statement-1 is True, Statement-2 is True; Statement -2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement -2 is NOT a correct explanation for Statement-1.
(C) Statement -1 is True, Statement-2 is False.
(D) Statement -1 is False, Statement-2 is True.
Sol. (B)
12. STATEMENT-1
A block of mass m starts moving on a rough horizontal surface with a velocity v. It stops due to friction between the
block and the surface after moving through a certain distance. The surface is now tilted to an angle of 300 with the
horizontal and the same block is made to go up on the surface with the same initial velocity v. The decrease in the
mechanical energy in the second situation is smaller than that in the first situation.
because
STATEMENT-2
The coefficient of friction between the block and the surface decreases with the increase in the angle of inclination.
(A) Statement -1 is True, Statement-2 is True; Statement-2 is a correct explanation for statement-1.
(B) Statement -1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for statement-1.
(C) Statement -1 is True, Statement-2 is False.
(D) Statement -1 is False, Statement-2 is True.
Sol. (C)
13. STATEMENT-1
In an elastic collision between two bodies, the relative speed of the bodies after collision is equal to the relative speed
before the collision.
because
STATEMENT-2
In an elastic collision, the linear momentum of the system is conserved.
(A) Statement -1 is True, Statement-2 is True; Statement -2 is a correct explanation for Statement-1.
(B) Statement -1 is True, Statement-2 is True; Statement -2 is NOT a correct explanation for Statement-1.
(C) Statement -1 is True, Statement-2 is False.
(D) Statement -1 is False, Statement-2 is True.
Sol. (B)
SECTION III
This section contains 2 paragraphs P14-16 and P17-19. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.
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IIT-JEE2007-PAPER-I-5
A fixed thermally conducting cylinder has a radius R and height L0. The cylinder is open 2R
at its bottom and has a small hole at its top. A piston of mass M is held at a distance L
from the top surface, as shown in the figure. The atmospheric pressure is P0. L
14. The piston is now pulled out slowly and held at a distance 2L from the top. L0
The pressure in the cylinder between its top and the piston will then be
P
(A) P0 (B) 0
2
P0 Mg P0 Mg
(C) + (D) Piston
2 R 2 2 R 2
Sol. (A)
15. While the piston is at a distance 2L from the top, the hole at the top is sealed. The piston is then released, to a position
where it can stay in equilibrium. In this condition, the distance of the piston from the top is
2P R 2 P R 2 Mg
(A) 2 0 ( 2L ) (B) 0 2 ( 2L )
R P0 + Mg R P0
P R 2 + Mg P R 2
(C) 0 2 ( 2L ) (D) 2 0 ( 2L )
R P0 R P0 Mg
Sol. (D)
Mg + P(R2) = P0R2
P0(2LR2) = P(xR2) (P1`V1 = P2V2 for isothermal process)
P R 2
x = 20 ( 2L )
R P0 Mg
16. The piston is taken completely out of the cylinder. The hole at the top is sealed. A
water tank is brought below the cylinder and put in a position so that the water surface
in the tank is at the same level as the top of the cylinder as shown in the figure. The
density of the water is . In equilibrium, the height H of the water column in the L0
cylinder satisfies
(A) g(L0H)2 + P0(L0 H) + L0P0 = 0 H
(B) g(L0H)2 P0(L0 H) L0P0 = 0
(C) g(L0H)2 + P0(L0 H) L0P0 = 0
(D) g(L0H)2 P0(L0 H) + L0P0 = 0
Sol. (C)
R2P0L0 = P(L0 H)R2 . . . (i)
P = P0 + g(L0 H) . . . (ii)
Solving (i) & (ii), we get the answer.
Two discs A and B are mounted coaxially on a vertical axle. The discs have moments of inertia I and 2I respectively about the
common axis. Disc A is imparted an initial angular velocity 2 using the entire potential energy of a spring compressed by a
distance x1. Disc B is imparted an angular velocity by a spring having the same spring constant and compressed by a distance
x2. Both the discs rotate in the clockwise direction.
2 2
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IIT-JEE2007-PAPER-I-6
1 2 1
kx 2 = ( 2I )( )
2
2 2
x1
= 2
x2
18. When disc B is brought in contact with disc A, they acquire a common angular velocity in time t. The average frictional
torque on one disc by the other during this period is
2I 9I
(A) (B)
3t 2t
9I 3I
(C) (D)
4t 2t
Sol. (A)
Applying conservation of angular momentum
I ( 2) + 2I ( ) 4
= = . . . (i)
3I 3
= + t . . . (ii)
2I
2I
From (1) & (ii), =
3t
19. The loss of kinetic energy during the above process is
I2 I2
(A) (B)
2 3
I2 I2
(C) (D)
4 6
Sol. (B)
SECTION IV
Matrix-Match Type
This section contains 3 questions. Each question contains statements given in two columns which have to be matched. Statements
(A, B, C, D) in column I have to be matched with statements (p, q, r, s) in column II. The answers to these questions have to be
appropriately bubbled as illustrated in the following example.
If the correct match are A-p, A-s, B-r, C-p, C-q and D-s, then the correctly bubbled 4 4 matrix should be as follows:
p q r s
A p q r s
B p q r s
C p q r s
D p q r s
20. Some physical quantities are given in Column I and some possible SI units in which these quantities may be expressed
are given in Column II. Match the physical quantities in Column I with the units in Column II and indicate your
answer by darkening appropriate bubbles in the 4 4 matrix given in the ORS.
Column I Column II
(A) GM e M s (p) (volt) (coulomb) (metre)
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22. (C)olumn I gives certain situations in which a straight metallic wire of resistance R is used and Column II gives some
resulting effects. Match the statements in Column I with the statements in Column II and indicate your answer by
darkening appropriate bubbles in the 4 4 matrix given in the ORS.
Column I Column II
(A) A charged capacitor is connected to the ends of the wire (p) A constant current flows through the wire
(B) The wire is moved perpendicular to its length with a constant (q) Thermal energy is generated in the wire
velocity in a uniform magnetic field perpendicular to the
plane of motion
(C) The wire is placed in a constant electric field that has a (r) A constant potential difference develops
direction along the length of the wire. between the ends of the wire
(D) A battery of constant emf is connected to the ends of the wire (s) Charges of constant magnitude appear at
the ends of the wire
Sol. A (q), B (r) & (s), C (r) & (s), D (p), (q) & (r)
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PART- II (CHEMISTRY)
SECTION I
This section contains 9 multiple choice questions numbered 23 to 31. Each question has 4 choices (A), (B), (C) and (D), out of
which ONLY ONE is correct.
Sol. (C)
C6H14
H3C CH2 CH2 CH2 CH2 CH3 H3C CH CH2 CH2 CH3
CH3
H3C CH CH CH2 CH3 H3C CH CH CH3 CH3
CH3
Hence (C) is correct.
(C) (D)
O O
N O2 N N
H H
NO2
Sol. (B)
O O
conc. HNO
N C 3
conc. H 2SO 4
O2 N NH C
H
Due to presence of lone pair of electron on nitrogen atom, it will activate the ring and it will stabilize
intermediate cation at o and p positions.
Hence (B) is correct.
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25. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50 g of benzene (Kf = 1.72 K kg mol1), a freezing point
depression of 2 K is observed. The vant Hoff factor (i) is
(A) 0.5 (B) 1
(C) 2 (D) 3
Sol. (A)
Tf = Kf molality i
20 1000
2 = 1.72 i
172 50
i = 0.5
Hence (A) is correct.
26. Among the following, the paramagnetic compound is
(A) Na2O2 (B) O3
(C) N2O (D) KO2
Sol. (D)
O 22 = 1s 2 *1s 2 , 2s 2 * 2s 2 , 2p z2 , 2p 2x = 2p 2y , * 2p 2x = * 2p 2y
Number of unpaired electrons = 0.
N = N O Number of unpaired electrons = 0
(A) 5 (B) 10
(C) 95 (D) 100
Sol. (B)
G = H TS = 54.07 1000 298 10 = 57050 J mol1
57050 = 5705 log10K
log10K = 10
Hence (B) is correct
P P
P
Hence (D) is correct.
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Sol. (B)
Option (B) is correct.
H2 C CH2
Alc. KOH
H2 C NaNH
CH HC
2
CH
Br Br
Br
Because CH2 = CH Br has partial C Br double bond character, it requires more stronger base to remove
HBr.
Hence(B) is correct.
SECTION II
Assertion-Reason Type
This section contains 4 questions numbered 32 to 35. Each question contains STATEMENT-1 (Assertion) and STATEMENT-2
(Reason). Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.
32. STATEMENT-1: p-Hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoic acid.
because
STATEMENT-2: o-Hydroxybenzoic acid has intramolecular hydrogen bonding.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement -2 is False.
(D) Statement-1 is False, Statement-2 is True.
Sol. (D)
O H
O
C OH
More stabilized by intramolecular hydrogen bonding
H O
H
O O C
More stronger intermolecular forces increases the boiling point.
C O O
H
O H
Hence (D) is correct.
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33. STATEMENT-1: Micelles are formed by surfactant molecules above the critical micellar concentration (CMC).
because
STATEMENT-2: The conductivity of a solution having surfactant molecules decreases sharply at the CMC.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
Sol. (B)
The formation of micelles takes places only above a particular temperature called Kraft temperature (Tk) and above a
particular concentration called critical micelle concentration (CMC).
Each micelle contains at least 100 molecules. Therefore conductivity of the solution decreases sharply at the CMC.
Hence (B) is correct.
Sol. (C)
H3BO3 (orthoboric acid) is a weak lewis acid.
H 3BO3 + H 2O B ( OH )4 + H
It does not donate proton rather it acceptors OH form water.
Hence (C) is correct
SECTION III
This section contains 2 paragraphs C36-38 and C39-41. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.
Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules (approximately 6.023 1023)
are present in a few grams of any chemical compound varying with their atomic/molecular masses. To handle such large numbers
conveniently, the mole concept was introduced. This concept has implications in diverse areas such as analytical chemistry,
biochemistry, electrochemistry and radiochemistry. The following example illustrates a typical case, involving
chemical/electrochemical reaction, which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to the evolution of
chlorine gas at one of the electrodes (atomic mass: Na = 23, Hg = 200; 1 Faraday=96500 coulombs)
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Sol. (B)
Na + + Cl
NaCl
At anode:
2Cl Cl2
Moles of Cl = 2 in 500 ml.
Therefore 1 mole of Cl2 evolves.
Hence (B) is correct.
37. If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is
(A) 200 (B) 225
(C) 400 (D) 446
Sol. (D)
Na Hg (amalgam) formed = 2 moles at cathode.
Hence (D) is correct.
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SECTION IV
Matrix-Match Type
This section contains 3 questions. Each question contains statements given in two columns which have to be matched. Statements
(A, B, C, D) in Column-I have to be matched with statements (p, q, r, s) in Column-II. The answers to these questions have to be
appropriately bubbled as illustrated in the following example.
If the correct matches are A-p, A-s, B-q, B-r, C-p, C-q and D-s, then the correctly bubbled 4 4 matrix should be as follows:
p q r s
A p q r s
B p q r s
C p q r s
D p q r s
42. Match the complexes in Column-I with their properties listed in Column-II. Indicate your answer by darkening the
appropriate bubbles of the 4 4 matrix given in the ORS.
Column-I Column-II
(A) [Co(NH3)4(H2O)2]Cl2 (p) geometrical isomers
(B) [Pt(NH3)2Cl2] (q) paramagnetic
(C) [Co(H2O)5Cl]Cl (r) diamagnetic
(D) [Ni(H2O)6]Cl2 (s) metal ion with +2 oxidation state
Sol. A p, q, s B p, r, s C q, s D q, s
(A)
2+ 2+
OH2 NH3
NH3 OH2
H3N H2O
Co Co
H3N NH3 H 3N NH3
OH2 OH2
(trans) (cis)
Co2+ = 3d7 (Paramagnetic)
(B) [Pt(NH3)2Cl2] is square planar.
Cl Cl
H3N H3N
2+ 2+
Pt Pt
H3N Cl Cl NH3
(cis) (trans)
Pt2+ = 5d84s0 (diamagnetic)
(C) (D)
+ 2+
OH2
OH2
OH2
H2O OH2
H 2O
Co
H 2O OH2 Co
Cl H2O OH2
OH2
Co2+ = 3d7 (paramagnetic) Ni2+ = 3d8 (weak field ligand, paramagnetic)
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43. Match gases under specified conditions listed in Column-I with their properties/laws in Column-II. Indicate your
answer by darkening the appropriate bubsbles of the 4 4 matrix given in the ORS.
Column-I Column-II
(A) hydrogen gas (P = 200 atm, T = 273K) (p) compressibility factor 1
(B) hydrogen gas (P 0, T = 273K) (q) attractive forces are dominant
(C) CO2 (P = 1 atm, T = 273K) (r) PV = nRT
(D) real gas with very large molar volume (s) P(V nb) = nRT
Sol. A p, s B r C p, q D p, s
PVm
(A) Z = at high pressure and low temperature.
RT
an 2
Equation P + 2 ( V nb ) = nRT reduces to P(V nb) = nRT.
V
(B) For hydrogen gas value of Z = 1 at P = 0 and it increase continuously on increasing pressure.
(C) CO2 molecules have larger attractive forces, under normal conditions.
PV
(D) Z = m , at very large molar volume Z 1.
RT
44. Match the chemical substances in Column-I with type of polymers/type of bonds in Column-II. Indicate your answer by
darkening the appropriate bubbles of the 4 4 matrix given in the ORS.
Column-I Column-II
(A) cellulose (p) natural polymer
(B) nylon-6, 6 (q) synthetic polymer
(C) protein (r) amide linkage
(D) sucrose (s) glycoside linkage
Sol. A p, s, B q, r; C p, r Ds
(A) Cellulose
O O O
O O
(Glycoside linkage)
(B) Nylon 6, 6
H O
N C
C N
O
(Amide linakge)
(C) Protein
H O
R H
C N C
N C N
R' H
H O H
(Amide linkage)
(D) Sucrose
CH2OH
H O H
H
OH H O CH2OH
OH O OH H
H OH H
H OH
(Glycoside linkage)
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This section contains 9 multiple choice questions numbered 45 to 53. Each question has 4 choices (A), (B), (C) and (D), out of
which ONLY ONE is correct.
45. A hyperbola, having the transverse axis of length 2 sin, is confocal with the ellipse 3x2 + 4y2 = 12. Then its equation is
(A) x2 cosec2 y2 sec2 = 1 (B) x2 sec2 y2 cosec2 = 1
2 2 2 2
(C) x sin y cos = 1 (D) x2 cos2 y2 sin2 = 1
Sol. (A)
x 2 y2
The given ellipse is + =1
4 3
1
a = 2, b = 3 3 = 4 (1 e2) e =
2
so that ae = 1
Hence the eccentricity e1, of the hyperbola is given by
1 = e1sin e1 = cosec
b2 = sin2(cosec2 1) = cos2
x2 y2
Hence the hyperbola is = 1 or x2cosec2 y2sec2 = 1
sin cos 2
2
46. The tangent to the curve y = ex drawn at the point (c, ec) intersects the line joining the points (c 1, ec1) and
(c + 1, ec+1)
(A) on the left of x = c (B) on the right of x = c
(C) at no point (D) at all points
Sol. (A) B
y
Slope of the line joining the points (c 1, ec 1) and (c + 1, ec + 1) is equal
ec +1 ec 1
to > ec
2
tangent to the curve y = ex will intersect the given line to the left of the A
line x = c. (c, ec)
Alternative x
The equation of the tangent to the curve y = ex at (c, ec) is O
y ec = ec(x c) (1)
Equation of the line joining the given points is
ec (e e1 )
y ec 1 = [x (c 1)] (2)
2
Eliminating y from (1) and (2), we get
[x (c 1)] [2 (e e1)] = 2e1
e + e1 2
or x c = < 0 x < c.
2 (e e1 )
the line (1) and (2) meet on the left of the line x = c.
47. A man walks a distance of 3 units from the origin towards the north-east (N 45 E) direction. From there, he walks a
distance of 4 units towards the north-west (N 45 W) direction to reach a point P. Then the position of P in the Argand
plane is
(A) 3ei/4 + 4i (B) (3 4i) ei/4
i/4
(C) (4 + 3i) e (D) (3 + 4i) ei/4
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Sol. (D) P y
Let OA = 3, so that the complex number 4
associated with A is 3ei/4. 3ei/4
If z is the complex number associated with P, A
3
z 3ei / 4 4 i / 2 4i /4
then = e = x
0 3ei / 4 3 3 O
3z 9ei/4 = 12iei/4
z = (3 + 4i)ei/4.
48. Let f(x) be differentiable on the interval (0, ) such that f(1) = 1, and
t 2f ( x ) x 2f ( t )
lim =1
t x tx
for each x > 0. Then f(x) is
1 2x 2 1 4x 2
(A) + (B) +
3x 3 3x 3
1 2 1
(C) + 2 (D)
x x x
Sol. (A)
t 2f (x) x 2f (t)
lim =1
t x tx
x2f(x) 2xf(x) + 1 = 0
1
f(x) = cx2 + also f(1) = 1
3x
2
c= .
3
2 1
Hence f(x) = x 2 + .
3 3x
Sol. (C)
1
2sin2 cos2 = 0 sin2 =
4
1
also 2cos2 = 3sin sin =
2
two solutions in [0, 2].
50. Let , be the roots of the equation x2 px + r = 0 and , 2 be the roots of the equation x2 qx + r = 0. Then the
2
value of r is
2 2
(A) ( p q )( 2q p ) (B) ( q p )( 2p q )
9 9
2 2
(C) ( q 2p )( 2q p ) (D) ( 2p q )( 2q p )
9 9
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Sol. (D)
The equation x2 px + r = 0 has roots (, ) and the equation
x2 qx + r = 0 has roots , 2 .
2
r = and + = p and + 2 = q
2
2q p 2(2p q)
= and =
3 3
2
= r = (2q p) (2p q).
9
51. The number of distinct real values of , for which the vectors 2 i + j + k , i 2 j + k and i + j 2 k are
coplanar, is
(A) zero (B) one
(C) two (D) three
Sol. (C)
2 1 1
6 2
1 2 1 = 0 3 2 = 0
1 1 2
(1 + 2)2 (2 2) = 0 = 2.
52. One Indian and four American men and their wives are to be seated randomly around a circular table. Then the
conditional probability that the Indian man is seated adjacent to his wife given that each American man is seated
adjacent to his wife is
(A) 1/2 (B) 1/3
(C) 2/5 (D) 1/5
Sol. (C)
Let E = event when each American man is seated adjacent to his wife
A = event when Indian man is seated adjacent to his wife
Now, n(A E) = (4!) (2!)5
Even when each American man is seated adjacent to his wife
Again n(E) = (5!) (2!)4
5
A n(A E) (4!) (2!) 2
P = = 4
= .
E n(E) (5!) (2!) 5
Alternative
Fixing four American couples and one Indian man in between any two couples; we have 5 different ways in which his
wife can be seated, of which 2 cases are favorable.
2
required probability = .
5
sec2 x
f ( t ) dt
2
53. lim equals
x
2
4 x2
16
8 ( ) 2 ( )
(A) f 2 (B) f 2
2 1
(C) f (D) 4f(2)
2
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Sol. (A)
sec 2 x
f (t)dt
0
2
lim 2 form
x
0
4 x2
16
f (sec 2 x)2sec x sec x tan x
Let L = lim
x
2x
4
2f (2) 8f (2)
L= = .
/4
SECTION II
This section contains 4 questions numbered 54 to 57. Each question contains STATEMENT 1 (Assertion) and STATEMENT -2
(Reason). Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.
54. Let the vectors PQ, QR, RS, ST, TU and UP represent the sides of a regular hexagon.
STATEMENT -1 : PQ ( RS + ST ) 0 .
because
STATEMENT -1 : The function F(x) satisfies F(x + ) = F(x) for all real x.
because
STATEMENT -2 : sin2(x + ) = sin2x for all real x.
(A) Statement -1 is True, Statement -2 is True; Statement-2 is a correct explanation for Statement-1
(B) Statement -1 is True, Statement -2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement -1 is True, Statement -2 is False
(D) Statement -1 is False, Statement -2 is True
Sol. (D)
1 cos 2x
sin xdx =
2
F(x) = dx
2
1
F(x) = (2x sin2x) + c.
4
Since, F(x + ) F(x).
Hence statement 1 is false.
But statement 2 is true as sin2x is periodic with period .
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56. Let H1, H2, , Hn be mutually exclusive and exhaustive events with P(Hi) > 0, i = 1, 2, , n. Let E be any other event
with 0 < P(E) < 1.
STATEMENT -1 : P(Hi | E) > P(E | Hi) . P(Hi) for i = 1, 2, , n
because
n
STATEMENT -2 : P ( Hi ) = 1
i =1
(A) Statement -1 is True, Statement -2 is true; Statement-2 is a correct explanation for Statement-1
(B) Statement -1 is True, Statement -2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement -1 is True, Statement -2 is False
(D) Statement -1 is False, Statement -2 is True
Sol. (D)
Statement : 1
H E
If P(Hi E) = 0 for some i, then P i = P = 0
E Hi
If P(Hi E) 0 for i = 1, 2 n, then
H P(H i E) P(H i )
P i =
E P(H i ) P(E)
E
P P(H i )
H E
= i > P P(H i ) [as 0 < P(E) < 1]
P(E) Hi
Hence statement 1 may not always be true.
Statement : 2
Clearly H1 H2 Hn = S (sample space)
P(H1) + P(H2) + + P(Hn) = 1.
57. Tangents are drawn from the point (17, 7) to the circle x2 + y2 = 169.
SECTION III
This section contains 2 paragraphs M5860 and M6163. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choice (A), (B), (C) and (D), out of which ONLY ONE is correct.
M5860 : Paragraph for question Nos. 58 to 60
Consider the circle x + y = 9 and the parabola y2 = 8x. They intersect at P and Q in the first and the fourth quadrants,
2 2
respectively. Tangents to the circle at P and Q intersect the x-axis at R and tangents to the parabola at P and Q intersect the x-axis
at S.
