Thermodynamics: Synopsis

THERMODYNAMICS JEE-MAIN & ADV CHEMISTRY-VOL-II
SR-MAIN-CHEM-VOL-II
THERMODYNAMICS
SYNOPSIS Types of system:
 Systems are classified on the basis of their
Introduction and Concepts interaction with the surroundings as follows:
Thermodynamics 1. Open System : The system where matter and
 The subject dealing with Quantitative relation energy are exchanged with surroundings.
between heat energy and other forms of energy in Boundary is not sealed and not insulated
physico - Chemical processes is called eg. All living beings, Reactants in open vessel.
Thermodynamics. 2. Closed system: The system where only the
Chemical Thermodynamics energy but not the matter is exchanged with the
surroundings. Boundary is sealed but not insulated.
 The branch of thermodynamics which deals with
eg. A closed steel container having hot water.
the study of process in which chemical energy is
involved is called chemical thermodynamics. 3. Isolated system: The system which does not
exchange either the matter or energy with the
 These results are formulated into four law’s namely
surroudings. Boundary is sealed and insulated
Zero, First , second and third laws of
eg. A perfectly insulated, closed flask containing
thermodynamics.
water.
 These laws are based on experimental facts but  On the basis of composition, there are two types
not on the theoretical facts. of systems.
 Thermodynamics predicts the energy 1) Homogeneous system : A system consisting
transformations and feasibility of a process. of one phase.
 Thermodynamics deals heat changes occuring eg: Pure solid, a liquid or a mixture of gases.
between system and surroundings. 2) Heterogeneous system : A system consisting
Limitations of Thermodynamics of two or more phases.
 These laws donot give any idea about the rates of eg: a solid in contact with liquid state.
the processes. State of a system
 It fails to explain the systems away from  The system is said to be in a certain state, when
equilibrium. it’s macroscopic properties have definite values.
It is defined in terms of its state functions such as
The terms used in thermodynamics: P, V, T etc.
System:  If any one of the state functions is changed, the
 It is any part of universe that is under state of that system is said to be changed.
thermodynamic study at that instant. eg: at 1atm pressure H2O is
e.g : a) A crystal (for a crystallographer) a) solid below 00C
b) A physical process (for a physicist) b) liquid between 00C - 1000Cand
c) gas above 1000C.
c) Chemical reaction (for a chemist)
State functions or state variables
Surroundings  The Thermodynamic properties whose values
 The remaining part of the universe, other than depend only upon the initial and final states of the
system is called surroundings. system and are independent of the path are called
Universe = system + surroundings state functions.
Boundary: Any real (or) imaginary, rigid (or) eg: Internal energy (E), Enthalpy (H),
non-rigid surface that separates system and Entropy (S), Gibb’s energy (G), Pressure (P),
surroundings. Temperature (T), Volume (V), Number of moles
etc.
148 VELAMMAL BODHI IIT ACADEMY
JEE-MAIN & ADV CHEMISTRY-VOL-II
SR-MAIN-CHEM-VOL-II THERMODYNAMICS
Path Function: b) Driving force is much higher than opposing force
 The property of a system that depends on the path c) Wrev  Wirr (Expansion)
of the process.  Graphical representation of thermodynamic
eg: work, heat. processes
Thermodynamic Process:
 The operation which brings about the changes in (1)
the state of the system is termed as thermodynamic
P
process. (2)
Isothermal Process : (4) (3)
 A process in which temperature of system does
V
not change throughout the studies. For an isothermal
process dT=0 and dU=0. An isothermal process WIsobaric > WIsothermal > WAdiabatic > WIsochoric
is achieved by using thermostatic control. 1) Isobaric process
Adiabatic Process: 2) Isothermal process
3) Adiabatic process
 A process in which exchange of heat between
4) Isochoric process
system and surroundings does not take place.
For an adiabatic process q = 0.
Extensive Property
 It is the property of a substance that depends on
It can be achieved by insulating the boundaries of
the quantity or size of matter present in the system.
system.
eg. Mass, volume of a gas, Internal energy, Enthalpy,
Isobaric Process: entropy, heat capacity, Gibbs energy, heat content,
 A process in which pressure of the system remains no of moles etc.
constant throughout the studies. Intensive Property
For an isobaric process  P  0  .  It is the property of a substance that does not depend
Isochoric Process: on the quantity or size of matter present in the
system.
 A process in which volume of the system remains
eg. Density, molar properties (such as molar
constant throughout the studies.
volume, molar entropy,molar heat capacity) surface
For an isochoric process V  0 . tension, viscosity, specific heat, refractive
Cyclic Process: index,pressure,temperature, boiling point,freezing
 A process in which initial state of system is regained point, vapour pressure etc.,
after a series of operations.  The product, ratio and sum of two extensive
For a cyclic process U  0 and H  0 properties is intensive.
Reversible Process: eg. Mass and volume are extensive but density =
 A reversible process (or quasistatic process) is one M
is an intensive property
in which all changes occuring at any part of the V
process are exactly reversed when change is carried Internal Energy (E or U) :
out in opposite direction. It gives rise to maximum  It is the sum of all types of potential and kinetic
work. energies of constituent particles of a given substance
Irreversible Process: at given temperature.
 An irreversible process is one in which direction of  It may be chemical, electrical, mechanical or any
the change cannot be reversed by small change in other type of energy. Denoted by U of the system,
variables. which may change, when
An irreversible process is a real one and all process a) Heat passes into (or) out of the system
which naturally occur are irreversible. b) Work is done on (or) by the system
It involves c) Matter enters (or) leaves the system.
a) A fast change during investigation  It is an extensive property and a state function.
VELAMMAL BODHI IIT ACADEMY 149
SR-MAIN-CHEM-VOL-II
 It is impossible to determine the absolute value of q = heat gained or lost by the system;
‘U’ of a substance. W = Work done by the system (or) on the system.
 But the change of Internal energy of a system  For absorption of heat ‘q’ is +ve and for release
(  U) can be determined. ‘q’ is –ve
  U = heat absorbed (or) released in a process at Discussion of Equation
constant volume.  When W=0 U  q
 U = Qv If heat is absorbed by system, internal energy
increases, If heat is lost by system, internal energy
(  U = Ufinal– Uinitial)
decreases.
  U of a chemical reaction is determined in a Bomb  When q = 0 (adiabatic) U  W
calori meter.
If work is done on the system, internal energy
 For any chemical reaction U = UP - UR
increases, If work is done by the system, internal
UP = Total internal energy of the products, U R = energy decreases.
Total internal energy of the reactants In adiabatic process work is done by the system at
a) For exothermic reaction, U is negative ( UP < UR) the expense of internal energy. (Tf < Ti)
b) For endothermic reaction, U is positive (UP > UR)  When U  0, q  W
Heat Heat absorbed by the system is equal to work done
 Heat is a mode of transfer of energy. It flows from by the system.
one system to another because of difference in If we write W  q
temparature.
If work is done on the system (when U  0 ) heat
 Heat absorbed by the system is positive, i.e., q>0.
flows from system to surroundings.
 Heat given out by the system is negativei.e., q<0.
 In Cyclic process U  0 q  W
Units : Cal. or J.
Work done by the system is equal to heat absorbed.
Mechanical Work (w)  Work Done in Isothermal Reversible
 Work is said to be done when an unbalanced force
Expansion of Ideal Gas :
causes some displacement in its own direction.
Totalworkdone on the gas infinite steps is equalto sumof
 The displacement of an object through a distance
all the infitismalworkdone in each step  pV
' dx ' against a force (F) is called work
With change in infitismal pressure on the system the
 W  F  dx ; W=force x distance = pex . A . l volume decreases by infitismal amount dV, then total
 This is measured in Joules (J), Kilo Joules (KJ), workdone in finite steps from V1 to V2 is given by
erg., Cal., etc. Vf
 It is calculated as the product of external pressure w    pex dV
and change in Volume Vi
W = –(P  V); (  V = Vfinal – Vinitial ); In Reversable Processes the changes can be

 ‘W’ is +ve when work is done on the system. reversed at any moment.
 ‘W’ is -ve when work is done by the system PV-plot when pressure is not constant and changes
First Law of Thermodynamics: in infinite steps (reversible conditions) during
 “It is impossible to construct a perpetual motion compression from initial volume, Vi to final volume,
machine of 1st kind that can work without Vf. Work done on the gas is represented by the
consuming any form of energy” area under the curve.
(or)
P
“The net energy change in a closed system is equal
to heat absorbed plus the work done by
the system”
The mathematical form of first law is
U=q+W
VF V1
 U = Change in Internal energy ; Volume (V)
PV-plot when pressure is not constant and changes
in finite steps during compression from initial P1 A B
volume, Vi to final volume, V f . Work done on
the gas is represented by the area under the curve.
C D
P P2
P
V1 V2
V
WAC  No area covered by straight line AC (if

V  0 )=0.
WBA  Area covered by square
ABFE= P2  V2  V1 
Vf Volume (V) V1 WCB  Area covered by BCEF
= Area of square CDEF + Area of triangle BCD
V
Wrev  2.303nRT log 2 1
V1 = Area of square CDEF +  Area of square ABDC
2
P
Wrev  2.303nRT log 1 1
P2  P1 V2  V1    P2  P1   V2  V1 
2
Work Done in Isothermal Reversible
1
Compression of Ideal Gas   P2  P1   V2  V1 
2
V
W  2.303nRT log 1  In a cyclic process work done is equal to the area
V2
under the cycle is negative work done if the cycle
P is clockwise and positive if the cycle is
W  2.303nRT log 2
P1 anticlockwise. Also work of complete cycle is equal
to area occupied by cycle in P-V diagram..
Free Expansion
Enthalpy (H) :
Expansion of a gas in vacuum [ Pext  0] is called
 The total heat content of a system at constant
free expansion. No work is done during free pressure and temperature is called enthalpy.
expansion of an ideal gas whether the process is It is a state function and an extensive property.
reversible (or) irreversible.  It is calculated as the sum of internal energy and
 For isothermal (T = constant) expansion of an ideal the product of pressure and volume.
gas into vacuum W = 0 since Pext  0 H = U+PV
Work Done in Isothermal Irreversible  It is impossible to determine the absolute value of
Expansion: enthalpy.
W   Pext V   H of a process can be calculated as
Work Done in Adiabatic Process: H= U+W
For finite changes at constant pressure, we can
qP  0, U  W write equation
In P–V diagram (called indicator diagram, the area H  U  PV
under P-V curves represents work done. If  In exothermic reactions
expansion W  -ve and if compression W  +ve)
H P  H R ; H  H P  H R ; H  ve
 In endothermic reactions
SR-MAIN-CHEM-VOL-II
WE-4. From the observations given below, suggest
H P  H R ; H  H P  H R ; H  ve the relation between X,Y and Z
 r H 0    f H 0  products     f H 0  reactants  Exper Heat supplied Work done e
i i
ment
 The difference between H and U is not usually
significant for systems consisting of only solids 200 J Done X
I 100 J Supplied
by the Joules
and / or liquids. The difference, however becomes to the system
system
significant when gases are involved.
Relation Between H&U:
200 J Supplied 200 J Done Y
 For any chemical reaction, at any constant
II to the system by the Joules
temperature H  U  nRT system
T = absolute temperature of the reaction
R = Universal gas constant 400 J lost on 100 J Done Z
III
n = n2 – n1 the system by the Joules
n2 = total number of moles of gaseous products system
n1 = total number of moles of gaseous reactants Sol. In the experiment I, U  q  w  100 J  X
 For any process which does not involve gases
In the experiment II, U  q  w  400 J  Y
H= U
In the experiment III,
 If n = 0 then H = E (or) U
U  q  w  500 J  Z
 If n < 0 then H < E (or) U
The relation between them is : Z < X < Y.
 If n > 0 then H > E (or) U
WE-5. What are the values of w and U , when a
WE-1. A chamber contains 77g of CO 2. The
system absorbs 250J of heat by expanding
chamber was divided into three
from 1 lit to 10 lit against 0.5 atm pressure
compartaments X, Y and Z as shown below.
and at constant temperature.
Suggest the relation between the internal
energies of the gas in the three compartments Sol. W   PV  0.5 10  1  4.5lit  atm
X,Y and Z. Work done, W=–4.5x101J=–454.5J.
X 11g CO2 Y 22g CO2 Z 44g CO2 U  q  W  250  454.5  204.5 J
Heat Capacity and Specific Heat
Sol. Under similar conditions the internal energy of a  Heat capacity (C) of a substance is the amount of
given substance depends on its quantity because it heat required to raise its temperature through one
is an extensive property. The internal energies of degree.
CO2 in the compartments X,Y and Z are in the  Heat capacity is the ratio of heat absorbed by a
ratio 1:2:4. system to the resulting increase in temperature
WE-2. In a process, a system loses 125J of heat q
when 400 J of work was done on the system. C
dT
Calculate the change in internal energy. q = heat absorbed by the system
Sol. q = -125J, W = +400 dT = rise in temperature
U  125  400  275 J  Heat capacity at constant volume (CV) gives the
WE-3. A system absorbs 100J of heat at constant measure of the change of internal energy (U) of a
volume and its temperature raises from 300K system with temperature
to 320K. Calculate the change in internal
 U 
energy. CV    = qv ; U  nCv T
Sol. At constant volume, work done is zero.  T  v dT
Hence change in internal energy, U =q=100J  Heat capacity at constant pressure (CP) gives the
measure of the change of enthalpy (H) of a system
with temperature
 H  qp  The first type is used in combustion reactions.
CP    = , H  nC p T  The second type is used in the other types of
 T  p dT
reactions such as dissolution of solid in water and
Specific Heat Capacity (c) neutralization reaction
The quantity of heat required to raise the First Type (for combustion reaction):
temperature of 1 gram of substance through 1K
 This type of calorimeter is known as bomb
(or 10C)
calorimeter.
Heat capacity q
specific heat capacity c    This bomb is made of steel coated inside with
Mass M
platinum or gold or some other non - oxidisable
q material.
c (or) q  c  m  T
mT  A known weight of combustible substance is ignited
1 1 1  0 1  by passing electric current through the platinum
Units of ‘c’ Jg K (or ) Jg  C 
wire. The substance undergoes combustion and the
Relation Between Cp and Cv for an Ideal heat liberated increases the temperature of water
Gas: in the calorimeter. The rise in temperature is
 C p  Cv  R measured accurately using a sensitive thermometer
(Beckmann thermometer)
CP  The heat capacity of the calorimeter is determined
 
