JAM PYQ Questions Merge Till 2022

TOPIC WISE
PYQ
(Physical)
1
SOLID STATE
IIT JAM 2021
1. Monochromatic X-rays having energy 2.8 × 10–15 J diffracted (first order) from (200) plane of a cubic crystal at
an angle 8.5º. The length of unit cell in Å of the crystal (rounded off to one decimal place) is
(Given: Planck’s constant, h = 6.626 × 10–34 J s; c = 3.0 × 108 m s–1)
(a) 9.8 (b) 4.8 (c) 2.4 (d) 3.4
2. Calcium crystallizes in fcc lattice of unit cell length 5.56 Å and density 1.4848 g cm–3. The percentage of Schottky
defects (rounded off to one decimal place) in the crystal is ________.
(Given: Atomic mass of Ca is 40 g mol–1; NA = 6.022 × 1023 mol–1)
3. MgO crystallizes as rock salt structure with unit cell length 2.12 Å. From electrostatic model, the calculated
lattice energy in kJ mol–1 (rounded off to the nearest integer) is _________.
(Given: NA = 6.022 × 1023 mol–1; Madelung constant = 1.748; 0 = 8.854 × 10–12 J–1 C2 m–1; charge of an
electron = 1.602 × 10–19 C)
IIT JAM 2020
4. Fullerene (C60) crystallizes in an FCC unit cell (edge length = 14.14 Å) with one C 60 centered at each lattice
point. The smallest distance (in Å) between the centers of two C60 molecules is _____ (Round off to two decimal
places)
IIT JAM 2019
5. The ratio of the nearest neighbour atomic distances in body-centered cubic (bcc) and face-centered cubic (fcc)
crystals with the same unit cell edge length is
3 3 1 1
(a) (b) (c) (d)
2 2 2 2
6. A first order reflection of X-ray from [220] plane of copper crystal is observed at a glancing angle of 22º. The
wavelength of the X-ray used is _________ pm. (Round off to one decimal place)
[Given: Copper forms fcc crystal with unit cell edge length of 361 pm.]
IIT JAM 2018
7. The number of crystal systems and the number of Bravais lattices are, respectively,
(a) 14 and 7 (b) 7 and 32 (c) 32 and 14 (d) 7 and 14
IIT JAM 2017
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8. Silver crystallizes in a face-centered cubic lattice. The lattice parameter of silver (in picometer) is _____
[Given: Avogadro’s number = 6.023 × 1023 mol–1, molar mass of silver = 107.87 g mol–1 and density of crystal
= 10.5 g cm–3]
9. The separation of 123 planes (in nm) in an orthorhombic cell with a = 0.25 nm, b = 0.5 nm and c = 0.75 nm is
______
(final answer should be rounded off to two-decimal places)
IIT JAM 2016
10. The coordination numbers of Cs+ and Cl– ions in the CsCl structure, respectively are
(a) 4, 4 (b) 4, 8 (c) 6, 6 (d) 8, 8
11. In a diffraction experiment with X-rays of wavelength 1.54 Å, a diffraction line corresponding to 2 = 20.8º is
observed. The inter-planar separation in Å is _____
12. The potential energy of interaction between two ions in an ionic compound is given by
Z Z 
U  1389.4  1 2  kJ mol 1 . Assuming that CaCl is linear molecule of length 5.6 Å, the potential energy for
 r/Å  2
–1
CaCl2 molecule in kJ mol is___.
IIT JAM 2015
13. At what angle(s) of incidence, X-rays of wavelength 5.0 Å will produce diffracted beam from the (110) planes in
a simple cubic lattice with a = 10 Å?
(a) 6.8º (b) 10.2º (c) 20.7º (d) 45.0º
14. The ionic radii of Cs2+ and Cl– ions are 181 and 167 pm, respectively. The Born2exponents for the He, Ne, Ar,
ANe
Kr and Xe configurations are 5, 7, 9, 10 and 12 respectively. If the value of is 2.45 × 10–4 J m, the lattice
40
energy (in kJ mol–1) of CsCl according to Born-Lande equation is _____
IIT JAM 2014
15. A first order reflection from (111) plane is observed for LiX with 2 = 24.6º (X-ray of wavelength 1.54 Å).
Assuming LiX to be a cubic crystal system, calculate the length of the side of the unit cell in Å.
IIT JAM 2013
16. CaO, VO and MnO have octahedral coordination of the metal ions in a rock-salt structure. The correct increasing
order of their lattice enthalpies is __________
17. A hypothetical element (atomic weight = 300) crystallizes in a simple cubic lattice. For this crystal, the first order
X-ray diffraction with wavelength of 5 Å appears at an angle of 30º. The density of the crystal is _____________g
cm–3. [Avogadro number, NA = 6.02 × 1023]
IIT JAM 2012
18. The lattice energy of LiF calculated from Born-Lande equation – 1000 kJ mol–1. Assume that for both LiF and
MgO the Madelung constants, interionic distances and Born exponents have the same value. The lattice energy
of MgO in kJ mol–1 is:
(a) –4000 (b) –2000 (c) 2000 (d) 4000
19. Draw the unit cell structure of NaCl. Calculate the limiting radius ratio of any ionic solid having NaCl like structure.
IIT JAM 2010
20. The structure of rock salt consists of
(a) A cubic close-packed array of anions with cations in all the octahedral sites
(b) A cubic close-packed array of cations with anions in all the tetrahedral sites
(c) A hexagonal close-packed array of anions with cations in all the octahedral sites
(d) A cubic close-packed array of anions with cations in all the tetrahedral sites
21. Draw a properly labeled unit cell diagram of CsCl. Show through calculations that there is only one CsCl per unit
cell.
IIT JAM 2009
22. The unit cell of diamond can be obtained from the unit cell of
(a) ZnS (b) NaCl (c) CsCl (d) AgCl
IIT JAM 2008
23. In CsCl structure, the number of Cs+ ions that occupy second nearest neighbour locations of a Cs+ ion is:
(a) 6 (b) 8 (c) 10 (d) 12
IIT JAM 2007
24. The ionic radii of Ca2+ and F– are 100 pm and 133 pm respectively. The coordination number of Ca2+ in the ionic
solid will be
(a) 8 (b) 6 (c) 4 (d) 2
IIT JAM 2006
25. Draw the unit cell of CsCl lattice. Draw the (100) and (110) places separately and indicate the position of
ceasium and chloride ions.
ANSWER KEY
2
CHEMICAL KINETICS
IIT JAM 2021
1. For the consecutive reaction,
kX kY
X   Y  Z
Co is the initial concentration of X. The concentrations of X, Y and Z at time t are CX, CY and CZ, respectively.
The expression for the concentration of Y at time t is
k X CX k X CX
(a) k  k e
kX t

 ek Y t  (b) k  k e 
kY t
 ek X t 
Y X Y X
k X C0 k X C0
(c) k  k e
kY t

 ek X t  (d) k  k e 
kX t
 ek Y t 
Y X Y X
2. Half-life (t1/2) of a chemical reaction varies with the initial concentration of reactant (A0) as given below:

A 0 mol L1  5 102 4  102 3  102
t1/ 2  s  360 450 600
The order of the reaction is

(a) 1 (b) 3 (c) 2 (d) 0
3. For the reaction,
1 k

Q  R  k2
X  P
k 1
k1 = 2.5 × 105 L mol–1 s–1, k–1 = 1.0 × 104 s–1 and k2 = 10 s–1. Under steady state approximation, the rate
constant for the overall reaction in L mol–1 s–1 (rounded off to the nearest integer) is _______.
4. The intensity of a monochromatic visible light is reduced by 90% due to absorption on passing through a 5.0 mM
solution of a compound. If the path length is 4 cm, then the molar extinction coefficient of the compound in M–1
cm–1 is ________
IIT JAM 2020
5. At a certain wavelength, liquid P transmits 70%, whereas liquid Q transmits 30% of the incident light when
separately placed in a spectrophotometric cell (path length = 1 cm). In a binary mixture of liquids P and Q
(assume non - interacting liquids), the absorbance in the same cell is 0.25. The volume fraction of liquid P in the
binary mixture is ______ (Round off to two decimal places)
IIT JAM 2019
6. For a reaction of the type A + B  Products, the unit of the rate constant is mol L–1 s–1.
The overall order of the reaction is
(a) 0 (b) 1 (c) 2 (d) 3
7. The half-life of the chemical reaction, A  Product, for initial reactant concentrations of 0.1 and 0.4 mol L–1 are
200 and 50 s, respectively. the order of the reaction is
(a) 0 (b) 1 (c) 2 (d) 3
8. The turnover frequency (TOF) for the catalytic reaction,
A 1 mol  
 
Catalyst 0.01 mol
5 hours
B
with 90% yield of the product is ________ hour–1. (Round off to the nearest integer)
IIT JAM 2018
9. The reaction, A  Products, follows first-order kinetics. If [A] represents the concentration of reactant at time t,
the INCORRECT variation is shown in
–d[A] log[A]
[A] dt
(a) (b) (c) (d)
t t t
10. The time for 50% completion of a zero order reaction is 30 min. Time for 80% completion of this reaction is
_______ min.
IIT JAM 2017
11. For a first order reaction A(g)  2B(g) + C(g), the rate constant is terms of initial pressure (p0) and pressure at
time t(pt) is given by
1 p0 1 2p0 1 3p0 1 3p0
(a) t ln p  p (b) t ln 3p  p (c) t ln p  p (d) t ln 3p  p
t 0 0 t t 0 t 0
12. For a reaction 2A + B  C + D, if rate of consumption of A is 0.1 mol L–1 s–1 , the rate of production of C (in
mol L–1 s–1) is _____
IIT JAM 2016
13. For a zero order reaction, the half-life depends on the initial concentration [C0] of the reactant as
(a) [C0] (b) [C0]0 (c) [C0]–1 (d) [C0]1/2
14. The rate constants for a reaction at 300 and 350 K are 8 and 160 L mol–1 s–1, respectively. The activation energy
of the reaction in kJ mol–1 is ____.
[Given R = 8.314 J K–1 mol–1]
IIT JAM 2015
15. The kinetics of the reaction 2N2O5  4NO2 + O2 in liquid bromine medium was measured independently for
three different initial concentration of N2O5 : 0.11, 0.07 and 0.05 mol L–1. The half-life of the reaction was found
to be 4.5 hours for all these concentrations. The order of the reaction is
(a) 0 (b) 1 (c) 2 (d) 0.5
16. –4
A 2.5 × 10 M solution of a complex exhibits an absorption maximum at 625 nm with an absorbance of 0.90
when measured in a cuvette with a path length of 1.5 cm. The absorbance of 1.5 × 10–3 M solution of the same
complex recorded in a cuvette with a path length of 0.2 cm is _______.
17. For a reaction, the rate constant at 25ºC is doubled when the temperature is raised to 45ºC. The activation
energy (in kJ mol–1) of the reaction is _______[Given: ln2 = 0.693]
IIT JAM 2014
18. An aqueous solution of hemoglobin has a molar absorptivity value of 18,600 L mol–1 cm–1 for an absorbance
value of 0.1 at 540 nm (Guiven: cell thickness = 1 cm). The concentration (in µM) of the haemoglobin solution is
(a) 0.537 (b) 5.37 (c) 53.7 (d) 537.0
19. For the reaction:
700ºC
2NO  2H 2  N 2  2H 2O
(i) Write the expression for the rate of the reaction in terms of the change in concentrations of NO and H2O.
(ii) Given the following data for the above reaction, find the order of the reaction with respect to (a) NO and (b)
H2 and the rate constant of the reaction along with the proper unit,
IIT JAM 2013
 1 
20. For a particular reaction at constant temperature, a plot of inverse of reactant concentration   versus time
 [A] 
is a straight line with a slope of 4.0 × 10–2 L mol–1 s–1. The time required (in seconds) for 1.0 M of reactant to
decrease to 0.25 M is:
(a) 18.8 (b) 34.7 (c) 75.0 (d) 187.5
21. A solution containing 250 ppm of CuSO4 · 5H2O (formula weight = 250) has an absorbance of 0.1 measured in
1 cm cell at 600 nm. Calculate the molar absorptivity () of CuSO4 · 5H2O in L M–1 cm–1. When 25 mL of
Na2EDTA (aq) solution is titrated against Na2EDTA (aq) solution, it consumes at 50 mL of Na2EDTA (aq)
solution. Calculate the concentration of Na2EDTA (aq) solution in moles L–1.
IIT JAM 2012
22. The half-life of any zero-order reaction is:
(a) independent of concentration (b) Proportional to inverse of concentration
(c) proportional to concentration (d) proportional to square to the concentration
23. The percent transmittance of a solution having absorbance (optical density) 1.0 is
(a) 1 (b) 10 (c) 50 (d) 99
24. The mechanism of isomerization of cyclobutene (CB) to 1, 3-butadiene (BD) is as follows.
k
1  CB*  CB
CB  CB 
k
CB*  CB 
1  CB  CB
k
CB* 
2 BD
d[BD] k 2 .k1.[CB]2
(a) Show that the rate law is 
dt k 1.[CB]  k 2
k 2 .k1.[CB]
(b) The apparent first-order rate constant, k app  k .[CB]  k . At the CB concentration of 1 × 10–5 mol
1 2
dm–3, the value of kapp reaches 50% of its limiting value obtained at very high concentrations of CB. Evaluate the
k2
ratio k .
1
IIT JAM 2011

25. (a) For the reaction R  P, the plot of ln[R] versus time (t) gives a straight line with a negative slope. The half life
for the reaction is 3 minutes.
(ln 2 = 0.693, ln 0.1 = –2.303)
(i) Derive the expression for t1/2.
(ii) Calculate the slope of the straight line
(iii) Calculate the time required for the concentration of R to decrease to 10% of its initial value.
(b) Shown below is the Jablonski diagram that describes various photophysical processes. The solid arrows ()
represent radiative transitions and the wave arrow ( ) represents a non-radiative transition.
(i) Name the photophysical pathways X, Y and Z.

(ii) Which of the radiative decays is faster?
IIT JAM 2010
26. For the reaction, H2(g) + Br2(g)  2HBr(g)
the following mechanism has been proposed.
ki
Initiation: Br2  M   Br   Br   M
k k
Propagation: Br   H 2  
p
 HBr  H ; H  Br2 
p´
HBr  Br 
kr
Retardation: H   HBr   H 2  Br 
k
Termination: Br   Br   M 
t
 Br2  M  energy
where M is the initiator/terminator.
(a) Write the differential rate equations for the formation of the two intermediates H and Br.
(b) Using the steady-state approximate calculate the concentration of the intermediate H and Br and obtain the
rate law for the formation of HBr.
IIT JAM 2009
27. For the formation of B from A, heat liberated is 20 kJ mol–1. If the activation energy for the reaction B  A is 100
kJ mol–1, then the activation energy (in kJ mol–1) for the reaction A  B is
(a) 120 (b) 100 (c) 80 (d) 60
28. For the reaction A + B  Z, the concentration of Z at time t is given by
[Z]  [A]t 0 (1  e  kt )  [Z]t 0 , where k is the rate constant. The rate law is:
d[Z] d[Z] d[Z] d[Z]

(a)   k[A] (b)  k[A] (c)  k[Z] (d)  k[A][B]
dt dt dt dt
29. The following initial rate data were obtained for the reaction
2NO(g) + O2(g)  2NO2(g)
Partial pressure of Initial rate
NO O2
Run 1 pNO p O2 v
Run 2 2 pNO p O2 4v
Run 3 pNO 2pO2 2v

(i) What is the rate law for this reaction ?
(ii) One of the mechanism proposed for this reaction is
k1

 NO3 (g)
NO(g)  O2 (g) 
 k 1
k
NO3 (g)  NO(g) 
2  2NO (g)
2
Obtain the rate law predicted for this mechanism, assuming a steady state concentration of NO3.
(iii) Predict the rate law for this mechanism, if the first equilibrium step is established quickly and the second step
is slow.
IIT JAM 2008
30. For a zero order reaction, units of the rate constant is expressed as
(a) M1s–1 (b) M0s–1 (c) M–1s–1 (d) M0s0
31. 1 × 10–6 moles of the enzyme carbonic anhyrase dehydrates H2CO3 to produce 0.6 mol of CO2 per second. The
turnover number of the enzyme is:
(a) NA × 6 × 10–5 (b) (1/6) × 10–5 (c) (6 × 105) / NA (d) 6 × 105
32. The rate of a chemical reaction doubles when the temperature is changed from 300 K to 310 K.
Calculate activation energy in kJ mol–1
IIT JAM 2007
33. For a reaction with rate equation –dC/dt = kC2, C0 and C are the concentrations of the reactant at time 0 and t
respectively. If 10 minutes were required for C0 to become C0/2, the time required for C0 to become C0/4 is:
(a) 10 min (b) 20 min (c) 30 min (d) 40 min
34. An enzyme following Michaelis-Menten kinetics was found to have highest activity at 37ºC and pH 7.0. If the
maximum velocity Vmax for this enzyme was 2.4 × 10–4 mol L–1 s–1 with an initial enzyme concentration [E]0 = 2.4
nM, calculate the turnover frequency.
IIT JAM 2006
35. Ozone seems to be formed in the atmosphere through the photolysis of diatomic molecule :
k0
O2 
hv
 2O
k1
O  O 2   O3
k2
O3  O   2O2
Applying steady-state approximation, determine the rate law for the formation of ozone. Show that the formation
of ozone follows first order kinetics when the concentration of O3 is extremely small.
IIT JAM 2005
1
36. From the reaction aA  products, the plot of versus time (t) gives a straight line. Order of the reaction is
[A]
(a) 0 (b) 1 (c) 2 (d) 3
3000
37. The rate constant k for a second order reaction P + Q  Products is expressed log10 k  20  , where
T
the concentration is in mol lit–1, T is in absolute temperature and time is in minutes. The initial concentrations of
both the reactants are 0.05 M. Calculate the activation energy and half life of the reaction at 27ºC. (R = 2
cal K mol )
–1 –1
ANSWER KEY
3
Mole Concept & Liquid Solutions
IIT JAM 2021
1. A dilute solution prepared by dissolving a nonvolatile solute in one liter water shows a depression in freezing point
of 0.186 K. This solute neither dissociates nor associates in water. The boiling point of the solution in K (rounded
off to three decimal places) is )_________.
(Given: For pure water, boiling point = 373.15 K; cryoscopic constant = 1.86 K (mol kg –1)–1; ebullioscopic
constant = 0.51 K (mol kg–1)–1)
2. A salt mixture (1.0 g) contains 25 wt% of M gSO4 and 75 wt% of M2SO4. Aqueous solution of this salt mixture
on treating with excess BaCl2 solution results in th precipitation of 1.49 g of BaSO4. The atomic mass of M in g
mol–1 (rounded off to two decimal places) is ________.
(Given: the atomic masses of Mg, S, O, Ba and Cl are 24.31, 32.06, 16.00, 137.33 and 35.45 g mol–1, respec-
tively)
IIT JAM 2019
3. One liter of an aqueous urea solution contains 6 g of urea. The osmotic presure of the solution at 300 K (assuming
an ideal behavior) is ____________ kPa. (Round off to one decimal place)
[Given: Molecular weight of urea is 60, gas constant (R) is 8.3 J K–1 mol–1]
4. Assume that the reaction of MeMgBr with ethylacetate proceeds with 100% conversion to give tert-butanol. The
volume of 0.2 M solution of MeMgBr required to convert 10 mL of a 0.025 M solution of ethylacetate to tert-
butanol is ________ mL. (Round off to one decimal place)
IIT JAM 2018
5. Elemental analysis of an organic compound contaming C, H and O gives percentage composition: C : 39.9% and
H : 6.7%. If the molecular weight of the compound is 180, the number of carbon atoms present in the molecule
is ________.
IIT JAM 2017
6. In 200 g of water, 0.01 mole of NaCl and 0.02 mole of sucrose are dissolved. Assuming solution to be ideal, the
depression in freezing point of water (in ºC) will be ______
(final answer should be rounded off to two decimal places)
[Given: Kf(H2O) = 1.86 K kg mol–1]
IIT JAM 2016
7. Cu(s) + 4H+(aq) + 2NO3– (aq)  2NO2(g) + Cu2+(aq) + 2H2O(l)
In the above reaction at 1 atm and 298 K, if 6.36 g of copper is used. Assuming ideal gas behavior, the volume
of NO2 produced in liters is ____.
[Given: atomic mass of Cu is 63.6; R = 0.0821 L atm K–1 mol–1]
8. A 10 L flask containing 10.8 g of N2O5 is heated to 373 K, which leads to its decomposition according to the
equation 2 N2O5(g)  4 NO2(g) + O2(g). If the final pressure in the flask is 0.5 atm, then the partial pressure of
O2(g) in atm is ____.
[Given R = 0.0821 L atm K–1 mol–1]
IIT JAM 2015
9. The amount (in grams) of potassium dichromate (MW = 294) present in 75 mL of 0.16 M aqueous solution is
_______
IIT JAM 2014
10. The vapour pressure of benzene is 5333 Pa at 7.6ºC and 53330 Pa at 60.6ºC. Calculate the heat of vapourization
of benzene and the normal boiling point of benzene.
IIT JAM 2013
11. A mixture of C3H8 and oxygen in 1L closed vessel has an internal pressure of 4 atm at 100ºC. When the mixture
is ignited, the reaction produces CO2(g) and H2O(g) until all oxygen is consumed. After the reaction, pressure of
the vessel is 4.2 atm at the same temperature. Calculate the weight of oxygen present before the reaction. [Gas
constant, R = 0.082 L atm mol–1 K–1].
IIT JAM 2012
12. An aqueous solution containing 1 g L–1 of a polymer exerts osmotic pressure of 4 torr at 300 K. Given R = 0.082
L atm, the molar mass (g mol–1) of the polymer is
(a) 4500 (b) 4564 (c) 4674 (d) 4800
IIT JAM 2011
13. The most viscous liquid is
(a) Water (b) Methanol (c) Ethylene glycol (d) Glycerol
IIT JAM 2010
14. Addition of 1.0 g of a compound to 10 g of water increases the boiling point by 0.3°C. The amount of
compound needed to prepare a 500 ml or 0.1 M solution is (given : assume negligible dissociation or association
of the compound, boiling point constant Kb of water = 0.513 K kg mol–1)
(a) 0.855 g (b) 17.1 g (c) 8.55 g (d) 85.5 g
IIT JAM 2007
15. The vapour pressure of D2O at 20ºC is 745 mm Hg. When 15 g of a non-volatile compound is dissolved in 200
g of D2O the pressure changes to 730 mm Hg. Assuming the applicability of Raoult’s law, calculate the molecular
weight of the compound.
IIT JAM 2005
16. At 20ºC, the vapour pressure of two pure liquids X and Y which form an ideal solution are 70 torr and 20 torr
respectively. If the mole fraction of X in solution is 0.5, find the mole fraction of X and Y in the vapour phase in
equilibrium with the solution.
ANSWER KEY
4
ATOMIC STRUCTURE
(IIT JAM-2005)
1. For an electron whose x-positional uncertainity is 1 × 1010 m, the uncertainity in x-component of the velocity in
ms–1 will be of the order of (Data: me = 9 × 10–31 kg, h = 6.6 × 1034 Js)
(a) 106 (b) 109 (c) 1012 (d) 1015
(IIT JAM-2009)
2. An electron is found in an orbital with one radial node and two angular nodes. Which orbital the electron is in?
(a) 1s (b) 2p (c) 3d (d) 4d
3. (a) In the Bohr model of a hydrogen-like atom with atomic number Z.
* The angular momentum of an electron (of mass me and charge e) is a non-zero integral (n) multiple of h/2, where
h is the Plank’s constant, and
* The electrostatic attraction exerted by the nucleus on the electron is balanced by the centrifugal force experienced
by the electron.
(i) Write mathematical expressions for the above statements.
(ii) Hence obtain the expression for the radius r of the Bohr orbit of the electron in terms of (E), n and Z.
(b) Complete the following nuclear reactions:
(i) 14 4 1
7 N  2 He  1H  .......... (ii) 37 Li  11H  ...........
(IIT JAM-2011)
4. Identify the correct statement regarding Einstein’s photoelectic effect
(a) The number of electrons ejected depends on the wavelength of incident radiation.
(b) Electron ejection can occur at any wavelength of incident radiation.
(c) The number of electrons ejected at a given incident wavelength depends on the intensity of the radiation.
(d) The kinetic energy of the ejected electrons is independent of the wavelength of incident radiation.
(IIT JAM-2014)
5. The energy of an electron in a hydrogenic atom with nuclear charge Z varies as:
(a) Z (b) Z2 (c) 1/Z (d) 1/Z2
(IIT JAM-2017)
6. Ionisation energy of hydrogen atom is ground state is 13.6 eV. The energy released (in eV) for third member of
Balmer series is
(a) 13.056 (b) 2.856 (c) 0.967 (d) 0.306
(IIT JAM-2018)
7. The electron of a hydrogen atom is in its nth Bohr orbit having de Broglie wavelength of 13.4 Å. The value of n is
_________ (rounded up to the nearest integer).
[Radius of nth Bohr orbit = 0.53 n2 Å,  = 3.14]
(IIT JAM-2019)
8. The ionization energy of hydrogen atom is 13.6 eV and the first ionization energy of sodium atom is 5.1 eV. The
effective nuclear charge experienced by the valance electron of sodium atom is ________. (Round off to one
decimal place)
9. Given that the radius of the first Bohr orbit of hydrogen atom is 53 pm, the radius of its third Bohr orbit is
________ pm. (Round off to the nearest integer)
(IIT JAM-2020)
10. The longest wavelength of light absorbed by a hydrogen – like atoms is 2.48 nm. The nuclear charge (Z) of the
atom is ______ (Round off to nearest integer)
(Rydberg constant RH = 109700 cm–1).
(IIT JAM-2021)
11. Two sets of quantum numbers with the same number of radial nodes are
(a) n = 3; l = 2; ml = 0 and n = 2; l = 1; ml = 0
(b) n = 3; l = 0; ml = 0 and n = 2; l = 0; ml = 0
(c) n = 3; l = 1; ml = 1 and n = 2; l = 1; ml = 0
(d) n = 3; l = 1; ml = –1 and n = 2; l = 1; ml = 0
(IIT JAM-2022)
12. The ratio of the 2p  1s transition energy in He+ to that in the H atom is closest to
(a) 1 (b) 2 (c) 4 (d) 8
ANSWER KEY
5
Thermodynamics & Thermochemistry
IIT JAM 2005
1. Justify the following
(a) Considering CO2 as an ideal gas, equipartition theorem products its total energy as 6.5 kT.
(b) S for a process is the same whether the process takes place reversibly or irreversibly.
(c) The quantity G equals the maximum non-expansion work done by a system in a constant temperaure-
pressure process.
(d) At constant temperature and pressure, G = 0 for a reversible phase change.
(e) Transition states cannot be isolated as independent chemical species.
IIT JAM 2006
2. The temperature (T) dependence of the equilibrium constant (K) of a chemical reaction is correctly described by
the following statement:
(a) For an endothermic reaction, the slope of ln K vs 1/T plot is positive.
(b) For an exothermic reaction, K is proportional to T
(c) For an exothermic reaction, K at a higher temperature is lower than K at a lower temperature
(d) If H is independent of temperature, the change in K with T is smaller at lower temperatures.
3. A system undergoes two cyclic processes 1 and 2. Process 1 is reversible and process 2 is irreversible. The
correct statement relating to the two processes is
(a) S (for process 1) = 0, while S (for process 2) 0
(b) qcycle = 0 for process 1 and qcycle  0 for process 2
(c) More heat can be converted to work in process 1 than in process 2
(d) More work can be converted to heat in process 1 than in process 2
IIT JAM 2007
4. For a cyclic process performed by an ideal gas, changes in some thermodynamic functions are zero. Indicate the
set in which all the functions are zero
(a) w, E, H, G (b) q, S, H, A (c) q, E, S, G (d) E, S, H, A
5. (a) When an ideal monoatomic gas is expanded adiabatically from 1.5 bar, 24.8 L and 298 K into an evacuated
container, the final volume becomes 49.6 L. Calculate H, S and G for the process.
IIT JAM 2008
6. When one mole of ice is converted to water at 0ºC and 1 atm, the work done (1 atm) is:
(a) 1.1 × 10–4 (b) 2.0 × 10–3 (c) 2.0 × 10–4 (d) 1.1 × 10–5
7. When 100 g of water is reversibly heated from 50ºC to 75ºC at 1 atm, the change in entropy (JK –1) of the
universe is:
(a) –0.31 (b) 0.31 (c) 0 (d) 3.1
IIT JAM 2009
8. (a) A container is partitioned into two compartments, one of which contains 2 moles of He while the other
contains 3 moles of Ar. The gases are ideal. The temperature is 300 K and the pressure is 1 bar:
R = 0.083 L bar mol–1 K–1, ln (2/5) = –0.92, ln (3/5) = –0.51
(i) If the partition between the two compartments is removed and the gases are allowed to mix, then what is the
Gibbs free energy of the mixture?
(ii) What is the change in enthalpy in this process?
(b) Obtain (i) the molar heat of formation of CH4(g) and (ii) the average C-H bond energy, to the nearest
kilojoule (kJ), from the given data:
G(kJ mol–1)
(1) CH 4 (g)  CH 3 (g)  H(g) 435
(2) CH 3 (g)  CH 2 (g)  H(g) 444
(3) CH 2 (g)  CH(g)  H(g) 444
(4) CH(g)  C(g)  H(g) 339
(5) C(graphite)  C(g) 717
(6) H 2 (g)  2H(g) 436
IIT JAM 2010
9. The molar internal energy of a gas at temperature T is Um(T). The molar internal energy at T = 0 is Um(0). The
correct expression that relates these two with appropriate contributions is :
(a) Um(T) = Um(0) + 3RT [Linear molecule; translation only]
(b) Um(T) = Um(0) + 5/2 RT [Linear molecule; translation and rotation only]
(c) Um(T) = Um(0) + 3/2 RT (Nonlinear molecule; translation and rotation only)
(d) Um(T) = Um(0) + RT (Nonlinear molecule; translation only)
10. Choose the INCORECT statement among the following:
(a) When ideal gases are mixed, the entropy of mixing is always positive
(b) At equilibrium, the chemical potential of a species is the same in all of the phases of the system
(c) The total pressure of a mixture of ideal gases is equal to the sum of the partial pressure of each gas in the
mixture.
(d) When a gas is allowed to expand, the maximum work is obtained when the process is carried out irreversibly.
11. The work done during the free expansion of one mole of an ideal gas at 27°C to twice its original volume is (given
: RT = 2494 J mol–1, ln 2 = 0.7, log 2 = 0.3)
(a) 1746 J mol–1 (b) –1746 J mol–1 (c) zero (d) 748.2 J mol–1
12. Calculate Hm and Sm for the process
Assume that at 273 K the molar enthalpy of fusion of ice is 6006 J mol–1, the heat capacity Cp,m (s) of ice is 38 J
K–1 mol–1 and heat capacity Cp,m () of liquid water is 76 J K–1 mol–1. Consider the heat capacities to be
constants. Consider the heat capacities to be constants. (given: ln = 263 = 5.57 and ln 273 = 5.61)
IIT JAM 2011
13. One mole of a van der waals gas undergoes reversible isothermal transformation from an initial volume V1 to a
final volume V2. The expression for the work done is:
V2 V2  b  1 1 
(a) RT ln V  a(V2  V1 ) (b) RT ln a  
1 V1  a  V1 V2 
P2 V2  b  1 1 
(c) RT ln P (d) RT ln a  
1 V1  a  V1 V2 
14. For an ideal gas undergoing reversible Carnot Cycle, the plot of enthalpy (H) versus entropy (S) is:
(a) (b)
(c) (d)
15. (a) One mole of an ideal gas initially at 300 K and at a pressure of 10 atm undergoes adiabatic expansion.
(i) Reversibly and
(ii) Irreversibly against a constant external pressure of 2 atm until the final pressure becomes equal to the external
pressure.
Calculate Ssystem for (i) and (ii). For (ii), express the final answer in terms of R. Given: Molar heat capacity at
constant volume Cv,m = 3R/2.
IIT JAM 2012
16. The enthalpy of vaporization (vapH) is zero at
(a) Boyle temperature (b) critical temperature
(c) Inversion temperature (d) boiling temperature
17.
0
 
The standard enthalpy of formation f H300 at 1 bar and 300 K for the formation of CF2ClCF2Cl(g) from its
constituent elements in the standard state is –900 kJ mol–1. Given R = 8.3 J K–1 mol–1, the standard internal
 0

energy of formation f H300 at the same pressure and temperature is
(a) –905 kJ mol–1 (b) –895 kJ mol–1 (c) 895 kJ mol–1 (c) 905 kJ mol–1
18. Consider ideal mixing of 2 moles of toluene and 2 moles of benzene at 1 atm and 300 K. Calculate the values of
mixV, mixU, mixH, mixG and mixS for the process. (ln 2 = 0.69)
IIT JAM 2013
19. The following reaction is carried out at 1 atm and 300 K
2H2(g) + O2(g)  2H2O (l)
U for the above reaction is 550 kJ. Assuming ideal gas behaviour for H2 and O2, calculate the value of H. The
value of gas constant, R = 0.082 L atm mol–1 K–1 = 8.314 mol–1 K–1.
[Given: The volume of 1 mole of liquid water is 18 mL under the above reaction condition]
IIT JAM 2014
20. The change in entropy for the following transformations is respectively: (+ indicates increase, – indicates decrease
and 0 indicates no change)

(i) SO 2 Cl2 (g)   SO 2 (g)  Cl2 (g)
Catalyst
(ii) nCH 2  CH 2 (g)   
[ CH 2  CH 2 
]n (s)

(iii) I 2 (s) 
1 atmosphere
 I 2 (V)
(iv) Adiabatic reversible expansion of an ideal gas
(a) +, –, 0, + (b) +, –, 0, 0 (c) –, +, +, 0 (d) +, –, +, 0
IIT JAM 2015
21. For an isothermal free expansion of an ideal gas into vaccum, which one of the following set of values is correct?
(a) U = 0, q > 0, w < 0 (b) U > 0, q > 0, w = 0

(c) U = 0, q = 0, w = 0 (d) U < 0, q = 0, w < 0
22. Which of the following thermodynamic relation(s) is/are correct?
 T   P   T   V   S   P   S   V 
(a)      (b)      (c)      (d)     
 V S  S V  P S  S P  V T  T  V  P T  T P
23. For the reaction, 2SO 2  O 2  2SO3 , the equilibrium constant KP = 5.0 at 207ºC. If the partial pressures of
SO2, O2 and SO3 are 1.0 × 10–3, 0.20 and 1.0 × 10–4, respectively, then the Gibbs free energy of the reaction
(rG) in kJ mol–1 at 20ºC is______[Given: R = 8.314 J K–1 mol–1]
= –2.303 × 8.314 × 480 × log 102
= –2.303 × 8.314 × 2 × log 10
24. Two moles of an ideal gas is expanded isothermally and reversibly from 5 to 1 bar at 298 K. The change in the
entropy (in J K–1) of the system is _______
IIT JAM 2016
25. The enthalpy of formation for CH4(g), C(g) and H(g) are –75, 717 and 218 kJ mol–1, respectively. The enthalpy
of the C – H bond in kJ mol–1 is ____.
26. The Hº for the reaction CO(g) + ½O2(g)  CO2(g) at 400 K in kJ mol–1 is ____.
Given at 298 K:
H0f C0p
kJ mol–1 J mol–1 K–1
O2 0 29.4
CO –110 29.1
CO2 –394 37.1
IIT JAM 2017
27. A straight line having a slope of –Uº/R is obtained in a plot between
(a) ln Kp versus T (b) ln (KC) versus T
(b) ln (KP) versus 1/T (d) ln (KC) versus 1/T
28. Intensive variable(s) is/are
(a) temperature (b) volume (c) pressure (d) density
29. At 298 K and 1 atm, the molar enthalpies of combustion of cyclopropane and propene are –2091 kJ mol–1 and
–2058 kJ mol–1, respectively. The enthalpy change (in kJ mol–1) for the conversion of one mole of propene to
one mole of cyclopropane is _______
30. Consider an isothermal reversible compression of one mole of an ideal gas in which the pressure of the system is
increased from 5 atm to 30 atm at 300 K. The entropy change of the surroundings (in J K–1) is _______

[Given: R = 8.314 J mol–1 K–1]
IIT JAM 2018
31. The correct expression(s) for isothermal expansion of 1 mol of an ideal gas is(are)
vinitial vinitial
(a) A  RT ln v (b) G  RT ln v
final final
v final vfinal
(c) H  RT ln v (d) S  R ln v
initial initial
32. The value of Cv for 1 mol of N2 gas predicted from the principle of equipartition of energy, ignoring vibrational
contribution, is _______ J K–1 mol–1 (rounded up to two decimal places).
[R = 8.3 JK–1 mol–1]
1
33. Consider the reaction CO  g   O 2  g   CO 2  g  .
2
The value of U for the reaction at 300 K is –281.8 kJ mol–1. The value of H at same temperature is ________
kJ mol–1 (rounded up to the first decimal place).
[R = 8.3 J K–1 mol–1]
1
34. For the reaction H 2  g   O 2  g   H 2 O  l  , the following information is given T = 300 K
2
Hº  285 kJ mol1 SHº 2O  l   70 J K 1 mol1
SOº 2  g   204 J K 1 mol1 SHº 2  g   130 J K 1 mol1
 Suniverse
o
for the reaction is _____ J K–1 mol–1
IIT JAM 2019
35. The thermodynamic criterion for spontaneity of a process in a system under constant volume and temperature
and in the absence of any work other than expansion work (if any) is
(a) change in entropy is positive (b) change in enthalpy is negative
(c) change in Helmholtz free energy is negative (d) change in Gibbs free energy is negative
36. One mole of an ideal gas is subjected to an isothermal increase in pressure from 100 kPa to 1000 kPa at 300 K.
The change in Gibbs free energy of the system is ________ kJ mol–1. (Round off to one decimal place)
[Given: Gas constant (R) = 8.3 J K–1 mol–1]
IIT JAM 2020
37. The graph that represents the temperature (T) – entropy (S) variation of a Carnot cycle is
T T
(a) (b)
S S
T T
(c) (d)
S S
38. At constant pressure the  – T diagram for a pure substance that sublimes is (s = solid, I = liquid and g = gas)
g
Chemical potential ()

l
s s
(a) (b) l
g
Temperature (T)  Temperature (T) 
g
s
(c) (d) s
l g
Temperature (T)  Temperature (T) 
39. The heat of formation of MgO at 300 K and 1 bar pressure is –600.60 kJ mol–1. The free energy (in kJ mol–1) of
formation of MgO at 280 K is _____ (Round off to nearest integer)
Given: In the range 280 – 300 K, the constant pressure heat capacities (CP) and molar entropies (Sm) are:
Mg O2 MgO
CP (in J mol–1 K–1) 24.9 29.4 27.0
Sm (in J mol K )
–1 –1
0 205.20
IIT JAM 2022
40. For an N-atom nonlinear polyatomic gas, the constant volume molar heat capacity Cv,m has the expected value of
3(N – 1) R, based on the principle of equipartition of energy. The correct statement(s) about the measured value
of Cv,m is/are
(a) The measured Cv,m is independent of temperature.
(b) The measured Cv,m is dependent on temperature.
(c) The measured Cv,m is typically lower than the expected value.
(d) The measured Cv,m is typically higher than the expected value.
41. The standard Gibbs free energy change for the reaction
1
H 2O  g   H 2  g   O2  g 
2
at 2500 K is +118 kJ mol–1.
The equilibrium constant for the reaction is
[Given: R = 8.314 J K–1 mol–1]
(a) 0.994 (b) 1.006 (c) 3.42 × 10–3 (d) 292.12
42. At constant volume, 1.0 kJ of heat is transferred to 2 moles of an ideal gas at 1 atm and 298 K. The final
temperature of the ideal gas is ______ K. (round off to one decimal place)
[Given: R = 8.314 J K–1 mol–1]
ANSWER KEY
6
GASEOUS STATE
IIT JAM 2005
1. For the distribution of molecular velocities of gases, identify the correct order from following (where vmp, vav,
vrms are the most probable velocity, average velocity, root mean square velocity, respectively):
(a) vrms > vav > vmp (b) vmp > vrms > vav (c) vav > vrms > vmp (d) vmp > vav > vrms
IIT JAM 2006
2. The molar heat capacity at constant volume of a colourless gas is found to be 25 J mol–1 K–1 at room temperature.
The gas must be
(a) N2 (b) O2 (c) CO2 (d) SO2
IIT JAM 2007
3. The Maxwell distribution function for the distribution of speeds of molecules in gaseous systems is given by
3/ 2
 m  2   mc 2 
f (c)  4  c exp 

 2kT   2kT 
 
1/ 2
 2kT 
Show that the most probable speed, cmps   
 m 
IIT JAM 2008
4. Given that the most probable speed of oxygen gas is 1000 ms–1, the mean/average speed (ms–1) under the same
conditions is:
(a) 1224 (b) 1128 (c) 886 (d) 816
IIT JAM 2009
5. For an ideal gas, the plot that is Nonlinear is:
(a) PV vs T (b) PV vs P, at constant T
(c) P vs V, at constant T (d) In P vs ln V at constant T
6. Consider two identical containers, one with 1 mole of H 2 and the other with 1 mole of He. If the root-mean
square (RMS) velocities of the two gases are the same, then the ratio of the temperature, T(H2)/T(He) is
(a) 1/2 (b) 2 (c) 1/ 2 (d) 2
7. (i) Write the expression for the vibrational contribution to the total energy of CH4(g) at 500 K. All the vibrational
modes are active a this temperature.
(ii) Calculate the total internal energy of 1 mole of the gas at this temperature. R = 8.314 J mol–1K–1.
IIT JAM 2011
8. Based on the principle of equipartition of energy, the molar heat capacity of CO2 at constant volume Cv,m is:
(a) 3.5 R (b) 6R (c) 6.5 R (d) 9R

9. The Maxwell probability distribution of molecular speeds for a gas is:
3/ 2
 m   mv 2 
F(v)dv  4v2  exp  
 2kT 
 dv
 2kT   
where ‘v’ is the speed, ‘m’ the mass of the gas molecule and k the Boltzmann constant.
(i) Use F(v) to show that the most probable speed vmp is given by the expression.
1/ 2
 2RT 
v mp  
 M 
(ii) Use R = 8 J K–1 mol–1 in the above expression to calculate the vmp for CH4(g) at 127ºC.
IIT JAM 2012
10. The average speed of H2, N2 and O2 gas molecules is in the order
(a) H2 > N2 > O2 (b) O2 > N2 > H2 (c) H2O2 > N2 (d) N2 > O2 > H2
11. An aqueous solution containing 1 g L–1 of a polymer exerts osmotic pressure of 4 torr at 300 K. Given R = 0.082
L atm, the molar mass (g mol–1) of the polymer is
(a) 4500 (b) 4564 (c) 4674 (d) 4800
IIT JAM 2013
12. A mixture of C3H8 and oxygen in 1L closed vessel has an internal pressure of 4 atm at 100ºC. When the mixture
is ignited, the reaction produces CO2(g) and H2O(g) until all oxygen is consumed. After the reaction, pressure of
the vessel is 4.2 atm at the same temperature. Calculate the weight of oxygen present before the reaction. [Gas
constant, R = 0.082 L atm mol–1 K–1].
IIT JAM 2014
13. According to the equipartition principle of energy, the molar heat capacity at constant volume for CO2(g), SO2(g)
and H2O(g) follows the trend:
(a) CO2 = SO2 = H2O (b) CO2 > SO2 = H2O
(c) H2O > SO2 = CO2 (d) CO2 = SO2 > H2O
IIT JAM 2015
14. The intermolecular van der Waals potential is inversely proportional to r6. The corresponding force is proportional
to
1 1 1 1
(a) 5 (b) 6 (c) 7 (d)
r r r r12
15. According to the equipartition principle, the predicted high temperature limiting value of the molar heat capacity
at constant volume for C2H2 is
(a) 5.5 R (b) 6.0 R (c) 9.0 R (d) 9.5 R
16. In the gas phase, the ratio of excluded volume to molecular volume for a spherical molecule is _______
5RT
17. In an ideal monoatomic gas, the speed of sound is given by . If the speed of sound in argon at 25ºC is
3M
1245 km h–1, the root mean square velocity in ms–1 is ______.
IIT JAM 2016
18. The relationship between the van der Waals ‘b’ coefficient of N2 and O2 is
(a) b(N2) = b(O2) = 0 (b) b(N2) = b(O2)  0
(c) b(N2) > b(O2) (d) b(N2) < b(O2)
19. From the kinetic theory of gases, the ratio of most probable speed (Cmp) to root mean square speed (Crms) is
(a) 3 (b) 2/ 3 (c) 3/ 2 (d) 3/ 2
20. Cu(s) + 4H+(aq) + 2NO3– (aq)  2NO2(g) + Cu2+(aq) + 2H2O(l)
In the above reaction at 1 atm and 298 K, if 6.36 g of copper is used. Assuming ideal gas behavior, the volume
of NO2 produced in liters is ____.
[Given: atomic mass of Cu is 63.6; R = 0.0821 L atm K–1 mol–1]
IIT JAM 2017
21. A vessel contains a mixture of H2 and N2 gas. The density of this gas mixture is 0.2 g L–1 at 300 K and 1 atm.
Assuming that both the gases behave ideally, the mole fraction of N2(g) in the vessel is _______
[Given: R = 0.082 L atm mol–1 K–1, atomic wt. of hydrogen = 1.0 and atomic wt. of nitrogen = 14.0]
IIT JAM 2018
22. The behavior of Cl2 is closest to ideal gas behavior at
(a) 100 ºC and 10.0 atm (b) 0 ºC and 0.50 atm
(c) 200 ºC and 0.50 atm (d) –100 ºC and 10.0 atm
23. Assuming ideal gas behavior, the density of O2 gas at 300 K and 1.0 atm is ______ gL–1 (rounded up to two
decimal places).
[R = 0.082 L atm mol–1 K–1, molar mass of O2 = 32]
IIT JAM 2019
24. According to the kinetic theory of gases, the ratio of the root mean square velocity of molecular oxygen and
molecular hydrogen at 300 K is
(a) 1 : 1 (b) 1: 2 2 (c) 1 : 4 (d) 1 : 16
25. The unit of the constant ‘a’ in van der Waals equation of state of a real gas can be expressed as
(a) m6 Pa mol–2 (b) m6 J mol–2 (c) m3 Pa mol–2 (d) m3 J mol–2
IIT JAM 2020
26. The Maxwell distribution of speeds of a gas at 300 K is given below.
Distribution function
0 250 500 750 1000 1250

The molar mass (in g mol–1) of this gas is _____ (Round off to one decimal place)
(R = 8.3 J mol–1 K–1)
IIT JAM 2021
27. If the root mean square speed of hydrogen gas at a particular temperature is 1900 m s –1, then the root mean
square speed of nitrogen gas at the same temperature, in m s–1 (rounded off to the nearest integer), is _________.
(Given: atomic mass of H is 1 g mol–1; atomic mass of N is 14 g mol–1)
28. The volume correction factor for a non-ideal gas in terms of critical pressure (pc), critical molar volume (Vc),
critical temperature (Tc) and gas constant (R) is
8p c Vc RTc 27R 2 Tc2

(a) 3T (b) 8p (c) 3pcVc2 (d)
c c 64p c
IIT JAM 2022
29. The Maxwell-Boltzmann distribution f(x) of one-dimensional velocities x at temperature T is

[Given: A is a normalization constant such that  f    d


x x  1 and k is the Boltzmann constant]
B
(a) A exp   m x / 2k B T  (b) A exp   m x / k BT 

2 2
(c) A x exp   m x / 2k B T  (d) A x exp   m x / k BT 

2 2 2 2
30. For a van der Waals gas, the critical temperature is 150 K and the critical pressure is 5 × 10 6 Pa. The volume
occupied by each gas molecule is _______ Å.
ANSWER KEY
7
CHEMICAL EQUILIBRIUM
IIT JAM 2005
1. The equilibrium constant for the reaction
Fe3O4(s) + CO(g)  3FeO(s) + CO2(g)
at 600°C is 1.00. If a mixture initially consisting of 1 mole of Fe3O4, 2 moles of CO, 0.5 mole of FeO and 0.3
mole of CO2 is heated to 600°C at constant total pressure of 5 atmosphere, how many moles of each substance
would be present at equilibrium ?
IIT JAM 2006
2. The temperature (T) dependence of the equilibrium constant (K) of a chemical reaction is correctly described by
the following statement:
(a) For an endothermic reaction, the slope of ln K vs 1/T plot is positive.
(b) For an exothermic reaction, K is proportional to T
(c) For an exothermic reaction, K at a higher temperature is lower than K at a lower temperature
(d) If H is independent of temperature, the change in K with T is smaller at lower temperatures.
3. The reaction N 2  3H 2  2NH3 is carried out at 300 K by mixing N2 and H2. The standard free energy of
formation of NH3 is –16.4 kJ/mol. After one hour of mixing, the partial pressures of N2, H2 and NH3 are 50 bars,
2 bars and 200 bars, respectively. What is the reaction free energy at this stage of the reaction?
IIT JAM 2008
4. Consider the reaction.
CH 4 (g)  2O 2 (g)  CO 2 (g)  2H 2O() Hº  606.9 kJ mol1
Assuming ideal behaviour, calculate Uº when 1 mol of CH4 is completely oxidized at STP.
IIT JAM 2010
5. Equilibrium constant for a reaction doubles as the temperature is increased from 300 K to 600 K. Calculate the
standard reaction enthalpy (in kJ mol–1) assuming it to be constant in this temperature range. (Given R = 8.3 J K–
1
mol–1, ln 2 = 0.7).
IIT JAM 2011
6. For the following equilibrium at 300ºC.
 2NO2 (g)