58. The ratio of the areas of the triangles PQS and PQR is
(A) 1 : 2 (B) 1 : 2
(C) 1 : 4 (D) 1 : 8
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Sol. (C) Y
( ) (
Coordinates of P and Q are 1, + 2 2 and 1, 2 2 . )
P
1
Area of PQR = 4 2 8 = 16 2 (1, 2 2)
2
R
1 S (1, 0)
Area of PQS = 4 2 2 = 4 2 O X
2 (3, 0) (1, 0)
(9, 0)
Ratio of area of triangle PQS and PQR is 1 : 4.
Q
(1, 2 2)
Let Vr denote the sum of the first r terms of an arithmetic progression (A.P.) whose first term is r and the common difference is
(2r 1). Let
Tr = Vr+1 Vr 2 and Qr = Tr+1 Tr for r = 1, 2,
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Sol. (B)
r 1
Vr = [2r + (r 1)(2r 1)] = (2r3 r2 + r)
2 2
1
Vr = 12 n(n + 1)(3n + n + 2).
2
62. Tr is always
(A) an odd number (B) an even number
(C) a prime number (D) a composite number
Sol. (D)
1 1
Vr + 1 Vr = (r + 1)3 r3 [(r + 1)2 r2] + (1)
2 2
= 3r2 + 2r + 1
Tr = 3r2 + 2r 1 = (r + 1)(3r 1)
which is a composite number.
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Sol. Ar Bq Cp Ds
a b c
1
= b c a = (a + b + c)[(a b)2 + (b c)2 + (c a)2]
c a b 2
(A). If a + b + c 0 and a2 + b2 + c2 = ab + bc + ca
= 0 and a = b = c 0
the equations represent identical planes.
(B). a + b + c = 0 and a2 + b2 + c2 ab + bc + ca
= 0 the equations have infinitely many solutions.
ax + by = (a + b)z
bx + cy = (b + c)z
(b2 ac)y = (b2 ac)z y = z
ax + by + cy = 0 ax = ay x = y = z.
(C). a + b + c 0 and a2 + b2 + c2 ab + bc + ca
0 the equation represent planes meeting at only one point.
(D). a + b + c = 0 and a2 + b2 + c2 = ab + bc + ca a = b = c = 0
the equation represent whole of the three dimensional space.
65. Match the integrals in Column I with the values in Column II and indicate your answer by darkening the appropriate
bubbles in the 4 4 matrix given in the ORS.
Column I Column II
1
dx 1 2
(A) 1 + x2 (p)
2
log
3
1
1
dx 2
(B) 1 x 2
(q) 2log
3
0
3
dx
(r)
(C) 1 x2 3
2
2
dx
(s)
(D) x 2
x 1
2
1
Sol. As Bs Cp Dr
1
dx
(A). 1 + x2 = 2
1
1
dx
(B). 1 x 2
=
2
0
3
dx 1 2
(C). 1 x 2 = 2 ln 3
2
2
dx
(D). x x 1 2
=
3
1
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66. In the following [x] denotes the greatest integer less than or equal to x.
Match the functions in Column I with the properties Column II and indicate your answer by darkening the appropriate
bubbles in the 4 4 matrix given in the ORS.
Column I Column II
(A) x |x| (p) continuous in (1, 1)
(B) x (q) differentiable in (1, 1)
Sol. A p, q, r B p, s C r, s D p, q
(D). |x 1| + |x + 1| = 2 in ( 1, 1)
the function is continuous and differentiable in ( 1, 1).
FIITJEE Ltd. ICES House, 29-A, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110016, Ph : 26515949, 26569493, Fax : 26513942
IIT-JEE - 2010
Paper-2
Chemistry
Section-1
Single Correct Choice Type
This section contains 6 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D) out of
which ONLY ONE is correct.
1.
In the reaction T, the structure of the product T is
1)
2)
3)
4)
2. Assuming that Hunds rule is violated, the bond order and magnetic nature of the diatomic molecule
B2 is
1) 1 and diamagnetic
2) 0 and diamagnetic
3) 1 and paramagnetic
4) 0 and paramagnetic
4) OSF 2
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1) Ni(CO)4
2) [NiCl4]2
3) Ni(PPh3)4
4) [Ni(CN)4]2
P.
Q.
S.
were separately subjected to nitration using HNO3/H2SO4 mixture. The major product formed in each
case respectively, is
1)
2)
3)
4)
6. The packing efficiency of the two-dimensional square unit cell shown below is
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1) 39.27%
2) 68.02%
3) 74.05%
4) 78.54%
Section-2
Integer Type
This section contains a group of 5 questions. The answer to each of the questions is a Single-digit Integer,
ranging from 0 to 9. The correct digit below the equation number in the ORS is to be bubbled.
7. Among the following, the number of elements showing only one non-zero oxidation state is
O, Cl, F, N, P, Sn, Tl, Na, Ti
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
9. One mole of an ideal gas is taken from a to b along two paths denoted by the solid and the dashed
lines as shown in the graph below. If the work done along the solid line path is Ws and that along the
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dotted line path is Wd, then the integer closest to the ratio Wd/Ws is
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
11. Silver (atomic weight = 108 g mol1) has a density of 10.5 g cm 3. The number of silver atoms on a
surface of area 1012 m 2 can be expressed in scientific notation as y 10x. The value of x is
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
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8) 7
9) 8
10) 9
Section-3
Paragraph Type
This section contains 2 paragraphs. Based upon each of the paragraphs 3 multiple choice questions have
to be answered. Each of these questions has four choices (A), (B), (C) and (D) out of which ONLY ONE is
correct.
Directions for question 12 to 14 :
The hydrogen-like species Li2+ is in a spherically symmetric state S1 with one radial node. Upon
absorbing light the ion undergoes transition to a state S2. The state S2 has one radial node and its
energy is equal to the ground state energy of the hydrogen atom.
12. The state S1 is
1) 1s 2) 2s 3) 2p 4) 3s
13. Energy of the state S1 in units of the hydrogen atom ground state energy is
1) 0.75 2) 1.50 3) 2.25 4) 4.50
2)
3)
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4)
2)
3)
4)
2)
3)
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4)
Section-4
Matrix Type
This section contains 2 questions. Each question has four choices (A), (B), (C) and (D) given in Column I
and five statements (p), (q), (r), (s) and (t) in Column II. Any given statement in Column I can have correct
matching with one or more statement(s) given in Column II. For example, if for a given question, statement
B matches with the statements given in (q) and (r), then for that particular question, against statement B,
darken the bubbles corresponding to (q) and (r) in ORS.
18. All the compounds listed in Column I react with water. Match the result of the respective reactions with
the appropriate options listed in Column II.
Column I Column II
A (CH3)2SiCl2 p Hydrogen halide formation
B XeF 4 q Redox reaction
C Cl2 r Reacts with glass
D VCl5 s Polymerization
t O2 formation
1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t
19. Match the reactions in Column I with appropriate option in Column II.
Column I Column II
Racemic
A p
mixture
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Addition
B q
reaction
Substitution
C r
reaction
Coupling
D s
reaction
Carbocation
t
intermediate
1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t
Mathematics
Section-1
Single Correct Choice Type
This section contains 5 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D) out of
which ONLY ONE is correct.
20.
Let f be a real-valued function defined on the interval (-1, 1) such that e -x f(x) = 2 + dt, for
all x (1, 1), and let f1 be the inverse function of f. Then (f1) (2) is equal to
1) 1 2) 1/3 3) 1/2 4) 1/e
21. A signal which can be green or red with probability (4/5) and (1/5) respectively, is received by station
A and then transmitted to station B. The probability of each station receiving the signal correctly is
(3/4). If the signal received at station B is green, then the probability that the original signal was green
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is
1) 3/5 2) 6/7 3) 20/23 4) 9/20
22. Let S = {1, 2, 3, 4}. The total number of unordered pairs of disjoint subsets of S is equal to
1) 25 2) 34 3) 42 4) 41
23. For r = 0, 1,. ., 10, let Ar, Br and Cr denote, respectively, the coefficient of xr in the expansions of (1 +
1) B10 C10
2) A10(B210 C10A10)
3) 0
4) C10 B10
24. If the distance of the point P(1, 2, 1) from the plane x + 2y 2z =, where > 0, is 5, then the foot
of the perpendicular from P to the plane is
1) (8/3, 4/3, -(7/3))
2) (4/3, -(4/3), 1/3)
3) (1/3, 2/3, 10/3)
4) (2/3, -(1/3), 5/2)
Section-2
Integer Type
This Section contains 5 questions. The answer to each question is a single-digit integer, ranging from 0 to
9. The correct digit below the question no. in the ORS is to be bubbled.
26. Let f be a function defined on R (the set of all real numbers) such that
f ' (x) = 2010 (x 2009) (x 2010) 2 (x 2011)3 (x 2012)4, for all x R.
If g is a function defined on R with values in the interval (0, ) such that f(x) = ln (g(x)), for all x R,
then the number of points in R at which g has a local maximum is
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
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9) 8
10) 9
27. Two parallel chords of a circle of radius 2 are at a distance (3) + 1 apart. If the chords subtend at the
center, angles of (/k) and (2/k), where k > 0, then the value of [k] is
[Note : [k] denotes the largest integer less than or equal to k]
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
29. Consider a triangle ABC and let a, b and c denote the lengths of the sides opposite to vertices A, B
and C respectively. Suppose a = 6, b = 10 and the area of the triangle is 153. If ACB is obtuse and
if r denotes the radius of the incircle of the triangle, then r 2 is equal to
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
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10) 9
30. Let a1, a2, a3,. ..., a11 be real numbers satisfying
a1 = 15, 27 2a2 > 0 and ak = 2ak 1 ak 2 for k = 3, 4,....., 11.
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
Section-3
Paragraph Type
This section contains 2 paragraphs. Based upon each of the paragraphs 3 multiple choice questions have
to be answered. Each of these question has four choices (A), (B), (C) and (D) out of which ONLY ONE is
correct.
Directions for question 31 to 33 :
Tangents are drawn from the point P(3, 4) to the ellipse (x2/9) + (y2/4) = 1 touching the ellipse at
points A and B.
31. The coordinates of A and B are
1) (3, 0) and (0, 2)
2)
3)
4)
33. The equation of the locus of the point whose distances from the point P and the line AB are equal, is
1) 9x2 + y2 6xy 54x 62y + 241 = 0
2) x2 + 9y2 + 6xy 54x + 62y 241 = 0
3) 9x2 + 9y2 6xy 54x 62y 241 = 0
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4) x2 + y2 2xy + 27x + 31y 120 = 0
35. The area bounded by the curve y = f(x) and the lines x = 0, y = 0 and x = t, lies in the interval
1) (3/4, 3)
2) (21/64, 11/16)
3) (9, 10)
4) (0, 21/64)
Section-4
Matrix Type
This Section contains 2 questions. Each question has four statements (A, B, C and D) given in Column I
and five statements (p, q, r, s and t) in Column II. Any given statement in Column I can have correct
matching with one or more statement(s) given in Column II. For example, if for a given question, statement
B matches with the statements given in q and r, then for that particular question, against statement B,
darken the bubbles corresponding to q and r in the ORS.
37. Match the statements in Column-I with the values in Column-II.
Column-I Column-II
A line from the origin meets the lines
and
A p -4
at P and Q
t 6
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t 6
1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t
1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
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13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t
Physics
Section-1
Single Correct Choice Type
This section contains 6 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONLY ONE is correct.
39. A biconvex lens of focal length 15 cm is in front of a plane mirror. The distance between the lens and
the mirror is 10 cm. A small object is kept at a distance of 30 cm from the lens. The final image is
1) Virtual and at a distance of 16 cm from the mirror
2) Real and at a distance of 16 cm from the mirror
3) Virtual and at a distance of 20 cm from the mirror
4) Real and at a distance of 20 cm from the mirror
40. A uniformly charged thin spherical shell of radius R carries uniform surface charge density ofper
unit area. It is made of two hemispherical shells, held together by pressing them with force F (see
figure). F is proportional to
1) (1/ 0) 2R2
2) (1/ 0) 2R
3) (1/ 0) (2/R)
4) (1/ 0) (2/R2)
41. A hollow pipe of length 0.8 m is closed at one end. At its open end a 0.5 m long uniform string is
vibrating in its second harmonic and it resonates with the fundamental frequency of the pipe. If the
tension in the wire is 50 N and the speed of sound is 320 ms1, the mass of the string is
1) 5 grams
2) 10 grams
3) 20 grams
4) 40 grams
42. A Vernier calipers has 1 mm marks on the main scale. It has 20 equal divisions on the Vernier scale
which match with 16 main scale divisions. For this Vernier calipers, the least count is
1) 0.02 mm
2) 0.05 mm
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3) 0.1 mm
4) 0.2 mm
43. A block of mass 2 kg is free to move along the x-axis. It is at rest and from t = 0 onwards it is
subjected to a time-dependent force F(t) in the x direction. The fore F(t) varies with t as shown in the
figure. The kinetic energy of the block after 4.5 seconds is
1) 4.50 J
2) 7.50 J
3) 5.06 J
4) 14.06 J
44. A tiny spherical oil drop carrying a net charge q is balanced in still air with a vertical uniform electric
field of strength (81/7) 10 5 Vm -1. When the field is switched off, the drop is observed to fall with
terminal velocity 2 103 ms1. Given g = 9.8 ms2, viscosity of the air = 1.8 105 Ns m 2 and the
density of oil = 900 kg m 3, the magnitude of q is
1) 1.6 1019 C
2) 3.2 1019 C
3) 4.8 1019 C
4) 8.0 1019 C
Section-2
Integer Type
This section contains 5 questions. The answer to each of the questions is a single-digit integer, ranging
from 0 to 9. The correct digit below the question number in the ORS is to be bubbled.
45. Image of an object approaching a convex mirror of radius of curvature 20 m along its optical axis is
observed to move from (25/3) m to (50/7) m in 30 seconds. What is the speed of the object in km per
hour ?
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
46. A diatomic ideal gas is compressed adiabatically to (1/32) of its initial volume. If the initial temperature
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of the gas is T i (in kelvin) and the final temperature is aT i, the value of a is
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
47. To determine the half life of a radioactive element, a student plots a graph of |dN(t)/dt| versus t. Here
(dN(t)/dt) is the rate of radioactive decay at time t. If the number of radioactive nuclei of this element
decreases by a factor of p after 4.16 years, the value of p is
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
48. At time t = 0, a battery of 10 V is connected across points A and B in the given circuit. If the capacitors
have no charge initially, at what time (in seconds) does the voltage across them become 4 V?
[Take : ln 5 = 1.6, ln 3 = 1.1]
1) 0
2) 1
3) 2
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4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
49. A large glass slab ( = 5/3) of thickness 8 cm is placed over a point source of light on a plane surface.
It is seen that light emerges out of the top surface of the slab from a circular area of radius R cm.
What is the value of R?
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
Section-3
Paragraph Type
This section contains 2 paragraphs. Based upon each of the paragraphs 3 multiple choice questions have
to be answered. Each of these questions has four choices (A), (B), (C) and (D) out of which ONLY ONE is
correct.
Directions for question 50 to 52 :
The key feature of Bohrs theory of spectrum of hydrogen atom is the quantization of angular
momentum when an electron is revolving around a proton. We will extend this to a general rotational
motion to find quantized rotational energy of a diatomic molecule assuming it to be rigid. The rule to
be applied is Bohrs quantization condition.
50. A diatomic molecule has moment of inertia l. By Bohrs quantization condition its rotational energy in
the nth level (n = 0 is not allowed) is
1) (1/n2) (h2/82l)
2) (1/n) (h2/82l)
3) n (h2/82l)
4) n2 (h2/82l)
51. It is found that the excitation frequency from ground to the first excited state of rotation for the CO
molecule is close to (4/) 10 11 Hz. Then the moment of inertia of CO molecule about its centre of
mass is close to (Take h = 2 1034 J s)
1) 2.76 1046 kg m 2
2) 1.87 1046 kg m 2
3) 4.67 1047 kg m 2
4) 1.17 1047 kg m 2
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52. In a CO molecule, the distance between C (mass = 12 a.m.u.) and O (mass = 16 a.m.u.), where 1
a.m.u. = (5/3) 10-27 kg, is close to
1) 2.4 1010 m
2) 1.9 1010 m
3) 1.3 1010 m
4) 4.4 1011 m
54. If r = 5 104 m, = 103 kgm 3, g = 10 ms2, T = 0.11 Nm 1, the radius of the drop when it detaches
from the dropper is approximately
1) 1.4 103 m
2) 3.3 103 m
3) 2.0 103 m
4) 4.1 103 m
Section-4
Matrix Type
This section contains 2 questions. Each Question has four statements (A, B, C and D) given in Column I
and five statements (p, q, r, s and t) in Column II. Any given statement in Column I can have correct
matching with one or more statement(s) given in Column II. For example, if for a given question, statement
B matches with the statements given in q are r, then for that particular question, against statement B,
darken the bubble corresponding to q and r in the ORS.
56. You are given many resistances, capacitors and inductors. These are connected to a variable DC
voltage source (the first two circuits) or an AC voltage source of 50 Hz frequency (the next three
circuits) in different ways as shown in Column II. When a current I (steady state for DC or rms for AC)
flows through the circuit, the corresponding voltage V1 and V2. (indicated in circuits) are related as
shown in Column I.
Column I Column II
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A I 0, V1 is proportional to I p
B I 0, V2 > V1 q
C V1 = 0, V2 = V r
D I 0, V2 is proportional to I s
1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t
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57. Two transparent media of refractive indices 1 and 3 have a solid lens shaped transparent material
of refractive index 2 between them as shown in figures in Column II. A ray traversing these media is
also shown in figures. In Column I different relationships between
1 , 2 and 3 are given. Match
them to the ray diagrams shown in Column II.
Column I Column II
A 1 < 2 p
B 1 > 2 q
C 2 = 3 r
D 2 > 3 s
1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t
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Answer Key
1) 3 2) 1 3) 4 4) 2 5) 3 6) 4 7) 3 8) 7 9) 3 10) 4
11) 8 12) 2 13) 3 14) 2 15) 2 16) 1 17) 4 18) 1,4,6,7,8,10,11,12,16 19) 3,4,10,11,12,18 20) 2
21) 3 22) 4 23) 4 24) 1 25) 2 26) 2 27) 4 28) 5 29) 4 30) 1
31) 4 32) 3 33) 1 34) 3 35) 1 36) 2 37) 5,6,8,12,18 38) 2,3,6,11,14,15,17,18,19,20 39) 2 40) 1
41) 2 42) 4 43) 3 44) 4 45) 4 46) 5 47) 9 48) 3 49) 3 50) 4
51) 2 52) 3 53) 3 54) 1 55) 2 56) 3,4,5,7,8,9,10,11,12,17,18,19,20 57) 1,3,7,9,10,11,13,15,17,19
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Prepared by Aneesh Damodaran
IONIC CRYSTALS
1) In the following diagram, the circles filled with black color represent the cations, whereas the big
circles represent the anions.
7) The number of NaCl units present in a single unit cell of NaCl crystal is
1) 1 2) 2 3) 4 4) 6
+
8) The number of octahedral holes occupied by Na ions in a single unit cell of NaCl is
1) 4 2) 8 3) 2 4) Zero
9) Which of the following does not crystallise in the rock salt structure
1) NaCl 2) KCl 3) CsCl 4) MgO
Note : Usually halides of Cesium assume BCC structures as the limiting radius ratio is greater than 0.732
10) The number of nearest Cl- ions around an Na+ ion in NaCl crystal is
1) 8 2) 6 3) 4 4) 12
- -
11) The number of nearest Cl ions arround a Cl ion in NaCl crystal is
1) 8 2) 6 3) 4 4) 12
+ -
12) The radii of Na and Cl ions are 95 pm and 181 pm respectively. The edge length of unit cell in
NaCl is
1) 457 pm 2) 552 pm 3) 190 pm 4) 362 pm
Note : edge length in NaCl = 2rc+ 2ra
13) The crystal structure present in CsCl is referred to as
1) FCC 2) BCC 3) HCP 4) None
Note : BCC structure is present when the limiting radius ratio isgreater than 0.732. The anions occupy the lattice points
of simple cubic lattice. The cations occcupy centred cubic voids. This structure can be considered as interpenetrating
primitive cubic lattices of cation and anion.
The co-ordination numbers are (8:8). The number of formula units present per a single unit cell is one (one cation and
one anion). The general formula is AB.
Examples : CsCl, CsBr, CsI, CsCN, TlCl, TlBr, TlI, TlCN etc.,
14) The number of nearest Cl- ions present around a Cs+ ions in CsCl crystal is
1) 6 2) 8 3) 12 4) 4
15) The number of nearest Cs+ ions present around a Cs+ ion in CsCl crystal is
1) 8 2) 6 3) 4 4) 12
Hint : If only Cs+ ions are considered they occupy lattice points of primitive cubic lattice
16) The number of second nearest Cs+ ions present around a Cs+ ion in CsCl is
1) 4 2) 8 3) 12 4) 6
+ -
17) The radii of Cs and Cl ions are 1.69 and 1.81 respectively. The edge length of the unit cell
in CsCl will be
1) 7 2) 3.38 3) 4.04 4) 3.5
Hint : In BCC, the ions touch along the body diagonal
Length of body diagonal = 2rc+2ra = 3a
18) The ionic compound which crystallises in anti-fluorite structure is
1) NaCl 2) Na2O 3) CaF2 4) Al2O3
Note : In the anti-fluorite structure, anions are arranged in cubic closest packing and cations occupy all the tetrahedral
voids. There are four anions and eight cations per unit cell of this structure and hence, the general formula of an ionic
compound is A8B4 or A2B.
The ideal radius ratio is between 0.225 - 0.414. But this ratio is not always maintained.The co-ordination numbers of
cation and anion are (4:8).
Examples : Na2O, K2O, Li2O, Rb2O, K2S, Cl2O, Na2S etc.,
19) In a unit cell of an ionic crystal, anions (Y) occupy the lattice points of face centred cubic lattice
and cations (X) occupy all the tetrahedral voids. The formula of the ionic compound will be
1) XY2 2) X2Y2 3) X2Y 4) XY
20) The number of anions per a single unit cell in antifluorite structure is
1) 2 2) 4 3) 8 4) 1
21) The type of voids occupied by cations in antifluorite structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
22) The co-ordination number of Na+ ions in Na2O is
1) 2 2) 4 3) 8 4) None
2-
23) The type of voids occupied by O ions in Na2O crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
+
24) The number of Na ions present per a single unit cell in Na2O crystal is
1) 4 2) 2 3) 8 4) 12
25) The fluorite crystal structure is present in
1) NaF 2) CaF2 3) AlF3 4) CsF
Note : In the fluroite structure, the cations are arranged into cubic close packing and the anions occupy all the tetrahedral
voids. Thus there are four cations and eight anions per a unit cell. Hence the formula of ionic compound is A4B8 or AB2.