CV using a known weight of benzoic acid prior to the
 Molar heat capacity or molar heat = Specific heat main experiment.
x molecular weight of the substance.  The heat of combustion of benzoic acid is - 3226
R KJ / mole.
 CP  CV  R , c p  cv 
 Calculations: Let ‘ ’ be the rise in temperature of
M
  CP CV  eg water in the calorimeter after complete combustion
of the experimental substance. The weight of the
5R 3R
monoatomic gases 1.66 Inert gases substance is ‘m’ gms. The molecular weight is ‘M’.
2 2
The heat capacity of (the calorimeter + water) is ‘
7R 5R Z’
diatomic gases and 1.4 O2, N2, CO2
2 2
polyatomic linear M
 The heat of combustion U = Z     cals 
m
polyatomic non-linear 4R 3R 1.33 O3.So3  In the above experiment, the volume is constant.
The Standard Conditions for a Chemical Hence heat of combustion is at constant volume
Reaction : (qv) . qv is converted into qp using the equation
 Temperature = 25oC = 298K q p  qv  nRT
 Pressure = 1 atmosphere = 760 mm of Hg
 The physical state of a substance under standard n = change in the number of gas molecules in
conditions (t = 25oC, P = 1 atm) is known as the combustion reaction.
standard physical state. Second Type of Calorimeter :
Measurement of U and H of Chemical  It is used for non combustion reactions such as
Reactions : solutions of Salt (or) organic compound in water
 U is determined at constant volume and H is (or) neutralisation reactions.
determined at constant pressure.  This calorimeter contains two beakers one placed
 The technique of measuring heats of reactions is inside the other one. In between two beakers non-
called calorimetry. heat conducting material is placed.
 The apparatus used is called calorimeter.  Dewar flask also can be used as calorimeter
 Water is the calorimetric liquid.  Water equivalent (W) of the calorimeter together
 Depending on the types of chemical reactions under with the stirrer and the thermometer is measured
study, two types of calorimeters are used.
first .
SR-MAIN-CHEM-VOL-II
 For this water at higher temperature (t20C) of H P  H R : H  H P  H R : H  ve
known mass (m2) and water at lower temperature
eg :1.N2(g) + O2(g)  2NO(g)-180.8 K J
(t10C) and mass (m1) are used. These two are
2. Cgraphite + 2S(g)  CS2 (g)-91.9 KJ
mixed in the calorimeter and the resultant
temperature (t30C) is noted. Heat of Reaction
 The quantity of heat liberated or absorbed at
 m t  t   constant temperature when the reactants undergo
W   2 2 3  m1 
a complete transformation into the products as per
  t3  t1  
the stoichiometric equation is called Heat of
 Heat liberated = reaction.
(W+ volume of reaction mixture )  rise in  The heat of the reaction depends on
temperature i) temperature of the reaction
Thermochemical Equations ii) pressure
 The chemcial equations in which heat change iii) volume
accompanying a reaction is also numerically iv) physical states of reactants and products
specified with proper sign by  H or  U by the v) stoichiometric equation
side of the equation are known as thermochemical vi) Concentrations of solutions (if any).
equations. eg. 1) N2 (g) + 3H2 (g)  2NH3 (g)
o o
 In these equations, the physical states of the \ H is -91.88 KJ at 27 C & -92.80 KJ at 80 C
reactants and the products are also mentioned in 2) C2H4 (g) + 3O2 (g)  2CO2 (g)+2H2O (l)
the brackets by the symbols at 25oC U =-1390.5 KJ & H = -1394.1 KJ
 Allotropes will also be mentioned 3) H2 (g) + ½O2 (g)  H2O(l) H is - 285.6 KJ
The enthalpy of an element in its standard physical H2 (g) + ½O2 (g)  H2O(g) H = -241.7 KJ
state is fixed as zero (actual enthalpy cannot be 4) 2H2 (g)+O2 (g)  2H2O(l),  H   571.3 kJ
determined).
H2 (g) + ½O2 (g)  H2O(l) , H  285.6 kJ
a) gases (H2, O2, N2, F2, Cl2 inert gases)
b) liquids (Br2, Hg ) Enthalpy of Phase Transition:
c) solids (All metals, Iodine) a) Molar enthalpy of Fusion:
 If the element exhibits allotropy, the enthalpy is fixed  The enthalpy change that accompanies melting of
as zero for the most stable and most abundant one mole of a solid substance in standard state is
called standard enthalpy of fusion or molar enthalpy
allotrope of the element.
0
eg.The enthalpy is taken as zero for rhombic of fusion  fus H
sulphur, graphite, white phosphorus etc.
H O  H 2O ;  H 0  6.00 KJmol 1
Exothermic and Endothermic 2 ( s) (l ) fus
Reactions : b) Molar Enthalpy of Vapourisation

Exothermic Reaction: (vapH0):
 Amount of heat required to vapourise one mole
 A chemical reaction, which occurs with the
evolution of heat, is known as Exothermic of a liquid at constant temperature and under
reaction. standard pressure (1bar) is called its standard
 In exothermic reactions enthalpy of vapourisation.
H P  H R , H  H P  H R , H  ve H 2 O  H O ;  vap H 0  40.79 KJmol 1
(l ) 2 (g)
eg :1.N2(g) + 3H2(g)  2NH3(g)+ 92 K J c) Molar enthalpy of Sublimation
2.Cgraphite + O2(g)  CO2(g)+ 393.5 K J (vapH0):
Endothermic Reactions The change in enthalpy when one mole of a solid
 A chemical reaction, which occurs with the substance sublimes at a constant temperature and
absorption of heat from the surroundings, is known under standard pressure
as Endothermic reaction. eg. 1) solid CO2or “dry ice” sublimes at 195K
 In endothermic reactions with  sub H 0  25.2 KJmol 1
 sub H   fus H   vap H  If the standard heat of formation is negative, the
 compound is called exothermic compound.
2) I 2( solid )   I 2( vapour )  If the standard heat of formation is positive, the
3) Naphthalene s  

 Naphthalene g  compound is called endothermic compound.
 Exothermic compounds are thermodynamically
 This type of change is possible when the pressure
more stable than endothermic compounds.
at which heating is carried out is much below the
 The following general equation can be used for the
triple point pressure of the compound subliming.
enthalpy change calculation.
 This process is an endot hermic process
 r H 0    f H 0 (products)    f H 0  reactants 
 H  ve  i i
 Solid - Liquid (fusion or melting) Enthalpy of Combustion

Liquid - Gas (Vapourization)  The quantity of heat evolved when one mole of a
Liquid - Solid (Freezing) substance burns completely in excess of oxygen at
Solid - Gas (Sublimation) a given temperature and constant volume is called
One crystalline form  Another crystalline form the heat of combustion of the substance.
eg :   sulphur    sulphur  The heat of combustion is always negative.
 The heat change involved in the change of phase  The heat of combustion of graphite is 393.5 kJ/
or physical state of one mole of compound at mole. The thermo chemical equation for the
atmospheric pressure is called enthalpy of phase combustion of one mole of graphite is
transition. C (gra) + O2(g)  CO2 (g) ; H = -393.5 kJ
 C s   C g  ; H  1439.2 KJ Standard Enthalpy of Combustion (CH0)
The enthalpy change per mole (or per unit amount)
S monoclinic   S r hom bic ; H  2.5 KJ
of a substance, when it undergoes combustion and
S r hom bic   S monoclinic  ; H  2.5 KJ all the reactants and products being in their standard
states at the specified temerature.
Enthalpy of Formation Enthalpy of Atomization(aH0)
 The amount of heat evolved or absorbed when one  The heat required to dissociate one mole of a simple
mole of compound formed from it’s constituent molecule in the gaseous state into its constituent
elements at constant temeprature is called heat of atoms is called enthalpy of atomization.
formation.  This is an endothermic process.
 The amount of heat energy released or absorbed,
when one mole of a compound is formed in its H 2 g   2 H  g  ; H  43.51 KJ
standard physical state by the combination of O2 g   2O g  ; H  489.5 KJ
elements taken in their standard physical states, is
known as the standard heat of formation of the N 2 g   2 N g  ; H  937.4 KJ
compound.
Enthalpy of Bond Dissociation
 The standard heat of formation of the compound
 The amount of energy required to break 1 mole of
is represented as  H f 0 .
a particular bond in a given compound and to
 The standard heat of formation of the compound
separate the resulting gaseous atoms or ions or
may be positive or negative.
eg 0
radicals is bond dissociation energy.
H f in
Compound kJ/mol H 2  2 H  g  H 0  435.9 KJ mol 1
CO 2 (g) -393.5  The bond dissociation energy in polyatomic
CO (g) -110.5 molecules will be only average value, because in
C (diamond) + 1.89 each step of dissociation different fragments are
C (graphite) 0 involved.
H (aq)
+
0 CH4 g   CH3 g   H g  H 0  427.0KJ
SR-MAIN-CHEM-VOL-II
CH 3 g   CH 2 g   H  g  H 0  418.4 KJ Lattice Enthalpy
The lattice enthalpy of an ionic compound is the
CH 2  g   CH  g   H  g  H 0  460.2 KJ enthalpy change which occurs when one m o l e
of an ionic compound dissociates into its ions in
CH g  C g   H  g  H 0  343.1 KJ gaseous state.
___________________________________ Na Cl   s   Na   g   Cl   g  ;
CH 4  g   C g   4 H  g  H 0  1648.7 KJ
lattice H 0  788kJ mol 1
___________________________________
Since it is impossible to determine lattice en thalpies
C  H bond dissociation energy = directly by experiment. It is determined by Born-
1648.7 Haber Cycle.
 412.2 KJ
4 Enthalpy of Ionization in Aqueous
Heat of Dissociationof thesubstance Solutions
Average bond energy = Number of covalent bondsbroken  The enthalpy change in the formation of an ion at
unit activity (or concentration) from its elements in
 For H2O,
aqueous solution is enthalpy of ionization.
Heat of dissociation of water  The absolute value is not possible. Therefore , the
B.E(avg)of O - H =
2 
enthalpy of H  aq  at 298 K is taken as zero
1
 Heat of formation of H-atom =  eH  H arbitarily
2
 Bond enthalpy of H - H = 2  Heat of formation  1 / 2 H 2 g   aq  H aq   e  ;  H 0  0.0 KJ
of H 2 . the enthalpy of formation of other ions are
Note: Note that symbol used for bond dissociation 
determined relative to this value of zero for H  aq 
enthalpy and mean bond enthalpy is the same.
If we use enthalpy of bond formation,   f H bond
0
,  For OH  it is -228.51 KJ
Enthalpy of Dilution
which is the enthalpy change when one mole of a
 The change of enthalpy when a solution containing
particular type of bond is formed from gaseous atom,
one mole of a solute is diluted from one
then
concentration to another is called enthalpy of
0 0
 r H 0    f H bonds of products    f H bonds of reac tan ts dilution
Enthalpy of Solution (solH0)  When a solution is so dilute that further dilution
 The Enthalpy change when one mole of substance causes no noticeable heat change, the solution is
is dissolved in a specified amount of solvent is called said to be at infinite dilution.
enthalpy of solution.  Ex : 1 mole of KCl dissolved in 20 moles of
 When an ionic compound dissolves in a solvent, water absorbed 15.90 KJ of heat . When 1 mole
the ions leave their ordered positions on the crystal of KCl is dissiolved in 200 moles of water, 18.58KJ
lattice. These are now more free in solution. But of heat is absorbed.
solvation of these ions (hydration in case solvent is The heat of dilution of KCl is, therefore, given as
water) also occurs at the same time. H 2  H1  18.58  15.90  2.68KJ
Heat of solution is the sum of Lattice energy and Enthalpy of Hydration (hydH):
Hydration energy The enthalpy change accompanying the
0
 sol H = lattice H 0 +  hyd H
0 hydration of one mole of an anhydrous salt by
combining with specific number of moles of water.
For most of the ionic compounds,  sol H 0 is CuSO4( s )  5 H 2 O(l )  CuSO4 .5 H 2O( s )  H   78.2 K . J
positive and t he dissociat ion process is
It is always exothermic.
endothermic. Therefore the solubility of most salts
in water increases with rise of temperature.
Hess’s Law of Constant Heat WE-8. One mole of solute AB dissolved in 20 moles
of water absorbed 15.9 kJ of heat. When one
Summation
mole of same solute is dissolved in 200 moles
 The heat energy released or absorbed in a process
of water 18.58 kJ of heat is absorbed. Calculate
is same whether the process occurs in one step or
the enthalpy of dilution.
in several steps.
Sol. During dilution, heat is absorbed from 15.9 kJ to
 According to Hess law the heat energy released or
18.58 kJ.
absorbed in a process depends only on the initial
Enthalpy of dilution = 18.58 kJ-15.9kJ=2.68kJ
state and final state but not on the path, in which
WE-9. The bond enthalpies of D-D and O-O and
the process occurs.
D-O are respectively,
 Hess law is applicable to both physical and chemical
+440,+498 and +491.5 kJ mol-1.
changes.
Calculate  H for the reaction
 Hess law is an application of first law of
1
thermodynamics or law of conservation of energy. D2 + O2  D2O l .
 g 2  g 
q = q1 + q2 + q3
Sol. Heat of reaction, H =(Enthalpy of bonds
Hess Law Can Be Used To Determine
dissociated)-(Enthalpy of bonds formed)
 Heat of formation of intermediate compounds
which are unstable and it cannot be isolated.  498 
H   440     2  491.5 
 Heat of combustion of a substance  2 
 Heat of transition =689-983=-294kJ
 Lattice energy of ionic compounds (Born-Haber Enthalpy of the given reaction is -294kJ.
cycle) WE-10. The heat of formation of crystalline sodium
WE-6. ΔH for the reaction, chloride is -410 kJ m ol -1 . The heat of
sublimation of sodium metal is 108.8 kJmol-1.
F2 + 2HCl  2HF + Cl2 is -352.8 kJ and
The heat of dissociation of chlorine gas into
standard heat of formation of HF is -268.3 kJ atoms is 242.7 kJ mol-1. The ionisation energy
-1
mol . Calculate standard heat of formation of Na and electron affinity of Cl are 493.7kJ
of HCl. and -368.2 kJ respectively. Calculate the
Sol. H  H P  H R  2 H HF  2 H HCl lattice energy of NaCl.
Sol. Based on the Hess law, Born-Haber cycle is
= 352.8KJ  2  268.3  2  H HCl 
constructed.
 