N 2O4 (g) 
Calculate Kp when N2O2 is 30% dissociated and the total pressure is 2 bar.
IIT JAM 2012
7. For the equilibrium N 2  3H 2  2NH3 , the equilibrium constant, KP is expressed as
3
p NH3 3
p 2NH3
(a) 3 K p  (b) 3 K p 
p2N 2 p N2 p3H2
3
p 2NH3 3/ 2
p 2NH3
(c) 3 K p  (d) 3 K1/
p
2

p4N 2 p 4N2
IIT JAM 2015

8. For the reaction, 2SO 2  O 2  2SO3 , the equilibrium constant KP = 5.0 at 207ºC. If the partial pressures of
SO2, O2 and SO3 are 1.0 × 10–3, 0.20 and 1.0 × 10–4, respectively, then the Gibbs free energy of the reaction
(rG) in kJ mol–1 at 20ºC is______[Given: R = 8.314 J K–1 mol–1]
IIT JAM 2016
9. A 10 L flask containing 10.8 g of N2O5 is heated to 373 K, which leads to its decomposition according to the
equation 2 N2O5(g)  4 NO2(g) + O2(g). If the final pressure in the flask is 0.5 atm, then the partial pressure of
O2(g) in atm is ____.
[Given R = 0.0821 L atm K–1 mol–1]
IIT JAM 2017
10. A vessel contains a mixture of H2 and N2 gas. The density of this gas mixture is 0.2 g L–1 at 300 K and 1 atm.
Assuming that both the gases behave ideally, the mole fraction of N2(g) in the vessel is _______
[Given: R = 0.082 L atm mol–1 K–1, atomic wt. of hydrogen = 1.0 and atomic wt. of nitrogen = 14.0]
IIT JAM 2018
1
11. Consider the reaction CO  g   O 2  g   CO 2  g  .
2
The value of U for the reaction at 300 K is –281.8 kJ mol–1. The value of H at same temperature is ________
kJ mol–1 (rounded up to the first decimal place).
[R = 8.3 J K–1 mol–1]
ANSWER KEY
8
IONIC EQUILIBRIUM
(IIT JAM 2005)
1. The pH of a solution prepared from 0.005 mole of Ba(OH)2 in 100 cc water is
(a) 10 (b) 12 (c) 11 (d) 13
(IIT JAM 2006)
2. The solubility products (Ksp) for three salts MX, MY2 and MZ3 are 1 × 10–8, 4 × 10–9 and 27 × 10–8, respectively.
The solubility of these salts follows the order
(a) MX > MY2 > MZ3 (b) MZ3 > MY2 > MX
(c) MZ3 > MX > MY2 (d) MY2 > MX > MZ3
3. (a) Calculate the pH of a solution obtained by mixing 50.00 mL of 0.20 M weak acid HA (Ka = 10–5) and 50.00
mL of 0.20 M NaOH at room temperature.
(b) One mole of a salt of type MX is dissolved in 1.00 kg of water. The freezing point of the solution is –2.4°C.
Calculate the percent dissociation of the salt in water.
(IIT JAM 2007)
4. The pH of a 1.0 × 10–3 M solution of a weak acid HA is 4.0. The acid dissociation constant Ka is:
(a) 1.0 × 10–3 (b) 1.0 × 10–4 (c) 1.0 × 10–5 (d) 2.0 × 10–5
5. Which one of the following species is the conjugate base of HO–?
(a) H2O (b) O2– (c) O2– (d) O32–
(IIT JAM 2009)
6. If Ksp is the solubility product of a sparingly soluble salt A3X2, then its solubility is
(a) (Ksp/108)1/5 (b) (Ksp)1/5 (c) (Ksp/72)1/5 (d) (Ksp)1/2
7. The pH of a 1 × 10–8 M HCl solution is close to
(a) 8.0 (b) 7.1 (c) 6.9 (d) 6.0
8. The indicator phenophthalein changes colour at pH ~ 9. This indictor is NOT suitable for accurate determination
of the end point in the titration of
(a) CH3COOH with NaOH (b) HCl with NH4OH
(c) HCl with NaOH (d) HCl with KOH
(IIT JAM 2010)
9. A 50 mL solution of 0.1 M monoprotic acid (Ka = 1 × 10–5 at 298 K) is titrated with 0.1 M NaOH at 298 K.
Calculate the solution after the addition of 50 mL of NaOH at this temperature. (Given Kw = 1 × 10–14 at 298 K)
(IIT JAM 2011)
10. The minimum concentration of silver ions that is required that is required to start the precipitation of Ag2S(Ksp =
1 × 10–51) in a 0.1 M solution of S2– is
(a) 1 × 10–49 M (b) 1 × 10–50 M (c) 1 × 10–26 M (d) 1 × 10–25 M
11. The hydrolysis constant (Kh) of NH4Cl is 5.6 × 10–10. The concentration of H3O+ in a 0.1 M solution of NH4Cl
at equilibrium is
(a) 5.6 10 11 (b) 5.6 1010 (c) 5.6 × 10–10 (d) 2.8 × 10–5
12. The acid dissociation constant (Ka) for HCOOH, CH3COOH, CH2ClCOOH and HCN at 25ºC are 1.8 × 10–
4, 1.8 × 10–5, 1.4 × 10–3 and 4.8 × 10–10, respectively. The acid that gives highest pH at the equivalence point
when 0.2 M solution of each acid is titrated with a 0.2 M solution of sodium hydroxide is:
(a) HCOOH (b) CH3COOH (c) CH3ClCOOH (d) HCN
(IIT JAM 2013)
13. At 298 K, calculate the solubility of metal sulfide, MS(s), in a saturated solution of H2S where the concentration
of H2S and pH are maintained at 0.1 M and 3.0, respectively
Given at 298 K,
H 2S(aq)  H 2O()  H 3O  (aq)  HS (aq) K = 10–7
MS(s)  H 2O()  M 2 (aq)  HS (aq)  OH  (aq) K = 5 × 10–19
(IIT JAM 2015)
14. At 25ºC, the solubility product (Ksp) of CaF2 in water is 3.2 × 10–11. The solubility (in mole per kg of water) of
the salt at the same temperature (ignore ion pairing) is
(a) 4.0 × 10–6 (b) 3.2 × 10–4 (c) 2.5 × 10–4 (d) 2.0 × 10–4
15. The pKa values of H3PO4 are 2.12, 7.21 and 12.67. The pH of a phosphate buffer containing 0.2 M NaH2PO4
and 0.1 M Na2HPO4 is ______
(IIT JAM 2016)
16. At 298 K, 0.1 mol of ammonium acetate and 0.14 mol of acetic acid are dissolved in 1 L of water. The pH of the
resulting solution is
[Given: pKa of acetic acid is 4.75]
(a) 4.9 (b) 4.6 (c) 4.3 (d) 2.3
(IIT JAM 2018)
17. The solubility of PbI2 in 0.10 M KI(aq) is ______ × 10–7 M (rounded up to two decimal places).
[The solubility product, K sp  7.1109 ]
(IIT JAM 2019)
18. One liter of a buffer solution contains 0.004 mole of acetic acid (pKa = 4.76) and 0.4 mole of sodium acetate.
The pH of the solution is ________. (Round off to two decimal places)
(IIT JAM 2021)
19. A buffer solution is prepared by mixing 0.3 M NH3 and 0.1 M NH4NO3. If Kb of NH3 is 1.6 × 10–5 at 25ºC, then
the pH (rounded off to one decimal place) of the buffer solution at 25ºC is_________.
ANSWER KEY
9
PHASE EQUILIBRIUM
IIT JAM 2005
1. For the following system in equilibrium, CaCO3 (s)  CaO(s)  CO 2 (g)
the number of components, (C), phases (P) and degrees of freedom (F), respectively, are
(a) 2, 2, 2 (b) 1, 3, 0 (c) 3, 3, 2 (d) 2, 3, 1
IIT JAM 2006
2. The phase diagram of a pure substance is sketched below.
The number of degrees of freedom at points P1, P2 and P3, respectively are
(a) 2, 1, 0 (b) 1, 2, 0 (c) 2, 0, 1 (d) 0, 2, 1
IIT JAM 2007
3. The solid-liquid phase diagram for the Mg-Zn system is shown in the figure below where the vertical line at
X(Mg) = 0.33 represents the formation of a congruent melting compound MgZn2. The figure is divided into seven
regions depending upon the physical state of the system. The composition of the region #6 represents.
(a) Single phase of a solution of Mg and Zn

(b) Two phase region between the solid Zn and solid MgZn2
(c) Two phase region between the liquid and solid MgZn2
(d) Two phase region between solid Mg and solid MgZn2
IIT JAM 2008
4. The maximum number of phases that can co-exist in equilibrium for a one component system is:
(a) 1 (b) 2 (c) 3 (d) 4
IIT JAM 2011
5. The phase diagram for the lead-antimony system at a certain pressure is given below.
(i) Identify the phases and components in region I and region II.
(ii) Calculate the number of degrees of freedom (variance) at point M.
IIT JAM 2013
6. The vapour pressures of solid and liquid chlorine are given by
3900 2600
log e Psolid  24  liq
and log e P  18 
T T
where Psolid and Pliq are the vapour pressures (in Torr) of solid and liquid chlorine near the triple point, respectively
and T is the absolute temperature. The ratio of the slope of the solid-gas curve to the slope of the liquid gas curve
at the triple point in the P-T diagram is________
IIT JAM 2014
7. The number of degrees of freedom in the homogeneous liquid region of a two component system with a eutectic
point, at one atmosphere pressure, is:
(a) 0 (b) 1 (c) 2 (d) 3
8. The vapour pressure of benzene is 5333 Pa at 7.6ºC and 53330 Pa at 60.6ºC. Calculate the heat of vapourization
of benzene and the normal boiling point of benzene.
IIT JAM 2017
9. The number of degrees of freedom of liquid water in equilibrium with ice is
(a) 0 (b) 1 (c) 2 (d) 3
IIT JAM 2021
10. A pure substance M has lesser density in solid state than in liquid state. The Sfusion of M is +25 J K–1 mol–1. The
CORRECT representative Pressure-Temperature diagram for the fusion of M is
(a) (b) (c) (d)
IIT JAM 2022

11. The phase diagram of water is best represented by
g g
T s P
l s l
(a) (b)
P T
l l
T s P s
(c) g (d) g
P T
ANSWER KEY
10
PHYSICAL SPECTROSCOPY
IIT JAM-2014
1. The carbon-oxygen bond in an organic compound absorbs electromagnetic radiation of frequency 6 × 1013 Hz.
This frequency corresponds to the region:
(a) Infrared (b) Microwave (c) Ultraviolet (d) Visible
IIT JAM-2015
2. The correct order of the fundamental vibrational frequencies of the following diatomic molecules is
(a) 1H35Cl > 1H37Cl > 2D35Cl (b) 2D35Cl > 1H37Cl > 1H35Cl
(c) 1H37Cl > 1H35Cl > 2D35Cl (d) 1H37Cl > 2D35Cl > 1H35Cl
IIT JAM-2018
3. For H2 molecule, the fundamental vibrational frequency  e  in wavenumbers can be taken as 4400 cm–1. The
zero-point energy of the molecule is _______ kJ mol–1 (rounded up to two decimal places).
[ h  6.6 10 34 Js, c  3  108 ms 1 , N A  6  10 23 mol 1 ]
IIT JAM-2019
4. Among the following, microwave active molecule(s) is/are
(a) trans-dichloroethene (b) 1,2-dinitrobenzene
(c) 3-methylphenol (d) para-aminophenol
IIT JAM-2020
5. The forces constant for H35Cl and D35Cl are the same and both can be considered as harmonic oscillators. H35Cl
has a fundamental vibrational transition at 2886 cm–1. The ratio of the zero – point energy of H35Cl to that of
D35Cl is
(a) 0.515 (b) 0.717 (c) 1.395 (d) 1.946
IIT JAM-2021
6. The separation of energy levels in the rotational spectrum of CO is 3.8626 cm–1. The bond length (assume it does
not change during rotation) of CO in Å (rounded off to two decimal places) is ______.
(Given: Planck’s constant h = 6.626 × 10–34 Js; NA = 6.022 × 1023 mol–1; atomic mass of C is 12 g mol–1; atomic
mass of O is 16 g mol–1; c = 3 × 108 m s–1)
IIT JAM-2022
7. The spacing between successive rotational energy levels of a diatomic molecule XY and its heavier isotopic
analogue X'Y' varies with the rotational quantum number, J, as
XY
EJ+1 – EJ
EJ+1 – EJ
XY X'Y'
(a) (b)
X'Y'
0 0
0 J 0 J
XY XY
EJ+1 – EJ
EJ+1 – EJ
(c) X'Y' (d)

X'Y'
0 0
0 J 0 J
ANSWER KEY
11
NUCLEAR CHEMISTRY
(IIT JAM 2005)
1. The radioactive isotope used to locate brain tumors is
(a) 12 D (b) 15
7 N (c) 131
53 I (d) 13
6 C
2. The radioactive element Ra (Z = 86) emits three alpha particles in succession. Deduce in which group the
resulting element will be found?
3. (b) A radioisotope sample has an initial activity of 23 dis/min. After 1/2 h, the activity is 11.5 dis/min. How many
atoms of the radioactive nuclide were present originally? [t1/2 = 0.69]
(IIT JAM 2006)
4. The half-life of a radioactive nuclide is 20 years. If a sample of this nuclide has an activity of 6400 disintegrations
per minute (dis/min) today, its activity (dis/min) after 100 years would be
(a) 850 (b) 1600 (c) 200 (d) 400
(IIT JAM 2007)
5. 215 undergoes an  emission to give element X followed by a  emission to give element Y..
84 Po
(i) Write the valence shell electronic configuration of Y.
(ii) Indicate the groups of the periodic table to which X and Y belong.
(IIT JAM 2008)
6. In the process
234 230
92 U 
 90 Th  X
X is:
(a)  particle (b) -particle (c) +-emission (d) -emission
(IIT JAM 2009)
7. Complete the following nuclear reactions:
(i) 14 4 1
7 N  2 He  1H  .......... (ii) 37 Li  11H  ...........
(IIT JAM 2011)
8. In the following equation X is:
241 243
95 Am   
97 Bk  X
(a) 2 10 n (b) 10 n (c) 2 11n (d) 42 He

(IIT JAM 2012)
238 208
9. The total number of steps involved and number of beta particles emitted in the spontaneous decay of 92 U 82 Pb
respectively, are
(IIT JAM 2014)
10. In boron neutron capture therapy, the initial boron isotope used and the particle generated after neutron capture
respectively are:
(a) 11B and  particle (b) 10B and  particle (c) 11B and  particle (d) 10B and  particle
11. The number of  and  particle(s), generated in the following radioactive decay process, are:
238 234
92 U 92 U
(a) one  and two  particle (b) two  and one  particles
(c) one  and four  particles (d) no  and four  particles
(IIT JAM 2015)
12. A wood specimen containing 14C taken from an ancient palace showed 24 counts in 3 minutes per gram of
carbon in a detector. however, a fresh wood showed 52 counts in 2 minutes per gram of carbon. Assuming no
background signal in the detector and half life of 14C as 5730 years, the age (in years) of the wood specimen is
______
(IIT JAM 2016)
13. 214
The isotope 84 Po undergoes one alpha and one beta particle emission sequentially to form an isotope “X”. The
number of neutrons in “X” is _____.
(IIT JAM 2017)
14. A radioactive element undergoes 80% radioactive decay in 300 min. The half-life for this species in minutes is
______
(IIT JAM 2018)
15. The decay modes of 14C and 14O are
(a) – decay (b) positron emission
(c) – decay and positron emission, respectively
(d) positron emission and – decay, respectively
16. 24
Na decays to one-fourth of its initial amount in 29.8 hours. Its decay constant is ______ hour–1 (rounded up to
four decimal places).
(IIT JAM 2019)
17. A radioactive sample decays to 10% of its initial amount in 4600 minutes. The rate constant of this process is
________ hour–1. (Round off to two decimal places)
(IIT JAM 2021)
18. For the following fusion reaction,
4 1H  4 He  2  2  
the Q-value (energy of the reaction) in MeV (rounded off to one decimal place) is ______.
(Given: Mass of 1H nucleus is 1.007825 u and mass of 4He nucleus is 4.002604 u)
ANSWER KEY
12
REDOX REACTION
REDOX (IIT JAM)
IIT JAM 2008
1. The compound having an S-S single bond is
(a) H2S2O3 (b) H2S2O4 (c) H2S2O7 (d) H2S2O8
2. In a reaction, Na2S2O3 is converted to Na2S4O6. The equivalent weight of Na2S2O3 for this reaction is (mol. wt
of Na2S2O3 = M)
(a) M (b) M/4 (c) M/2 (d) M/3
IIT JAM 2009
3. The number of P = O bonds present in the tetrabasic acid H4P2O7 is:
(a) Three (b) Two (c) One (d) None
IIT JAM 2011
4. The most probable oxidation states for both Cr and Mo are
(a) +2, +3, +4 (b) +2, +3, +5 (c) +2, +3, +6 (d) +3, +4, +5
IIT JAM 2012
5. Number of moles of ions produced by complete dissociation of one mole of Mohr’s salt in water is
(a) 3 (b) 4 (c) 5 (d) 6
IIT JAM 2016
6. Indicator used in redox titration is
(a) Eriochrome black T (b) Methyl orange
(c) Phenolphthalein (d) Methylene blue
7. The number of P-H bonds in hypophosphorus acid is _____.
IIT JAM 2017
8. The number of S-S bond(s) in tetrathionate ion is _____.
IIT JAM 2018
9. The volume of 0.3 M ferrous ammonium sulphate solution required for the completion of redox titration with 20
mL of 0.1 M potassium dichromate solution is _______ mL.
IIT JAM 2020
10. The number of lone pairs present in phosphonic acid (phosphorus acid) is______
11. The value of ‘n’ in [PnO18]6– is______
REDOX (GATE) PREVIOUS YEAR
GATE 2001
12. The volume of 1 N KMnO 4 required to reach equivalence point in the titration with 0.01 mole of ferrous
oxalate dissolved in dilute H 2SO 4 is
(a) 3 cm 2 (b) 30 cm3 (c) 10 cm3 (d) 20 cm3
GATE 2014
13. The number of S–S bonds in H2S5O6 is _________
ANSWER KEY
13
QUANTUM CHEMISTRY
IIT JAM - 2005
1. Use the time-independent Schrodinger equation to calculate the energy of a particle of mass “m” with V = 0 in the
8 x y z
state   3
sin sin sin in a cubical box of length “a”.
a a a a
IIT JAM - 2006
2. The wavelength for a particle (moving in a ring) is (2)–1/2 exp (2i), where  is the polar angle. The probability
of finding the particle in a small interval d when the value of  = /2 is
(a) d (b) d/ 2 (c) d exp (i) (d) d exp (i) / 2
3. (a) The electronic wavefunction () for hydrogen atom in the 2s state is given as
 r   r 
   2   exp   
 a0   2a 0 
Determine the most probable radial distance for the electron in this state and also the position of the node (in
terms of a0)
(b) Calculate the wavelength corresponding to the lowest energy excitation of an electron confined to a one-
dimensional box of length 1 nm. (Energy levels for a particle in a one dimensional box are given by En = n2h2/
8ma2).
IIT JAM 2007
4. The normalisation constant ‘A’ for the wavefunction () = Ae(im) where 0 <  < 2 is:
1 1
(a) (b) 2 (c) 2 (d)
2 2
5. Deduce whether the matrices A and B commute or not.
 2 1  1 1
A  B 
 0 1  0 1
IIT JAM - 2008
6. If the electron were spin 3/2 particles, instead of spin 1/2, then the number of electrons that can be accomodated
in a level are
(a) 2 (b) 3 (c) 4 (d) 5
7. For a particle in a cubic box, the total number of quantum number needed to specify its state are
(a) 1 (b) 3 (c) 4 (d) 9
8. Using Heisenberg’s uncertainty principle, derive an expression for the approximate ground state energy of a
particular of mass m in a one dimensional box of length L.
9. Find the eigenvalues of the following 3 × 3 matrix given that 2 is one of the eigen values. Compute the determinant
of matrix using the eigen values.
1 1 1 
 
1 0 2 
1 1 1 
 
IIT JAM 2009
d2x
10. Which of the following is NOT a solution of the equation 2
 2 x  0
dt
(a) x  A cos t (b) x  A sin t (c) x  Ar 2 it
(d) x  A e  e
 it

(a) 1s (b) 2p (c) 3d (d) 4d
IIT JAM 2010
12. If  is the eigenfunction to the Hamiltonian operator with  as the eigenvalue, then  MUST be
(a) positive (b) negative (c) an integer (d) real
13. A quantum mechanical particle of mass m free to rotate on the surface of a sphere of radius r is in the state with
10 2
energy . The degeneracy of this state is
mr 2
(a) 20 (b) 10 (c) 9 (d) 4
14. An atomic orbital is described by the wavefunction
 r 
 
1 a
 (r)  e  0 , where a0 is the Bohr radius.
a 30

n r n!
Given: d = r2 sin  drdd and r e d 
n 1
(n is a positive integer)
0
(a) Identify the atomic orbital and calculate the mean or the average radius of this orbital in terms of a0.
(b) Calculate the most probable radius (in terms of a0) at which an electron will be found when it occupies this
orbital.
IIT JAM 2011
14. The wavefunction of a quantum state of hydrogen atom with principal quantum number n = 2 is:
3/ 2
1  1   r   r 
 2m (r, , )     2   exp   
32  a 0   a0   2a 0 
(i) Identify the values of quantum numbers l and m and hence the atomic orbital.
(ii) Find where the radial node of the wavefunction occurs.
IIT JAM 2012
h 2 d 2 (x)
15. A solution of a free particle Schrodinger equation  E(X) is
82 m dx 2
(x) = eikx = cos kx + i sin kx
(a) Derive expressions for energy ‘E’ and momentum ‘p’ of the particle.
h
(b) Using the above relations, show that the wavelength () is .
p
IIT JAM 2013
1
16. The function y = x exp (–x2) has a minimum at x = – . The second derivative of the function at the minimum
2
is
 1  1  1
(a) 2 2 exp    (b) 2 2 exp    (c) 0 (d)  2 exp   
 2  2  2
 2r  r  2   r 
 
17. For unnormalized wave-function,  (r, , )  sin  cos   a   a   exp   a  , the number of radial
 0  0   0
node(s) is __________
IIT JAM 2014
 h 2 d h 2 2 x 2  2 h2
18.  2 2
 2  exp(  x )  C 2
exp( x 2 ) , where h, , m and  are constants. Then C is
 (8 m) dx (2 m)  (4 )
(a) 2 / m (b)  / 2m (c)  / m (d) 2 / m

IIT JAM 2015
h d
19. If x̂ = x × p̂ x  , then the value(s) of pˆ x xˆ  xp
ˆ ˆ x is/are
2i dx
 i
(a) (b) i (c) 0 (d)
i 
IIT JAM 2016
20. The maximum of a function Aeax 2 (A > 0; a > 0) is at x =
(a) 0 (b) +  (c) – (d) 1/ a
21. The 3pz orbital has
(a) one radial node (b) two radial nodes
(c) one angular node (d) two angular nodes
IIT JAM 2017
22. For a particle in one-dimensional box of length L with potential energy V(x) = 0 for L > x > 0 and V(x) =  for
x > L and x < 0 an acceptable wave function consistent with the boundary conditions is (A, B, C and D are
constants)
D
 nx 
(a) A cos   (b) B(x + x2) (c) Cx3 (x – L) (d) sin  nx 
 L   L 
IIT JAM 2018
23. Which of the following set(s) of quantum numbers is (are) NOT allowed?
(a) n = 3, l = 2, m1 = –1 (b) n = 4, l = 0, m1 = –1
(c) n = 3, l = 3, m1 = –3 (d) n = 5, l = 3, m1 = +2
IIT JAM 2019
The function f  x   x e  x has a minimum at

2
24.
1 1
(a) x  2 (b) x   2 (c) x  (d) x  
2 2
1 2 
25. The eigenvalue(s) of the matrix   is/are
2 1
(a) –1 (b) 1 (c) 2 (d) 3
26. Given that the radius of the first Bohr orbit of hydrogen atom is 53 pm, the radius of its third Bohr orbit is
________ pm. (Round off to the nearest integer)
IIT JAM 2020
27. The d – orbitals involved in the hybridization to form square planar and trigonal bipyramidal geometries are,
respectively.
(a) d z2 and d z2 (b) d yz and d z2 (c) d x 2  y2 and d z2 (d) d x 2  y2 and d yz
IIT JAM 2021
(a) n = 3; l = 2; ml = 0 and n = 2; l = 1; ml = 0
(b) n = 3; l = 0; ml = 0 and n = 2; l = 0; ml = 0
(c) n = 3; l = 1; ml = 1 and n = 2; l = 1; ml = 0
(d) n = 3; l = 1; ml = –1 and n = 2; l = 1; ml = 0
IIT JAM 2022
29. The potential for a particle in a one-dimensional box is given as:
V(x) = 0 for 0 < x < L, and V(x) =  elsewhere.
The locations of the internal nodes of the eigenfunctions n (x) , n > 2, are
[Given: m is an integer such that 0 < m < n]
1
m m m m 1
(a) x  2L (b) x  L (c) x  L (d) x  L
n n n 1 n 1
ANSWER KEY
14
ELECTROCHEMISTRY
(IIT JAM 2005)
o o o
1. Given that E Fe2 / Fe   0.44V and E Fe3 / Fe2  0.77 V, the E Fe3 / Fe is :
(a) 1.21 V (b) 0.33 V (c) –0.036 V (d) 0.036 V
(IIT JAM 2006)
2. The statement that is correct for both electrochemical (galvanic) cells and electrolytic cell is :
(a) G = –nFE
(b) Free energy decreases in both cells
(c) The cell potential are temperature independent
(d) Chemical energy is converted into electrical energy in both cells
(IIT JAM 2007)
3. The standard potential of a Daniel cell is +1.10 V and the equilibrium constant for the cell reaction is 1.5 × 1037.
It can be concluded that
(a) Zinc oxidises copper
(b) Displacement of copper by zinc goes to near completion
(c) Copper oxidises zinc
(d) Displacement of zinc by copper goes to completion.
(IIT JAM 2008)
4. Consider the following redox system.
Q  2H   2e  QH 2 Eº = 0.699 V
Calculate the pH of the solution at 298 K, if the redox potential of the system is 0.817 V.
(IIT JAM 2009)
5. The Zn2+ | Zn half cell (E = –0.762 V) is connected to a Cu2+ | Cu half cell (E = 0.340 V). What is the value of
Eºcell for spontaneous conversion of chemical energy to electrical energy? What is the value of log10 K, where K
is the equilibrium constant? Use (2.303 RT/F) = 0.06.
(IIT JAM 2011)
6. For a cell reaction, E(at 25ºC) = 1.26 V, n = 2 and S = –96.5 J K–1 mol–1. Calculate E at 85ºC by assuming S
to be independent of temperature. (F = 96500 C mol–1).
(IIT JAM 2012)
7. The molality of (NH4)2SO4 solution that has the same ionic strength as 1 mol kg–1 solution of KCl is
1 1 2 3
(a) mol kg–1 (b) mol kg–1 (c) mol kg–1 (d) mol kg–1
3 2 5 5
8. A concentration cell with two hydrogen electrodes at two different pressures is depicted as
H 2 (g)(Pt) HCl(aq) H 2 (g)(Pt)
p H2  p1 pH2  p2
The potential (Ecell) of the cell is
RT p 2 RT p1 RT p 2 RT p1
(a) F n p (b) F n p (c) 2F n p (d) 2F n p
1 2 1 2
(IIT JAM 2013)
9. MnO4– (aq) + Zn(s) + H3O+ (aq)  Mn2+ (aq) + Zn2+ (aq) + H2O (l)
For the above reaction if the equilibrium constant at 298 K is represented by 10x, then the value of X is _________
2.303RT
[Given: The standard cell potential Eº = 2.4 V and = 0.06 V at 298 K]
F
(IIT JAM 2015)
10. The concentration of K+ ion inside a biological cell is 20 times higher than outside. The magnitude of potential
difference between the two sides is [Given: 2.303 RT/F = 59 mV].
(a) 0 mV (b) 26 mV (c) 77 mV (d) 177 mV
11. 3+ 2+ 2+
The standard reduction potentials of the Fe /Fe and Fe /Fe couples are 0.77 and –0.44 V, respectively. The
standard reduction potential (in V) for the Fe3+/Fe couple is _______.
(IIT JAM 2016)
12. An electrochemical cell consists of two half-cell reactions
AgCl(s) + e–  Ag(s) + Cl–(aq)
Cu(s)  Cu2+(aq) + 2e–
The mass of copper (in grams) dissolved on passing 0.5 A current for 1 hour is
[Given: atomic mass of Cu is 63.6; F = 96500 C mol–1]
(a) 0.88 (b) 1.18 (c) 0.29 (d) 0.59
(IIT JAM 2017)
 Eº 
13. For a cell reaction, Pb(s) + Hg2Cl2(s)  PbCl2(s) + 2Hg(l),   is 1.45 × 10–4 VK–1. The entropy
 T P
change (in J mol–1 K–1) for the reaction is ______
[Given: 1F = 96500 C mol–1]
14. The standard reduction potentials of Ce4+/Ce3+ and Fe3+/Fe2+ are 1.44 and 0.77V, respectively. The log10 K
(K is the equilibrium constant) value for the following reaction is ______
Ce 4  Fe 2  Ce3  Fe3
[Given: RT / F = 0.0257 V]
(IIT JAM 2018)
15. The emf of a standard cadmium cell is 1.02 V at 300 K. The temperature coefficient of the cell is 5.0  105 V K 1 .
The value of Hº for the cell is _____ kJ mol (rounded up to two decimal places).
–1
[1 F = 96500 C mol–1]
(IIT JAM 2019)
16. The limiting molar conductivity of La3+ and Cl– ions in aqueous medium at 298 K are 209.10 × 10–4 and 76.35
× 10–4 S m2 mol–1, respectively. The transport number of Cl– in an infinitely dilute aqueous solution of LaCl3 at
298 K is ________. (Round off to two decimal places).
(IIT JAM 2020)
17. The mean ionic activity coefficient for a 0.01 M aqueous solution of Ca3(PO4)2 is _______ (Round off to three
decimal places)
(Given : log10    0.509 z  z  1 )
18. For the reaction, CuSO4(aq) + Zn(s)  ZnSO4(aq) + Cu(s), the value of Gº (in kJ mol–1) is ____ (Round off
to the nearest integer)
(Reduction potential: Cu2+ (aq)/Cu(s) = + 0.34 V: Zn2+ (aq)/Zn(s) = –0.76 V)
(Faraday constant = 96485 C mol–1)
(IIT JAM 2021)
19. The mean ionic activity coefficient of 0.004 molal CaCl2 in water at 298 K (rounded off to thre decimal places)
is ___________.
(Given: Debye-Huckel constant for an aqueous solution at 298 K is 0.509 kg1/2 mol–1/2)
ANSWER KEY
TOPIC WISE PYQ
(Sol.)
(Physical)
1
SOLID STATE
HINTS & SOLUTIONS
hc
1. E  h  

6.626 10 34 Js  3 108 m / s
2.8 10 15 J 

6.626 1034 Js  3 8 m / s

2.8 1015 J
= 7.099 × 10–11 m
 = 0.7099 Å
n = 2d sin 
0.7 = 2 × d sin (8.5º)
0.7
d  2.38 Å
2  0.147
a 9
d  2.38 
h k   2
2 2 2 2
 0 2  02
9
2.38   a  4.76
2
= 4.8 Å
2. Ca2+  fcc  2= 4
a = 5.56 Å
D = 1.4848 g/cm–3
Zm
D
NAV
Z  40
1.4848 
6.022  10   5.563  108 
23 3
Z = 38.421 × 10–1 = 3.8

 4  3.842  100
% schottky effect 
4
= 3.94%
VIGYAN VRIKSH |Physical Chemistry (IIT-JAM)(Solutions)
3. Rock salt type structure
MgO  Mg2+ O 2–
Z+ = 2 Z– = – 2
r0 = r+ + r–
2.12
r0   1.06 Å
2
n=7
1 Z Z N A e 2 M  1 
U 1  
40 r0  n
 1
 9  109   2  2   6.022  1023  1.6 10 19  1.748 1  
2
 7
1.06
= – 7880 kJ/mol
4. Edge length = 14.14 Å
given : one C60 centered at each lattice point.
We know that
4r  2a
Face of FCC lattice
a 2
2a
r
4
To find: The smallest distance (in Å) between the centres of two C60 molecule i.e. 2r
2 2a 2a
So, 2r  
4 2
2
2r   14.14 Å
2
2r  9.998 Å  10Å
3
5. Nearest neighbours in body center lattice are a distance apart where as in face center limit cell this distance
2
a
is
2
bcc 3a/2 3
Therefore  
fcc a/ 2 2
Correct option is (c)
6. n  2d sin 
a
n = 1,   ? d 
h  k 2  2
2
Where a is edge length = 361 pm.

hk is (2, 2, 0)
361
1   2   sin 22º
2  22  02
2
722
 sin 22º
8
  95.6 pm
7. There are 7 crystal systems and 14 number of bravis lattices in solid state
System Number of bravis lattice
Cubic 3
Tetragonal 2
Hexagonal 1
Trigonal 1
Orthorhombic 4
Monodinic 2
Triclinic 1
ZM
8. 
NA  a3
Given that:
FCC  Z = 4
NA = 6.023 × 1023
M = 107.87 g mol–1
 = 10.5 g cm–3
4 107.87
10.5 
6.023 1023  a 3
a = 408.6 pm
9. For orthorhombic unit cell
1 h2 k2 l2
  
d 2hkl a2 b2 c2
h=1 a = 0.25
k=2 b = 0.5
l=3 c = 0.75
dhkl = 0.144 nm.
10. Cs+ = at body centre
Cl– = At corners
One Cs+ ion surrounded by 8 Cl– ion and vice versa.

Correct option is (D)
11. According to Bragg’s law, 2d sin  = n
where, d = interplanar distance,  = angle of diffraction, n = order of reflection
2 = 20.8   = 10.4
2dsin 10.4º = 1 × 1.54 Å
1.54Å 1.54
 d   4.266Å
2sin10.4º 0.1805  2
12.
U = U1 + U 2 + U 3
U U U
(Ca 2 Cl ) Ca 2 Cl (Cl Cl )
 2  ( 1)  1  2  ( 1)  1  ( 1)  ( 1)  1

 1389.4   kJmol  1389.4   kJmol  1389.4   kJmol
 2.8   2.8   5.6 
 2 2 1   4 1   7 
 1389.4       1389.4     1389.4  
 2.8 2.8 5.6   2.8 5.6   5.6 
 U = –1736.7 kJ mol–1
13. 2d sin   n
a
d
h 2  k 2  2
n h 2  k 2   2
sin   (n = 1)
2a
5Å  1  1  0 5  2
 
2  10Å 2 10
2
sin    sin   0.3535    20.7º
4
2d sin  = 2 for second order reflection
   h 2  k 2  2 
   sin 1    sin 1  
d  a 
 
 5Å  1  1  0 
 sin 1  1
  sin (0.707)  45º
 10Å 
Correct answer is (c), (d)
N 0 AZ Z e 2  1   12  9 21 
14. U 1  
40 r0  n   n  2  2  10.5
NAe 2 Z Z  1 
U 1   [r0 = 181 + 167 pm = 348 pm]
40 r0  n 
2.45  104 J  m Z  Z   1 
 1  
r0  n
2.45 104 J  m  1 1 9.5 2.45  104  9.5
 
348 pm 10.5 348  10 12 mtr 10.5
23.275 104 1012
 J  0.00636 108 J  636 103 J  (636 to 637)kJ / mol
3654
Correct answer is –636 to –637 kJ/mol.
2a
2d sin  = n sin(12.3)  1 1.54Å
15.  2 2 2
h k 
1 1.54Å  3 1.54Å  1.732 2.667Å
 a    6.260Å
2  sin(12.3) 2  0.213 0.426
16. CaO < MnO < VO
z z
Because lattice energy  r
0
17. According to Bragg’s equation 2d sin   n
1
 2d sin 30 = 1 × 5 Å  2d   5Å  d = 5Å
2
And for SCC, first plane reflection [001] or [100] or [010]
d=a
Now density will be given as
ZM 1 300 g mole 1
P  = 3.9867 g cm–3
Na 3 6.02 1023 mole 1  (5 108 cm)3
18. From Born-Lande equation
N A A Z Z e 2  1 
U0    1 because ‘n’ is always greater than one.
r0 n 
1 NAA 1 
LiF = 1000 kJ mole  (1)(1) e2   1 ... (1)
r0 n 
NAA 1 
MgO  x  (2)( 2) e2   1 ... (2)
r0 n 
(2) x 4
 1
  x = – 4000 kJ mole–1
(1) 1000 kJ mole 1
Correct option is (a)
19. Unit cell of NaCl
Cl– = F.C.C arrangement
Na+ = All octahedral voids.
Limiting Radius Ratio:

Let a = Edge length
a  r  2r  r  2r  2r ; a  2(r  r ) ; AC = d = 4r–
AC2 = AB2 + BC2; d2 = a2 + a2 = 2a2 d  a 2 i.e. face diagonal
da 2; 4r  a 2 ; 4r  2(r  r ) 2
4 r  r r r r
  1; 2 1;  2  1  1.414  1  0.414
2 2 r r r r
r
 0.414
r
20.
The rock salt face-centered cubic structure and each atom has six nearest neighbours, with octahedral
geometry.
21.
As Cs+ atom is at center only = number of Cs+ atoms/cell = 1

1
Cl– atoms are at all corners of the cube = Number of atoms of Cl–/cell = 8 × 1
8
One formula unit of CsCl is present per unit cell.
22. The unit cell of diamond is cubic and has the same overall geometry as ZnS (blende).
23. The second nearest Cs+ to Cs+ distance is a 3 .
Hence the number is 8
Correct option is (b)
r 100 pm
Ca 2
24. Radius ratio = r   0.75
133 pm
F
rcation
As, according to radius ratio rule, if 0.732 < r  1 So, C.N. of cation = 8
anion
25.
2
CHEMICAL KINETICS
HINTS & SOLUTIONS
1. X  Kx
 Y  y
Z
K
This is a consecutive reaction and [Y] at any time ‘t’ is given by
Y 
K x Co
Ky  Kx
K t
e K x t  e y 
2. For nth order
t1/2  a1–n
So, Substituting value
1 n
 t1/2 1  a0 
 1 
 t1/ 2 2  a0
 2 
1 n
360  5  102 
 
450  4 10 2 
 360  5
log    1  n  log  
 450  4
P=2
k
3. 
Q  R 1

x
k 1
X  Pk2
d P
rate   k2 x
dt
d x
Applying SSA on x   k 2  x   k1  Q R   k 1  x 
dt
k1 Q  R 
x 
k 2  k 1
k1 k 2
rate   Q R 
k 2  k 1
k 1k 2 2.5 10  10
5
Overall rate unit K  

k 2  k 1 10  110 4
2.5 106

10 4
= 250
4. Since intensity reduced by 90%
I = 0.10 (remains 10% only)
I0
Absorbance = ECl
I 
log  0   E  5.0  103 M  4 cm
 I 
1
E  103
20
E = 50 M–1 cm–1
70
5. For, P, T = 70% or
100
As, – log T = A
– log 0.7 = A1
A1 = 0.155
30
For, Q, T 
100
– log T = A
– log 0.3 = A2
0.523 = A2
AT = A1C + A2 (1 – C)
Let the volume fraction of liquid P in the binary mixture be C
AT = A1C + A2 (1 – C)
0.25 = 0.155 C + 0.523 (1 – C)
0.25 = 0.155 C + 0.523 – 0.523
0.25 – 0.523 = 0.155 C – 0.523
0.273 = 0.368 C
0.273
C
0.368
C = 0.74
6. For any nth order reaction
A1n  A10 n   n  1 kt
For zero order reaction, n = 0
A = A0 – kt
A  A0
k.
t
Units of k is mol L–1 s–1.
So above A  B conversion follows zero order kinetics.
7. Let A  Product, be an nth order reaction
Than (A)1–n = (A0)1–n + (n – 1)kt
When A0 = 0.1, t1/2 = 200 s
(0.05)1–n = (0.1)1–n + (n – 1) 200 k
 0.05   0.1  200 k  n  1

1 n 1 n
... (1)
Similarly when
A0 = 0.4, t1/2 = 50 s
 0.2    0.4   50 k  n  1
1 n 1 n
... (2)
Divide equation (1) by (2), we get
 0.05   0.1
1 n 1 n
4
 0.2    0.4 
1 n 1 n
 0.05    0.1  4  0.2   4  0.4 

1 n 1 n 1 n 1 n
When n = 2 above equation holds good

 A  Product is 2nd order reaction.

Catalyst 102 mol 
8. A 1 mol  
5hr
B
turnover frequency means amount of reactant converted to product per mole of catalyst per hour. As 90% of
0.9 mol
product is formed and 1 mole of A gives 1 mole B  2 = 18 hr–1.
10  5 mol hr
9. For 1st order reaction
A 
K
P
dA
  K A
dt mx
y
dA
So, Graph between  and [A] will be a straight line having slope k
dt
–dA slope = K
dt
[A]
Correct option is (B)
10. For zero order reaction, concentration – time relation
A – A0 = –kt
A0
At t = t1/2, A =
2
A0
 A 0   kt1/ 2
2
A0
   kt1/ 2
2
t1/2 = 30 min
A0
 k  30
2
A0
k= min–1
60
When reaction is 80% completed only 0.2 A0 is left.
0.2 A0 – A0 = – k t80
A0
– 0.8 A0 = – t 80
60
0.8 × 60 = t80
t80 = 48 min.
11. A(g)  2B(g)  C(g)

A  2B + C
at t = 0 P0 – –
at time (t) P0 – P 2P P
Pt = P0 – P + 2P + P
 Pt = P0 + 2P Pt = total pressure
 P  P0 
 P t 
 2 
1 P0
k  ln
t P  P 
P0   t 0 
 2 
1 P0
k  ln 1 2P0
t 2P0  Pt  P0 k  ln
t 3P0  Pt
2
Hence correct answer is (B)
12. 2A + B  C + D
1 d[A] d[C]
Rate  
Rate of reaction 
2 dt dt
d[A]
Rate of consumption of [A] =   0.1mol L1s 1
dt
1
Rate of production of [C] =  0.1 mol L–1 s–1
2
Rate of production of [C] = 0.05 mol L–1 s–1
Hence correct answer is 0.05.
13. As for nth order reaction:
1
t1/ 2 
C0n 1
for zero order reaction n = 0
1
t1/ 2 
C01  t1/ 2  C0 where C0 is concentration.
Correct option is (A)

14. T1 = 300 K, k1 = 8 L mole–1 s–1
T2 = 350 K, k2 = 160 L mole–1 s–1
 k  E  1 1  E T  T 
ln  2   a     a  2 1 
 k1  R  T1 T2  R  T1T2 
RT1T2  k 2  8.314 JK 1mole1  300K  350K  160 

Ea  ln    ln    52.30368 kJ mole–1
T2  T1  k1  (350  300)K  8 
15. t1/2 remains constant in first order reaction, and is independent of initial concentration of reactant.
16. A1   · c1 · 1
4 0.90 104
0.90   · 2.5  10 1.5 cm  
2.5M 1.5cm
90  10 4 60000 1 1
  M cm    2400 M/cm = 
25  15 25
2400
A 2   c2  2 ; A2   1.5  103 M  0.2cm
M.cm
= 2400 × 1.5 × 0.2 × 10–3
24  1.5  0.2 720
=   0.72
1000 1000
Correct answer is (0.72)
 k  E T T 
17. ln  2   a  2 1 
 k1  k  T1T2 
kT1T2  k 2  8.314JK 1mole 1  298K  318K

Ea  ln    ln(2)  27.299 kJ mole 1
T2  T1  k1  (318  298)K

0.1 mol
18. A  c  c  A/   1 1
 5.37 106  5.37µM
18600mol cm 1cm 
Correct answer is (b).
700ºC
19. 2NO  2H 2  N 2  2H 2O
(i) Expression for rate of reaction in terms of change in concentration of NO and H2O is
1 d 1 d
 [NO]   [H 2 O]
2 dt 2 dt
d d
Or,  [NO]   [H 2 O]
dt dt
And complete rate law expression is
1 d[NO] 1 d d[N 2 ] 1 d
  [H 2 ]    [H 2O]
2 dt 2 dt dt 2 dt
(ii) From experiment (1) and experiment (2), we observe that
On doubling the concentration of H2, rate becomes double
Therefore, order of reaction w.r.t. H2 = 1
And from experiment (1) and experiment (3), we observe that
On doubling the concentration of NO, rate becomes 4 times
Therefore, order of reaction w.r.t. NO = 2
Therefore, rate law is r = k[NO]2[H2]
From experiment (1),
2
6 3 1  mol   mol 
 2.4 10 (mol dm ) sec  k  0.025 3   0.01 3 
 dm   dm 
2
2.4  106  mol 
 k   sec1
(0.025)  (0.01)  dm3 
2
= 0.3840 mol–2 dm6 sec–1

1
20. vs ‘t’ graph gives straight line for a second order reaction
[A]
1 1
 k2 t =  ... (1)
ax a
where k2 is rate constant for second order reaction.
1 1
Or,  k2t  ;
ax a
by comparing the above equation with y = mx + C
Slope = k2 = 4 × 10–2 L mol–1 sec–1
And a = 1.0 M and a – x = 0.25 M
1 0.75
Therefore, (1), 4 × 10–2 t = 1   t = 75
0.25 0.25
21. C = 250 ppm = 10–3 mol ltr.
A = 0.1, x = 1 cm
A 0.1
A  cx   3 1
 102 litr mol1cm 1
cx 10 mol litr 1cm
22. for nth order reaction
1
t1/ 2 
(a 0 ) n 1
When n = 0
t1/ 2  a 0
23. A = –log T; –A = log T, 10–A = T
1
T = 10–A = 10–1 =  0.1
10
 %T = 0.1 × 100 = 10
24. k
1  CB*  CB
CB  CB 
k
CB*  CB 
1  CB  CB
k
CB* 
2  BD
(a) The rate of formation of BD is

d[BD]
 k 2 [CB* ] ... (1)
dt
d[CB* ]
Applying SSA on CB*, 0
dt
k1[CB]2  k 1[CB* ][CB]  k 2 [CB* ]  0
k1[CB]2  (k 1[CB]  k 2 )[CB* ]
* k1[CB]2
[CB ] 
k 1[CB]  k 2
d[BD] k 2 k1[CB]2
Therefore, (1) dt  Hence proved.
k 1[CB]  k 2
k 2 k1[CB]
(b) Given, k app  ... (2)
k 1[CB]  k 2
At very high concentration of CB, k 1[CB]  k 2
k 2 k1[CB] k 2 k1
Therefore, (2) k app  k [CB]  k
1 1
k 2 k1
k app 
k 1  limiting value.
k 2 k1
And at [CB] = 1 × 10–5, k app  50% of
k 1
k 2 k1 (1105 ) 1 k 2 k1 105 1
  ; 
k 1 (1105 )  k 2 2 k 1 k 1105  k 2 2k 1
5 k 1  105  k 2
5
2 10 k 1  k 110 5
 k 2 ; 2  10  k 1
k2 k2
2 105  105  ;  2  10 5  105  105 (2  1)
k 1 k 1
k2
 1 105
k 1
25. (a) (i) For the reaction,
k where k = rate constant.
R 
P
The plot of ln[R] vs t is straight line with –ve slope.
Above reaction is a first order reaction
d[R]
   k[R]
dt
On rearranging and then integrating we get,
[R]0
 n  kt ... (1)
[R]
Where [R]0 = initial concentration of reactant.
[R] = Concentration of R at time t
[R]0
At t = t1/2, [R] 
2
[R]0 n2
 n  kt1/ 2   t1/ 2
[R]0 / 2 k
(i) From equation (1),
ln[R]0  n[R]  kt
 n[R]  n[R]0  kt
n2 0.693
Slope =  k  t   0.231min 1
1/ 2 3
1
(iii) t=? When [R] = [R]0 ×
10
[R]0 1 2.303
n  kt  t n10   9.97 min
([R]0 /10) k 0.231
(b) (i) X  Fluorescence
Y  Phosphorescence
Z  Inter system crossing
(ii) Among radiative decays (Fluorescence and (ISC) phosphorescence), Fluorescence is faster because this
transition is spin allowed, while Phosphorescence is spin forbidden.

d[H]   
26. (a)  k p [Br][H 2 ]  k p´[H][Br2 ]  k r [H][HBr]
dt

d[Br]    
And  2k i [Br2 ][M]  k p [Br][H 2 ]  k p´[H][Br2 ]  k r [H][HBr]  2k t [Br]2 [M]
dt
 
(b) As H and Br are intermediates,
So, applying steady-state approximation of them,

d[H]
 0
dt
  
k p [Br][H 2 ]  k p´[H][Br2 ]  k r [H][HBr]  0 ... (1)

d[Br]
and 0
dt
   
2k i [Br2 ][M]  k p [Br][H 2 ]  k p´[H][Br2 ]  k r [H][HBr]  2k t [Br]2 [M]  0 ... (2)

Adding equation (1) and (2), we get, 2k [Br ][M]  2k [Br]2 [M]  0
i 2 t
1/ 2
 k 
 [Br]   i  [Br2 ]1/ 2 ... (3)
 kt 
Substituting the value of [Br] from equation (3) in equation (1), we get,
QUANTA CHEMISTRY CLASSES |Physical Chemistry (IIT-JAM)(Solutions)
1/ 2
k 
k p  i  [Br2 ]1/ 2 [H 2 ]
 k
 [H]   t  ... (4)
k p´[Br2 ]  k r [HBr]
Rate of formation of HBr,
d[HBr]   
 k p [Br][H 2 ]  k p´[H][Br2 ]  k r [H][HBr]
dt
d[HBr]  
  k p [Br][H 2 ]  (k p´[Br2 ]  k r [HBr])[H]
dt
 
Substituting value of [Br] and [H] from equation (3) and (4),
1/ 2
k 
1/ 2 k p  i  [Br2 ]1/ 2 [H 2 ]
d[HBr] k  k
  k p  i  [Br2 ]1/ 2 [H 2 ]  (k p´[Br2 ]  k r [HBr])  t 
dt  kt  k p´[Br2 ]  k r [HBr]
1/ 2
d[HBr] k   k p´[Br2 ]  k r [HBr] 
  kp  i  [Br2 ]1/ 2 [H 2 ]  1  
dt  kt   k p´[Br2 ]  k r [HBr] 
 
1/ 2
k 
2k p k p´  i  [Br2 ]3/ 2 [H 2 ]
 d[HBr]
  kt 
dt k p´[Br2 ]  k r [HBr]
1/ 2
k 
2k p  i  [Br2 ]1/ 2 [H 2 ]
d[HBr]
  kt 
dt k [HBr]
1 r
k p´ [Br2 ]
27. The activation energy for the reaction A  B can be calculated after drawing energy profile diagram
as:
Ea (A  B)
Ea (B  A)
P.E.
A H
B
Progress of reaction
AB H = –20 kJ mol–1
Ea (B  A) = 100 kJ mol–1
Ea (A – B) = ?
H = Ea(A B) –Ea (B  A)
 –20 kJ mol–1 = Ea(A B) – 100 kJ mol–1
Ea (A  B) = (100 – 20) kJ mol–1
Ea (A  B) = 80 kJ mol–1
28. A+BZ
Given, [Z] = [A]t = 0 (1 – e–kt) + [Z]t = 0
d(Z)
  [A]t 0 ke  kt  0 ... (1)
dt
We have
d[A] d[B] d[Z]
Rate of reaction =     k[A]0 e kt ... (2)
dt dt dt
d[A]
   k[A]0 e  kt
dt
On integration:
 [A]t = [A]0e–kt ... (3)
d[Z]
 From equation (1) and (3),  k[A]t Correct option is (b)
dt
29. (i) On doubling the pressure of NO, keeping the pressure of O 2 constant, the rate becomes 4 times.
 Order with respect to [NO] = 2
On doubling the pressure of O2, keeping PNO = constant.
The rate becomes double.
 Order with respect to O2 = 1
Hence, rate law:
R = k[NO]2[O2]1
1 d[NO 2 ]
(ii) rate law =  k 2 [NO3 ][NO] ... (1)
2 dt
As NO3 is an intermediate
So applying steady state approximation on NO3.
d[NO3 ]
 0
dt
k1[NO][O 2 ]  k 1[NO3 ]  k 2 [NO3 ][NO]  0

k1[NO][O 2 ]
 [NO3 ]  ... (2)
k 1  k 2 [NO]
Substituting [NO3] in equation (1)
k1k 2 [NO]2 [O 2 ]
Rate law =
k 1  k 2 [NO]
(iii) If first equilibrium step is established quickly and second step is slow, then k–1 >> k2
 k 1  k 2 [NO]  k 1
k1k 2 2
 Rate law = k [NO] [O 2 ]
1
k
30. A 
 products
d[A] d[A]
For zeroth order reaction,   k[A]0 ;  k
dt dt
 Unit of k = M s–1
31. Turnover number = number of moles of products formed per mole of catalyst (enzyme)
0.6
 6
 6  105
1 10
Correct optin is (d)
32. We have,
k 2 Ea  1 1 
ln     ... (1)
k1 R  T1 T2 
Doubling of rate of reaction is related to doubling of rate constant,
 k2 = 2k1 and T1 = 300K, T2 = 310 K
So, from equation (1)
Ea  1 1 
ln 2  
8.314  300 310 

E a  10 
 0.693 
8.314  300  310 

 Ea = 53582.8 J/mole = 53.58 kJ/mole

dC
33.   kC2 , t = 0, C = C0
dt
On integration, by taking limit 0 to t. we get
1 1
  kt ... (1)
C t C0
At t = 10 min, Ct = C0/2
2 1 1
   k 10   k 10 ... (2)
C0 C0 C0
C0
At t = ?, Ct = from equation (1) we get,
4
4 1 3
   kt ... (3)
C0 C 0 C0
3 t
From equation (2) and (3), 
1 10
 t = 30 min.
34. Michaelis-Menten kinetics has mechanism
k1 k2 k 1  k 2

E  S  
 ES 
k 1
 Product , where k m  k1
k 2 [E]0 [S]
Rate = k  [S]
m
k2 = Turnover frequency
Vmax = maximum rate of reaction = k2[E]0 = 2.4 × 10–4 Ms–1 and [E]0 = 2.4 × 10–9 M
Vmax 2.4  104 Ms 1

 k2 = turnover frequency =  ; k  105 s 1
[E]0 2.4 10 9 M 2
35. For the reaction

k
O 2 0  2O
h
k
O  O 2 
1 O
3
k
O3  O 
2  2O
2
d[O3 ]
 k1[O][O 2 ]  k 2 [O3 ][O]
dt
As ‘O’ is an intermediate, So, applying S.S.A on ‘O’.
d[O]
 0
dt
 2k0[O2] – k1[O][O2] – k2[O3][O] = 0
2k 0 [O 2 ]
 [O]  ... (2)
k1[O 2 ]  k 2 [O3 ]
Substituting [O] from equation (2) in equation (1),
d[O3 ] 2k 0 [O 2 ]
  (k1[O 2 ]  k 2 [O3 ])
dt k1[O 2 ]  k 2 [O3 ]
When [O3] is extremely small, then [O3]  0
Then k1[O 2 ]  k 2 [O3 ]  k1[O 2 ] and k1[O 2 ]  k 2 [O3 ]  k1[O 2 ]
d[O3 ] k1[O 2 ]
  .2k 0 [O 2 ]
dt k1[O 2 ]
d[O3 ]
Rate of formation of O3   2k 0 [O 2 ]
dt
Hence, formation of Ozone follows first order kinetics w.r.t. O2
36. For nth order reaction, aA k products
1  1 1 
We have, (n  1)  n 1    k eff .t;
 [A] [A]0n 1 
 1 1 
  n 1    k eff .t  n  1 ;
 [A] [A]0n 1 
 1  1
  n 1   k eff .t  n  1  ;
 [A]  [A]0n 1
1 1
Here, when n = 2; A  A  kt
0
1 1
So, vs t gives a straight line having slope = k and intercept = A
A 0

37. For the second order reaction
P + Q 

k Products
t = 0, 0.05 m 0.05 m 0
t=t (0.05 – x) (0.05 – x) x
Given,
3000
log10 k  20  ... (1)
T
At T = 300 K, k = 1010.
We have,
Ea
 log10 k  log A  ... (2)
2.303RT
From (1) and (2)
Ea = 3000 × 2.303 × 2 cal/mol = 13818 cal/mol = 13.818 kcal/mol
3000
logK  20 
T
When T = 27ºC = 300 K
and, For a second order reaction
1
t1/2 
A 0 .K
1
 K
A 0 .t1/ 2
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3
Mole Concept & Liquid Solutions
HINTS & SOLUTIONS
1. Tf = 0.186 K
kf = 1.86
Tf = kf m
0.186 100
m=  = 0.1 m
1.86 100
Elevation in boiling point
Tb = kb × m
= 0.51 × 0.1
= 0.051
Boiling point of solution = 373.15 + Tb
= 373.15 + 0.051
= 373.201 K
2. 1g = 25 wt% of MgSO4 + 75% of M2SO4
 1g = 0.25 g of MgSO4 + 0.75 g of M2SO4
1 mole MgSO4  1 mole SO42–
1 mole M2SO4  1 mole of SO42–
Mole of SO42– ppt = mole of BaSO4 ( 1 BaSO4  1 SO42–)
1.49 (mass ppt)
= (137  96) (Molar mass)
= 6.39 × 10–3
Total SO42– mole ppt out = mole of SO42– from MgSO4 + Mole of SO42– from M2SO4
0.25g 0.75
6.34 × 10–3 = 120 (MM of MgSO )  (24  96) (Molar Mass of M)
4
24 + 96 = 174.14 = 39.07 g/mol

n
3.  RT
V
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6g
n  101 mol
60 g / mol
V = 1L, R = 0.0821 L atm k–1 mol–1
101
 mol  0.0821 300 / L atm k 1 mol 1 L
1L
  30  0.0821 atm
 = 2.46 atm
 = 2.46 × 101325 Pa
= 249.56 kPa.
O
4.
H3C OAc + 2MeMgBr t-butanol
1 mol of ethylacetate reacts with 2 mol of MeMgBr.
Millimoles of ethylacetate = 10 × 0.025 = 0.25 millimoles.
So for complete reaction MeMgBr must be 0.50 millimoles
Volume of 0.2M MeMgBr containing 0.50 millimoles would be
0.2 × V = 0.5
5
V ml
2
V = 2.5 ml.
5. In given organic compound % of C is 39.9 therefore fraction of C is 0.399.
So, weight of C in given compound = 0.399 × Molecular weight of compound
= 0.399 × 180
= 71.82 g  72 g/mol.
72g / mol
No. of carbons in 72 g = mass of 1 mole of carbon
72
= =6
12
6. Tf = i1m1kf + i2m2kf
Tf  (i1m1  i 2 m 2 )k f
For sucrose i1 = 1
For NaCl i2 = 2
0.02
For sucrose m1   1000  0.1 mol kg–1
200
0.011000
For NaCl m2   0.05 mol kg–1
200
Tf = (1 × 0.1 + 2 × 0.05)1.86
 0.37
7. Cu(s) + 4H+(aq) + 2NO3– (aq)  2NO2(g) + Cu2+ (aq) + 2H2O (l)
6.36
Wt. of Cu = 6.36 gm. So, moles of Cu =  0.1
63.6
0.1 mole of Cu will produce 0.2 moles of NO2(g).
PV = nRT
nRT (0.2)(0.0821)  (298)
V   4.89L
P 1
Correct answer is 4.89.
8. 2N 2O5 (g) 
 4NO2 (g)  O 2 (g)
10.8
Number of moles of N2O5 = M
N 2O5
10.8
 n N 2O5   0.1
108
At 373 K temperature, pressure is 0.5 atm
V = 10L, So, PV = nRT
PV 0.5  10
Total number of moles (n) =   0.1632
RT 0.0821  373
After decomposition, let x moles of N2O5 decomposed
2N 2O5 
 4NO2 (g)  O 2 (g)
x
0.1 – x 2x
2
x x 3x
Total number of moles = 0.1  x  2x   0.1  x   0.1 
2 2 2
3x
0.1   0.1632 (total number of moles)
2
3x x 0.0632
 0.1632  0.1  0.0632    0.0210
2 2 3
x
= number of moles of O2 = 0.021
2
number of moles of O 2 0.021
PO2   total pressure   0.5 = 0.0643 atm
total number of moles 0.1632
9. M = 0.16 M; Vml = 75 ml; MB = 294
W 1000
M B
M B V(mL)
W 1000
0.16 = 
294 75
3528
W
1000
W = 3.528
WB  3.52  3.54 Ans.