The co-ordination numbers of cation and anion are (8:4).
Examples : CaF2, ZrO2, UO2, ThO2, BaF2, BaCl2, SrCl2, PbCl2 etc.,
26) The number of anions per a single unit cell in fluorite structure is
1) 2 2) 4 3) 8 4) 1
27) The type of voids occupied by anions in fluorite structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
28) The co-ordination number of Ca2+ ions in CaF2 is
1) 2 2) 4 3) 8 4) None
29) The type of voids occupied by Ca2+ ions in CaF2 crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
2+
30) The number of Ca ions present per a single unit cell in CaF2 crystal is
1) 4 2) 2 3) 8 4) 12
2+ -
31) The radii of Ca and F ions respectively are 100 pm and 131 pm. The edge length of the unit
cell in CaF2 is
1) 231 pm 2) 533.5 pm 3) 462 pm 4) 362.5 pm
Hint: The Fluoride ions are present along the body diagonal at one fourth distance from the corner of the cube. Hence the
distance between calcium and fluoride ions is 1/4th of length of body diagonal.
32) The substance containing zinc-blende crystal structure is
1) NaCl 2) ZnCl2 3) BeO 4) CsCl
Note: In zinc-blende or sphalerite structure, anions occupy the face centred cubic lattice points and cations occupy half of
the tetrahedral holes (of one type). The ideal radius ratio is in between 0.225 to 0.414. There are four anions and four
cations in the unit cell. Therefore the formula is A4B4 or AB. The co-ordination numbers of cation and anion are (4:4).
Examples: ZnS, BeO etc.,
33) The number of anions per a single unit cell in zinc-blende structure is
1) 2 2) 4 3) 8 4) 1
34) The type of voids occupied by cations in zinc-blende structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
35) The co-ordination number of Zn2+ ions in ZnS is
1) 2 2) 4 3) 8 4) None
36) The type of voids occupied by S2- ions in ZnS crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
2+
37) The number of Zn ions present per a single unit cell in ZnS crystal is
1) 4 2) 2 3) 8 4) 12
2-
38) The co-ordination number of S ions in ZnS is
1) 2 2) 4 3) 8 4) None
39) The compound containing spinel structure is
1) MgAl2O4 2) Fe2O3 3) ThO2 4) KCl
Note: In spinel structure, the oxide ions are arranged in cubical closest packing and one eighth of the tetrahedral holes are
occupied by divalent metal ion (A2+) and one half of the octahedral holes are occupied by trivalent metal ions (B3+). Thus
in a unit cell there are four oxide ions, one divalent metal ion(A2+) and two trivalent metal ions (B3+). The general formula
of the compound is AB2O4.
Examples: MgAl2O4,ZnAl2O4, ZnFe2O4 etc.,
40) The crystal structure present in Al2O3 is called as
1) corundum structure 2) spinel structure 3) rock-salt structure 4) Fluorite structure
Note: In the corundum structure, anions form hexagonal closest packing and cations are present in 2/3 of the octahedral
holes. The general formula of the compound is M2O3.
Examples: Fe2O3, Al2O3, Cr2O3 etc.,
41) Inverse spinel structure is found in
1) Chromite 2) Magnetite 3) Spinel 4) Corundum
KEY
1) 3 2) 3 3) 2 4) 2 5) 1 6) 2 7) 3 8) 1 9) 3 10) 2 11) 4 12) 2
13) 2 14) 2 15) 2 16) 3 17) 3 18) 2 19) 3 20) 2 21) 2 22) 2 23) 3 24) 3
25) 2 26) 3 27) 2 28) 3 29) 3 30) 1 31)2 32) 3 33) 2 34) 2 35) 2 36) 1
37) 1 38) 3 39) 1 40) 1 41) 2
METALLURGY
IIT-JEE
ORES
1) The characteristics of an ore is/are
1) high percentage of metal 2) low amounts of easily removable impurities
3) Low expenditure needed for the exraction 4) All
2) Which one of the following is not an oxide ore ?
1) Bauxite 2) Cuprite 3) Magnetite 4) Iron pyrites
Note : Bauxite Al2O3. 2H2O
Cuprite Cu2O
Magnetite Fe3O 4
Iron pyrites FeS2
3) Which one of the following is not an ore of iron
1) Magnetite 2) Hematite 3) Siderite 4) Cassiterite
Note : Hematite - Fe2O 3
Siderite - FeCO 3
Cassiterite - SnO2
4) The ore which does not contain Zinc is
1) Zinc blende 2) Zincite 3) Calamine 4) Zircon
Note : Zincite - ZnO
Zinc blend - ZnS
Calamine - ZnCO3
Zircon - ZrSiO4
5) Match the following
A) Malachite 1) AgCl
B) Horn Silver 2) PbSO4
C) Anglesite 3) Cr2O3. FeO
D) Chromite 4) CuCO3.Cu(OH)2
The correct Matching is
A B C D
1) 4 1 3 2
2) 4 1 2 3
3) 2 1 4 3
4) 3 1 2 4
6) The phosphate ore of calcium is
1) Dolomite 2) Barytes 3) Monite 4) Argentite
Note : Dolomite : CaCO3. MgCO3
Barytes : BaSO4
Monite : Ca3 (PO4)3. H2O
Argentite : Ag2S
7) Which among the following is a sulphide ore of copper
1) Malachite 2) Azurite 3) Copper pyrites 4) Cuprite
Note : Malachite - CuCO3 . Cu(OH)2
Azurite - [2 CuCO3]. Cu(OH)2
Copper pyrites - Cu2S. Fe2S3
Cuprite - Cu2O
8) The silicate mineral of Thorium is
1) Thorite 2) Monazite 3) Cryolite 4) None
Note : Thorite - ThSiO4
Monazite - Phosphate mineral of Thorium and other rare earths
Cryolite - Na3AlF6
9) Galena is the mineral of
1) Zn 2) Pb 3) Pd 4) Ni
Note : Galena - PbS
10) The element(s) that may occur in the native form in the nature is
1) Gold 2) Silver 3) Copper 4) All
11) The mineral which does not contain fluorine as one of the constituent element is
1) Cryolite 2) Fluorite 3) Both 1 & 2 4) None
Note : Cryolite - Na3AlF6
Fluorite - CaF2
12) Match the following
A) Cerussite 1) MgSO4. 7H2O
B) Copper glance 2) 3Fe2O3. 3H2O
C) Limonite 3) Cu2S
D) Epsomite 4) PbCO3
The correct matching is
A B C D
1) 1 2 4 3
2) 4 3 2 1
3) 2 4 3 1
4) 4 3 1 2
13) The chemical composition of wulfenite is
1) CuCO3. Cu(OH)2 2) PbMnO4 3) WO3 4) TiO2
14) The chemical composition of ruby copper is
1) Cu2O 2) Cu2S 3) CuCO3 4) Cu (OH)2
15) The ore of mercury is
1) Cinnabar 2) Fluorspar 3) Phosphorite 4) Argentite
Note : Cinnabar - HgS
16) The chemical composition of pyrolusite is
1) PbSO4 2) MnO2 3) PbS 4) Al2O3
17) Pitch blend is the chief ore of
1) Palladium 2) Lead 3) Uranium 4) Cesium
Note : Pitch blend - U3O8
18) The silicate ore of zinc is
1) Zinc blend 2) Willemite 3) Mica 4) Zincite
Note : Willemite - Zn2SiO4
19) The chemical composition of chile salt petre is
1) KNO3 2) NaNO3 3) AgNO3 4) Fe2O3
Note : KNO3 - Indian salt peter
NaNO3 - Chile salt peter
20) The composition of spathic iron ore is
1) Fe2S 2) FeS2 3) FeCO3 4) None
Note : Sideritic or spathic iron ore - FeCO3
21) Match the following
A) CaMg3 (SiO3)4 1) Pentlandite
B) KCl. MgCl2. 6H2O 2) Carnallite
C) (Ni, Fe) S 3) Asbestos
D) TiO2 4) Rutile
The correct matching is
A B C D
1) 3 2 1 4
2) 1 2 3 4
3) 3 2 4 1
4) 4 2 1 3
22) The chemical composition of ruby silver is
1) AgCl 2) Ag3SbS3 3) Ag2S 4) AgCO3
23) The sulfide ore of copper which does not contain iron is
1) Copper pyrites 2) Cuprite 3) Chalcocite 4) Cobaltite
Note : Chalcosite - Cu2S
Cobaltite - CoAsS
24) Wolframite and Scheelite are the ores of
1) Zinc 2) Manganese 3) Tungsten 4) Gold
Note : Wolframite - (Fe, Mn) WO4
Scheelite - CaWO4
25) The silicate form of beryllium is
1) Beryl 2) Emerald 3) Aquamarine 4) All
Note : Beryl is the silicate ore of beryllium (Be3Al2 (SiO3)6)
Emerald and Aquamarine are the gemstone varieties of beryl.
Emerald - Green colored due to presence of chromium
Aquamarine - Transparent variety of beryl with a delicate blue color.
26) The chemical composition of sphalerite is
1) ZnS 2) MnS 3) ZnSO4 4) NaCl
Note : ZnS is also called as Zincblend.
27) Ruby and sapphire are the gemstone varieties of
1) Bauxite 2) Corundum 3) Gibbsite 4) Gold
28) The stone which floats on water is
1) Sand stone 2) Pumice 3) Topaz 4) Hyacinth
29) Cooperite is the ore containing
1) Pt 2) Pd 3) Ni 4) All
Note : Cooperite - (Pt, Pd, Ni) S
30) The mineral containing Lithium is
1) Spodumene 2) Lepidolite 3) Petalite 4) All
Note : Spodumene - LiAl (SiO3)2 - (an inoslilicate)
Lepidolite - K Li2Al (Al, Si)3O10(F, OH)2 - (A phyllosilicate)
Petalite - LiAlSi4O10 (a tecto silicate)
31) The formula of stibnite (antimonite) is
1) SbS2 2) Sb2S 3) Sb2S3 4) Sb2S5
ORE DRESSING
1) Choose the incorrect statement
i) The rocky, sandy and siliceous impurities associated with minerals are called gangue
ii) Flux is the chemical substance that reacts with infusible gangue by forming a fusible mass
called slag.
iii) The density of slag is less than that of metal
iv) All minerals are ores.
The correct statement (s)
1) i & iii 2) i only 3) iv only 4) iii & iv
2) The chemical composition of Thomas slag, used as a fertilizer, is
1) CaSO4. 2H2O 2) Ca3(PO4)2 3) Ca(NO3)2 4) CaSiO3
3) The basic flux used to remove SiO2 is
1) Al2O3 2) CaO 3) MgCl2 4) None
Note : SiO 2 + CaO CaSiO3
Acidic gangue basic flux slag
4) Which of the following ore concentration methods depends upon difference in specific gravity of
the ore particles and impurities
1) Levigation method 2) Washing method 3) Wilfley method 4) All
5) The ore which can be concentrated by liquation method is
1) Stibnite 2) Heamatite 3) Magnesite 4) All
6) The ore cassiterite is concentrated by
1) Magnetic method 2) Liquation 3) Froath floatation 4) Wilfley method
7) The separation of magnetite (Fe3O4), Chromite (Cr2O3. FeO) and pyrolusite (MnO2) ores
from the non magnetic gangue is usually done by
1) Leaching 2) Magnetic separation 3) Liquation 4) None
8) The magnetic impurity present in cassiterite (SnO)2 is
1) Wolframite 2) Bauxite 3) Galena 4) Willemite
9) The usual technique employed in separation of gangue from hydrophobic sulfide ores is
1) Froth floatation 2) Leaching 3) Roasting 4) Levigation
10) Choose the correct statement related to froth flotation process
a) Collectors like potassium ethyl xanthate are used to enhance the non wettability
(hydrophobicity) of mineral particles.
b) Pine oil is used as frother, which helps in formation of froth
c) Froth is stabilised by adding froth stabilizers like aniline or cresol
d) The gangue particles are more hydrophilic than ore particles and sink to the bottom
The correct statement (s)
1) a & c 2) a only 3) c & d 4) All
H
11) The modifier used to increase the p during froth flotation process is
1) Soda ash 2) Lime 3) H2SO4 4) 1 or 2
12) The depressant used to suppress the floating of galena is
1) Lime 2) Soda ash 3) NaCN 4) All
13) The depressant used to prevent ZnS to form froth is
1) Soda ash 2) NaCN 3) Aniline 4) None
Note : NaCN forms a layer of Na2[Zn(CN)4] on the surface of ZnS particle and thus by preventing if from the ormation of
froth.
ZnS + NaCN Na2[Zn(CN)4] + Na2S
This technique is used to separate Galena - PbS (which forms froth selectively) from ZnS particles
14) The separation of ore by converting it into a water soluble compound by reacting with a suitable
chemical subtance is called
1) Roasting 2) Leaching 3) Liquation 4) Smelting
15) In the Bayers process, the leaching of alumina is done by using
1) Na2CO3 2) NaOH 3) SiO2 4) CaO
Note : Alumina is converted to water soluble sodium meta aluminate by treating with sodium hydroxide
Al2O3 + 2NaOH 2NaAlO2 + H2O
(or)
2 Al2O3 (s) + 2OH- (aq) + 3H2O 2[Al(OH)4]- (aq)
16) The leaching agent used in concentration of argentite ore is
1) NaCN 2) NaCN + O2 3) NaOH 4) O2
Hint : Ag2S + 4NaCN + 2O2 2Na[Ag(CN)2] + Na2SO4
Soluble complex
17) Cupric oxide can be leached by using
1) NaOH 2) NaCN 3) H2SO4 4) O2
Hint : CuO + H2SO4 CuSO4 + H2O
water soluble
REFINING OF METALS
1) Impure tin can be refined by
1) Roasting 2) Liquation 3) Smelting 4) Calcination
2) The method which uses green wood poles to reduce the oxide impurites from impure metals is
called
1) Cupellation 2) Green wood process 3) Poling 4) Smelting
3) The metal which can be refined by distillation process is
1) Zn 2) Cd 3) Hg 4) All
4) The best method used to refine gold metal is
1) Distillation 2) Electrolysis 3) Bassemerization 4) Oxidation
5) The suitable method used to remove lead impurity from impure silver is
1) Poling 2) Cupellation 3) Distillation 4) All
6) Highly pure silicon can be obtained by
1) Electrolysis 2) Roasting 3) Zone refining 4) Liquation
7) The complex of nickel formed during Monds process is
1) NiCl4 2) Ni(CO)4 3) Ni(CO)6 4) K2[Ni (CN)4]
Note : Monds process is a vapour phase refining method of nickel. In this process, nickel is converted to volatile nickel
tetracarbonyl by heating in a stream of carbon monoxide at 330-350K. Then the complex is subjected to dissociation by
heating at higher temperature (450 - 470K) to get pure nickel
330-350K 450-470K
Ni + 4 CO Ni (CO) 4 Ni + 4CO
impure Volatile Pure
PERIODIC TABLE
* He corrected the atomic weights of some elements like Beryllium, Indium, Uranium.
Periodic Table 2
Limitations :
* Zero group elements were not known at the time of Mendeleef.
* In every group lanthanides were placed though they have dissimilar properties.
* At some places it violates the increasing order of atomic weight rule.
Ar40 & K39
Co59 & Ni58
Te128 & I127
Th 232 & Pa 231
These four pairs are called anomalous pairs or inverted pairs.
* Elements with dissimilar properties were grouped together.
E.g. ' Th' is placed in III group and Ag is placed in I group.
* Atomic mass is taken as fundamental property.
Groups:
* The 18 groups in the periodic table are numbered as IA , IIA, IIIB. .... VIII (3 groups) IB ,IIB,
IIIA - VIIA and zero group.
* I A to VII A group elements are called representative elements.
* Zero group elements are called inert gases.
* IB to VII B and VIII B group element are called transition elements.
* The elements present in a group show similar chemical properties as they have similar outer
electronic configuration.
Periods:
* Each period starts with alkali metals (IA) and ends with inert gas elements.
* The first period is a very short period with only two elements i.e., Hydrogen (H) & Helium (He).
* The second period starts with Lithium (Li) and ends with Neon (Ne) and contains 8 elements. It
is called first short period.
* The third period also contain 8 elements i.e., from Sodium (Na) to Argon (Ar). It is called
second short period.
* The fourth period is the first long period with 18 elements , it starts Potassium (K) &
ends with Krypton (Kr). It also includes 10 elements belonging to 3d series i.e., from
Scandium (Sc) to Zinc (Zn).
* The fifth period is the second long period with 18 elements, it starts with Rubidium (Rb) and
ends with Xenon (Xe). It also includes 10 elements belonging to 4d series i.e. from Yttrium (Y) to
Periodic Table 3
Cadmium (Cd).
* The sixth period is the longest period with 32 elements. It not only includes 10 elements belong-
ing to 5d series i.e., Lanthanum (La), Hafnium (Hf) to Mercury (Hg) but also contain 14 elements
belonging the 4f series called lanthanides (Cerium(Ce) to Lutetium (Lu)).
* The seventh is an incomplete period which starts with Fr. It includes the 14 elements belonging
to 5f series called actinides (Thorium (Th) to Lawrencium (Lr)).
* Lanthanides and actinides are placed below the period separately.
Advantages:
1. The chemical and physical properties of the elements can be studied easily.
2. Position of metals and nonmetals can be know.
3. The chemistry of transition elements can be studied along with d-block elements.
THE RELATION BETWEEN THE NUMBER OF ELECTRONS FILLED INTO THE SUB
SHELLS AND THE NUMBER OF ELEMENTS IN A PERIOD
In the long form of periodic table, there are seven periods according to the number of main shells
being filled up by electrons.
Each period starts with filling up of a new quantum level. In each period, the number of elements is
equal to the number of electrons filled into the subshells as shown below.
2) p - block
* In p-block elements, the differentiating electrons enter into p-orbitals of outer shell.
* The general electronic configuration is ns 2 np1 6
* The IIIA to 'zero' group elements belong to this block. These are present at the right hand side
of the periodic table.
Periodic Table 4
Group III A Boron family ns2np1
Group IV A Carbon family ns2np2
Group V A Nitrogen family ns2np3
Group VI A Oxygen family ns2np4
Group VII A Halogen family ns2np5
Group O Inert gases ns2np6 (except He which has 1s2 configuration)
* These elements constitute nonmetals, metals and metalloids and inert gases.
* These elements can exhibit both negative and positive states.
3) d - block
* In d - block elements, the differentiating electron enters into d - orbitals of (n-1) shell.
* The general outer electronic configuration is (n-1)d1-10 ns1,2
* These elements are present in between s and p-block elements.
* Depending on the principal quantum number of d - orbital into which the last electron enters,
these elements are again divided into following series.
3d series Sc to Zn 4th Period
4d series Y to Cd 5th Period
5d series La, Hf to Hg 6th Period
6d series Ac - (incomplete) 7th Period
* All the d-block elements are metals and are usually called as transition elements.
* These elements show variable oxidation states, paramagnetism and color. They can effectively
form complex compounds, alloys and non-stoichiometric compounds.
* These elements and their compounds are good catalysts.
E.g., 1) Ni in hydrogenation of oils
2) Fe / Mo in Haber's process of synthesis of NH3.
3) Platinized asbestos in the manufacture of H2SO4.
* These elements can form alloys effectively.
E.g., Brass, Bronze, German silver, etc.,
4) f -block
* In f-block elements, the differentiating electrons enter into f-orbitals of (n-2) shell.
1-14 0 or 1 2
* The general outer electronic configuration is (n-2)f (n-1)d ns
* These elements belong to IIIB group and are placed below the table separately these are also
called as inner transition elements.
* The 14 elements from Cerium(Ce) to Lutetium (Lu) which follow the elements Lanthanum are
called as Lanthanoids or rare earth elements.
In these elements the differentiating electrons enter into 4f-orbitals and hence are also
called as 4f -series.
* The 14 elements from Thorium (Th) to Lawrencium (Lr), which follow Actinium are called
Actinoids. In these element the differentiating electrons enter into 5f-orbitals and hence these are also
known as 5f-series.
* All of these elements are radioactive. The elements after Uranium are called trans uranic ele-
ments. These are artificially prepared elements.
* These elements show +3 common oxidation state.
Periodic Table 5
s-block p-block
d-block
f-block
2) Representative elements :
* The s & p-block elements except zero group elements are called representative elements.
* The outer electronic configuration is ns1-2 np 0 5
* In these elements, the outer shell is incompletely filled.
* This group includes metals, nonmetals and metalloids.
* These elements can share or gain or lose electrons to get octet configuration.
3) Transition elements :
* The d-block elements except II B group (Zn, Cd and Hg), are called as transition elements.
* In these elements the last two shells (n and n-1) are incompletely filled
* The general outer electronic configuration is (n-1)d1-10 ns1,2
* Due to small size, high nuclear charge and presence of incompletely filled d-orbitals, these
elements show characteristic properties as given below.
i) These elements are very hard and heavy metals with high melting and boiling points.
ii) These are good conductors of heat and electricity.
iii) They exhibit variable oxidation states.
E.g., Fe exhibits +2 and +3 oxidation states.
iv) The transition metal ions show colors due to d-d transitions.
v) They show paramagnetism due to presence of unpaired electrons.
vi) Transition metals and their compounds are good catalysts.
E.g., 1) Ni in hydrogenation of oils.
2) Fe / Mo in Haber's process of synthesis of NH3.
3) Platinized asbestos in the manufacture of H2SO4.
Periodic Table 6
vii) These elements can form alloys effectively.
E.g., Brass, Bronze, German silver, etc.,
PERIODICITY
The recurrence of similar chemical and physical properties at regular interval of atomic numbers in
a periodic table is called Periodicity.
Periodic Properties : The properties which show periodicity.
E.g., (i) Density
(ii) Melting and boiling points
(iii) Hardness
(iv) Conductivity
(v) Magnetic property
(vi) Atomic radius
(vii) Ionic radius
(viii) Ionization potential
(ix) Electronegativity
(x) Electron affinity
(xi) Electropositivity
(xii) Valency
(xiii) Oxidation number
(xiv) Metallic and non metallic nature
(xv) Nature of oxides
ATOMIC RADIUS :
The average distance between the centre of the nucleus and the electron cloud of outermost orbit
is called atomic radius.