2 H HCl  536.6  352.8  183.8kJ .
Q  S 
1
D  I  E U
2
(or) H HCl  91.9kJ mol 1 Substituting the respective values, we get
WE-7. Calculate enthalpy of ionisation of OH- ion.
1
Given: 410  108.8   242.7  493.7  368.2  U
2
H 2 O l  H +  aq  + OH -aq  ; ΔH 0 = 57.32KJ Lattice energy of sodium chloride,

U=-765.65kJ mol-1.
1
H2 + O2  H O l ; ΔH 0 = -285.83KJ Spontaneous Process
 g 2  g 2    A process is said to be spontaneous if it occurs on
Sol. On adding given equations, its own without the intervention of any external
agency of any kind.
1
H2 + O2  H + aq  +OH -  aq  ; eg. Flow of Heat from high temperature to lower
g 2 g temperature.
H 0  228.51KJ Flow of water from high level to low level.
 0 Flow of gas from high pressure to low pressure.
But for H  aq  ; H  0 .  Sponteneous (or) natural processes are
Therefore heat of ionisation of OH– is -228.51KJ. thermodynamically irreversible.
SR-MAIN-CHEM-VOL-II
Enthalpy Diagram for Endothermic  Entropy is a state function and an extensive
Reactions property
 S =  Sfinal–  Sinitial
=  Sproducts –  S reactants
qrev
 S=
T
For Advanced:
Integrated expression For entropy change
in reversible process:
T2 P
S  2.303nC p log  2.303nR log 1
T1 P2
T2 V2
= S  2.303nCV log T  2.303nR log V
1 1
P1
 for isothermal process S  2.303 nR log10 P
2
Enthalpy Diagram for Exothermic
V2
Reactions S  2.303 nR log10
V1
 for isobaric process
T 
S  2.303 nCP log  2 
 T1 
 For isochoric process
T 
 S  2.303 nCV log  2 
 T1 
Where , qrev is the heat supplied to a system at
temperature T(K) under reversible conditions.
 Entropy of one mole of a substance in pure state at
one bar and 250 C is termed as standard entropy,,
Driving Forces for Spontaneous S0

Processes: For a reaction in standard state, A  B
1.Tendency of a system to achieve a state of S 0  S B0  S A0
minimum energy .  For a spontaneous process in an isolated system
2.Tendency of a system to achieve a state of
 S>0 i.e positive.
maximum randomness (entropy).  When a system is non isolated the entropy changes
The above two tendencies are independent of each of the surroundings also must be considered.
other i.e both may act in same or opposite
Then  STotal =  Ssystem +  S surroundings
directions in a process.
Entropy(S) (for a spontaneous process  Stotal > 0).
 Entropy is a meassure of randomness (or )  When  S = 0, the process is in equilibrium or
disorderness of the particles of a system” reversible.
 It depends on the temperature, pressure of the  In a reversible adiabatic process q = 0,
state. S sys  S surr  Stot  0
 The entropy of a system increases when it absorbs Entropy of Sublimation: It is the change of
heat. entropy when one mole of solid changes into
  S is more +ve when the system absorbs heat at vapour at a particular temperature.
lower temp rather that at higher temp. Hsub
 Ssub = Svapour – Ssolid =
 Units of S and  S are J.K-1, mol-1 T
 At a given temp Sliquid > Ssolid and Sgas> Sliquid. Calculation of Entropy in Chemical
Standard Entropy Reactions
When entropy of one mole of a substance is  For the general reaction
expressed at 298K and 1atm pressure it is called
pA  qB  mC  nD
standard entropy of that substance.
It is denoted by S 0 . S 0 is given by ,
S 0   S 0(products)   S 0 (reactants ) S 0   mSC0  nS D0    pS A0  qS B0 
= [sum of the standard entropies of products] - S 0 are molar entropies
[sum of the standard entropies of reactants]  Eg:- For a reaction H2(g) + 1/2O2(g)  H2O(l)
Entropy Change in Exothermic and
Endothermic Reactions
 1 
 In exothermic reactions heat released by the S 0  S H0 2O (l )   S H0 2 ( g )  SO02 ( g ) 
 2 
reaction increases the dissorderness of the
surroundings and overall entropy change is WE-11. Latent heat of fusion of ice is 6kJ mol-1.
Calculate the entropy change in the fusion of
positive.  S  ve  ice.
 In endothermic reactions heat flows from the Sol. Change in entropy, S  qrev / T
surroundings into the system. The entropy of the
surroundings decreases and the system increases. qrev  Latent heat of fusion
 Total entropy change is positive. The change is =6kJ mol-1 = 6000 J mol-1.
spontaneous. T = Freezing point of water = 273K
Entropy Change During Phase 6000

S   21.98 JK 1mol 1  or 
Transformation :- 273
Entropy of Fusion 6000

S   1.22 JK 1 g 1
 It is the change in entropy when one mole of a 273  18
solid changes to a liquid at its melting point. WE-12. The entropy change for vaporisation of a
liquid is 109.3JK-1mol-1. The molar heat of
qrev vaporisation of that lqiudi is 40.77 kJ mol-1.
S fusion 
T Calculate the boiling point of that liquid.
Sol. Entropy change for vapourisation,
H fusion
S  melting po int( K ) S =109.3JK-1 mol-1
Molal heat of vapourisation of water is 40.77kJmol–1.
Entropy of Vapourisation From the entropy change S  qrev / T .
 It is the change in entropy when one mole of a qrev
liquid changes to vapour at its boiling point. Boiling point, T  (or)
S
H vapourisation
Svapourisation = 40.77  1000
Boiling po int( K ) T  373K
109.3
SR-MAIN-CHEM-VOL-II
WE-13. Based on entropy change predict a  G has units of energy because, both H and
spontaneous reaction among the following. the T S are energy terms.
A :  NH 4  2 CO3 S   2 NH 3 g   CO2 g   H 2 O l  Criteria of Spontaneity:
and Stotal  S sys  S surr
B : NH 3 g   H 2 S g   NH 4 HS s  . If the system is in thermal equilibrium with the
surroundings, then the temperature of the
Sol. Reaction ‘A’ is spontaneous based on the entropy surrounding is same as that of the system. Also,
change. One mole of solid ammonium carbonate increase in enthalpy of the surrounding is equal to
gives three moles of gaseous products, there by decrease in the enthalpy of the system.
increasing the disorderliness and entropy. The Therefore, entropy change of surroundings.
entropy change is positive. H surr H sys
S surr  
Second law of Thermodynamics: T T
It is stated in various forms.
 Heat cannot flow from a colder body to a hotter  H sys 
Stotal  S sys    
body on its own.  T 
 Heat cannot be converted into work completely Rearranging the above equation:
without causing some permanent changes in the
system or in the surroundings. T Stotal  T S sys  H sys
 All spontaneous processes are thermodynamiclly Gsystem  T S
irreversible and entropy of the system inereases. total
 It is impossible to construct a machine working in For spontaneous process, Stotal  0,
cycles and transfers heat from a lower temperature
region to a higher temperature region without T Ssys  H sys  0
intervension of an external agency (such an    H sys  T S sys   0
imaginery machine is called perpetual motion
machine of second kind). Using G  H  T S equation the above
Gibb’s Energy (or) Gibb’s Function (G) equation can be written as
 H  ve may be a condition but not a necessary G  0
and sufficient condition for the spontaneous nature G  H  T S  0
of a reaction. H sys is the enthalpy change of a reaction.
 S   ve is a condition but is not necessary and
sufficient condition for the spontaneous nature of T S sys is the energy which is not available to do
the reaction. useful work. So G is the net energy avail able to
 Gibbs introduced another thermodynamic function do useful work and is thus a measure of the ‘free
which involved both enthalpy (H) and entropy (s) energy’. For this reason, it is also known as the
function. This is known as free energy function G free energy of the reaction.
is referred as Gibbs energy (or) Gibbs function.  G gives a criteria for spontaneity at constant
G  H  TS pressure and temperature.
 Gibbs function is an extensiveproperty and a state If G is negative (< 0), the process is
function.
spontaneous.
The change in Gibbs energy for the system,
If G is positive (> 0), the process is non
Gsys can be written as spontaneous.
Gsys  H sys  T S sys  S sys T If G = 0 the process is at equilibrium.
At constant temperature T  0  G o of a reaction can be calculated from the
 Gsys  H sys  T S sys following equation.
 r G o    f G o (products)    f G o (reactants)
G  H  T S
The above equation is referred to as the Gibbs =[sum of standard energies of formation of
equation. products] -[sum of standard energies of formation
of reactants]
WE-15. The equilibrium constant of a reaction is
Nature of Reaction G H S 73. Calculate standard free energy change.
Sol. Equilibrium constant K is related to G 0 as,
Spontaneous at all – – +
temperature G 0  2.303RT log K . Substituting the values,
K = 73, T=298K and R=8.314 JK-1.mol-1
Non-spontaneous + + –
at all temperatures G 0  2.303  8.314  298  log10
73
= -10,632 J mol-1
Spontaneous at Standard free energy change=-10.632kJ mol-1.
low ‘T’ – – –
1
Non-spontaneous at – – WE-16.The reaction, H 2 g   O2 g   H 2O l  , is
+ 2
high ‘T’
spontaneous. The S 0  163.1J mol 1 K 1 .
Non-spontaneous at
low ‘T’ + + + The absolute entropies of H 2 g  and O2 g  are
spontaneous at 130.6JK-1mol-1 and 205 JK-1mol-1 respectively.

high ‘T’ – + + Calculate the absolute entropy of water.
Sol. Change in standard entropy,
Gibb’s Energy Change and  1 
Equilibrium S 0  S H0 2 Ol    S H0 2  SO02 
 2 
 r G 0 is related to the equilibrium constant of the
reaction as follows:  205 
163.1 Jmol 1 K 1  S H0 2Ol   130.6 
 r G 0 =-RT ln K  2 
G 0  2.303RT log K eq
Absolute entropy of water = 69.9 JK-1 mol-1.