Correct answer is 3.52 to 3.54
10. Since Clausius Clapeyron equation,
 P  H  1 1   53330Pa  H  1 1 
n  2       n  5333Pa   R  280.6  333.6 
P
 1 R  T1 T2     
H  104 
 n(10)   5.66  
R  K 
(Rn10) 8.314J / mol K n 10 kJ

 H  4
 4
 33.822
mol
10 5.66 10 /K
5.66 
K
H
According to Trouton’s rule,  88 J mol–1 K–1
Tb
H
 Tb = Normal Boiling point = 88 J mol 1K 1
J
33.822 103
mol  384.35K
= J or 111.35ºC
88
mol  K
11. C3H8(g) + 5O2(g) 
 3CO2(g) + 4H2O(g)
n x 0 0
x 3 4
(n – x) x x
5 5 5
P1V1 4 1
Initial number of moles, n    0.1306
RT 0.0821  373
Final number of moles,
x 3 4 6 6 6x  5x
n f  (n  x)   x  x  (n  x)  x  n  x  x  n 
5 5 5 5 5 5
x
nf  n 
5
Pf V 4.2  1
nf    0.137
RT 0.0821 373
x x x x
nf  n   0.137  0.1306   0.1370  0.1306   0.0064 
5 5 5 5
x = 5 × 0.0064  x = 0.032
weight of O2 = x × 32 = 0.032 × 32 = 1.024 gm
12. Given that mass of solute, w = 1.0 g L
Volume, V = 1 ltr.
Osmotic pressure, P = 4 Torr
T = 300 K
w
 PV  nRT  RT
m
wRT (1g)(0.082L atm K 1 mole 1 )  300K
 Molar mass = 
PV 4torr  1L
atm
= 6.15g. mole–1 = 6.15 × 760 g mole–1 ( 1 atm = 760 torr)
torr
= 4674 g mole–1
13. Due to 3 O – H groups there will be large number of intermolecular H–bonding possible, which in turn increases
the viscosity, as cross linked polymer like network is formed.
Correct option is (d)

14. Tb  m(solute) k b
 1.0 
   1000
 0.3   M   0.513  M  171 [M = mol. wt. of solute]
10
 wt 
   1000
We have, Molarity = M
Volume of solution (in m)
wt
 1000
 0.1  171 ; wt  8.55 gm
500
15. PD0 2O = 745 mm Hg at 20ºC
 200 
200 gm D 2O    mole of D2O.
 22 
 15 
15 gm of non-volatile compound    mole of non-volatile compound
M
PD2O = 730 mm of Hg (M = molecular weight of non-volatile compound).
From Raoult’s law,
Relative lowering of vapour pressure = (Mole fraction of non volatile solute)
 15 
PD0 2O  PD2O   745  730 1 15 1
 M ;  ; 
 PD0 2O  200   15  745  20M  745 20M  1
     1 33
 22   M   33 
20M 146 11

  3  149 ; M   80.3 ; M  80.3
11 20
16. P T = PX + PY  PX  x X PX* , PY  x Y PY*
Where, PT = Total pressure
xX = Mole fraction of X in solution
xY = mole fraction of Y in solution
PX* , PY* = vapour pressure of pure liquids X and Y respectively..
PT  x X PX*  x Y PY*
= 0.5 × 70 + 0.5 × 20 = 35 + 10 = 45 torr
PX 35 P 10
yX    0.78; y Y  Y   0.22
PT 45 PT 45
yX(x), yY(y) = mole fraction of X and Y in vapour phase.
4
ATOMIC STRUCTURE
HINTS AND SOLUTIONS
h h
1. We have, x Px   x m Vx 
4 4
6.625 1034
 Vx 
11010  4 9  1031
 Vx  5.8  105  Vx ~ 106

2. 4d  number of radial node = n – l – 1 = 4 – 2 – 1 = 1
Number of angular node = l = 2.
nh
3. (a) (i) m e v n rn  , ... (1)
2
Where n = 1, 2, 3, ........
vn = velocity of electron in nth Bohr orbit.
rn = Radius of nth Bohr orbit.
Ze 2 m e Vn2
 ... (2)
4 0 rn2 rn
(ii)
Substituting the value of Vn from equation (1) in equation (2),

2
Ze2m  nh 
 e 
2
4 0 rn rn  2me rn 
On rearranging and cancelling the similar term we get,
0 h 2  n 2 
rn     ... (3)
m e e 2  z 2 
8.854  1012  (6.625  10 34 ) 2  n 2 

  
3.14  9.11031  z 
 n2 
rn  0.529   Å where n = 1, 2, 3, .....
 z 
 
Total energy of electron in nth Bohr orbit, = En = K.E. + P.E.
1  Ze2
 m e Vn2  ... (4)
2 4 0 rn
From equation (2) and (4)
Ze2 Ze 2
En  
8 0 rn 4 0 rn
Ze2
 En  
8 0 rn
Substituting the value of rn from equation (3) in the above expression,
me e4  z 2 
 En    
8 02 h 2  n 2 
(9.11031 )(1.6 1019 ) 4  Z2 

 En    
8  (8.854 1012 ) 2 (6.625 1034 ) 2  n 2 
18  Z2 
 E n  2.18  10  2  Joule
n 
 Z2 
E n  13.6  2  e.V
n 
 
14 4
(b) (i)  11H  17
7 N  2 He  8 O (ii) 7 1
 84 Be
3 Li  1H 
4.
0 = threshold wavelength (wavelength above which electrons cannot be ejected)

hc hc
 K.E. of ejected electron =  
incident 0
 K.E. is dependent on lincident.
Number of ejected electrons depends on intensity of incident radiation only.
13.6z 2
5. The energy of H like species is given by E 
n2
 E  z2
Correct answer is (b)
n=5
n=4
n=3
6. n=2
n=1
For Balmer series electron finally comes to n = 2.

For third member of Balmer series transition from n  5 to n  2.
 1 1
E  13.6    eV
 25 4 
E  2.856eV .
h
7. 
mv
h 6.6 10 34

V 
m 9.1 1031  13.4  1010
v  541249.795 m / s
z
v n  2.18  106 
n
2.18 106
n  4.02  4
541249.795
2
13.6 z eff
8. I.E n  
n2
Where –ve sign suggests binding energy.
n value is orbit from which electron is ejected.
For Na last e– stays in 3s orbital.
2
13.6 z eff
5.1 
32
5.1  9  13.6 z 2eff
45.9
 z eff
2
13.6
z eff  1.8
a 0n2
9. Bohr radius rn   a 0  52.9 pm 
z
a 0  32
r3 
1
r3 = 9a0
r3 = 9 × 52.9 pm
r3 = 476.1 pm.
10. For longest wavelength
n1 = 1
n2 = 2
1 1
  Z2 R H  2  2  =   Z 2 R H   2 
1 1
 n1 n 2  1 2 
3 1 3
=   Z RH  =    Z RH 
2 2
4  4
1 3
 Z2  R H 
2.48  10 cm
–7 –1
4
4
Z2 = Z=7
2.48  10  1096700  3
–7
11. As we know that

n – l – 1 = no. of radial node
n=3
l=2
3 – 2 – 1 = no. of radial node = 0
No. of radial node = 2 – 1 – 1 = 0
12. For H, Z = 1
Z2 12
E1  13.6  2  13.6  2 = – 13.6
h 1
12 13.6
E 2  13.6  2

2 4
E for 2p  1s
 13.6  13.6
E1  E 2  13.6      13.6 
 4  4
3
E H    13.6
4
He+ Z = 2
 2
2
E1  13.6  2 = – 13.6 × 4
1
 2
2
E 2  13.6  = – 13.6
 2
2
E for 2p  1s
E1 – E2 = – 13.6 × 4 – (–13.6)
= – 13.6 × 4 + 13.6
E He  3  13.6
E He 3  13.6
  4
E H 3 / 4  13.6
5
Thermodynamics & Thermochemistry
HINTS & SOLUTIONS
1. (a) From Equipartition theorem,
1
Energy per translational or rotational degree of freedom = kT
2
Energy per vibration degree of freedom = kT
CO2 has 3 translational degree of freedom, 2 rotational degree of freedom and vibrational degree of freedom =
(3 × 3 – 5) = 4.
 Energy per molecule of CO2 from euipartition theorem.
1 1
 3  kT  2   4  kT  6.5kT
2 2
(b) If initial and final states achieved by any reversible and irreversible process are same, then S will be same,
because entropy is a state function. So, it is independent of path.
(c) Phase I  Phase II, (Let Hsystem be the enthalpy change from phase I to phase II).
Total entropy change for any process is given by,
Stotal = Ssystem + Ssurrounding ... (1)
If surrounding is at temperature ‘T’ (same as system temperature) and heat absorbed by the surrounding is qrev.
 qrev = –DHsystem (at constant pressure) ... (2)
Hsystem
 Ssurrounding =
T
Therefore, from equation (1) and (2),
Hsystem
Stotal  Ssystem  (at constant T and P)
T
 –T Stotal = –TSsystem + Ssystem
– T Stotal = G ... (3)
As Stotal = Sphase I  Phase II + SPhase  Phase I
 Stotal = 0 (because entropy is a state function)
(d) dG = VdP – SdT
At constant P, dP = 0 and at constant T, dT = 0
From equation (3)
 G  0 (substitute value of Stotal)
So, at constant T and P, G = 0, for reversible phase change.
(e) In transition state theory, a reaction is assumed to involve the attainment of an activated complex that goes on
to product at an extremely rapid rate. The rate of decomposition of the activated complex about 6 × 1012 s–1 at
room temperature.
2. From Van’t hoff equation

H
ln K  C; where C = constant
RT
For endothermic reaction, H = +ve
1 K 2 H  1 1 
 ln K vs graph slope is –ve and ln    
T K1 R  T1 T2 
For exothermic reaction, H = –ve,
So, if T2 > T1, then K2 < K1
dq
3. From Clausius inequality, ds 
T
Here equality holds for reversible process,
q cycle q cycle
  ds 
T
; 0
T
; q cycle  0
cycle
So for reversible process, qcycle = 0 and for irreversible process, qcycle < 0.
4. As E, S, H and A are state functions, so they are path independent and in a cyclic process, net change is zero.
5. (a) As work done by gas, W = –Pext V
As Pext = 0  W  0
From first law of thermodynamics.
U  q  W
Since process is adiabatic
So, q = 0
H = U + PV
H = U = 0
 H  0
Also U = 0
So, temperature of container will remain same.
V2
 S  nR ln V (at constant temperature)
1
PV  V  1.5  24.8   49.6 
  1 1  R ln 2    8.314 ln    8.76 J / mol
 RT  V1  0.0821 298   24.6 
G = H – TS = –298 × 8.76 = –2610.48 J/mol = –2.61 kJ/mol
6. Work done = –PV
 W = –P(Vwater – Vice)
Density of water at 0°C is 1kg L–1
Density of ice at 0°C is 0.92 Kg L–1
18gm
Vwater = Volume of 1 mole of H2O(l) in litre = = 18 × 10–3 L
1103 gmL1
18gm
Vice = Volume of 1 mole of H2O(s) in litre = = 20 × 10–3 L
0.9 103 gmL1
 W = –P(Vwater – Vice) = –1 atm (18 × 10–3 – 20 × 10–3) L = 2 ×10–3atm L
 W = 2× 10–3 atm L
T2  100  348
7. Ssystem  Swater  n(CP )H 2O n    (4.2 18)n  31.31 Jk 1
T1  18  323
For reversible process, Ssurrounding = –Swater = –31.13 J k–1
Suniverse = Ssystem + Ssurrounding = 0
8. (ii)
Partition between gases has been removed.

As the gases are ideal, so there will not be any change in temperature and pressure, even after removal of
partition.
G mixing  RT(n He nx He  n Ar nx Ar )
 2 3
= 8.314  300  2n    3n  J / mole = –8393.12 J/mole
 5 5
= –8.39 kJ/mole
 G mixing 
(iii) Smixing      R(n He ln x He  n Ar nx Ar )  27.97 J / mole
 T 
(b) (i) C(graphite)  H 2 (g) 
 CH 4 (g)
Molar heat of formation of CH4(g)
Hf(CH4) = (Sublimation energy of graphite + atomisation energy at H2(g))–Energy released for formation of
C(g) to CH4(g).
= (717 + 436) kJ/mole – (339 + 444 + 444 + 435) kJ/mole = –509 kJ/mole
(ii) Average C-H bond energy
(B.E.)(C  H)  B.E.(CH  H)  B.E.(CH 2  H)  B.E.(CH 3  H)

4
 (339  444  444  435) 
  kJ / mole  415.5 kJ / mole
 4 
9. U m  C v T
5
 U m (T)  U m (O)  C V (T  O)  U m (T)  U m (O)  RT
2
 5 
C V  2 R, for linear molecule, by taking translational and rotational degree of freedom 
5
 U m (T)  U m (O)  RT
2
10. Maximum work is obtained in reversible process only.
2v0
11. Work done =  Pext dv  0 [ In free expansion, Pext  0 ]

v0
12.
Above change can be brought as,
Tfusion = 273 K
H m  H I  H II  H III
= Cp,m(  ) (T1) + (–Hfusion) + Cp,m (s)(T2) = 76 × 10 – 6006 + 38 × (–10)
= 760 – 6006 – 380
 Hm = –5626 J/mole
273 263
dT H fusion dT
Sm  SI  SII  SIII  C p,m ()  ln
T

Tfusion
 Cp,m (s)  ln
T
263 273
273 6006 263 273 6006

 76 ln   38 ln  (76  38) ln 
263 273 273 263 273
=38(5.61 – 5.57) – 22 = 1.52 – 22 = –20.48 J/(mole-K)
V2 V2
 RT a 
13. w    Pdv      2  dv
V1 V1 
(V  b) V 
  a  RT a 
  P  2  (V  b)  RT  P  (V  b)  2 
  V  V 
For isothermal proces, T = constant
V
a 2 V b 1 1 
   RTn(V  b) 
V2
V1
     RT n 2 a  
 V  V1 V1  b  V1 V2 
14. First point on carnot cycle is at high pressure, low volume, high temperature
dH = CpdT
Step-1: Isothermal reversible expansion, in this process heat is gain and temperature is constant.
 H = 0 whereas S = positive
Step-2: Adiabatic reversible expansion, in this process heat exchange is zero and temperature is decreasing.
 H = +ve, S = 0.
15. (a) From Clausius inequality
q q rev
S  ; equality holds for reversible process i.e. when q = qrev, then S 
T T
(i) For reversible adiabatic process
q = qrev = 0
 S  0  0.R
(ii) For adiabatic irreversible process,
q=0
 S > 0
From 1st law of thermodynamics, q = U – W
Or, 0 = CV (T2 – T1) + Pext (V2 – V1) (n = 1 mole)
 RT2 RT1 
Or, 0 = CV (T2 – T1) + Pext   
 P2 P1 

Given, P1 = 10 atm, P2 = 2 atm = Pext, Cv = R, T1 = 300 K
2
3  RT R  300  3
 0 R(T2  300)  2  2    0  T2  450  T2  60
2  2 10  2
 T2  204K
As entropy is a state function, so it is independent of path followed (i.e. reversible or irreversible) if initial and final
states are same.
 Net entropy change can be written as,
T  V 
S  nC v n  2   nRn  2 
 T1   V1 
3  204   RT2 / P2 
 1 Rn    1  R n  
2  300   RT1 / P1 
3  204   204 / 2 
 R n    R n  
2  300   300 /10 
3  204   102 
 Rn    R n    0.645R
2  300   30 
16. The heat of vaporization diminishes at the critical temperature because above the critical temperature the liquid
and vapour phase no longer co-exist.
17. H = U + ngRT
Formation of CF2ClCF2Cl(g)
2C(s) + 2F2(g) + Cl2 (g)  CF2ClCF2Cl(g)
ng = gaseous mole of product – gaseous mole of reactant.
ng = 1 – 3 = – 2; H = U + ngRT
U = H – ngRT = H + 2RT = –900 kJ / mole + 2 × 8.314 × JK–1 mole–1 300K
= –900 kJ / mole + 5kJ / mole = –895 kJ/mole
1 1 1 1   1
18.  mix G  nRT[x A n x A  x B n x B ]  4  8.314  300  n  n   4  8.314  300  n 
2 2 2 2  2
= 1200 × 8.314 × 2.303 × (–0.3010) = –6.915 kJ
  mix G  (–6915.9)
  mix S     23.05 J / K
 T  300
For ideal mixing mixV = 0; mixH = 0; mixU = 0
19. H  U  n g RT
n g = number of gaseous moles of product – number of gaseous moles of reactant
n g = 0 – 3
n g = – 3
U = 550 kJ
k = 550 kJ + (–3) × 8.314 × 300
= 550 kJ – 90058.314 = 550kJ – 7482.600
= 550 kJ – 7.4826 kJ = 542.51 kJ

SO2Cl2 (g) 
 SO2 (g) Cl2 (g)
20. (i) (1) (1) (1)
Entropy positive; one gaseous molecule form two gaseous molecule (2–1) = +ve
catalyst
(ii) nH 2C  CH 2 (g)   —[–CH 2  CH 2 –—
]n [S]
Gas to solid random ness decreases.
S = (–ve)

(iii) I2(s) 
1 atmosphere
 I2 [V]
Solid to vapour randomness increases S = (+ve)
q
(iv) S  q = 0
T
S = 0
Correct answer is (d)
21. U = nCvdT
Since isothermal expansion  dT = 0
 U = 0
Since, free expansion into vacuum
Pext = 0
w = –PdV = 0
From first law of thermodynamics
U  w  q
0  0q  q0
S H P
U G
22.
T
V A
 T   V 
   
 P S  S P
 S   P 
   
 V T  T  V
Correct option is (b, c)
23. G = Gº – 2.303RT log Kp = 2.303 RT log Q – 2.303 RT log Kp
Q 5 102
 2.303RT log  2.303  8.314  480  log
Kp 5
= –2.303 × 8.314 × 480 × log 102

= –2.303 × 8.314 × 2 × log 10
 PSO3 2 
Q  
 PSO2 2  PO2 
 4
10 10 4 
2
  3  5  10 
 10 103  0.2 
= –2.303 × 8.314 × 480 × 2 × 1 = –18381.256 JK–1 mol–1.
Correct answer is –18.3 to –18.5
P1 5
24. S  nRn  S  2  2.303log
P2 1
S = 2 × 2.303 × 8.314 × log 5
= 2 × 2.303 × 8.314 × 0.6989 = 26.76 JK–1
Correct answer is (26.76 JK–1)
25. C(g) + 4H(g)  CH4(g)
H r  H f (P)  Hf (R)  75  (717  4  218)
H r  1664 kJ mol–1 ... (i)
(B.E.)R = 0 because no bond in reactant side
H r  (B.E.) R  (B.E.) P
H r  0  4E(CH) ... (ii)
From equation (i) and (ii),
4E (CH)  1664 kJ mol1
1664
E (CH)   416 kJ mol1
4
26. Hº at 298
 1
Hº  H 0f (products)  H f0(reactants)  ( 394)kJmol 1   110  0   kJmol1
 2
= – 394 kJ mol + 110 kJ mol = –284 kJ mol = –284 × 10 J mol–1
–1 –1 –1 3
H02 T2
0 d(Hº )   CPdT
H1 T1
 1 
C P  CP(products)  CP(reactants)  37.1   29.1   29.4   37.1  (43.8)  6.7 J mol 1K 1
 2 
H 02  H10  C P (T2  T1 ); H 02  H10  6.7(400  298)
H02  H10  6.7(102)  284 103  683.4  (284 103  0.68 103 )kJ mol1
= –284.68kJ mol–1
27. From vant-hoff equation
d Hº
(ln K p ) 
dT RT 2
 ng
by putting the value of K p  K c (RT)
d Uº
 dT (ln k c )   RT 2
Uº
ln k c  k U
RT 
ln kc T
Uº
slope =
R 1/T
28. Intensive variable are temperature, pressure and density. Because these properties are independent of bulk of
system.
29. At 298 K & 1 atm
Given:
9 –1
 O 2(g)  3CO2(g)  3H 2O(l )
(g)
–2091 kJ mol
2
9 –2058 kJ mol
–1
C3H 6(g)  O 2(g)  3CO 2(g)  3H 2O (l )
2
C3H 6(g)  (g)
H = ?
by reversing the first reaction and adding in second reaction we will get the desired reaction
9
3CO2(g)  3H 2O(l )  (g)
 O 2(g) –2091 kJ mol
–1
2
9 –1
C3H 6(g)  O 2(g)  3CO 2(g)  3H 2O (l ) –2058 kJ mol
2
C3H 6(g)  (g)
From Hess Law
H = H1 + H2
= (2091 – 2058) kJ mol–1 = 33 kJ mol–1
30. Reversible isothermal compression of one mole of ideal gas from 0.5 atm to 30 atm at 300 K
A  B
P1 = 5 atm P2 = 300 atm
T = 300 K (isothermal)
T2 P
Ssystem  nCp ln  nR ln 2
T1 P1
P2
 nR ln (For isothermal reversible process)
P1
30
= 1 × 8.314 ln
5
= –8.314 ln 6
= –14.896
Ssurrounding  Ssystem for isothermal reversible compression of ideal gas.
Ssurrounding = 14.90 J K–1
31. dA  PdV  SdT dG  VdP  SdT
for dT = 0 for dT = 0
vinitial vinitial
 A  RT ln v G  RT ln
v final
final
1
32. According to law of equipartition of energy each coordinate axis is associated with KT energy for rotational
2
and transitional degrees of freedom for N2 linear molecule
There is 2 rotational degree of freedom 3 translational degree of freedom
1 1
 U  2  KT  3  KT
2 2
For 1 mole N2
3
U m  KT  N A  KTN A
2
3
U m  RT  RT
2
5
Um  RT
2
dU m 5
 CV  R
dT 2
5
  8.314 JK 1mol1
2
 20.75 JK 1 mol1 .
33. H = U + PV
H = U + (PV) ... (1)
From ideal gas equation, PV = nRT.
(PV) = ngRT ... (2)
Put value of equation (2) in Equation (1)
H = U + ngRT
1
Co(g)  O 2 (g)  Co 2 (g)
2
ng = 1 – (1/2 + 1)
= 1 – 3/2
= –1/2
 1 8.314  3000 
H = 281.8     
 2 1000 
 281.8  1.2
= –283.0 kJ mol–1
1
34. Ssys  SH 2O  SO2  SH 2 Stotal  Ssys  Ssurr.
2
1
 (70)   204  130
2
= 70 – 102 – 130
= 70 – 232 = –162
Ssys = (–162) JK–1 mol–1
H sys
Ssurr  
T
Hsys
Stotal = Ssys –
T
 285  1000 
 ( 162)J / K mol   J / K mol 
 300 
 (162)  (950)J / K mol
= 788 J/K mol
S H P
U G
35.
T
V A
(A)V, T < 0
as A is a function of V & T.
36. dG = VdP – SdT
at isothermal condition, dT = 0
dG = VdP
nRT
for ideal gas V 
P
dP
dG  nRT
P
Intergrating both sides
P2
dP
 dG  RT  P1
P  n  1 mole 
P2
G  RT ln
P1
1000
G  8.3  300 ln
100
G  8.3  300ln10
= 8.3 × 300 × 2.303 log 10
= 8.3 × 300 × 2.303
= 5.73 kJ mol–1.
T
37.
S
38. Change in chemical potential w.r.t. change in T at constant P:
 µi 
   Si [ SV > S l > S s]
 T  P
g
Temperature (T) 
1
39. Mg  O 2  MgO
2
1
S  SMgO  SO 2  SMg
2
1
 0  2052   0
2
= – 102.6
G = H – TS
= – 600600 – 280 (–102.6)
= –600600 + 28728
= –571,872 J mol–1
or –572 kJ mol–1
40. Cv is always temperature dependent and observed value is always less than expected by equipartition function.
1
41. H 2 O  g  
 H 2  g   O2  g 
2
Gº = 118 kJ mol–1 at 2500 K
Gº = – RT lnk
118 × 103 J mol–1 = – 8.314 JK–1 mol–1 × 2500 K ln k
K = 3.42 × 10–3
42. q = nCVdT
3
q=2×  (T2  298)
2
1000 = 3(T2 – 298)
1000
 298 = T2
3
T2 = 631K
6
GASEOUS STATE
HINTS & SOLUTIONS
1. Expression representing value of most probable, average velocity and root mean square velocity are as shown
below.
3RT 8RT 2RT
Vrms  , Vav  , Vmp 
M M M
8
Vrms : Vavg. : Vmp = 3 : : 2

1
2. CV = 25 J mol–1 K– = 3R = fR
2
 Degree of freedom (f) = 6
Which is only possible for any non-linear molecule (SO2). (Neglecting vibrational degree of freedom as at room
temperature)
3. Given, Maxwell distribution function
  mc2 
3/ 2  
 m  2  2kT 
f (c)  4   c e
 2kT 
For finding most probable speed,
d f (c)  d 2 f (c) 
 0 and  0
dc  ccmps dc2  cc
mps
3/ 2  mc 2
d f (c)  m   mc3 
  4   e 2kT  2c  
dc  2kT   kT 
3/ 2 mc2
d f (c)  m    mc 2  d f (c)
  4   ce 2kT  2   ; 0
dc  2kT   kT  dc
2kT
When, c = 0, ,  but most probable velocity can not be  .
m
mc 2
d 2f (c)  m 
3/ 2   3mc2 mc  mc2  
Now,  4   e 2kT 2    2c  
dc2  2kT   kT kT  kT  
2
3/ 2  mc
d 2 f (c)  m   5mc 2 m 2c 4 
  4   e 2kT 2   2 2
dc 2  2kT   kT k T 
d 2f (c) 
    ve  minimum
dc2  c0
d 2 f (c) 
   ve 2kT
dc 2  c 2kT  maximum  c  cmps 
m
m
2RT
4. Vmp  1000  ... (1)
M
8RT
V(Mean/average) = ... (2)
M
Vmean 2
Equation (2) divided by (1), 
1000 
2000
 Vmean  = 1128.3 m/sec

5. PV vs T graph is same as, nRT vs T, so as T increases, nRT increases too, So there is linear relationship between
PV vs T.

6. (Vrms ) H2  (Vrms )He
3RTH2 3RTHe
• 
M H2 M He
TH 2THe THe 1
•   
2 4 THe 2
7. (i) For CH4,
Number of atoms N = 5
 Number of vibrational modes for nonlinear polyatomic molecule
= 3N – 6
= 3 × 5 – 6 = 9 modes
 Vibrational contribution to the total energy = 9 × kT per molecule
= 9 × RT per mole
= 9 × 8.314 × 500
= 37.4 kJ/mole
(ii) Total internal energy of 1 mole CH4(g)
= Translational contribution + Rotational contribution + Vibrational contribution
3 3
 RT  RT  9RT  12RT  12  8.314  500 kJ / mole  49.88 kJ / mole .
2 2
8. For CO2, translational degree of freedom = 3
rotational degree of freedom = 2 (because molecule is linear)
and vibrational degree of freedom = 3N – 5 = 3 × 3 – 5 = 4 (because CO 2 is linear)
Therefore, total internal energy of CO2 molecule, is
1 1 1
U  3  kT  2  kT  4  kT  kT
2 2 32
U 13
 C v,m   k = 6.5 k (per molecule)
T 2
= 6.5 k × NA = 6.5 R (per mole)
9. From Maxwell probability distribution, the number of molecules having velocity between v and v + dv is,
3/ 2
2
m   mv 2 
F(v)dv  4v  exp  
 2kT 
 dv
 2kT   
So, velocity (v) at which F(v) will be maximum is said to be most probable velocity,
 at v = vm,p, F(v) is maximum
For F(v) to be maximum,
dF(v)  d 2 F(v) 
0  0
dv  V Vmp and dv 2  V V
mp
3/ 2
 m   mv 2
F(v)  4v2  exp  

 2kT   2kT 
 
3/ 2
dF(v)  m   mv 2    2mv  
  4   exp     2v  v 2   
dv  2kT   2kT    2kT  
 
dF(v)
For, 0
dv
 2mv 
2v  v 2   0
 2kT 
2kT
Or, v2  [ neglecting, v = 0, value because at v = 0, F(v) = 0]
m
2kT 2kT d 2 F(v)
Or, v and also at v  , 0
m m dv 2
2kT 2RT
 v  vmp  
m M
(ii) For CH4(g)
M = 16 × 10–3 kg/mol
T = 127º = 400 K
R = 8 J k–1 mol–1.
2  8  400
 Vm,p  3
 4 105  200 10  632.45 m / s
16 10
8RT 1
10 The average speed, vavg  
M M
Molar mass of H2 = 2 g mol–1
Molar mass of O2 = 32 g mol–1
Molar mass of N2 = 28 g mol–1
1 1 1 1
vH2    0.707 ; vO2   0.176; v N2   0.189
2 1.414 32 28
So, velocity of N2 > velocity of O2 > Velocity of H2
11. Given that mass of solute, w = 1.0 g L
Volume, V = 1 ltr.
Osmotic pressure, P = 4 Torr
T = 300 K
w
 PV  nRT  RT
m
wRT (1g)(0.082L atm K 1 mole 1 )  300K
 Molar mass = 
PV 4torr 1L
atm
= 6.15g. mole–1 = 6.15 × 760 g mole–1 ( 1 atm = 760 torr)
torr
= 4674 g mole–1
12. C3H8(g) + 5O2(g) 
 3CO2(g) + 4H2O(g)
(n – x) x 0 0
x 3 4
(n  x)  0 x x
5 5 5
P1V1 4 1
Initial number of moles, n    0.1306
RT 0.0821  373
Final number of moles,
x 3 4 6 6 6x  5x
n f  (n  x)   x  x  (n  x)  x  n  x  x  n 
5 5 5 5 5 5
x
nf  n 
5
Pf V 4.2  1
nf    0.137
RT 0.0821 373
x x x x
nf  n   0.137  0.1306   0.1370  0.1306   0.0064 
5 5 5 5
x = 5 × 0.0064  x = 0.032
weight of O2 = x × 32 = 0.032 × 32 = 1.024 gm
13. CO2 is a linear molecule
U = translational contribution + rotational contribution + vibrational contribution
3 1 3
= RT  2  RT  (3N  5)RT  RT  RT  (3N  5)RT
2 2 2
3 5
= RT  RT  (3  3  5)RT  RT  4RT  6.5RT
2 2
 U   T
CV     6.5RT  6.5R  6.5R
 T V T T
For non-linear molecule (SO2 or H2O)
U = translational contribution + vibrational contribution + rotational contribution
3 3
 RT  RT  (3N  6)RT
2 2
=3RT + (3 × 3 – 6)RT = 6RT
U = 6RT
 U   T
CV     6RT  6R  C V  6R
 T V T T
CV of linear molecule is greater than CV of non linear.
CO2 > H2O = SO2.
Hence, correct answer is (a)
dV  1 d1 d 6 7
14. F  Given : V  6   F    6   F   r  F  6r
dr  r  dr  r  dr
6 1
F 7  F 7
r r

3
15. U RT  RT  (3N  5)RT (For linear molecule)
2
C2H2 (Linear molecule) HC  CH
For N = 4, (3N–5) = 3 × 4 – 5 = 7
3 3 19
U RT  RT  7RT  RT  8RT  RT
2 2 2
 U  19  T  19
CV     R    R  9.5R
 T V 2  T V 2
4 3 4 3
d d  8
excluded volume
Ratio   3  3 8
16. molecular volume 4  d 3 4 3
  d
3 2 3
Correct answer is (8)
3RT
17. Root mean square velocity =
M
5RT
Speed of sound =
3M
5RT 5RT 3
1245 km/h =  1245 km/h = 
3M 3M 3
5 3RT 1245  9 3RT

1245 km/h =  km / h 
9 M 5 M
1245  9 5 1245  3  5 18675

 m/s    463.99
5 18 2.236 18 40.247
Correct answer is (463 to 464).
18. As ‘b’ represents (4 × molecular volume per mole)
b(N2) > b(O2) As molecular of N2 is larger than O2.
Correct option is (C)
2RT 3RT Cmp 2

19. Cmp   C rms   
M M C rms 3
20. Cu(s) + 4H+(aq) + 2NO3– (aq)  2NO2(g) + Cu2+ (aq) + 2H2O (l)
6.36
Wt. of Cu = 6.36 gm. So, moles of Cu =  0.1
63.6
0.1 mole of Cu will produce 0.2 moles of NO2(g).
PV = nRT
nRT (0.2)(0.0821)  (298)
V   4.89L
P 1
21. dRT  P(EMM)
dRT
 EMM  where EMM = Effective molar mass of gaseous mixture.
P
Given that: d = 0.2 g L–1; T = 300 K; P = 1 atm; R = 0.082 L atm mol–1 k–1
dRT
Also  X H2 M H2  X N2 M N 2
P
dRT
  (1  X N 2 )M H 2  X N 2 M N 2
P
 X N2  0.11
22. Any gas can behave like ideal gas at extremely high temperature and low pressure, therefore for Cl2 to behave
ideally 200ºC and 0.50 atm is required.
23. From ideal gas low
PV = nRT
W
PV  RT
M
W RT
P 
V M
 RT
P
M
PM

RT
1 atm  32g / mol

0.0821 L atm k 1mol1  300 k
32

24.63
24. According to KTG, root mean square speed of gas is given as
3RT
 rms 
M
3RT 3RT
 O2 :  H 2  :
M O2 M H2
 T is same for both gases ie 300 k
1 1 1 1
Then  O2 :  H2  M : M  32 : 2
O2 H2
 O2 :  H2  1: 4
25. Vander Waal’s equation of state
 n2 
 P  a   v  nb   nRT
v2 
 
Pr essure term
n2
it means a must have units of pressure
v2
n 2a
P
v2
 mol 
2
a  Pa
 m3 
2
a = Pa·m6 mol–2
Also m3Pa = J
 a  m 3  m3 Pa  mol 2
a  m3J mol 2
So option (a) and (d) are correct unit of (a).
26. As from the graph, it is observed that, most probable speed is 500 ms–1.
Temperature = 300 K
2 RT
As  mp 
M
2  8.3  300
 500 
M
 M = 19.9 g/mol
 Molar mass of gas is 19.9 g/mol.
27. (rms)H2  1900 ms 1
(rms) N 2  ?
(rms) H2 M N2 28
   14
(rms) N2 M H2 2
1900
 (rms) N 2
14
= 508 m/s
a 8a
28. Pc  2
, Tc  , Vc  3b
27b 27Rb
8a
R=
27b.Tc
a
Pc =
27.b.b
a
b.Pc =
27b
8.Pc b
R= T
c
8Pc Vc
= 3T
c
29. According to Maxwell Boltzmann probability distribution law,

3/2 Mu 2
1 dN  M  
 f (u)  4   ue 2 2RT
N dU  2 RT 
if speed is x.
3/ 2 2
M x
 M  
4   x e
2 2RT
 2RT 
f(x) = 

Constant=A
 M 2x
f ( x )  A. e 2
x
2RT
or f(x) = A x exp   m x / 2k B T 
2 2
Correct answer is (c)

30. Vanderwaal gas,
Tc = 150K
Pc = 5 × 106 Pa = 5 × 10 × 105 Pa
= 5 × 10 atm
= 50 atm
8a a2
Tc = Pc 
27Rb 27b 2
RTc
b = 8P
c
0.0821 L atm K –1 mol –1 150K

b=
8  5 10 atm
b = 0.03078 L mol–1
if means
1 mol  Has ‘b’ value = 0.03078 L
NA molecules  b = 0.03078 L
0.03078
1 molecules 
6.022 10 –23
= 0.00511 × 10–23
1m = 1010Å
1 m3 = 1030Å3
5.11 × 10–29 m3 = 5.11 × 10–29 × 1030 Å3.
Volume occupied by one molecule = 5.11 × 10 = 51.1Å3
7
CHEMICAL EQUILIBRIUM
HINTS & SOLUTION
1. Fe3O4(s) + CO(g)  3FeO(s) + CO2(g)
t = 0, 1 mol 2 mol 0.5 mol 0.3 mole
at equi (1 – x)
m
(2 – x) (0.5 + 3x) (0.3 + x)
(0.3  x)
 5 atm
PCO2 (0.3  x)  (2  x)
K  Kp  ;1
eq m PCO 2x
 5atm
(0.3  x)  (2  x)
0.3  x
 1 ; 2 – x = 0.3 + x; x = 0.85 mole
2x
 At equilibrium, Fe3O4 (s) = 1 – x = 0.15 mole
CO(g) = 2 – x = 1.15 mole
FeO(s) = 0.5 + 3x = 3.05 mole
CO2(g) = 0.3 + x = 1.15 mole
2. From Van’t hoff equation
H
ln K  C; where C = constant
RT
For endothermic reaction, H = +ve
1 K 2 H  1 1 
 ln K vs graph slope is –ve and ln    
T K1 R  T1 T2 
For exothermic reaction, H = –ve,
So, if T2 > T1, then K2 < K1
3. N 2  3H 2  2NH3 T = 300 K
G 0f  16.4kJ / mole
After 1 hr of mixing PN2  50 bars
PH2 = 2 bars and PNH3 = 200 bars

At constant temperature T, G for the above reaction can be written as,
 P 
2
  NH3  
  P0  
G  Gº  RT ln  3
  PN2   PH2   (where P = 1 barr)
0
 0  0  
 P  P  
 (200)2 
 16.4  103  8.31 300 ln  3
 (50)(2) 
= –16400+8.31× 300 × 2.303 log [100] = –16400 + 8.31 × 300 × 2.303 log 2
= –14672.3 J/mole = 14.67 × 103 J/mole = –14.67 kJ mol–1
4. CH 4 (g)  2O 2 (g)  CO2 (g)  2H 2 O() , Hº = –606.9 kJ mole
–1
At S.T.P., T = 273 K Uº = ?

We have,
Hº  Uº n g RT
(where ng = change in number of moles of gaseous product and reactant).
 –606.9 × 103 = Uº + (1 – 3) × 8.314 × 273
 U–  602.36 kJ / mole
5. From van’t Hoff equation,
K 2 Hº  1 1 
n     ... (1)
K1 R  T1 T2 
Where K1 and K2 are equilibrium constant at temperature T1 and T2 and Hº standard enthalpy of reaction
Given, T1 = 300 K, T2 = 600 K
K2 = 2K1
From equation (1),
2K1 Hº  1 1 
ln    
K1 8.3  300 600 
Hº  1  Hº  1 
 ln 2  8.3  600  ; 0.7  8.3  600 
   
 Hº = 0.7 × 8.3 × 600 J/mole = 3486 J/mole = 3.486 kJ/mole
6. N2O4(g)  2NO2(g)
t = 0 1 mole 0
at eqm (1–0.3) mole 0.6 mole Ptotal = 2 bar
n N 2O 4 0.7 7
Mole fraction of N2O4(g) = n  
N 2O 4  n NO 2 0.7  0.6 13
n NO2 0.6 6
Mole fraction of NO2(g) = n  
N 2O 4  n NO 2 0.7  0.6 13
2
PNO (X NO2 . Ptotal )2 X 2NO 2 .Ptotal
 kP   
2
PN 2O 4 (X N 2O4 .Ptotal ) X N 2O 4
2
6
  2
13
kp    ; k p  0.79
Or, 7
 
 13 
7. N 2  3H 2  2NH3
2
PNH 3
kp  ... (1)
PN2 PH3 2
2 2 2
PNH 3
PNH 3 3
PNH 3
kp   ;3 k p 
PN2  (3PN2 )3 33 PN 2 PN3 2 PN4 2
8. G = Gº + 2.303RT log Q = 2.303 RT log Q – 2.303 RT log Kp
 PSO2 
Q  3 
2
Q 5 102  PSO 2
 PO2 
 2.303RT log  2.303  8.314  480  log   4 4 
Kp 5   10 10  5  10 2 
 103  103  0.2 
= –2.303 × 8.314 × 480 × log 102
= –2.303 × 8.314 × 480 × 2 × log 10
= –2.303 × 8.314 × 480 × 2 × 1 = –18381.256 J mol–1 = – 18.3 kJ mol–1
Correct answer is –18.3 to –18.5
9. 2N 2O5 (g) 
 4NO2 (g)  O 2 (g)
10.8
Number of moles of N2O5 =  0.1
108
At 373 K temperature, pressure is 0.5 atm
V = 10L, So, PV = nRT
PV 0.5  10
Total number of moles (n) =   0.1632
RT 0.0821  373
After decomposition, let x moles of N2O5 decomposed
2N 2O5 
 4NO2 (g)  O 2 (g)
x
0.1 – x 2x
2
x x 3x
Total number of moles = 0.1  x  2x   0.1  x   0.1 
2 2 2
3x
0.1   0.1632 (total number of moles)
2
3x x 0.0632
 0.1632  0.1  0.0632    0.0210
2 2 3
x
= number of moles of O2 = 0.021
2
number of moles of O 2 0.021
PO2   total pressure   0.5 = 0.0643 atm
total number of moles 0.1632
Correct answer is (0.0643 atm)
10. dRT  P(EMM)
dRT
 EMM  where EMM = Effective molar mass of gaseous mixture.
P
Given that: d = 0.2 g L–1; T = 300 K; P = 1 atm; R = 0.082 L atm mol–1 k–1
dRT
Also  X H2 M H2  X N 2 M N 2
P
dRT
  (1  X N 2 )M H 2  X N 2 M N 2
P
 X N2  0.11
11. H = U + PV
H = U + (PV) ... (1)
From ideal gas equation, PV = nRT.
(PV) = ngRT ... (2)
Put value of equation (2) in Equation (1)
H = U + ngRT
1
CO(g)  O 2 (g)  CO 2 (g)
2
ng = 1 – (1/2 + 1)
= 1 – 3/2
= –1/2
 1 8.314  3000 
H = 281.8     
 2 1000 
 281.8  1.2
= –283.0 kJ mol–1
Correct answer is (–283.0 kJ mol–1)
8
IONIC EQUILIBRIUM
HINTS & SOLUTIONS
1. Ba(OH)2  Ba+2 + 2OH–
0.005 mole 0.005 mole 2 × 0.005 mole
2  0.005  1000
 [OH  ]  M  0.1M  101 M
100
1014
 [H  ]  1
 1013 M
10
 pH   log[H  ]   log[1013 ]  13
2. MX(s)  M  (aq)  X  (aq)
ksp = S × S,  S  k sp  S = 10–4 M
MY2 (S)  M 2 (aq)  2Y  (aq)

1/ 3
 k sp 
k sp 2
 S  (2S) ; S    ; S  103 M
 4 
MZ3 (S)  M 3 (aq)  3Z (aq)
1/ 4
 k sp 
3
k sp  S  (3S) ;  S    ; S  102 M
 27 
3. (a) HA + NaOH 
 Na+A– + H2O
(50 ml of 0.2 M) (50 ml of 0.2 M) 100 ml of 0.1 M Na+ A–
Now this weak acid salt will undergo hydrolysis.
A   H 2O  HA  OH 
1 1
We have, pH  7  pK a  log c [C = concentration acid of weak salt]
2 2
1 5 1
 pH  7  (  log10 )  log 0.1
2 2
5 1
 pH  7  
2 2
 pH  9.0
(b) Given, kf  1.8º C / m
1
molality (m) =  1m
1
Tf  0  (2.4)  2.4º C

We have, Tf = imkf
 2.4 = i × 1.8 × 1  i  1.33
MX  Mn+ + Xn–
t=0 1 0 0
at eq. 1 –   
 i = (1 – ) +  +  = 1.5   = 0.50 = 50% dissociation
4. HA  H+ + A–
t=0 C 0 0
at equim C(1–) C C
[H  ][A  ] (C)(C)  2C
ka  k
 a   ... (1)
[HA] C(1   ) 1  
 pH = –log [H+] = 4  [H+] = 10–4 M

At equilibrium [H+] = C
104
 C = 10   –4  0.1
103
(0.1) 2 (103 ) 105

 From equation (1), k a    105
(1  0.1) 0.9
5. HO–  O2– + H+
6. A3X 2  3A 2  2X 3
t=0 C 0 0
at equi, C–S 3S 2S (S = solubility in ‘M’ unit)
1/5
3  K sp 
2
 K sp  (3s) (2s)  S   
 108 
7. [H+] = 10–8 M (from HCl dissociation) + 10–7 M (from H2O dissociation)
= 1.1 × 10–7 M
 pH = – log[H+] = –log(1.1 × 10–7) ~ 6.9
8. Titration curve for strong acid vs. weak base
Here, pehnolphthalein (pH  8 to 10) would be completely useless for strong acid versus weak base.
9. HA + NaOH 
 Na+A– + H2
(50 ml, 0.1 M) (50ml, 0.1 M) (100 ml of 0.05 M)
Na+A– will undergo hydrolysis, A   H 2O  HA  OH 
1 1 1
pH for the above hydrolysis can be approximated as, pH  pK w  pK a  log c
2 2 2
(where c = constant of NaA salt)
1 6 1 1 1 1
 pH  7  ( log(10 ))  log 0.05  7  3  log  10  (log1  (log 2  log10))
2 2 2 20 2
1
pH  10  (0  1.3)  10  0.65  9.35
2
  log[H  ]  9.35  [H  ]  109.35  [H  ]  4.46 1010 M
10. Ag 2S  2Ag   S2
K sp  [Ag  ]2 [S2 ]
1/ 2
 K   1051 
1/ 2
  sp   1025 M
 [Ag ]    2   
 
S
   0.1 
So, for the precipitation of Ag2S, [Ag+] must be greater or equal to 10–25 M.
[NH3 ][H3O  ]
11. NH 4  H 2O  NH3  H3O   k h 
0.1 x x x [NH 4 ]
x.x
 kh   x2 = kh (0.1 – x)
0.1  x
 x2 + kh x – kh (0.1) = 0
k h  k h2  4(1)(0.1 k h ) k h  k h2  0.4k h
 x 
2 1 2
As kh is very small. So, neglecting k 2h .
k h  0.4k h
 (Removing negative sign, as concentration can not be – ve)
2
5.6  1010  2.24 10 10

  5.6  10 11 [neglecting the first term of numerator].
2
12. For any acid base titration, HA + NaOH ® NaA + H2O
1 1
Now, NaA can undergo hydrolysis and will give, pH = 7 + Pk a  log c
2 2
As Conc. of NaA is same in all cases, so higher pka (lower ka) will have higher pH.
For HCN pH will be highest.
Correct option is (d).
13. H 2S(Aq)  H 2O(l )  H3O (aq)  HS (aq)K  10 7
MS(s)  H 2O(l )  M 2 (aq)  HS (aq)  OH  (aq), K = 5 × 10–19
pH = 3, [H+] = 10–3  [H3O+] = 10–3
[H 3O  ][HS ] 107 101

K  107 , [HS–] =  105
[H 2S] 3
10
Ksp = [M2+] [HS–], 5 × 10–19 = [M2+] × 10–5
5 1019
[M 2 ]  5
 5 1014
10
Therefore, solubility of metal sulphide = 5 × 10–14 M.
14.  Ca 2  2F
CaF2 
S 2S
K sp  S  (2S)2
K sp 3.2 1011 3
 0.8  1011  8 1012  2 104
3
S 3 3
4 4
(salt)
15. pH  pK a  log
(acid)
Here, pKa is pK a 2 as NaH2PO4 is acting as acid and Na2HPO4 is acting as salt.
0.1 1
pH  7.21  log  7.21  log  7.21  0.3
0.2 2
pH = 6.9
Correct answer is (6.9 to 7.0)
0.1
16. 0.1 mole of ammonium acetate in 1L of water, [salt]  = 0.1 mole/L
1
0.14 mol
0.14 mole of acetic acid in 1L of water, [acid] = = 0.14 mol/L
1
As it is an acidic buffer solution.
[salt] [0.1] 10
pH  pK a  log  4.75  log  4.75  log  4.75 + (log 10 – log 14) = 4.60.
[acid] [0.14] 14
17. PbI 2  Pb 2   2I 
0.1
– S 0.1 + 2S
2
K sp   Pb 2    I  
From KI,  I   0.1


7.1109  S  101  2S 
2
S can be neglected in comparison to 10–1.

 7.1  109  S  10 2
9
S  7.1 10  10 2
S  7.1  10 7
 7.1
18. This is a acidic boffer composed of weak acid and its conjugate bane.
CH 3COOH  NaOH  CH 3COO  Na   H 2O
pH  pK a  log
Salt 
 Acid 
0.4
pH  4.76  log
0.004
pH  4.76  log102
pH = 4.76 + 2
pH = 6.76
pOH  pK b  log
salt 
19.
 base 
0.1
pOH   log 1.6 10 5   log
0.3
pOH = 4.3
pH + pOH = 14
pH = 14 – pOH = 14 – 4.3
= 9.7
9
PHASE EQUILIBRIUM
HINTS & SOLUTIONS
1. CaCO3 (s)  CaO(s)  CO 2 (g)
Phase = 3
Component (C) = N – E
N = 3 (No. of species)
E = 1 Equilibrium
C=2
F=C–P+2
=2–3+2=1
2. At Pl, F (degree of freedom) = C – P + 2 = 1 – 1 + 2 = 2
At P2, F (degree of freedom) = C – P + 2 = 1 – 2 + 2 = 1
At P3 (triple point), F (degree of freedom) = C – P + 2 = 1 – 3 + 2 = 0
3.