There are three types of atomic radii based on the nature of bonding.
(i) Crystal radius ( atomic radius ) : The half of inter nuclear distance between two adjacent atoms
in a metallic crystal.
It is applicable to metals.
e.g.
3.72
1) The distance between two Na atoms is 3.72 A0. Hence its crystal radius is =1.86 A o .
2
Periodic Table 7
5.24
2) The distance between two Cs atoms is 5.24 A0. Hence its crystal radius is =2.62 A o .
2
(ii) Covalent radius : The half of inter nuclear distance between two atoms held together by a
covalent bond.
0.99A 0
1.
86
A 0
In periods : Atomic radius decreases across the period from left to right as the nuclear charge and
atomic number increase. The differentiating electron enters into same shell.
In a given period IA group element is bigger in size and VII A group element is smaller in size. The
abnormal increase in case of zero group element is due to its van der Waal's radius.
E.g., Order of atomic size in 2nd period
Li > Be > B > C > N > O > F < Ne
In transition elements : The atomic size decreases slightly across the period in d-block elements
due to shielding effect of inner d- electrons.
In Lanthanoids : The atomic radius decreases with increase in atomic number in Lanthanoids due to
poor shielding effect of inner f - electrons. This is called Lanthanoid contraction.
Periodic Table 8
Consequences of Lanthanoid contraction
i) Lanthanoids possesses similar crystalline structures and hence their separation is difficult.
ii) Elements of 4d and 5d series show more similarity in their properties.
E.g., Zirconium (Zr), ( 4d series) and Hafnium (Hf), ( 5d series) have almost same atomic radii.
IONIC RADIUS
* The ionic radius decreases with increase in effective nuclear charge.
* In case of cations, the ionic radius decreases with increase in the positive charge.
A+ > A2+ > A3+ . .............
* In case of anions, the size increases with increase on the negative charge.
A- < A2- < A3- . .............
* In a group, for same type of ions the ionic radius increases from top to bottom.
E.g., The ionic radii of M+ ions in I A group elements increase in the following order.
Li+ < Na+ < K+ < Rb+ < Cs+ < Fr+
* In a given period, the ionic radius decreases with increase in effective nuclear charge for isoelec-
tronic ions.
C4- > N3- > O2- > F-
Nuclear charge 6 7 8 9
No. of electrons 10 10 10 10
In periods : In general, the ionization energy increases from left to right in a period with decrease in
atomic radius. But this increment is not regular.
In a given period, IIA (ns2) and VA (ns2np3) group elements have higher ionization energies than
elements in their next groups i.e., III A and VI A respectively. It is due to stable electronic configura-
tions.
E.g., The order of ionization energies in 2nd period is given below
Li < Be > B < C < N > O < F << Ne
2s2 2s22p3 2s22p6
2 2 3
'Be' with 2s (full filled) and 'N' with 2s 2p (half filled) configurations are more stable and hence
possess higher ionization potentials than 'B' and 'O' respectively.
Ne
F
Ionization Energy
2s22p3
N
C O
2s2
Be
B
Li
Atomic number(Z)
Periodic Table 10
In a given period alkali metals possess low ionization energies and inert gases possess very high
ionization energies.
Cs ---- Element with lowest ionization energy
He ---- Element with highest ionization energy.
In d-block elements : Due to shielding effect of inner d-electrons, the ionization energy is increased
slowly across the period in transition elements.
O
C
Electron affinity
B N
Li 2s22p3
Be
2s2 Ne
Atomic number(Z)
ELECTRONEGATIVITY
The tendency of the atom of an element to attract the shared electron pair towards itself in a
hetero nuclear diatomic molecule is called Electronegativity.
Electronegativity values can be expressed by using following two scales.
1) Pauling scale :
In this scale, the electronegativity values of elements are calculated from the bond energies. The
difference in electronegativity of atom A & B in a molecule AB can be given as follows.
X A - X B 0.208 AB K .cal / mol
(or)
X A - X B 0.1017 AB K . J / mol
where X A Electronegativity of A
X B Electronegativity of B
AB polarity of bond A - B
AB E A-B E A-B
E A-B = Experimental bond energy of AB
E A-B = The bond energy of AB
E A-B E AA .E BB
On Pauling scale fluorine has highest electronegativity value of 4.0
Element Electronegativity
F 4.0
O 3.5
N 3.0
Cl 3.0
H 2.1
C 2.5
Mulliken Scale :
According to this scale, electronegativity is the average of ionization energy and electron affinity.
Periodic Table 12
Ionization energy + Electon affinity
Electronegativity =
2
In this scale, the electronegativity values are 2.8 times larger than those of pauling values. The
electronegativity values equal to those in pauling scale are obtained by using following formulae.
Electronegativity =
I.E in K J / mole + E.A in K.J / mol
544
Periodicity in electronegativity
Electronegativity decreases down the group as atomic size increases. Whereas it increases from
left to right in a period since the atomic size decreases.
Applications :
* The nature of bond formed between two atoms can be predicted from their electronegativity
difference.
If the electronegativity difference is 1.7, the bond would be more than 50% ionic.
If the electronegativity difference is less than 1.7, the bond formed will be more than 50% cova-
lent.
* From the electronegativity values, proper chemical formulae of compounds can be written.
* It is possible to calculate oxidation states by comparing electronegativity values.
VALENCY
Valency indicates the combing power of an atom. It is equal to the number of hydrogen atoms or
double the number of oxygen atoms with which the atom of an element combines.
The valency with respect to hydrogen is equal to group number in IA to IVA groups. But in VA to
Zero group, valency with respect to hydrogen is equal to (8 - group number).
The maximum valency with respect to oxygen or fluorine is equal to the group number
* The elements of groups from IVA to VIIA also exhibit negative oxidation states equal to group
number -8.
E.g.,
IVA VA VIA VIIA
Oxidation number -4 -3 -2 -1
* The p-block elements can show variable oxidation states-both negative and positive.
E.g., Phosphorus can show +3 (PCl3) and +5 (PCl5) oxidation states.
Inert pair effect : The reluctance of the electron pair in the outer 'ns' orbital to get unpaired and
involved in the bond formation is called inert pair effect.
Inert pair effect is caused due to poor shielding effect of inner f-electrons.
Due to inert pair effect, the heavier elements of IIIA, IVA and VA group elements are more stable
in oxidation numbers less by two units of the group oxidation number.
E.g., (i) Thallium (Tl) is more stable in +1 oxidation state then in +3 state.
(ii) Tin (Sn) and Lead (Pb) are more stable in +2 oxidation state than in +4 oxidation state.
(iii) Bismuth (Bi) is more stable in +3 state than in +5 state.
* d-block elements show variable oxidation numbers. Their common oxidation state is +2 due to
presence of two electrons in the ns orbital.
* Ruthenium (Ru) and Osmium (Os) can show a maximum oxidation state of +8.
* Lanthanoids show +3 as common oxidation state.
ELECTROPOSITIVITY
The tendency of an element to lose electrons is called electropositivity.
Electropositivity increases with increase in the atomic size. It increases down the group and de-
creases across the period from left to right. Highly electropositive elements are called metals. They
possess low ionization energies.
IA and IIA group elements are highly electropositive elements.
NATURE OF OXIDES
* Oxides are the binary compounds of elements with oxygen. These are of three types as follows.
i) Basic oxides : These oxides dissolve in water by giving alkaline solutions.
E.g., Na2O, CaO etc.......
Na 2 O + H 2 O
2 NaOH
Ca OH 2
CaO + H 2O
Metal oxides are usually basic in nature
ii) Acidic oxides : These oxides dissolve in water by giving acidic solutions.
E.g., CO2 , SO3 , Cl2O7 etc.,
CO 2 + H 2 O
H 2 CO 3
Cl 2 O 7 + H 2 O
2HClO 4
SO 3 + H 2 O
H 2SO 4
Non metal oxides are usually acidic in nature.
iii) Amphoteric oxides: These oxides show both acidic and basic properties.
E.g., BeO, Al2O3 etc....
DIAGONAL RELATIONSHIP
In the periodic table, an element of second period in a group is similar in properties with the third
period element of next group. This is known as diagonal relationship.
E.g., Following diagonally placed elements exhibit similar chemical properties.
3rd period Na Mg Al Si
Diagonally related elements possess similar ionic sizes, similar electronegativities and same polar-
izing power.
Periodic Table 15
ionic charge
Polarizing power =
( ionic radius )2
E.g., Be and Al exhibit similar properties as given below.
* BeO and Al2O3 amphoteric oxides.
* Carbides of both the elements produce methane (CH4) gas on hydrolysis.
Al4C3 + 12H2O 4Al(OH)3 + 3CH4
Be2C + 4H2O
2 Be(OH)2 + CH4
SOLID STATE CHEMISTRY
IIT-JEE
TYPES OF CRYSTALS
1) The characteristics of crystalline solids
1) Definite shape 2) Long range orders 3) Anisotropic 4) All
2) Choose the incorrect statement
1) Amorphous solids are isotropic and have only short range orders.
2) Crystalline solids have sharp melting points.
3) Amorphous solids have sharp melting points.
4) Amorphous solids are also called as super cooled liquids.
3) Match the following.
A) Ionic crystals 1) Diamond, Silicon etc.,
B) Molecular crystals 2) Cu, Zn, Na etc.,
C) Covalent crystals 3) Solid CO2, I2 etc.,
D) Metallic crystals 4) KCl, Na2SO4 etc.,
The correct match is
A B C D
1) 1 2 4 3
2) 4 3 2 1
3) 4 3 1 2
4) 3 4 1 2
4) The substance which exhibits electrical conductivity in the solid state is
1) NaCl 2) Diamond 3) Silver 4) Both 1 & 3
5) The molecular crystal which shows electrical conductivity is
1) Diamond 2) Silica 3) Silver 4) Graphite
6) Conversion of amorphous substances into crystalline state by slow cooling of liquids of
amorphous substances is called
1) Crystallization 2) Annealing 3) Racemization 4) None
7) Low melting points, bad electrical conductivity and softness are the characteristics of
1) Ionic crystals 2) Covalent crystals 3) Metallic crystals 4) Molecular crystals
8) The type of attractions present between molecules in ice are
1) vander Waals attractions 2) Covalent bonds
3) Hydrogen bonds 4) Both vander Waals attractions and Hydrogen bonds
9) Ionic solids are generally
1) Good conductors of electricity 2) Quite hard 3) Quite brittle 4) Volatile
CRYSTAL SYSTEMS
1) The number of basic crystal systems based on their symmetry elements and crystallographic
parameters is
1) 14 2) 7 3) 230 4) 32
Note : In the seven basic or primitive crystal systems, the lattice points are present only at the corners of unit cell.
But in case of fourteen Bravais lattices, the lattice points are also present at the centre or at the edges or at the centre of
faces of unit cell.
2) Match the following
Crystal system Parallelopiped dimensions
A) Cubic 1) a b c; 900
B) Tetragonal 2) a = b = c; 900
C) Orthorhombic 3) a = b c; 900
D) Triclinic 4) a b c; 900
Correct Matching is
A B C D
1) 2 3 1 4
2) 2 3 4 1
3) 2 4 3 1
4) 4 2 1 3
3) Which of the following crystal system has not been correctly characterized ?
1) Rhombohedral ; a = b = c ; 900
2) Monoclinic ; a b c ; 900 ; 900
3) Hexagonal ; a = b c ; = =900 , 1200
4) Orthorhombic ; a = b = c;
4) Match the following
A) Triclinic 1) NaCl, diamond & ZnS
B) Cubic 2) KNO3, - S & MgSO4.7H2O
C) Orthorhombic 3) CuSO4. 5H2O, K2Cr2O7 & H3BO3
D) Monoclinic 4) -S, NaHCO3 & FeSO4.7H2O
Correct matching is
A B C D
1) 3 1 4 2
2) 2 3 4 1
3) 1 2 3 4
4) 4 3 2 1
5) Rhombohedral crystal system is present in
1) KMnO4 2) Calcite 3) Bi 4) Calcite
Note: Other examples are KMnO 4,Bi, As, Sb, NaNO 3 etc.,
6) Choose the incorrect statement (s)
1) Ice and quartz can crystallise in either hexagonal or trigonal forms
2) Cinnabar has hexagonal crystal system
3) Tetragonal crystal system is present in CaF2
4) 1 & 2 only.
7) The substance with monoclinic crystal system is
1) Glaubers salt 2) - sulfur 3) K2Cr2O7 4) All
Note: - sulfur, Monoclinic gypsum, NaHCO 3, FeSO 4.7H 2O etc.,
8,) The parameters of crystal system in graphite are
1) a = b c ; 900 ; 1200 2) a = b = c ;
3) a b c ; 4) All
Note : Other examples with hexagonal arrangement are Mg, SiO 2 and ZnO
9) The crystal system present in white tin is
1) Hexagonal 2) Tetragonal 3) Triclinic 4) Cubic
Note : Other examples with tetragonal arrangement are TiO 2 , NiSO 4 , SnO 2 and K4 [Fe(CN) 6 ]
10) The crystal system without any rotational axis of symmetry is
1) Triclinic 2) Cubic 3) Hexagonal 4) None
11) The relation between crystallographic angles in monoclinic crystal system is
1) 900 ; 900 2) 900
3) 4) 900 ; 1200
12) The correct parallelopiped dimensions for the crystal system in baryta (BaSO4) are
1) a b c; 900 2) a b c; 900
3) a b c; 900 4) a b c;
13) The crystal system with the crystallographic angles 900 is
1) Cubic 2) Tetragonal 3) Orthorhombic 4) All
14) The relation between crystallographic axes in Na2B4O7.10H2O and H3BO3 is
1) a b c 2) a = b = c 3) a b = c 4) a = b c
Hint : Na2B 4O 7.10H 2O - Monoclinic
H 3BO 3 - Triclinic
15) The changes in the crystallographic parameters in the following conversion are
S S
1) a b c a = b = c 2) 900 ; 900
3) 4) a b c a b c
16) The unit cell present in the crystal lattice of diamond is
1) Cubic 2) Tetragonal 3) Hexagonal 4) Trigonal
17) CuSO4.5H2O belongs to
1) Triclinic system 2) Cubic system 3) Tetragonal system 4) Hexagonal system
18) The number of bravais lattices possible in a cubic crystal system is equal to
1) 1 2) 2 3) 3 4) 4
Note : Simple cube (P), fcc (F) and bcc ( I ) are possible for cubic system.
19) In which of the following bravais systems, only the primitive arrangement of lattice points in the unit
cell is possible ?
1) Hexagonal 2) Trigonal 3) Triclinic 4) All
Note : In the primitive unit cell, the lattice points are present only at the corners.
20) The types of bravais lattices possible for orthorhombic system are
1) P only 2) P & I 3) P, I & F 4) P, I, F & C
Note : P - Primitive
I - Body - centred
F - Face - centred
C - End - centred
21) The number of C3 axes (three fold axes) of symmetry present in a cubic system
1) 2 2) 3 3) 4 4) No C3 axis of symmetry
Note : C 3 axis of symmetry passes through the diagonally opposite corners
22) Which of the following crystal system possesses C6 axis of symmetry ?
1) Trigonal 2) Hexagonal 3) Cubic 4) All
6) The number of nearest atoms surrounding a given atom in a metallic crystal containing primitive
cubic unit cell is
1) 6 2) 8 3) 12 4) 4
Hint : There is one atom at the centre of the unit cell along with atoms at eight corners
1
no. of atoms per unit cell = 1+ (8 x 8 ) =2
10) The number of atoms per a single face centred cubic unit cell is
1) 2 2) 4 3) 8 4) 12
Hint : In the face cented cubic unit cell, there are atoms at of 6 faces along with atoms at 8 corners.
1 1
no. of atoms = (8 x 8 ) + (6 x 2 ) = 4
1 1
Note : contribution from top & bottom layers 2x[(6x 6 ) 2 ] 3
contribution from middle layer = 3
Total no.of atoms = 3 + 3 = 6
13) The relation between radius (r) of atom and edge length (a) in the primitive cubic unit cell of
closest packed atoms is
1) r = 2a 2) r = a / 2 3) r = a 4) r = 4a
14) The relation between radius (r) of atom and edge length (a) in the body centred cubic unit cell of
closest packed atoms is
3 2 3
1) r = a 2) r = a 3) r = 2a 4) r = a
4 4 2
Derivation :
In BCD
2 2 2 2 2 2
BC BD DC a a 2 a
In ABC
2 2 2 2 2 2 2 2
AC AB BC a BC a 2a 3a
But AC 4 r
AC 4 r 3a
3
r a
4
15) The relation between radius (r) of atom and edge length (a) in the face centred cubic unit cell is
3 2 3
1) r = a 2) r = a 3) r = 2a 4) r = a
4 4 2
Derivation :
In ABC
2 2 2
AC AB BC
2 2 2 2
4r a a 2a
4r 2a
2
r a
4
3
Nearest distance = d = 2r = a
2
27) The nearest distance (d) between two atoms in Nickel metal is 248 pm. The edge length (a) of the
unit cell will be
1) 124 pm 2) 350.6 pm 3) 68 pm 4) 412 pm
Hint : The two nearest atoms in fcc are arranged along the face diagonal of the unit cell.
3
Nearest distance (d) = 2r = a ( 4r = 2 a)
2
Note: Nickel crystallises in face centred cubic lattice.
28) A metal crystallises into a lattice containing a sequence of layers of ABC ABC-----. If the radius of
metal atoms is 174 pm, then the distance between the two successive layers (i.e., A and B) is
1) 348 pm 2) 174 pm 3) 284. 2 pm 4) 492. 2 pm
Hint : ABCABC ---- pattern gives rise to face centred cubic lattice. The layers (ABCA) are present perpendicular to the body
diagonal of the unit cell.
length of body diagonal
The distance between two successive layers = 3
3a 3 4 2
= = . r 2r
3 3 2 3
29) Magnesium crystallises into a lattice containing closely packed layers in ABAB____ pattern. The
distance between each successive layers is 217 pm. What is the radius of magnesium atom?
1) 133 pm 2) 217 pm 3) 108.5 pm 4) 266 pm
Hint: ABAB---- pattern of arrangement of layers is otherwise known as hexagonal cubib packing. The distance between two
successive layers in this type of packing is same as that of cubic close packing i.e.,
2
2r
3
30) The volume occupied by atoms in a primitive cubic unit cell is (where a is edge length)
3 3 3
4 a 4 3 4 2 4 3
1) 2) 2 x a 3) 4 x a 4) r
3 2 3 4 3 4 3
31) The volume occupied by atoms in a body centred cubic unit cell is (where a is edge length)
3 3 3
4 a 4 3 4 2 4 3
1) 2) 2 x a 3) 4 x a 4) r
3 2 3 4 3 4 3
32) The volume occupied by atoms in a face centred cubic unit cell is (where a is edge length)
3 3 3
4 a 4 3 4 2 4 3
1) 2) 2 x a 3) 4 x a 4) r
3 2 3 4 3 4 3
33) The percentage of packing of a simple cubic unit cell is
1) 52.4% 2) 47.6% 3) 74% 4) 68%
The volume occupied by the atoms in a single unit cell
Hint: The packing fraction of a unit cell =
The volume of the unit cell
4 3 4 a 3
r
3 3 2
The packing fraction of body centred cubic unit cell = = = 0.5238
a 3 a 3 6
36) The percentage of packing of hcp and ccp type of unit cells is
1) 74% 2) 52.4% 3) 92% 4) none
3
4 3 4 2
4 X r 4 X a
3 3 4 2
Hint: The packing fraction of cubic close packed unit cell = = = 0.74
a 3 a3 6
Note: The packing fraction of hexagonal cubic packed unit cell is also 0.74
Derivation:
BE
In BDE, cosDBE =
BD
o
rsphere
cos30 =
rsphere rvoid
rsphere rsphere
rsphere rvoid o
2.
cos30 3
rvoid =1.155 rsphere rsphere 0.155 rsphere
rvoid
0.155 rsphere
rsphere
43) The ratio of radius of tetrahedral void to the radius of the sphere in closest packed arrangement is
1) 0.414 2) 0.225 3) 0.732 4) None
Derivation:
AC
In OAC , sinAOC =
AO
o ,
109 28 rsphere
sin = ( AOB 109o 28, )
2 rsphere rvoid
rsphere rsphere
rsphere rvoid o ,
sin 54 44 0.8164
rvoid =1.225 rsphere rsphere 0.225 rsphere
rvoid
0.225 rsphere
rsphere
44) The ratio of radius of octahedral void to the radius of the spheres in closest packed arrangement is
1) 0.414 2) 0.155 3) 0.225 4) 0.732
Derivation:
BD
In ABD , cosABD =
AB
o
rsphere
cos45 =
rsphere rvoid
rsphere
rsphere rvoid o
2 rsphere
cos45
rvoid =1.414 rsphere rsphere 0.414 rsphere
rvoid
0.414 rsphere
rsphere
45) The ratio of radius of cubic void to the radius of surrounding closely packed atoms whose centres
lie at the corners of a cube is
1) 0.414 2) 0.155 3) 0.225 4) 0.732
IONIC CRYSTALS
1) In the following diagram, the circles filled with black color represent the cations, whereas the big
circles represent the anions.
7) The number of NaCl units present in a single unit cell of NaCl crystal is
1) 1 2) 2 3) 4 4) 6
+
8) The number of octahedral holes occupied by Na ions in a single unit cell of NaCl is
1) 4 2) 8 3) 2 4) Zero
9) Which of the following does not crystallise in the rock salt structure
1) NaCl 2) KCl 3) CsCl 4) MgO
Note : Usually halides of Cesium assume BCC structures as the limiting radius ratio is greater than 0.732
10) The number of nearest Cl- ions around an Na+ ion in NaCl crystal is
1) 8 2) 6 3) 4 4) 12
- -
11) The number of nearest Cl ions arround a Cl ion in NaCl crystal is
1) 8 2) 6 3) 4 4) 12
12) The radii of Na+ and Cl- ions are 95 pm and 181 pm respectively. The edge length of unit cell in
NaCl is
1) 457 pm 2) 552 pm 3) 190 pm 4) 362 pm
Note : edge length in NaCl = 2rc+ 2ra
13) The crystal structure present in CsCl is referred to as
1) FCC 2) BCC 3) HCP 4) None
Note : BCC structure is present when the limiting radius ratio isgreater than 0.732. The anions occupy the lattice points of
simple cubic lattice. The cations occcupy centred cubic voids. This structure can be considered as interpenetrating primitive
cubic lattices of cation and anion.