K eq  equilibrium constant WE-17. The standard free energy of Cu aq  is 50
G 0 2
K eq  e G
0
/ RT
or  2.303 RT kJmol-1 and that of Cu aq  is 66 kJ.mol-1.
K eq  10
Calculate the change in free energy for the
Free Energy Change and Electrical
 2 
Work Done in a Cell reaction, Cu aq   Cuaq   e .
G  nFE Sol. Standard free energy change,
F =Faraday = 96,500 coulomb
E =E.M.F of the cell G 0  GCu
0
2  G
0
Cu 
n =no.of electrons involved in balanced =66 kJ mol-1 - 50 kJ mol-1 = 16 kJ mol-1.
electrochemical reaction. 2
WE-18. Zn s   Fe aq  Zn2aq   Fe s  . The value of
G 0  nFE 0
E 0 = standard E.M.F of the cell KC for this reaction is 1023. Calculate the
WE-14. Calculate G 0 for the following reaction, standard free energy change.
Sol. Change in standard free energy,
Zn s   Cu2aq   Zn2aq   Cu s  .G 0f of Cu2aq  is
G 0  2.303RT log10 K c
1 0 2
65 kJ mol and G f of Zn aq  is -147.2 kJ
G 0  2.303  1.987  298  log1023
-1
mol = -31.36 K.cal mol–1
Sol. Standard free energy change, Standard free energy change for the reaction is
0 0
G  G f of products G f of reactants. 0
-31.36 K.cal mol–1
G 0   147.2  0    0  65 
= -212.2 kJ mol–1.
SR-MAIN-CHEM-VOL-II
WE-19. Calculate G 0 for conversion of oxygen  Absolute entropy of a substance
T
CP
3 at a temperature T, ST   T dT
to ozone, O2 g   O3 g  at 298 K, if KP for 0
2
this conversion is 2.4710–29  Accurate determination of entropy  ST  requires
Sol. We know G 0 =-2.303 RT log K P and that the heat capacity at constant pressure  CP 
R=8.314JK–1mol–1. Therefore must be determined accurately.
G 0  2.303  8.314 JK 1 mol 1   But  CP  cannot be measured at absolute zero
 298K   log 2.47 10 29   273 C  (or) around absolute zero.
0
= 163000 J mol-1 or 163 kJ mol-1

WE-20. A swimmer coming out from a pool is Conceptual
covered with a film of water weighing about Introduction and Types Of Systems
18g. How much heat must be supplied to 1. Thermodynamic laws speak about
evaporate this water at 298 K ? Calculate the 1) rates of chemical changes
internal energy of vaporisation at 1000C. 2) feasibility and energy transformations of a
0
H vap for water at 373K = 40.66 kJ mol-1 process
3) Both the rate and energy changes of a process
Sol. We can represent the process of evaporation as 4) Energy changes in chemical reactions only
vaporisation 2. The object under thermodynamical study is
H 2O l  H 2O g  ; n  1  0  1
 called
vap E  vap H  pV  vapH  nRT 1) System 2) Universe
3) Surrounding 4) Boundary
(assuming steam behaving as an ideal gas).
3. Which of the following are true about a
 vap E  40.66kJmol 1  1 “system”
8.314 10 KJk 1mol 1   373K   37.56kJmol 1
3 1) Will do not have definite amount of substance
2) Energy and matter may not be exchanged with
WE-21. Find out the value of equilibrium constant
surroundings
for the following reaction at 298 K 3) (Universe+surroundings)
2 NH 3 g   CO2 g  NH 2CONH 2 aq   H 2 O l  4) (Universe-surroundings)
4. Hot water in a thermos flask is an example
Standard Gibbs energy change, G 0 at the
for
given temperature is -13.6kJ mol-1. 1) Isolated system 2) Open system
G 0 3) Closed system 4) Adiabatic system
Sol. We know, log K   2.38 5. In open system, system and surroundings
2.303RT
exchange
K = antilog 2.38 = 2.4 x 102.
1) Energy only 2) Matter only
Third law of Thermodynamics :- 3) Energy and matter
 This is also known as NERNST HEAT 4) Neither energy nor matter
THEOREM. 6. In a closed system
 It was proposed by Max plank W.Richard & 1) Energy is not exchanged
walter in different forms. 2) Matter is exchanged
 “The entropy of a pure and perfectly crystalline 3) Energy is only exchanged
substance is zero at the absolute zero 4) Energy and matter are exchanged
temperature.(-2730C) 7. “Closed system” is
SlimT 0  0 1) Perfectly sealed 2) Perfectly insulated
 Third law imposes a limitation on entropy value 3) Both 1 & 2
but not leads to any new thermodynamic concept. 4) Neither insulated nor sealed
State Functions and Path Functions: 3) The path if irreversible
8. Which one of the following statement is false 4) Initial, final states and also on the path
1) Work is a state function 17. Correct expression among the following:
2) Temperature is a state function 1) E = H + PV 2) H = E + PV
3) Change in the state is completely defined when 3) H = E - PV 4) P = E + HV
the initial and final states are specified 18. Enthalpy change during a reaction does not
4) Work appears at the boundary of the system depend upon
9. Which of the following is a path function 1) Conditions of a reaction
1) Internal energy 2) Enthalpy 2) Initial and final concentration
3) Work 4) Entropy 3) Physical states of reactants and products
10. Which of the following statement is correct ? 4) Number of steps in the reaction
1) Only internal energy is a state function but not 19. If a gas, at constant temperature and
work pressure expands, then its
2) Only work is a state function but not internal 1) Entropy increases and then decrease
energy 2) Internal energy increases
3) Both internal energy and work are state 3) Internal energy remains the same
functions 4) Internal energy decreases
4) Neither internal energy nor work is a state 20. Heat change in a chemical reaction, at
function constant temperature and pressure is called
Thermo Dynamical Processes 1) Entropy 2) Enthalpy
11. A process in which no heat change takes place 3) Internal energy 4) Free energy
is called 21. The standard enthalpies of n-pentane,
1) An isothermal process 2) An adiabatic process isopentane and neopentane are -35.0, -37.0
3) An isobaric process 4) An isochoric process and -40.0 K.cal/mole respectively. The most
12. A gaseous system changes from state stable isomer of pentane in terms of energy is
A(P1,V1,T1) to B (P2,V2,T2), B to C (P3,V3T3) 1) n-pentane 2) Iso pentane
and finally from C to A. The whole process 3) neo pentane
may be called 4) n-pentane and iso pentane both
1) Cyclic process 2) Reversible process 22.The internal energy change when a system goes
3) Isobaric process 4)Spontaneous process from state A to B is 40Kj/Mol. If the system
13. For a cyclic process, the condition is goes from A and B by the a reversible path
and returns to state A by an irrerversible path
1) U  0 2) H  0
what would be the change in internal energy?
3) U  0 and H  0 1) Zero 2) 40Kj 3) >40 Kj 4) <40Kj
4) both U  0 and H  0 23.Assume each reaction is carried out in an open
14. An adiabatic expansion of an Ideal gas always container. For which reaction will H  E ?
has
1) Constant in Temperature 2) q=0 1) 2CO  g   O2  g   2CO2  g 
3) w=0 4) H  0 2) H 2  g   Br2 ( g )  2 HBr  g 
Internal Energy and Enthalpy
15. Internal energy does not include 3) C  s   2 H 2O  g   2 H 2 ( g )  CO2  g 
1) Vibrational energy 2) Rotational energy 4) PCl5  g   PCl3 ( g )  Cl2 ( g )
3) Energy arising by gravitational pull
4) Nuclear energy 24. The heat change associated with reactions at
16. The change in internal energy of a system constant volume is due to the difference in
depends on which property of the reactants and the
1) Initial and final states of the system products
2) The path if reversible 1) Internal energy 2) Enthalpy
3) Heat capacity 4) Free energy
SR-MAIN-CHEM-VOL-II
25. Regarding a thermochemical equation a wrong 34. According to 1 st law of Thermodynamics
statement is 1) The energy of system is constant
1) It tells about the physical states of reactants and 2) The energy of universe is constant
products 3) The energy of surroundings is constant
2) It tells whether the reaction is exothermic or 4) The energy of system and surroundings are not
endothermic constant
3) It tells about the allotropic form (if any) of the 35. In a closed insulated container, a liquid is stirred
reactant with a paddle to increase the temperature.
4) It tells whether the reaction is possible or not Which of the the following is true ?
26. The enthalpies of the elements in their 1) U  W  0, q  0 2) U  W  0, q  0
standard states are arbitrarily assumed to be
3) U  0, W  q  0 4) W  0, U  q  0
1) Zero at 298 K and 1 atm
2) Unity at 298 K and 1 atm Intensive and Extensive Properties
3) Zero at all temperatures 36. Which is an extensive property of the system ?
4) Zero at 273 K and 1 atm 1) No.of moles 2) Viscosity
27. The standard enthalpy is zero for the substance 3) Temperature 4) Refractive index
1) C (graphite) 2) C (diamond) 37. In which of the following sets, all properties
3) CO2 4) O3 belong to same category (all extensive or all
28. Heat of a reaction (Q) at constant pressure is intensive) ?
equal to 1) Mass, Volume, Specific heat
1) E P  E R 2) E R  E P 2) Temperature, Concentration, Volume
3) Heat capacity, Concentration, Entropy
3) H P  H R 4) H R  H P
4) Enthalpy, Entropy, Volume
29. Energy hidden in a definite quantity of 38. Which one of the following pairs represents
substance the intensive properties? EAM-2011
1) Enthalpy 2) Internal energy 1) Specific heat and Temperature
3) Free energy 4) Entropy 2) Entropy and density
First Law of Thermo Dynamics : 3) Enthalpy and molefraction
30. Mathematical representation of 1 st law 4) Heat and temperature
1) Q =  E +W 2)  H =  E+P  V Heat Capacity and Specific Heat:
39. Heat capacity is
3) W = Q x  E 4) E  H  VP
dQ
31. I st law can explain 1) 2) dQ  dT
1) Spontaneity of process dT
2) Perpetual machine of 2 nd kind 1
3) Perpetual machine of 3 rd kind 3)  Q . 4) dQ  dT
dT
4) The total energy of an isolated system remains 40. The heat required to raise the temperature of
constant
a body by 1o C is called
32. According to 1st law of Thermodynamics
1) Energy can be created but not destroyed 1) specific heat 2) Heat capacity
2) Energy cannot be created but can be destroyed 3) water equivalent 4) Heat energy
3) Energy can be created and destroyed Measurement of H and E:
4) Energy can not be created nor destroyed 41. The difference between heats of reaction at
33. The limitation of 1st law of thermodynamics is constant pressure and at constant volume for
1) Energy can neither be created nor destroyed the reaction
st
2)Impossible to construct the 1 kind of perpetual 2C6 H 6l   15O2  g   12CO2  g   6H 2 Ol 
motion machine
3) Law of conservation of energy at 250C in KJ is
4) Spontaneous nature of a process 1) -7.43 2) +3.72 3) -3.72 4) +7.43
42. For which of the following reactions 50. In the hydrogenation of ethylene,  n is
H  E  2RT equal to
1) N 2 g   3H 2 g   2 NH 3 g  1) 1 2) -2 3) -1 4) 2
51. The difference in H and E for the
2) N 2 g   O 2 g   2 NOg 
combustion of ethane at 270C would be
3) NH 4 HSs   NH 3 g   H 2Sg  1) H >E 2) H <E
4) PCl g   PCl g   Cl g  3) H =E 4) No relation
5 3 2
43. For the reaction