4. As F(minimum) = 0
F=C–P+2
 P = C + 2 – F; C = 1
 P=1+2–F
 P=3–F
 Pmax = 3 – F(minimum) = 3 – 0 = 3
5. (i) Region I has solid (Sb) and melt (Sb + Pb).
 Components(C) = 2 (Sb and Pb)
Phases (P) = 2 (Solid and melt)
(ii) From phase rule, F = C – P + 2
but at constant pressure,
F=C–P+1
At point M, C = 2 [Sb and Pb]
P = 2 [Solid (Pb) and Liquid (Pb + Sb)]
F=2–2+1
F=1
Therefore, variance or degree of freedom at M = 1
H sub
6. log P(solid)  I
RT
1 H
log P vs  Slope =
T R
Now,
Slope of sublimation curve = – 3900
Slope of vapour pressure curve = –2600
 dP  Hs
 
 dT S 3900 3
  R   1.5
 dP  H V 2600 = 2
  R
 dT  V
7. Two component with a eutectic point
In the liquid region,

P = 1, C = 2
F = C – P + 1 (reduced phase rule)
=2–1+1=2
8. Since Clausius Clapeyron equation,
 P  H  1 1   53330Pa  H  1 1 
n  2       n      
 P1  R  T1 T2   5333Pa  R  280.6 333.6 
(Rn10) 8.314J / mol  K n 10 kJ
H    33.822
  n(10) 
H
R
5.66  
10 4 1
K  5.66 
10 4
5.66 10 4
/K mol
K
H
According to Trouton’s rule,  88 J mol–1 K–1
Tb
H
 Tb = Normal Boiling point = 88 J mol 1K 1
J
33.822 103
mol  384.35K
= J or 111.35ºC
88
mol  K
9. H 2O(s)  H 2O(l )
Total number of phase is equal to (2).
Total number of component given = (1)
P = 2; C = 1
Phase rule: F  C  P  2
F = 1 – 2 + 2 = 1 (degree of freedom)
Answer is 2
Hence correct answer is (c)
10.  s  l
Vs > Vl
Using clapeyron equation
 dP  Sm(fusion )
  
 dT fusion Vm(fusion )
Vm (fusion )  Vm,l – Vm,s = negative
Sfusion = positive
 dP   ve
  
 dT fusion  ve
 dP 
    ve
 dT fusion
Thus, melting point decreases with increase in pressure.
l
P s
11. g
T
10
PHYSICAL SPECTROSCOPY
HINTS & SOLUTIONS
1. The regions of the electromagnetic spectrum can be represented as
C-O bond in an organic compound absorbs electromagnetic radiation of frequency 6 × 10 13 Hz. This range
absorb in IR (3 × 1012 – 3 × 1014 Hz)
Correct answer is (a)
1 k 1
2.  ; 
2 µ 
1 m1  m 2
 
m1m 2 m1·m 2
m1  m 2
36
  1.0285 1H 35Cl
35
38
  1.027 1H 37Cl
37
37
  0.52 2D 35Cl
70
1H35Cl > 1H37Cl > 2D35Cl

 1
3. Ev =  V   h e
 2
 1
EV =  V   hc e (V = vibrational quantum number)
 2
For zero point energy V = 0
1
E0 = hc e
2
1
  6.626  1034 J / S  3  108 m / s  44  104 m 1
2
1
=  6.6  3  44 1022
2
E0 = 435.6 × 10–22 J
for 1 mole H2 molecule energy will be
Em = 435.6 × 10–22 J × 6 × 1023 mol–1
= 26136 J mol–1
= 26.13 kJ mol–1
4. For a molecule to be microwave active, it must be a permanent dipole. (Polar in nature)
NO2 OH OH
Cl H NO2
, , ,
So H Cl CH3
NH2
(A) (B) (C) (D)
Non polar Polar Polar Polar
So B, C and D are microwave active molecules.
 HCl µDCl
5. 
 DCl µHCl
71
37.5  1.9466
35.5
36.5
= 1.395
 Correct option is (c)
6. 2B = Spacing between energy line
2B = 3.8626 cm–1
B = 1.9313 cm–1
h
B=
82 Ic
h 6.626 10 –34
I= 
82 Bc 8  3.14  3.14 1.9313  3 1010
= 0.0144 × 10–44 kg m2
I = µr2
0.0144 10 –44
r2 =
11.136 10 –27
= 0.00130 × 10–17
r2 = 1.3 × 10–20 m2
= 1.14 × 10–10 m
= 1.14Å
EJ+1 – EJ = 2B J + 2B
7.
y m x c
slope = 2B, intercept = 2B
 slope B, intercept B
1
Now B 

and let µ´ = reduced mass of X´Y´
µ = reduced mass of XY
Now as X´Y´ is heavier isotopic analogue  µ´ > µ
 B´ < B
 Slope as well as intercept both will be higher for XY.
 d is the correct option.
11
NUCLEAR CHEMISTRY
HINTS & SOLUTIONS
1. 131 is used to locate brain tumors.
53 I

A 3 particle in succession
A 12
2. 86 Ra  82 X
Atomic number 82 is for Pb and it belongs to group 14.
3. t = 0, activity (A0) = N0 = 23 dis/min
1
t hr , activity (At) = Nt = 11.5 dis/min
2
1 A0 1
As after t  hr , activity A t   t  t1/ 2  hr = 30 min
2 2 2
0.693 0.693
 N0 = 23 dis/min  t N 0  23  N 0  23
1/2 30
23  30
 N0   1000 atoms
0.693
4. For the given radioactive nuclide
t1/2 = 20 years, Initial activity (A0) = N0 = 6400 dis/min
t = 100 years, = 5t1/2 Final activity (At) = ?
Nt At 1
We have, N  A  n
0 0 2
100 A0 6400 6400
Number of t1/2 'n '  5  At  n
 5
  200dpm
20 2 2 32
215 emission 211 emission 211
5. 84 Po   82 X   83 Y [Y = Bi]
(i) Valence shell electronic configuration of Y is, 6s2 6p3
(ii) X belongs to group 14 (carbon group)
Y belongs to group 15 (Nitrogen group)
234 230
6. 92 U 
 90 Th  42 He ;  - particle is 42 He
7. (i) 14 4
 11H  17
7 N  2 He  8 O (ii) 7 1
 84 Be
3 Li  1H 
241 4 243
8. 97 Bk  210 n
95 Am  2 He 

238 206
9. 92 U 82 Pb  x 24 He  yo1
Let ‘x’ = number of alpha-particles emitted
y = No. of beta-particles emitted.
Conserving the number of nucleons-
238 = 206 + 4x + y(0)
4x = 238 – 206 = 32
x=8
Now, 92 = 82 + 8(2) + y(–1)
92 = 82 + 16 – y
y = 98 – 92 = 6
Number of beta particles = 6
Total steps = 8 + 6 = 14
10. 10B has high absorption cross-section for thermal neutron, even for high energy neutron (104–106 eV) it is more
effective than any other nuclide. The accompanying (n, ) reaction produces Li and He which are non-radioactive
and harmless.
10 1 7
5 B  0n 3 Li  42 He

This fact recently has used in B-10 neutron capture therapy of brain tumours.
238 234
11. 92 U 
92 U
Change in A = 238 – 234 = 4.
Hence, only one ‘’ is emitted. Now increases in z = 92 – 2 + 2 = 92
Hence, two  particle will be emitted
t1/ 2  activity of fresh sample 
t ln 
12.
0.693  activity of dead sample 
5730 yr  52 / 2 
 t  0.693 ln  24 / 3  (count per minute)
 
5730 year  26 
t ln    9745.58 year..
0.693 8
13. 214  210  210
84 Po  82 X 83 X
Therefore, number of neutron = 210 – 83 = 127.
2.303 100
14. K log A  P
300 20
2.303
  0.6990 t=0 N
300
= 0.00536599 min–1 t = 300 min N – 0.8 N = 0.2 N
0.693
t1/2 =
k
0.693
=  129.15 min
0.00536599
14 14 0
15. 6 C  7 N  1e hence – decay
14 14 0
8 O  7 N  1e Positron decay
Hence correct answer is (d)
A  A 0e kt
A0
 A 0e  k(29.8)
4
1
 e  k(29.8)
4
1
ln   k(29.8)
4
1.3862   k(29.8)
.38 1
k hr
29.8
k = 0.0465 hr–1
17. Radioactive decays occur via 1 order kinetics
A  A 0 e t
A = 0.10 A0
0.10 A 0  A 0 e t
t = 4600 min
4600 230
t hr  hr
60 3
230

0.1  e 3
taking ln both sides

  230
ln 0.1  
3
 230 2.303  3
2.303log101     
3 230
 = 0.03 hr–1.
18. Q-value = m × 931.5 MeV.
= (mR – mP) × 931.5
= (4 × 1.007825 – 1 × 4.002604) × 931.5
= 0.0287 × 931.5
= 26.7 MeV.
12
REDOX REACTION
HINTS & SOLUTIONS
1.

2 1 2.5
2. Na 2 S 2 O3   Na 2 S4 O6
2
Net change in oxidation number of ‘S’ per mole of Na2S2O3( O.S.) = 0.5 × 2 = 1
mol. wt M
 Equivalent w.t. =  M
nf 1
3. 2, P = O bonds,

4. +2 oxidation state, CrX2, MoX2 (where X = F, Cl, Br, I)
+3 oxidation state, CrX3, MoX3, CrO3
+6 oxidation state, CrO3, CrO42–, MoO3
5. Iron (II) ammonium sulfate (NH4)2Fe(SO4).6H2O ions produced by complete dissociation of Mohr salt
 2NH 4  Fe 2  2SO 42
(NH 4 ) 2 Fe(SO 4 ) 2 6H 2O 
Total ions = 5
6. Methylene blue is an indicator used in redox titration.
In oxidised form it is blue and will turn colourless if exposed to reducing agent.
7. Hypophosphorus acid is H3PO2.
It structure is
Hence, number of P-H bonds is two.

O O
8. O S S S S O tetrathionate ion is S4O62–.
O O
Number of S-S bond = 3.
Hence correct answer is 3.
6
9. Fe2  Cr2 O72  Fe 3  2Cr 3
No. of g equivalents of Fe2+ = No.of g equivalents of Cr2O72–
(n f ) 6
Cr2O72 
(n f ) 1
Fe2
(n f  M  V)  (n f  M  V)
Fe2  Cr2O72
1 × 0.3 × V = 6 × 0.1 × 20
0.3 V = 12
12
V= = 40 mL
0.3
10. Number of lone pairs in phosphonic acid (Phosphorous Acid) is
O
P
H O H
H O
Correct answer is 6
11. [PnO18]6–
Metaphosphoric acid with empirical formula HPO3 basic unit is [PO3]–1,
Given formula [PnO18]6–
Here number of oxygen atom is 18.
So, multiply basic unit by 6 to make number of oxygenation equal to 18.
[PO3]1– × 6 = [P6O18]6–
O O
O
P O P O
O O O
O P P
O O O
O
P O P
O O
O O
REDOX (GATE) PREVIOUS YEAR

12. At equivalence point,
N KMnO 4 VKMnO 4 = NFe oxalate VFe oxalate
N KMnO 4 VKMnO 4 = (MV)Ferrous oxalate × nf
1  VKMnO4 = 3 × 0.01
VKMnO 4 = 0.03 L = 0.03 × 103 cm–3 = 30cm3

13. O O
HO OH
S S S
O S S O
Correct option is (4)
13
QUANTUM CHEMISTRY
HINTS & SOLUTIONS
8 x y z
1.  3
sin sin sin ... (1)
a a a a
Schrodinger equation is, Ĥ  E
2 2 2 2 
ˆ           V
H ˆ
Time independent t, 2m  x 2 y 2 z 2 
 2   2 2 2  
        V̂    E
2m  x 2 y 2 z 2 
   
As V = 0,
 2   2   2  2  
 2m  2  2  2   E
 ... (2)
 x y z 
Substituting  from equation (1), in L.H.S. of equation (2),
  x   y   z  
d 2 sin d 2  sin  d 2 sin  
2  8 y z  
a  8 x sin z  a  8 x z  a 
  sin .sin  3 sin . .  3 sin .sin 
2m  a 3 a a dx 2 a a a dy2 a a a dz 2 
 
= E
2
2 8   x y z 
       3sin .sin .sin  E
2m a 3 a  a a a 
3 2 2  8 x y z 
  sin .sin .sin   E
2ma 2  a 3 a a a 
3 2 2
   E
2ma 2
3 2 2 3h 2  h 
 E 2
 2    2 
2ma 8ma
1 i2 1 i2
2.  e and *  e
2 2
Since,  *  |  |2 = Probability density
1
Probability in interval ‘d’ =  * d  d
2
r
 r   2a
3. (a)    2   e 0
 a0 
r
 r   2a 0
   A  2  e , where A is proportionality constant.
 a 0
As  is function of ‘r’ only, so probability of finding electron at distance ‘r’ is given by
2 r
r   2 2
P(r) |  | 4r ; P(r)  4A r  2   e a 0
2 2
 a0 
dP(r)  d 2 P(r) 
0
For probability to be maximum, dr  = 0 and dr 2 
r  rmp  rr mp
dP(r)
 0
dr
2r
   r 
2
 1  2 r   1  2  r  
2
2 a0  2r  2    2    r  2       r  2     0
 4A e   a0  a0  
  a0   a0   a0   
2r

2 a0  r   r  2r r  r 
 4A e r  2   2  2      2     0
 a0    a0  a0 a0  a0 
2r
 r  a  r 2 6r 
 8r  2   e 0  2   4  0
 a0   a 0 a 0 
 r  0, 2a 0 , (3  5)a 0 , (3  5)a 0
But r cannot be ‘0’ and  because at nucleus and at infinite distance P(r) = 0
  
 r  2a 0 , 3  5 a 0 , 3  5 a 0 
d 2 (P(r)) 
 0
For P(r) to be maximum at any of the above values it must satisfy, dr 
r  rmp
d 2 (P(r)) 
 0
 dr   at r = 2a0; P(r) will be minimum
r  2a 0
d 2 P(r) 
 0
dr  ,  Maximum
r (3 5 )a 0
d 2 P(r) 
 0
and dr   maximum
r (3 5)a 0
 
 rmp  3  5 a 0 and 3  5 a 0  
r
 r   a0
For node, A
  0;  2  e 0
 a0 
Only possible solution, r  2a 0  r(node)  2a 0
(b) Let  be the wavelength of wave required to exite electron from ground state to 1st exited state.
 E  E 2  E1
hc 22 h 2 12.h 2 hc 3h 2
    ; 
8me L2 8me L2  8me L2
8me L2c 8  9.11031  (109 )2  3 108

   m = 1.098×10–8 m = 0.11 nm
3h 3  6.625 1034
4. For wave function, normalization constant ‘A’ can be calculated by applying normalization condition as  = Aeim
 2  2
1
  d  1  A
2 2
For  to be normalized,   * d  1  A (2)  1  A 
0 0
2
 2 1  1 1  1 1 2 1  2 3   2 2   0 1 
5. [A, B]  AB  BA         
 0 1  0 1  0 1 0 1  0 1   0 1   0 0 
0 0
As, [A, B] = AB – BA   
0 0
 A and B do not commute.
3 3 1 1 3
6. When S  , then ms can have value, from +s to –s, ms =  ,  ,  , 
2 2 2 2 2
3
As 4-values of ms are possible for S = , so 4-electrons can be accomodated, without violating Pauli’s exclu-
2
sion principle.
7. Wave function for a particle in 3-D cubic box (box side = L)
8 n x x n y y n z z
 sin sin sin
L3 L L L
where nx, ny, nz are 3-quantum numbers.
8. From Heisenberg’s uncertainity principle
h
xp x ~
2
Maximum uncertainity in measurement of position can be approximated to box length ‘L’

h
So, x  L  p x ~
2L
Momentum of particle of mass ‘m’ can be approximated to error in momentum measurement,
So, Energy of particle (E) = K.E.
p 2x  h  h2
 E  Px  2L   E
2m 8mL2
1 1 1 
9. If  is the eigen value for the matrix 1 0 2  , then
 
1  1 
1  1 1  
1  2  0
1 1 1  
Expanding the determinant, we get (1 – ) (– + 2 – 2)–1(1 –  + 2)+1 (–1 + ) = 0

    2  2   2   3  2  1    2  1    0
  3  2 2  3  6  0
 3  2 2  3  6  0
As one of eigen value is ‘2’. So, ( – 2) will be one of its factor,
 (  2)( 2  3)  0;   2, 3,  3
10. As only x = Ar2, do not satisfy the differential equation, so it is not the solution.
12. As eigen value represents the property (e.g. energy, momentum etc.) of real physical quantity. So  must real.
J(J  1) 2 102

13. EJ   [I  mr 2 ]
2I mr 2
J(J  1)2 10 2

   J4
2mr 2 mr 2
 Degeneracy for rotational quantum number.
(gJ) = 2J + 1 = 2 × 4 + 1 = 9
 r 
 
1 a
14. (a)  (r)  e  0
a 30
As (r) is a function of radial distance from nucleus (i.e. ‘r’), only and has no angular dependence (i.e. dependence
on  and ).
Also (r) has no radial angular node, so (r) can only be ‘1s’ orbital.
Mean radius =
r    *(r)r (r)d
volume
[As   *(r)(r)d  1
, because (r) is normalised)
volume
  2 r

1 1
 r     e r / a 0 .r. e a 0 r 2dr sin dd
r 0 0 0
a 0 a 30
 2r  2

1 1 3
 r  
3
r e a0
dr  sin d  d; r  .[  cos ]0 []02 
a 30 r 0  0 0 a 30  2 
4
 
 a0 
1 6a 04 3
 r  3 16 .2.2; r  2 a 0
a 0
(b) Probability of finding electron in a spherical shell of thickness ‘dr’, at a distance ‘r’ from the nucleus is given
by
2r 2r

2 1 a0 4r 2 a0
P(r)dr  4r 2 (r) dr  4r 2 e dr  e dr
a 30 a 30
As at r = 0, probability P(r) = 0 and also
As r  , probability P(r) = 0,
So, there will exist a ‘r’ for which probability will be maximum,
For P(r) to be maximum
 2r 
dP(r) d  4 2  a0 0
 0; r e
dr dr  a 30 
 
2r 2r
4 
a0  2r 2  8 
a0  r 
 e  2r    0; r e 1    0
a 30  a0  3
a0  a0 
As, r = 0, (no maximum)
2r r

a0 (this is zero only at r = ); 1  a  0; r  a 0
e 0 0
 Most probable distance = a0.

3/ 2
1  1   r   r 
14. Given  2m (r, , )     2   exp   
32  a 0   a0   2a 0 
(i) As the above function is independent of angle (i.e.  and ), So, []2 (probility density) is also independent of
angle. This is only possible for s-orbital (which is spherical)
  = 0, m = 0
(ii) For radial node;  2,,m (r, )r r 0

node
and  must have different sign (i.e. + ve or –ve for r < rnode and r > rnode)
 rnode 
  2, ,m (r, , )  0 only when  2  0
 a0 
 r 
[because exponial term exp    is zero only when r  ].
 2a 0 
 rnode = 2a0
h 2 d 2 (x)
15. Schrodinger equation,  E(x)
82 m dx 2
Solution this equation is (x) = eikx = cos kx + i sin kx
h 2 d 2 (x) d 2 (x) 82 mE

(a) Expression for energy ‘E’  E(x);  (x)  0
82 m dx 2 dx 2 h2
d 2(x) 82 mE 82 mE

 k 2(x)  0 k2  ; k
dx 2 h2 h2
(Solution is eikx = cos kx + i sin kx for x-direction)
Particle is free so potential is constant. Since the particle is not subjected to any external force. Its potential
energy assume zero. There is no boundary condition and no restriction.
k 2h 2
Energy, E 
82 m
h d kh
The function e+ikx are eigen function of the linear momentum operator with eigenvalues .
2i dx 2
kh 82 mE h
Expression for momentum    2mE . So, momentum is 2mE .
2 h2 2
2
(b) As we know from quantum mechanics, k

We have derived above that,
k 2h 2
E ... (1)
82 m
p2
and E ... (2)
2m
p2 k 2h 2 2
 putting k 
2m 82 m 
2
 2  2
2   h h
p    that gives 
 p
2m 8 2 m
1
16. y = xe x 2 minimum at x =  second derivative of the function.
2
dy 2 2 2 2 2
 x(2x)e  x  e  x  2x 2 e x  e  x  (1  2x 2 )e  x
dx
d2 y 2 2
 e  x (4x)  e  x (2x)(1  2x 2 )
dx 2
1 1/ 2  1
Put x =  =e ( 2 2)  e1/ 2 (  2) 1  2. 
2  2
   
 e1/ 2 2 2  e1/ 2  2 (1  1)  2 2e1/ 2  0  2 2e1/ 2
 2r  r 2   r
a0
17. Un normalized wave function (r, , ) = sin  cos   a   a   e
 0  0 
Number of radial node.
Radial node is n –  – 1 for given function n = 3, l = 1
 r 
Because one node at  2    0  r = 2a0
 a0 
r
 r  r a
Function written as sin  cos   2   e 0
 a0  a0
zr r
 
Function is He+ because the part na 0 a0
e e
z r
 
na 0 a 0
z
1
n
z=n
z=3
Function related to 3px orbitals.
 h2 d 2 h 2  2 x 2  x 2 h 2 x 2
18.  2 2
  e  C e
 (8 m) dx (22 m)  42

19. pˆ x xˆ  xp
ˆ ˆ x is commutator of [px, x]
[px, x]
pˆ x xˆ   xp
ˆˆx
 
i xˆ   xˆ  i 
x x
  x  
i  xˆ     ixˆ
 x x  x
  
ixˆ  i  ixˆ   i     i or i
x x
Correct answer is (a, b)
d 2 2
20. Ae ax   A2xe  ax  0 ; xeax 2  0  at x  0
dx
x = 0, x = 
Let at ,  = 0
So, x = 0
21. 3pz
n = 3, l = 1
Number of radial node = n – l – 1 = 3 – 1 – 1 = 1
Number of angular node = l = 1
Correct options are (A) and (C).
22. For particle in 1-D box of length 0 to l acceptable wave function is
  (x 3 (x  l ))
only this wave function satisfy boundary condition because when x = 0,  = 0 also when n = l,  = 0.
23. (B) n = 4 principle quantum number
l = 0 means S orbital and for S orbital M   1 is not valid or allowed.
(C) n = 3
l=3
M   3
Radial Nodes = n – l – 1 can never be negative
=3–3–1
=3–4
=–1
So (C) is not allowed.
y  x  e x
2
24.
y  e  x  x 2xe  x  0
2 2
y  e  x 1  2x 2   0
2
  
never 
zero Possible
1 – 2x2 = 0
2x2 = 1
1
x2 
2
1
x
2

y  2xe  x 1  2x 2  e x  4x  
2 2
 e  x  2x 1  2x 2  4x   
2
 

 e x 2x  4x 3  4x 
2
e  x 4x 3  6x
2
1 1
 
2 2
2 2
 1   1 
    1 3 1      1 3 6 
e  2  4    6  e  2  4  
  2  2    2  2 
   
 4 2 6   42 6 
e1/ 2    e 1/ 2   
 2 2 2  2 2 2
always(  )   always(  )  
 2 6   4  e1/ 2 4
e1/ 2    e 1/ 2    
 2 2  2 2
4 1
e1/ 2 always negative maximum at
2 2
1
always potitive minimum at 
2
1 2
25. A 
2 1
A  I  0
1 2   0 
2 1    0  
   
1  2
0
2 1 
1   2  4  0
 2  1  2  4  0
 2  2  3  0
 2  3    3  0
    3   1   3   0
   1   3  0
  1, 3
Correct options are (a, d)
a 0n2
26. Bohr radius rn   a 0  52.9 pm 
z
a 0  32
r3 
1
r3 = 9a0
r3 = 9 × 52.9 pm
r3 = 476.1 pm.
2
27. Square planar : dsp : d x2  y2
Trigonal Bipyromidal : sp d  d z2
3
28. Radical node = n – l – 1
(a) node = 3 – 2 – 1 = 0 node = 2 – 1 – 1 = 0
(b) node = 3 – 0 – 1 = 2 node = 2 – 0 – 1 = 1
(c) node = 3 – 1 – 1 = 1 node = 2 – 1 – 1 = 0
(d) node = 3 – 1 – 1 = 1 node = 2 – 1 – 1 = 0
29. For 1 – D box position of internal nodes is for n > 2
Where m = interger Omn
mL
n
For every integer of m and every value of n > 2
We get our positions
n Position node of
2 L
2
3 L 2L
,
3 3
4 L 2L 3L
, ,
4 4 4
14
ELECTROCHEMISTRY
HINTS & SOLUTIONS
Fe3  e – 
 Fe2 , G1  (1)(F)(E 0 ) ...(i)
Fe3 /Fe2
1.
Fe2  2e – 
 Fe, G 2  (2)(F)(E 0 2 ) ...(ii)
Fe /Fe
(i) + (ii) Net reaction: Fe+3 + 3e–  Fe,G3 = G1 + G2

0 0 0
 –(3)(F) (E Fe3 / Fe )   F[E Fe3 / Fe2  2E Fe2 / Fe ]
0 1
 E Fe3 / Fe  [0.77V  2( 0.44V)]  0.036V
3
0
 E Fe3 / Fe  0.036V
2. Only statement (a) is correct
Free energy decreases only in case of galvanic cells
In case of electrolytic cells, a non spontaneous redox takes place
Correct answer is (a).
3. As Keq value is very large, so the cell reaction almost goes to completion.
Zn  Cu 2  Zn 2  Cu
4. Q  2H   2e  QH 2 , Eº = 0.699V
0.059 1
E cell  E 0cell  log  2
n [H ]
0.059
 0.817  0.699  (2 log[H  ]) [n = 2] [ pH   log[H  ]]
2
 pH  2  The dissociation of QH2 is not complete. It behaves as weak acid.
5. E0  0.762 and E 0 2  0.340V

Zn 2 / Zn Cu / Cu
So, in the net cell reaction Zn will get oxidized and Cu+2 will get reduced.
Cell reaction: Zn  Cu 2  Zn 2  Cu
Cell Zn(s) | Zn 2 (aq.) || Cu 2 (aq.) | Cu(s)
For spontaneous, conversion of chemical energy to electrical energy.
E 0cell  E 0 2  E 0 2  0.340  ( 0.760)  1.10V

Cu / Cu Zn / Zn
From Nernst cell equation at 25ºC,
0.06
E cell  E 0cell  log k
2
At equilibrium , Ecell = 0, so
E 0cell 1.10
 log k    36.67
0.03 0.03
6. From relation derived, in part (ii), we have
 E 
S  nF  
 T P
S
 dE  dT (at constant pressure)
nF
 On integration
E2 T
S 2
 dE 
nF T
dT [ Given S is independent of temperature]
E1 1
S S
 E 2  E1  (T2  T1 )  E85  E 25  [(273  85)  (273  25)]
nF nF
96.5
 E 85  1.26   60  E85 –1.26  0.03
2  96500
 E85 = 1.23 V Ans.
7.  2NH 4  SO 4 2
(NH 4 ) 2 SO 4 
m 2m m
If molality is m.
m1z12  m 2 z 22 2m  4m 6m
I  ; I  3m  I [I is equal to one same as KCl]
2 2 2
1 mol
I = 3m; m =
3 kg
H 2 (g)(Pt) HCl(aq) H 2 (g)(Pt)
8. p H2  p1 pH2  p2
RHE 2H   2e  H 2 (P2 )

LHF H 2 (P1 )  2H   2e  reduction
Overall, H 2 (P1 )  H 2 (P 2 )
RT P2
Nernst equation, E  Eº  ln
2F P1
RT P
E= ln 1 ( Eº  0)
2F P2
9. A: Zn  Zn 2  2e
C: MnO  
4  5e  8H  Mn
2
 4H 2O
5Zn  2MnO4  16H   5Zn 2  2Mn 2  8H 2O
n = 10
nEº 102.4
So, K  10 0.06 = 0.06
eq 10
= 10400
x = 400
10. K   e  K
0.0591 1
E  Eº  log 
1 (K )
2.303RT 1
E1  Eº  log
F x
2.303RT 1
E 2  Eº  log
F 20x
Now, E = E2 – E1 (Eº = 0)
RT 1
 E  2.303 log
F 20
2.303RT 2.303RT
E   (log1  log 20)   [0  (log 2  log10)]
F F
2.303RT 2.303RT
E   (0.3010  1)   ( 1.3010)
F F
= +59(1.3010) = 76.7 = 77 mV
Fe3  1e 
 Fe2 0.77 (i)
11. Fe 2 
 2e 
 Fe 0.44 (ii)
Fe3  3e 
 Fe E3 (iii)
G3 = G1 + G2
  n 3FE 3o  n1FE1o  n 2 FE o2
n1E1  n 2 E 2 1 0.77  (0.44  2) 0.77  0.88 0.11
E3      0.036
n3 3 3 3
Correct answer is (–0.03 to –0.04).
12. Method - 1:
Amount of charge passed = i × t = 0.5 × 60 × 60 coulomb.
0.5  60  60
Number of Faraday passed = = 0.01865
96500
Since, two Faraday disolves 1 mole of Cu.
1 0.01865
Therefore, So, 0.01865 Faraday’s will dissolve = moles of Cu
2
0.01865
So, weight of Cu dissolved =  63.6 = 0.59 gm
2
Method-2:
E 3.6
w = z × i × t; Z ; E Cu 
96500 2
63.6
w × 0.5 × 60 × 60 = 0.59 gm
2  96500
13. Sº  n  F   where  = temp. coefficient
= 2 × 96500 × 1.45 × 10–4 Pb(s) + Hg2Cl2(s)  PbCl2(s) + 2Hg(l)
–1
Sº = 27.985 J K mol –1
total number of electron transfer in above reaction is two. Hence n = 2

14. Ce 4  Fe 2  Ce3  Fe3
Eo  1.44V
Ce4 / Ce3
Eo  0.77V
Fe2 / Fe3
E ototal  1.44  0.77 = 0.67

n  Eº
log10 k   RT 
RT Given   0.0257V 
2.303  F 
F
1 0.67
log10 k  log10k = 11.32
2.303  0.0257
 E 
15. Hº  nFEº  nFT  
 T P
 E  5 1
   5 10 V k
 T P
Eº = 1.02 V; T = 300 K
For cadmium cell, number of electron exchanged n = 2
Hº = –2 × F × 1.02 + 2F × 300 (–5 × 10–5)
= –2.04 F – 0.03 F
= –2.07 F
= –2.07 × 96500
= –199755 J mol–1
= –199.75 kJ mol–1
16. LaCl3  La 3  3Cl
 0LaCl3   0La 3  3 Cl
0

 209.10  10 4   3  76.35 10 4 

 0LaCl3  438.05 104
3 0Cl 229.35 104
t Cl    0.52
 0LaCl3 438.05 104
17. Ca3(PO4)2  3Ca2+ + PO43–
1
I
2
 mi zi 2
1
0.03  2   0.02  3  
2 2

2  
1
  0.03  4  0.02  9 
2
1
  0.12  0.18
2
1
  0.30   0.15
2
log    0.509  z  z   I
 0.509  2  3  0.15
r  0.066
18. Cathode
Cu2+ + 2e–  Cu (reduction)
Anode
Zn  Zn2+ + 2e– (Oxidation)
overall reaction
Cu2+ + Zn  Cu + Zn2+
E ocell  E o  Eo
Cu 2 /Cu Zn 2 /Zn
= 0.34 + 0.76
= 1.1V
Gº   nF E ocell
–2 × 96500 × 1.1
= –212, 267
or –212.267 kJ mol–1
Gº  212 kJ mol1
19. log ± = –A | Z+ Z– | I
log ± = –0.509 | (2) (–1) | I
Calculation of Ionic strength (I)
 
CaCl2  Ca 2(aq)  2Cl(aq)
0.004 – –
– 0.004 0.008
1
I= m i z i2
2
1
=  (0.004)(2) 2  0.008( 1) 2 
2
1
= [0.016  0.008]
2
= 0.012
log ± = –0.509 | 2 (–1) | 0.012
log ± = 0.773
Correct answer is (0.772 – 0.775)
TOPIC WISE
PYQ
(Inorganic)
1
PERIODIC PROPERTIES
IIT JAM 2021
1. For Na+, Mg2+, Al3+ and F–, the CORRECT order of ionic radii is
(a) Al3+ > Mg2+ > Na+ > F– (b) Al3+ > Na+ > Mg2+ > F–
(c) Na+ > F– > Mg2+ > Al3+ (d) F– > Na+ > Mg2+ > Al3+
(a) n = 3; l = 2; ml = 0 and n = 2; l = 1; ml = 0
(b) n = 3; l = 0; ml = 0 and n = 2; l = 0; ml = 0
(c) n = 3; l = 1; ml = 1 and n = 2; l = 1; ml = 0
(d) n = 3; l = 1; ml = –1 and n = 2; l = 1; ml = 0
IIT JAM 2018
3. With respect to periodic properties, the CORRECT statement is
(a) Electron affinity order is F > O > Cl
(b) First ionisation energy order is Al > Mg > K
(c) Atomic radius order is N > P > As
(d) Ionic radius order is K   Ca 2   Mg 2
4. Which of the following set(s) of quantum numbers is (are) NOT allowed?
(a) n = 3, l = 2, m1 = –1 (b) n = 4, l = 0, m1 = –1
(c) n = 3, l = 3, m1 = –3 (d) n = 5, l = 3, m1 = +2
IIT JAM 2017
5. The correct order of the boiling points of the compounds is
(a) CH4 > SiH4 > SnH4 > GeH4 (b) SiH4 > CH4 > GeH4 > SnH4
(c) SnH4 > GeH4 > CH4 > SiH4 (d) SnH4 > GeH4 > SiH4 > CH4
IIT JAM 2016
6. Among the following, the compound that has the lowest degree of ionic character is
(a) NaCl (b) MgCl2 (c) AlCl3 (d) CaCl2
IIT JAM 2015
7. The common feature(s) of Rb+, Kr and Br– is/are that they
(a) have same number of valence electrons
(b) have same magnitude of effective nuclear charge
VIGYAN VRIKSH |Inorganic chemistry (IIT-JAM)
(c) have same magnitude of first ionization potential
(d) are isoelectronic species
IIT JAM 2014
8. The energy of an electron in a hydrogenic atom with nuclear charge Z varies as:
(a) Z (b) Z2 (c) 1/Z (d) 1/Z2
9. Among the following, the element having maximum inert pair effect is
[Given: Atomic number of Ge = 30, Pb = 82, Si = 14 and Sn = 50]
(a) Ge (b) Pb (c) Si (d) Sn
IIT JAM 2011
10. The pair of semimetals in the following is:
(a) Al, Si (b) Ge, As (c) Sb, Te (d) Ca, B
11. The correct order of acidic character is:
(a) Al2O3 > MgO > SiO2 > P4O10 (b) P4O10 > Al2O3 > MgO > SiO2
(c) P4O10 > SiO2 > Al2O3 > MgO (d) SiO2 > P4O10 > Al2O3 > MgO
IIT JAM 2010
12. Among lithium, nitrogen, carbon and oxygen, which element has the highest first ionization potential?
(a) Lithium (b) Nitrogen (c) Carbon (d) Oxygen
13. Which one of the following has the highest lattice energy?
(a) LiCl (b) CaCl2 (c) LiF (d) KCl
IIT JAM 2009
(a) 1s (b) 2p (c) 3d (d) 4d
15. The acceptable valence shell electronic arrangement is:
(a) (b)
(c) (d)
16. Identify the correct option:

In the periodic table, on moving from left to right along a period,
(a) The atomic size of the element increases.
(b) The first ionization potential of the element decreases.
(c) The oxide of the element becomes less basic
(d) The oxide of the element becomes more basic.
IIT JAM 2008
17. The correct order of the mean bond energies in the binary hydrides is:
(a) CH4 > NH3 > H2O > HF (b) NH3 > CH4 > H2O > HF
(c) HF > H2O > CH4 > NH3 (d) HF > H2O > NH3 > CH4
IIT JAM 2007
18. The correct order of the ionic radii is:
(a) In3+ > Sn4+ > Sr2+ > Rb+ (b) Sn4+ > In3+ > Sr2+ > Rb+
(c) Rb+ > In3+ > Sr2+ > Sn4+ (d) Rb+ > Sr2+ > In3+ > Sn4+
19. The correct valence shell electronic configuration of the element with atomic number 22 is
(a) [Ar]4s23d2 (b) [Ar]3d4 (c) [Ar]3d24s2 (d) [Ar]4s24p2
IIT JAM 2006
20. The decreasing order of the first ionization energy of the following element is
(a) He > H > Be > B (b) Be > B > H > He
(c) H > He > Be > B (d) B > Be > He > H
21. The decreasing order of ionic nature of the following compound is:
(a) LiI > NaBr > KCl > CsF (b) LiI > KCl > NaBr > CsF
(c) CsF > NaBr > KCl > LiI (d) CsF > KCl > NaBr > LiI
IIT JAM 2005
22. The compound having the highest melting point is:
(a) LiCl (b) LiF (c) LiI (d) LiBr
23. The decreasing order of the first ionization energy of the following elements is:
(a) Xe > Be > As > Al (b) Xe > As > Al > Be
(c) Xe > As > Be > Al (d) Xe > Be > Al > As
ANSWER KEY
1. (d) 2. (a) 3. (d) 4. (c) 5. (d) 6. (c) 7. (a,d)

8. (b) 9. (c) 10. (c) 11. (c) 12. (b) 13. (b) 14. (d)
15. (c) 16. (c) 17. (c) 18. (d) 19. (a) 20. (a) 21. (d)
22. (b) 23. (c)
2
CHEMICAL BONDING
IIT JAM 2021
1. Hybridization of the central atoms in I3–, ClF3 and SF4, respectively, are
(a) sp3d, sp2 and dsp2 (b) sp, sp2 and sp3d
(c) sp, sp3d and dsp2 (d) sp3d, sp3d and sp3d
IIT JAM 2020
2. The geometries of the species [Br3]+, [Br3]– and [BrF3] are, respectively
(a) linear, trigonal bipyramidal and trigonal bipyramidal
(b) linear, linear and trigonal planar
(c) tetrahedral, trigonal bipyramidal and trigonal bipyramidal
(d) tetrahedral, trigonal pyramidal and trigonal planar
IIT JAM 2019
3. Correct trend in the bond order is
(a) O 2  O 22  O 2 (b) O 2  O 2  O 22 (c) O 22  O 2  O 2 (d) O 2  O 2  O 22
4. The correct statement regarding the observed magnetic properties of NO, O2, B2 and C2 in their ground state is
(a) NO, B2, and C2 are paramagnetic (b) B2, O2 and NO are paramagnetic
(c) O2, C2 and NO are paramagnetic (d) O2, B2 and C2 are paramagnetic
5. The correct statement(s) about NO2, NO2+ and CO2 is/are
(a) Both NO2 and CO2 are paramagnetic.
(b) NO2 is paramagnetic and NO2+ is diamagnetic
(c) Both CO2 and NO2+ have linear geometry.
(d) CO2 and NO2+ are isoelectronic.
6. The bond order of N2+ ion is __________. (Round off to one decimal place)
IIT JAM 2018
7. Consider the following four xenon compounds: XeF2, XeF4, XeF6 and XeO3 The pair of xenon compounds
expected to have non-zero dipole moment is
(a) XeF4 and XeF6 (b) XeF2 and XeF4
(c) XeF2 and XeO3 (d) XeF6 and XeO3
IIT JAM 2017
8. Among the following, the species having see-saw shape is/are
(a) SF4 (b) XeF4 (c) ClF4+ (d) ClF4
IIT JAM 2016
9. The correct order of bond angles in BF3, NH3, NF3 and PH3 is
(a) BF3 > NH3 > NF3 > PH3 (b) PH3 > BF3 > NF3 > NH3
(c) PF3 > PH3 > NH3 > NF3 (d) NH3 > NF3 > BF3 > PH3
10. The diatomic molecule(s) that has (have) two -type bonds is(are)
(a) B2 (b) C2 (c) N2 (d) O2
11. The bond order of Be2 molecule is ____.
12. Effective nuclear charge for 3d electron in vanadium (atomic number = 23) according to Slater’s rule is ____.
13. The bond angle in PBr3 is 101º. The percent ‘s’ character of the central atom is ____.
IIT JAM 2015
14. The intermolecular vander Waals potential is inversely proportional to r6. The corresponding force is proportional
to
1 1 1 1
(a) (b) (c) (d)
r5 r6 r7 r12
15. The species having trigonal pyramidal shape is
(a) NO3– (b) CO32– (c) BrF3 (d) SO32–
IIT JAM 2014
16. The predicted geometry of TeF4 by VSEPR theory is
(a) octahedral (b) Square planar
(c) Tetrahedral (d) Trigonal bipyramidal
17. Among the following, the isoelectronic pair is
(a) NO and CO (b) O2– (superoxide anion) and NO–
(c) NO+ and CO (d) O2– (superoxide anion) and NO+
18. Among Ar, NH4Cl, HF and HCl, the strength of interatomic / intermolecular forces follows the order:
(a) NH4Cl > HF > HCl > Ar (b) HF > HCl > Ar > NH4Cl
(c) HCl > Ar > NH4Cl > HF (d) Ar > NH4Cl > HF > HCl
IIT JAM 2013
19. The most polar compound among the following is:
(a) SF4 (b) BF3 (c) XeF4 (d) SO3
20. The shape of the interhalide IF8– is __________
IIT JAM 2012
21. Molecular shape of SOCl2 is
(a) Square planar (b) Trigonal pyramidal
(c) Triangular planar (d) T-shape
22. Identify the most acidic compound from the following: CH3 – CH3, CH2 = CH2 and CH  CH, and justify your
answer. Draw overlap of the orbitals to show bonding in the most acidic compound using the concept of
hybridization.
23. Draw the structures of NO 2 , NO2 and NO 2 . Arrange them in the increasing order of O–N–O bond angles.
IIT JAM 2011
24. Hybridization of the atoms indicated with the asterisk (*) in the following compounds sequentially, are
(a) sp2, sp2, sp3, sp2 (b) sp2, sp3, sp3, sp2 (c) sp3, sp3, sp3, sp2 (d) sp2, sp2, sp3, sp3
IIT JAM 2010
25. Which of the following has a square planar geometry according to the VSEPR theory? Atomic number: B = 5, S
= 16, Xe = 54.
(a) XeO2F2 (b) SF4 (c) BF4– (d) XeF4
26. In which of the following C–H bond has the highest ‘s’ character?
(a) Acetylene (b) Ethylene (c) Methane (d) CH radical
27. At room temperature, HCl is a gas while HF is a liquid because
(a) Of a strong bond between H and F in HF
(b) HF is less acidic as compared to HCl
(c) Of strong intermolecular H-bonding in HF
(d) HCl is less acidic as compared to HF
28. (b) Draw Lewis structures of SF4 and NO3–.
IIT JAM 2009
29. The formal charges on the nitrogen atom from left to right in the azide anion, [N = N = N]– are
(a) + 1, –1, –1 (b) –1, +1, –1 (c) –1, –1, +1 (d) –2, +1, 0
IIT JAM 2008
30. The V-shape of SO2 is due to the presence of
(a) Two -and one -bonds.
(b) Two -and two -bonds.
(c) Two -bonds and one lone pair of electrons
(d) Two - and two -bonds, and one lone pair of electrons.
31. Based on VSEPR theory draw the most stable structure of CIF3 and XeF4.
IIT JAM 2007
32. The overlap between the atomic orbitals sketched below is:
(a) Positive (b) Negative (c) Zero (d) No overlap
33. Which one of the following species is NOT isoelectronic with CO?
(a) N2 (b) CN– (c) NO+ (d) O2+
34. The shape of CH3– ion is:
(a) trigonal planar (b) tetrahedral (c) trigonal pyramidal (d) linear
IIT JAM 2006
35. The fluoride, whose value of dipole moment is not equal to zero, is
(a) XeF4 (b) CF4 (c) SF4 (d) PF5
36. The average value of C-C bond in graphite is:
(a) 1 (b) 3/2 (c) 3/4 (d) 4/3
IIT JAM 2005
37. The geometry of SF4 is
(a) tetrahedral (b) trigonal bipyramidal
(c) square planer (d) octahedral
ANSWER KEY
1. (d) 2. (c) 3. (d) 4. (b) 5. (b.c.d) 6. (2.5) 7. (d)

8. (a) 9. (a) 10. (b,c) 11. (0) 12. (4.3) 13. (16.02)
14. (c) 15. (d) 16. (d) 17. (c) 18. (a) 19. (a)
20. (Square antiprismatic) 21. (b) 22. (*) 23. ( NO 2  NO 2  NO2 )
24. (a) 25. (d) 26. (a) 27. (c) 28. (*) 29. (b) 30. (c)
31. (*) 32. (a) 33. (d) 34. (c) 35. (c) 36. (d) 37. (b)
HINTS & SOLUTION

22. (a) CH  CH is the most acidic compound among ethane and ethylene.
CH3CH3  CH 3CH 3  H 
CH 2  CH 2  CH 2  CH  H 
CH  CH  CH  C  H 
CH3CH  
CH 2 CH < HC  C 
2
  
sp3 hybridized  sp 2 hybridized  sp hybridized 
 25% s character  33% s scaracter  50% s character 

   
Increasing % s-character increasing stability
• The acidity of H–A increases as the percent S-character of the A– increases.