The co-ordination numbers are (8:8). The number of formula units present per a single unit cell is one (one cation and
one anion). The general formula is AB.
Examples : CsCl, CsBr, CsI, CsCN, TlCl, TlBr, TlI, TlCN etc.,
14) The number of nearest Cl- ions present around a Cs+ ions in CsCl crystal is
1) 6 2) 8 3) 12 4) 4
+ +
15) The number of nearest Cs ions present around a Cs ion in CsCl crystal is
1) 8 2) 6 3) 4 4) 12
Hint : If only Cs+ ions are considered they occupy lattice points of primitive cubic lattice
16) The number of second nearest Cs+ ions present around a Cs+ ion in CsCl is
1) 4 2) 8 3) 12 4) 6
17) The radii of Cs+ and Cl- ions are 1.69 and 1.81 respectively. The edge length of the unit cell in
CsCl will be
1) 7 2) 3.38 3) 4.04 4) 3.5
Hint : In BCC, the ions touch along the body diagonal
Length of body diagonal = 2rc+2ra = 3a
18) The ionic compound which crystallises in anti-fluorite structure is
1) NaCl 2) Na2O 3) CaF2 4) Al2O3
Note : In the anti-fluorite structure, anions are arranged in cubic closest packing and cations occupy all the tetrahedral
voids. There are four anions and eight cations per unit cell of this structure and hence, the general formula of an ionic
compound is A8B4 or A2B.
The ideal radius ratio is between 0.225 - 0.414. But this ratio is not always maintained.The co-ordination numbers of
cation and anion are (4:8).
Examples : Na2O, K2O, Li2O, Rb2O, K2S, Cl2O, Na2S etc.,
19) In a unit cell of an ionic crystal, anions (Y) occupy the lattice points of face centred cubic lattice
and cations (X) occupy all the tetrahedral voids. The formula of the ionic compound will be
1) XY2 2) X2Y2 3) X2Y 4) XY
20) The number of anions per a single unit cell in antifluorite structure is
1) 2 2) 4 3) 8 4) 1
21) The type of voids occupied by cations in antifluorite structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
22) The co-ordination number of Na+ ions in Na2O is
1) 2 2) 4 3) 8 4) None
23) The type of voids occupied by O2- ions in Na2O crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
24) The number of Na+ ions present per a single unit cell in Na2O crystal is
1) 4 2) 2 3) 8 4) 12
25) The fluorite crystal structure is present in
1) NaF 2) CaF2 3) AlF3 4) CsF
Note : In the fluroite structure, the cations are arranged into cubic close packing and the anions occupy all the tetrahedral
voids. Thus there are four cations and eight anions per a unit cell. Hence the formula of ionic compound is A4B8 or AB2.
The co-ordination numbers of cation and anion are (8:4).
Examples : CaF2, ZrO2, UO2, ThO2, BaF2, BaCl2, SrCl2, PbCl2 etc.,
26) The number of anions per a single unit cell in fluorite structure is
1) 2 2) 4 3) 8 4) 1
27) The type of voids occupied by anions in fluorite structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
2+
28) The co-ordination number of Ca ions in CaF2 is
1) 2 2) 4 3) 8 4) None
2+
29) The type of voids occupied by Ca ions in CaF2 crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
30) The number of Ca2+ ions present per a single unit cell in CaF2 crystal is
1) 4 2) 2 3) 8 4) 12
2+ -
31) The radii of Ca and F ions respectively are 100 pm and 131 pm. The edge length of the unit cell
in CaF2 is
1) 231 pm 2) 533.5 pm 3) 462 pm 4) 362.5 pm
Hint: The Fluoride ions are present along the body diagonal at one fourth distance from the corner of the cube. Hence the
distance between calcium and fluoride ions is 1/4th of length of body diagonal.
32) The substance containing zinc-blende crystal structure is
1) NaCl 2) ZnCl2 3) BeO 4) CsCl
Note: In zinc-blende or sphalerite structure, anions occupy the face centred cubic lattice points and cations occupy half of
the tetrahedral holes (of one type). The ideal radius ratio is in between 0.225 to 0.414. There are four anions and four
cations in the unit cell. Therefore the formula is A4B4 or AB. The co-ordination numbers of cation and anion are (4:4).
Examples: ZnS, BeO etc.,
33) The number of anions per a single unit cell in zinc-blende structure is
1) 2 2) 4 3) 8 4) 1
34) The type of voids occupied by cations in zinc-blende structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
35) The co-ordination number of Zn2+ ions in ZnS is
1) 2 2) 4 3) 8 4) None
2-
36) The type of voids occupied by S ions in ZnS crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
2+
37) The number of Zn ions present per a single unit cell in ZnS crystal is
1) 4 2) 2 3) 8 4) 12
2-
38) The co-ordination number of S ions in ZnS is
1) 2 2) 4 3) 8 4) None
39) The compound containing spinel structure is
1) MgAl2O4 2) Fe2O3 3) ThO2 4) KCl
Note: In spinel structure, the oxide ions are arranged in cubical closest packing and one eighth of the tetrahedral holes are
occupied by divalent metal ion (A2+) and one half of the octahedral holes are occupied by trivalent metal ions (B3+). Thus in
a unit cell there are four oxide ions, one divalent metal ion(A2+) and two trivalent metal ions (B3+). The general formula of
the compound is AB2O4.
Examples: MgAl2O4,ZnAl2O4, ZnFe2O4 etc.,
40) The crystal structure present in Al2O3 is called as
1) corundum structure 2) spinel structure 3) rock-salt structure 4) Fluorite structure
Note: In the corundum structure, anions form hexagonal closest packing and cations are present in 2/3 of the octahedral
holes. The general formula of the compound is M2O3.
Examples: Fe2O3, Al2O3, Cr2O3 etc.,
41) Inverse spinel structure is found in
1) Chromite 2) Magnetite 3) Spinel 4) Corundum
2) Creation of holes due to transfer of a cation from its lattice point to the interstitial space is called
1) Schottky defect 2) Metal excess defect 3) Frenkel defect 4) F-centre formation
Note: In Frenkel defect, the cations, being small can move from the lattice points to interstitial spaces and thus by creating
holes. This is a stoichiometric point defect. The defected crystal is electrically neutral. But density and covalent nature are
decreased. Dielectric constant and hence ionic nature are increased. Defected crystals show little electrical conductivity. This
defect is shown by ionic compounds with low co-ordination numbers. The difference in the sizes of oppositely charged ions
must be large. Usually these defects are shown by compounds of small sized transition metals.
Eg., AgCl, AgBr, ZnS etc.,
It is also a thermodynamic defect. The number of defects increase with increase in temperature.
9) In which of the following non-stoichiometric defect, the cation occupies the interstitial site
1) Schottky defect 2) Frenkel defect
3) Metal excess defect 4) Metal deficiency defect
10) LiCl shows pink color when heated in Li vapour due to
1) Metal deficiency defect 2) Schottky defect 3) F-Centre formation 4) Frenkel defect
Note : F-Centres are formed when an electron occupies anion vacancty in the crystal. They import color and paramagnetic
nature to the crystals
Eg : KCl in K vapours is blue lilac in color NaCl in Na vapour is yellow is color.
11) ZnO turns yellow upon heating because of
1) Metal excess defect 2) Metal deficiency defect 3) Frenkel defect 4) All
Note : When heated ZnO loses oxide ions reversibly. Excess Zn2+ ion and electrons are accomodated interstitially. Due to
presence of odd electrons, ZnO turns yellow. The electrical conductivity is also improved.
This type of defect due to pressence of extra cation and electtrons is also shown by CdO, Cr2O3 and Fe2O3.
12) The formula of wustite ranges from Fe0.93O to Fe0.96O instead of FeO. It is due to presence of
1) Frenkel defect 2) Schottky defect 3) Metal deficiency defect 4) Metal excess defect
Note : Some compounds cannot be prepared in ideal stiochimetric proportions due to metal dificiency defect. This defect
arises when a metal cation is missing from its lattice points and the cahrge is balanced by an adjacent metal ion with extra
exhibited by compounds of transition metals which can exhibit variable valency. As a result, there compounds show non
stoichiometric formulae. Eg : VOX (x can be 0.6 - 1.3), Fe0.95O
13) Following are the statements relating to defects in crystals
a) Frenkel defect is shown by ionic compounds where there is large difference in size between posi-
tive and negative ions.
b) Zinc oxide turns yellow upon heating due to formation of metal deficiency defect
c) The vacant anion sites occupied by electrons are called F-Centres
d) The number of schottky and Frenkel defects decreases with increase in temperature
The correct statements are
1) a only 2) a & c 3) a, b & c 4) a, c & d
14) Select the incorrect statement.
1) Schottky defect is shown by CsCl
2) Frenkel defect is shown by ZnS
3) F-Centres are formed due to leaving of metal ion from the lattice point.
4) Metal deficiencies defect is formed when the metal can exhibit variable oxidation number.
15) The composition of a sample of wustite is Fe0.93O. What percentage of iron is present as Fe(III)?
1) 7% 2) 15.05% 3) 30% 4) 26.3%
16) Addition of little SrCl2 to NaCl produces
1) Cation vacancies 2) Anion vacancies 3) Both cation & anion vacancies 4) None
Note : When NaCl is doped with SrCl2, Sr2+ ions displace Na+ ions from their lattice points. Also at the same time, equal number
of Na+ ions from other lattice sites move out of the crystal and thus by creating cation vacancies. Thus formed solids are called
substitutional solids other examples:- AgCl doped by CdCl2.
17) If NaCl is doped with 10-4 mole% of SrCl2, the concentration of cation vacancies would be
1) 10-4 mole-1 2) 6.022 x 1017 mole-1 3) 6.002 x 10-4mole-1 4) 6.022 x 10-8 mole-1
18) Which one of the following is the correct statement ?
1) Brass is an interstitial alloy, while steel is a substitutional alloy.
2) Brass is a substitutional alloy, while steel is an interstitial alloy.
3) Brass & steel are both substitutional alloys.
4) Brass & steel are both interstitial alloys.
19) AgCl is crystallised from molten AgCl containing little CdCl2. The solid obtained will have
1) Cationic vacancies equal to number of Cd2+ ions incorporated
2) Cationic vacannies equal to double the number of Cd2+ ions incorporated.
3) Anionic vacancies
4) Neither cationic nor anionic vacancies.
20) The type of electrical conductivity shown by crystals with F - Centres is
1) n-type semiconductivity 2) p-type semiconductivity 3) Super conductivity 4) None
21) The conductivity of semiconductors is in the range of
1) 10-20 ohm-1 cm-1 2) 107 ohm-1 cm-1 3) 10-6 to 104 ohm-1 cm-1 4) None
22) Choose the correct statement
1) The energy gap between conduction band and valence band in metallic conductors is very large.
2) The energy gap between conduction band and valence band in semiconductors is very large.
3) Electrical conductivity of semiconductors increases with increasing temperature.
4) Electrical conductivity of conductors increases with increasing temperature.
23) Which of the following is an intrinsic semiconductor
1) Si 2) Si doped with As 3) Fe 4) Both 1 & 2
24) Silicon doped with III A group elements exhibit
1) n-type semi conductivity 2) p-type semi conductivity 3) Both 1 & 2 4) None
25) Germanium doped with phosphorus acts as
1) n-type semiconductors 2) p-type semiconductor
3) super conductor 4) Intrinsic conductor.
26) Solar photovoltaic cell used to convert radiant energy into electrical energy consists of
1) a pnp triode 2) a pn diode 3) an npn triode 4) None
27) Which of the following is incorrect statement about super conductivity.
1) Super conductors show zero resistance to electrical conductivity.
2) The electrical resistance becomes zero at absolute zero temperature for all the substance
3) Super conductors are good insulators
4) None
28) Match the following
A) Ferro magnetic 1) MnO, MnO2, FeO, NiO etc.,
B) Dia magnetic 2) Fe3O4, MgFeO4 etc.,
C) Anti ferri magnetic 3) ZnO, TiO2, NaCl etc.,
D) Ferri magnetic 4) Fe, Co, Ni etc.,
The correct matching is
A B C D
1) 4 3 2 1
2) 4 3 1 2
3) 3 4 1 2
4) 4 2 3 1
29) The temperature above which the ferromagnetism is lost is called
1) Transition temperature 2) Bohr temperature 3) Curie temperature 4) none
30) The phenomenon of production of electricity by a polar crystal when mechanical stress is applied to
it is called.
1) Antiferro electricity 2) Piezoelectricity 3) Magnetic electricity 4) None
31) A ferro electric substance is
1) KH2PO4 2) BaTiO3 3) Rochelle salt 4) All
Note : Ferroelectric substances are piezoelectric crystals with permanent dipoles.
32) Piezo-electric crystals with zero net dipole moment are called
1) Ferro electric 2) Pyro electric 3) Antiferro electric 4) None
33) The substance which exhibits anti-ferroelectricity is
1) BaTiO3 2) PbZrO3 3) KH2PO4 4) All
34) The crystals which produce electricity upon heating are referred to as
1) Ferro electric 2) Pyro electric 3) Antiferro electric 4) None
35) The Ferro magnetic substance used in audio and video tapes is
1) FeO 2) CrO2 3) MnO 4) BaTiO3.
REVISION
1. An AB2 type structure is found in :
a) N2O b) NaCl c) Al2O3 d) CaF2
2. If the number of atoms per unit in a crystal is 2, the structure of crystal is :
a) Simple cubic b) body centred cubic ( bcc )
c) octahedral d) face centred cubic ( fcc )
3. The intermetallic compound LiAg crystallizes in cubic lattice in which both lithium and silver have
co - ordination number of eight. The crystal class is :
a) Simple cubic b) body centred cube
c) face centred cube d) none of these
4. The vacant space in the bcc unit cell is :
a) 23% b) 26% c) 32% d) none of these
5. Potassium fluoride has Nacl type structure. What is the distance between K+ and F- ions if cell
edge is a cm ?
a a
a) cm b) cm c) 2a cm d) 4a cm
2 4
6. Braggs law is given by the equation :
d
a) n 2 sin b) n 2 d sin c) 2 n d sin d) n sin
2 2
7. The interionic distance for cesium chloride crystal will
a 2a 3a
a) a b) c) d)
2 3 2
8. Sodium metal crystallizes as a body centred cubic lattice with the cell edge 4.29A0. what is the
radius of sodit atom ?
a) 1.857 x 10-8 cmb) 2.371 x 10-7 cm c) 3.817 x 10-8 cm d) 9.312 x 10-7 cm
9. The edge of unit cell of fcc crystal of Xe is 620 pm. The radius of Xe atom is :
a) 189.37 pm b) 209.87 pm c) 219.25 pm d) 235.16 pm
10. A metal has bcc structure and the egde length of its unit cell is 3.04 A0. The volume of the unit cell
in cm3 will be :
a) 1.6 x 1021cm3 b) 2.81 x 10-23 cm3 c) 6.02 x 10-23 cm3 d) 6.6 x 10-24 cm3
11. A compound is formed by elements A and B. This crystallizes in the cubic structure when atoms
A are at the corners of the cube and atoms B are at the centre of the body. The simplest formula
of the compound is :
a) AB b) AB2 c) A2B d) AB4
12. In a cubic structure of compound which is made from X ad Y, where X atoms are at the corners of
the cube. The molecular formula of the compound is :
a) X2Y b) XY2 c) XY3 d) X3Y
13. The structure of MgO is similar to NaCl. what would be the co-ordination number of magnesium?
a) 2 b) 4 c) 6 d) 8
14. Most crystals show good cleavage because their atoms, ions or molecules are :
a) weakly bonded together b) strongly bonded together
c) spherically symmetrical d) arranged in planes
15. An example of a non - stoichiometric compound is :
a) PbO b) NiO2 c) Al2O3 d) Fe3O4
16. Doping of silicon ( Si ) with boron ( B ) leads to :
a) n - type semiconductor b) p - type semiconductor
c) metal d) insulator
17. In the laboratory, sodium chloride is made by burning the sodium in the atmosphere of chlorine
which is yellow in colour. The cause of yellow colour is :
a) presence of electrons in the crystal lattice
b) presence of Na+ ions in the crystal lattice
c) presence of Cl- ions in the crystal lattice
d) presence of face centred cubic crystal lattice
18. Frenkel defect is caused due to :
a) the shift of a positive ion from its normal lattice site to an interstitial site.
b) An ion missing from the normal lattice site creating a vacancy
c) An extra positive ion occupying an interstitial position in the lattice
d) An extra negative ion occupying an interstitial position in the lattic
19. Schottky defect generally appears in :
a) KCl b) NaCl c) CsCl d) all of these
20. Due to Frenkel defect, the density of ionic solids :
a) increases b) decreases c) does not change d) change
21. Na and Mg crystallize in bcc and fcc type crystals respectively, then the number of atoms of Na
and Mg present in the unit cell of their respective crystal is :
a) 2 and 4 b) 4 and 2 c) 9 and 14 d) 14 and 9
22. An ionic compound has a unit cell consisting of A ions at the corners of a cube and B ions on the
centres of the faces of the cube. The empirical formula for this compound
a) AB b) A2B c) A3B d) AB3
10g
23. The number of atoms in 100g of an fcc crystal with density, d and cell edge equal to100
cm 3
pm, is equal to :
a) 1 x 1025 b) 2 x 1025 c) 3 x 1025 d) 4 x 1025
24. Potassium has a bcc structure with nearest neighbour distance 4.52 A0. Its atomic weight is 39. Its
density ( in kg m 3 ) will be :
a) 454 b) 804 c) 852 d) 908
25. In orthorhombic, the value of a , b and c are respectively 4.2 A , 8.6A and 8.3 A0.Given the
0 0
molecular mass of the solute is 155 g mol 1 and that of density is 3.3 g / cc, the number of
formula units per unit cell is
a) 2 b) 3 c) 4 d) 6
26. A solid has a structure in which W atoms are located at the corners of a cubic lattic O atoms
at the cube. The formula for the compound is
a) Na2WO3 b) Na2WO2 c) NaWO2 d) NaWO3
27. In a solid AB having the NaCl structure, A atoms occupy the corners of the cubic unit cell. If
all the centre of the face - centred atoms along one of the axes are removed, then the resultant
stoichiometry of the solid is :
a) AB2 b) A2B c) A3B4 d) A4B3
28. The pyknometric density of sodium chloride crystal is 2.16 x 103 kg m-3, while its X - rays density
is 2.178 x 103 kg m-3. The fraction of unoccupied sites in sodium chloride crystal is :
a) 5.96 b) 5.96 x 101 c) 5.96 x 102 d) 5.96 x 103
29. What type of crystal defect is indicated in the diagram below ?
Na+ Cl- Na+ Cl- Na+ Cl-
Cl- Cl- Na+ Na+
Na+ Cl- Na+ Na+ Cl-
Cl- Na+ Cl- Na+ Cl-
a) Schottky defect b) Frenkel defect
c) Interstitial defect d) Frenkel and Schottky defect
30. Assertion : In any ionic solid ( MX ) with schottky defects, the number of positive and negative
ions are same
Reason : Equal number of cation and anion vacancies are present.
Choose the correct answer.
a) Both assertion and reason are true and the reason the correct explanation of the assertion
b) Both assertion and reason are true but reason is reason the correct explanation of the assertion
c) Assertion is true but reason is false
d) Assertion is false but reason is true
31. Total volume of atoms present in a face - centred cubic cell of a metal is ( r is atomic radius ) :
20 3 24 3 12 3 16 3
a) r b) r c) r d) r
3 3 3 3
SOLUTIONS & COLLIGATIVE PROPERTIES
IIT-JEE
CONCENTRATION
1) Match the following
A) Gas in solid 1) Soda water
B) Solid in liquid 2) Brine solution
C) Solid in solid 3) Air
D) Gas in liquid 4) H2 occluded in Pd
5) Magnalium
Correct matching
A B C D
1) 4 2 5 3
2) 4 5 2 1
3) 4 2 3 5
4) 4 2 5 1
Hint : Soda water = CO 2 in water
Brine = NaCl in Water
Air = O 2 (and other gases) in N 2
Magnalium = Mg (1-15%) in Al (99-85%)
2) Not a homogeneous mixture
1) Soda water 2) aqueous sugar solution
3) Sodium amalgam 4) Milk
Note : In case of milk, fine liquid fat particles are dispersed in water. It is not a true solution.
3) The molarity of 500 cc of solution containing 0.2 moles of NaCl.
1) 0.2 mole L-1 2) 0.4 mole L-1 3) 0.1 mole L-1 4) 0.8 mole L-1
Hint : Molarity is no. of moles of solute per litre of solution.
4) The molarity of H2SO4 solution is 2 M at 27oC. What will be its molarity at 100oC ?
1) = 2 M 2) < 2 M 3) > 2 M 4) All
Hint : Molarity is altered with volume of the solution.
5) The molarity of 250 ml of solution containing 0.365 g. of HCl.
1) 0.04 M 2) 0. 04 m 3) 0.01 M 4) 0. 02 M
6) What is the molarity of 2% NaOH solution ?
1) 20 M 2) 10 M 3) 0.5 M 4) 0.2 M
% WV X 10
Formula : M
Formula weight
22) 4.9 g of H2SO4 is present in 250 mL of solution. The molarity and normality of the solution are ,
respectively.
1) 0.1 M & 0.2N 2) 0.2M & 0.4N 3) 0.2 M & 0.2N 4) 0.1 M & 0.1N
23) The weight of H3PO4 in 500 mL of 0.3N H3PO4 solution is.