Exothermic and Endothermic Reactions:
52. In exothermic reaction
C H 4  g  + 3O  g   2CO + 2H O
2 2 2(g) 2 l the 1) HR = HP 2) HR > HP
difference between enthalpy change and 3) HR < HP 4) H = 0
internal energy change is 53.  H is negative for the reaction
1) -RT 2) +RT 3) -2RT 4) +2RT 1) Neutralization of HCl with NaOH
44. A mixture of 2 mole CO and 1 mole O2 in a 2) Formation of NO
closed vessel is ignited to convert CO into CO2. 3) Boiling of water
Then 4) Dissociation of NaCl
1) H   E 2) H   E 54. The incorrect IUPAC convention
3) H   E 1) Heat gained by system +ve sign
4) The relationship depends upon the capacity of 2) Work done by system - ve sign
the vessel 3) Work done on the system +ve sign
45. The difference in H and E for the reaction 4) Heat gained by system -ve sign
55. Which of the following is an endothermic
BaCl2  aq   K 2SO 4  aq  reaction?
 BaSO 4  s   2KCl  aq  is 1) C + O2  CO2 2) N2 + O2  NO
3) 3H2 + N2  2NH3
1) RT 2) 2RT 4) PCl3 + Cl2  PCl5
3) Zero 4) Can’t predicted 56. When water is added to quick lime, the
46. For an ideal gas, the relation between the reaction is
enthalpy change and internal energy change 1) Explosive 2) Endothermic
at constant temperature is given by. 3) Exothermic 4) Photochemical
1) H  E  PV 2) H  E  n RT 57. Of the following an endothermic reaction is
3) H  E  P  V 4) Both (2)&(3) 1) 2H 2  O2  2H 2O
47. For the reaction Cs   O 2 g   CO2 g ; n 2) C graphite   H 2O g   CO g   H 2 g 
value is
3) 2 NaOH  H 2SO4  Na 2SO 4  2H 2O
1) Zero 2) +1 3) -1 4)Unpredictable
48. H   E for the reaction 4) C 2 H 5OH  3O 2  2CO 2  3H 2 O
1) CH 4 g   2 O 2 g   CO 2 g   2 H 2 O g  58. Which of the following reactions is not
exothermic?
2) N 2 g   3H 2 g   2 NH 3 g 
1) CaCO 3  CaO  CO 2
3) C 2 H 4 g   3O 2 g   2CO 2 g   2H 2 Og 
2) Fe  S  FeS
4) CaCO 3  s   CaO  s   CO 2  g 
3) NaOH  HCl  NaCl  H 2 O
49. For a reaction involving only liquid reactants
& liquid products the relationship between H 4) CH 4  2O2  CO 2  2H 2O
and E is
1) H >E 2) H <E
3) H =E 4) E  H
SR-MAIN-CHEM-VOL-II
59. Of the following a correct statement is 66. Among the following gases, heat of combustion
is highest for
1) H is positive for exothermic reaction
1) Methane 2) Ethane
2) H is negative for endothermic reaction
3) Ethylene 4) Acetylene
3) The heat of neutralization of strong acid with
strong base is always the same 67. The standard enthalpy of formation  H 0f  at
4) The enthalpy of fusion is negative
60. change in enthalpy and change in internal 298 K for methane, CH 4  g  is 74.8KJmol  .
energy are equal at room temperature for The additional information required to
1) Combustion of glucose determine the average energy for C - H bond
2) Combustion of ethylene formation would be
3) Combustion of methane 1) The dissociation energy of H 2 and enthalpy of
4) Combustion of ethyl alcohol sublimation of carbon
Enthalpy of Reaction 2) The latent heat of vaporisation of methane
(Enthalpy of Phase Transitions): 3) The first four ionisation energies of carbon and
electron gain enthalpy of hydrogen
61. For the transition C diamond   C graphite ; 4) The dissociation energy of hydrogen molecule
H  1.5KJ . It follows that 68. Heat of combustion of H 2 (g)= - 241.8 KJ /mol
1) Graphite is stable than diamond
2) Diamond is stable than graphite C(s) =-393.5 Kj/mol; C2 H5OH(l ) = - 1234.7KJ/mol.
3) Graphite is endothermic substance Hence, heat of formation of C2 H 5OH (l) is
4) Diamond is exothermic substance
62. The enthalpy change for the process 1) 2747.1KJmol  2) 277.7KJmol 

C graphite  C g  ; H   x KJ represents 3) 277.7KJmol 4) 2747.1KJmol 
69. The enthalpy of NH3(g) is -46.2 KJ mol-1.The
enthalpy of
1) Fusion 2) Sublimation heat of the reaction, 2 NH 3 g   N 2 g   3H 2 g  is
3) Combustion 4) Vapourisation 1) -46.2 Kj 2) +46.2 KJ
Enthalpy of Formation: 3) -92.4 KJ 4) +92.4 KJ
63. H 2  g   I 2  g   2 HI  g  ,  H  51.9 KJ . Hess Law
70. Hess’s law of constant heat summation is
According to this, heat of formation of HI is
based on
1) 51.9 KJ 2) -51.9 KJ
1) E = mc2 2) E=h
3) -25. 95 KJ 4) 25.95 KJ
3) First law of thermodynamics
64. The equation in accordance with the definition
4) Conservation of mass
of standard heat of formation of CO2 g  is 71. According to Hess’s law, the thermal effects
1) C graphite   O 2 g   CO 2 g  of a reaction depends on
1) Initial and final conditions of the reacting
2) CH 4 g   O2 g   CO2 g   2 H 2Ol  substances
2) Initial conditions of reactants
1 3) Final conditions of the reacting substances
3) CO g   O2 g   CO2  g 
2 4) Not on initial and final conditions of the reacting
1 substance
4) C6 H6(l) +7 O2(g)  6CO2(g) +3H 2O(l )
2 Enthalpy of Combustion
65. Which of the following values of heat of 72. The standard heat of combustion of graphite
formation indicates that the product is least carbon is -393.5 KJ mol-1. The standard
stable? enthalpy of CO2 is
1) -393.5 KJ 2) -972.7 KJ 1) +393.5 KJ mol–1 2) -393. 5 KJ mol–1
–1
3) +89.9 KJ 4) +272.2 KJ 3) +196.75 KJ mol 4) -196.75 KJ mol–1
73. The heat of combustion is 81. The Entropy of the universe
1) Always -ve 2) Always +ve 1) Tends towards a maximum
3) Zero 4) May be +ve or -ve 2) Tends towards a minimum
74. Calculate the calorific value of octane. a 3) Tends to zero
component of gasoline with the help of 4) Temains constant
following reaction. 2C8H18(l) + 25O2(g)  82. In which of the following cases, the reaction is
16CO2(g) + 18H2O ,H= –10920KJ spontaneous at all temperatures
1) 478.9 kJ 2) 47.89 kJ 1)  H>0,  S>0 2)  H<0, S  0
3) 95.78 kJ 4) 957.8 kJ
75. The following is not a combustion reaction 3)  H < 0,  S <0 4)  H > 0, S  0
83. When potassium chloride is dissolved in water
1 1) Entropy increases 2) Entropy decreases
1) CO  O2  CO2 2) C  O2  CO2
2 3) Entropy increases and then decreases
1 4) Free energy increases
3) C  O2  CO 84. For the process CO2(s)  CO2(g)
2
4) CH 4  2O2  CO2  2H 2O 1) Both  H and  S are +ve
76. With increase in number of carbon atoms in 2)  H is - ve,  S is +ve
alkanes, heat of combustion 3)  H is +ve,  S is - ve
1) Increases 2) Decreases 4) Both  H and  S are - ve
3) Does not change 85. A reaction will never be spontaneous at any
4) Changes can’t be predicted temperature and pressure provided.
77. The number of water molecules formed in the
1)  S positive and  H positive
combustion of one mole of alkane containing
‘m’ carbon atoms is 2)  S positive and  H negative
1) m 2) m/2 3) m +1 4) m -1 3)  S negative and  H positive
Enthalpy of - Atomisation, Bond 4)  S negative and  H negative
Dissociation, Solution, 86. Which of the following reaction is associated
with an increase in entropy?
Dilution and Hydration :
1) N 2(g) + 3H 2(g)  2NH 3(g)
78. NH 4Cl  s   H 2 O  NH 4Cl  aq 
 H  16 .3 K J 2) 2H 2(g) + O 2(g)  2H 2 O l 
H in the above reaction represents 3) H 2(g) + I 2(g)  2HI (g)
1) Heat of solution 2) Integral heat of solution
3) Heat of dilution 4) Heat of ionization 4) C (graphite) + H 2 O(g)  CO (g) + H 2(g)
79. When ammonium chloride is dissolved in water 87. For the reaction, 2HgO(s)  2Hg(/) + O2(g)
the solution becomes cold because 1)  H>0&  S<0 2)  H>0&  S>0
1) Heat of solution of ammonium chloride is positive 3)  H<0&  S<0 4)  H<0&  S>0
2) Heat of solution of ammonium chloride is
88. The value of  S is negative for the process
negative
1) Burning of rocket Fuel 2) Dissolution of sugar
3) Heat of dilution of ammonium chloride is positive
3) Sublimation of Iodine 4) Freezing of water
4)Heat of formation of ammonium chloride is
89. The quantity which is not zero for an element
positive
in its standard state at 298 K is
Entropy-Spontaneous Process 1) S0 2) H0
Entropy 3) G0 4)Both H0 and S0
80. Entropy is a measure of
1) Disorder 2) Internal energy
3) Efficiency 4) Useful work done by the system
SR-MAIN-CHEM-VOL-II
90 In which of the following process entropy spontaneous, by
increases? 1) Decreasing temperature
a) Rusting of iron 2) Increasing temperature
b) Vapourisatin of Camphor 3) Maintaining temperature constant
c) Crystallisation of sugar from syrup 4) Does not maintain temperature
d) Atomisation of dihydrogen 100. Thermodynamic parameter which is a state
1) a and b 2) b and c function and is also used to measure disorder
3) b and d 4) Only d of the system is
91. For the spontaneous process 2F(g)  F2 (g), 1) Entropy 2) Fugacity
the sign of  H and  S respectively are 3) Viscosity 4) Periodicity
1) +ve, -ve 2) +ve, +ve 101. The most random state of H2O system is
3) -ve, -ve 4) -ve, +ve 1) Ice 2) H2O (l) at 800 C; 1 atm
92. Entropy of a perfect crystalline solid at 3) Steam 4) H2O(l) at 250C; 1 atm
absolute zero is II Law Of Thermo Dynamics
1) Zero 2) Less than zero 102. Which of the following Process is non-
3) Greater than zero spontaneous
4) Depends upon nature of the solid 1) Heat flow from hot end to cold end
93. Which of the following has highest Entropy 2) Water flow from higher level to lower level
1) Mercury 2) Hydrogen 3) Gas flow from lower pressure region to higher
3) Water 4) Graphite pressure region
94. Entropy change for an adiabatic reversible 4) Gas flow from higher pressure region to lower
process is pressure region
1) zero 2) +ve 103. Machine which transfers heat from lower
3) - ve 4) negative or zero temperature region to higher temperature
95. Which of the following statements is incorrect regions on its own without the interference of
1) The entropy of an isolated system increases in any external agency is
an irreversible process 1) Perpetual motion machine of 1 st kind
2) The entropy of an isolated system remains 2) Perpetual motion machine of 2nd kind
unchanged in a reversible process 3) Perpetual motion machine of 3rd kind
3)  Ssystem as well as  SSurrounding are negative 4) Perpetual motion machine of 4th kind
quantities 104. All natural processes are
4) Entropy of universe can never decrease 1) Spontaneous 2) non- spontaneous
96. For reversible process at equilibrium,the 3) Exothermic 4) Endothermic
change in entropy may be expressed as 105. The statement “Heat cannot flow from colder
body to hotter body” is known as
1)  S = Tqrev 2) s  qrev 1) 1 st law of Thermodynamics
T 2) Zeroth law
  3) 2nd law of Thermodynamics
3) s  4)  S =  H 4) Law of conservation of energy
T
97. The units of entropy are 106. Which statement is true about 2nd law of
1) J mol-1 2) J K-1mol-1 Thermodynamics
3) J g-1
4) J K mol-1 1) Heat can be converted into work without
98. For a spontaneous process, which of the changes in system or surroundings
following is true? 2) It is possible to construct a perpetual motion
machine of second kind
1)  Ssys positive 2)  Ssurr positive
3)All spontaneous process are thermo dynamically
3)  Stotal positive 4)  Stotal negative irreversible
99. For a non-spontaneous reaction, at 30°C, 4)All spontaneous process are thermo dynamically
 H>0 &  S > 0. The reaction becomes reversible
107. ‘Energy of Universe is conserved but entropy 115. For a spontaneous process.
of Universe always increases during any 1)  Gsystem = +ve only 2)  Gsystem = zero
natural process’. The statement is based on
3)  Stotal = - ve 4)  Stotal = +ve
1) Faradays laws
116. Which of the following is incorrect
2) 3rd law of thermodynamics
3) 1st and 2nd law of thermodynamics 1) When  G < 0 process is spontaneous
4) Zeroth law of thermodynamics 2) When  G > 0 process is non spontaneous
108. All the naturally occurring processes proceed 3) when  G = 0 process is at equilibrium
spontaneously in a direction which leads to 4) When  G > 0 process is spontaneous
1) Increase in enthalpy of system 117. At the vicinity of absolute zero
2) Decreases in entropy of system l) Cp+Cv = 0 2) Cp< Cv
3) Increase in entropy of system 3) Cp-Cv = 0 4) Cp > Cv
4) Increse in entropy of Universe 118. Correct relation among the following
Gibbs Free Energy (or) Gibbs
1)  Gsystem . = –  Stotal
Function:
109. Which fo the following relations is not correct. 2)  Gsystem = – T  Stotal
1) G=H-TS 3)  G =  H + T  S
2)  Gsystem =  H system –T  Ssystem
G  H
3) T  Ssystem =  Hsystem–  Gsystem 4)  S =
T
4)  Hsystem =  G system – T  Ssystem 119. For a spontaneous process, the change in
110. Gibbs energy change  G is related to Gibbs function is equal to the
equilibrium constant ‘K.’ as 1) Heat content of the system
1)  G0 = - RT lnk 2)  G0 = RT lnk 2) Entropy change of the system
3) Work of expansion 4) Useful work
RT G0
3) ln k =  4) ln k = 120. For the precipitation reaction of Ag+ ions with
G0 RT NaCl, which is true?
111.  Ssurroundings = + 959.1 JK-1mol-1 1)  H = 0 2)  G=0
 Ssystem= –163.1 Jk–1 mol–1 Then the process is 3)  G = -Vee 4)  G=  H
1) Spontaneous 121. For an endothermic reaction,  S is positive.
2) Non spontaneous Then the reaction is
3) At equilibrium
4) Cannot be predicted from the information 1) Feasible when T  S>  H
112. The mixing of gases is generally accompanied by 2) Feasible when  H > T  S
1) Decrease in entropy 3) Feasible at all temperatures
2) Decrease in free energy 4) Not feasible at all
3) Change in heat content 122. For the process
4) Increase in free energy H2O  l  (1bar,373K)  H2O  g 1bar,373K  ,
113. The value of  G for the process the correct set of thermodynamic parameters
H2O(s)  H2O(l) at 1 atm and 260 K is is:
1) < 0 2) =0 3) > 0 4) Unpredictable
1) G  0, S   ve
114. For a reactoin to occur spontaneously
2) G  0, S  ve
1) (  H-T  S) must be negative
2) (  H+T  S) must be negative 3) G  ve, S  0
3)  H must be negative 4) G  ve, S   ve
4)  S must be negative