• The higher the percent s-character of the hybrid orbital, the closer the lone pair is held to the nucleus, and the
more stable the conjugate base.
Acetylene  H  C  C  H
28. SF4
O O O
NO3–: O Trigonal planar.
N O N O N
O O O
31.
trigonal bypyramidal geometry
3
COORDINATION COMPOUNDS
(IIT JAM 2005)
1. Among the following complexes,
(i) [Ru(bipyridyl)3]+
(ii) [Cr(EDTA)]–
(iii) trans-[CrCl2(oxalate)2]3– (iv) cis-[CrCl2(oxalate)2]3–
the ones that show chirality are
(a) (i), (ii), (iv) (b) (i), (ii), (iii) (c) (ii), (iii), (iv) (d) (i), (iii), (iv)
2. The crystal field stabilization energy of high spin d7 octahedral complex is
4 4 9 9
(a)  0  2P (b)  0  3P (c)  0  2P (d)  0  3P
5 5 5 5
3. (A) Between [Cu(H2O)6]2+ and [Co(H2O)6]2+, which one has more distorted structure and why?
(B) Calculate CFSE (in units of 0) and spin only magnetic moment for the following complexes:
(i) [CoF6]3– (ii) [Fe(CN)6]3– (iii) [NiCl4]2–

4. The complex with the most intense colour among the following is
(a) [FeF6]3– (b) [MnCl4]2– (c) [CoCl4]2– (d) [CoF6]3–
5. The electronic configuration that have orbital angular momentum contribution in an octahedral environment are
(a) d1 and high spin d4 (b) d1 and d2
(c) d2 and high spin d6 (d) high spin d4 and high spin d6
(IIT JAM 2006)
6. The octahedral crystal field splitting (0) of d orbital energies of the following metal ions decreases in the order
(a) Co2+ > Co3+ > Rh3+ (b) Rh3+ > Co3+ > Co2+
(c) Rh3+ > Co2+ > Co3+ (d) Co3+ > Co2+ > Rh3+
7. The optical absorption spectrum of [Ti(H2O)6]3+ has its absorption maximum at 20300 cm–1. The magnitude of
crystal field stabilization energy in cm–1 is
(a) 8120 (b) 16240 (c) 24360 (d) 50750
8. Write the structure of possible isomers of [CoCl2(en)2]Cl.
9. The hydration enthalpies of divalent metal ions of ten elements from calcium to zinc are plotted against their
atomic numbers. Why do the hydration enthalpies of only three elements, Ca, Mn and Zn fall on a straight line,
whereas values for other metal ions deviate from this line?
(IIT JAM 2007)

10. The ligand with only sigma () bonding character is
(a) CN– (b) CH3– (c) CO (d) NO
11. [Cr(H2O)6]3+ gave an absorption at 208 kJ/mol which corresponds to 0. Calculate the crystal field stabilisation
energy of this complex in kJ/mol.
(IIT JAM 2008)
12. (a) For the complexes [FeF6]3– and [Fe(CN)6]3–.
(i) Show the hybridization using VB(valence bond) theory
(ii) Calculate the CFSE (crystal field stabilization energy)
(b) Identify the dark blue complex formed when [Fe(CN)6]3– is treated with FeSO4 and account for the origin of
its colour.
13. For tetrahedral complexes, which always exhibit high spin states, the maximum CFSE (crystal field stabilization
energy) is:
(a) –8 Dq (b) –12 Dq (c) –16 Dq (d) –20Dq
14. In general, magnetic moment of paramagnetic complexes varies with temperature as
(a) T2 (b) T (c) T–2 (d) T–1
(IIT JAM 2009)
15. (A) Provide IUPAC names for the following complexes:
(i) [CoCl(NH3)5] (ii) K2[PdCl4]
(B) The magnetic moment of [Mn(H2O)6] (NO3)2 is approximately 6.0 µB. Find the number of unpaired electrons,
show crystal field splitting and calculate the CFSE.
(IIT JAM 2010)
16. (a) Draw the crystal field splitting diagram with appropriate labels for [NiCl4]2–. Determine the spin only
magnetic moment and the crystal field stabilization energy (CFSE) for this complex. (Given : Atomic number of
Ni = 28)
17. Which one of the following configuration will show Jahn-Teller distortion in an octahedral field?
(a) high spin d8 (b) high spin d4 (c) high spin d5 (d) low spin d6
18. The colour of potassium dichromate is due to
(a) d-d transition (b) transition in K+ ion
(c) Ligand-to-metal charge transfer (d) metal-to-ligand charge transfer
(IIT JAM 2010)
19. Addition of an aqueous solution of Fe(II) to potassium hexacyanochromate (III) produces a brick-red coloured
complex, which turn dark green at 100ºC. The dark green complexes is
(a) Fe4[Cr(CN)6]3 (b) KFe[Cr(CN)6] (c) KCr[Fe(CN)6] (d) Fe[Cr(CN)6]
20. The oxide that has the inverse spinel structure is
(a) FeCr2O4 (b) MnCr2O4 (c) CoAl2O4 (d) CoFe2O4
21. The magnetic moment of [Fe(phen)2(NCS)2] varies with temperature. The magnetic moments at 200 K and 50
K are 4.9 BM and 0 BM, respectively. Write the d-electron configurations of Fe at both temperatures and give
reason for the observed change in the magnetic moment. (phen = 1,10-phenanthroline)
(IIT JAM 2012)
22. A coordination compound is composed of one Co(III), one chloride, one sulphate and four molecules of ammonia.
The aqueous solution of the compound gives no precipitate when combined with aqueous BaCl2, while a white
precipitate is formed with aqueous AgNO3 solution. Draw its structure and explain the observations with chemical
equations.
23. The spin-only magnetic moments of K3[Fe(oxalate)3] and K3[Ru(oxalate)3] are 5.91 µB and 1.73 µB, respectively.
Write down their ligand field electronic configurations. Justify your answer. Atomic number of Fe and Ru are 26
and 44 respectively.
24. The tetrachloro complexes of Ni(II) and Pd(II) respectively, are (atomic numbers of Ni and Pd are 28 and 46
respectively)
(a) diamagnetic and diamagnetic (b) paramagnetic and paramagnetic
(c) diamagnetic and paramagnetic (d) paramagnetic and diamagnetic
25. Show with labels the splitting of d-orbitals in an octahedral ligand field. Calculate the CFSE of (i) high spin d6 and
(ii) low spin d6 metal ions in octahedral field.
(IIT JAM 2013)
26. CaO, VO and MnO have octahedral coordination of the metal ions in a rock-salt structure. The correct increasing
order of their lattice enthalpies is __________
27. Assume the complex [Ni(PPh3)2(SCN)2] is paramagnetic. The analogous complex of Pd(II) is diamagnetic.
Draw all the probable isomers for both the complexes considering SCN– is an ambidentate ligand.
(IIT JAM 2014)
28. The correct order of crystal field strength is : (Given: en = enthylenediamine)
(a) Cl– < H2O < en < (5 – C5H5)– (b) H2O < Cl– < (5 – C5H5)– < en
(c) H2O < (5 – C5H5)– < en < Cl– (d) en < Cl– < H2O < (5 – C5H5)–
29. Using crystal field theory (CFT), for the [Co(NH3)6]3+ ion
(a) Draw the d-orbital splitting including their orbital labels (designations) and show their electron occupancy.
(b) Calculate the crystal field stabilization energy (ignore pairing energy) and spin-only magnetic moment values.
(Given: atomic number of Co = 27).
30. The electronic transitions responsible for the colour of K2Cr2O7 and porphyrin in their solid state respectively are:
(a) d  d;    (b) M  L charge transfer;   
(c) L  M charge transfer;    (d) L  M charge transfer; d  d
(IIT JAM 2015)
31. A filter paper moistened with cadmium acetate solution turns yellow upon exposure to H 2S. The transition
responsible for the yellow colour is
(a) d-d (b) metal to ligand charge transfer
(c) ligand to metal charge transfer (d) –*
32. The first row transition metal complexes having tetrahedral geometry are high-spin due to
(a) t > P (b) t < P (c) t = P (d) t > 0
33. Given that the crystal field stabilization energy for [Co(H2O)6]2+ is 7360 cm–1, the calculated value of 0 in kJ
mol–1 is ________.
34. The normal spinel among the following mixed metal-oxides is
(a) CoFe2O4 (b) NiFe2O4 (c) CuFe2O4 (d) ZnFe2O4
35. The ground state term for a free ion with 3d7 configuration is
(a) 4F3/2 (b) 4F9/2 (c) 4F1/2 (d) 4F5/2
36. Given that the expected spin-only magnetic moment for (Et4N)2[NiCl4] is 2.83 µB, the total number of unpaired
electrons in this complex is ________.
37. The complex that is expected to show orbital contribution to the overall magnetic moment is
(a) [Cr(CN)6]3– (b) [Co(H2O)6]2+ (c) [Ni(en)3]2+ (d) [Cu(NH3)6]2+
(IIT JAM 2016)
38. The total number of isomers possible for the molecule [Co(NH3)4Cl(NO2)]+ is ______.
39. The complexes [Pt(CN)4]2– and [NiCl4]2–, respectively are
(a) paramagnetic, paramagnetic (b) diamagnetic, diamagnetic
(c) paramagnetic, diamagnetic (d) diamagnetic, paramagnetic
40. The crystal field stabilization energy (CFSE) in [Mn(H2O)6]2+ is
(a) 0 0 (b) 2.0 0 – 2P(c) 0.4 0 – 2P (d) 2.0 0
41. The True Statement about [Cu(H2O)6]2+ is
(a) All Cu–O bond lengths are equal
(b) One Cu–O bond length is shorter than the remaining five
(c) Three Cu–O bond lengths are shorter than the remaining three
(d) Four Cu–O bond lengths are shorter than the remaining two
42. The ion(s) that exhibit only charge transfer band in the absorption spectra (UV-visible region) is(are)
(a) [Cr(C2O4)3]3– (b) [CrO4]2– (c) [ReO4]– (d) [NiO2]2–
43. The red colour of ruby is due to
(a) d-d transition of Cr3+ ion in Cr2O3 lattice (b) d-d transition of Cr3+ ion in Al2O3 lattice
(c) ligand to metal charge transfer transition (d) metal to metal charge transfer transition
(IIT JAM 2017)
44. Nitrosyl ligand binds to d-metal atoms in linear and bent fashion and behaves, respectively, as
(a) NO+ and NO+ (b) NO+ and NO– (d) NO– and NO– (d) NO– and NO+
45. The number of unpaired electron(s) in K2NiF6 is _______.
46. The correct order of enthalpy of hydration for the transition metal ions is
(a) Cr2+ > Mn2+ > Co2+ > Ni2+ (b) Ni2+ > Co2+ > Mn2+ > Cr2+
(c) Ni2+ > Co2+ > Cr2+ > Mn2+ (d) Cr2+ > Mn2+ > Ni2+ > Co2+
47. The correct order of wavelength of absorption (max) of the Cr-complexes is (en = ethylenediamine)
(a) [CrF6]3– > [Cr(H2O)6]3+ > [Cr(en)3]3+ > [Cr(CN)6]3–
(b) [Cr(H2O)6]3+ > [CrF6]3– >[Cr(en)3]3+ > [Cr(CN)6]3–
(c) [Cr(CN)6]3– > [Cr(en)3]3+ > [Cr(H2O)6]3+ > [CrF6]3–
(d) [Cr(en)3]3+ > [Cr(CN)6]3– > [Cr(H2O)6]3+ > [CrF6]3–
48. Jahn-Teller distortion is/are observed in octahedral complexes with d-electron configuration of
(a) d5-high spin (b) d5-low spin (c) d6-high spin (d) d6-low spin
(IIT JAM 2018)
49. The number of possible isomers for  Pt  py  NH 3  BrCl  is _______ (py is pyridine)
50. The correct order of 0 (the octahedral crystal field splitting of d orbitals) values for the following anionic metal
complexes is
(a) [Ir(CN) 6 ]3  [Rh(CN)6 ]3  [RhI6 ]3  [CoI6 ]3
(b) [CoI6 ]3  [RhI6 ]3  [Rh(CN)6 ]3  [Ir(CN) 6 ]3
(c) [CoI6 ]3  [Rh(CN)6 ]3  [RhI6 ]3  [Ir(CN)6 ]3
(d) [Ir(CN) 6 ]3  [CoI6 ]3  [Rh(CN)6 ]3  [RhI6 ]3
3
51. The magnitude of crystal field stabilization energy (CFSE) of octahedral Ti  H 2 O 6  complex is 7680 cm–1.
The wavelength at the maximum absorption   max  of this complex is ______ nm (rounded up to the nearest
integer).
(IIT JAM 2019)
52. The observed magnetic moments of octahedral Mn3+, Fe3+ and Co3+ complexes are 4.95, 6.06 and 0.00 BM,
respectively. The correct option for the electronic configuration of Mn 3+, Fe3+ and Co3+ metal ions in these
complexes, respectively, is
(a) t 42g eg0 , t 2g
2 2 4 2
eg and t 2g eg (b) t 32g e1g , t 52g eg0 and t 62g e0g
(c) t 32g e1g , t 32g eg2 and t 62g eg0 (d) t 32g e1g , t 32g eg2 and t 2g
4 2
eg
53. The correct order of wavelength (max) of the halide to metal charge-transfer band of [Co(NH3)Cl]2+ (I),
[Co(NH3)5Br]2+ (II) and [Co(NH3)5I]2+ (III), is
(a) III < II < I (b) I < II < III (c) II < III < I (d) I < III < II
54. The correct trend in the rate of substitution of Cl– by pyridine in the following complexes is
Et 3P Cl Et 3P Cl Et 3P Cl Et3P Cl
Pt Pt Pt Pt
(I) (II) (III) (IV)
H3C PEt3 C6H5 PEt3 Cl PEt3 H PEt3
(a) III < II < I < IV (b) II < III < I < IV (c) I < II < III < IV (d) III < II < IV < I
(IIT JAM 2020)
55. The total number of all possible isomers of [Co(H2NCH2CH2NH2)2Cl2]+ and [Co(H2NCH2CH2NH2)3]3+
56. The d – orbitals involved in the hybridization to form square planar and trigonal bipyramidal geometries are,
respectively
(d) d z2 and d z2 (b) d yz and d z2 (c) d x 2  y2 and d z2 (d) d x 2  y2 and d yz
57. The transition metal complexe(s) with zero magnetic moment, zero dipole moment and CFSE of 2.4 0 is (are)
(a) [Mn(CO)5(CH3)] (b) [trans - Ni(ethylene diamine)2Cl2]
(c) [trans-Co(CN)4(H2O)2]– (d) [trans - Fe(CN)4Cl2]4–
58. The number of d – d transition(s) expected for the complex [Cu(NH3)2(H2O)4]2+ is
(a) 1 (b) 2 (c) 3 (d) 4
(IIT JAM 2021)
59. Reaction of [Ni(CN)4]2– with metallic potassium in liquid ammonia at –33ºC yields complex E. The geometry and
magnetic behavior of E, respectively, are
(a) Octahedral and paramagnetic (b) Tetrahedral and diamagnetic
(c) Square pyramidal and paramagnetic (d) Square planar and diamagnetic
60. If the crystal field splitting energy of [Co(NH3)4]2+ is 5900 cm–1, then the magnitude of its crystal field stabilization
energy, in kJ mol–1 (rounded off to one decimal place), is __________.
61. The complex (es) that show (s) Jahn – Teller distortion is(are)
(a) [Co(CN)5(H2O)]3– (b) [NiF6]2–
(c) [Co(en)2F2]+ (d) [Mn(CNMe)6]2+
62. According to the crystal field theory, d–d transition observed in [Ti(H2O)6]3+ is
(a) Laporte forbidden and spin allowed (b) Laporte allowed and spin forbidden
(c) Laporte forbidden and spin forbidden (d) Laporte allowed and spin allowed
63. The total number of microstates possible for a d8 electronic configuration is_______.
64. Spin-only magnetic moments (in BM) of [NiCl2(PPh3)2] and [Mn(NCS)6]4–, respectively, are
(a) 2.83 and 5.92 (b) 0.00 and 5.92 (c) 2.83 and 1.89 (d) 0.00 and 1.89
65. The total number of optically active isomers of dichloridobis (glycinato)cobaltate(III) ion is ______.
(IIT JAM 2022)
66. The ground state and the maximum number of spin-allowed electronic transitions possible in a Co2+ tetrahedral
complex, respectively, are
(a) 4A2 and 3 (b) 4T1 and 2 (c) 4A2 and 2 (d) 4T1 and 3
67. The number of unpaired electrons in [Co(H2O)6]2+ is _______.
68. Total degeneracy (number of microstates) for a Ti3+ ion in spherical symmetry is ______.
ANSWERS KEY
1. (a) 2. (a) 3. (*) 4. (c) 5. (b,c) 6. (b) 7. (a)
8. (3) 9. (*) 10. (b) 11. (-249.5) 12. (a) 13. (b)
14. (d) 15. (*) 16. (a) 17. (b) 18. (c) 19. (c) 20. (d)
21. (*) 22. (*) 23. (*) 24. (d) 25. (*) 26. (*)
27. (*) 28. (a) 29. (0) 30. (c) 31. (c) 32. (b) 33. (110.75)
34. (d) 35. (b) 36. (2) 37. (b) 38. (4) 39. (d) 40. (a)
41. (d) 42 (b,c) 43. (b) 44. (b) 45. (0) 46. (c) 47. (a)
48. (b,c) 49. (3) 50. (b) 51. (1nm) 52. (c) 53. (b) 54. (a)
55. (5) 56. (c) 57. (c,d) 58. (b) 59. (b) 60. (– 84.58)
61. (a,d) 62. (a) 63. (45) 64. (a) 65. (6) 66. (3) 67. (3)
68. (10)
Check Hints solution (*)
HINTS & SOLUTION

3. (A) [Cu(H2O)6]2+ – more distorted
Magnitude of JTD  eg (unsymmetry) > t2g (unsymmetry)
 More electron density, more distortion.
(B) (I) [CoF6]3–  d6 CFSE  [(–0.4 × 4) + (2 × 0.6)] o  – 0.4 0
M.M.  4(4  2)  24 BM
(II) [Fe(CN)6]3–  d5 Low spin CFSE  (–0.4 × 5)0 + 2P = –2.0 0 + 2P
M.M.  1(1  2)  3 BM
(III) [NiCl4]2– d8
tetrahedral CFSE  [(–0.6 × 4) + (4 × 0.4)]t = –0.8 t
M.M.  2(2  2)  8 BM
9. Hydration of metal ions (M+2) produces an enthalpy change that is commensurate with the size, charge of the ion
and crystal field stabilisation energy (CFSE).
So, Hhydration shows non-linear variation if C.F.S.E.  0. If CFSE = 0 (i.e. for Ca, Mn and Zn which has d0,
d5 and d10 configuration respectively), then it lies on the straight line.
15. (A) (I) Pentamminechlorocobalt (I)

(II) Potassium tetrachloropalladate (II)
(B) [Mn(H2O)6](NO3)2
d5  high spin system 5 unpaired electron
M.M.  5(5  2)  35 CFSE = [–3 × 0.4 + 2 × 0.6] 0 = 0

= ~ 6 B.M.
21. [Fe(phen)2(NCS)2]
Fe2+  d6
when temperature is high 200 K When temperature is low,
High spin Low spin
M.M.  4(4  2)  4.9 BM M.M. = 0

22. Gives ppt. with AgNO3 means Cl is outside the coordination sphere
 [Co(NH3 )4 (SO 4 )]Cl
[Co(NH 3 ) 4 (SO 4 )]Cl  AgNO3  [Co(NH 3 ) 4 (SO 4 )]NO3  AgCl 

23. K3[Fe(oxalate)3] K3[Ru(oxalate)3]
 
Weak field ligand In 4d series, almost all are strong field ligands.
Fe3+ Ru3+
eg2 d5 system
t 32g 5 unpair electron one pair electron
M.M.  5(5  2)  35 M.M.  1(1  2)  3
t 32g eg2 t 52g e0g
25.
eg
0.6 0
e.s.
0.4 0
t2g
g.s.
d6 high spin CFSE = 4 × (–0.4 0) + 2 × 0.6 0

= – 1.6 0 + 1.2 0
 –0.4 0
d6 low spin CFSE = 6 × (–0.4 0) + 2 P P = pairing energy
= –2.4 0 + 2P
26. CaO < MnO < VO
z z
0
27. [Ni(PPh3)2(SCN)2]  Paramagnetic, therefore, tetrahedral
Isomers:
[Pd(PPh3)2(SCN)2]  Diamagnetic, therefore, square planar
4
ORGANOMETALLICS
IIT JAM 2008
1. Metal-carbon multiple bonds in metal carbonyl are preferably identified from the stretching frequency of
(a) Carbon-oxygen bond (b) Metal-carbon bond
(c) Metal-oxygen bond (d) Carbon-carbon bond
IIT JAM 2009
2. Highly pure nickel metal can be prepared from its sulphide ore via Ni(CO) 4. Write the chemical equations
involved.
IIT JAM 2010
3. B2H6 and B4H10, respectively, are examples of
(a) Nido and arachno boranes (b) Nido and closo boranes
(c) Closo and arachno boranes (d) Nido boranes
IIT JAM 2012
4. Schematically represents orbital overlaps in metal carbonyls. Show the correct signs of the lobes.
IIT JAM 2013
5. The Correct order of CO vibrational stretching frequency in the following complexes is
(I) (PF3)3Mo(CO)3 (II) (PCl3)3Mo(CO)3 (III) {P(OMe)3}3Mo(CO)3
(a) I < II < III (b) III < II < I (c) II < I < III (d) III < I < II
IIT JAM 2014
6. The carbonyl stretching frequency (C = O) is highest for:
O O O O
(a) (b) (c) (d)
H3C OH H3C H H3C Cl H3C NH2
7. Among the following, the isoelectronic pair is
(a) NO and CO (b) O2– (superoxide anion) and NO–
(c) NO+ and CO (d) O2– (superoxide anion) and NO+
8. The correct order of M–C(M = Ti, V, Cr and Mn) bond stretching frequency is:
(Given: Atomic number of Ti = 22, V = 23, Cr = 24 and Mn = 25)
(a) [V(CO)6]– < Cr(CO)6 < [Mn(CO)6]+ < [Ti(CO)6]2–
(b) [Ti(CO)6]2– < [V(CO)6]– < Cr(CO)6 < [Mn(CO)6]+
(c) [Mn(CO)6]+ < Cr(CO)6 < [V(CO)6]– < [Ti(CO)6]2–

(d) [Mn(CO)6]+ < [V(CO)6]– < Cr(CO)6 < [Ti(CO)6]2–
9. For the following reactions, the metal complexes X and Y are
CO(g)
(i) Ni(s) 
1 atm / 25ºC
 X (ii) FeCl 
2
2NaC5H5
Y
(a) X = Ni(CO)4; Y = Fe(5-C5H5)2 (b) X = Ni(CO)4; Y = Fe(1-C5H5)2
(c) X = Ni(CO)5; Y = Fe(5-C5H5)2 (d) X = Ni(CO)6; Y = Fe(1-C5H5)2
IIT JAM 2015
10. Which of the following statement(s) is/are true about the transition metal-alkene complexes?
(a) Back-bonding weakens the double bond of the alkene
(b) -Bonding and back bonding synergistically strengthen metal-alkene interaction
(c) Electron-withdrawing substituents on alkene reduce back-bonding
(d) -acidic co-ligands on metal strengthen back-bonding
IIT JAM 2016
11. The value of ‘x’ in [Cu(CO)x]+ such that it obeys the 18 electron rule is
(a) 6 (b) 5 (c) 4 (d) 3
12. The correct order of NO (cm–1) in the following compound is
(a) NO+ > NO > [NiCp(NO)] > [Cr(Cp)2(NO)4]
(b) [Cr(Cp)2(NO)4] > [NiCp(NO)] > NO+ > NO
(c) NO+ > [Cr(Cp)2(NO)4] > NO > [NiCp(NO)]
(d) [NiCp(NO)] > NO > [Cr(Cp)2(NO)4] > NO+
IIT JAM 2017
13. The homogeneous catalyst used in water-gas shift reaction is
(a) PdCl2 (b) Cr2O3 (c) [RhCl(PPh3)3] (d) [RuCl2(bipyridyl)2]
14. Nitrosyl ligand binds to d-metal atoms in linear and bent fashion and behaves, respectively, as
(a) NO+ and NO+ (b) NO+ and NO– (d) NO– and NO– (d) NO– and NO+
IIT JAM 2018
15. Among the following metal carbonyl species, the one with the highest metal-carbon back bonding is
(c) Cr  CO 6
2  
(a)  Ti  CO 6  (b)  V  CO 6  (d)  Mn  CO 6 
16. The correct statement(s) about carbene is(are)
(a) Carbene is a neutral species
(b) Carbene is an intermediate in the Curtius rearrangement
(c) Carbene can insert into both  and -bonds
(d) Carbene is generated from amines on reaction with nitrous acid
IIT JAM 2019
17. The correct option having one complex from each of the following pairs which is more reactive towards the
oxidative addition reaction by hydrogen molecule is
Pair 1: IrCl(PMe3)3 (I) and IrCl(CO)(PMe3)2 (II)
Pair 2: IrCl(CO)(PPh3)2 (III) and IrCl3(PPh3) (IV)
(a) (I) and (III) (b) (I) and (IV) (c) (II) and (III) (d) (II) and (IV)
18. The value of n for the complex [Fe(CO)4(SiMe3)]n satisfying the 18-electron rule is ________.
19. Number of vertices in an icosahedral closo-borane is _________.
IIT JAM 2020
20. The order of the M – C bond strength in the following species is (Atomic number for Cr = 24, Mn = 25, Ti = 22,
Co = 27)
[Cr(CO)6] [Mn(CO)6]+ [Ti(CO)6]2– [Co(CO)4]–
I II III IV
(a) II > I > IV > III (b) I > III > II > IV (c) III > IV > I > II (d) III > I > II > IV
21. The cage – type structure adopted by boron hydride [B5H11], is
(a) closo (b) nido (d) hypo (d) arachno
22. The complex which does NOT obey 18 – electron rule is
(atomic number for Mn = 25, Fe = 26, Co = 27, Ru = 44)
(a) [Co2(CO)8] (b) [Fe(CO)4]2–
(c) [HMn(CO)5] (d) [(5–C5H5)RuCl(CO)(PPh2)]
23. The organometallic reagent(s) among the following is(are)
(a) Lithium divinylcuprate (b) Lithium diisopropylamide
(c) Potassium tert - butoxide (d) Isopropyl magnesiumiodide
IIT JAM 2021
24. The CORRECT order of pKa for the compounds I to IV in water at 298 K is
HCo  CO 4 HCo  CO 3  PPh 3  
HCo  CO 3 P  OPh 3  HCo  CO 2  PPh 3 2
I II III IV
(a) I > III > II > IV (b) IV > II > III > I (c) IV > III > II > I (d) I > II > III > IV
25. The complex that does NOT obey the 18-electron rule is
(Given: Atomic numbers of Ti, Mn, Ta and Ir are 22, 25, 73 and 77, respectively)
(a) [(5-C5H5)Ti(CO)4]– (b) [TaCl3(PEt3)2(CHCMe3)]
(c) [Mn(SnPh3)2(CO)4]– (d) [(5-C5H5)Ir(CH2)(PMe3)]
26. The decreasing order of C=C bond length in the following complexes is
[Cl3Pt(CH2=CH2)]– [Cl3Pt(C(CN)2=C(CN)2)]– [Cl3Pt(CF2=CH2)]– [Cl3Pt(CF2=CF2)]–
I II III IV
(a) II > III > IV > I (b) IV > II > III > I (c) II > IV > III > I (d) IV > II > I > III
27. The CORRECT statement(s) about the species is (are)
(a) CpMo(CO)3 and CpW(CO)3 are isoelectronic (wher Cp is cyclopentadienyl)
(b) BH and CH are isolobal and isoelectronic
(c) CH3 and Mn(CO)5 are isolobal
(d) CH2– and NH2 are isolobal and isoelectronic
IIT JAM 2022
28. The structure types of B10H102– and B10H14 , respectively, are
(a) closo and nido (b) nido and arachno
(c) nido and closo (d) closo and arachno
29. The order of increasing CO stretching frequencies in [Co(CO)4]–, [Cu(CO)4]+, [Fe(CO)4]2– and [Ni(CO)4] is
(a) [Cu(CO)4]+ < [Ni(CO)4] < [Co(CO)4]– < [Fe(CO)4]2–
(b) [Fe(CO)4]2– < [Co(CO)4]– < [Ni(CO)4] < [Cu(CO)4]+
(c) [Co(CO)4]– < [Fe(CO)4]2– < [Cu(CO)4]+ < [Ni(CO)4]
(d) [Ni(CO)4] < [Cu(CO)4]+ < [Co(CO)4]– < [Fe(CO)4]2–
30. The number of CO stretching bands in the infrared spectrum of Fe(CO)5 is
(a) 1 (b) 2 (c) 3 (d) 4
31. The reaction
PPh3 H
H H Me PPh3
Rh Rh
Ph3P Cl PPh3
Cl
Me
involve(s)
(a) migratory insertion (b) change in electron count of Rh from 18 to 16
(c) oxidative addition (d) change in electron count of Rh from 16 to 18
ANSWER KEY
1. (a) 2. (*) 3. (a) 4. (*) 5. (b) 6. (c) 7. (c)
8. (c) 9. (a) 10. (a,b) 11. (c) 12. (a) 13. (d) 14. (b)
15. (a) 16. (a,c) 17. (a) 18. (-1) 19. (12) 20. (c) 21. (d)
22. (d) 23. (a,d) 24. (d) 25. (b) 26. (c) 27. (a,c,d) 28. (a)
29. (b) 30. (b) 31. (a,b)
HINTS & SOLUTION

2. Sulfide ore in first roasted in air to give NiO.
2NiS + 3O2  2NiO + 2SO2
NiO is then reduced by water gas.
NiO + H2  Ni + H2O
To refine Ni, it is heated to about 50–60ºC in a steam of CO gas. Nickel passes off as its volatile carbonyl,
Ni(CO)4, this volatile product is passed over nickel shot at about 200ºC. Nickel is deposited by Ni(CO)4 and is
almost pure.
5060ºC
Ni(s)  4CO  Ni(CO) 4 (g)
Ni, 200ºC
Ni(CO) 4  Ni  4CO(g)
4. Orbital overlaps in metal carbonyls:
5
MAIN GROUP ELEMENTS
IIT JAM 2005
1. Arrange BF3, BCl3 and BBr3 in the increasing order of Lewis acidity and justify.
IIT JAM 2006
2. (a) Write the steps involved in the production of pure elemental silicon from silica.
(b) Both the products A and B in the following reactions, contain boron and nitrogen. Identify A and B
C H Cl LiAlH
3NH 4Cl  3BCl3 
6 5  A 
heat THF
4 B
IIT JAM 2007

3. Which of the following reactions does not give H3PO4?
(a) Ca 3 (PO 4 ) 2  H 2SO 4 
 (b) P4O6  H 2 O 

(c) PCl5  H 2O 
 (d) P4S10  H 2O 

4. (a) Consider the ethers H3SiOSiH3 and H3COCH3.
(i) Which ether has more lewis base character?
(ii) Which angle [Si-O-Si and C-O-C] is greater? Justify your answer.
(b) Starting from SiO2, show how the following polymer is prepared industrially?
5. (a) Al2Cl6 and Al2Me6 are dimeric in gas phase. Draw their structures. Which compound has more Lewis acid
character? Explain.
(b) Arrange the halides SnCl2, PbCl2, SiCl2 in increasing order of their stability. Give reasons for your answer.
IIT JAM 2008
6. The compound having an S-S single bond is
(a) H2S2O3 (b) H2S2O4 (c) H2S2O7 (d) H2S2O8
IIT JAM 2009
7. Among the following, the incorrect statement is
(a) Diamond and graphite are two allotrops of carbon
(b) In diamond, each carbon is sp3 hybridized.
(c) In graphite, each carbon is sp2 hybridized
(d) Graphite shows high electrical conductivity in one direction only
8. The number of P = O bonds present in the tetrabasic acid H 4P2O7 is:
(a) Three (b) Two (c) One (d) None
9. Calgon used for water softening is Na2[Na4(PO3)6] and it is prepared by heating microcosmic salt. The microcosmic
salt is:
(a) Na2HPO3 (b) NaH2PO4 (c) Na2HPO4 (d) Na(NH4)HPO4
IIT JAM 2011
10. In the structure of B4O5 (OH)42–
(a) All four B atoms are trigonal planar
(b) One B atom is tetrahedral and the other three are trigonal planar
(c) Three B atoms are tetrahedral and one is trigonal planar.
(d) Two B atoms are tetrahedral and the other two are trigonal planar
11. Hydrolysis of (CH3)2 SiCl2 and CH3SiCl3 leads to
(a) Linear chain and cross-linked silicones, respectively
(b) Cross-linked and linear chain silicones, respectively
(c) Linear chain silicones only (d) Cross-linked silicones only
12. (a) In the following reactions, identify X, Y and Z.
boiling water
Na 2SO3  S  X(colorless complex)
excess X
AgBr  Y(soluble complex)
boiling water
X  Cl2  H 2O  Z  HCl
(b) Draw the structure of S4N4H4 and N4S4F4.
IIT JAM 2012
13. Number of three-centre two-electron (3e-2e) bonds present in diborane is:
(a) 2 (b) 4 (c) 6 (d) 8
IIT JAM 2013
14. Which one of the following order of the carbonates is Correct for their decomposition temperature?
(a) BaCO3 > CaCO3 > SrCO3 > MgCO3 (b) BaCO3 > SrCO3 > CaCO3 > MgCO3
(c) MgCO3 > CaCO3 > SrCO3 > BaCO3 (d) MgCO3 > CaCO3 > BaCO3 > SrCO3
IIT JAM 2015
15. The species responsible for the superacidity of SbF5-HSO3F system is
(a) HSO3F (b) SbF5 (c) HF (d) H2SO3F+
IIT JAM 2016
16. The final products in the reaction of BF3 with water are
(a) B(OH)3 and OF2 (b) H3BO3 and HBF4
(c) B2O3 and HBF4 (d) B2H6 and HF
17. The number of P-H bonds in hypophosphorus acid is _____.
IIT JAM 2017
18. The correct order of the boiling points of the compounds is
(a) CH4 > SiH4 > SnH4 > GeH4 (b) SiH4 > CH4 > GeH4 > SnH4
(c) SnH4 > GeH4 > CH4 > SiH4 (d) SnH4 > GeH4 > SiH4 > CH4
19. The number of S-S bond(s) in tetrathionate ion is _____
20. The number of isomeric structures of di-substituted borazine (B3N3H4X2) is ______
IIT JAM 2018
21. The CORRECT order of melting points of group 15 trifluorides is
(a) PF3  AsF3  SbF3  BiF3 (b) BiF3  SbF3  PF3  AsF3
(c) PF3  SbF3  AsF3  BiF3 (d) BiF3  AsF3  SbF3  PF3
22. On hydrolysis, aluminium carbide produces
(a) CH4 (b) C2H6 (c) C2H4 (d) C2H2
IIT JAM 2019
23. Among the following compounds, the one having the lowest boiling point is
(a) SnCl4 (b) GeCl4 (c) SiCl4 (d) CCl4
24. Among the following, the correct statement is
(a) The density follows the order, Cs > Rb > Li > Na.
(b) The solubility in water follows the order, Cs 2CO3 > K2CO3 > Na2CO3 > Li2CO3.
(c) The first ionization potential follows the order, Li > K > Na > Cs.
(d) The melting point follows the order, MgCl2 > BeCl2 > CaCl2 > SrCl2.
25. In the structure of P4O10, the number of P-O-P bond(s) is _______.
IIT JAM 2020
26. Treatment of formic acid with concentrated sulfuric acid gives
(a) CO+H2O (b) CO2 + H2 (c) HCHO + ½ O2 (d) no product (no reaction)
27. One of the products of the hydrolysis of calcium phosphide at 25ºC is
(a) phosphine (b) phosophoric acid
(c) phosphorus pentoxide (d) white phosphorus
28. The coordination number of aluminium ion and the number of bridging hydrogen atoms in [Al(BH4)4]– are respec-
tively,
29. The solid state structure of HF is
F F F
(a) H F H F H F H F (b) H H H H H
F F
H H H
F F F F F
(c) F F F F F (d) H H H H H
H H
30. The soft Lewis base(s) is(are)
(a) I– (b) CO (c) H– (d) CH3NC
31. The value of ‘n’ in [PnO18]6– is______
IIT JAM 2021
32. Reaction of BCl3 with NH4Cl at 140ºC produces compound P. further, P reacts with NaBH4 to give a colorless
liquid Q. The reaction of Q with H2O at 100ºC produces compound R and a diatomic gas S. Among the
following, the CORRECT statement is
(a) S is Cl2 (b) P is B3N3H6 (c) R is [B(OH)NH]3 (d) Q is [BClNH]3
IIT JAM 2022
33. The major product formed in the following reaction
K+ O2 is
(a) K2O (b) K2O2 (c) KO2 (d) K2O3
34. Among the following, the compound that forms the strongest hydrogen bond is
(a) HF (b) HCl (c) HBr (d) HI
35. The stability of adducts H3B·PF3, H3B·NMe3, H3B·CO, H3B·OMe2 follows the order
(a) H3B·OMe2 < H3B·CO < H3B·PF3 < H3B·NMe3
(b) H3B·PF3 < H3B·CO < H3B·NMe3 < H3B·OMe2
(c) H3B·CO < H3B·PF3 < H3B·NMe3 < H3B·OMe2
(d) H3B·PF3 < H3B·CO < H3B·OMe2 < H3B·NMe3
36. The reason(s) for the lower stability of Si2H6 compared to C2H6 is/are
(a) silicon is more electronegative than hydrogen
(b) Si – Si bond is weaker than C – C bond
(c) Si – H bond is weaker than C – H bond
(d) the presence of low-lying d-orbitals in silicon
ANSWER KEY
1. (*) 2. (*) 3. (b) 4. (*) 5. (*) 6. (b) 7. (d)

8. (b) 9. (d) 10. (d) 11. (a) 12. (a) 13. (a) 14. (b)
15. (d) 16. (b) 17. (*) 18. (d) 19. (3) 20. (4) 21. (a)
22. (a) 23. (c) 24. (b) 25. (4) 26. (a) 27. (a) 28. (a)
29. (b) 30. (a,b,c,d) 31. (*) 32. (*) 33. (c) 34. (a)
35. (d) 36. (b,c)
HINTS & SOLUTION

1. Increasing lewis acidity order:
BF3 < BCl3 < BBr3
In BF3  2p –2p back bonding most effective due to similar size and energy of ‘p’ orbitals.
BCl3  2p – 3p back bonding less effective because difference in p-orbital energy and also bond length is
large.
In BBr3  2p – 4p least back bonding, due to larger difference in size and energy of p orbital and also bond
length is large.
1
Lewis acidity  back bonding
2. (a) Production of elemental silicon from silica involves these steps:

(i) Reducing SiO2 with high purity coke
SiO 2  2C  Si  2CO
(ii) Converting Si to SiCl4 and purifying this SiCl4 by distillation,
Si + 2Cl2  SiCl4
(iii) Reduction of SiCl4 by Mg or Zn.
SiCl 4  2Mg  Si  MgCl 2
SiCl 4  2Zn  Si  ZnCl2
Ultra pure Si can be made from above obtained Si via Zone refining.
(b)
4. (a) (i) H3COCH3 has more Lewis base character.
Lone pair of oxygen in (I) is delocalized in vacant d orbital of silicon via p-d back bonding, so l.p. on oxygen
is not available. But in case of dimethyl ether ((CH3)2O), oxygen l.p. is available, so it can act as stronger lewis
base.
(ii) Due to back bonding in (SiH3)2O, double bond character arises (as shown in canonical structure II and III
above), which leads to increment in bond angle as the structure approaches more towards linearity. So Si–O–Si
bond angle is larger w.r.t. C–O–C angle where bonds have single bond character only.
(b) Pure Si is produced from reduction of SiO2 in an electric furnance in presence of coke.
SiO2 + C  Si + CO2
5.
Al2(CH3)6 is more lewis acidic in character, as bridging Al–C–Al bonds are 3-center-2-electron bonds, so, Al
has incomplete octet, but in Al2Cl6 all bonds are 2-centere-2-electron bonds. So has complete octet, so less
tendency to accept electron-pair (i.e. less lewis acidic character).
(b) Stability order
2 2 2
Si Cl2  Sn Cl 2  Pb Cl2
Si, Sn and Pb belong to group 14 and each one of them has ns2 np2 configuration, but due to inert pair effect, as
we go down the group ns2 electron gets inert, and shows reluctancy towards removal.
So, stability of +2 oxidation state increases down the group 14.
As, Si+2 < Sn+2 < Pb+2, but +4 o.s. stability is as, Si+4 > Sn+4 > Pb+4
So, stability order in MCl2 salt is, SiCl2 < SnCl2 < PbCl2
(CH3)2SiCl2 on hydrolysis gives silicon polymer.
It structure is

31. [P nO18]6–
[PO3]1– × 6 = [P6O18]6–
O O
O
P O P O
O O O
O P P
O O O
O
P O P
O O
O O
BCl3  NH 4 Cl 
140ºC
 B3 N 3Cl3 H 3 
NaBH 4
 B3 N 3 H 6 
H 2O
  B  OH  NH  3  H 2
32. P  Q  
S
R
6
BIOINORGANIC
IIT JAM 2013
1. For each of the following metallo-proteins identify the metal-ion at the active-site and the function of the proteins:
deoxy-hemoglobin, deoxy-myoglobin, oxy-hemocyanin, cytochrome-C and carbonic anhydrase.
IIT JAM 2014
2. The metal ion of an enzyme involved in hydration of CO2 is
(a) Cu(II) (b) Fe(II) (c) Mg(II) (d) Zn(II)
IIT JAM 2015
3. Low-spin iron(III) centre is present in
(a) deoxy form of hemoglobin (b) oxy form of hemoglobin
(c) hemocyanin (d) carbonic anhydrase
IIT JAM 2016
4. The protein(s) that belong to the class of blue copper protein is(are)
(a) ceruloplasmin (b) superoxide dismutase
(c) hemocyanin (d) azurin
IIT JAM 2017
5. The “heme” containing protein(s) is/are
(a) cytochrome C (b) hemocyanin (c) hemerythrin (d) myoglobin
IIT JAM 2018
6. Carbonic anhydrase is an example of
(a) Hydrolysis enzyme (b) Redox enzyme
(c) O2 transport protein (d) Heme protein
IIT JAM 2019
7. The correct option for the metal ion present in the active site of myoglobin, hemocyanin and vitamin B12, respec-
tively, is
(a) iron, iron and zinc (b) molybdenum, iron and copper
(c) iron, copper and cobalt (d) molybdenum, copper and cobalt
8. The true statement(s) regarding the carbonic anhydrase enzyme is/are
(a) It is involved in peptide bond cleavage.
(b) Redox inactive Zn2+ ion is involved in the catalytic activity of this enzyme.
(c) Activated M–OH2 (M = metal ion) acts as the nucleophile in the enzyme.
(d) The metal ion is coordinated to the side chain of histidine residues.
IIT JAM 2020
9. The plot showing the magnetic behavior of oxy – (solid line) and deoxy – heamoglobin (dashel line) is
(M= molar magnetic susceptibility, T = temperature)
4 4
cm K mol 
–1
–1
3 3
2 2
3
3
1 1
(a) (b)
0 0
100 200 300 100 200 300
T(K) T(K)
4 4
–1
–1
3 3
2 2
3
3
1 1
(c) (d)
0 0
100 200 300 100 200 300
T(K) T(K)
IIT JAM 2021
10. The CORRECT combination for metalloenzymes given in Column I with their catalytic reactions in Column II is
Column-I Column-II
(i) Cytochrome P-450 (K) 2H2O2  2H2O + O2
(ii) Catalase (L) R–CH2OH + O2  R–CHO + H2O2
(R = alkyl or aryl)
(iii) Galactose oxidase (M) O2 + 4H+ + 4e–  2H2O
(iv) Cytochrome c oxidase (N) R–H + O2 + 2e– + 2H+  R–OH + H2O
(R = alkyl or aryl)
(a) (i)–(M); (ii)–(K); (iii)–(L); (iv)–(N) (b) (i)–(N); (ii)–(K); (iii)–(L); (iv)–(M)
(c) (i)–(M); (ii)–(N); (iii)–(K); (iv)–(L) (d) (i)–(N); (ii)–(L); (iii)–(K); (iv)–(M)
(IIT JAM 2022)
11. Among the following, the biomolecule with a direct metal-carbon bond is
(a) coenzyme B12 (b) nitrogenase (c) chlorophyll (d) hemoglobin
12. Zinc containing enzyme(s) is/are
(a) carboxypeptidase (b) hydrogenase (c) carbonic anhydrase (d) urease
ANSWER KEY
1. (*) 2. (d) 3. (b) 4. (a,c,d) 5. (a,d) 6. (*)
7. (c) 8. (b,c,d) 9. (*) 10. (b) 11. (*) 12. (*)
HINTS & SOLUTION

1. Deoxy-hemoglobin
6. Carbonic anhydrase is a enzyme that catalyse rapid interconversion of carbon dioxide and water to bicarbonate.
It is a hydrolysis enzyme.
CO 2  H 2O 
Carbonic
Anhydrase
 H 2CO 3 .
9. m = molar magnetic susceptibility
C
m  , C = Curie constant
T
mT = constant
deoxy Hb is paramagnetic oxy Hb is diamagnetic.
The value of magnetic suspectibility for paramagnetic substances is greater the Diamagnetic Substance.
4
–1
3
2
3
1
0
200 100 300
T(K)
11. The reaction of adenosine phosphate (ATP) with Vit-B12S field direct cobalt – carbon bond between adenosyl
and cobalt the resulting molecule is known as B12 coenzyme.
OH2 OH2
Zn2+ Zn2+
12. (a) (His)N Glu (His)N N(His)
N(His) N(His)
(b) in hydrogenase Fe and Ni metal present

(d) in urease Ni metal present
7
D BLOCK
IIT-JAM 2005
1. On addition of a solution of AgNO3 to a solution of Na2S2O3, it turns black on standing due to the formation of:
(a) Ag (b) Ag2S (d) Ag2S2O2 (d) Ag2SO4
IIT-JAM 2006
2. (a) Addition of potassium oxalate solution to a hot solution of potassium dichromate containing dilute sulfuric acid
leads to effervescence and formation of potassium trisoxalatochromate (III).
(i) Write the chemical formula of the chromium complex formed.
(ii) Write the balanced chemical formula for the formation of the complex.
(iii) Calculate the room temperature spin-only magnetic moment, in Bohr magnetons, of the complex.
(b) Write the structure of possible isomers of [CoCl2(en)2]Cl.
IIT JAM-2007
3. (a) M is a first row transition metal. MCl2 on treatment with aqueous ammonia gives a blue coloured solution of
complex N. A solution of MCl2 also gives a bright red precipitate of complex O with ethanoic dimethylglyoxime.
(i) Identify M and draw the structure of O.
(ii) Determine the hybridisation of M in complex N.
(iii) Identify the paramagnetic complex.
(b) [Cr(H2O)6]3+ gave an absorption at 208 kJ/mol which corresponds to 0. Calculate the crystal field stabilisation
energy of this complex in kJ/mol.
4. (a) A solution of metal ion (M2+) when treated with H2S gas gives a black precipitate A. Precipitate A dissolved
in hot concentrated nitric acid to give B along with elemental sulfur. The metal ion soluion also gives a white
precipitate C with an excess of KI. Write the chemical formulae of A, B and C
(b) Why are potassium permanganate solutions unstable in the presence of Mn2+ ions? In the quantitative estima-
tion of iron present in iron ores dissolved in dilute HCl, titrations with dichromate are preferred over titrations with
permanganate. Rationalise.
5. (a) Acidification of an aqueous solution of yellow sodium chromate gives an orange coloured A. A compound
solution of A on treatment with concentrated H2SO4 gives a bright orange solid B. Compound A in the presence
of concentrated H2SO4 reacts with anion C to give a deep red coloured liquid. Identify A, B and C.
215
(b) 84 Po undergoes an  emission to give element X followed by a  emission to give element Y..
IIT JAM-2008
6. (a) Consider the reaction
2
 Cr 3
A room temperature
(I) Cr2O7  H 2O 2  CrO(O 2 ) 2 
Unstable
(II) Cr 3  H 2O 2 
B
 Cr2O72
(i) Identify A and B.
(ii) What is the role of H2O2 in (I) and how does A favour the formation of Cr3+?
(iii) What is the role of H2O2 in (II) and how does B favour the formation CrO42–?
(b) With the help of equations, illustrate the role of a cis-1, 2-diol in the titration of boric acid with sodium
hydroxide.
7. (a) Identify A, B and C in the following reaction scheme
(b) From the Ellingham diagram given below, identify the metal oxide that can be reduced at a lower temperature
by carbon. Justify.
IIT JAM-2009
8. (a) Highly pure nickel metal can be prepared from its sulphide ore via Ni(CO)4. Write the chemical equations
involved.
(b) Addition of excess of aqueous NH3 followed by ethanolic solution of dimethylglyoxime to a dilute aqueous
solution of nickel sulphate changes the solution colour from green to blue to red. Write the structures of the metal
complexes corresponding to green, blue and red colours.
9. A metal salt on heating with a mixture of KCl and conc. H2SO4 yields a deep red vapour J. The vapour on
passing through an aqueous solution of KOH gives a yellow solution of compound K. Passing SO2 gas through
acidified solution (with H2SO4) of K leads to green colouration of the solution due to the formation of M. Identify
J, K and M giving balanced equations for the transformations, J  K and K  M.
IIT JAM-2011
10. The most probable oxidation states for both Cr and Mo are
(a) +2, +3, +4 (b) +2, +3, +5 (c) +2, +3, +6 (d) +3, +4, +5
11. The pair of amphoteric oxides is:
(a) VO, Cr2O3 (b) V2O3, Cr2O3 (c) VO2, Cr2O3 (d) V2O5, CrO3
12. The transition metal monoxide that shows metallic conductivity is:
(a) NiO (b) MnO (c) TiO (d) CoO
13. The metal that is extracted by the reduction method is:
(a) Al (b) Au (c) Hg (d) Mg
14. Addition of an aqueous solution of Fe(II) to potassium hexacyanochromate (III) produces a brick-red colured
complex, which turns dark green at 100ºC. The dark green complex is
(a) Fe4[Cr(CN)6]3 (b) KFe[Cr(CN)6] (d) KCr[Fe(CN)6] (d) Fe[Cr(CN)6]
15. In the following equilibrium and reactions, identify species B to E.
Write the balanced chemical equation for the conversion of C to E.
A pH  6 B dil. HCl C

 
 

oxide of Cr Yellow colour strong oxidizing agent
solid tetrahedral
no d-electrons
B + diphenylcarbazide 
 D (violet colour)
C + HCl 
 E (greenish yellow gas)
16. (a) Identify species A and C in the following:
Write the balanced chemical equation for the conversion of A and A3+.
A + aqua regia 
 A + NO
3+
A3+ + I– 
 B (black precipitate)
B + I– (excess) 
 C (orange colour)
Hint: C on the dilution with water gives B
(b) Draw the structures of X and Y in the following reactions.
(i) Borazine + HCl 
X
(ii) Borazine + Br2 
Y
IIT JAM-2012
17. The compound formed by dissolving elemental gold in aqua regia is:
(a) AuCl (b) AuNO3 (c) H[AuCl4] (d) H[Au(NO3)4]
18. Number of moles of ions produced by complete dissociation of one mole of Mohr’s salt in water is
(a) 3 (b) 4 (c) 5 (d) 6
19. A filter paper moistioned with ammonical sodium nitroprusside solution turns violet on contact with a drop of
alkaline Na2S solution. The violet colour is due to the formation of
(a) [Fe(SCN)5(NO)]– (b) [Fe(SCN)5(NO)]2–
(c) [Fe(CN)5(NOS)]3– (d) [Fe(CN)5(NOS)]4–
IIT JAM-2013
20. Among the following, the ligand that BEST stabilizes low oxidation state of tungsten (W) is
(a) H2O (b) NH3 (c) CO (d) F–
21. The reaction of anhydrous FeCl2 with sodium-pentadienyl in ether gives an air-stable diamagnetic orange solid,
which on oxidation gives an air-sensitive paramgnetic blue-green compound in solution. The blue-green compound
is _____________
IIT JAM-2015
22. The amount (in grams) of potassium dichromate (MW = 294) present in 75 mL of 0.16 M aqueous solution is
_______
IIT JAM-2016
23. Effective nuclear charge for 3d electron in vanadium (atomic number = 23) according to Slater’s rule is ____.
IIT JAM-2017
24. In the following Latimer diagram, the species the undergoes disproportionation reaction is
0.56 0.15 0.25 1.56
MnO 4  MnO 42 
0.93
 MnO 2  Mn 2 O3  Mn(OH) 2  Mn
(a) MnO42– (b) MnO43– (c) Mn2O3 (d) Mn(OH)2
25. A yellow precipitate is formed upon addition of aqueous AgNO3 to a solution of
(a) phosphite (b) pyrophosphate (c) metaphosphate (d) orthophosphate
26. The metal ion (M2+) in the following reaction is
M 2  S2  Black precipitate 

hot conc. HNO
3  White precipitate
(a) Mn2+ (b) Fe2+ (c) Cd2+ (d) Cu2+

IIT JAM-2018
27. Which of the following metal(s) is(are) extracted from its(their) sulfide ore(s) by self-reduction air reduction
method?
(A) Cu (B) Al (C) Au (D) Pb
28. In a saturated calomel electrode, the saturation is with respect to
(A) KCl (B) Hg2Cl2 (C) HgCl2 (D) AgCl
IIT JAM-2019
29. In qualitative inorganic analysis of metal ions, the ion which precipitates as sulfide in the presence of H2S in warm
dilute HCl is
(a) Cr3+ (b) Al3+ (c) Co2+ (d) Bi3+
30. The true statement(s) regarding the brown ring test carried out in the laboratory for the detection of NO3– is/are
(a) Brown ring is due to the formation of the iron nitrosyl complex.
(b) Concentrated nitric acid is used for the test.
(c) The complex formed in the reaction is [Fe(CN)5NO]2–.
(d) The brown colored complex is paramagnetic in nature.
IIT JAM-2020
31. Titanium tetrachloride (TiCl4) reacts with THF to form an octahedral complex X under inert atmosphere at 25ºC.
If 5.0 g of TiCl4 is used and the yields is 80%, the amount of X (in grams) formed is _______ (Round off to one
decimal place)
(Use atomic weights: Ti = 48, Cl = 35.5 Q = 16, C = 12 and H = 1)
ANSWER KEY
1. (b) 2. (*) 3. (a) 4. (*) 5. (*) 6. (a) 7. (*)

8. (*) 9. (*) 10. (c) 11. (c) 12. (c) 13. (c) 14. (c)
15. (*) 16. (*) 17. (c) 18. (c) 19. (d) 20. (b) 21. (*)
22. (294) 23. (4.3) 24. (*) 25. (d) 26. (*) 27. (a,d) 28. (a,b)
29. (d) 30. (a,d) 31. (6.96 g)
HINTS & SOLUTION

2. (a) (i) Chromium complex  K3[Cr(Ox)3]
where Ox  C2O42–
(ii) K 2 Cr2 O 7  9K 2C 2 O 4  7H 2SO 4  2K 3[Cr(C 2O 4 )3 ]  6CO 2  7K 2SO 4  7H 2 O
(ii) In complex, K3[Cr(Ox)3], Cr+3 has 3d3 electrons in its t2g orbital.
Number of unpaired electron (n) = 3
Spin only magnetic moment (s )  n(n  2) B.M.  3  5 B.M.  15 B.M.
(b) [CoCl2(en)2]Cl
4. (a) A  CuS; B  Cu(NO3 ) 2

C  CuI or Cu 2I 2
(b) Mn+2 catalyses the decomposition of KMnO4, as KMnO4 oxidises Mn+2 and itself gets reduced.
2MnO 4  3Mn 2  2H 2O  5MnO 2 (s)  4H 
Also KMnO4 is not a primary standard, because it undergoes decomposition in water solution,
2KMnO4 + H2O  2KOH + 2MnO2 + 3[O]
So, KMnO4 solution is not suitable for estimation of Fe dissolved in HCl.
But K2Cr2O7 solution can be used as a primary standard, because it is stable in aqueous medium, thats
why it is prefered over KMnO4 solution.
2 Na 2CrO 4  2H   Na 2Cr2O 7  2Na   H 2O

5. (a) (Yellow) Orange
(A)
Na 2CrO7  2H 2SO4  2CrO3  2NaHSO 4  H 2O

(A) (conc.) (B)
Bright orange
solid
Na 2Cr2O7  4Cl  6H 2SO 4  CrO2Cl2  2NaHSO 4  4HSO 4  3H 2O

(A) (C) (conc.) (deep red liquid)
So, A  Na 2Cr2 O7
B  CrO3
C  Cl
(b) 84 Po   82 X   83 Y [Y = Bi]
7. (a)
(b)
As after temperature T1 the G of reaction, C  Co, becomes more negative than Mg  MgO reaction,
So carbon can reduce MgO above temperature T1 but G of reaction C  CO, becomes more -ve than
Ca CaO reaction only above T2.
As T1 < T2
So, MgO can be reduced at lower temperature than CaO.
8. (a) Sulfide ore in first roasted in air to give NiO.
2NiS + 3O2  2NiO + 2SO2
To refine Ni, it is heated to about 50–60ºC in a steam of CO gas. Nickel passes off as its volatile
carbonyl, Ni(CO)4, this volatile product is passed over nickel shot at about 200ºC. Nickel is
deposited by Ni(CO)4 and is almost pure.
5060ºC
Ni(s)  4CO  Ni(CO) 4 (g)
Ni, 200ºC
Ni(CO) 4  Ni  4CO(g)
(b)
9. J  CrO 2Cl 2 (Chromyl chloride)

K  K 2 CrO 4 (Potassium chromate)
M  Cr2 (SO 4 )3 (Chromium (III) sulfate)
J  K transformation,
2K 2CrO 4  3SO2  2H 2SO 4 
 Cr2 (SO 4 )3  2K 2SO 4  2H 2O
(K) (M)
15. Complete chemical reaction occurs in above chemical transformation can be shown as
pH 6 dil. HCl
CrO3  CrO 42 
 2
 Cr2 O7
(A) (B) (C)
Cr2O72  6HCl  8H  
 Cl2  2Cr 3  7H 2O
(C) (E)
greenish yellow gas
16. (a)
BiI3  I  [BiI 4 ]
(B) (C) orange colour (soluble complex)
(b)
Br
H B H
N N
B B
(ii) (Y)  Br
 HBr N Br
H
(B3N3H3Br3)
21.
0.56 0.27 0.93 0.15 0.25