1) 0.3 g 2) 9.8 g 3) 0.98 g 4) 4.9 g
Hint : Basicity of H PO = 3
3 4
24) The normality of 5.7% Al2(SO4)3 solution is
1) 5.7 N 2) 2 N 3) 1 N 4) None
FW
Hint: EW of Al 2 (SO 4 ) 3
6
25) The specific gravity of 31.6% w/w KMnO4 solution is 1.5. The normality of the solution in the
acidic medium is
1) 15 2) 1.5 3) 31.6 4) 3.16
w
% X d X 10
w
Formula : N
G .E .W
7+ 2
Hint : Mn Mn (in acidic medium)
N N
35) 10 mL of HCl solution is mixed with 125 mL of H 2 SO4 and the resultant solution is
2 5
made up to 1 Litre. The normality of the final solution is
1) 0.03 N 2)0.01 N 3) 0.3 N 4) 0.5 N
36) What are the volumes of 3M HCl and 5M HCl solutions, respectively, to be mixed to get 2
litres of 3.5M HCl solution?
1) 1.5 L & 5 L 2) 2 L & 3 L 3) l L & l L 4) 1.5 L & 0.5 L
-
37) Equal volumes of lM KNO3 and lM Al (NO3)3 solutions are mixed. The concentration of NO3
ions in the final solution is
1) 2M 2) 1M 3) 4M 4) 0.5M
-
Note : 1M Al(NO 3)3 contains 3M NO ions.
3
38) 10 mL of 1M Na2 CO3 solution is made upto 1 litre by adding water. The normality of the final
solution is
1) 0.01 N 2) 0.1 N 3) 0.2 N 4) 0.02 N
-
39) 20 mL of 1M NaCl is added to 10 mL of 2 M AgNO3 . The concentration of Cl ions in the final
solution is
1) 0.5M 2) 0. 4M 3) 1.5M 4) None
- -
Note : All the Cl ions are precipitated out as AgCl. Hence the final concentration of Cl will be almost zero.
40) Which of the following solutions contains more number of ions?
1) 9M KNO3 2) 8M NaCl 3) 4M Al2 (SO4 )3 4) 6M Na2 SO4
41) A 0.02N NaCl solution is diluted by 100 times. The number of moles of NaCl will be
1) increased 2) decreased 3) unchanged 4) Cannot say
Hint : There is no change in the number of moles of solute during dilution. Only the concentration is changed.
42) Which of the following graph represents the variation of molality (m) with temperature (T)
1) 2)
Molality (m)
Molality (m)
3) 4)
Molality (m)
Molality (m)
53) 'x' g of a metal 'M' is completely reacted with 100 ml of 0.2N HCl. If the atomic weight of metal
is 100x g, then the formula of its sulfate salt is
1) M2 SO4 2) MSO4 3) M2 (SO4 )3 4) M(SO4 )2
54) 20g of a bivalent metal liberates 11.2 litres of H2 gas at STP by reacting with excess of acid
solution . The metal is
1) Mg 2)Al 3) Ca 4) Ba
55) 10mL of 0.2M KMnO4 solution is required to oxidise 20mL of 0.3M KI solution completely.
The change in oxidation state of Mn in this reaction is.
1) Mn7+ Mn2+ 2) Mn7+ Mn3+
3) Mn4+ Mn7+ 4) Mn7+ Mn4+
H.W : Write the balanced equation for the reaction
56) 18g of glucose is dissolved in 1800 g of water. The mole fraction of glucose is
1) 0.1 2) 0.01 3) 0.001 4) 1
n glucose
Formula : X =
glucose n glucose+ n water
57) The mole fraction of urea in its aqueous solution is 0.23. The mole fraction of water is
1) 0.46 2) 0.77 3) 0.23 4) 1.8
58) Which method of expression of concentration has no units and independant of temperature?
1) Normality 2) Molality 3) Mole fraction 4) All
w
59) The mass percentage of ethyl alcohol in water is 23% . The mole fraction of alcohol is
w
1) 0.208 2) 0.104 3) 1.04 4) 3.26
Hint : solution contains 23 g ethyl alcohol + 77g water
-1
60) 10 mL of a liquid (density = 4.9 g. mL ) is dissolved in 0.18Kg of water. If the mole fraction of the
liquid is 0.01, then its molecular weight will be
1) 98 g 2) 49 g 3) 4.9 g 4) 490 g
Hint : For very dilute solutions
nsolute
X
solute nsolvent
61) The molality of an aqueous solution of urea is 3 m. What will be its mole fraction?
1) 0.3 2) 0.18 3) 0.054 4) 0.003
Hint : For dilute solutions
molality x MWsolvent
X solute
1000
VAPOUR PRESSURE
vapour pressure
A
3) 4)
A B C A B C
vapour pressure
vapour pressure
6) Which of the following represents graph of logP against 1/T according to Clausius-clapeyron
equation (where P = vapour pressure and T = temperature)
1) 2)
log P
log P
1/ T 1/T
3) 4)
log P
log P
1/ T 1/ T
Hint : Clausius - clapeyrons equation is
H va p
ln P C
RT
H.W : What is the slope of the curve in the given graph ?
H vap
Ans :
2 .3 0 3 R
7) Which characterizes the weak inter molecular forces of attraction in a liquid ?
1) High boiling point 2) High vapour pressure
3) High critical temperature 4) High heat of vapourisation
8) At equIlibrium, the kinetic energies of vapour and liquid are
1) Equal 2) Not equal 3) Equal only at boiling point 4) All
9) According to Raoults law, the partial vapour pressure of a liquid in a solution is
1) inversly proportional to its mole fraction 2) directly proportional to its mole fraction
3) equal to its mole fraction 4) greater than the vapour pressure of pure liquid.
10) According to Raoults law, the vapour pressure (P) of an ideal solution containing two miscible
liquids i.e., A and B, is
1) P PAo X A PBo X B 2) P PAo X A PBo X B
3) P PAo X A PBo X B 4) All
11) A solution of two liquids behaves ideally when
1) Hmixture 0 2) Smixture 0 3) Vmixture 0 4) Hmixture 0
12) An ideal solution is
1) Benzene + toluene 2) n-Hexane + n-Heptane
3) Chloroben zene + Bromobenzene 4) All
13) Which, among the following solutions, shows positive deviation from Raoults law
1) Ethanol + Water 2) Ether + Acetone
3) Carbontetrachloride + acetone 4) All
14) The partial vapour pressure of liquid A in a solution showing positive deviation from Raoults law
is given by
1) PA = P0A XA 2) PA > P0A XA
3) PA < P0AXA 4) PA = XA
15) The vapour pressure (P) of a solution showing negative deviation from Raoults law is given by
(solution contains two liquids i.e, A and B)
1) P = P0A XA+ P0BXB 2) P = P0A XA - P0B XB
1) P
total 0
2) 0
P P P
A total A
vapour pressure
vapour pressure
0 0
P P
B B
0 X 1 0 X 1
A A
1 XB 0 1 XB 0
3) 0
4) P
P total 0
A P
A
P
vapour pressure
vapour pressure
P total 0
B P
B
0 X 1 X 1
A 0 A
1 XB 0 XB
1 0
21) The vapour pressure of water at 300K in a closed container is 0.4 atm. If the volumeof the con-
tainer is doubled its vapour pressure at 300K will be
1) 0.8 atm 2) 0.2 atm 3) 0.4 atm 4) 0.6 atm
22) The vapour pressure of deliquescent substance is
1) Equal to the atmospheric pressure 2) Equal to the pressure of water vapour in air
3) Greater than the pressure of water vapour in air
4) Less than the pressure of water vapour in air
Note : Deliquescent substance absorbs water from air and becomes liquid (by dissolving in water).
COLLIGATIVE PROPERTIES
1) The property which depends only on the number of particles and not on the nature of particles is
1) Relative lowering of vapour pressure 2) Elevation in boiling point
3) Depression in freezing point 4) All
2) Choose the incorrect statement
1) The vapour pressure of a solution containing a non volatile solute is inversely proportional to the
mole fraction of solute.
2) The lowering of vapour pressure of a solution containing a non volatile solute is proportional to
the mole fraction of solute.
3) The vapour pressure of a solution containing a non volatile solute is proportional to the mole
fraction of volatile solvent.
4) None.
3) The vapour pressure of a dilute solution (P) containing a non volatile solute is ( Let P01 = vapour
pressure of pure solvent, X1 & X2 = molefractions of solvent and solute respectively)
1) P = P01 X1 2) P = P01 (1-X2) 3) both 1 & 2 4) None
4) The relative lowering of vapour pressure of a dilute solution containing a non volatile solute is
1) equal to mole fraction of solute 2) equal to mole fraction of solvent
3) equal to mole fraction of solution 4) greater than mole fraction of solvent
5) 6 g of Urea is dissolved in 90g of water. The relative lowering of vapour pressure is equal to
1) 0.01 2) 0.06 3) 1.1 4) 0.02
Hint: Urea (NH 2 CONH 2 ) is a non volatile and non electrolytic substance.
P
Formula : Relative lowering of vapour presure X2
P0
6) Calculate the amount of glucose present in 90g of water when the relative lowering of vapour
pressure is 0.02.
1) 9g 2) 12g 3) 18g 4) 24g
Hint: The molecular formula of Glucose is C 6 H 12 O 6
7) The lowering of vapour pressure of a solution containing 15g of non electrolyte in 90g of water at
373K is 1.013 X 103N.m-2. The molecular weight of the solute is
1) 300g.mole-1 2) 90g.mole-1 3) 150g.mole-1 4) 135g.mole-1
Hint: 1 atm = 1.013 X 10 5 N.m -2
8) 1g of a non volatile and non electrolytic solute is dissolved in 78g of benzene at 780C. The molecu-
lar weight of solute is 100g.mole-1. What will be the vapour pressure of solution at 780C.
1) 75.24 mm Hg 2) 780 mm Hg 3) 684 mm Hg 4) 752.4 mm Hg
Hint: The boiling point of benzene is 78 0 C
9) 10g of a non volatile and non electrolytic solute is dissolved in 1000g of benzene. The vapour
pressure is lowered by 0.5%. What is the molecular weight of solute?
1) 312g.mole-1 2) 156g.mole-1 3) 78g.mole-1 4) 100g.mole-1
P 0.5
Hint :
p0 100
10) The vapour pressure of an a aqueous solution of sucrose is 0.99 atm at 373 K. The molality (m) of
the solution is
1) 0.99m 2) 0.55m 3) 5.5m 4) 37.3m
P molality x MWsolvent
Hint: p0 =X solute
1000
11) The lowering of vapour pressure of 1% (w/w) aqueous solution of a non volatile and non electro-
lytic solute is 1.52 mm of Hg at 373K. The molecular weight of the solute is
1) 91g 2) 180g 3) 30g 4) 909g
12) The vapour pressure of a solvent is decreased by 10mm of Hg by adding a non volatile solute. The
mole fraction of solute is 0.14. What would be the molefraction of solvent if decrease in vapour
pressure is 20 mm of Hg
1) 0.28 2) 0.14 3) 0.72 4) 0.86
13) A 6 % glucose solution and 2 % solution of 'x' show same relative lowering of vapour pressure.
Assuming 'x' to be a non-electrolyte, the molecular weight of 'x' is
1) 30g.mole-1 2) 60g.mole-1 3) 90g.mole-1 4) 180g.mole-1
Hint : Molefractions and hence the number of moles of glucose and x are equal.
16) The lowering of vapour pressure of solution containing 'X' is twice of solution
containing 'Y', then (both 'X' & 'Y' are non electrolytes)
1) The MW of 'X' is twice of 'Y' 2) The MW of 'Y' is twice of 'X'
3) The mole fraction of 'X' is twice of 'Y' 4) The mole fraction of 'Y' is twice of 'X'
17) An aqueous solution of Ca(HCO3)2 is heated strongly and filtered. The vapour pressure of clear
filtrate is
1) Greater than that of pure water 2) less than that of pure water
3) Equal to that of pure water 4) Can not say
2+
Hint : Ca aq 2 HCO3 aq CaCO3 s CO2 g H 2 O( l )
m Molality
-1
Note : The unit of K b is Kelvin.Kg.mole
21) 0.2g of a non volatile and non electrolytic solute is dissolved in 20g of a liquid to elevate the boiling
point of the liquid by 0.180C. The ebbulioscopic constant of the liquid is 4.212 K.Kg. mole-1 .
What is the molecular weight of solute ?
1) 23.4g.mole-1 2) 234 g.mole-1 3) 117 g.mole-1 4) 202g. mole-1
w2 1000
Hint : Tb K b . m K b . .
MW2 w 1
Hint : K b
M
R Tb
0
1
H vap 1000
2 2
Hint : K f
R Tf M
0
1
0
R Tf
Hfusion = lf .M1
Hfusion 1000 lf .1000
2
T f
R Tf
0
.m
lf .1000
m = Molality
27) The freezing point of acetamide in glacial acetic acid is 298K. At this temperature, the crystals of
1) acetamide appear first 2) acetic acid appear first
3) both appear together 4) None
Hint : Always crystals of pure solvent seperate out first at the freezing point of solution.
28) How many grams of glucose should be dissolved in 100g of water in order to produce a solution
with a 1050C difference between the freezing point and the boiling point. (Kf = 1.86K.Kg.mol-1
and Kb = 0.51K.Kg.mole-1).
1) 18.2g 2) 37.9g 3) 180g 4) 72g
Hint : T f Tb
Tf T f0 Tb0 Tb
0
Tf +Tb + Tb0 -Tf0 =105 C
0
or Tf +Tb + 1000C-00C =105 C
Tf +Tb =50 C
But Tf = K f m
and Tb = K b m
0
Kf m + Kbm = 5 C
29) Ethylene glycol is used as an anti freeze in radiators to
1) increase the boiling point of water 2) decrease the freezing point of water
3) decrease the boiling point of water 4) freeze the water above 00C.
30) The depression in freezing point of an aqueous solution is 0.670C. What is its relative lowering of
vapour pressure?(Kf= 1.8 K.Kg.mole-1)
1) 0.0067 2) 0.042 3) 0.21 4) 0.42
31) Choose the correct statement
1) Spontaneous flow of solvent from dilute solution to concentrated solution through a semi
permeable membrance is called osmosis.
2) According to vant Hoff, the solute behaves as a gas and the osmotic pressure of solution is
equal to the pressure exerted by solute if it were a gas at the same temperature and occupying the
same volume as that of solution.
3) Reverse osmosis occurs, when a pressure greater than the osmotic pressure of solution is
applied over it
4) All
32) The osmotic pressure of 0.2 molar solution of urea at 270C is
1) 4.92 atm 2) 1 atm 3) 2.7 atm 4) 8.2 atm
Hint : Osmotic pressure ( ) = CRT
n
where C = = molar concentration
V
-1 1
R = Gas constant (0.0821 L.atm.mole .K )
T = Absolute temperature
33) 20g of a non electrolytic solute is present in 500 mL of solution at 270C. The osmotic pressure of
this solution is 1.8 atm. What is the molecular weight of the solute (in g.mole-1) ?
1) 426. 2 2) 547. 3 3) 671.7 4) 323.2
34) The elevation in boiling point of an aqueous solution of glucose is 0.60C. What is its osmotic
pressure at 300K ? (Kb = 1.2 K.Kg. mole-1 & density of solution = 1.09 g. mL-1)
1) 623.6 N.m-2 2) 1247.1 N.m-2 3) 600 N.m-2 4) None
35) The aqueous solution which is isotonic with 0.1M NaCl is
1) 0.1M Glucose 2) 0.1M CH3COOH 3) 0.1M KCl 4) All
36) Insulin is dissolved in a suitable solvent and the osmotic pressures ( in atm.) of solutions of
various concentrations (C) in g/cc are measured at 270C. The slope of a plot of against C is
calculated to be 5 X 10-3. The approximate molecular weight of insulin is
1) 4.51 X 106 g 2) 4.926 X 106 g 3) 6.32 X 105g 4) 9.12 X 107g
n W 1000
Hint : = RT= X X RT
V M.W V
where C = W in grams
1000 RT
Slope = =
C M.W
V in cc
1000 RT W
note : = . is in y = mx form
MW V
37) The correct order of osmotic pressure of equimolar solutions of BaCl2, NaCl and C6H12O6 is
1) NaCl > C6 H12 O6 > BaCl2 2) BaCl2 > NaCl > C6 H12 O 6
3) C6 H12O6 > NaCl > BaCl2 4) All are equal
38) The osmotic pressure of 0.1M NaCl is greater than that of 0.1M CH3COOH. It is due to
1) NaCl is a weak electrolyte 2) CH3COOH is acid
3) CH3COOH is a weak electrolyte 4) All
39) When mercuric iodide is added to an aqueous solution of KI, the
1) Osmotic pressure is decreased 2) Vapour pressure is increased
3) Freezing point is raised 4) All
Hint : 2KI + HgI 2 K 2 [HgI 4 ]
41) The relation between vant Hoff factor (i) and degree of dissociation ( ) of a weak electrolyte A
which dissociates by giving n number of ions ( A nB ) is
i 1 i 1 i
1) 2) 3) 4) None
n 1 n 1 n
Hint : A nB
initia l 1 mole 0
equilibrium (1 - ) n
Total no.of particles in the solution = (1- ) + n
= 1+n -
= 1+ (n-1)
42) The relation between vant Hoff factor (i) and degree of association ( ) of A which associates
as follows nA An .
i 1 i 1 i 1 i 1
1) 2) 3) 4)
n 1 1 n 1 1
1 1
n n
Hint : A An
initial 1 mole 0
at equilibrium (1- )
n
1
Total no.of particles in the solution = (1- ) + = 1+ = 1+ ( -1)
n n n
no.of particles in the solution
van't Hoff factor (i) =
no.of particles taken
1
1+ ( -1)
n
1
1 1
i .e., i = 1+ ( -1) i-1= ( -1)
n n
i-1
= 1
1
n
43) Choose the incorrect statement.
1) Vant Hoff factor (i) for aqueous solution of sucrose is one.
2) Vant Hoff factor (i) for aqueous solution of acetic acid is greater than one
3) Vant Hoff factor (i) for a solution of acetic acid in benzene is less than one
4) None
Hint : Vant Hoff factor i = 1 when there is no dissociation or association
i > 1 when there is dissociation
i < 1 when there is association
Acetic acid dimerizes in benzene (a solvent with low dielectric constant)
44) The degree of dissociation ( ) of a weak electrolyte AX BY is related to vant Hoff factor (i) by
the expression.
i 1 i 1 i 1 x y 1
1) 2) 3) 4)
x y 1 x y 1 x y 1 i 1
45) If vant Hoff factor of Ca(NO3)2 is 2.3, then its percentage of dissociation is
1) 22% 2) 65% 3) 60% 4) 44%
46) The molecular weight of acetic acid dissolved in benzene is calculated as 90g.mole-1 by using
osmotic pressure method. What is the percentage of association of acetic acid.
1) 0.33% 2) 0.66% 3) 90% 4) 66.6%
0
47) 0.01m aqueous solution of K3[Fe (CN)6] freezes at -0.062 C. Its % of dissociation is
(Kf =1.86K.Kg. mole-1)
1) 72% 2) 88% 3) 78% 4) 56%
-1
48) A solution containing 0.8716 mole.L of sucrose is iso-osmotic with a 0.5M NaCl solution. What
is the degree of dissociation of NaCl
1) 0.7432 2) 74.32% 3) 0.8716 4) 0.3716
49) The minimum value of vant Hoff factor if a solute undergoes trimerization in a solution is
1) 0.5 2) 1.33 3) 0.33 4) 3
50) The observed molar mass of KCl obtained by freezing point depression method is related to the
actual molar mass (M) as (the degree of dissociation is x)
1) M (1 + x) 2) M / 2x 3) M (1 + x)-1 4) M (1 - x)-1
0
51) At 25 C, a solution containing 0.2g of poly ethene in 100 mL of toluene shows a rise of 4.8mm at
osmotic equilibrium. The molecular weight of polyethene will be (density of the solution =
0.44g.mL-1)
1) 5.29 X 103g 2) 2.98 X 105g 3) 2.39 X 103g 4) 2.39 X 105g
52) A boy manured a rose plant with highly concentrated solution of urea. On the next day
1) the green colour of the plant will be improved. 2) the plant will grow taller.
3) the plant will bear more number of roses. 4) the plant will die.
1
28) 25 L of an ideal gas is compressed isothermally under constant atmospheric pressure until the vol-
ume becomes 5 L. The change in internal energy is
1) 20 J 2) -2026.5 J 3) +2026 J 4) 0 J
29) There is a balloon of given volume, V1, containing a gas at temperature, T1. When the balloon is
placed in a colder room at temperature, T2, the balloons temperature starts to drop. What are the
signs of the systems q, w, and E for this process?
1) +q, +w, +E 2) -q, -w, -E 3) -q, -w, +E 4) -q, +w, -E
30) 11.2 L of a hydrogen gas at 273 K temperature and 1 atm of pressure in a sealed rigid container is
heated to double its temperature. The change in internal energy dU will be equal to
1) +w 2) +q 3) -w 4) -q
Note: As the process is isochoric, the change in internal energy is only due to exchange of heat
qv dU =
31) An ideal gas at 10 atm pressure and occupying 0.1 L is expanded to 1.1 L by supplying 101.325 J
of heat against constant atmospheric pressure irreversibly. The change in the temperature of the gas
during this process is
1) 10 K 2) 1.1 K 3) 1K 4) No change
Hint: dU = q+w = 101.325 J + (-101.325 J) = 0
4
32) A gas is allowed to expand at constant temperature from a volume of 1.0 L to 10.1 L against an
external pressure of 0.50 atm. If the gas absorbs 250 J of heat from the surroundings, what are the
values of q, w, and E respectively?
1) 250 J, -461 J & -211 J 2) -250 J, -461 J & -711 J
3) 250 J, -461 J & -711 J 4) 250 J, -4.55 J & 245 J
33) In a process, 800 J of heat is absorbed by a system and 350 J of work is done by the system. The
change in internal energy for the process is
1) 350 J 2) 450 J 3) -450 J 4) -350 J
34) When is dHsys= dEsys?
1) When qv= qp.
2) In reactions involving only liquids and solids.
3) In reactions running under a vacuum (P=0).
4) All
35) Which of the following reactions could do work of expansion on the surroundings?
1) 2CO(g) + O2(g)
2CO2(g)
2) Fe2O3(s) + 2Al(s)
Al2O3(s) + 2Fe(s)
3) CH4(g) + 2O2(g)
CO2(g) + 2H2O(g)
4) 2N2O(g) 2N2(g) + O2(g)
36) Suppose a gas in a piston is expanded at constant pressure and the temperature goes down. Which
of the following correctly describes the signs for the work, the heat for the system and the energy
change of the system?
1) Work is positive, q is negative, and dU is negative.