SR-MAIN-CHEM-VOL-II
Conceptual - Key R
01) 2 02) 1 03) 4 04) 1 05) 3 06) 3 1) R 2) 2 R 3) 4) 3 R
2
07) 1 08) 1 9) 3 10) 1 11) 2 12) 1
5. A certain electric motor produced 15 KJ of
13) 4 14) 2 15) 3 16) 1 17) 2 energy each second as numerical work and lost
18) 4
19) 4 20) 2 21) 3 22) 1 23) 2 2KJ as heat to the surroundings . What is the
24) 1
25) 4 26) 1 27) 1 28) 3 29) 2 change in the internal energy of the motor and
30) 1
31) 4 32) 4 33) 4 34) 2 35) 1 its power supply each second.
36) 1
37) 4 38) 1 39) 1 40) 2 41) 1 1) -17 KJ
42) 3 2) -17 J 3) 27 KJ 4) 23 KJ
6. Two liters of N2 at O0C and 5atm are expanded
43) 3 44) 3 45) 3 46) 4 47) 1 48) 4
exothermally against a constant external
49) 3 50) 3 51) 2 52) 2 53) 1 54) 4
pressure of 1atm untill the pressure of gas
55) 2 56) 3 57) 2 58) 1 59) 3 60) 1
reaches 1atm. Assuring gas to be ideal.
61) 1 62) 2 63) 4 64) 1 65) 4 66) 2
Calculate work of expansion
67) 1 68) 3 69) 4 70) 3 71) 1 72) 2
1) 400 J 2) -810 J 3) -810 KJ 4) 600 KJ
73) 1 74) 2 75) 3 76) 1 77) 3 78) 1
7. When work done by a system was 10J , the
79) 1 80) 1 81) 1 82) 2 83) 1 increase in the internal energy of the system
84) 1
85) 3 86) 4 87) 2 88) 4 89) 1 was 30J. The heat ‘q’ supplied to the system
90) 3
91) 3 92) 1 93) 2 94) 1 95) 3 was:
96) 2
97) 2 98) 3 99) 2 100) 1 101) 3 1) -40J
102) 3 2) +20J 3) 40J 4) -20J
8. The work done when 6.5g of zinc reacts with
103) 2 104) 1 105) 3 106) 3 107) 3 108) 4
dil HCl is an open beaker at 298 K is
109) 4 110)1 111) 1 112) 2 113) 3 114) 1
1) -495.52 J 2) 247.76 J
115) 4 116) 4 117) 3 118) 2 119) 4 120) 3
3) -247.76 J 4) -123.88 J
121) 1 122) 1 9. The work done in heating one mole of an ideal
Level - I (C.W) gas at constant pressure from 150 C to 250 C is
1) 1.987 cal 2) 198.7 cal
Thermo Dynamical Processes: 3) 9.935 cal 4) 19.87 cal
1. Which is an irreversible process ? 10. A gas expands from 1.5 to 6.5 L against a
A) Mixing of two gases by diffusion constant pressure of 0.5 atm and during this
B) Evaporation of water at 373K and 1atm process the gas also absorbs 100 J of heat.
pressure The change in the internal energy of the gas is
C) Dissolution of NaCl in water 1) 153.3J 2) 353.3J 3) –153.3J 4) -353.3J
D) Burning of Coal 11. 10 g of argon gas is compressed isothermally
The correct answer and reversibly at a temperature of 27º C from
1) A,B 2) B,C 3) A,B,C 4) A,C,D 10 L to 5 L. Calculate q and H for this
2. U  0 for process. Atomic wt. of Ar = 40.
1) Cyclic process, Adiabatic process 1) + 103.99 cal, 0 2) + 39.99 cal, 3 J
2) Isothermal, Adiabatic process 3) - 39.99 cal, 3 J 4) -103.99 cal, 0
3) Cyclic process, Isothermal process First Law of Thermo dynamics :
4) Isochoric process, Isothermal process 12. A system absorbs 20 KJ of heat and also does
Internal Energy, Enthalpy and Work 10KJ of work. The net internal energy of the
done : system
3. The work done when a gas is compressed by 1) Increases by 10 KJ 2) Decreases by 10 KJ
an average pressure of 0.50 atm so as to 3) Increases by 30 KJ 4) Decreases by 30 KJ
decrease its volume from 400 cm3 to 200cm3 13. If a gas absorbs 200 J of heat and expands by
1) 10.13 J 2) 20.13J 3) 30.13 J 4) 40.13 J 500 cm3 against a constant pressure of 2 x 105
4. Temperature of 1 mol of a gas is increased Nm–2, then change in internal energy is
by 1º at constant pressure. Work done is : 1) -300 J 2) -100 J 3) +100J 4)+300 J
14. In an insulated container 1 mole of a liquid. 22. 1gr of graphite is burnt in a bomb calormeter
molar volume 100 ml at 1 bar. Liquid is steeply in excess of oxygen at 298 K and 1atm
taken to 100 bar, when volume of liquid pressure according to the equation
decreases by 1 ml. Find H for the process. C graphite   O2( g )  CO2( g ) during the reaction
1) 7900 bar ml 2) 8900 bar ml
temperature rises from 298K to 299K If the
3) 9900 bar ml 4) 10900 bar ml
heat capacity of the bomb calormeter is 20.7
Heat Capacity and Specific Heat KJ/Mole what is the enthalphy change for the
15. The molar heat capacity of water at constant above reaction at 298K and 1atm.
pressure, C, is 75JK-1 mol-1. When 1.0KJ of 1) -20.7 KJ / K 2) -2.48 x 102 KJ/ mol
heat is supplied to 100g of water which is free 3) -20.7J/K 4) -2.48 J / K
to expand, the increase in temperature of 23. The combustion of one mole of benzene takes
water is : (EAMCET- 2012) place at 298K and 1 atm after combustion
1) 0.24K 2) 2.4K 3) 1.3K 4) 0.13 K
16. For a gas having molar mass M, specific heat CO2( g ) , and H 2O( l ) are produced and 3267.0
at constant pressure can be given as : KJ of heat is liberated . Calculate the standard
R enthalpy of formation Hf of benzene .

1) M    1 2) Standard enthalpy of formation of CO2(g) and
RM H2O(l) are – 393.5Kj and -285.83 Kj/Mole
M  RM 1) -48.51 KJ/Mole 2) 48.51 KJ/Mole
3) R    1 4) 3) -24.5KJ 4) 24.5KJ
 1
24. For the reaction at 1240K and 1 atm.
17. Molar heat capacity of water is equilibrium
decomposition of CaCO3 has H value 176
with the ice at constant pressure is :
1) Zero 2) Infinity (  ) KJ/mol. The U equals :
3) 40.45 KJK-1 mol-1 4) 5.48 JK-1 mol-1 1) 165.6 K J 2) 160.0 K J
3) 186.4 K J 4) 180.0 K J
18. C values for monoatomic and diatomic gases
respectively are
2CO  g   O2  g   2CO2  g  ;
1 3 3 5
1) R, R 2) R, R H  560 KJmol  In 1 litre vessel at 500K,
2 2 2 2
the initial pressure is 70 atm and after the
5 7 3 3
3) R, R 4) R, R reaction , it becomes 40 atm at constant volume
2 2 2 2
of one litre. All the above gases show
Measurement of H and E significant deviation from ideal behaviour
19. The difference in H and E for the (1 L atm = 0.1 Kj).The change in internal
combustion of methane at 270C would be energy will be
1) -1800 Cal 2) -162 Cal 3) -1200 Cal 4) 0 1) 10KJmol  2) 557KJmol 
3) 106KJmol  4) 106KJmol 
C2 H 4  g   3O2  g   2CO2  g   2 H 2O  l  ;
Exothermic and Endothermic
E  1415 KJ. The H at 270C is 26. Which of the following is an endothermic
1) -1410 KJ 2) -1420 KJ reaction
3) +1420 KJ 4) +1410 KJ
1) N 2 (g)  3H 2 (g)  92 kJ  2NH 3 (g)
21. One mole of ideal gas expands freely at 310
K from five litre volume to 10 litre volume. 2) N 2 (g)  O2 (g)  180.8 kJ  2NO(g)
Then  E and  H of the process are 3) H2 (g)  Cl2 (g)  2HCl(g)  184.6 kJ
respectively
1) 0 and 5 cal 2) 0 and 5  300 cal 4) C(graphite)  2H2 (g)  CH4 (g)  74.8kJ
3) 0 and 0 4) 5 and 0 cal
SR-MAIN-CHEM-VOL-II
27. When 10 grams of methane is completely burnt 1) -196 KJ/mole 2) -494 KJ/mole
in oxygen, the heat evolved is 560 kJ. What 3) 146 KJ/mole 4) -98 KJ/mole
is the heat of combustion (in kJ.mol1 ) of 34. Heats of formation of SiO2 and MgO are -
methane? 48.24 and -34.7 KJ respectively. The heat of
1) -1120 2) -968 3) -896 4) -560 the reaction: 2Mg  SiO2  2MgO  Si is
Enthalpy of Reaction 1) 21.64 KJ 2) -21.16 KJ
(Enthalpy of Phase Transitions): 3) -13.62 KJ 4) 13.62 KJ
28. Given that C graphite   C g  ; H  716.7 KJ. 35. AB, A2 and B2 are diatomic molecules . If the
bond enthalpies of A2, AB and B2 are in the
C diamond   Cg ; H  714.8 KJ. The H ratio 1:1:0.5 and enthalpy of formation of AB
for the following reaction is from A2 and B2 is -100 KJ mol-1. What is the
C graphite   C diamond  bond energy of A2 :
1) 200 KJmol–1 2) 100 KJmol–1
1) 1.9 KJ 2) -1.9 KJ 3) 300 KJmol–1 4) 400 KJmol–1
3) Zero 4) 714.8 KJ
29. At 250C the heat of formation of H2O(l) is
Hess Law
-285.9 KJ mole-1 and that for H2O(g) is -242.8 1
36. Given that Zn  O 2  ZnO  35.25 KJ.
KJmole-1. The heat of vaporization of water 2
at the same temperature is
1
1) 43.1 KJ mole–1 2) 242.8 KJ mole–1 HgO  Hg  O 2  9.11 KJ. The heat of the
3) -43.1 KJ mole–1
4) -242.8 KJ mole–1 2
Thermo Chemical Equations reaction Zn  HgO  ZnO  Hg is
30. H value for the manufacture of NH3 is 1) -26.14 KJ 2) 44.39 KJ
3) -44.39 KJ 4) 26.14 KJ
H  91.8KJ . The correct thermo chemical
equation for dissociation of NH3 is 37. The enthalpies of combustion of carbon and
carbon monoxide are -390KJ mol-1 and -
1) N 2  3H 2  91.8  2 NH 3 278KJ mol-1 respectively. The enthalpy of
2) 2 NH 3  N 2  3H 2 H  91.8 KJ formation of carbon monoxide is
1) 668 KJ mol–1 2) 112 KJ mol–1
3) 2 NH 3  N 2  3H 2 H  91.8 KJ 3) -112 KJ mol–1 4) -668 KJ mol–1
1 3 38. N 2 g   2O2 g   2 NO2  X KJ
4) N 2  H 2  NH 3 H  91.8KJ
2 2
2 NO g   O2 g   2 NO2 g   Y KJ
Enthalpy of Formation:
The enthalpy of formation of NO is
31. The heat of formation of H2O(l) is -286.2 KJ. 1) (2X–2Y) 2) X–Y
The heat of formation of H2O(g) is likely to be 3) (Y–X)/2 4) (X–Y)/2
1) -286.2 KJ 2) -290.78 KJ 39. Calculate the heat of formation of KOH from
3) -335.2 KJ 4) -242.76 KJ the following data in K.Cal.
32. When hydrogen gas is burnt in chlorine 2000
cals of heat is liberated during the formation 1
K  s   H 2O  aq  KOH  aq   H2 ;
of 3.65 g of HCl, H of formation of HCl is 2
1) 2 K.cal 2) -20 K.cal H  48.4 K .Cal
3) +20 K.cal 4) -2 K.cal 1
0 H 2  g   O2  g   H 2O l  ; H  68.44 K .Cal
33. If H for H2O2 and H2O are -188 KJ/mole
f 2
and -286 KJ/mole, what will be the enthalpy KOH  s   aq  KOH  aq ; H  14.0 K .Cal
change of the reaction.
1) +102.83 2) +130.85
2 H 2O2  l   2 H 2O  l   O2  g 
3) -102.83 4) -130.85
40. Given Then on increasing the temperature, its
C  2 S  CS2 , Hf 0  117.0 kJ mol 1 solubility in water
1) Decreases 2) Increases
C  O2  CO2 , Hf 0  393.0 kJmol 1 3) Remains same
4) Increases initially and then decreases
S  O2  SO2 , Hf 0  297.0 kJmol 1
47. The bond energy of an O- H bond is 109 K.cal.
The heat of combustion of mole-1. When a mole of water is formed
CS2  3O2  CO2  2 SO2 is 1) 218 K. cal. is released
1) -807 KJ mol–1 2) -1104KJ mol–1 2) 109 K. cal. is released
3) +1104KJ mol –1
4) +807 KJ mol–1 3) 218 K. cal. is absorbed
Enthalpy of Combustion: 4) 109 K. cal. is absorbed
41. Heat of combustion of benzene is 718 K.cals. 48. The heat of atomisation of PH 3 is 228KCal/
When 39 gms of benzene undergoes
mol and that of P2 H 4 is 335KCal/mol. The
combustion, the heat liberated is
1) 718 K.cals 2) 359 K.cals energy of P-P is (in Kcal)
3) 135 K.cals 4) 1436 K.cals 1) 31 2) 102 3) 93 4) 26
42. According to the equation Entropy-Spontaneous Process
7
Entropy
C 6 H 6 l   O 2  g   6 CO 2  g   3 H 2 O l  ,  H   xKJ 49. When enthalpy and entropy change for a
2
chemical reaction are –2.5 x 103cals and
The energy evolved when 3.9 gm of benzene 7.4cals deg –1 respectively. Predict that
is burnt in air is - 163.2KJ heat of combustion reaction at 298 K is
of benzene is 1) Spontaneous 2) Reversible
1) 32.46 KJ 2) 16.32 KJ 3) Irreversible 4) Non-spontaneous
3) 326.4 KJ 4) -3264 KJ 50. The enthalpy and entropy change for the
43. Human body requires 2370 K.cal of energy
daily. If the heat of combusition of glucose is reaction Br2  l   Cl2  g   2 BrCl  g  are
790 K.cal/mole the amount of glucose required 30KJ mol 1 and 105J mol 1 respecively. The
for daily consumption is temperature at which the reaction will be in
1) 650 g 2) 540 g 3) 327 g 4) 490 g equilibrium is:
Enthalpy of - Atomisation, Bond 1) 300K 2) 285.7K 3) 273K 4) 450K
Dissociation, Solution, Dilution And 51. If  Hvap of pure water at 100°C is 40.627
Hydration kJ mol-1 The value of  Svap is
44. Energy required to dissociate 4 gms of H2 (g) 1) 108.91 kJmol–1 2) 108.91 Jk-1 mol-1
into free atoms is 208 K.cals at 250C. The H- -1
3) 606.27 JK mol -1
4) 808.27 JK-1mol-1
H bond energy will be 52. The temperature at which the reaction
1) 104 K.cals 2) 1040 K.cals
3) 10.4 K.cals 4) 208 K.cals 1
Ag 2 O  s   2 Ag  s   O2  g  at
45. The enthalpy change when 1.00 g of water 2
freezes at 00C and 1.00 atm is ( H fusion = 1 atmospheric pressure will be in equilibrium
is ___K. The value of H and S for the
1.435 K.cal/mol)
1) 0.079 cal/g 2) -79.2 cal/g reaction are 30.58 Kj and 66.11 JK -1
3) 99.7 cal/g 4) -79.7 cal/g rspectively and these value do not change
much with temperature.
46.  x is given by: 1) 462.6 K 2) 486.4 K
 x = (hydration energy) - (lattice energy). 3) 364.5 K 4) 521.2 K
For a salt,  x is found to be - 300 k cal mol-1.