24. MnO 4 
(I)
 MnO 24 
(II)
 MnO34 
(III)
 MnO 2 
(IV)
 Mn 2O3 
(V)
 Mn(OH) 2
7 6 5 4 3 2
1.56
 Mn
(VI) 0
For MnO43– its standard reduction potential is greater value than the standard oxidation potential hence it will
undergo dispropotionation reaction due to overall standard potential is positive
e  MnO34  MnO 2 Eº  0.93
MnO34  MnO 24  e  Eº  0.27
2MnO34  MnO 2  MnO 42
Eºtotal = 0.93 – 0.27 = +0.66 V
Hence it will undergo disproportionation reaction.
26. Cu+2 + S2–  CuS (Black Precipitate)
CuS + conc. HNO3  Cu(NO3)2 + NO2 + S  (white ppt.)
8
Analytical Chemistry & Instrumental
Method of Analysis
IIT JAM 2009
1. The indicator phenolphthalein changes colour at pH ~ 9. This indicator is NOT suitable for accurate determination
of the end point in the titration of
(a) CH3COOH with NaOH (b) HCl with NH4OH
(c) HCl with NaOH (d) HCl with KOH
IIT JAM 2011
2. In ammonical buffer, oxine (8-hydroxyquinoline) forms yellow precipitate with
(a) Mg(II) (b) Ca(II) (c) Ba(II) (d) Sr(II)
IIT JAM 2014
3. In the measurement of hardness of water by complexometric titration, identify P and Q in the following equation.
[ P] – + [H2Y]2–  [Q]2– + [HIn]2– + H+
red colourless colourless blue
(a) P = MgY, Q = MgIn (b) P = MgY2, Q = MgIn2
(c) P = MgIn2, Q = MgY2 (d) P = MgIn, Q = MgY
IIT JAM 2015
4. The reagent ‘oxine’ commonly used in analytical chemistry is
(a) N CH 3 (b) N
OH OH
OH
O H 3C N
(c) N (d)
OH H 3C N
OH
IIT JAM 2016

5. Indicator used in redox titration is
(a) Eriochrome black T (b) Methyl orange
(c) Phenolphthalein (d) Methylene blue
IIT JAM 2017
6. The indicator(s) appropriate for determination of end point in the titration of a weak acid with a strong base is/are
(a) Phenolphthalein (b) thymol blue (c) bromophenol blue (d) methyl orange
IIT JAM 2018
7. Which plot represents a spectrophotometric titration, where the titrant alone absorbs light in the visible region?
Absorbance in the
Absorbance in the
visible region
visible region
end point
(a) end point (b)
Volume of titrant Volume of titrant

Absorbance in the
Absorbance in the
visible region
visible region
end point
(c) (d) end point
Volume of titrant Volume of titrant

8. Choose the correct answer(s) with respect to the magnesium-EDTA titration carried out in the pH range 7 –
10.5, using solochrome black as indicator
(a) Magnesium-indicator complex is more stable than the magnesium-EDTA complex
(b) At the end point, the colour changes from red to blue
(c) After the end point, the colour of the solution is due to the indicator.
(d) pH range of 7 – 10.5 is necessary for observing the specific colour change
ANSWER KEY
1. (b) 2. (a) 3. (d) 4. (b) 5. (d) 6. (*) 7. (a)

8. (b,c,d)
HINTS & SOLUTION

6. Titration of weak acid with strong base
14
13
Indicator Range
12
11 phenolphthalein 8.3 to 10.0
10 Steep curve
9 8 to 11 Thymol blue 8 to 9.6
8
7
6
Bromophenol blue 3.0 to 4.6
5
4 Methyl orange 3.1 to 4.4
3
2
1
Vol. of NaOH
Only those indicators having pH range equal to the range that lie within steep curve can be used for titration
 phenolphthalein and thymol blue are suitable indicators.
9
Nuclear Chemistry
(IIT JAM 2005)
1. The radioactive isotope used to locate brain tumors is
(a) 12 D (b) 15
7 N (c) 131
53 I (d) 13
6 C
2. The radioactive element Ra (Z = 86) emits three alpha particles in succession. Deduce in which group the
resulting element will be found?
3. A radioisotope sample has an initial activity of 23 dis/min. After 1/2 h, the activity is 11.5 dis/min. How many
atoms of the radioactive nuclide were present originally? [t1/2 = 0.69]
(IIT JAM 2006)
4. The half-life of a radioactive nuclide is 20 years. If a sample of this nuclide has an activity of 6400 disintegrations
per minute (dis/min) today, its activity (dis/min) after 100 years would be
(a) 850 (b) 1600 (c) 200 (d) 400
(IIT JAM 2007)
5. 215 undergoes an  emission to give element X followed by a  emission to give element Y..
84 Po
(IIT JAM 2008)
6. In the process
234 230
92 U 
 90 Th  X
X is:
(a)  particle (b) -particle (c) +-emission (d) -emission
(IIT JAM 2009)
7. Complete the following nuclear reactions:
(i) 14 4 1
7 N  2 He  1H  .......... (ii) 37 Li  11H  ...........
(IIT JAM 2011)
8. In the following equation X is:
241 243
95 Am   
97 Bk  X
(a) 2 10 n (b) 10 n (c) 2 11n (d) 42 He
(IIT JAM 2012)
9. 238
The total number of steps involved and number of beta particles emitted in the spontaneous decay of 92 208
U 82 Pb
respectively, are
(IIT JAM 2014)
10. In boron neutron capture therapy, the initial boron isotope used and the particle generated after neutron capture
respectively are:
(a) 11B and  particle (b) 10B and  particle (c) 11B and  particle (d) 10B and  particle
11. The number of  and  particle(s), generated in the following radioactive decay process, are:
238 234
92 U 92 U
(a) one  and two  particle (b) two  and one  particles
(c) one  and four  particles (d) no  and four  particles
(IIT JAM 2015)
12. A wood specimen containing 14C taken from an ancient palace showed 24 counts in 3 minutes per gram of
carbon in a detector. however, a fresh wood showed 52 counts in 2 minutes per gram of carbon. Assuming no
background signal in the detector and half life of 14C as 5730 years, the age (in years) of the wood specimen is
______
(IIT JAM 2016)
13. 214
The isotope 84 Po undergoes one alpha and one beta particle emission sequentially to form an isotope “X”. The
number of neutrons in “X” is _____.
(IIT JAM 2017)
14. A radioactive element undergoes 80% radioactive decay in 300 min. The half-life for this species in minutes is
______
(IIT JAM 2018)
15. The decay modes of 14C and 14O are
(a) – decay (b) positron emission
(c) – decay and positron emission, respectively
(c) positron emission and – decay, respectively
16. 24
Na decays to one-fourth of its initial amount in 29.8 hours. Its decay constant is ______ hour–1 (rounded up to
four decimal places).
(IIT JAM 2019)
17. A radioactive sample decays to 10% of its initial amount in 4600 minutes. The rate constant of this process is
________ hour–1. (Round off to two decimal places)
(IIT JAM 2021)
18. For the following fusion reaction,
4 1H  4 He  2  2  
the Q-value (energy of the reaction) in MeV (rounded off to one decimal place) is ______.
(Given: Mass of 1H nucleus is 1.007825 u and mass of 4He nucleus is 4.002604 u)
ANSWER KEY
1. (c) 2. (14) 3. (1000) 4. (c) 5. (*) 6. (a) 7. (*)

8. (a) 9. (b) 10. (b) 11. (a) 12. (*) 13. (127) 14. (129.15)
15. (d) 16. (*) 17. (*) 18. (26.7)
HINTS & SOLUTION

5. 84 Po   82 X   83 Y [Y = Bi]
7. (i) 14 4
 11H  17
7 N  2 He  8 O (ii) 7 1
 84 Be
3 Li  1H 

t ln 
12. 0.693  activity of dead sample 

5730 yr  52 / 2
 
5730 year  26 
t ln    9745.58 year..
0.693 8
A  A 0e kt
A0
 A 0e  k(29.8)
4
1
 e  k(29.8)
4
1
ln   k(29.8)
4
1.3862   k(29.8)
.38 1
k hr
29.8
k = 0.0465 hr–1
A  A 0 e t
A = 0.10 A0
0.10 A 0  A 0 e t
t = 4600 min
4600 230
t hr  hr
60 3
230

0.1  e 3

  230
ln 0.1  
3
 230
2.303log101  
3
2.303  3
  
230
 = 0.03 hr–1.
TOPIC WISE PYQ
(Sol.)
(Inorganic)
1
Periodic Properties
HINTS & SOLUTIONS
1. Ionic radii  –ve charge, here shielding effect increase because electron is added here, so size increase.
1
Ionic radii   ve charge , here shielding effect decrease because electron is remove here & size will decrease.
2. radial node = n – l – 1
(a) n – l – 1 = 3 –2 – 1 & 2 – 1 – 1
=0 & =0
(b) n – l – 1 = 3 –0 – 1 & 2 – 0 – 1
=2 & =1
(c) n – l – 1 = 3 –1 – 1 & 2 – 1 – 1
=1 & =0
(d) n – l – 1 = 3 –1 + 1 & 2 – 1 – 1
=3 & =0
3. Ionic radius of any cation depends on its valance shell number, n and charge on cation
Ionic radius  principle quantum number, n
1
 .
charge on cation
For K+ and Ca2+
n=3 [Ne]3s 2 3p 6
but Ca2+ has higher charge than K+
therefore smaller radius than K+.
For Mg2+ n = 2. 1s2 2s2 2p6
So smallest ionic radius
4. (b) n = 4 principle quantum number
l = 0 means s orbital and for s orbital M   1 is not valid or allowed.
(c) n = 3
l=3
VIGYAN VRIKSH |Inorganic chemistry (IIT-JAM)Solution
M   3
Possible value of l are 0 to (n – 1) i.e. 0 to (3 – 1) = 0, 1, 2
So (c) is not allowed.
5. In a group going from up to down molecular weight increases hence boiling point also increases.
Hence correct sequence of boiling point is CH4 < SiH4 < GeH4 < SnH4
Hence Correct answer is (d).
6. More the polaristion, lesser will be ionic character.
NaCl MgCl2 AlCl3
CaCl 2
 
positive charge on cation increases
size of cation decreases
Therefore, polarisation increases (Fajan Rule)
Therefore, co-valent character increases
Therefore, ionic character decreases.
7. Rb+, Kr and Br– have same number of valence electrons and are isoelectronic species.
Correct option is (a, d)
13.6Z2
8. The energy of H like species is given by E 
n2
 E  Z2
9. Inert pair effect is reluctance in bonding capacity of ns pair of electron on moving down in the group. Down the
group, Inertness of lone pair increases.
 Maximum inert pair effect = Pb.
10. Al  Metal
Si  Non-metal
Ge  Semimetal, but more like Si.
As  Semimetal
Sb  Semimetal
Te  Semimetal
Ca  Metal
B  Nonmetal
11. Oxides of metal are basic in character and also higher the electropositive character of metal, higher will be basic
character of the oxide, so MgO is more basic than Al2O3.
Oxides of non metals are acidic character.
5 4 3 3
P4 O10 Si O 2 Al 2 O3 Mg O
Oxidation state  acidic strength.
12. As N has half filled 2p orbital, which is more stable configuration than oxygen which has 2p4 and carbon has 2p2
configuration.
As half filled are more stable, so it requires higher energy to remove the outermost electron.
13. Compound Lattice Energy (kJ/mole)
LiCl 852
CaCl2 2256
LiF 1036
KCl 715
L.E.  charge (primary factor)
1

size
2 2
Ca Cl2  Max. ch arg e  Max L.E.
  LiCl  K
LiF
  Cl
small greater
size size

15. According to Hund’s rule of maximum multiplicity states that for a given electron configuration, the lowest energy
term is the one with the greatest value of spin multiplicity. This implies that if two or more orbitals of equal energy
are available, electrons will occupy them singly before filling them in pair, and, “According to Pauli exclusion
principle, it is impossible for two electrons of a poly-electron atom to have the same values of the four quantum
numbers”.
So, from the above rule only (c) is the acceptable valence shell electronic arrangement.
16. As we move from left to right in periodic table, then we move from metal to non-metal. So, their oxides will
change its character from basic to acidic.
17. In H-F, H2O, NH3 and CH4 all bonds are formed by 1s(H) and sp3 orbital of F, O, N and C respectively.
18. Rb, Sr, In, Sn all lie in the same period of periodic table. As charge on metal ion increases its size decreases.
19. The correct valence shell electronic configuration of the element with atomic number 22 is [Ar]4s23d2.
20. Elements IE1
H 13.6 eV (non-metal)
Be 9.3 eV
B 8.29 eV
He 24.58 eV (inert gas)
Here He and Be has more IE than corresponding H and B due to the completly filled 1s and 2s subshell.
21. According to Fajan’s rule, if cation is large and anion is small, then ionic character is higher. So, correct order is
represented by (d)
22. LiF has highest lattice energy and also maximum ionic character, so it has highest melting point.
23.
2
Chemical Bonding
HINTS & SOLUTIONS
–
I F F F
I Cl F S
1. F
I F F
sp3d sp3d sp3d
7  2 1 Br
 Br3 

2. , 4 Tetrahedral
2
Br Br
Br
7  2 1 Br
 Br3 

, 5 Trigonal Bipyramidal
2
Br
F
73 F Br
 BrF3  , 5 Trigonal Bipyramidal
2
F
3. Species No. of Bonding e– s No. of Antibonding e– B.O
O2 +
10 5 2.5
O 2– 10 7 1.5
O 2 2– 10 8 1
 O 2  O 2  O 22 is correct bond order sequence.
4. Observed magnetic properties depends on electronic arrangement whether electrons are unpaired or paired.
(1) NO there is one unpaired electron
(2) O2 there are 2 unpaired electrons
(3) B2 there are 2 unpaired electrons
(4) C2 all electrons are paired.
So NO, O2, B2 are paramagnetic.
5. NO2 is odd electronic species and therefore have one unpaired electron and exhibit paramagnetism where as
NO2+ and CO2 are diamagnetic have linear geometry and are also isoelectronic.
Correct options are (b, c and d)
6. Bond order of N2+ is calculate through its molecular electronic configuration.
N 2 : 1s2 1s*2  22s *2
2s x   y  2p z
2 2 1
1
B.O   Nb  Na 
2
1
  9  4   2.5
2
7. XeF6 is capped octahedral with partial participation of lone pairs in hybridization which import distorted structure
to XeF6 therefore exhbit non zero dipole moment.
In XeO3 there is one lone pair and 3 bond pairs possessing sp3 hybridization and hence pyramidal shape with non
zero dipole moment.
8. SF4
V X A C
Steric Number =
2
A = Anionic charge, C = Cationic charge, V = Valence electron of central atom, X = monovalent atoms
64
Steric Number = 5
2
Hybridisation  sp3d with one lone pair
F
F
S
F
F
see-saw shape
XeF4
8 4
Steric Number = 6 sp3d2 = octahedral geometry with two lone pair
2
F F
Xe square planar
F F
ClF4+
7  4 1
Steric Number =  5 sp3d with one lone pair  see saw
2
ClF4–
7  4 1
Steric Number = = 6 sp3d2 with two lone pair  square planar
2
Hence SF4 and ClF4+ have see-saw shape.
9. BF3 is trigonal planar hence
If the molecules have same hybridization and same number of lone pair on central atom then, the bond angle
decrease, if the electronegativity of the surrounding atom increases (VSEPR theory).
PH3 is a drago molecule.
because PH3 is a drago molecule
The correct bond order, BF3 > NH3 > NF3 > PH3.
10. The configuration are
B2  2s 2  * 2s 2 2p1x 2p1y 42
Bond order =  1 , 1
(one ) 2
C 2  2s 2  * 2s 2 2p 2x 2p 2y 62

Bond order =  2 , 2
(two ) 2
N2 is N  N 1 and 2
O2 is O = O 1 and 1
hence, correct options are (b) and (c).
11. Be2 = ls2 *1s2 2s2 *2s2
44
 Bond order = 0
2
12. Z = 23
1s2/2s22p6/3s23p63d3/4s2
 = (2 × 0.35) + (18 × 1) = 18.7
Z* = Z –  = 23 – 18.7 = 4.3
s
13. cos  
s 1
s
cos101º   0.1908
s  100
0.1908
%s =  100  16.02%
1.1908
dV  1 d1 d 6 7
14. F  Given : V  6   F    6   F   r  F  6r
dr  r  dr  r  dr
6 1
F 7  F 7
r r
15.
sp2 hybridisation and one lone-pair

While NO3– and CO32– are trigonal planer and BrF3 is having T-shape.
16. In TeF4
Number of bond pairs = 4
Number of lone pairs = 1
Therefore, steric number = 4 + 1 = 5
Hence geometry is trigonal bipyramidal. But shape will be see-saw.
F
F
Te
F
F
17. Species having equal number of electrons are known as isoelectronic species. In NO+ total electrons = 7 + 8 –
1 = 14
In CO total electrons = 6 + 8 = 14
18. NH4+Cl–  ionic forces (electrostatic)
HF  H-bonding
HCl  dipole-dipole interaction
Ar  London forces
19.

20. Square antiprismatic
21.

22. (a) CH  CH is the most acidic compound among ethane and ethylene.
CH3CH3  CH 3CH 3  H 
CH 2  CH 2  CH 2  CH  H 
CH  CH  CH  C  H 
CH3CH  
CH 2 CH < HC  C 
2
  
sp3 hybridized  sp 2 hybridized  sp hybridized 
 25% s character  33% s scaracter  50% s character 

   
Increasing % s-character increasing stability
• The acidity of H–A increases as the percent S-character of the A– increases.

• The higher the percent s-character of the hybrid orbital, the closer the lone pair is held to the nucleus, and the
more stable the conjugate base.
Acetylene  H  C  C  H
23. NO2+ O N O
increasing order of ONO bond angles NO 2  NO 2  NO2

24. Whenever there is possibility of resonance, then l.p. of oxygen align itself in a orbital such that it can participate in
resonance (i.e. sidewide overlap of orbitals) is possible, which causes change in hybridisation of oxygen from sp3
to sp2.
25.
XeO2F2  see-saw
SF4  see-saw
BF4–  tetrahedral
26. C–H bond
Acetylene sp(C) – 1s (H)
(50% s character)
Ethylene sp2(C) – 1s (H)
(33% s character)
Methane sp3(C) – 1s (H)
(25% s character)
27. The electronegativity of F is higher than Cl. So, strong intermolecular hydrogen bonding in HF than
HCl.
28. SF4
O O O
NO3–: O Trigonal planar.
N O N O N
O O O
  
29. N1  N 2  N3 (azide ion)
Formal charge = (no. of valence e– in free neutral atom)
1
– (number of bonding e–) – (number of non-bonding e–)
2
N1 = 5 – 2 – 4 = – 1; N2 = 5 – 4 – 0 = +1; N3 = 5 – 2 – 4 = – 1
S
30. SO2  O 2-bond, 2-bond and 1 l.p. on sulfur. But  bond has no role in shape
O
31.
trigonal bypyramidal geometry
32. Since lobes will the interacting in same phase, the overlap between atomic orbitals will be positive.
33. N2, CN– and NO+ all have 14 electrons, same as CO, but O2+ has 15 electrons.
34.

35. SF4 has not zero dipole moment due to its unsymmetrical see-saw structure.

36. In graphite all carbon are sp2 hybridized and 1-electron lies in p-orbital of all carbon atoms which are
4
delocalized such that there is partial double bond character, such that bond order is .
3
OR
Total no. of bond 4
Bond order = Total no. of resonating structure =
3
37.
3
Coordination Compounds
HINTS & SOLUTIONS
1. (a) (I), (II), (IV)
If an octahedral complex has two bidentate ligands then cis isomer will be definitely optically active.
If an octahedral complex has 3 chelate rings then it is always optically active.
In case of trans – [CrCl2(oxalate)2]3– POS is present therefore is not chiral.
2. d7 high spin, octahedral
  2 3 4
(a) CFSE  5    5   2  5   0   5  0 (P = pairing energy)
   
3. (A) [Cu(H2O)6]2+ – more distorted
Magnitude of JTD  eg (unsymmetry) > t2g (unsymmetry)
 More electron density, more distortion.
(B) (I) [CoF6]3–  d6 CFSE  [(–0.4 × 4) + (2 × 0.6)] o  – 0.4 0
M.M.  4(4  2)  24 BM
(II) [Fe(CN)6]3–  d5 Low spin CFSE  (–0.4 × 5)0 + 2P = –2.0 0 + 2P
M.M.  1(1  2)  3 BM
(III) [NiCl4]2– d8
tetrahedral CFSE  [(–0.6 × 4) + (4 × 0.4)]t = –0.8 t
M.M.  2(2  2)  8 BM
4. (c) [CoCl4]2– Intense blue colour.
Tetrahedral  Relaxation in laporte selection rule
Tetrahedral  Pd mixing
Tetrahedral  Intense colour than octahedral
5. (b), (c)
for orbital angular momentum contribution, t2g must be unsymmetrically filled.
6. (b) Rh3+ > Co3+ > Co2+
oxidation state   Zeff   o
In transition metals, down the group, Zeff increases.
7. Ti(H2O)63+  d1
CFSE = [–0.4 × 1 + 0.6 × 0]0
= – 0.4 0
= – 0.4 × 20300 cm–1
= 8120 cm–1
8. [CoCl2(en)2]Cl
9. Hydration of metal ions (M+2) produces an enthalpy change that is commensurate with the size, charge of the ion
and crystal field stabilisation energy (CFSE).
So, Hhydration shows non-linear variation if C.F.S.E.  0. If CFSE = 0 (i.e. for Ca, Mn and Zn which has d0,
d5 and d10 configuration respectively), then it lies on the straight line.
10. CH3– is a ligand which is  donor and lies high in spectro chemical series as it is a strong sigma base.
11. [Cr(H2O)6]+3
 2  6
C.F.S.E.  3     0     208 kJ  249.5kJ
 5  5
[FeF6 ]3 
12. (a) (i) Here Fe is in +3 O.S. and F– is a weak field ligand.
(octahedral complex)
[Fe(CN)6]3–  Here Fe is in +3 o.s. and CN– is a strong field ligand.

Octahedral complex.
(ii) [FeF6]3–
(iii) [Fe(CN)6]3–
Let P0 = Pairing energy.
 2 
 CFSE = 5    0   2P0
 5 
CFSE  2  0  2P0
(b) [Fe(CN)6]3– ion oxidizes Fe+2 to Fe+3, and itself get reduced to [Fe(CN)6]4–
 Fe2  [Fe(CN)6 ]3  Fe 3  [Fe(CN)6 ]4

Then Fe+3 & [Fe(CN)6]4– combine to give a precipitate called Turbull’s blue.
4Fe 3  3[Fe(CN)6 ]4  Fe 4[Fe(CN)6 ]3  Turnbull 's blue
dark blue complex
The intense blue colour arises from electron transfer between Fe+2 and Fe+3.
13.
Maximum CFSE is possible for e2, t20 or e4, t23 configuration.

Therefore, CFSE (maximum) = –2 × 6 Dq
= –12 Dq.
N 2 2
14. (d)  M 
3RT
15. (A) (I) Pentamminechlorocobalt (I)
(II) Potassium tetrachloropalladate (II)
(B) [Mn(H2O)6](NO3)2
d5  high spin system 5 unpaired electron
M.M.  5(5  2)  35 CFSE = [–3 × 0.4 + 2 × 0.6] 0 = 0

= ~ 6 B.M.
16. (a) In case of [NiCl4]2–, there is crystal field splitting of 3d-orbitals in presence of tetrahedral field of 4Cl– ligands.
In [NiCl4]2– complex Ni is in +2 oxidation state.

Ni 2  [Ar]3d8 4sº 4p0x 4p0y 4p0y
 
sp3  hybrization
Spin only magnetic moment (µs) = n(n  2) B.M.  2(2  2)  8 B.M.
 3  2 
C.F.S.E. = 4    t   4   t 
 5  5 
4
 C.F.S.E. =  t
5
17. (b) d4 high spin  eg unsymmetrically filled
18. (c) K2Cr2O7

O  Cr
  3d LMCT
19. Fe  2   K 3 Cr  CN 6   KFe Cr  CN 6  

100ºC
 KCr  Fe  CN 6 
brick red colour dark green
20. (d) CoFe 2O 4 CFSE

y
X
|x| > |y|  Inverse spinel
21. [Fe(phen)2(NCS)2]
Fe2+  d6
when temperature is high 200 K When temperature is low,
High spin Low spin
M.M.  4(4  2)  4.9 BM M.M. = 0

22. Gives ppt. with AgNO3 means Cl is outside the coordination sphere
 [Co(NH3 )4 (SO 4 )]Cl
[Co(NH 3 ) 4 (SO 4 )]Cl  AgNO3  [Co(NH 3 ) 4 (SO 4 )]NO3  AgCl 

23. K3[Fe(oxalate)3] K3[Ru(oxalate)3]
 
Weak field ligand In 4d series, almost all are strong field ligands.
Fe3+ Ru3+
eg2 d5 system
t 32g 5 unpair electron one pair electron
M.M.  5(5  2)  35 M.M.  1(1  2)  3
t 32g eg2 t 52g e0g

24. [NiCl4]2– Paramagnetic
Pairing occurs in case of Pd since it has greater nuclear charge leading to pairing of electrons.
25.
eg
0.6 0
e.s.
0.4 0
t2g
g.s.
d6 high spin CFSE = 4 × (–0.4 0) + 2 × 0.6 0

= – 1.6 0 + 1.2 0
 –0.4 0
d6 low spin CFSE = 6 × (–0.4 0) + 2 P P = pairing energy
= –2.4 0 + 2P
26. CaO < MnO < VO
z z
0
27. [Ni(PPh3)2(SCN)2]  Paramagnetic, therefore, tetrahedral
Isomers:
[Pd(PPh3)2(SCN)2]  Diamagnetic, therefore, square planar
28. (a) A ccording to spectrochemical series: I – < Br– < SCN– < Cl– < S2– < N3– < F– < ONO– < OH– < SO42– <
C2O42– < O2– < H2O < EDTA4– < NH3 < Py < en < bpy < NO2– < PR3 < CH3 < CN– < CO.
29. In [Co(NH3)6]3+ cobalt is in +3 oxidation state i.e. Co3+ = [Ar]3d64s0
The complex is octahedral in which splitting takes place as
+0.6 0
0
–0.4 0
As NH3 is strong ligand hence here 0 is high.
Each electron entering in t2g looses 0.40. Hence, crystal field stabilisation energy will be CFSE = –(6 ×0.4)0
= –2.4 0
As number of unpaired electrons and zero hence spin only magnetic moment is given by
µ  n(n  2) B.M.
µ  0(0  2)  0
30. (c) K2Cr2O7 Porphyrin  highly conjugated system
LMCT  - 
O  Cr
P (3d)
H S
31. Cd(CH3COO) 2 
2  CdS  2CH COOH
3
(yellow)
The ligand to metal charge transfer transition is responsible for yellow colour.
32. Tetrahedral complexes are always high spin as splitting energy is lower in case of tetrahedral complexes.
33.
CFSE = –0.80
7360 cm–1 = –0.80
7360cm 1
  0
0.8
7360cm 1  6.63  10 34 Js  3  10cm / s  6.023 10 23 mol
  110.75kJ / mol
0.8
Correct answer is (110.75 kJ/mole)
34. Zn 2 (Td)  CFSE  0
Fe3 (Oh)  CFSE  0
But Fe3+ due to greater positive charge prefer to go in Oh void. Hence, behaves as normal spinels.
35.
1 1 1 3
S  s1  s 2  s3 .....    
2 2 2 2
L=3
J = |L + S|  more than half filled
J = |L – S|  less than half filled
As in d7 configuration it is more than half filled
J = |L + S|
3 9
J = 3 
2 2
0 1 2 3
L=
S P D F
3
 2S  1  2   1  4
2
Ground state term = 2S + 1LJ (for L = 3) = 4F9/2 (more than half field)
36. (Et 4 N)2 [NiCl 4 ]  [NiCl 4 ]2
Unpaired electron = 2
B  n(n  2)  2(4)  8  2.83
37.  t2g symmetrically filled
 t2g unsymmetrically filled
 t2g symmetrically filled
 t2g symmetrically filled
For orbital contribution t2g should be unsymmetrically filled.

Correct answer is (b).
38. 4
+
[Co(NH3)4Cl(NO2)]
a b ambident ligand
b b a a
a a a a a b a b
Co Co Co Co
a a a a a a a a
ONO NO 2 ONO NO 2
39. [Pt(CN)4]2– [NiCl4]2–

Square Planar – dsp2 Tetrahedral – sp3
d8 system d8 system
CN– strong ligand pair up the electron Cl– weak ligand can’t pair up electron
so 2
so, has unpair electron, Paramagnetic
dsp
No unpair electron, Diamagnetic
40. Mn 2  3d5 (HS)  t 32g eg2

CFSE = [–0.4 × 3 + 0.6 × 2] 0 = 0 0
Correct option (a)
41. (d) Due to JTD
2+
Cu
d9 configuration Zout Cu2+  d9
42. In [Cr(C2O4)3]3– the electronic configuration of Cr3+ is d3. So, here d-d transitions are also possible. In [NiO2]2–
 Ni2+ has electronic configuration d. Here also d-d transitions are possible.
But in case [CrO4]2– and [ReO4]– electronic configuration of central atom is d0.
So, there only charge transfer is possible.
Correct option is b, c
43. (b) Stable octahedral Al2O3 lattice, colourless when Cr3+ replaces an aluminium atom, the octahedral arrangement
is distorted & d-d transition occurs which impart red colour.
44. W hen NO binds in linear fashion, it acts as 3e– donor, the formal charge is +1 and shows  and  interaction
(NO+)
When NO binds in bent fashion, it acts as 1e– donor, formal charge is –1 and show only  interaction (NO–)
45. K2NiF6
When Ni+4, F– will act as strong field ligand  Ni+4 form low spin system  d6(LS)
 Number of unpaired electron = 0
n=0
eg
t2g
+2
+2
Cu
46. Ni
+2
+2
Zn
Co
Fe +2
+2 +2
+2 V Cr
Ti
Hydration Energy
+2
Mn
Sc +2
+2
Ca Z
Observed H.E. = calculated H.E. + CFSE
As Mn+2 is d5 system
 CFSE = 0 hence lowest H.E.
Correct order is Ni > Co+2 > Cr+2 > Mn+2
+2
1
47. Wavelength of absorption  splitting energy
Also, splitting energy depends on field on ligand, stronger the field of ligand, more will be splitting energy.
Order of ligand strengthCN– > en > H2O > F
Correct order of max is
[CrF6]3– > [Cr(H2O)6]+3 > [Cr(en)3]+3 > [Cr(CN)6]+3.
48. JTD is observed whenever their is electronic degeneracy or t2g / eg are unsymmetrically filled.
d5 high spin d5 low spin
eg eg
t2g t2g (unsymmetrical)

No JTD JTD
d6 high spin d6 low spin
eg eg
t2g (unsymmetrical) t2g

JTD No JTD
Correct option is (b, c)

Br Py Br Py Br Cl
Pt , Pt , Pt
49. Cl NH3 H3N Cl H3N Py
1 2 3
3 isomers are possible for [Pt(Py)BrCl].
50. Ir+3 is a 5d6 metal ion having highest Zeff. complexes with strong  acceptor CN– to provide largest splitting of d
orbital in octahedral environment.
Rh+3 is 4d6 metal ion shows larger splitting with  acceptor CN– is compared to  donor I– ligands.
Therefore,  0 :  Rh  CN 6    RhI 6 
3– 3
For Co3+ which is 3d6 I– is weaker field ligand therefore  0 is smallest in  CoI6 
3
3 3
So  Ir  CN 6    Rh  CN 6    RhI 6    CoI 6 
3 3

51. Electronic contant Ti3+ 3d1 4s0
CFSE = – 0.4 0
7680
 0
0.4
1
 0  19200 cm 1  wavenumber  

1
19200 

1
  0.0000521 cm
19200
  521 10 7 cm
  521 107 10 2 m 
= 521 × 10–9 m
= 521 nm
 10–9 m = 1 nm
52. Magnetic moment values suggests no. of unpaired electrons in given metal ions
Species Magnetic moment Unpaired electrons Configuration
Mn3+ 4.95 4 t 32g e1g
Fe+3 6.06 5 t 32g eg2
Co+3 0.0 0 t 62g e0g

*
eg (Metal character orbitals)
53.
 (I )
* –
 (Br )
* –
 (Cl )
* –
eg
t2g
*(I–)
 (Br )
* –
 (Cl )
* –
(Ligand character orbitals)
Charge transfer is due to t2g () bonding to eg* antibonding MO’s electronic transistion
Energy gap between   I e is minimum and maximum for   Cl e

 *  *
g g and hence max value of photon
to effect charge transfer follows the order
 I   Br    Cl
III > II > I
54. Rate of Cl– substitution by nucleophile is governed by kinetic trans effect of trans ligand. (opposite and leaving
group) Strength of trans ligand depends on  donar and  acceptor tendency of ligands.
 H   CH 3  Ph   Cl is order of ligand to exert trans effect, therefore rate of substituion of Cl– is fastest
in (iv) and slowest in (iii)
55. [Co(NH2 – CH2 – CH2 – NH2)Cl2]+
Possible geometrical isomer
Cl N
N N Cl N
en Co en Co
N N Cl N
Cl N
Trans Cis
Cl N N N N Cl
Co Co
Cl N N Cl
N N
Total isomer = 3
for [Co(H2N – CH2 – CH2 – NH2)3]3+
en
N
N N
geometrical en Co
N N
N
en
[Co(en)3]3+ is chiral. Complex can exist in two entaiomeric forms. [d and l]

en en
N N
N N N N
en Co Co en
N N N N
N N
en en
l - Isomer d - Isomer
Total isomer = 2
Hence, total isomer which possible for both compounds are 3 + 2 = 5
Correct option answer is 5
2
56. Square planar : d x 2  y2 sp
3
Trigonal Bipyromidal : sp d z2
57. (c) trans – [Co(CN)4(H2O)2]–
OH2
CN CN
Co
CN CN
OH2
dipole moment = 0
oxidation state of Co is
x – 4 = –1
x=3 eg
Co3+ d6 t2g
Number of unpaired e– = 0
So,  = 0
CFSE = (–0.4 0 × 6)
= –2.4 0
(d) trans – [Fe(CN)4Cl2]4–
4–
Cl
CN CN
Fe
CN CN
Cl
dipole moment = 0
oxidation state of Co is
x–4–2=–4
x = –4 + 6
x=+2 eg
Fe2+ : d6 t2g
Number of unpaired e– = 0
CFSE = –6 × 0.4 0
= –2.4 0
Correct option is (c, d)
58. [Cu(H2O)4(NH3)2]2+
Cu2+ = d9
2
Eg
2
T2g 2
B2g
2
E D
2
A1g
2
Eg 2
B1g
one transition 2Eg  2T2g.

But due to Jahn Teller distortion 2Eg splits into B1g (lower energy) and A1g (Higher energy) and 2T2g splits into B2g
and Eg.
Now transition occur from B1g to the A1g, B2g or the Eg states.
Hence: If consider Jahn Teller distortion then expected d - d transition is 3.
If not consider Jahn Teller distortion then d - d transition is 1.
Ni  CN 4   Ni  CN  4
2
K/liq.NH3 4
59. 33 ºC
Ni  CN 4  Ni  0   d10  tetrahedral geometry

4
60. [Co(NH3)4]2+  Co2+  d7
CFSE = (– 0.6 × 4 + 0.4 × 3)o

= (– 2.4 + 1.2)o
= – 1.2 o
= – 1.2 × 5900
= – 7080 cm–1
7080
 KJ / mol
83.7
= – 84.58 KJ / mol
61. [Co(CN)5(H2O)]3–
eg
t2g unsymmetrical
Co2+  d7
t2g
eg
t2g unsymmetrical
[Mn(CNMe)6]2+  d5(LS)
t2g
Therefore both (a) and (d) complex show Jahn Teller Distortion
62. [Ti(H2O)6]3+  d1
eg eg
h
d1 d1
t 2g t 2g
S =1–1=0 spin allowed transition

L =d =2
=2–2=0 l  ± 1 Laporte forbidden transition.
63. No. of microstates for d8 electronic configuration
n!
No. of microstates 
 n  r !r!
10!

10  8!8!
10!

2! 8!
10  9  8!

2  8!
= 45
64. [NiCl2(PPh3)2]  tetrahedral complex  Ni2+  d8.
d8
No. of unpaired electron = 2
Magnetic moment (µ) = n  n  2
 2  2  2
 2 4
 8
= 2.82 BM
[Mn(NCS)6]  Mn  d54– 2+
d5
No. of unpaired electron = 5
Magnetic moment (µ) = n  n  2
 5 5  2
 5 7
 35
= 5.92 BM
dichloridobis (glycinato) cobaltate (III) ion

O O
C C
O CH2 H2C O
Cl NH2 H2N Cl
65. Co Co
Cl NH2 H2 N Cl
O CH2 H2 C O
C C
O O
I IV
Mirror
H2 H2
C C
H2 N C O O C NH2
Cl O O Cl
Co Co
Cl O O Cl
C O O C
H2N C C NH2
H2 H2
II IV
Mirror
O O
C C
O CH2 H2C O
Cl NH2 H2N Cl
Co Co
Cl O O Cl
C O O C
H 2N C C NH2
H2 H2
III VI
Mirror
Total number of opticla active isomerss = 6 (six)
66. Co2+(td)  d7  2e– system
Ground state 4A2
Number of transition observed = 3
67. [Co(H2O)6]2+
–1 –2
7
d
+2 +1 0
The number of unpaired electrons in [Co(H2O)6]2+ is 3.
68. Ti3+  d1 system
Number of microstate = nCr
n!

r! n  r  !
n = 10 (d orbital)
r=1
10
C1
10!
Number of microstate   10 microstates
1!9!
4
Organometallics
HINTS & SOLUTIONS
1. As metal donates electrons to antibonding -orbital of CO, C – O bond stretching frequency decreases, which
can be studied by IR-spectroscopy.
2. Sulfide ore in first roasted in air to give NiO.
2NiS + 3O2  2NiO + 2SO2
To refine Ni, it is heated to about 50–60ºC in a steam of CO gas. Nickel passes off as its volatile carbonyl,
Ni(CO)4, this volatile product is passed over nickel shot at about 200ºC. Nickel is deposited by Ni(CO)4 and is
almost pure.
5060ºC
Ni(s)  4CO  Ni(CO) 4 (g)
Ni, 200ºC
Ni(CO) 4  Ni  4CO(g)
3. BnH(n+4)  nido-boranes BnH(n+6)  arachno-boranes
B2H6 = [B2H2]4– B4H10 = [B4H4]6–
4. Orbital overlaps in metal carbonyls:
5. Since the -accepters attached to central metal cause the increase in the B.O. of CO, CO vibrational frequency
increases. The order of -acceptor is PF3 > PCl3 > P(OR)3
Therefore, order of vibrational stretching frequency is {P(OMe3)3} Mo(CO)3 < (PCl3)3Mo(CO)3 <
(PF3)3Mo(CO)3.
6.
Due to –I effect of chlorine group increases the double bond character. So, option (c) having highest carbonyl
stretching frequency.
7. Species having equal number of electrons are known as isoelectronic species. In NO+ total electrons = 7 + 8 –
1 = 14
In CO total electrons = 6 + 8 = 14
8. In metal carbonyl as electron density on metal increases back donation from metal to * orbital of CO increases
and M-C bond strength increases while C-O bond strength decreases.
1
Electron density on metal  M-C bond order  C  O bond order
[Mn(CO)6 ]  Cr(CO)6  [V(CO) 6 ]  [Ti(CO)6 ]2

On moving left to right
Electron density increases
M-C bond order increases.
4CO(g)
9. Ni(s) Ni(CO) 4 
1 atm / 25º C
2NaC H
FeCl2 
5 5 2NaCl  [Fe(5C5 H 5 ) 2 ]
ferrocene
10. In transition metal alkene complex backbonding weakness the double bond of the alkene and -bonding and
back-bonding synergistically strengthen metal-alkene interaction.
Correct option (a, b)
11. Value of ‘x’ in [Cu(CO)x]+
Valence electron in Cu = 3d104s1
Cu+ = 3d10. So, 2x + 10 = 18  2x = 8 x=4
Correct option is (C)
12. (Free) NO    N O  2250 cm–1
(Free) NO   N O  1896 cm–1
In NO+ bond order is 3 and in NO bond order is 2.5. Higher the bond order, higher the bond strength. So, higher
1 k
the bond strength higher the frequency,   , where k is bond strength.
2 
NO linear  N O  1830 cm–1
Due to back -bonding, the bond order of N-O will decrease and hence N-O stretching frequency decreases.
NO linear 1672 cm–1
NO bridge 1505 cm–1

Due to more back -bonding in the complex, the N-O bond order will decreases and its N–O stretching
frequency decreases consequently.
13. The homogeneous catalyst used in water gas shift reaction is RuCl2 (bipyridyl)2.
14. When NO binds in linear fashion, it acts as 3e– donor, the formal charge is +1 and shows  and  interaction
(NO+)
When NO binds in bent fashion, it acts as 1e– donor, formal charge is –1 and show only  interaction (NO–)
15. Strength of Metal-Carbonyl back bonding depends on availability of electron density on metal.
2
In Ti  CO 6  Ti is in –2 oxidation state and has highest donating tendency towards * of carbonyl
2
Therefore highest metal-carbon back bonding is observed with  Ti  CO 6  .
16. (a) Carbene is neutral species
H
C not charged.
H
(b) Nitrene is intermediate in curtius rearrangement
(c) Carbene shows N–H/O–H and C–H insertions and also cyclopropanation ring formation with alkenes so
can insert in both ,  bonds.
(d) No carbene can never be generated from amine on reaction with nitrous acid, it gives carbocation, not
carbene.
Correct options are (a and c)
17. For oxidative addition reaction, metal center should be electronically rich which can be achieved only when there
are relatively poor  acceptors ligands in the complex.
 PMe3 PPh3 are weaker  acceptor than CO
 Complex I[IrCl(PMe3)3] in pair 1 relatively easily undergo oxidative addition reaction.
In pair 2, complex IV [IrCl3(PPh3)], Ir is in +3 oxidation state.
So, less electron density in case of IV in comparison to III in which metal in +1 oxidation state.
If  Fe  CO 4  SiMe3   is a 18e– species then 8e– from Fe + 8e– from 4CO + 1e– from SiMe3  n  18
n
18.
8 + 8 + 1 + n = 18
17 + n = 18
n = 18 – 17 = 1
As n = 1 must be added to achieve 18e–
 n must be an extra e– and hence n = –1
So correct formula of complex is

  Fe  CO  4  SiMe3  
19. Number of vertices in iscosahedral closo borane is 12.
20. Higher the negative oxidation state of metal ion more will be the backbonding, greater will be the M – C bond
strength
III > IV > I > II
21. B5H11
[B5H5]6–
Arachno
22. (a) [Co2(CO)8]
VEC = 9 × 2 + 2 × 8 + 2
= 18 + 16 + 2
= 36 e–
(follows 18 e– rule)
(b) [Fe(CO)4]2–
VEC = 8 + 2 × 4 + 2
= 18 e–
(c) [HMn(CO)5]
1+7+2×5
= 18 e–
(d) [(5 –C5H5)RuCl(CO)(PPh2)]
VEC = 5 + 8 + 1 + 2 + 1
= 17 e–
(does not follows 18 e– rule)
R
23. (a) Cu Li
R
Lithium divinylcuprate also called the gilman reagent is an organocopper reagent.
(d) Isopropyl magnesium iodide
H3C
Structure Mg Cl
H3C
This is an example of the organomagnesium reagent.
Hence, correct option is (a) and (d)
1
24. Acidic strength   – acceptor ligands and  acidic strength
 Order of  – acceptor ligands are

CO > P(OCH)3 > PPh3
 Order for pKa value will be
HCo(CO)4 < HCo(CO)3[P(OCH)3] > HCo(CO)3(PPh3) < HCo(CO)2(PPh3)2
25. (a) [(5 – C5H5]Ti (CO)4]–
TVE = 5 + 4 + 4 × 2 + 1
= 18 e–
(b) [TaCl3(PEt3)2(CHCMe3)]
TVE = 5 + 3 × 1 + 2 × 2 + 2
= 14 e–
(c) [Mn(SnPPh3)2(CO)4]–
TVE = 17 + 1 × 2 + 4 × 2 + 1
= 18 e–
(d) [(5 – C5H5)Ir(CH2)(PMe3)]
TVE = 5 + 9 + 2 + 2
= 18 e–
26. Greater the electron wighdrawing group greater will be the  – back bonding and greater will be the C = C bond
length.
 Order of electron withdarwing group is CN > HF > H
 Order of C = C bond length will be
II > IV > III > I
27. (a) CpMo(CO)3 = 5 + 6 + 3 × 2
= 17 e–
Cpw (CO)3 = 5 + 6 + 3 × 2
= 17 e–
Both are isoelectronic
(b) BH = 3 + 1
= 4 e– (deficiency of 4e–)
CH = 4 + 1
= 5e– (deficiency of 3 e–)
Neither isolobal nor isoelectronic
(c) CH3 Mn(CO)5

4 + 3 = 7 e – 7 + 5 × 2 = 17 e–
CH2– NH2
(d)
4 + 2 + 1 = 7 e– 5 + 2 = 7 e–
isolobal as well as isoelectronic
Correct option is (a, c, d)
28. [B10H10]2– [B10H14]
 
Closo [B10H10]4–

Nido
1
29. Stretching frequency of CO  extent of back bonding
extent of back bonding  magnitude of –ve charge on complex / metal i.e. more e– rich the metal is, more will be
the extent of back bonding.
Trend of e– richness:
[Fe(CO)4]2– > [Co(CO)4]– > [Ni(CO)4] > [Cu(CO)4]+
 extent of back bonding follows the same trend.
Hence, the order of increasing CO stretching frequency will be [Fe(CO) 4]2– < [Co(CO)4]– < [Ni(CO)4] <
[Cu(CO)4]+
CO
OC
30. Fe CO
OC
CO
One band equatorial CO and one band for axial CO.
PPh3 H
H H Me PPh3
Rh Rh
31. Ph3P Cl PPh3
Cl
Me
18 e– 16 e–
1. Complex goes from 18 e– to 16 e–.

2. Migratory insertion is taking place.
5
Main Group Elements
HINTS & SOLUTIONS
1. Increasing lewis acidity order:
BF3 < BCl3 < BBr3
In BF3  2p –2p back bonding most effective due to similar size and energy of ‘p’ orbitals.
BCl3  2p – 3p back bonding less effective because difference in p-orbital energy and also bond length is
large.
In BBr3  2p – 4p least back bonding, due to larger difference in size and energy of p orbital and also bond
length is large.
1
Lewis acidity  back bonding
2. (a) Production of elemental silicon from silica involves these steps:

(i) Reducing SiO2 with high purity coke
SiO 2  2C  Si  2CO
(ii) Converting Si to SiCl4 and purifying this SiCl4 by distillation,
Si + 2Cl2  SiCl4
(iii) Reduction of SiCl4 by Mg or Zn.
SiCl 4  2Mg  Si  MgCl 2
SiCl 4  2Zn  Si  ZnCl2
Ultra pure Si can be made from above obtained Si via Zone refining.
(b)
3.  4H3PO3 ; PCl5  H 2O  H 3PO 4 ;

P4O6  6H 2O 
P4S10  H 2O  H3PO 4  H 2S
Ca 3 (PO 4 ) 2  H 2SO 4  H3PO 4  CaSO 4
4. (a) (i) H3COCH3 has more Lewis base character.
Lone pair of oxygen in (I) is delocalized in vacant d orbital of silicon via p-d back bonding, so l.p. on oxygen
is not available. But in case of dimethyl ether ((CH3)2O), oxygen l.p. is available, so it can act as stronger lewis
base.
(ii) Due to back bonding in (SiH3)2O, double bond character arises (as shown in canonical structure II and III
above), which leads to increment in bond angle as the structure approaches more towards linearity. So Si–O–Si
bond angle is larger w.r.t. C–O–C angle where bonds have single bond character only.
(b) Pure Si is produced from reduction of SiO2 in an electric furnance in presence of coke.
SiO2 + C  Si + CO2
(CH3)2SiCl2 on hydrolysis gives silicon polymer.
5.
Al2(CH3)6 is more lewis acidic in character, as bridging Al–C–Al bonds are 3-center-2-electron bonds, so, Al
has incomplete octet, but in Al2Cl6 all bonds are 2-centere-2-electron bonds. So has complete octet, so less
tendency to accept electron-pair (i.e. less lewis acidic character).
(b) Stability order
2 2 2
Si Cl2  Sn Cl 2  Pb Cl2
Si, Sn and Pb belong to group 14 and each one of them has ns2 np2 configuration, but due to inert pair effect, as
we go down the group ns2 electron gets inert, and shows reluctancy towards removal.
So, stability of +2 oxidation state increases down the group 14.
As, Si+2 < Sn+2 < Pb+2, but +4 o.s. stability is as, Si+4 > Sn+4 > Pb+4
So, stability order in MCl2 salt is, SiCl2 < SnCl2 < PbCl2
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6.

7. Graphite has a layered, planer structure. In each layer, the carbon atom are arranged in a honeycomb lattice with
separation of 0.142 nm, and the distance between planes is 0.335 nm. Atoms in the plane are bonded covalently,
with only three of the four potential bonding sites satisfied. The fourth electron is free to migrate in the plane,
making graphite electrically conductive. However, it does not conduct at right angles to the plane.
8. 2, P = O bonds,

9. Microcosmic salt is sodium ammonium hydrogen phosphate Na(NH4)HPO4.
10. [B4O5(OH)4]2–
Boron with –ve charges, are tetrahedral and Boron with no charge are trigonal planar.
11. Hydrolysis of (CH3)2SiCl2 and CH3SiCl3 can be illustrated by following chemical reactions.
CH 3 CH3
| |
Cl  Si  Cl + H2O  
Polymerisation
HO  Si  OH  
| |
Cl OH
CH3
|
O  Si  O
|
O Cross linked polymers
| n

12. (a) Complete chemical reaction occuring in above chemical transformate can be shown as
boiling water
Na 2SO3  S  Na 2S2 O3 (colourless solid)
Sodium thiosulfate
(X)
AgBr  2Na 2S2 O3 

 Na 3[Ag(S2O3 )2 ]  NaBr
soluble complex
(Y)
Na 2S2 O3  4Cl 2  5H 2O 
 2NaHSO 4  8HCl
(X) (Z)
S S S F F
N N N S
S N
S4N 4H4 H H S4N 4H4
(b) S
N S
N N N S
H H F
F
13. two (3c – 2e) bonds are present in diborane
14. CO32 is a polyatomic anion to which in larger in size so interacts better with larger atoms, so BaCO3 is most
stable among all alkaline earth metal carbonates.
 BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3
 SbF5 ·SO3F 
SbF5  HSO3F  H 2 SO3F
15. (responsible for
superacid behaviour)
H 2SO3F  SbF5 
 H   HSO5F....SbF5
16. BF3 is a Lewis acid.
BF3  3H 2O 
 B(OH)3  3HF
[BF 3  HF   HBF4 ]  3


4BF3  3H 2 O   B(OH)3  3H[BF4 ]
It structure is

18. In a group going from up to down molecular weight increases hence boiling point also increases.
Hence correct sequence of boiling point is CH4 < SiH4 < GeH4 < SnH4
Hence Correct answer is (d).
O O
19. O S S S S O tetrathionate ion is S4O62–.
O O
Number of S-S bond = 3.
Hence correct answer is 3.
20. For B3N3H4X2
Total isomers possible are
H X
H B X
H B H N N
N N
B B
B B H N H
H N H
H
H (1)
B3N3H6
X X H
H B H H B H H B X
N N N N N N
B B B B B B
H N X H N H H N H
H X X
(2) (3) (4)
hence correct answer is 4.
21. Melting point depends on strength of intermolecular forces of attractions between molecules.
As molecular mass increases, vander waal forces of attraction becomes higher and hence none energy is needed
to convert into gaseous form from solid state therfore melting point increases
PF3  AsF3  SbF3  BiF3
22. Hydrolysis of aluminium carbide is given as
4Al  3C  Al 4C3
Al4C3  12H 2O  4Al  OH 3  3CH 4 
23. CCl4 molecules are smaller than SiCl4 molecules, and can get closer to one another which would lead to a larger
contact area between molecules and therefore a larger intermolecular force.
Also, C–Cl bond in CCl4 is more polar than SiCl4. Hence, in CCl4 there exist high intermolecular attractions due
to polarity.
Therefore, the correct order for the boiling point between CCl4 and SiCl4 is:
CCl4 > SiCl4
SiCl4 has lowest boiling point value.
24. Solubility of any ionic compound depends on balance of solvation and lattice enthalpy. If solvation enthalpy is
greater than lattice enthalpy then considered ionic compound is soluble.
trend of lattice enthalpy changes as
1
Lattice enthalpy 
Polarization
anion CO 32  is same in all compounds but metal ion changes from Li+ to Cs+ their ionic size increases and hence
charge density decrease, therefore, polarization decrease and lattice enthalpy increases.
Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3.
25. P 4O10
O
P
O O
O
P P O
O O
O O
P
O
Number of P–O–P bonds = 6
Number of P = O bonds = 4.
O O –H2 –H+
+ H2SO4 H H C O CO + H+
26. H OH H O
H
27. Ca 3P2  s   6H 2O  l   3Ca  OH 2  2PH 3

Correct, option is (a)
–
H
H
B H
H HB H
28. H Al H
H H
H
H B H
H B H
H
Coordination number of Aluminium = 8

Number of Bridging Hydrogen = 8
Correct option (a)
m
5p F
95
F 5
1
pm
29. H 160º H H H
F F
n
Solid HF consists of zig – zag chains of HF molecules.
Correct optio is (b)
30. I–, CO, H–, CH3CN
All the molecules are the examples of soft Lewis bases.
Soft Lewis bases are generally the ones that contains larger, relatively polarizable donor atoms.
Correct options are (a, b, c, d)
31. [P nO18]6–
[PO3]1– × 6 = [P6O18]6–
O O
O
P O P O
O O O
O P P
O O O
O
P O P
O O
O O
BCl3  NH 4 Cl 
140ºC
 B3 N 3Cl3H 3 
NaBH 4
 B3 N 3H 6 
H 2O
  B  OH  NH  3  H 2
32. P  Q  
S
R
33. K + O2  KO2
Correct optio is (c)
34. The strongest H-bond is formed by HF
35. The stability of adduct varies in the order:
H3B·PF3 > H3B·CO < H3B·OMe2 < H3B·NH3 because the donor capacity varies in order:
NMe3 > OMe2 > CO > PF3
36. The strength of C – C bond and C – H bond is greater than the strength of Si – Si and Si – H bond.
Correct options are (b, c)
6
Bioinorganic
HINTS & SOLUTIONS
1. Deoxy-hemoglobin
2. The metalloenzyme carbonic anhydrase is responsible for hydration of CO2 and the said metalloenzyme have
Zn2+ at their active site.
3. The low spin iron (III) centre is present in oxy form of hemoglobin
The size of Fe2+ increase by 28% on going from
The globular protein prevents the irreversible oxidation of Fe(II) to Fe(III).