2) Work is negative, q is may be positive or negative, and dU is negative.
3) Work is positive, q is may be positive or negative, and dU is negative.
4) Work is positive, q is positive, and dU is negative.
37) In order to have E 0 for a process, which of the following conditions must be obeyed ?
a) q > 0
b) w > 0
c) q + w > 0
d) q > 0 such that |q| > |w| (where |q| and |w| are absolute values)
The correct options are
1) a,b,c & d 2) b &d 3) a & d 4) c & d
38) When 2.0 mol O2(g) is heated at a constant pressure of 4.25 atm, its temperature increases from
260 K to 285 K. Given that the isobaric molar heat capacity of O2 is 29.4 J.K-1 mol-1, the change in
the internal energy during the process will be
1) 1054 J.K-1 mol-1 2) 416 J.K-1 mol-1 3) 1470 J.K-1 mol-1 4) 1887 J.K-1 mol-1
Formula: U H ng RT
Where n g = no. of moles of gaseous products - no. of moles of gaseous reactants
11) The heat capacity of methyl alcohol (MW = 32.05 g/mol) is 80.3 J mol-1 K-1. The quantity of heat
that will be evolved when the temperature of 2610 g of methyl alcohol falls from 22oC to 2oC
1) 1.5 x 102 kJ 2) 1.3 x 102 kJ 3) 1.7 x 102 kJ 4) 7 kJ
12) The amount of heat absorbed by one mole of an ideal gas in an isochoric process to raise the
temperature from 1.1oC to 11.1oC is 120 kJ/mol. The Cv and Cp values of the gas in kJ mol-1K-1 will
be
1) 12 kJ & 3.7 kJ 2) 10 kJ & 12 kJ 3) 12 kJ & 20.3 kJ 4) 20.3 kJ & 12 kJ
6
Cp
H
T p
qp
T
C p C v nR
13) The difference in Cp and Cv values for liquids and solids will be equal to
1) R 2) nR 3) 2R 4) 0
14) Choose the incorrect statement
1) The molar heat capacities of the metallic elements are almost identical. This is the basis of the Law
of Dulong and Petit, which served as an important tool for estimating the atomic weights of some
elements.
2) The intermolecular hydrogen bonding in water and alcohols results in anomalously high heat
capacities for these liquids; the same is true for ice, compared to other solids.
3) The heat capacity values for graphite and diamond are very high as the solids that are more
ordered tend to have larger heat capacities.
4) None.
Note: The molar heat capacities of metals are almost equal to 3R.
15) The molar heat capacity values of noble gases at contant volume are almost equal to
3R 5R 7R
1) 2 2) 3) 4) R
2 2
Note: In case of noble gases (which are mono-atomic) only three translational degrees of freedom are possible and each of
1 3R 5
these contribute R to heat capacity and hence the Cv = . The Cp value will be given by Cv + R = R
2 2 2
16) The theoretical molar heat capacities of diatomic molecules at constant volume and at fairly high
temperatures is almost equal to
3R 7R 5R
1) 2) R 3) 4)
2 2 2
Note: Diatomic molecules have 3 translational degrees of freedom (contribution of 3R/2), 2 rotational degrees of freedom
7R
(contribution of 1R/2 from each) and 1 vibrational degree of freedom ( contribution of R). Hence Cv = (at high temp.)
2
5R
But at low temperatures (eg., room temperature), the vibrational degree of freedom can be neglected and hence Cv =
2
In the same way, for poly-atomic molecules, the contributions are as follows
1 1 1 3
From three translational degrees of freedom -- R R R R
2 2 2 2
1 1 1 3
From three rotational degrees of freedom -- R R R R
2 2 2 2
From 3N-6 vibrational modes -- (3N-6)R (where N = number of atoms in poly-atomic molecule)
17) Calculate the enthalpy change on freezing of 1.0 mol of water at10.0oC to ice at 10.0oC. Given
fusH = 6.03 kJ mol1 at 0C; Cp [H2O(l)] = 75.3 J mol1 K1 ; Cp [H2O(s)] = 36.8 J mol1 K1
1) 7.151 kJ 2) -6.03 kJ 3) 3.63 kJ 4) -7.151 kJ
18) If 1000 calories are added to 20 g of ice at -10oC, the final temperature will be
(Specific heat of ice = 0.48 cal/g-K and Heat of fusion of ice = 80 cal/g.)
1) 380 K 2) 0 K 3) 273 K 4) 283.2 K
Note: As the heat supplied is not sufficient to melt the ice completely, finally there will be a mixture of ice and water at 0oC
7
19) A coffee-cup calorimeter is calibrated by adding 1840 J of heat to the water in the calorimeter and
measuring a 1.72oC rise in temperature. When some NH4Cl(s) is added to the same water in the
calorimeter, the temperature falls by 1.04oC. The enthalpy change due to the dissolving of NH4Cl(s)
is
1) -1112 J 2) +1250 J 3) +3040 J 4) +1112 J
20) Which of the following statements is true?
1) q = dH at constant P; q = dE at constant T
2) q = dH at constant T; q = dE at constant V
3) q = dH at constant V; q = dE at constant P
4) q = dH at constant P; q = dE at constant V
21) An ice cube at 0oC weighing 9.0 g is dropped into an insulated vessel containing 72 g of water at
50oC. What is the final temperature of water after the ice has melted and a constant temperature has
been reached? The latent heat of fusion of ice is 6.01 kJ/mol and the molar heat capacity of H2O is
75.4 J mol-1K-1.
1) 36oC 2) 40oC 3) 44oC 4) 32oC
o
22) What is U o when one mole of liquid water vaporises at 100 C if the heat of vaporisation vap H o
o -1
of water at 100 C is 40.66 kJ.mol ?
1) 40.66 kJ.mol-1 2) 24.66 kJ.mol-1 3) 36.73 kJ.mol-1 4) -40.66 kJ.mol-1
23) The value of Helium gas is equal to
1) 1.67 cal 2) 1.4 cal 3) 6 cal 4) 10 cal
Cp 5
Note: 1.67 cal
Cv 3
3R
For mono atomic gases Cv 3 cal
2
C p Cv R 5 cal
24) Temperature of one mole of Neon gas is increased by 1oC, hence, increase in internal energy is
1) 5 cal 2) 3 cal 3) 9 cal 4) 2 cal
25) Enthalpy change for a reaction does not depend upon
1) the physical states of reactants and products.
2) use of different reactants for the same product.
3) the nature of intermediate reaction steps.
4) the differences in initial or final temperatures of involved substances.
26) The specific heat of water is 4.18 J g-1 K-1 and that of stainless steel is 0.51 J g-1 K-1. The heat that
must be supplied to a 750.0 g stainless steel vessel containing 800.0 g of water to raise its tempera-
ture from 20.0oC to the boiling point of water
1) 6.98 kJ 2) 29.8 kJ 3) 69.8 kJ 4) 298 kJ
27) The temperature of a substance represents
1) the total heat content of a the particles in a substance
2) the speed of the fastest particles in the substance
3) the speed of the slowest particles in the substance
4) the average kinetic energy of the particles in a system.
28) A bomb calorimeter was calibrated by burning a sample of benzoic acid (C6H5COOH) which has
a known heat of reaction, H = 3227 kJ/mol. When 1.22 g of benzoic acid is burned in the
calorimeter, the temperature is increased by 0.75 C. The heat capacity of the calorimeter and its
contents will be
1) 32 kJ K-1 2) 4.3 kJ K-1 3) 83 kJ K-1 4) 43 kJ K-1
29) The heat of combustion of methyl alcohol, CH3OH, is -715 kJ mol-1. When 2.85 g of CH3OH
8
was burned in a bomb calorimeter, the temperature of the calorimeter changed from 24.05 C to
29.19 C. The heat capacity of the calorimeter is
1) 12.4 kJ/C 2) 124 kJ/C 3) 12.4 J/C 4) 1.24 kJ/C
THERMOCHEMISTRY
1) Which statement is incorrect about endothermic reactions?
1) the system absorbs energy from its surroundings
2) the enthalpy of products is lower than the enthalpy of the reactants
3) the thermal kinetic energy of the surroundings will decrease
4) the enthalpy change will have a positive value
2) Which of the following is the standard state of carbon at STP?
1) C as CO2 (g) 2) C as graphite (s) 3) C as CH4 (g) 4) C as diamond (s)
3) Which of the following statements is/are true about an exothermic reaction?
I) the energy absorbed in bond breaking is more than the energy released in bond formation
II) the system absorbs energy
III) the potential energy of the reactants is less than the potential energy of the products
IV) the thermal kinetic energy of the surroundings will increase
1) I and III only 2) II and III only 3) II and IV only 4) IV only
4) How much heat is absorbed when 3.00 grams of SiO2 react with excess carbon according to the
reaction below? r H o for the reaction is +624.7 kJ.
SiO2(s) + 3C(s) SiC(s) + 2CO(g)
1) 208 kJ 2) 5.06 kJ 3) 10.4 kJ 4) 31.2 kJ
5) H of which of the following reactions is equal to the standard enthalpy of formation( f H o ) of
NH3?
1) 2NH3(g)
3H2(g) + N2(g)
2) NH3(g)
3/2H2(g) + 1/2N2(g)
3) 3H(g) + N(g)
NH3(g)
4) 3/2H2(g) + 1/2N2(g)
NH3(g)
o
Note: The standard enthalpy of formation, f H , is the amount of heat either liberated or absorbed during the formation
of one mole of a compound from its elements under standard conditions.
o
6) Given: H2(g) + Br2(l) 2 HBr(g) ; r H = 72.8 kJ
Calculate the amount of energy absorbed or released when 15.0 g of HBr (g) is formed.
1) 6.75 kJ released 2) 13.5 kJ released 3) 4.85 kJ absorbed 4) 607 kJ absorbed
7) Which of the following has non zero standard enthalpy of formation at 25oC?
1) Cl2(g) 2)O2(g) 3) Na(g) 4) F2(g)
8) The standard heat of formation of NH3 is
(Given N2(g) + 3H2 (g) 2NH (g) ; r H o = -91 kJ )
3
1) +91 kJ 2) + 45.5 kJ 3) -19 kJ 4) -45.5 kJ
9) The enthalpy change for the reaction of 50 mL of ethylene with 50 mL of H2 at 1.5 atm pressure is
H = -0.31 kJ. The change in internal energy will be
1) 0.66 kJ.mol-1 2) -0.3024 kJ.mol-1 3) +0.3024 kJ.mol-1 4) -0.66 kJ.mol-1
10) In a constant-volume bomb calorimeter an unknown compound reacted with excess oxygen to give
carbon dioxide and water. The temperature of 2 kg of water in the calorimeter rose from 12.72oC
to 20.72oC. The heat capacity of the calorimeter is 2.02 kJ.K-1 and the specific heat of water is
4.184 J/goC. The heat given off by the combustion reaction under these conditions is:
1) 41,600 J 2) -41.6 kJ 3) -83.2 kJ 4) -33.5 kJ
Note: The heat given off indicates the internal energy change, as the reaction is occuring at constant volume, and
9
not is not equal to the enthalpy change.
11) In a constant - volume bomb calorimeter, 4g of methane is burned in excess of oxygen. The tem-
perature of 0.5 Kg of water in the calorimeter rose from 12oC to22oC The heat capacity of calorim-
-1
eter is 20.1 kJ.K . The enthalpy of combustion of methane under standard conditions will be
1) 223.1 kJ.mol-1 2) 891.6 kJ.mol-1 3) 888 kJ.mol-1 4) 20.92 kJ.mol-1
Note: Enthalpy of combustion is the amount of heat liberated when one mole of substance is completely burned in excess of
oxygen at standard conditions (constant temperature and pressure). In this case the amount of heat liberated is equal to U .
This value should be converted to H by using the formula. H U n g RT
12) B5H9 burns in air according to the following reaction.
2B5H9(g) + 12O2(g) 5B2O3(s) + 9H2O(l)
What is the molar heat of reaction for the combustion of B5H9 if the reaction between 0.1 g of B5H9
and excess oxygen in a bomb calorimeter raises the temperature of the 852 g of water surrounding
the calorimeter by 1.57oC? [At wts: B = 10.81 amu; H = 1.008 amu; O = 16.00 amu; the heat
capacity of water is 4.184 J / goC]
1) 5.60 x 103 J/mol 2) 9.14 x 102 kJ/mol
3) 3.54 x 103 kJ/mol 4) 4.46 x 103 kJ/mol
13) In the reaction,
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ; r H o = -890.4 kJ
At 1.0 atm and 273 K , how much work is involved per mole of CH4(g) with the volume change that
occurs upon reaction.
1) -4.5 kJ 2) -2.2 kJ 3) 2.2 kJ 4) 4.54 kJ
Note: The work is done on the system and is equal to 4.54 kJ. Here n g =-ve and hence, H E i.e., -890.4 kJ< - 885.8 kJ.
But if the absolute values are considered, the decrease in internal energy is less than heat liberated. This is because Some
amount of decrease in internal energy, due to loss of heat, is compensated by compression work done on the system.
14) When burned in oxygen, 10.0 g of phosphorus generated enough heat to raise the temperature of
2950 g of water from 8.0oC to 28.0oC. The heat of formation of P4O10 from P4(s) and O2(g) is
1) -30.6 kJ mol-1 2) -306 kJ mol-1 3) -3060 kJ mol-1 4)-6120 kJ mol-1
15) Using the following data:
I) N2(g) + 3O2(g) + H2(g) 2HNO3(aq) ; H = -414.8 kJ
II) N2O5(g) + H2O(g) 2HNO3(aq) ; H = 218.4 kJ
III) 2H2O(g) 2H2(g) + O2(g) ; H = 483.6 kJ
What is the H for the reaction: 2N2O5(g)
2N2(g) + 5O2(g)
1) 90.8 kJ 2) -876.4 kJ 3) 782.8 kJ 4)1750 kJ
16.
33. Calculate the enthalpy change, Ho, for the combustion of benzene, C6H6, given the following
C6H6(l) + 15/2O2(g)
6CO2(g) + 3H2O(l)
f H o values in kJ/mol are as follows:
C6H6(l) = 49.0; CO2(g) = -393.5; H2O(l) = -285.8
1) -3169.4 kJ 2) 3267.4 kJ 3) -728.3 kJ 4) -3267.4 kJ
o
34. Calculate H for the reaction: Na2O(s) + SO3 (g) Na2SO4(s) given the following:
(1) Na(s) + H2O(l)
NaOH(s) + 1/2 H2(g) Ho = 146 kJ
(2) Na2SO4 (s) + H2O(l) 2NaOH(s) + SO3(g) Ho = + 418 kJ
(3) 2Na2O (s) + 2H2(g) 4Na(s) + 2H2O(l) Ho = + 259 kJ
1) + 823 kJ 2) 581 kJ 3) 435 kJ 4) + 531 kJ
35. Given equations (1) and (2), calculate the enthalpy change for equation (3).
(1) Pb(s) + PbO2(s) + 2 SO3(g) 2 PbSO4(s) Ho = -775 kJ
(2) SO3(g) + H2O(l) H2SO4(aq) Ho = -133 kJ
(3) Pb(s) PbO2(s) 2 H2SO4(aq) 2 PbSO4(s) 2 H2O(l)
1) 908 kJ 2) 642 kJ 3) 509 kJ 4) + 642 kJ
36. Given that : S(s) + O2(g) SO2(g) H = 296.8 kJ/mol
2 SO3(g) 2 SO2(g) + O2(g) H = + 197.8 kJ/mol
Determine the enthalpy change of the reaction: 2 S(s) + 3 O2(g) 2 SO3(g)
1) 99 kJ 2) 495 kJ 3) + 495 kJ 4) 791.4 kJ
37. Use the following reactions to calculate H for: 4 HCl (g) + O2(g) 2 Cl2(g) + 2 H2O(g)
H2(g) + Cl2 (g) 2 HCl(g) H = 185.0 kJ
2 H2(g) + O2(g) 2 H2O(g) H = 483.7 kJ
1) +113.7 kJ 2) 298.7 kJ 3) +298.7 kJ 4) 113.7 kJ
38. Given equations (I), (II), and (III), calculate the standard enthalpy of formation of acetylene,
C2H2, as shown in equation (IV).
(I) C (s) + O2 (g) CO2 (g) H = 393.5 kJ
(II) H2 (g) + O2 (g) H2O (l) H = 285.8 kJ
(III) 2 C2H2 (g) + 5 O2 (g) 4 CO2 (g) + 2 H2O (l) H = 2598.8 kJ
(IV) 2 C (s) + H2 (g) C2H2 (g)
1) 253.6 kJ 2) 226.6 kJ 3) 1801 kJ 4) -3278 kJ
39) A volume of 50.0 mL of 0.5 M NaOH was added to 20.0 mL of 0.5 M H2SO4 in a calorimeter
whose heat capacity is 39.0 J/K. The temperature of the resulting solution increased by 3.6 C.
The standard enthalpy of neutralization of H2SO4(aq) with NaOH(aq) will be
1) 13.7 kJ mol-1 2) 53.7 kJ mol-1 3) 5.37 kJ mol-1 4) 23.7 kJ mol-1
40) The standard enthalpy of neutralization of acetic acid with sodium hydroxide will be
1) =53.7 kJ mol-1 2) <53.7 kJ mol-1 3) >53.7 kJ mol-1 4) None
Hint: When weak acids or bases participate in the neutralisation, some amount of heat is required for their complete
dissociation. Hence the amount of heat liberated during neutralisation will be less than 53.7 kJ mol-1.
41) The heat of neutralisation of a strong acid and a strong alkali is 57.0 kJ mol-1. The heat released
when 0.5 mole of HNO3 solution is mixed with 0.2 mole of KOH is
1) 57.0 kJ 2) 11.4 kJ 3) 28.5 kJ 4) 34.9 kJ
42) If the bond dissociation energies of XY, X2 and Y2 are in the ratio of 1:2:0.5 and standard heat of
formation of XY is -100 kJ mol-1, then the bond dissociation energy of Y2 will be
1) 400 kJ mol-1 2) 100 kJ mol-1 3) 200 kJ mol-1 4) 800 kJ mol-1
CHEMICAL THERMODYNAMICS (PART-II)
IIT-JEE
ENTROPY
1) The Kelvins statement of second law of thermodynamics is
1) The entropy of universe increases in a spontaneous process.
2) It is impossible to take heat from a hotter reservoir and completely convert into work by a
cyclic process with out transferring a part of heat to a cooler reservoir.
3) It is impossible for a cyclic process to transfer heat from a body at lower temperature to one at a
higher temperature with out converting some work to heat.
4) All.
Note: 3rd statement is known as Clausius statement of second law of thermodynamics.
2) Choose the incorrect statement.
1) Entropy is a measure of the degree of spreading and sharing of thermal energy within a system.
2) The total change in entropy of system and surroundings is zero in a reversible process.
3) Change in entropy is inversely proportional to the temperature at which the process occurs.
4) Entropy of a perfectly-ordered solid at 0C is zero.
Note: 1) According to third law of thermodynamics, the entropy of a perfectly ordered crystal is zero at absolute zero
temperature.
2) Absolute entropy value of the system is proportional to temperature. But the change in entropy is inversely
related to temperature.
3) The thermodynamical expression for change in entropy is given by
qrev q w q w
1) 2) irrev 3) 4) irrev
T T T T
4) The unit of molar entropy is
1) J.mol-1 2) J.K-1.mol-1 3) J.K-1 4) J.K.mol-1
5) Which of the following is true.
1) Entropy is an intensive property but a state function.
2) Entropy is an extensive property and not a state function.
3) Molar entropy is an extensive property but not a state function.
4) Entropy is an extensive property and a state function.
6) The enthalpy of vaporisation of a substance is 72 J mol-1 and its boiling point is -73oC. The entropy
of vaporization is
1) 72 J mol-1 K-1 2) 0.36 J mol-1 K-1 3) 0.986 J mol-1 K-1 4) 72 J mol K
7) For a process at 350 K and constant pressure, Ssurr is -315 J K-1. The quantity of heat (in kJ)
absorbed by the system is
1) 72 2) 3.15 3) 99.2 4) 3.5
8) Consider the following statements about entropy.
a) An ideal gas occupying larger volume has higher entropy than when it occupies smaller volume
under given conditions.
b) The gases with higher atomic or molecular weights possess greater entropy values.
c) The change in entropy of an ideal gas in isothermal free expansion is always negative.
d) The molar entropy of a dilute solution is greater than that of concentrated solution.
e) Solids possess very high entropy values than liquids and gases.
The incorrect statments are
1) c & e 2) a,c & d 3) a,b & c 4) b,c & e
9) Which of the following contain higher entropy?
1) 1 mole acetylene 2) 1 mole ethane 3) 1 mole ethylene 4) 1 mole methane
Hint: Entropy will be higher for those molecules with more number of atoms and bonds.
10) Which of the following produces an increase in entropy of the system ?
1) H2O(l) H2O(s)
2) O2(g) + 2SO2(g) 2SO3(g)
3) 2CH3OH(g) + 3O2(g) 2CO2(g) + 4H2O(l)
4) I2(s) I2(l)
11) Which of the following is the significance of Third law of thermodynamics?
1) The absolute entropy of a substance decreases with increasing temperature.
2) The change in entropy of the universe must be positive for a spontaneous process.
3) The absolute value of entropy can be measured for some very pure substances.
4) The entropy of the universe is constant.
12) For which of the following processes does the entropy of the system decrease?
1) Precipitation of silver chloride from a solution containing silver ions and chloride ions.
2) Dissolving table salt in water.
3) Decomposition of liquid hydrogen peroxide to produce liquid water and oxygen gas..
4) Melting of ice.
13) For which one of the following reactions does the entropy of the system increase?
1) NH3(g) + HCl(g) NH4Cl(s) 2) 2H2(g) + O2(g) 2H2O(g)
+ -
3) NH3(g) + H2O(l) NH4 (aq) + OH (aq) 4) 2H2O2(l) 2H2O(l) + O2(g)
14) Which of the following statements best describes the spontaneity of a reaction at 25oC for
which Ssys is negative and Ssurr is positive?
1) The reaction cannot be spontaneous at 25oC.
2) The reaction will be spontaneous at all temperatures.
3) The reaction will be spontaneous only if Ssys is greater in magnitude than Ssurr.
4) The reaction will be spontaneous only if Ssurr is greater in magnitude than Ssys.