SR-MAIN-CHEM-VOL-II
53. The latent heat of fusion of ice is 5.99 KJ/mol 1
at its melting point . Then 60. C O ( g )  2 O 2 ( g )  C O 2 ( g )
(i) S for fusion of 900 g ice and
H  67.37 K .cal at 25 0C the change in
(ii) S for freezing of liquid water are entropy accompanying process is -20.7
respectively cal.deg-1 mol-1 then at 250C the change in free
1) 8698 JK 1 ; 16.8 J mol 1 K 1 energy is
1) -10 K.cal mol-1 2) -15K.cal.mole-1
2) 9269 J K 1 ; 12.6 J mol 1 K 1 3) -32 K.cal mol -1
4) -61.2 K.cal mol-1
3) 1097 JK 1 ; 21.9 Jmol 1 K 1 61. The standard Gibb’s free energy change, G0
4) 1236 JK 1 ; 28.6 J mol 1 K 1 is related to equlibrium constant, Kp as
54. The entropy change for the conversion of 1 G 0
 e 
mole of  –tin (at 13°C, 1 atm)to 1 mole of  – 1) Kp   RT ln G 0 2) Kp   
 RT 
tin (13°C, 1 atm) if the enthalpy of transition is
2.095K J mol–1 G 0
3) Kp   4) Kp  e G / RT
–1 –1
1) 7.32J mol K 2) 14.62 J K mol –1 RT
3) 56.J mol-1K-1 4) 0 62. What is the free energy change, ' G ' When
55.  H (vap) for water is 40.7 KJ mol-1. The 1.0 mole of water at 1000C and 1atm pressure
entropy of vapourisation of water is is converted into steam at 1000C and 1atm
l) – 40.7KJ mol–1 2)407 J mol–1K–1 pressure
–1 –1
3) 109 J mol k 4) 722 J mol –1 1) 540 cal 2) -9800 cal 3) 9800cal 4) 0 cal
56. The following data is known about the melting Key Level-I (C.W)
of a compound AB.  H = 9.2KJ mol-1  S = 01) 4 02) 3 03) 1 04) 1 05) 1 06) 2
0.008 KJK–1 mol–1. It s melting point is 07) 3 08) 3 09) 4 10) 3 11) 1 12) 1
1)736K 2) 1050K 3)1150K 4)1150°C 13) 3 14) 3 15) 2 16) 1 17) 2 18) 2
Gibbs Free Energy (Or) Gibbs Function 19) 3 20) 2 21) 3 22) 2 23) 2 24) 1
57. Combustion of hydrogen in a fuel cell at 25) 2 26) 2 27) 3 28) 1 29) 1 30) 2
300kJ is represented as 31)4 32) 2 33) 1 34) 2 35) 4 36) 1
2H 2(g) + O2(g)  2H 2 O(g) . If  H and  G are 37) 3 38) 3 39) 3 40) 2 41) 2 42) 4
-241.60 KJ mol-1 and -228.40 KJ mol-1 of H2O. 43) 2 44) 1 45) 4 46) 1 47) 1 48) 1
49) 1 50) 2 51) 2 52) 1 53) 3 54) 1
The value of  S for the above process is
55) 3 56)3 57) 2 58) 2 59) 3 60) 4
1) 4.4 kJ 2) -88 j 3) +88 J 4) -44 J
61) 4 62) 4
58. What will be the value of G0 . If equlibrium
Hints Level-I (C.W)
constant for a reaction is 10. 1. All natural processes are thermodynamically
1) 50.44 KJ mol 1 2) 5.705 KJ mol 1 irreversible.
2. U  0 for isothermal and cyclic processes
3) 25.44 KJ mol 1 4) 10 KJ mol 1 3. W   PV
59. Zn( s )  Cu 2( aq )  Cu( s )  Zn 2( aq) 4. PV = RT at TK; P V  V   R T  1 at
Given that  f G 0 for Cu 2( aq ) and Zn 2(aq) as

T  1 K  PV  R
5. Q  U  W
65 K . J m ol  1 and 147.2K .J mol 1 respectively..
6. W  P V2  V1 
then the standard Gibb’s energy change for
the above reaction is 7. Q  U  W
1) 266.2 K J 2) 111.2 K J 8. Zn S   2HCl aq  ZnCl2 aq   H 2 g 
3) -212.2 K J 4) -122.2 K J
9. Rise of 100 C  1.987  10  19.87cal 34. H  H p  H R
10. Q  U  W 35. H  H R  H P
11. W   P V2  V1  H  U  PV 36. H  H p  H R
12. U  Q  W
37. H  H p  H R
13. U  Q  W U  Q  W 1 1
14. Volume of 1 mole liquid = 100 ml at pressure one 38. N 2  O2  NO
2 2
bar = 99 ml at pressure 100 bar
1 1 H 2O
W   P V2  V1  H  U  PV 39. K  s   O2  H 2  KOH  S    KOH  aq 
2 2
H 40. H  H p  H R
15. C p  for 1 mole (18 gm of H 2 O )
T 41. 78 gm  718 k cal.
18 gm  75 39 gm  ?
100 gm  x 42. 3.9 gm  163.2 K J
16. C P  CV  R 78 gm  ?
17. Ice water phase change takes place at constant 2370
43.  3 moles of glucose is required
H 790
T and P. Hence T  0  C p  
T 44. 4 gm  2 moles of H 2  208 k cal
3 2 gm  1 moles of H 2  104 k cal
18. CV  R , C P  CV  R
2 45. 18 gm  1435 cal of water
19. CH 4 g   2O2 g   CO2 g   2 H 2Ol  1 gm  ?
46. If enthalpy of solution is negative, solubility
n  1  2  1 H  U  nRT decreases with temperature
20. H  U  nRT 47. In water there are 2 O-H bonds
21. Free expansion W=0. Since Temparature is 48. H  H R  H P
constant U  0, H  0 49. G  H  T S
M 50. G  H  T S
22. U  Z   
W H
23. H  H p  H R 51. S 
T
6C  3H 2  C6 H 6 H  ? 52. G  H  T S
24. H  U  nRT H
53 & 54. S 
25. H  U  nRT T
26. N 2  O2  180.8 kJ  2 NO H
55. S 
27. For 10gm  560 KJ T
16 gm  ? 56. G  H  T S
28. H  H  Diamond   H  Graphite  57. G  H  T S
58. G  2.303RT log K C
29. H  H H 2O  g   H H 2Ol 
59. G  GP  GR
30. 2 NH 3  N 2  3H 2 ; H  91.8kJ
60. G  H  T S
31. < -286.2 as energy is absorbed for l  g
1 1 61. G 0   RT ln K eq
32. H 2  Cl2  HCl
2 2 62. H 2O l  H 2O v  since it is an equilibrium
1 process G  0
33. H 2O2  H 2 O  O2 H  H p  H R
2