Here, it should be pointed out that there are evidences to support that the oxygenated form of Hb, iron exists as
Fe(III) and O2 as O2– (superoxide) because of the, O–O stretching frequency ~1106cm–1 is close to that of O2–
(O–O = 1097 cm–1). The Fe–O–O bond angle is close to 120º. In fact, Fe(II) is reversible oxidised to Fe(III)
in this O2– uptake process and at the site of delivery of O2, it again attains the Fe(II) state through deoxygenation.
4. Ceruloplasmin, hemocyanin and azurin are blue copper proteins. Super oxide dismutase may be Cu-ZnSOD,
MnSOD or FeSOD.
Correct option are (A), (C) and (D)
5. Heme group  (Fe + Porphyrin Ring)
N N
Fe
N N
Myoglobin and cytochrome-C contain Heme group. Whereas Hemocyanin and hemerythin are non-Heme protein.
H
His
O
(II) His
His Fe(II) Fe His His
His His Cu Cu His
His O O
His His
Glu
O O
Asp Deoxy Hemocyanin
Deoxy Hemerythin
Correct Answer is (a, d)
6. Carbonic anhydrase is a enzyme that catalyse rapid interconversion of carbon dioxide and water to bicarbonate.
It is a hydrolysis enzyme.
CO 2  H 2O 
Carbonic
Anhydrase
 H 2CO 3 .
7. Metallo enzyme Metal at active site
Myoglobin Fe (Iron)
Hemocyanin Cu (Copper)
Vitamin B12 Co (Cobalt)
8. Carbonic anhydrase enzyme involved hydration of CO2
9. m = molar magnetic susceptibility
C
m  , C = Curie constant
T
mT = constant
deoxy Hb is paramagnetic oxy Hb is diamagnetic.
The value of magnetic suspectibility for paramagnetic substances is greater the Diamagnetic Substance.
4
–1
3
2
3
1
0
200100 300
T(K)
10. (i)–(N); (ii)–(K); (iii)–(L); (iv)–(M)
11. The reaction of adenosine phosphate (ATP) with Vit-B12S field direct cobalt – carbon bond between adenosyl
and cobalt the resulting molecule is known as B12 coenzyme.
OH2 OH2
Zn2+ Zn2+
12. (a) (His)N Glu (His)N N(His)
N(His) N(His)
(b) in hydrogenase Fe and Ni metal present

(d) in urease Ni metal present
7
D Block
HINTS & SOLUTIONS
1. (b) Chemical reaction occuring in above reaction can be represented as
2AgNO3 + Na2S2O3  Ag2S2O3 + NaNO3
Ag2S2O3 + H2O  Ag 2S  H 2SO 4

(black)

2. (a) (i) Chromium complex  K3[Cr(Ox)3]
where Ox  C2O42–
(ii) K 2 Cr2 O 7  9K 2C 2 O 4  7H 2SO 4  2K 3[Cr(C 2O 4 )3 ]  6CO 2  7K 2SO 4  7H 2 O
(ii) In complex, K3[Cr(Ox)3], Cr+3 has 3d3 electrons in its t2g orbital.
Number of unpaired electron (n) = 3
Spin only magnetic moment (s )  n(n  2) B.M.  3  5 B.M.  15 B.M.
(b) [CoCl2(en)2]Cl
3. (a)
(ii) N  [Ni(NH 3 )6 ]Cl2

Ni is sp3d2 hybridized.
Ni 2  [Ar]3d8 4s0 4p0
(iii) N  [Ni(NH3)6]Cl2 is paramagnetic complex, because it has ‘2’ unpaired electrons in its 3d orbital.
(b) [Cr(H2O)6]+3
 2  6
C.F.S.E.  3     0     208 kJ  249.5kJ
 5  5
4. (a) A  CuS; B  Cu(NO3 ) 2
C  CuI or Cu 2I 2
(b) Mn+2 catalyses the decomposition of KMnO4, as KMnO4 oxidises Mn+2 and itself gets reduced.
2MnO 4  3Mn 2  2H 2O  5MnO 2 (s)  4H 
Also KMnO4 is not a primary standard, because it undergoes decomposition in water solution,
2KMnO4 + H2O  2KOH + 2MnO2 + 3[O]
So, KMnO4 solution is not suitable for estimation of Fe dissolved in HCl.
But K2Cr2O7 solution can be used as a primary standard, because it is stable in aqueous medium, thats
why it is prefered over KMnO4 solution.
2 Na 2CrO 4  2H   Na 2Cr2O 7  2Na   H 2O

5. (a) (Yellow) Orange
(A)
Na 2CrO7  2H 2SO4  2CrO3  2NaHSO 4  H 2O

(A) (conc.) (B)
Bright orange
solid
Na 2Cr2O7  4Cl  6H 2SO 4  CrO2Cl2  2NaHSO 4  4HSO 4  3H 2O

(A) (C) (conc.) (deep red liquid)
So, A  Na 2Cr2 O7
B  CrO3
C  Cl
(b) 84 Po   82 X   83 Y [Y = Bi]
6. (a) (i) A  H  ; B  OH 
(ii) In reaction (I), H2O2 acts as a bidentate ligand as well as a reducing agent in acidic medium in order
to form CrO(O2)2 and Cr+3.
In acidic condition (i.e. in presence of H+) H2O2 acts as an reducing agent such that Cr+6 in Cr2O72– gets
reduced to Cr+3.
Oxidation Half-Cell:
 O 2  2H   2e
H 2O 2  ... (1)
Reduction half cell:
Cr2O72  14H  
  2Cr
3
 7H 2O  6e ... (2)
6e
equation (1) × 3 + equation (2),
3H 2O 2  Cr2 O72  8H   2Cr 3  3O 2  7H 2O

(iii) H2O2 in reaction (2) act as a oxidizing agent.
In presence of OH– the recuction potention of H2O2 is more than reduction potential of Cr+6 / Cr+3.
  oxidation half cell reaction, Cr 3  8OH   CrO 42  4H 2O  3e  ... (1)
reduction half cell reaction, H 2 O 2  2e  2OH  ... (2)
Equation (1) × 2 + equation (2) × 3
2Cr 3  3H 2O 2  10OH   2CrO 42  8H 2O
(b) As H3BO3 is a weak lewis monobasic acid, so it is titrated with NaOH, a sharp end point is not obtained
because no indicator is present in the range of end point.
Once cis-diol is added to the above titration mixture, it consumes Na[B(OH)4] so net reaction proceeds for-
ward, So, H3BO3 acts as a stronger acid and can be titrated in presence of phenophthalein indicator
7. (a)
(b)
As after temperature T1 the G of reaction, C  Co, becomes more negative than Mg  MgO reaction, So
carbon can reduce MgO above temperature T1 but G of reaction C  CO, becomes more -ve than Ca 
CaO reaction only above T2.
As T1 < T2
So, MgO can be reduced at lower temperature than CaO.
8. (a) Sulfide ore in first roasted in air to give NiO.
2NiS + 3O2  2NiO + 2SO2
To refine Ni, it is heated to about 50–60ºC in a steam of CO gas. Nickel passes off as its volatile
carbonyl, Ni(CO)4, this volatile product is passed over nickel shot at about 200ºC. Nickel is
deposited by Ni(CO)4 and is almost pure.
5060ºC
Ni(s)  4CO  Ni(CO) 4 (g)
Ni, 200ºC
Ni(CO) 4  Ni  4CO(g)
(b)
9. J  CrO 2Cl 2 (Chromyl chloride)

K  K 2 CrO 4 (Potassium chromate)
M  Cr2 (SO 4 )3 (Chromium (III) sulfate)
J  K transformation,
2K 2CrO 4  3SO2  2H 2SO 4 
 Cr2 (SO 4 )3  2K 2SO 4  2H 2O
(K) (M)
10. +2 oxidation state, CrX2, MoX2 (where X = F, Cl, Br, I)
+3 oxidation state, CrX3, MoX3, CrO3
+6 oxidation state, CrO3, CrO42–, MoO3
11. Amphoteric oxides get dissoved in both acids as well as bases.
VO  dissolves in acids but not in bases.
V2O3  dissolves in acids but not in bases.
VO2  dissolves in acids as well as bases, so it is an amphoteric oxide.
V2O5  dissolves in acids as well as bases, so it an amphoteric oxide.
Cr2O3  dissolves in acids as well as bases, so it is an amphoteric oxide.
CrO3  dissolves only in bases, but not in acids.
12. 3d metal mono-oxide like TiO and VO have high electrical conductivities that decrease with increasing temperature.
As in these compound conduction band is formed by the overlap of t2g orbitals of metal ions in neighbouring
octahedral sites that are oriented towards each other. The radial extension of the d-orbitals of these early d-block
elements is greater than for element later in period, hence a band result from their overlap this band is only partly
filled. Hence these oxide so metallic conductivity.
However in MnO, FeO, CoO and NiO, no such type of band formation result due to smaller radial extension of
d-orbital, and they behaves as semiconductor.
[overlap of the dzx orbitals in TiO to give a t2g band. In perpendicular direction the dyx and dzx orbitals overlap in
an identical manner]

13. Metal Extraction method
Al Electrolysis of Al2O3 in molten Na3AlF6.
Au Leading with CN– first, so soluble complex [Au(CN)2]– is formed then reduction with Zn.
Hg Direct reduction of HgS by heat alone (HgS + O2  Hg + SO2)
Mg Electrolysis of fused MgCl2 with added KCl.
(II) (III) III II
Fe 2  K   [Cr(CN)6 ]3  K Fe[ Cr (CN)6 ]; KFe[Cr(CN) 6 ]  K Cr[Fe(CN)6 ]
100ºC
14.
Brick red dark green

15. Complete chemical reaction occurs in above chemical transformation can be shown as
pH 6 dil. HCl
CrO3  CrO42 
 2
 Cr2O7
(A) (B) (C)
Cr2O72  6HCl  8H  
 Cl2  2Cr 3  7H 2O
(C) (E)
greenish yellow gas
16. (a)
BiI3  I   [BiI 4 ]
(B) (C) orange colour (soluble complex)
(b)
Br
H B H
N N
B B
(ii) (Y)  Br
 HBr N Br
H
(B3N3H3Br3)
17. Au(S)  3NO3 (aq)  6H  (aq) 
 Au 3 (aq)  3NO 2 (g)  3H 2O(l )
Au 3  4Cl (aq) 
 AuCl4 (aq)
18. Iron (II) ammonium sulfate (NH4)2Fe(SO4)2.6H2O ions produced by complete dissociation of Mohr salt
 2NH 4  Fe 2  2SO 24

(NH 4 )2 Fe(SO4 ) 2 6H 2O 
Total ions = 5
S2
19.  Na 4 [Fe(CN)5 (NOS)]4
Na 2 [Fe(CN)5 NO] 
Sodium nitroprusside

20. Low oxidation state of W is stabilized by CO because of M  CO back -bonding.
21.
W 1000
22. M B M = 0.16 M; VCml = 75 ml; MB = 294
M B V(mL)
WB  3.52  3.54 Ans.
Correct answer is 3.52 to 3.54
23. z = 23 = 1s22s22p63s23p64s23d3
or (1s2)(2s2p)8(3s3p)8(3d)3(4s)2
 3 n  2 n 1 n
n
S = [18 × 1] + [2 × 0.35] = 18 + 0.7 = 18.7
Therefore, zeff = 23 – 18.7 = 4.3
0.56 0.27 0.93 0.15 0.25
24. MnO 4  MnO 42  MnO34  MnO 2  Mn 2O 3  Mn(OH) 2
(I) (II) (III) (IV) (V)
7 6 5 4 3 2
1.56
 Mn
(VI) 0
For MnO43– its standard reduction potential is greater value than the standard oxidation potential hence it will
undergo dispropotionation reaction due to overall standard potential is positive
e  MnO34  MnO 2 Eº  0.93
MnO34  MnO 24  e  Eº  0.27
2MnO34  MnO 2  MnO 42
Eºtotal = 0.93 – 0.27 = +0.66 V
Hence it will undergo disproportionation reaction.
Aqueous AgNO3  Na 2 HPO 4 (orthophosphate)

25. 
Ag3PO 4  (yellow ppt.)
Hence correct answer is (d).

26. Cu+2 + S2–  CuS (Black Precipitate)
CuS + conc. HNO3  Cu(NO3)2 + NO2 + S  (white ppt.)
27. Hg, Pb and Cu are extracted from their PhS and CuS over through air reduction method.
2CuFeS2  2SiO 2  4O 2  Cu 2S  2FeSiO3  3SO 2
Cu 2S  O 2  2Cu  SO 2
Correct options are (A and D)
28. Saturated calomel electrode is composed of saturated solution of KCl and paste of Hg2Cl2. Sparingly soluble
salt.
Correct options are (A and B)
29. 2Bi3  3H 2S 
 Bi 2S3  6H 
brown
30. A brown ring test is employed for detection of NO3– ions using concentrated sulfuric acid. Presence of nitrate is
indicated by appearance of brown ring [Fe(OH2)5NO]2+ at interface of sample solution and concentrate H2SO4.
Rxn.1  NO3  H 2SO 4  HNO 3  HSO 4
Rxn. 2  HNO 3  3Fe 2  3H   NO  3Fe 3  2H 2 O

2 2
Rxn. 3   Fe  OH 2 6   NO   Fe  OH 2  5 NO   H 2 O
here NO exists as NO+ and Fe is in +1 oxidation state which is d7 system and hence paramagnetic.
Correct options are (a and d)
31. As TiCl4 reacts with THF to form TiCl4(THF)2
i.e. TiCl4 + THF  TiCl4(THF)2
190 g. 334 g.
As 190 g of TiCl4 gives 334 g of TiCl4 (THF)2.
334  5
 5g of TiCl4 gives =  8.7 g of TiCl4(THF)2
190
Experimental value
as percentage yield  Theoretical value
Experimental value
 80% 
8.7
80
 Experimental value of TiCl4(THF)2 formed   8.7  6.96 g
100
 amount of TiCl4(THF)2 formed is 6.96 g.
8
Analytical Chemistry &
Instrumental Method of Analysis
HINTS & SOLUTION
1. Titration curve for strong acid vs. weak base
Here, pehnolphthalein (pH  8 to 10) would be completely useless for strong acid versus weak base.
in ammonical
2. Mg+2 + oxine reagent 
buffer
yellow ppt.
3. Hardness is determined by titration by using EBT indicator.
Mg-In complex Edta Mg-Edta complex Free-In
(Red wine) + (Colourless)  (Colourless) + (Blue)
(MgIn)– + (H2Y)2– = (MgY)2– + (HIn)2– + H+
4. The reagent ‘Oxine’ commonly used in analytical chemistry is 8-hydroxyquinoline. It is a chelating agent which is
used in the quantitative determination of metal ions.
5. Methylene blue is an indicator used in redox titration.
In oxidised form it is blue and will turn colourless if exposed to reducing agent.
6. Titration of weak acid with strong base

Indicator Range
14
13
12
11 phenolphthalein 8.3 to 10.0
10 Steep curve
9
8
8 to 11 Thymol blue 8 to 9.6
7
6
Bromophenol blue 3.0 to 4.6
5
4 Methyl orange 3.1 to 4.4
3
2
1
Vol. of NaOH
Only those indicators having pH range equal to the range that lie within steep curve can be used for titration
 phenolphthalein and thymol blue are suitable indicators.
7. When titrant is added from burette into the conical flask; it reacts with titrand and gets eliminated from solution.
Till titrant reacts with titrand, there will be no change in absorbance. When all titrand is consumed and still if we
add titrant, there will be no reaction and hence in conical flask, there is titrant only and its concentration increases
and therefore absorbance rises after equivalence.
Absorbance
Volume of titrant
8. Mg  In 
 Mg  In complex
 less stable   red wine 
Mg  In complex  Edta 
 Mg  Edta complex  In
 more stable   blue 
(a) Magnesium – Indicator complex is less stable than the magnesium – EDTA complex.
(b) At the end point, the colour changes from red to blue
(c) After the end point, the colour of the solution is due to the indicator.
(d) pH range of 7 – 10.5 is necessary for observing the specific colour change
9
Nuclear Chemistry
HINTS & SOLUTIONS
1. 131 is used to locate brain tumors.
53 I

A 3 particle in succession
A 12
2. 86 Ra  82 X
Atomic number 82 is for Pb and it belongs to group 14.
3. t = 0, activity (A0) = N0 = 23 dis/min
1
t hr , activity (At) = Nt = 11.5 dis/min
2
1 A 1
As after t hr , activity A t  0  t  t1/ 2  hr = 30 min
2 2 2
0.693 0.693
 N0 = 23 dis/min  t N 0  23  N 0  23
1/2 30
23  30
 N0   1000 atoms
0.693
4. For the given radioactive nuclide
t1/2 = 20 years, Initial activity (A0) = N0 = 6400 dis/min
t = 100 years, = 5t1/2 Final activity (At) = ?
N t At 1
We have, N  A  n
0 0 2
100 A0 6400 6400
Number of t1/2 'n '  5  At     200dpm
20 2n 25 32
5. 84 Po   82 X   83 Y [Y = Bi]
234 230
6. 92 U 
 90 Th  42 He ;  - particle is 42 He
7. (i) 14 4
 11H  17
7 N  2 He  8 O (ii) 7 1
 84 Be
3 Li  1H 
241 4 243
8. 97 Bk  210 n
95 Am  2 He 
238 206
9. 92 U 82 Pb  x 24 He  yo1
Let ‘x’ = number of alpha-particles emitted
y = No. of beta-particles emitted.
Conserving the number of nucleons-
238 = 206 + 4x + y(0)
4x = 238 – 206 = 32
x=8
Now, 92 = 82 + 8(2) + y(–1)
92 = 82 + 16 – y
y = 98 – 92 = 6
Number of beta particles = 6
Total steps = 8 + 6 = 14
10. 10B has high absorption cross-section for thermal neutron, even for high energy neutron (104–106 eV) it is
more effective than any other nuclide. The accompanying (n, ) reaction produces Li and He which are non-
radioactive and harmless.
10 7
B 1 n  Li 4
5 0 3 2He
This fact recently has used in B-10 neutron capture therapy of brain tumours.
238 234
11. U 
92 92 U
Change in A = 238 – 234 = 4.
Hence, only one ‘’ is emitted. Now increases in z = 92 – 2 + 2 = 92
Hence, two  particle will be emitted
t ln
12. 0.693  activity of dead sample 

5730 yr  52 / 2
 
5730 year  26 
t ln    9745.58 year..
0.693 8
13. 214  210  210
84 Po 82 X 83 X
Therefore, number of neutron = 210 – 83 = 127.
2.303 100
14. K log A  P
300 20
2.303
  0.6990 t=0 N
300
= 0.00536599 min–1 t = 300 min N – 0.8 N = 0.2 N
0.693
t1/2 =
k
0.693
=  129.15 min
0.00536599
14 14 0
15. 6 C  7 N  1e hence – decay
14 14 0
8 O  7 N  1e Positron decay
Hence correct answer is (d)
A  A 0e kt
A0
 A 0e  k(29.8)
4
1
 e  k(29.8)
4
1
ln   k(29.8)
4
1.3862   k(29.8)
.38 1
k hr
29.8
k = 0.0465 hr–1
A  A 0 e t
A = 0.10 A0
0.10 A 0  A 0 e t
t = 4600 min
4600 230
t hr  hr
60 3
230

0.1  e 3

  230
ln 0.1  
3
  230
2.303log10 1  
3
2.303  3
  
230
 = 0.03 hr–1.
18. Q-value = m × 931.5 MeV.

= (mR – mP) × 931.5
= (4 × 1.007825 – 1 × 4.002604) × 931.5
= 0.0287 × 931.5
= 26.7 MeV.
TOPIC WISE
PYQ
(Organic)
1
STEREOCHEMISTRY
IIT JAM 2006
1. After the following interchanging of groups in the Fischer projection of 2-bromobutane, the configuration of (X)
and (Y) will be
(a) X = R, Y = S (b) X = R, Y = R (c) X = S, Y = R (d) X = S; Y = S

2. The number of enantiomers of camphor
(a) Four (b) Two (c) Three (d) One

IIT JAM 2007
3.
The given compounds 1 and 2 are

(a) Identical (b) Diastereomeric
(c) Enantiomeric (d) Constitutionally isomeric
4. Which one of the following compounds is optically active?
(a) 1 (b) 2 (c) 3 (d) 4

IIT JAM 2008
VIGYAN VRIKSH |Organic Chemistry (IIT-JAM)(PYQ)
5. Among the following, the correct statement concerning the optical activity is:
(a) A molecule containing two or more chiral centres is always optically active.
(b) A molecule containing just one chiral centres is always optically active.
(c) A molecule possessing alternating axis of symmetry is optically active
(d) An optically active molecule should have at least one chiral centre.
6. R(–)2–Bromooctane on treatment with aqueous KOH mainly gives 2-octanol that is:
(a) Optically active with ‘R’ configuration (b) Optically active with ‘S’ configuration
(c) A racemic mixture (d) A meso compound
IIT JAM 2009
7. The structure of D-galactose is
Which one of these structures is L-galactose?
(a) (b) (c) (d)
8. The maximum number of stereoisomers possible for 4-phenylbut-3-en-2-ol is

(a) 1 (b) 2 (c) 3 (d) 4
9. Which of the following is achiral?
(a) Alanine (b) Glycine (c) Proline (d) Phenylalanine
IIT JAM 2010
10. The absolute configurations at the two chiral centers in D-Ribulose are
(a) 3R, 4R (b) 3R, 4S (c) 3S, 4R (d) 3S, 4S

11. Benzene and Dewar benzene are
(a) Canonical forms (b) Structural isomers

(c) Tautomers (d) Conformational isomers
12. The most stable conformation of the molecule shown below is correctly represented by
(a) (b)
(c) (d)
13. The energy profile diagram that corresponds to 1,2-dihydroxyethane for rotation around the C–C bond is
(a) (b)
(c) (d)
IIT JAM 2011

14. The Cahn-Ingold-Prelog (CIP) priorities of the group and the absolute configuration (R/S) of the following
compounds are
(a) CH2OH > CH(CH3)2 > CH = CH2 > CH3 and S
(b) CH2OH > CH = CH2 > CH(CH3)2 > CH3 and S
(c) CH2OH > CH = CH2 > CH(CH3)2 > CH3 and R
(d) CH2OH > CH(CH3)2 > CH = CH2 > CH3 and R
15. The correct sequence of relationship between the compounds of the following pairs i-iv is
(a) Identical, enantiomers, diastereomers and structural isomers.

(b) Enantiomers, identical, structural isomers and diastereomers.
(c) Enantiomers, identical, diasteromers and structural isomers.
(d) Identical, identical, diastereomers and structural isomers.
16. The optically active stereoisomer of the following compound is
(a) (b)
(c) (d)
IIT JAM 2012

17. The pair of conformation that has maximum energy difference is:
(a) and (b) and
(c) and (d) and

IIT JAM 2014
18. Specific rotations of freshly prepared aqueous solutions of I and II are +112 and +18.7, respectively. On standing
the optical rotation of aqueous solution of I slowly decreases to give a final value of +52.7 due to equilibrium with
II. Under this state of equilibrium, what is the ratio II : I?
CHO
OH OH
H OH
O H HO H O OH
HO HO
HO OH H OH HO OH
OH H OH H
I CH2OH II
[]25
D  112 []25
D  18.7
(a) 0.57 (b) 1.00 (c) 1.75 (d) 5.9

19. Which one among the following molecules is chiral?
H Cl H
Cl
(a) C (b) C C C C
Cl Cl H Cl
Cl Cl
Cl Cl
(c) C (d)
H H
Cl H
IIT JAM 2015
20. The structure of (2S, 3R)-2-amino-3-hydroxy butanoic acid is
COOH COOH COOH COOH

H NH2 H 2N H H 2N H H NH2
(a) HO H (b) HO H (c) H OH (d) H OH
CH3 CH3 CH3 CH3
IIT JAM 2016

21. The correct statement(s) about the following species is(are)
O OH Ph N
(I) Ph N (II) Ph N (III)
OH
(a) I and II are resonance structures (b) II and III are resonance structures
(c) II and III are diastereomers (d) III is a tautomer of I
22. Among the following, the most stable conformation of meso-2,3-dibromobutane is
Br Br Br Br
Br Me H Me H Me Me Br
(a) (b) (c) (d)
H Me Me H H Me H Me
H Br Br H
23. The number of all possible isomers for the molecular formula C6H14 is ____.
24. Among the following, the number of molecules that possess C2 axis of symmetry is ____.
Me
Me
Cl Cl
H H Me
Me
Cl Cl
BF3 CHCl3 2,5-dimethylthiophene
H H
IIT JAM 2017
25. Catalytic hydrogenation of the following compound produces saturated hydrocarbon(s). The number of
stereoisomer(s) formed is
Me Me
Me
Me
(a) 1 (b) 2 (c) 3 (d) 4
26. The total number of pair of enantiomers possible with molecular formula C5H12O is _____
27. The compounds having C3-axis of symmetry are
(a) I, III and IV(b) I, II and III (c) I and III (d) III and IV
IIT JAM 2018
28. The number of compounds having S-configuration among the following is ______.
H3CH2C CH2CH3 H H
H
H OH C C C
H 3C Br CH3
H3C CH3
NC H CH 3
CH2CH3
H 3C H
29. Among the dimethylcyclohexanes, which one can be obtained in enantiopure form?
CH3
CH3
(a) (b)
CH3 CH3
CH3
(c) (d) H3C CH3
H3C
30. The number of stereoisomers possible for the following compound is __________.
H H
Ph C C Ph
OH OH
IIT JAM 2019
31. The diastereomeric pair(s) among the following option(s) is/are
Br Br
Ph Et Ph H Me Me
(a) (b)
Me H Me Et
Bu Bu
OH OH
OH OH
O O
(c) (d) HO
Br Br OH OH
OH
32. The number of gauche-butane interaction(s) in the following compound is __________.
CH3
CH3
33. (R)-2-methyl-1-butanol has a specific rotation of +13.5º. The specific rotation of 2-methyl-1-butanol containing
40% of the (S)-enantiomer is _______º. (Round off to one decimal place)
IIT JAM 2020
34. Achiral stereisomer(s) is(are) possible for
CO2H
Br
(a) C (b)
Br
HO2C
OH OH
(c) HO2C CO2H (d)

OH
35. The dihedral (torsional) angle (in degrees) between the two methyl groups in the most stable conformation of n –
butane is ______ (Round off to nearest integer)
36. The more stable species in each pair of conformers are
I II
O O
O O
III IV
OH
O OO
O OH
V VI
(a) II, IV and V (b) I, IV and V (c) II, III and V(d) I, IV and VI
37. Total number of constitutional isomers possible for trimethyl cyclohexane is _____.
IIT JAM 2021
38. For the molecule,
CH3–CH=CH–CH(OH)–CH=CH–CH=C(CH3)2
the number of all possible stereoisomers is_______.
ANSWER KEY
1. (c) 2. (b) 3. (d) 4. (d) 5. (b) 6. (b) 7. (d)
8. (d) 9. (b) 10. (a) 11. (b) 12. (d) 13. (c) 14. (b)
15. (c) 16. (b) 17. (a) 18. (c) 19. (c) 20. (c) 21. (c,d)
22. (b) 23. (5) 24. (7) 25. (c) 26. (*) 27. (*) 28. (4)
29. (a) 30. (3) 31. (a,b,d) 32. (3) 33. (2.7º.) 34. (*) 35. (1800)
36. (b) 37. (6) 38. (8)
HINTS & SOLUTION
* CH 3
CH3  CH 2  CH 2  C H  CH 3 | *
| CH3  CH  C H  CH3
26. (1) (2) |
OH
OH
CH 3 CH 3
| |
(3) CH  O  C H  C H (4) HO  CH  C H  C H
3 2 5 2 2 5
* *
Four pair of enantiomers are possible.

C3
C3
Br
CH3
27. Cl3
CH3 Br Br
these two compounds contains C3 symmetry.

34. Achiral stereoisomers are those which are optically inactive but have the chiral centres within the same molecule
OH OH
2
1 * 4*
HOOC * 3 COOH
5
OH
The molecule contains plane of symmetry hence is achiral but has 3 stereogenic centres (C2, C3 and C4)
Similarly
H3C CH3
dimethyl cyclopentane also contains plane of symmetry with 2 chiral centre hence is not optically active i.e.
Achiral.
2
GENERAL ORGANIC CHEMISTRY
IIT JAM 2005
1. Arrange the following in the decreasing order of acidity of the hydrogen indicated in italic
(i) CH3COCH3 (ii) CH3COCH 2COCH3
(iii) CH3OOCCH 2COOCH 3 (iv) CH3COCH 2 NO2

(a) (ii) > (iii) > (i) > (iv) (b) (iv) > (ii) > (iii) > (i)
(c) (iv) > (iii) > (ii) > (i) (d) (ii) > (iv) > (iii) > (i)
2. The increasing order of the acidity of the hydrogen marked in bold italics among the following is:
(a) III < II < I (b) II < I < III (c) I < II < III (d) II < III < I
IIT JAM 2007
3. The value of ‘n’ for the following molecule according to Huckel’s rule is
(a) 16 (b) 4 (c) 3 (d) 14

IIT JAM 2008
4. The correct order of acidity among
is
(a) (i) < (ii) < (iii) < (iv) (b) (iv) < (iii) < (i) < (ii)
(c) (ii) < (i) < (iii) < (iv) (d) (ii) < (iv) < (i) < (iii)
5. The correct statement describing the relationship between
is
(a) X and Y are resonance structures and Z is a tautomer

(b) X and Y are tautomers and Z is a resonance structure.
(c) X, Y and Z are all resonance structures.
(d) X, Y and Z are all tautomers.
IIT JAM 2009
6. Which of the following are aromatic?
(a) P and Q (b) Q and R (c) R and S (d) Q and S

7. Arrange the following in the correct order of acidity of the hydrogen indicated in bold.
(a) P > Q > R (b) R > Q > P (c) Q > R > P (d) P > R > Q
IIT JAM 2010
8. In which of the following C–H bond has the highest ‘s’ character?
(a) Acetylene (b) Ethylene (c) Methane (d) CH radical
IIT JAM 2011
9. The product P and Q in the following reactions, respectively, are
(a) (b)
(c) (d)
IIT JAM 2012

10. The species/compounds that are aromatic among the following are
O
H
P Q R S
(a) R and S (b) P and Q (c) Q and S (d) P and S
11. Electrophilic nitrations of the following compounds follow the trend
(a) S . R > P > Q (b) R > S > P > Q (c) R > P > S > Q (d) P > S > R > Q
IIT JAM 2013
12.
Calixene is a polar hydrocarbon with a high dipole moment. The most stable dipolar canonical structure is
_________
13. The Correct order of stability of the following carbonium ions is
(a) II > I > III (b) III > II > I (c) I > II > II (d) II > III > I
IIT JAM 2014
14. The homolytic breaking of the Ca – Cb bond is easiest in:
H H H3C H
(a) H Ca Cb H (b) H Ca Cb H
H H H CH 3
H3C CH3 H3C CH3
(c) H Ca Cb H (d) H3C Ca Cb CH3

H3C CH 3 H3C CH3
IIT JAM 2015
15. Which of the following species is/are aromatic in nature?
O
N N
(a) (b)
N
O
(c) (d)
O
16. The correct order of the pKa values for the conjugate acids of heterocyclic compounds given below is
(I) N (II) N (III) N (IV)

H H H N
(a) II > III > I > IV (b) IV > II > III > I
(c) III > II > IV > I (d) III > IV > II > I
IIT JAM 2016
17. Among the following, the number of molecules that are aromatic is ____.
H Me
N
Me
18. The correct order of pKa for the following compounds is

OH CO2H
OH
O
(I) (II) (III) (IV)
OH
N NO2
(a) II > I > III > IV (b) II > I > IV > III
(c) III > IV > I > II (d) IV > II > I > III
19. The correct statement(s) about the following species is(are)
O OH Ph N
(I) Ph N (II) Ph N (III)
OH
(a) I and II are resonance structures (b) II and III are resonance structures
(c) II and III are diastereomers (d) III is a tautomer of I
IIT JAM 2017
20. Among the following, the number of aromatic compound(s) is ______
IIT JAM 2018

21. The compound that contains the most acidic hydrogen is
(a) H2C=CH2 (b) CH  CH (c) H 2 C  C  CH 2 (d) H3C–CH3
22. The correct order of stability for the following carbocations is
I II III IV
(a) I < III < IV < II (b) III < II < IV < I
(c) II < IV < III < I (d) IV < III < I < II
ANSWER KEY
1. (b) 2. (d) 3. (c) 4. (b) 5. (a) 6. (d) 7. (b)
8. (a) 9. (c) 10. (d) 11. (b) 12. (*) 13. (d) 14. (d)
15. (a,b,c) 16. (c) 17. (3) 18. (b) 19. (c,d) 20. (4) 21. (b)
22. (*)
HINTS & SOLUTION
12.
Canonical
Because in this form both the rings are aromatic hence stable.
22. (i) It has 6 hydrogens hyperconjugation stablization.
Resonance stablization from electron delocalization of

phenyl ring towards vacant P orbital.
(ii) Bridge head carbocation are very unstable because these are too stained and can never
become planar. It has high energy vacant sp3 orbital.
(iii) It has 9 hydrogen, hyperconjugation stablization therefore more stable than IV as

hyperconjugation of 9H dominates over allylic conjugation.
(iv) Which enjoys no hyper conjugation but resonance gives some sort of stablization to allylic
carbocation.
3
NATURAL PRODUCTS &
BIOMOLECULES
IIT JAM 2005
1.
In the scheme shown above (P), (Q), (R) and (S) are
(a) (P) = purine bases, (Q) = pyrimidine bases, (R) = nucleotides, (S) = nucleosides
(b) (P) = nucleosides, (Q) = nucleotides, (R) = pyrimidine bases, (S) = purine bases
(c) (P) = nucleosides, (Q) = nucleotides, (R) = (S) = purine bases
(d) (P) = nucleotides, (Q) = nucleosides, (R) = pyrimidine base, (S) = purine base
2. Match the isoelectric point with the amino acids.
Amino acids
Isoelectric point
(X) H2NCH2COOH (I) 9.5
(Y) HOOCCH2CH2CH(NH2)COOH (II) 6.0
(Z) H2N(CH2)4CH(NH2)COOH (III) 3.1
(a) (X)-(II), (Y)-(III), (Z)-(I) (b) (X)-(III), (Y)-(I), (Z)-(II)
(c) (X)-(I), (Y)-(II), (Z)-(III) (d) (X)-(II), (Y)-(I), (Z)-(III)
IIT JAM 2006
3. A dipeptide on hydrolysis gives two amino acids (X) and (Y). If the dipeptide is first treated with HNO2 and then
hydrolysis is carried out, (X) and lactic acid are obtained. (X) on heating gives 2, 5-diketopiperazine as shown
below. Identify (X) and (Y), and write their sequence in the dipeptide.
H
N O
O N CH 3
H
IIT JAM 2007
4. The complementary strand of DNA for the following single stranded DNA sequence,
5´–A–T–C–A–T–G–C–3´ is
(a) 5´–A–T–C–A–T–G–C–3´ (b) 5´–T–A–G–T–A–C–G–3´
(c) 5´–G–C–A–T–G–A–T–3´ (d) 5´–C–G–T–A–C–T–A–3´
5. (a) For the following scheme of transformations, draw the structures of A, B, C and D.
(b) Complete hydrolysis of a pentapeptide with 6N HCl at 110ºC in a sealed tube gave 2 equivalents of glycine,
one equivalent each of tyrosine, leucine and phenylalanine. Reaction of the pentapeptide with Sanger’s reagent
(2,4-dinitrofluorobenzene, DNFB) and subsequent hydrolysis gave the DNFB derivative of tyrosine. Chymotryspin
cleavages of this peptide yielded tyrosine, leucine and a tripeptide. Deduce the sequence of the pentapeptide.
IIT JAM 2008
6. A disaccharide K gives a silver mirror with Tollen’s reagent. Treatment of K with MeOH/HCl gives a monomethyl
derivative L, which does not react with Tollen’s reagent. Methylation of K with Me2SO4 and NaOH affords an
octamethyl derivative of K, which upon acidic hydrolysis gives a 1:1 mixture of 2, 3, 4, 6-tetra-O-methyl-D-
glucose and 2, 3, 4-tri-O-methyl-D-glucose. Disaccharide K is also hydrolysed by the enzyme maltase. Identify
K and L with proper stereochemistry.
IIT JAM 2009
7. The structure of D-galactose is
Which one of these structures is L-galactose?
(a) (b) (c) (d)
8. Predict the product in each of the following reactions.
9. Calculate the isoelectric point (p.I.) of lysine, given the pKa of .NH3 is 8.95 pKa of side chain NH3 is 10.53 and
pKa of .COOH is 2.18.
IIT JAM 2010
10. The absolute configurations at the two chiral centers in D-Ribulose are
(a) 3R, 4R (b) 3R, 4S (c) 3S, 4R (d) 3S, 4S

IIT JAM 2011
11. The correct relationship within each pair of the natural products is:
(a) Camphor – terpene; insulin – protein; nicotine – alkaloids; streptomycin – carbohydrate
(b) Camphor – terpene; insulin – carbohydrate; nicotine – alkaloid; streptomycin – lipid
(c) Camphor – alkaloid; insulin – protein; nicotine – terpene; streptomycin – carbohydrate.
(d) Camphor – carbohydrate; insulin – protein; nicotine – alkaloid; streptomycin – terpene.
12. The INCORRECT statement in the following is:
(a) The nucleobase pairs are aligned perpendicular to the helical axis in DNA.
(b) RNA contains uracil and thymine, but DNA contains only thymine.
(c) All naturally occuring amino acids with the exception of glycine are chiral
(d) All enzymes are proteins, but all proteins are not necessarily enzymes.
IIT JAM 2012
13. The Haworth projection for -anomer of D-glucose is
(a) (b) (c) (d)
14. The complementary DNA sequence of the given DNA 5’-G-A-A-T-T-C-3’ is:
(a) 5’-C-T-T-A-A-G-3’ (b) 5’-C-U-U-A-A-G-3’
(c) 3’-C-T-T-A-A-G-5’ (d) 3’-G-A-A-T-T-C-5’
15. The correct C3 epimeric pair of the following is
(a) P and Q (b) R and Q (c) Q and S (d) R and S

16. -Farnesene shown below is a
(a) diterpene having two isoprene units (b) triterpene having three isoprene units
(c) triterpene having four isoprene units (d) Sesquiterpene having three isoprene units.
17. Write the structure of E, F and G in the following scheme of reactions.
18. Given below are structure of some natural products. Identify them as vitamin A, B6, C and D and classify them
according to their classes (isoprenoid, alkaloid, carbohydrate and steroid)
IIT JAM 2013

19. Which one of the following statements is Correct?
(a) Naturally occuring DNA has -configuration.
(b) Nucleic acids are derived from proteins.
(c) Proteins store genetic information
(d) Vitamins generally act as enzymes
IIT JAM 2014
20. Tollen’s test will be negative for:
(a) Glucose (b) Mannose (c) Sucrose (d) Galactose
21. Which one among the following is a sesquiterpene?
CH3 CH3
H
(a) H3C (b) OH

H
H3C CH3 H3C CH3
CH3
H3C
CH3 CH3 HH
N S CH3
H 3C CH3 CH3
(c) (d) O N
CH 3 O
CH3
H COOH
HO
22. Specific rotations of freshly prepared aqueous solutions of I and II are +112 and +18.7, respectively. On standing
the optical rotation of aqueous solution of I slowly decreases to give a final value of +52.7 due to equilibrium with
II. Under this state of equilibrium, what is the ratio II : I?
CHO
OH OH
H OH
O H HO H O OH
HO HO
HO OH H OH HO OH
OH H OH H
I CH2OH II
[]25
D  112 []25
D  18.7
(a) 0.57 (b) 1.00 (c) 1.75 (d) 5.9

IIT JAM 2015
23. The pKa values of lysine are 2.18, 8.95 and 10.79. The isoelectric point of lysine is _______
IIT JAM 2016
24. The most basic amino acid among the following is
(a) tyrosine (b) methionine (c) arginine (d) glutamine
25. Consider the following reaction:
Ph-NH-NH 2
(3 equiv)
(D)-glucose 
 X
cat. H
Among the following, the compound(s) whose osazone derivative(s) will have the same melting point as that of X
is(are)
CHO CH2OH CHO CHO

HO H O HO H H OH
H OH HO H HO H H OH
(a) HO H (b) H OH (c) H OH (d) HO H
HO H H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH
IIT JAM 2017

26. Among the following the correct statement(s) is/are
(a) Guanine is a purine nucleobase
(b) Glycine and proline are achiral amino acids
(c) DNA contains glycosidic bonds and pentose sugars
(d) Sucrose is a non-reducing sugar
27. The maximum number of dipeptides that could be obtained by reaction of phenylalanine with leucine is ______
28. The number of reducing sugars among the following is ______
IIT JAM 2018

29. The C-2 epimer of D-glucose is
(a) D-Mannose (b) D-Fructose (c) D-Galactose (d) D-Gulose
30. Tetrapeptide(s) that gives (give) the following product on reaction with Sanger’s reagent followed by hydrolysis
is(are)
NO2 H
N CO2H
CH3
O2N
(a) Ala-Gly-Leu-Phe (B) Asp-Phe-Leu-Pro
(c) Asp-Gly-Tyr-Phe (D) Ala-Phe-Tyr-Pro
IIT JAM 2019
31. The complementary strand for the following single strand of DNA is
5  A — T — G — C — T  3
(a) 3  T — A — C — G — A  5 (b) 3  A — T — G — C — T  5
(c) 5  T — A — C — G — A  3 (d) 5  A — A — C — G — T  3
32. In the following reaction of (D)-Glucose, a product P is formed.
1. Br / H O
(D)-Glucose  2 2
P
2. H O , Fe SO
2 2 2  
4 3
Among the following compounds, the one which will give the same product (P) under identical reaction condi-
tions is
CHO CHO CHO CHO

H OH HO H H OH HO H
HO H HO H H OH H OH
(a) H OH (b) H OH (c) H OH (d) H OH
HO H H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH
33. The correct statement(s) among the following is/are

(a) Secondary structure of a polypeptide describes the number and type of amino acid residues.
(b) Uracil is a pyrimidine nucleobase.
(c) Natural fatty acids have odd number of carbon atoms.
(d) Reaction of (D)-glucose with Ca(OH)2 gives a product mixture containing (D)-fructose, (D)-mannose, and
(D)-glucose.
34. Based on the information given below, the isoelectric point (pI) of lysine is _________. (Round off to one
decimal place)
NH3 OH NH3 OH
OH O
H3N H3N
H3O H3O
O O
pKa = 2.2 pKa = 9.1
NH2 OH NH 2
O O
H2N H3N
H3O
O O
pKa = 10.5
IIT JAM 2020
35. The amino acid R configuration is
CO2H CO2H CO2H CO2H

(a) H2N H (b) H2N H (c) H2N H (d) H2N H
CH2CH3 CH2SH CH2Ph CH2CH2SCH3
36. The nucleobase NOT found DNA is
(a) Thymine (b) Uracil (c) Guanine (d) Adenine
37. The total number of head to tail isoprene linkages in the following molecule is _______
Me Me Me
Me
Me
Me Me Me
IIT JAM 2021
38. The functional group (s) in reducing sugar that tests positive with Tollen’s reagent is (are)
(a) Aldehyde (b) Ketone (c) Acetal (d) Hemi – acetal
39. Among the following, the total number of terpenes (terpenoids) is ________.
HO
HO OH
O
HO O
ANSWER KEY
1. (d) 2. (a) 3. (*) 4. (c) 5. (*) 6. (*) 7. (d)
8. (*) 9. (9.74) 10. (a) 11. (a) 12. (b) 13. (c) 14. (c)
15. (a) 16. (d) 17. (*) 18. (*) 19. (a) 20. (c) 21. (a)
22. (c) 23. (9.87) 24. (c) 25. (a,b,c) 26. (a,c,d) 27. (2) 28. (3)
29. (a) 30. (*) 31. (a) 32. (b) 33. (b,d) 34. (9.8) 35. (b)
36. (b) 37. (4) 38. (*) 39. (*)
HINTS & SOLUTION
3.
5. (a)
(b) Correct sequence of pentapeptide is
6.
OH
OCH3 OH
O 1
H2C 4
O OCH3
8. (i) HIO H O / H
3
HC
2 2
OH 
4 OH 
2
O O
OH OH HH
OH
O
OH OH
O O
+ H + CH3OH
H
1 mole 1 mole
HIO4 cleave the C–C bond

–OH group containing
OH O OH
4 5 6
4 6 O
HO 5 O HH
(ii) HO 2 2eq HIO4 HO 2 H  / H 2O
OCH3 
OCH 3  3
3 1 HO 1
OH O
O OH
4 6
H OH
5 H–OCH3
OH H
O 3 2
H
H O 1
O
Product are
O
||
1 mole H  C  OH
H
O
1 mole O
H
O OH
1 mole
H OH
1 mole CH3 – OH
17. Chemical transformation involved in above chemical reaction can be illustrated as
18.
38. Aldehyde and Hemi-acetal reduced tollen’s reagent.
39. HO
HO OH
O
O
4
REAGENTS
IIT JAM 2007
1. The main product obtained in the following reaction is
(a) (b)
(c) (d)
2. Identify reagent (P) and write the structure of products (Q, S and T) in the following
Identify the structures of the intermediate compounds Q, R and S. Show the transformation for each step.
IIT JAM 2008
3. Explain with the help of mechanisms, the observed stereoselectivity in the following epoxide formation reactions.
IIT JAM 2010

4. (a) Write the structures of P, Q and R in the given reaction sequence.
(b) Identify S and T in the reactions given below:
IIT JAM 2011

5. Write the structures of products A to E in the following reaction sequence
N(CH3)2
Li, NH (liq.) H O isomerization

 3
t  BuOH
(A) 
3 (B)  C
CH3
CH3
(H3C)3SiO
H3O 
D 
 E
IIT JAM 2014

6. The structure of the major product in the following reaction is:
O
Me CuLi

2  Product
0ºC
Br
O CH 3 O O
H 3C O
(a) (b) (c) (d)
CH 3 CH3 CH3
7. The major product formed in the following reaction is
COOH
(i) Na / liquid NH3
(ii) C 4H9Br Product


COOH
COOH COOH COOH
(a) C4H9 (b) (c) (d)
C4H 9 C4H9 C4H9
IIT JAM 2015

8. The ene-yne that produces a chiral compound upon treatment with Lindlar’s catalyst is
(a) (b) (c) (d)
9. The correct set of reagents required for the following transformation is

OH O O

 O
(a) (i) CrO3; (ii) acrylonitrile; (iii) H3O+

(b) (i) O2; (ii) methyl acrylate
(c) (i) CrO3; (ii) NaOMe/MeOH, methyl acrylate; (iii) H3O+
(d) (i) H2O; (ii) methyl acrylate
10. Identify the correct reagents required for the following transformation
CHO CH2OH
?