Note: For a spontaneous process, S universe S sys S surr 0
15) Which of the following processes will result in a decrease in the entropy of the closed system?
1) Zn2+ (aq) + 4 NH3 (aq) Zn(NH3)42+ (aq)
2) Cl2 (g) (298 K) Cl2 (g) (450 K)
3) ZnS (s) Zn2+ (aq) + S2- (aq)
4) NH3 (g) (3 atm, 298 K) NH3 (g) (1 atm, 298 K)
16) For a certain process S(system) > 0 and S(surroundings) > 0. The process:
1) is spontaneous. 2) is exothermic. 3) is endothermic. 4) is at equilibrium.
17) Arrange the following compounds in order of increasing standard molar entropy at 25oC.
1) ZnS(s) < H2O(l) < C3H8(g) < C2H4(g)
2) ZnS(s) < C3H8(g) < C2H4(g) < H2O(g)
3) C3H8(g) < C2H4(g) < H2O(l) < ZnS(s)
4) ZnS(s) < H2O(l) < C2H4(g) < C3H8(g)
18) The significance of the Second Law of Thermodynamics is that for spontaneous processes the:
1) entropy of the universe is increasing.
2) entropy is the driving force of all chemical reactions.
3) entropy of an ideal solid does not change.
4) absolute value for entropy can be calculated.
19) A change of state occurs within a system and produces 64.0 kJ of heat. This heat is transferred to the
surroundings at a constant pressure and a constant temperature of 300 K. For this process, S of
the surroundings is :
1) 64.0 J/K 2) -213 J/K 3) 213 J/K 4) 0.00 J/K
20) The normal freezing point of water is 0oC. Predict the signs of Ssys, Ssurr and Suniv when H2O
is supercooled and freezes at -10oC and 1atm.
1) Ssys < 0; Ssurr < 0; Suniv < 0
2) Ssys > 0; Ssurr < 0; Suniv = 0
3) Ssys = 0; Ssurr < 0; Suniv > 0
4) Ssys < 0; Ssurr > 0; Suniv > 0
21) The volume of an ideal gas is doubled in an isothermal process. The change in entropy during this
process is
1) -5.76 J K-1mol-1 2) +5.76 J K-1mol-1 3) +8.3 J K-1mol-1 4) 0 J K-1mol-1
Vf
Formula: For isothermal processes, S 2.303 x nR log
Vi
22) The pressure of 2 moles of a gas is changed from 1 atm to 10 atm at 355.5 K. The change in the
entropy of gas during this process is
1) -38.29 J K-1mol-1 2) +38.29 J K-1 3) -38.29 J K-1 4) +38.29 J K-1mol-1
Pi
Formula: For isothermal processes, S 2.303 x nR log
Pf
23) The absolute entropy of a substance under given conditions cannot be always calculated accurately
T
dT
by using the formula ST C . This is because
0 T
1) The value of C is dependent on temperature and is not a constant.
2) The value of C under constant pressure is always not equal to that under constant volume.
3) The temperature range may encompass the phase change and the entropy change during this
process must be taken into account.
4) All.
24) For mercury the molar entropy of vaporization is 92.92 J K-1 mol-1 and the molar enthalpy of vapor-
ization is 58.51 kJ mol-1. Therefore, the normal boiling point of mercury in oC is:
1) 273oC 2) 357oC 3) 516oC 4) 670oC
vap H
Formula: S
Tb
25) The enthalpy of vaporization of ethanol is 38.7 kJ/mol at its boiling point of 78oC. The change in
entropy of the surroundings when one mole of ethanol is vaporized at 78oC and one atm of pressure
will be
1) +110 J K-1mol-1 2) +220 J K-1mol-1 3) -110 J K-1mol-1 4) 0 J K-1mol-1
26) The significance of the Second Law of Thermodynamics is that for spontaneous processes the:
1) entropy of the universe is increasing.
2) entropy of the surroundings must decrease.
3) entropy of an ideal solid does not change.
4) absolute value for entropy can be calculated.
27) For HI the molar entropy of vaporization is 89.0 J/K mol and the molar enthalpy of vaporization is
21.16 kJ/mol. Therefore, the normal boiling point of HI is:
1) -273oC 2) -35.4oC 3) 23.8 K 4) 42oC
28) A change of state occurs within a system and produces 64.0 kJ of heat. This heat is transferred to the
surroundings at a constant pressure and a constant temperature of 300 K. For this process, S of
the surroundings is :
1) 64.0 J/K 2) -213 J/K 3) -64.0 J/K 4) 213 J/K
29) Which of the following statements is false?
1) Entropy is a measure of the driving force behind chemical reactions.
2) Entropy is a measure of disorder or randomness.
3) Entropy can be created and destroyed.
4) Entropy is a measure of the number of ways energy can be distributed among the motions of
particles.
Note: Strictly speaking, entropy is a measure of spreading and sharing of thermal energy among the microstates possible in
a system under given conditions.
30) Boiling point of Bromine is 59.20C. The standard molar enthalpy of it is
1) 28 kJ mol-1 2) 38 kJ mol-1 3) -28 kJ mol-1 4) -38 kJ mol-1
Note: According to Troutons rule, the standard molar entropy of vaporisation values of a wide range of liquids are almost
same (85 J K-1mol-1)
o
o
vap H -1 -1
vap S 85 J K mol
Tb
31) The efficiency of engine that is working between a lower temperature 27oC and a higher temperature
327oC is
1) 0.2 2) 0.35 3) 0.5 4) 1
TH TL
Formula: Efficiency of engine =
TH
32) The heat efficiency of an engine will be 100% when the operating lower temperature is
1) 0oC 2) 273 K 3) 0 K 4) 273oC
33) For which one of the following reactions does the entropy of the system decrease?
1) NH4NO3 (s) NH4+ (aq) + NO3- (aq)
2) Ba(OH)2.8H2O (s) + 2 NH4SCN (s) Ba(SCN)2 (aq) + 2 NH3 (aq) + 10 H2O (l)
3) NO (g) + NO2 (g) N2O3 (g)
4) CO2 (s) CO2 (g)
34) Precipitation of the Group I ions in the qualitative analysis scheme as AgCl, Hg2Cl2 andPbCl2 is
spontaneous because
1) Entropy of the system decreases. 2) Entropy of the surroundings decreases
3) Entropy of the universe increases 4) Entropy of the system increases.
35) The standard entropy values (in JK-1 mol-1) of H2(g) = 130.6 Cl2 (g) = 223.0 and HCl (g) = 186.7 at
298 K and 1 atm pressure, then the entropy change for the reaction will be (in JK-1 mol-1)
H2(g) + Cl2 (g) 2HCl(g) is :
1) + 540.3 2) +727.3 3) -166.9 4) +19.8
36) If 900 J/g heat is exchanged at boiling point of water then increase in entropy
1) 43.4 J/mol 2) 87.2 J/mol 3) 900 J/mol 4) zero
37) Oxygen and Helium gases are mixed in ratio of 1 : 1 by weight in a container, then in this process :
1) internal energy decreases 2) internal energy increases
3) entropy increases 4) entropy decreases
1
6) The reaction H 2 ( g ) O2 ( g ) H 2O (l ) is used in fuel cells to produce an electric current.
2
Given the thermodynamic data:
Molar entropies in J mol-1 K-1 for O2(g) =205; for H2(g)=130.6; for H2O(l) =70
and f H o of H2O(l) = 285.9 kJ mol1.
What is the amount of electrical work the same reaction can perform in the fuel cell when carried out
reversibly at 298 K.
1) -237.2 kJ mol-1 2) +285.9 kJ mol-1 3) +237.2 kJ mol-1 1) +2.859 kJ mol-1
Note: The amount of electrical work done by this reaction is equal to the Gibbs free energy change(-237.2kJ mol-1 ). As it is
negative, the reaction is spontaneous. This is the maximum useful work.
During this process some amount of heat is liberated and is given by
o o
T S f H G = 285.9 kJ mol-1 - (-237.2 kJ mol-1 ) = 48.7 kJ mol-1
This is the amount of heat liberated during the compression work done on the system as1.5 moles of gas during the reaction
are disappeared. This is equal to PV work and is not useful.
7) For a particular chemical reaction, Ho is positive and So is negative. Which of the following
statements about the spontaneity of the reaction under standard conditions is TRUE?
1) The reaction will be spontaneous only if the magnitude of Ho is large enough to overcome the
unfavorable entropy change.
2) The reaction will be spontaneous only if the magnitude of So is large enough to overcome the
unfavorable enthalpy change.
3) The reaction will be spontaneous regardless of the magnitudes of Ho and So.
4) The reaction cannot be spontaneous at all temperatures.
8) Which of the following is TRUE for an operating voltaic cell? (Where Ecell = emf of the cell)
1) G > 0 ; Ecell = 0 2) G < 0 ; Ecell < 0
3) G < 0 ; Ecell > 0 4) G = 0 ; Ecell = 0
9) An exothermic reaction which is spontaneous at all temperatures is
1) C(graphite) + O2(g) CO2(g) ; H = 393 kJ
2) 3H2 (g) + N2(g) 2NH3(g) ; H= 46.2 kJ
3) N2O4(g)
2NO2(g) ; H = + 55.3 kJ
4) All
10) For a particular chemical reaction, both Ho and So are negative. Which of the following state-
ments about the spontaneity of the reaction under standard conditions is true?
1) The reaction will be spontaneous at any temperature.
2) The reaction will be spontaneous only at higher temperatures
3) The reaction will be spontaneous regardless of the magnitudes of Ho and So.
4) The reaction will be spontaneous only if the magnitude of Ho is large enough to overcome the
unfavorable entropy change.
11) Which of the following reactions is unfavorable at low temperatures but becomes favorable as the
temperature increases?
1) 2 CO(g) + O2(g) CO2(g); Ho = -566 kJ; So = -173 J/K
2) 2 H2O(g) 2 H2(g) + O2(g); Ho = 484 kJ; So = 90.0 J/K
3) 2 N2O(g) 2 N2(g) + O2(g); Ho = -164 kJ; So = 149 J/K
4) PbCl2(s) Pb2+(aq) + O2(g); Ho = 23.4 kJ; So = -12.5 J/K
12) For a particular chemical reaction, the values for H and S are both positive. Which of the
following statements is TRUE about this reaction?
1) The reaction is spontaneous at any temperature.
2) The reaction is not spontaneous at any temperature.
3) The reaction is spontaneous when the temperature is high enough to overcome H.
4) The reaction is spontaneous when the temperature is low enough to overcome H.
13) A spontaneous reaction always occurs when:
1) Ho < 0 and So < 0 2) Ho > 0 and So < 0
3) Ho < 0 and So > 0 4) Ho > 0 and So > 0
14) In which case does the spontaneity of a reaction depend on the temperature?
1) H = 0 and S < 0 2) H > 0 and S > 0
3) H < 0 and S = 0 4) H > 0 and S = 0
15) Which of the following statements is True?
1) A process in which the entropy of the system increases will always be spontaneous.
2) An endothermic process can never be spontaneous.
3) An exothermic process that is accompanied by an increase in the entropy of the system will always
be spontaneous.
4) A process in which the entropy of the surroundings increases will always be spontaneous.
16) For a particular chemical reaction at 25oC, H = -536 kJ. Which of the following statements is
TRUE?
1) The reaction will be spontaneous, at any temperature, if S is positive.
2) The reaction will be spontaneous, at any temperature, if S is negative.
3) The reaction will be spontaneous only if G is positive.
4) The reaction can never be spontaneous, at any temperature.
17) All of the gas-phase reactions listed below are endothermic. Which one of these reactions is
most likely to be non-spontaneous at all temperatures?
1) COCl2(g) CO(g) + Cl2(g)
2) 4NO(g) + 6H2O(g) 4NH3(g) + 5O2(g)
3) 2SO3(g) 2SO2(g) + O2(g)
4) N2O4(g) 2NO2(g)
18) For a particular chemical reaction, Ho = +70 kJ and So = +210 J/K. The temperature at which
this reaction would become spontaneous is
1) below 60.3 oC 2) above 333.3 oC 3) above 60.3 oC 4) below 333.3 oC
Note: For reactions with identical signs of H and S there is a unique temperature at which when G = 0 and T S H .
This is the temperature at which G changes its sign. This is also the temperature at which the system reaches equilibrium.
19) A change in which of the following will also change the value of G for a chemical reaction?
1) partial pressures of either gaseous reactants or products
2) temperature
3) concentration of either reactants or products in aqueous solution
4) All
20) For a particular process at 450 K, G = -5.2 kJ and H = -43.7 kJ. If the process is carried out
reversibly, the amount of useful work that can be performed is
1) -48.9 kJ 2) -5.2 kJ 3) -43.7 kJ 4) -38.5 kJ
21) The following thermite reaction is initiated by burning of a magnesium ribbon.
Fe2O3(s) + 2 Al(s) 2 Fe(l) + Al2O3(s)
For this reaction, the standard enthalpy change is equal to -851.5 kJ and the standard entropy
change is equal to -38.58 J/K. This reaction cannot occur at low temperatures because
1) Enthalpy is favorable and entropy is unfavorable.
2) Neither enthalpy nor entropy are favorable.
3) Both enthalpy and entropy are favorable at high temperatures only.
4) The activation energy is very high.
22. Chemical thermodynamics predicts that materials made of wood, metal, paper, plastic, leather and
rubber react with oxygen in the atmosphere and decompose at 25oC and 1 atm pressure. Which of
the following is responsible for the fact that these reactions are very slow under these conditions?
1) low entropy 2) high enthalpy 3) high activation energy 4) low activation energy
23) Which of the following statements is true?
1) Endothermic reactions are never spontaneous, at any temperature.
2) Exothermic reactions are always spontaneous, at any temperature.
3) Exothermic reactions in which the entropy change for the system is negative are spontaneous at
any temperature.
4) None of the above statements is true.
24) A mixture of hydrogen and chlorine gas remains unreacted until exposed to UV light.Then the follow-
ing reaction occurs very rapidly:
H2(g) + Cl2(g) 2 HCl(g) ; G= -45.54kJ, H= -44.12kJ, S = -4.76 J/K
Select the statements below which best explains this behaviour.
1) The reactants are thermodynamically less stable than the products.
2) The reaction is thermodynamically spontaneous, but the reactants are kinetically stable.
3) The ultraviolet light raises the temperature of the system and makes the reaction spontaneous.
4) The negative value for S slows down the reaction.
25) If a reaction is spontaneous at 27oC and has a standard enthalpy change equal to +150 kJ/mol,
which of the following must be true about the standard entropy of reaction?
1) Standard entropy change < 0 J/mol K
2) Standard entropy change = 27 J/mol K
3) Standard entropy change > 500 J/mol K
4) Standard entropy change = 150 J/mol K
26) The normal freezing point of water is 0oC. Predict the signs of H, S and G when H2O is
supercooled and freezes at -10oC and one atmosphere.
1) H < 0, S < 0, G < 0
2) H < 0, S > 0, G = 0
3) H > 0, S = 0, G > 0
4) H > 0, S > 0, G = 0
27) S > 0 for a certain chemical reaction carried out at constant temperature and pressure . Which of
the following will be true about spontaneity of the reaction?
1) The reaction is spontaneous if it is endothermic and the temperature is sufficiently high.
2) The reaction is spontaneous, if it is exothermic, at any temperature.
3) The reaction is not spontaneous if it is exothermic and the temperature is sufficiently low.
4) Both 1 and 2.
28) Chloroform, CH3Cl, is a common organic solvent. Consider the following process at 70oC, in a
closed system:
CH3Cl(l) -> CH3Cl (g)
This process is endothermic. Which of the following statements is most likely true regarding the
spontaneity of this process at 70oC?
1) The process will be spontaneous because Ssys is negative.
2) The process will be spontaneous because Ssurr is positive.
3) The process will be spontaneous if the boiling point of CH3Cl is less than 70oC.
4) The process will be spontaneous if the boiling point of CH3Cl is greater than 70oC.
29) Which of the following thermodynamic properties cannot be experimentally determined?
1) So 2) Go 3) Go 4) So
30) An ideal solution is formed spontaneously by mixing equal volumes of benzene and touene. For this
process Hsoln is almost zero. Which of the following will be responsible for the spontaneity of this
process?
1) positive Ssoln 2) negative Ssoln 3) positive Vsoln 4) positive Gsoln
31). Consider the gas-phase reaction of hydrogen, H2, and chlorine, Cl2, to produce hydrogen chloride,
H2(g) + Cl2(g) 2HCl(g)
and the following thermodynamic data :
substance fGo, kJ/mol
H2(g) 0
Cl2(g) 0
HCl(g) -95.30
The value of H (in kJ) for this reaction at 25oC if the standard state entropy change is equal to
o
20.0 J/K.
1) 184.6 kJ 2) 101.26 kJ 3) 196.56 kJ 4) 51.3 kJ
o
o
Note: H of the given reaction is to be calculated and not f H .
32) At elevated temperatures, hydrogen iodide, HI, decomposes to produce hydrogen, H2, and iodine,
I2, as shown in the equation below:
2 HI (g) H2 (g) + I2 (g)
Using the thermodynamic data below, calculate the standard free energy change (in kJ) for this
reaction.
Compound fHo, kJ mol-1 So, J mol-1 K-1
HI(g) 25.9 206.3
H2(g) 0 131.0
I2(g) 62.4 260.6
1) 62.4 kJ 2) 16.9 kJ 3) 32.8 kJ 4) 8.45 kJ
33) Consider the following gas-phase reaction and average bond enthalpies,
2NOCl(g) 2NO(g) + Cl2(g)
bond average bond enthalpy, kJ mol-1
N-Cl 201
N=O 716
Cl-Cl 243
Which of the following statements about the spontaneity of this reaction is true at 25oC?
1) The reaction will be spontaneous only if the magnitude of H is large enough to overcome the
unfavorable entropy change.
2) The reaction will be spontaneous only if the magnitude of S is large enough to overcome the
unfavorable enthalpy change.
3) The reaction will be spontaneous if both H and S are negative.
4) The reaction cannot be spontaneous at any temperature.
34) Solid ammonium nitrate, NH4NO3 (s), dissolves spontaneously in water at 25oC,
NH4Cl (s) NH4+ (aq) + Cl- (aq)
If this process is endothermic, which of the following is most likely true ?
1) G > 0 2) G = 0 3) S < 0 4) S > 0
o
35) The normal freezing point of NH3 is -78 C at one atmosphere. Predict the signs of H, S, and
G for NH3 when NH3 supercools and then freezes at -80oC and one atmosphere.
1) H < 0, S < 0, G = 0 2) H < 0, S > 0, G < 0
3) H < 0, S < 0, G < 0 4) H > 0, S > 0, G = 0
36) Consider the following gas-phase reaction
H2(g) + CO(g) <==> H2CO(g)
and the following thermodynamic data,
substance Hfo, kJ mol-1 So, J mol-1 K-1
H2(g) 0 131
CO(g) -110 198
H2CO(g) -116 219
Which of the following best explains why this reaction is not spontaneous under standard conditions?
1) Both Ho and So oppose spontaneity..
2) Both Ho and So favor spontaneity..
3) Ho favors spontaneity but So opposes spontaneity..
4) Ho opposes spontaneity but So favors spontaneity..
37) Adsorption of gases on solid surfaces is generally exothermic because:
1) Entropy of the gas and solid increases.
2) Entropy of the gas and solid decreases.
3) Free energy increases.
4) The total entropy of the system and surroundings decreases.
38) The correct relation between change in free energy in a reaction and the corresponding equilibrium
constant Kc is given by:
1) G RT ln K c 2) G RT ln K c 3) G o RT ln K c 4) G o RT ln K c
39) When a reaction is at equilibrium, which of the following statements is true?
1) G = Go 2) G = 0 3) ln Keq = 0 4) Go = 0
40) For the boiling of methanol,
CH3OH(l) CH3OH(g) ; Ho = +38.0 kJ and So = +113.0 J/K.
The temperature at which the value of G becomes equal to zero for this process will be
1) Greater than its boiling point
2) Less than its boiling point.
3) Equal to its boiling point.
4) Can not be calculated unless the G value is given.
41) The following reaction is spontaneous as written:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Which of the following statements is true?
1) Keq > 1 and Go = 0 2) Keq > 1 and Go < 0
3) Keq < 1 and Go < 0 4) Keq > 1 and Go > 0
42) The equilibrium constant for a chemical reaction will be equal to one when
1) Ho < 0 and So = 0 2) Ho = 0 and So = 0
3) Ho < 0 and So > 0 4) Ho > 0 and So < 0
43) The standard free energy change for the following reaction if the complex ion formation equilibrium
constant, Kf , is equal to 2.1 x 1013.
Cu2+ (aq) + 4 NH3 (aq)
Cu(NH3)42+ (aq)
1) -150 kJ 2) -76 kJ 3) -6.4 kJ 4) 19 kJ
44) Consider the following gas-phase reaction,
2 H2 (g) + O2 (g) 2 H2O (g)
and the corresponding thermodynamic data:
substance Gfo, kJ/mol
H2(g) 0
O2(g) 0
H2O(g) -228.6
The value of the equilibrium constant for this reaction under standard conditions will be
1) 1.4 x 1040 2) 1.4 x 1020 3) 1.4 x 1080 4) 1.4 x 1010
45) Which of the following statements concerning the change in Go and G during a chemical reac-
tion is most correct?
1) Go remains constant while G changes and becomes equal to Go at equilibrium.
2) Both Go and G remain constant during a chemical reaction.
3) Go remains constant if the reaction is carried out under standard conditions; G remains
constant if the reaction is carried out under non-standard conditions.
4) Go remains constant while G changes and becomes equal to zero at equilibrium.
46). Calculate the value of Ka for hydrofluoric acid (HF) at 25oC if the standard free energy change for
the following reaction is equal to +17.9 kJ/mol:
HF (g) + H2O (l)
H3O+ (aq) + F- (aq)
1) 4.0 x 10-38 2) 7.4 x 10-4 3) 9.2 x 10-1 4) 1.4 x 103
47) Hydrogen peroxide decomposes according to the following reaction:
H2O2(l) H2O(l) + 1/2 O2(g)
For this reaction H = -98.2 kJ and S = 70.1 J/K. The approximate value of Kp for this reaction
at 25oC is
1) -1 x 1013 2) -3 x 102 3) 5 x 10-2 4) 7 x 1020