COOEt CHO
(a) (i) NaBH4; (ii) H3O +
(b) (i) LiAlH4; (ii) H3O+

(c) (i) HOCH2CH2OH, H+; (ii) LiAlH4 (iii) H3O+
(d) (i) HSCH2CH2SH, H+; (ii) LiAlH4; (iii) H3O+
IIT JAM 2016
11. The major products X and Y in the following reaction sequence are
O
(i) MeMgBr
Cul
ether m CPBA

(ii) Mel
 X  Y
MeO MeO MeO MeO
(a) X = ;Y= O (b) X = ;Y= O
O O
O O
O
O
(c) X = ;Y= (d) X = ;Y=
12. The appropriate reagents required for carrying out the following transformation are
CO2H
OH


(a) (i) PCC, CH2Cl2; (ii) Ph3P = CHCO2Et; (iii) aq. NaOH, heat, then acidify
(b) (i) CrO3, H2SO4, aq. acetone (ii) Ac2O, NaOAc
(c) (i) MnO2; (ii) CH2(CO2H)2, piperidine, pyridine
(d) (i) PCC, CH2Cl2; (ii) BrCH2CO2C(CH3)3, Zn (iii) H3O+, heat
O


(a) (i) succinic anhydride, AlCl3; (ii) Zn/Hg, HCl; (iii) polyphosphoric acid
(b) (i) maleic anhydride, AlCl3; (ii) H2N-NH2, KOH; (iii) H2SO4
(c) (i) succinic anhydride, FeCl3; (ii) LiAlH4; (iii) H2SO4
(d) (i) Phthalic anhydride, F3B · OEt2; (ii) HS(CH2)2SH, H+; (iii) Raney Ni; (iv) polyphosphoric acid
IIT JAM 2017
14. The product R in the following reaction is
(a) (b) (c) (d)
15. The following conversion is carried out using
(a) hydroboration oxidation followed by Jones oxidation

(b) Wacker oxidation followed by haloform reaction
(c) oxymercuration-determination followed by Jones oxidation
(d) ozonolysis followed by haloform reaction
IIT JAM 2018
16. The product X in the following reaction sequence is
1. TiCl , Zn Cu
 3 X
O 2. Cold alkaline KMnO
3. H 2SO 4
4
O O O
O
(a) (b) (c) (d)
IIT JAM 2019

17. The major product of the following reaction is
Me
Me
OH
CH2 meta-chloroperbenzoic acid
OH
Me
Me
O O
(a) (b) Me
OH Me
Me Me
Me Me
O
OH
(c) (d)
O OH
18. The compound(s) formed as intermediate(s) in the following reaction sequence is/are
OMe 1) Li, NH3, THF OH
2) O 3, MeOH, H2S
3) NaBH4, EtOH Me
4) tosyl chloride (TsCl), pyridine
Me Me
5) LiAlH4, Et2O
OMe OMe OMe OMe
O CHO O
(a) (b) OTs (c) CHO (d) O
Me Me Me Me H
IIT JAM 2020
CO2H
I2, NaHCO3
H2O
O O O O
O O O O
(a) (b) (c) (d)
I I I I
20. The major product formed in the following reaction sequence is
O
i. EtMgBr, Et2O
ii. CrO3, CH2Cl2
iii. Ph3P=CH2, THF
(a) (b) (c) (d)
IIT JAM 2021
S S CF3COOH/H2O
H3CO
CHCl3, 0ºC, 1 h
H3CO O
O
O O S S
O
O
(a) H (b)
H O
O O
H O S S
O
O
(c) O (d)
H H O
H
IIT JAM 2022
22. The reagent required for the following transformation
CO2H CO2H is
(a) NaBH4 (b) LiAlH4 (c) H3B·THF (d) Zn(Hg)/HCl

23. The major product formed in the following reaction
Me
(1) BD3·THF
is
(2) H2O2/NaOH
OH Me Me Me
Me D D
O
(a) D (b) OH (c) (d) H
H H D OH
(±) (±) (±) (±)
24. Which one of the following options is best suited for effecting the transformation?
CHO CO2H
HO HO
(a) MnO2 (b) DMSO, (COCl)2, Et3N
(c) Al(Oi-Pr)3 (d) Ag2O/NH4OH
ANSWER KEY
1. (a) 2. (*) 3. (*) 4. (*) 5. (*) 6. (d) 7. (a)
8. (b) 9. (c) 10. (c) 11. (d) 12. (a,c,d) 13. (a) 14. (d)
15. (b) 16. (d) 17. (b) 18. (b) 19. (b) 20. (b) 21. (*)
22. (*) 23. (*) 24. (*)
HINTS & SOLUTION
2.
Syn hydroxylation of alkene followed by oxidation gives-dial compound ‘Q’.
3.
NBS acts as the source of Br2
4. (a)
(b)
NMe2 NMe2
H

H O
2
 

CH3 CH3
(A)
S S O S S
H 3CO
H 3CO O H O
21. Acyclic
O O
Acetal
Acyclic
Acetal
Acyclic acetal deprotect first with mild acid.
O
Zn – Hg
CO2H CO2H
22. HCl
Clemmenson - reduction
Rest of the reagents will reduce O to – CH2OH
BD 3, THF H2O2
D D D
23. NaOH
BD2 OH
3 B
CHO Ag2O COOH

24. NH4OH
HO HO
Al(O – iso – Pr)3 and DMSO, (CoCl)2, NH3 will also react with – OH
MnO2 is generally used to oxidise allylic – OH.
5
REACTION MECHANISM-I
IIT JAM 2005
1. For the reaction shown below if the concentration of KCN is increased four times, the rate of the reaction will be
:
(a) doubled (b) increased four times

(c) unaffected (d) halved
2. Benzyl chloride is reacted with different nucleophiles shown below. Arrange them in the decreasing order of
reactivity.
Nucleophiles : HO, CH3COO, PhO, CH3O
(a) CH3O > HO > PhO > CH3COO (b) HO > CH3O > PhO > CH3COO
(c) HO > PhO > CH3O > CH3COO (d) CH3COO > CH3O > HO > PhO
3. The reaction of (+)2-iodobutane and NaI* (I* is radioactive isotope of iodine) in acetate was studied by measuring
the rate of racemization (kr) and the rate of incorporation of I* (ki).
(+)CH3CH(I)CH2CH3 + NaI*  CH3CH(I*)CH2CH3 + NaI
For the reaction, the relationship between kr and ki is:
(a) ki = 2 × kr (b) ki = (1/2) × kr (c) ki = kr (d) ki = (1/3) × kr
4. Rationalize the following observations using suitable mechanism.
(a) Nitratino of 4t-butyltoluene gives 4-nitrotoluene as one of the products.
(b) cis-1-t-butylcyclohexyltrimethylammonium hydroxide undergoes Hoffmann elimination to yield 4-t-
butylcyclohexene whereas the trans isomer does not (use conformations) explain.
1. dry ether
(c) PhMgBr + 2PhCHO 
2. acid workup
 PhCOPh + PhCH OH
2
5. Write the products of the following reactions:

(i) CH3I + HO–  (ii) CF3I + HO–  (iii) 2CF3I + Na[Mn(CO)5] 
IIT JAM 2006
6. For the reaction
(a) what is the optical activity of the product ?
(b) draw the energy profile for the reaction
(c) wrtie the structure of the intermediate
(d) what is the effect of doubling the concentration of KOH in the rate of the products?
(e) If aqueous KOH is replaced by alcoholic KOH. Write the structure of the products formed.
IIT JAM 2007
7. Identify reagent (P) and write the structure of products (Q, S and T) in the following
Identify the structures of the intermediate compounds Q, R and S. Show the transformation for each step.
8. The optically pure ester [J] is hydrolysed in aqueous acetic acid to form a racemic mixture of cis-4, 4-dimethyl-
2-acetoxycyclopentanol [K]. Give a mechanistic explanation to account for the formation of [K] and the ob-
served change in the optical activity.
IIT JAM 2008

9. The major product obtained in the following reaction.
is
(a) (b) (c) (d)
10. The major product obtained in the following reaction
is
(a) (b)
(c) (d)
11. R(–)2–Bromooctane on treatment with aqueous KOH mainly gives 2-octanol that is:
(a) Optically active with ‘R’ configuration
(b) Optically active with ‘S’ configuration
(c) A racemic mixture (d) A meso compound
IIT JAM 2009
OH
H CH3 SOCl2
is
C6H13
Cl H
H CH3 Cl CH3 H3C
(a) (b) (c) (d)
C6H13
C6H13 C6H 13 C5H11
13. Identify K and M in the following reaction sequence.
CH 3 H3C
NaOEt M
H 3C Br K CH – CH 2 – Br
EtOH
CH 3 H3C
IIT JAM 2010
14. The reaction of the bromo compound shown below with sodium ethoxide gives predominantly
H Br
H3C D
NaOEt
H H
H H
H3C D H3C D
(a) (b)
H H
H H H
H3C H D H3C D
H3C
(c) (d)
H H and H
15. Write the structures of P, Q and R in the given reaction sequence.
16. Identify X, Y and Z in the following reactions.
IIT JAM 2011

17. Write the possible substitution products in the following reactions. Indicate the types of mechanisms (SN1/SN2)
that is/are operative in each reaction.
Br
(i) CN  , DMF
Br  (ii) CH OH
? 
3 ?
IIT JAM 2012
18. The rates of acetolysis for the following norbornyl derivatives are in the order
(a) R > Q > P (b) Q > R > P (c) P > R > Q (d) R > P > Q
19. The order of nucleophilicity of the following anions in a SN2 reaction is:
(a) Q > R > S > P (b) Q > P > R > S (c) Q > R > P > S (d) P > S > R > Q
20. In the following reaction scheme, write the structure of O, P and Q
21. Choose the correct stereoisomer between U and V that would furnish W on controlled hydrolysis. Write the
stable conformation of W.
IIT JAM 2013

22. Write the structure of A to E in the following reaction sequence:
IIT JAM 2014

23. The structure of the major product in the following reaction is:
O
Me CuLi

2  Product
0ºC
Br
O CH 3 O O
H 3C O
(a) (b) (c) (d)
CH 3 CH3 CH3
IIT JAM 2015

24. Which of the following statement(s) is/are true about the reaction given below?
O
* NaOMe, MeOH
O
 MeO *
Br
(a) It involves a carbocation intermediate
(b) Rearrangement is due to SN1 reaction mechanism
(c) It proceeds via a concerted SN2 pathway
(d) It involves neighbouring group participation
IIT JAM 2017
25. The correct order of rate of solvolysis for the following compound is
(a) III > II > I (b) II > I > III (c) III > I > II (d) II > III > I
IIT JAM 2020
26. The rate of solvolysis of I – IV follows
Br Br
Br
Br
(I) (II) (III) (IV)
(a) I > II > III > IV (b) III > I > II > IV (c) III > II > I > IV (d) IV > I > II > III
ANSWER KEY
1. (c) 2. (b) 3. (b) 4. (*) 5. (*) 6. (*) 7. (*)

8. (*) 9. (c) 10. (a) 11. (b) 12. (a) 13. (*) 14. (c)
15. (*) 16. (*) 17. (*) 18. (d) 19. (b) 20. (*) 21. (*)
22. (*) 23. (d) 24. (c,d) 25. (d) 26. (c)
HINTS & SOLUTION

4. Chemial reaction occuring in above transformation can be illustrated as
As shown in the above mechanism, electrophilic substitution of t-butyl carbocation by H+, takes place, because
tertiary - butyl carbocation is quite stable, so it is completetively replaced by H+.
cis-4t-butylcyclohexyltrimethylammonium hydroxide undergoes Hoffmann elimination, because ‘H’ anti to

trimethylammonium is present.
Here ‘H’ anti to leaving group is not present, so elimination is not possible.
(c) Chemical reaction occuring in statement given above can be illustrated as
5. (i) CH3 – OH + I– (ii) I – O– + HCF3 (iii) Mn(CO)5I + C2F6 + NaI

6. (i) Since in aqueous medium reaction proceeds through SN1 mechanism. Therefore, product is optically
inactive and racemic mixture will be formed.
(ii)
(iii) 3º carbocation intermediate
(iv) Since reaction proceeds through SN1 mechanism. Therefore, rate of reaction will remain unaffected, w.r.t. to
change in KOH concentration,
(b) In presence of alcoholic KOH reaction will undergo elimination reaction.
7.
8.
As (I) and (II) are enantiomers, and they are formed in 1:1 ratio, So, it forms a recemic mixture, so ‘K’ is optically
inactive.
NaOET HBr/H2O2
Br
13. EtOH M
K Br
15.
16.
17.
Only SN2 mechanism is operating here because.


(a) C N is a strong nucleophilic.
(b) DMF is an aprotic polar solvent in which nucleophilic does not get solvated.
(c) Alkyl halide is primary, so steric hinderence is less.
(d) Allylic group increases the electropositive character (because, sp2 carbon is more electronegative than sp3
carbon), so nucleophile can attach faster.
(ii)
here SN1 mechanism is operative because:
(a) CH3OH is a weak nucleophile.
(b) CH3OH is a protic polar solvent which stablises the carbocation formed in SN1 mechanism.
(c) Alkyl halide is tertiary,
(d) In SN1 mechanism, carbocation formed is stablished by resonance with double bond.
21.
In both U and V, V is the correct choice. Since in V both groups are anti to each other. (Suitable condition for
SN2)
Stable conformation of W  due to presence of three membered ring. The cyclohexane ring is deformed chair.
O
H
O HO
O H
O O O H

 O
H H H
H
D = C11H 16O2
(C)
OH 
6
REACTION MECHANISM-II
IIT JAM 2005
1. The rate of nitration of the following aromatic compounds decreases in the order
(i) benzene (ii) pyridine (iii) thiophene (iv) toluene
(a) (iv) > (i) > (iii) > (ii) (b) (iii) > (iv) > (i) > (ii)
(c) (iii) > (ii) > (i) > (iv) (d) (ii) > (i) > (iv) > (iii)
IIT JAM 2006
2. The major product of the reaction
(a) (b) (c) (d)
3. The major product (X) in the reaction
(a) (b) (c) (d)
4. The product of the reaction

AlCl / Cu Cl
C6 H 6  CO  HCl 
3
heat
2 2
gives positive test with Fehling’s solution. The product is

(a) C6H5OH (b) C6H4 (Cl) CHO (c) C6H4 (OH)CHO (d) C6H5CHO
5. Identify reagent (P) and write the structure of products (Q, R, S and T) in the following series of the reactions.
6. Suggest a method for the following transformation involving minimum number of steps
Indicate the reagents/reaction conditions required at each step clearly.

IIT JAM 2007
7. Account fot the following transformation with an appropriate mechanism. Give the structure of the Hoffmann
exhaustive methylation product of 1, 2-dihydro derivative of [X].
IIT JAM 2008

8. The major product of the following reaction
is
(a) (b)
(c) (d)
is
(a) (b)
(c) An equimolar mixture of
(d)
IIT JAM 2009
10. The major product of the reaction is:
(a) (b)
(c) (d)
11. The major product formed in the reaction
is:
(a) (b)
(c) (d)
12. Among the following the major product obtained in the reaction below is:
(a) (b)
(c) (d)
13. Identify E and F in the following reactions and suggest a suitable reason for their formation.
IIT JAM 2010

14. Complete the following sequence by identifying E, F and G.
15. Identify the products J, K and L in the following reactions. Lassigne’s test for L shows the presence of nitrogen
only.
IIT JAM 2011

16. Write the possible substitution products in the following reactions. Indicate the types of mechanisms (SN1/SN2)
that is/are operative in each reaction.
Br
(i) CN , DMF
Br  (ii) CH3OH
?  ?
17. Write the structures of A to C in the following reaction sequence.
1. CF3COOOH, CH 2Cl2
2. NaOH, 
HCl, AlCl3 CH3COCl, AlCl3 3. H3O
+ H3C  HC  CH 2   A   B(Major product) 
C
IIT JAM 2012

18. The major mono-sulfonation product of -tetralone is
(a) (b)
(c) (d)
19. Electrophilic nitrations of the following compounds follow the trend
(a) S . R > P > Q (b) R > S > P > Q (c) R > P > S > Q (d) P > S > R > Q
20. Identify the structures of M and N in the following synthetic transformation
IIT JAM 2015

21. The reaction(s) which give(s) phenol is/are
Cl
(i) conc. H 2SO4 , 
(ii) KOH
(a) 

 (b) KOH, 300ºC

(iii) H
NO2
(i) H 2 , Pd / C (i) CH3CH CH 2 , H 
(ii) NaNO 2 , HCl, 05ºC (ii) O 2 , KOH
(c)   (d) 
 
(iii) NaOH (iii) H
22. The number of possible monoalkylated products formed in the Friedel-Crafts reaction of anisole with 2-chloro-
3-methylbutane in the presence of anhydrous AlCl3 at 50ºC is _______
IIT JAM 2016
O


(a) (i) succinic anhydride, AlCl3; (ii) Zn/Hg, HCl; (iii) polyphosphoric acid
(b) (i) maleic anhydride, AlCl3; (ii) H2N-NH2, KOH; (iii) H2SO4
(c) (i) succinic anhydride, FeCl3; (ii) LiAlH4; (iii) H2SO4
(d) (i) Phthalic anhydride, F3B · OEt2; (ii) HS(CH2)2SH, H+; (iii) Raney Ni; (iv) polyphosphoric acid
IIT JAM 2017
24. In the following reactions, the major products E and F, respectively are
(a) (b)
(c) (d)
25. The major product S of the following reaction is
(a) (b)
Br O
O
(c) N (d) N
H H
Br
26. The correct set of reagents for the following conversion is
(a) (i) NaNH2/liq. NH3; (ii) NaNO2/dil. HCl; (iii) CuCN, heat
(b) (i) HNO3/H2SO4; (ii) Zn/HCl; (iii) NaNO2/dil. HCl; (iv) CuCN, heat
(c) (i) Mg/ether, H2O+; (ii) (EtO)2CO; (iii) NH4OH; (iv) PCl5
(d) (i) Mg/ether, H2O+; (ii) HNO3/H2SO4; (iii) NaNO2/dil. HCl; (iv) CuCN, heat
IIT JAM 2018
Cl NaNH2
CN Liq. NH3
NH2
NH 2
(a) (b)
CN CN
CN O
(c) (d)
28. The sequence of three steps involved in the following conversion is
(a) (i) Friedel-Crafts alkylation; (ii) Reduction; (iii) Friedel-Crafts acylation

(b) (i) Friedel-Crafts acylation; (ii) Friedel-Crafts alkylation; (iii) Reduction
(c) (i) Friedel-Crafts acylation; (ii) Reduction; (iii) Friedel-Crafts alkylation
(d) (i) Friedel-Crafts alkylation; (ii) Friedel-Crafts acylation; (iii) Reduction
IIT JAM 2019
29. The correct option for the product(s) of the following reaction is
Cl NaNH 2
NH3 (l)
N
NH 2
H2N
+
(a) (b)
H 2N N N H2N N
NH2
H2N
H 2N
(c) + (d)
H2N N
N N
ANSWER KEY
1. (b) 2. (c) 3. (b) 4. (d) 5. (*) 6. (*) 7. (*)
8. (d) 9. (b) 10. (b) 11. (a) 12. (d) 13. (*) 14. (*)
15. (*) 16. (*) 17. (*) 18. (b) 19. (b) 20. (*) 21. (a,b,c,d,)
22. (4) 23. (a) 24. (d) 25. (*) 26. (a) 27. (c) 28. (b)
29. (c)
HINTS & SOLUTION
5.
7. First step is similar to Beckmann rearrangement in which migration of group takes place from C to N. Second
step is intramolecular electrophilic aromatic substitution reaction
Product (F) is kinetically controlled and product (E) is thermodynamic controlled product.
Greater unstability of 1-acid (i.e. F) is due to steric repulsion of H at C–8 with SO3H group.
In case of attack of SO3, electrophile at C2, the stabilization of carbocation is only at the cost of loss of aromaticity
of nearby ring, but attack at C1 gets some extra stability via resonance with nearby double bond without costing
the aromaticity of other ring, thats why kinetically favourable at lower temperature.
14.
15.
16.


(ii)
17.
O HO
N
H 2SO 4 . H 2O
25. NH 2OH.HCl Backmann
 
rearrangement

OH 2
N H
N N
H 2O


O
Br 
O
Br / FeBr

2 3 N Br
H
due to +M effect of nitrogen ring linked with nitrogen give electrophilic substitution on that ring.
Hence both ortho and para product forms but para one is the major product hence (C) is the correct answer.
TOPIC WISE PYQ
(Sol.)
(Organic)
1
STEREOCHEMISTRY
HINTS & SOLUTIONS
1.

2. The given structure of the camphor is and chiral centre are shown as follows:
1
O
Carbon-one and carbon-fourth both are chiral centres as both carbon atoms have four different substituents.
So, the number of chiral centres in camphor is 2.
The formula of determine the number of enantiomers is as follows:
No. of enantiomers = 2n–1
Where, n is the number of chiral centres.
On substituting 2 for n we get = 22–1.
= 21
=2
So, the number of enantiomers of camphor is 2.
The enantiomers of camphor are shown as follows:
O O
(I) (II)
Both above structures are mirror images of each other and are non-superimposable.
VIGYAN VRIKSH |Organic Chemistry (IIT-JAM)(PYQ)Solutions
3.
As connectivity of atoms in (1) and (2) is different, so they are constitutional (structural) isomers.
4. Compound (1), (2) and (3) has plane of symmetry, so they are optically inactive. While (4) does not contain
plane of symmetry so (4) is optically active.
5. For a molecule to be chiral, it should not have any of these three symmetries
(i) Alternate axis of symmetry
(ii) Plane of symmetry
(iii) Centre of symmetry
If there are more than one chiral centre in a compound, then it can have any of the above three symmetry
elements, so it can become optically inactive.
6. As the reaction is SN2 predominantly, so inverted product is formed.
Correct opion is (b)
7. D galactose and L-galactose are enantiomer.
L-Galactose is mirror image of D-galactose.

8.
maximum 4-isomers are possible as,
9. Since it doesn’t contain all four different substituents.
and it has a plane of symmetry. Hence it is achiral.
 Correct option is (b)
10.

11. Structural isomer have different connectivity of atoms.
12.
13.
Stability of conformations:
(I) = (V) > (III) > (II) = (IV) > (VI)

14. Since 4th group (CH3) is present at above the plane. So, absolute configuration is inverted.

15. In (i) both are known superimposable mirror image \ enantiomers.
In (ii) both are identical.
In (iii) Both are not the mirror images of each other  diastereomers.
In (iv) Since the connectivity is different  structural isomers.
16. Options given in (a), (c) and (d) has plane of symmetry, so they are optically inactive
17. Chair form is the most stable and half chair is the least stable. hence maximum energy difference is between half
chair and chair form.
Energy: Chair < twist boat < boat < half chair.
[Chair < half chair]
18. The -stereoisomers of glucose contain specific rotation +112 and -isomer contain specific rotation +18.7.
Let us suppose I have x fraction and thus II have (1–x) fraction present at equilibrium.
(112.2 × x) + (18.7 × (1 – x)) = 52.7
112.2x + 18.7 – 18.7x = 52.7
93.5x = 34
34
x  0.363  
93.5
(1 – x) = (1 – 0.363) = 0.637 = 
 0.637 637
=   1.75
 0.363 363
19. for allene to be optically active it should fulfill following condition.
(a) The number of double bond should be even.
(b) There should be proper substitution
Condition for proper substitution
H Cl H
Cl
(1) C (2) C C C C
Cl Cl H Cl
Optically inactive (no proper substitution) odd number of double bonds
For biphenyl the substituent must be bulky

to inhibit rotation, containing P.o.S
 optically inactive
20.
21.
In resonating structure there is no shift of atom takes place.

cis and trans stereoisomer are a pair of diastereoisomers.
Hence, III and II are diastereoisomer and III is also a tautomeric form of I.
Hence (c), (d) is correct.
22. Only (a) and (b) represents meso form

23. C6H14 hexane
Correct answer is (5).
24.
Me Me Me Me
Me Me
25. H

2 * *
Me Me
Total number of stereocentres in product is two and it contains symmetry hence total number of stereoisomers
formed is calculated by
n
1
n 1
2  22
2
1 =3
21
2  22
Hence (c) is correct answer.
* CH 3
CH3  CH 2  CH 2  C H  CH 3 | *
| CH3  CH  C H  CH3
26. (1) (2) |
OH
OH
CH 3 CH 3
| |
(3) CH  O  C H  C H (4) HO  CH  C H  C H
3 2 5 2 2 5
* *
Four pair of enantiomers are possible.
C3
C3
Br
CH3
27. Cl3
CH3 Br Br
these two compounds contains C3 symmetry.

2 4
Et H
28. (1) Least priority should always from observer.

Me Br
3 1
Anticlockwise arrangement these have S configuration.
2
4
Et 1
H OH
(2) Since least priority is at horizontal, therefore Anticlockwise S configuration will revert to
Me
3
R configuration.
(4) (2)
H H
C C C
(3)
H3C CH3
(3) (1) S
Anticlockwise arrangement so, S configuration.
away
Me H
NC CH2NH2 Rotate by 180º
C2 see NC CH NH
Me H from
(4)
this
side Anticlockwise
so S configuration
4 3
Me H H CH3
1 2
rotate by

180º

(5)
Anticlockwise
C2 so S configuration
CH3 is Optically active  exist as enantiomers

29. CH3
CH3 is Optically inactive undergoes flipping  non resolvable

CH3
CH3 is Optically inactive  PoS Present

H3 C
H3 C
CH3 is Optically inactive  PoS Present
Hence correct option is (a)

30. No. of stereoisomer for molecule having internal plane of symmetry / meso compound.
n = number of chiral centers = 2
no. of stereoisomer = 2n – 1
= 22 – 1
=4–1
= 3.
Ph Et Ph H
31. (a) are distereomers
Me H Me Et
Z E
Br
1
1
(b) 3 Br 3
Me Me
tBu 2 tBu 2
Configuration at C2 and C3 are same in both isomers but there is a difference in configuration at C1 of both
isomers and hence these are not mirror image therefore diasteromers
OH
(c) are mirror images and hence enantiomers.
Br
Br
OH
OH OH
3 1 3 1
2 O 2 O
HO 5
(d) 5 6 4 6
4
OH OH OH
Configuration at C2 and C5 are same whereas at C4 there is difference in configuration therefore both are
diasteromers.
Correct options are (a, b and d)
1 CH3
H 2 3
H
32.
CH2
Total 3 Gauche butane interactions

33. If R isomer has specific rotation = 13.5º then S isomer must have rotation value –13.5º
Also 0.4   13.5º   0.6  13.5º  gives
Specific rotation of mixture containing 40% S and 60% R isomer
= 8.1º – 5.4º = 2.7º.
34. Achiral stereoisomers are those which are optically inactive but have the chiral centres within the same molecule
OH OH
2
1 * 4*
HOOC * 3 COOH
5
OH
The molecule contains plane of symmetry hence is achiral but has 3 stereogenic centres (C2, C3 and C4)
Similarly
H3C CH3
dimethyl cyclopentane also contains plane of symmetry with 2 chiral centre hence is not optically active i.e.
Achiral.
35. Most stable conformation of n – butane is.
CH3 H
H
H H CH3
CH3
H H H H
CH3
(Staggered)
The angel between the 2 methyl groups is 180º in the most stable conformation.
Correct Answer is 180º.
CH3
36.
(I)
This is comparatively more stable since t - Butyl group is on equvitorial position.
H
OH
O
O
(V)
Since, the oxygen lone pair have small steric requirement, more over this structure is stabalised by hydrogen
bonding.
So, the correct option is (b)
37. Trimethyl cyclohexane is
H
H 4
H3C H3C CH3
CH3 H3C
3
1 H C2 1 2 1 2 3
3
CH3 CH3 H CH3
(A) (B) (C)
(1, 2) (1, 3) (1, 4
Me
2 4 Me
Me Me Me Me Me
1 Me 3 H 1 2 3
H H H Me
(A) (B) (C)
(1, 2, 3) (1, 3, 5) (1, 2, 4)
All the substituted product i.e. conformational isomers are shown and hence the answer is 6.
OH CH3
H3C C C C C C C C
H H H H H H
38. * CH3
n=1 n=1 n=1
(E/Z) (R/S) (E/Z)
total n = 3
Possible stereoisomers = 2n = 23 = 8
2
GENERAL ORGANIC CHEMISTRY
HINTS & SOLUTIONS
1. Conjugate base of strong acid is weak (i.e. stable), so stability of conjugate base of CH3COCH3,
CH3COCH2COCH3, CH3COOCCH2COOCH3 and CH3COCH2NO2 can be arranged as
Here has greater electron withdrawing ability than Therefore, (ii) has greater
acidity than (iii).
2.
Resonance energy of conjugate base of I, II and III has order. I > III > II
Resonance energy is proportional to stability of compound (strong acid has stable conjugate base).
III is less aromatic than I due to annelation effect.
3. There are 16 -electrons in the molecule, but this can not be aromatic by Huckel rule, so in order to be aromatic
and to follow Huckel rule, only 14 -electrons should be involved in making the ring current.
14 = 4n + 2  n3
here only 14 -electrons will form the ring current.
Correct option is (c).
4. (b) A strong acid has conjugate base most stable (i.e. weakest base).
Acidic strength of these acid is just opposite to the basic strength of their conjugate bases.
Strength of conjugate bases
CH3
> > > NH

N N N
H
Therefore, trend of acidic strength of corresponding acids is just opposite.
So, (ii) is weak base
+ localised + +I effect of CH3.
Due to +I effect of CH3 group, conjugate base of (iii) is more basic than (i). So, (iii) is less acidic than (i).
As conjugate base of (iv) is strongest base w.r.t. conjugate base of (i), (ii) and (iii), so (iv) is weaker acid.
 Acidity order (iv) < (iii) < (i) < (ii)
5. In resolving structure, there is movement of l.p. and -electrons only, but in tautomerism there is movement of ‘H’
atom.
So, ‘X’ and ‘Y’ are resonating structure and Z is tautomer.
6.
Non aromatic Aromatic Non aromatic Aromatic

Only Q and S are aromatic so correct option is (d)
7.
P  after proton abstraction one new aromatic ring is formed but there is no extra stabilisation from the phenyl
ring.
Q  after proton abstraction one new aromatic ring is formed and there is extra stabilisation from the phenyl
ring.
R  after proton abstraction two new aromatic rings are formed.

Therefore, stability of conjugate bases follows the trend.
R > Q > P and same is the trend of acidic strength as acidic strength is directly proportional to the stability of
conjugate base.
8. C–H bond
Acetylene sp(c) – 1S (H)
(50% s character)
Ethylene sp2(c) – 1S (H)
(33% s character)
Methane sp3(c) – 1S (H)
(25% s character)
sp2(c) – 1S (H)
(33% s character)
10.
(1) Planar (2) Fully conjugated (3) 4n + 2 = 2 electron

n = 0 (following Huckel Rule)
Hence aromatic,
1. Planar 2. Fully conjugated 3. 4n + 2 = 14 electron

n = 3 (following Huckel rule)
Hence, it is aromatic.
11.
Among P, Q, R and S, NHCOCH3 and –C2H5 groups are ring activators and –Cl, SO3H are ring deactivators.

Resonance effect dominates over hyper-conjugation hence — N HCOCH is the more powerful activator..
3
between –Cl and –SO3H, –SO3H is the powerful deactivator.
P>Q
Correct order  R > S > P > Q
12.
Canonical
Because in this form both the rings are aromatic hence stable.
13. Carbocation at bridge head position is less stable because their rigid framework.
tertiary no bridged
 most stable
So, stability of the carbocation follows the order.
14.
15.
• It is planar.
• Complete delocalisation of electrons.
• Follows Huckel rule.
• It is planar.
• It is planar.
Correct option is (a, b, c)
16. Acidic strength of conjugate acid of these bases is just opposite to their basic strength.
which means pKa of conjugate acid is  basic strength of base.
Basic strength trend III > II > IV > I
III is more basic than II because as ring size increases percentage s character decreases basic strength increases.
IV is more basic than I because lone pair is localised in IV but delocalised in I.
II is more basic than IV and I because lone pair is present on sp3 nitrogen.
17.
C exist as in which both the rings exhibit aromaticity..
Both are antiaromatic.
Non planar.
Exists as tub shaped.
Since compound is not planar. Thus, it is non-aromatic.
The number of aromatic compound = 3
18.
• Generally carboxylic acids are more acidic than phenyls.

 III & IV are more acidic than I & II.
• Electron withdrawing group increases the acidic character
• Electron donating group decreases the acidic behaviour
• Acid  conjugate Base + H+
Higher the ka, lowe will be pKa, higher will be acidity
1
 acidic behaviour  pK
a
Thus order of acidic behaviour will be III > IV > I > II
Hence, correct order of pKa will be III < IV < I < II
Correct Option is (b)
19.
In resonating structure there is no shift of atom takes place.

cis and trans stereoisomer are a pair of diastereoisomers.
Hence, III and II are diastereoisomer and III is also a tautomeric form of I.
Hence (C), (D) is correct.
In resonance structure, there is movement of l.p. and -electrons only, but in tautomerism there is movement of
‘H’ atom.
So, ‘X’ and ‘Y’ are resonating structure and Z is tautomer.
O O OH
O
NH N
20. 
 O N O 
 N OH
O Aromatic
Aromatic H
N
6 electron S take part in
N resonance
Hence 6e– f ollows
CH
Huckel rule
Follow Huckel rule
Planar
Planar
Hence Aromatic Hence Aromatic
 The number of aromatic number compound = 4

21. Acidity of proton depends upon the hybrization of carbon to which it is attached. A sp hybridised carbon is very
electronegative and can easily stabilize the negative charge on it.
CH  CH  CH  C  H 
Most acidic sp carbanion most stable conjugate base.
22. (i) It has 6 hydrogens hyperconjugation stablization.
Resonance stablization from electron delocalization of

phenyl ring towards vacant P orbital.
(ii) Bridge head carbocation are very unstable because these are too stained and can never
become planar. It has high energy vacant sp3 orbital.
(iii) It has 9 hydrogen, hyperconjugation stablization therefore more stable than IV as
hyperconjugation of 9H dominates over allylic conjugation.
(iv) Which enjoys no hyper conjugation but resonance gives some sort of stablization to allylic
carbocation.
3
NATURAL PRODUCTS &
BIOMOLECULES
HINTS & SOLUTIONS
1. Correct option is (d)
2. As the number of basic (–NH2) units increases, the pI value increases.
As the number of acidic (–COOH) units increases, the pI value decrease.
3.
4. In complementary strand ‘A’ will be replaced by ‘T’ and vice-versa and ‘G’ by ‘C’and vice-versa. Therefore,
complementary stand will be determined as
5. (a)
(b) Correct sequence of pentapeptide is
6.
7. D galactose and L-galactose are enantiomer.
L-Galactose is mirror image of D-galactose.

OH
OCH3 OH
H2C O 1
4
O OCH3
8. (i) HC OH HIO H O / H
3 2 2 
4 OH 
2
O O
OH OH HH
OH
O
OH OH
O O
+ H + CH3OH
H
1 mole 1 mole
HIO4 cleave the C–C bond

–OH group containing
OH O OH
4 5 6
4 6 O
HO 5 O HH
(ii) HO 2 2eq HIO4 HO 2 H  / H 2O
OCH3 
OCH 3  3
3 1 HO 1
OH O
O OH
4 6
H OH
5 H–OCH3
OH H
O 3 2
H
H O 1
O
Product are
O
||
1 mole H  C  OH
H
O
1 mole O
H
O OH
1 mole
H OH
1 mole CH3 – OH
9.
pI = the average pKa values of two similar ionisable groups
pK a1  pK a 2 8.95  10.53
pI    9.74
2 2
10.

11. Correct option is (a)
12. RNA contains adenine guanine, uracil and cytosine, but DNA contains adenine, guanine, thymine and cytosine.
1
H O H OH
2
H OH H 2C OH
H OH HO
3
H H O H
HO H 4
H OH OH H
13. H H
OH  5 
 H O OH OH
H OH
H C OH H OH
H2C OH
D    anomer
–OH which is right will be downward
–OH which is left will be upward.
14. Complementary DNA sequence of
5´– G – A – A – T – T – C – 3´  3´ – C – T – T – A – A – G – 5´
This is called base pairing in DNA
A (adenine) pair with T (thymine)
G (guanine) pair with C (cytosine)
15. Two diastereomers that differ in the configuration around one only stereogenic centre are called epimers.
So, the configuration is changed at the only C3 carbon. Hence it is called epimer and epimer is also called
diastereomer.
16.
d-farmesene has 3 isoprene unit hence it is a sesquiterpene. (Molecular formula = (C15H24))

18.
19. Because nucleic acids are polymer whose monomer is nucleotides not protein. So, (b) not correct.
Proteins are generally acts as enzyme but not vitamins. Proteins do not contain genetic information, its DNA
which contain genetic information.
20. Tollen’s reagent is oxidising agent carbohydrate which have easily oxidisable carbonyl group give positive Tollen’s
test by reducing it. Since, in given four sachharides sucrose is the only whose both oxidisable group are linked
together by 1, 2 linkage [i.e. C-1 of glucosyl unit and C-2 of fructosyl unit]. Since, it contains no anomeric
hydroxyl group; thus it is classified as non-reducing sugar. Hence, it give negative Tollen’s test.
21. Terpenes have general formula (C5H8)n; when n = 3, then the terpenes is known as sesquiterpene.
Thus, sesquiterpene has formula C15H24.
In the given structure; structure a has this formula.
22. The -stereoisomers of glucose contain specific rotation +112 and -isomer contain specific rotation +18.7.
Let us suppose I have x fraction and thus II have (1–x) fraction present at equilibrium.
(112.2 × x) + (18.7 × (1 – x)) = 52.7
112.2x + 18.7 – 18.7x = 52.7
93.5x = 34
34
x  0.363  
93.5
(1 – x) = (1 – 0.363) = 0.637 = 
 0.637 637
=   1.75
 0.363 363
pk a1  pk a 2
23. pI 
2
Where pI is the average pka values of two similarly ionisable groups.
pka = 10.79
H3 N
H3N COO 2.18 pka
pka = 8.95
10.79  8.95 19.74

pI    9.87
2 2
24. If the number of amine (basic) groups are more than carboxylic (acidic) groups then the amino acid will be basic
in nature.
Hence, correct option is (C)

25. All C2 epimers form same osazone moiety. During osazone formation the chirality of C2 carbon is lost.
For example: D-glucose, D-mannose are C2-epimers and they form same osazone. Fructose also form the same
osazone like that of D-glucose.
The osazone formed by D-glucose, L-glucose, D-mannose and D-fractose are structurally similar. Hence, they
have the same melting point.
Correct options are (A), (B) and (C).
O
N NH
26. (A) Guanine
N N NH 2
Because it contains pyrimidine ring fused to an imidazole ring hence it is purine nucleobase.
O
(B) Glycine H2N achiral
OH
O
Proline * OH Chiral
N
H
Because glycine does not contains chiral carbon hence it is achiral aminoacids but proline is chiral amino acid.
(C) DNA contains pentose sugar joined together by phosphate groups and it contains glycosidic bonds.
CH2OH
H O O H
H
OH H OH
(D)
O H
OH CH2OH
glycosidic
H OH bond
OH H
Sucrose contains glycosidic bond between its anomeric carbons thus can not converted to an open chain form
with an aldehyde group.
Hence A, C, D are correct answers.
Ph * COOH * COOH
27. NH 2 + NH 2
Phenylalanine Leucine
(a) If only cross reaction is considered then

(natural L form exist)
O COOH
Ph N
NH2 H
O
H
N C
Ph
NH2
COOH
Hence answer is 2.
(b) If self reaction and cross reaction both considered then the answer will be four.
(c) If D and L both form considered (not natural form) then answer will be eight.
28. Condition for reducing sugar
 Monosaccharide that have a aldehyde group. They can act as reducing sugar by converting it to carboxylic
group.
OMe OMe
O OH H
HO HO
(1)  OH
OH OH
OH OH O
HOH2C O OH
(2) Similarly for
HO OH
CH2OH
O
H OH
(3) H OH this keto group can be converted into aldehyde group under basic condition.
H OH
CH2OH
Rest of all structure will not able to give sugar with aldehyde group
Hence answer is 3.
29. C–2 epimer mean configuration at C2 only is different and rest of he molecule is same.
C–2 epimer of D-glucose is D-Mannose.
CHO CHO
H C OH HO C H
HO C H HO C H
H C OH H C OH
H C OH H C OH
CH 2OH CH2OH
D-Glucose D-Mannose
30. To react with sanger reagent nucleophilic nitrogen is required. Tertiary and amide nitrogens are not nucleophilic.
Hence only A and D will produced the above product.
31. In DNA the two strands must be antiparallel (if one is 3' to 5' then other is 5' to 3') and complementary (A pairs
with T and G pairs with C)
CHO COOH
CHO
H OH H OH CaCO3, H 2O2
Br2/H2O HO Fe(OAc)3 HO H
HO H H
H OH
H OH H OH –CO2 H OH
32. H OH H OH
CH2OH
CH2OH CH2OH
D glucose Final product
D-arabinose
Br2/H2O, oxidation does not affect configuration of C 2 and in 2nd step C2 carbon atom is eliminated as CO2
without affecting configuration at C3 or any other carbon in given chain. Therefore
CHO
HO H
HO H
H OH
H OH
CH2OH
Reacts similarly with Br2/H2O and H2O2/Fe+3 reagent to give same D-arabinose as configuration C3 onward in
(B) is same as D glucose.
33. Statments (b and d) are correct
34. Lysine is a basic amino acid. To determine P value we need to add two higher pKa values out of given three and
then find the average of this value.
 pK a 2   pK a 3
P 
2
9.1  10.5
P 
2
19.6
P 
2
P  9.8
2 3 3 2
CO2H CO2H CO2H CO2H
1 1 1 1
H2 N H4 H2 N H H2 N H H2 N H4
'S' 'R' 4 'S' 4 'S'
35. CH2CH3 CH2SH CH2Ph CH2CH2SCH3
3 2 2 3
(A) (B) (C) (D)
Hence, correct option is (b)
36. Uracil replaced by Thymine in DNA
37. Isoprene is a hemiterpene having formula
In the given molecule,

Me Me Me
Me
Me
Me Me Me
As in this there are 4 head to tail isoprene linkage.
Correct option is (4)
38. Aldehyde and Hemi-acetal reduced tollen’s reagent.
39. HO
HO OH
O
O
4
REAGENTS
HINTS & SOLUTIONS
1. The compounds containing acidic hydrogen when reacted with RMgX. First acid base reaction occurs, acid
alkene will form
Chemical transformation involved in above chemical reaction can be illustrated as
2.
3.
NBS acts as the source of Br2
QUANTA CHEMISTRY CLASSES |Organic Chemistry (IIT-JAM)(PYQ)Solutions
4. (a)
(b)
NMe2 NMe2
H 

H O
2
 

CH3 CH3
(A)
6. With Gilman reagent 1, 4 addition is favoured.

The chemical reaction involved in above transformation can be illustrated as

7. The chemical reaction involved in above transformation can be illustrated as
e–
Correct answer is (a).

8. Lindlar’s catalyst selective reducing agent for alkynes over alkenes. Lindlar’s catalyst convert alkynes into z-
alkenes.
9.
10.
11.
12.
Reaction (A):
Reaction (B):
O
OH
All primary alcohols oxidized with Johe’s reagent and give overoxidation product due to formation of stable
hydrate formed after aldehyde formation.
However, Benzyl alcohol and allyl alcohols doesn’t form stable hydrates after aldehyde stage oxidation. Hence,
can be selectively.
Oxidized to aldehyde.
Reaction (C):
Mechanism:
Reaction (D)
O Br O CH3
| || |
OH CH 2 CO CCH3
PCC H
 |
CH3
DCM
 
Zn
O O ZnBr
H HC C O
Reformatsky reaction
OH
OZnBr O
O
H O O
O 
3

Hydrolysis of ester
OH
O
O
H O OH
OH 
2
H
Correct options are (A), (C), (D).
13.
Correct option is (A).
7 9 7
O Me
8 8
6
O Me OH 1 H 
Me  6 Me 
O
O 1
Me
aq. NaOH 3 2
14. 
3 5
4
3
2 5 4
Me H O
OH 
OH Me Me

Me  
Me
OH
H
O O
Hence the correct answer is (D)
Me Me Me
O
15. Wac ker Oxidation


+ CHX3
NaOH / X 2 O
O
Me
OH
H


O
Hence correct answer is B.
Ti Ti
TiCl3/Zn–Cu O O O O
16. O
Mcmurry Reaction
Ti surface H
+
O O O O OH OH
2) cold KMnO4
dihydroxylation
Alkene (pinacol)
H O
O OH2 O
3) H2SO4
Me Me Me Me O O
OH OH
CH2 Peracid CH2 H
17. O
Oxidation of alkene to epoxide
Me
Me O OH
OH
Ring OH ±H OH
O Contraction Me Me
Me Me
OMe OMe OMe OMe
Li, NH3 O3, MeOH, H2S NaBH4 TsCl
O O
18. O EtOH
Reductive ozonolysis OH
of relatively electron
Me Me rich double bonds. Me H Me H
(A) (D)
OMe H
LiAlH4, Et 2O OH
O
OTs
CH3
Me Me
(Final product)
(B)
H O O
OH
O C O C
CO2H I , NaHCO C
19. 2 3 O
I
I I
O HO Et
(i) EtMgBr (ii) CrO3 (iii) PPh3=CH2
20. Et2O CH2Cl2
O
Babler oxidation
S S O S S
H 3CO
H 3CO O H O
21. Acyclic
O O
Acetal
Acyclic
Acetal
Acyclic acetal deprotect first with mild acid.
O
CO2H Zn – Hg CO2H
22. HCl
Clemmenson - reduction
Rest of the reagents will reduce O to – CH2OH
BD 3, THF H2O2
D D D
23. NaOH
BD2 OH
3 B
CHO Ag2O COOH

24. NH4OH
HO HO
Al(O – iso – Pr)3 and DMSO, (CoCl)2, NH3 will also react with – OH
MnO2 is generally used to oxidise allylic – OH.
5
REACTION MECHANISM-I
HINTS & SOLUTIONS
1. This reaction follows SN1 – pathway due to living group is present at tertiary carbon atom.
The rate of SN1 reaction  reactant.
So, rate will be independent of nucleophilic concentration.
2. In PhO– and CH3COO– negative charge on oxygen is delocalized via resonance, but CH3COO– has more

delocalization than PhO–, so CH3COO– is less nucleophilic than PhO–, O H and CH3O–
3.
1 1
When mole of NaI* reacts with (I), then it causes formation of mole of (II) (i.e. inversion product), but
2 2
1 1
mole of (I) and mole of (II) , give 1 mole of racemic mixture (I)
2 2
 1 1 
    mole(I)  () mole(II)  .
 2 2 
So rate of racemisation is twice of inversion.
1
 kr = 2ki  ki  kr
2
4. Chemial reaction occuring in above transformation can be illustrated as
As shown in the above mechanism, electrophilic substitution of t-butyl carbocation by H+, takes place, because
tertiary - butyl carbocation is quite stable, so it is completetively replaced by H+.
cis-4t-butylcyclohexyltrimethylammonium hydroxide undergoes Hoffmann elimination, because ‘H’ anti to

trimethylammonium is present.
Here ‘H’ anti to leaving group is not present, so elimination is not possible.
(c) Chemical reaction occuring in statement given above can be illustrated as
5. (i) CH3 – OH + I– (ii) I – O– + HCF3 (iii) Mn(CO)5I + C2F6 + NaI

6. (i) Since in aqueous medium reaction proceeds through SN1 mechanism. Therefore, product is optically
inactive and racemic mixture will be formed.
(ii)
(iii) 3º carbocation intermediate
(iv) Since reaction proceeds through SN1 mechanism. Therefore, rate of reaction will remain unaffected, w.r.t. to
change in KOH concentration,
(b) In presence of alcoholic KOH reaction will undergo elimination reaction.
7.
8.
As (I) and (II) are enantiomers, and they are formed in 1:1 ratio, So, it forms a recemic mixture, so ‘K’ is optically
inactive.
9.


11. As the reaction is SN2 predominantly, so inverted product is formed.
Correct opion is (b)
Chlorination with retention of relative configuration.

NaOET HBr/H2O2
Br
13. EtOH M
K Br

Since E2 reaction is anti-elimination reaction. Here Br and D are anti to each other. So D-Br will remove.

15.
16.
17.


(ii)
IIT JAM 2012
18.
Removal of the tosyl group (the rate determining step) is subject to strong anchimeric assistance by the double
bond and forms non-classical carbocation. Hence acetolysis is fastest in case of R. Among P and Q.
Rate of acetolysis for P is faster than Q due to participation of -electrons of two allylic 1-6, and 4-5 bonds. Rate
of acetolysis R > P > Q
19. Among P, R and S conjugate base of the weakest acid is the strongest nucleophile
Between P and Q, PhS is better nucleophilic than PhO . (Large size of anion better nucleophile)
21.
In both U and V, V is the correct choice. Since in V both groups are anti to each other. (Suitable condition for
SN2)
Stable conformation of W  due to presence of three membered ring. The cyclohexane ring is deformed chair.
O
H
O HO
O H
O O O H

 O
H H H
H
D = C11H 16O2
(C)

OH
23. With Gilman reagent 1, 4 addition is favoured.
The chemical reaction involved in above transformation can be illustrated as
24.
From above mechanism:

If process via a concerted SN2 pathway.
It involves neighbouring group participation.
So, correct option is (c, d)
25. Rate of solvolysis depends upon stability of carbocation formed in the SN1 solvolysis reaction.
Hence
Br
(I) 

RDS + Br–
Br
(II) 

RDS + Br–
Br
(III) 

RDS + Br–
> >
Stability of carbocation follows
6  (aromatic) benzylic anti
carbocation aromatic
Hence correct answer is (D) II > II > I
Br Br
Br
26.
Br
(I) (II) (III) (IV)
As more is the stability of carbocation, higher will be the rate of solvolysis. Stability of carbocation follows the
order:-
> > >

Aromatic Non-aromatic Anti-aromatic
(III) (II) (I) (IV)
 rate of solvolysis is III > II > I > IV.

correct option is (c)
6
REACTION MECHANISM-II
HINTS & SOLUTIONS
1. The rate of electrophilic substitution reaction is depends on the electron density in ring. Thiophene has most
electron density in the ring and pyridine has least. Hence, the order towards the electrophilic substitution will be
thiophene > toluene > benzene > pyridine
2. Chemical transformation involved in above reaction can be illustrated as:

3. Chemical transformation involved in above reaction can be illustrated as:
4.
5.
7. First step is similar to Beckmann rearrangement in which migration of group takes place from C to N. Second
step is intramolecular electrophilic aromatic substitution reaction

  
9. The reaction is Beckmann rearrangement, so the group anti to leaving group   O H 2 
 
i.e. Ph-migrates.

Ac2O  Acetic anhydride


Product (F) is kinetically controlled and product (E) is thermodynamic controlled product.
Greater unstability of 1-acid (i.e. F) is due to steric repulsion of H at C–8 with SO3H group.
In case of attack of SO3, electrophile at C2, the stabilization of carbocation is only at the cost of loss of aromaticity
of nearby ring, but attack at C1 gets some extra stability via resonance with nearby double bond without costing
the aromaticity of other ring, thats why kinetically favourable at lower temperature.
14.
15.
16.


(ii)
17.
18. E+ (SO3) can attack at different positions.
among I, II and III (I and III) are unstable so II is the more appropriate choice.
19.
Among P, Q, R and S, NHCOCH3 and –C2H5 groups are ring activators and –Cl, SO3H are ring deactivators.

Resonance effect dominates over hyper-conjugation hence — N HCOCH is the more powerful activator..
3
between –Cl and –SO3H, –SO3H is the powerful deactivator.
P>Q
Correct order  R > S > P > Q
21.
Mechanism
Mechanism:
Mechanism:
Correct option (a,b,c,d).
22.
Friedal-Craft alkylation reaction:
So, four possible monoalkylated product are formed.

Correct answer is 4.
23.
Correct option is (a).
O
OH OH O C CH3
1. NaOH / CO 2 COOH COOH
125ºC / 47 atm (CH CO) O
24.  
3 2 

2. H3O
(E) (F)
Hence the correct answer is (d).
O HO
N
H 2SO 4 . H 2O
25. NH 2OH.HCl Backmann
 
rearrangement

OH 2
N H
N N
H 2O


O
Br 
O
Br / FeBr

2 3 N Br
H
due to +M effect of nitrogen ring linked with nitrogen give electrophilic substitution on that ring.
Hence both ortho and para product forms but para one is the major product hence (C) is the correct answer.
OMe OMe
OMe H
Br  |
Na N H / liq. NH NH 2

2 3  
NH
2
26. H NH 2
Benzyne
intermediate
OMe OMe OMe

H CuCN, 
NaNO / dil. HCl

2  
NH N Cl CN
Hence answer (a) is correct
27. Strong base amide abstract acidic proton
H
Cl NaNH2 Cl
CN Liq NH3 CN

C N C N
H H
NH 2
CN CN
NH2(l)

Product
28. Friedel craft acylation of benzene
O O O
AlCl3
AlCl3
H 3C C Cl H3CH2C Cl
H CH2CH 3
O O
O
H 3C
C –HCl H3CH 2C
CH 2 H2 H
CH 3 Friedel craft Alkylation
of this ketone with
Cl
Keto group is meta director
O
towards Electrophiles
C CH3
H2
O
AlCl3 AlCl3 CH2CH3
Cl Cl
O O Clemensen
H (Zn/HCl)
CH 2CH3 HCl CH 2CH3 Reduction CH2CH3
Desired product
H
Cl
29. both protons are acidic and hence in the presence of sodamide strong base we have
N H
Cl –NH3 NH 2 NH2 Protonation NH2
N H NH 2 –Cl N N N
A Stablised due to –I
ef f ect of electronegative
Nitrogen
NH2
H NH2 NH2
Cl –NH3 NH2 Protonation
N –Cl N N N
B

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TOPIC WISE

The order of the reaction is

IIT JAM 2013

IIT JAM 2011

(i) Name the photophysical pathways X, Y and Z.

d[Z] d[Z] d[Z] d[Z]

Run 3 pNO 2pO2 2v

(a) U = 0, q > 0, w < 0 (b) U > 0, q > 0, w = 0

(final answer should be rounded off to two decimal places)

Hº  285 kJ mol1 SHº 2O  l   70 J K 1 mol1

SOº 2  g   204 J K 1 mol1 SHº 2  g   130 J K 1 mol1

[Given: Gas constant (R) = 8.3 J K–1 mol–1]

Chemical potential ()

Chemical potential ()

(a) 3.5 R (b) 6R (c) 6.5 R (d) 9R

0 250 500 750 1000 1250

8p c Vc RTc 27R 2 Tc2

[Given: A is a normalization constant such that  f    d

(a) A exp   m x / 2k B T  (b) A exp   m x / k BT 

(c) A x exp   m x / 2k B T  (d) A x exp   m x / k BT 

 2NO2 (g)

IIT JAM 2015

(a) Single phase of a solution of Mg and Zn

(a) (b) (c) (d)

IIT JAM 2022

(c) X'Y' (d)

(a) 2 10 n (b) 10 n (c) 2 11n (d) 42 He

(a) 2 / m (b)  / 2m (c)  / m (d) 2 / m

The function f  x   x e  x has a minimum at

Z = 38.421 × 10–1 = 3.8

Where a is edge length = 361 pm.

One Cs+ ion surrounded by 8 Cl– ion and vice versa.

 2  ( 1)  1  2  ( 1)  1  ( 1)  ( 1)  1

Limiting Radius Ratio:

a  r  2r  r  2r  2r ; a  2(r  r ) ; AC = d = 4r–

AC2 = AB2 + BC2; d2 = a2 + a2 = 2a2 d  a 2 i.e. face diagonal

da 2; 4r  a 2 ; 4r  2(r  r ) 2

As Cs+ atom is at center only = number of Cs+ atoms/cell = 1

Correct option is (a)

This is a consecutive reaction and [Y] at any time ‘t’ is given by

Overall rate unit K  

 0.05   0.1  200 k  n  1

 0.05    0.1  4  0.2   4  0.4 

When n = 2 above equation holds good

11. A(g)  2B(g)  C(g)

Correct option is (A)

RT1T2  k 2  8.314 JK 1mole1  300K  350K  160 

kT1T2  k 2  8.314JK 1mole 1  298K  318K

Correct answer is (27.99)

= 0.3840 mol–2 dm6 sec–1

(a) The rate of formation of BD is

k1[CB]2  k 1[CB* ][CB]  k 2 [CB* ]  0

k1[CB]2  (k 1[CB]  k 2 )[CB* ]

Rate of formation of HBr,

k1[NO][O 2 ]  k 1[NO3 ]  k 2 [NO3 ][NO]  0

 Ea = 53582.8 J/mole = 53.58 kJ/mole

Vmax 2.4  104 Ms 1

35. For the reaction

Correct option is (c)

24 + 96 = 174.14 = 39.07 g/mol