SR-MAIN-CHEM-VOL-II
internal energy of gas is
Level-I (H.W) 1) +20.26J 2) +20.26Kj
Thermo Dynamical Processes 3) -20.26 KJ 4) 10Kj
63. Boiling water in a closed steel tank is an 71. Frictionless and weightless piston was fitted
example of into a cylinder containing a gas This gas was
1) Closed system 2) Insulated system allowed to expand from one litre to 5 litre
3) Open system 4) Adiabatic system against a constant pressure of one atmosphere
64. Which parameter is not constant in an in doing so, 200 J of heat was absorbed from
adiabatic Process the surrounding . The change in the internal
1) Temperature 2) Enthalpy energy of the system is:
3) Internal energy 4) 1 and 3 1) +205.2 J 2) +205.2 KJ
65. In isothermal process if heat is evolved from 3) -205.2 J 4) -405.2J
the system then 72. A given mass of gas expands from the state A
1) Internal energy remains constant to the state b by three paths 1, 2 and 3 as
2) Change in internal energy is zero shown in the figure. If w1 ,w2 and w3
3) Change in entropy is zero respectively be the work done by the gas
4) Change in free energy is zero along three paths then.
Internal Energy, Enthalpy & Work
Done & Ist Law: P A
66. One mole of an ideal gas is allowed to expand
reversibly and adiabatically from temperature 3
of 270 C . If the work done during the process 2
is 3KJ, the final temperature will be equal to
C
v  20 JK   B
1) 100K 2) 150K 3) 295 4) 26.850 C
V
67. Work done on a system when one mole of an
an ideal gas at 500 K is compressed 1) w1  w2  w3 2) w1  w2  w3
isothermally and reversibly to 1/10th of its 3) w1  w2  w3 4) w2  w3  w1
original volume. (R = 2cal)
1) 1 Kcal 2) 2.303 Kcal First Law of Thermodynamics
3) 4.606 Kcal 4) 2.303 cal 73. One mole of liquid water at its boiling point
vaporises against a constant external
68. 2.8g of N 2 gas at 300 K and 20 atm was
pressure of 1 atm.at the same temperature .
allowed to expand isothermally against a Assuming ideal behaviour and initial volume
constant external pressure of 1 atm. Calculate of water vapours are zero , the work done by
W for the gas. the system nearly
1) + 236.95 J 2) + 136.95 J 1) -3102 J 2) +3102 J 3) -4268 J 4) + 4268 J
3) - 236.95 J 4) + 136.95 J Heat Capacity and Specific Heat
69. When a sample of gas expands from 4.0L to
74. Heat capacity of water is 18 cal-degree-1-mol-
12.0 L against a constant pressure of 0.30 atm, 1
. The quantity of heat needed to rise
the work involved is
temperature of 18g water by 0.20C is X cal.
1) 243.19 J 2) -243.19 J
T hen amount of CH4(g) to be burnt to produce
3) 234.19 J 4) -234.19 J
X cal heat is
70. 5 mol of gas at 5 atmospheric pressure
contained in a 100 L cylinder absorbed 30.26  CH 4  2O2  CO2  2 H 2O, H  200 K .Cal 
Kj of heat when it expanded to 200 L at 2 1) 1.810–3 mol 2) 3.610–5 mol
atmospheric pressure. The change in the 3) 0.0288 g 4) 0.288 mg
75. Heat capacity (CV) of an ideal gas is X KJ/ Enthalpy of Reaction
mole/K. To rise its temperature from 298K to
(Enthalpy of Phase Transitions)
318K, heat to be supplied per 10g gas will be
82. The heats of combustion of rhombic and
(in KJ) [MW=16]
monoclinic sulphur are respectively 70960 and
1) 16X 2) 6.25X 3) 32X 4) 12.5X
71030 calories. What will be the heat of
Mesurement Of H And E conversion of rhombic sulphur to monoclinic ?
76. The relationship between H and E for the 1) 70960 calories 2) 71030 calories
reaction PCl 3 g   Cl 2 g   PCl 5 g  is given as 3) -70 calories 4) +70 calories
1) H  E  RT 2) H  E  RT Thermo Chemical Equation
3) H  E  2 RT 4) H  E  2RT 83. Conversion of sulphur to SO 3 has
77. If E is the heat of reaction for H  2 x Kcal and conversion of SO2 to SO3
C 2 H 5 OH (1)  3O 2(g)  2CO 2(g )  3H 2O (1)
at involves H   ykcal . The correct
thermochemical equation for formation of SO2 is
constant volume, the H (Heat of reaction at
constant pressure) at constant temperature is 1) S  O2  SO2 H   y  2 x 
1) H  E  2RT 2) H  E  2 RT
2) S  O2  SO2 H    y  2 x 
3) H  E  RT 4) H  E  RT
78. For the system S (s) + O2 (g)  SO2 (g) ? 3) S  O2  SO2 H   x  y 
1) H   E 2) E  H
4) S  O2  SO2 H  2 y  3x
3) H  0 4) H   E
Enthalpy of Formation
79. In the complete combustion of butanol
84. In which of the following reactions, heat
C4H9OH (l), if H is enthalpy of combustion
liberated is known as standard heat of
and E is the heat of combustion at constant formation of CO2?
volume, then
1) 2CO g  O2  g   2CO2  g   135.5 K .cal
1) H   E 2) H   E  
3) H   E 2) C ( diamond )  O2 ( g )  CO2( g )  19.5 k .cal
4) H, E relation can’t be predicted
3) C ( graphite )  O2 ( g )  CO2( g )  94.05 k .cal
Exothermic And Endothermic
Reactions 4) CH 4 ( g )  2O2 ( g )  2 H 2 O( l )  212.8 k .cal
80. Which one of the following is an endothermic 85. In which of the following reactions does the
reaction? heat change represent the heat of formation
of water?
1) PCl5  g   PCl3  g   Cl2  g 
1) 2 H 2 g   O2  g   2 H 2 O l  ; H  116 Kcal
2) 2SO2  g   O2  g   2SO3  g 
1
3) C  graphite   2 H 2  g   CH 4  g  2) H 2 g   O2  g   H 2 O l  ; H  6.8 Kcal
2
 
4) HCl aq   NaOH aq   NaCl aq   H 2O 3) H ( aq )  OH ( aq )  H 2 O l  ; H  13.7 Kcal
81. Which of the following is an example of 4) C2H2( g )  2O2( g )  2CO2 g   H2O l  ; H  310 Kcal
exothermic reaction ? 86. For the reaction
1) H 2 (g) + Cl2 (g) ® 2HCl(g); D H = -184.6 KJ 3N 2O  2 NH 3  4 N  3H 2O H 0  879.6 KJ
g g 2 g  g
2) N2(g) +O2(g) ® 2NO(g) ; ΔH = 180.8kJ if standard heat of formation of ammonia and
water are -45.9KJ/mol and -241.8KJ/mol. Then
3) C(graphite) + H2O(g)  CO(g)+H2(g)-1314 KJ standard heat of formation of nitrous oxide in
4) C(graphite) + 2 S(s) + 91.9 KJ  CS2(l) KJ/mol is
1) -102 2) -82 3) 82 4) 98
SR-MAIN-CHEM-VOL-II
87. In order to decompose 9 grams of water 142.5 0 -1 -1
KJ heat is required. Hence the enthalpy of 94. S H 2 g  = 130.6 J K mol ;
formation of water is 0 -1 -1
SH O  = 69.9JK mol
1)+142.5 KJ 2) -142.5 KJ 2 l 
 
3) +285 KJ 4) -285 KJ
88. The standard heat of formation of carbon S00 = 205JK -1 mol -1 , then the absolute
2 g 
disulphide (l) given that standard heat of
combustion of carbon (s), sulphur (s) and 1
entropy change of H 2 g   O2 g   H 2O l  is
carbon disulphide (l) are -393.3, -293.72 and - 2
1108.76 KJ mol-1 respectively is 1) -163.2 J mol–1K–1 2) +163.2 J mol–1K–1
1) -12.502 KJ. mol-1 2) +128.02 KJ.mol-1 3) -303 J mol–1K–1 4) +303J mol–1K–1
3) -128.02 KJ.mol-1 4) +12.802 KJ.mol-1 95. Melting & boiling point of NaCl respectively
Hess Law are 1080 K & 1600 K. S for stage –I & II in
I
89. H 2  g   Cl2  g   2 HCl  g  , H  44 K .cals NaCl  s  
Hfus  30 KJ
 NaCl  l 
2 Na  s   2 HCl  g   2 NaCl  s  H2  g  ,  II
 NaCl  g 
H vap 160 KJ
H  152 K.cal
S  I  (KJ/mol/K) S  II  (KJ/mol/K)
1
Na  s  Cl2  g NaCl  s ,  H  ? 1) 1/36 1/10
2 2) 36 100
1) +108 K.cal 2) -196 K.cal 3) 1/36 10
3) -98 K.cal 4) 50 K.cal 4) 36 1/10
90. If S  g  e S1  g ,  H  207.6 KJ 96. S sur for H 2  1/ 2O2  H 2O, H  280 KJ at
S g   2e  S g ,  H  335.2 KJ.
 2
400K is
The enthalpy for the reaction 1) 700 J/g/K 2) 700 KJ/mol/K
S1 g   e   S2 g  : 3) 700 J/mol/K 4) 0.7 J/mol/K
1) +127.6 KJ 2) -127.6 KJ Gibbs Free Energy (or) Gibbs
3) +542.8 KJ 4) -641.8 KJ Function
Enthalpy of Combustion 97. The change in entropy, S is positive for an
91. 1 gram graphite on combustion in oxygen endothermic reacition, If enthalpy change
liberates 7.82 K.cal of heat. The amount of H occurs at the same temperature T, then
heat evolved when 1 mole of oxygen is used the reaction is feasible
in this oxidation process is 1) At all temperatures 2) When H  T S
1) 7.82 K.cal 2) 78.2 K.cal 3) When H  T S 4) Not feasible at all
3) 9.384 K.cal 4) 93.84 K.cal 98. Standard enthalpy and standard entropy for
Enthalpy of - Atomisation, Bond the oxidation of NH 3 at 298K are
Dissociation, Solution, Dilution and 382.64 K .Jmol 1 and 145.6 J .mol 1
Hydration respectively. Standard free energy change for
92. Lattice energy of NaCl is 788KJ and enthalpy the same reaction at 298K is
of hydration is -784KJ/mol. Hence heat of
1) 221.1KJmol 1 2) 339.3 K .Jmol 1
solution of NaCl (solid) is
1) -4KJ 2) 4KJ 3) -6KJ 4) 2KJ 3) 439.3 K .Jmol 1 4) 523.2 K .Jmol 
Spontaneous Process - Entropy 99. The G in the process of melting of ice at
93. Enthalpy of vapourisation for water is
150 C is
186.5KJmole-1. The entropy change during
vapourisation is ___ KJmole-1 1) G is -Vee 2) G is +Vee
1) 0.5 2) 1.0 3) 1.5 4) 2.0 3) G =0 4) All of these
100. For a reaction A( g ) B( g ) at equilibrium the 82. H  H  H
p R
partial pressure of B is found to be one fourth 3
S  O  SO3 g  ;  2 x
of the partial pressure of A. The value of G0 83.  s  2 2 g 
of the reaction A  B is 1
1) RT ln 4 2) -RT ln 4 SO2 g   O2  g   SO3 g  ;  y
2
3) RT log 4 4) -RT log 4
86. H  H p  H R
Key Level -I (H.W)
87. 9 gm  142.5 KJ
63) 1 64) 4 65) 1,2 66) 2 67) 2 68) 3 18 gm  ?
69) 2 70) 4 71) 3 72) 2 73) 1 74) 4 88. C  S 2  CS 2
75) 4 76) 2 77) 4 78) 4 79) 1 80) 1
81) 1 82) 3 83) 1 84) 3 85) 2 86) 3 89&90. H  H P  H R
87) 4 88) 2 89) 3 90) 3 91) 4 92) 2 91. C  O2  CO2
93) 1 94) 1 95) 1 96) 3 97) 3 98) 3 92. heat of solution = L.E + H.E
99) 2 100) 1 H
93&95. S 
Hints Level -I (H.W) T
63. Closed vessel 94. S  S P  S R
64. In adiabatic process work is done at the cost of
internal energy 96. S sys  S surr
65. U  f  T  for ideal gas 97. G  ve if H  T S
98. G  H  T S
q
66. Cv  For adiabatic Process q=0, E  W 99. Ice water is not possible at -15degree
T centigrade. So, G  0
; W  P V2  V1  100. G 0   RT ln K
V2
67. W  2.303nRT log V Level -II (C.W)
1
68. PV  nRT W   PV Internal Energy, Enthalpy and Work
69. W   PV Done, First Law
70&71. U  q  W 1. The workdone in ergs for the reversible
72. More the area under the curve, more is the work expansion of one mole of an ideal gas from a
done volume of 10 litres to 20 litres at 250C is
73. W   PV ; U  q  W 1) 2.303  298  0.082 log2
2) –298  107  8.31  2.303log2
M
74. U  Zx x ; H  U  nRT ; Q = mst 3) 2.303  298  0.082 log 0.5
W 4) –2.303 298  2 log2
q 2. An ideal gas expands from 10-3m3 to 10-2m3 at
75. C  T  T CV for 1 mole 16 gm  x KJ 300K against a constant pressure of 105Nm-2.
2 1
The workdone is
10 x 10 x
10 gm  ? ; 1 C 0
1) -103 kJ 2) 102kJ
16 16 3) -0.9 kJ 4) -900 kJ
0
?  20 C 3. A system has internal energy equal to E1,
76. n  1  2  1 450J of heat is taken out of it and 600J of
77. n  2  3  1 work is done on it. The final energy of the
78. n  0 system will be
1) (E1+150) 2) (E1+1050)
79. C4 H 9OH  l   6O2 g   4CO2  g   5 H 2Ol  3) (E1-150) 4) None of these
80. Dissociation is always endothermic
81. H  ve , exothermic
SR-MAIN-CHEM-VOL-II
4. If the internal energy of 22g CO2 at 273K is Exothermic and Endothermic
‘U’, internal energy of which of the following Reactions
is ‘4U’ at same T ?
12. Which of the following is an exothermic
1) 5.5 CO2 2) 88g CO2
reaction?
3) 1 mol CO2 4) 33.6 lit CO2
5. A system is provided with 50 Joules of heat 1) N 2 g   O2 g   180.8kJ  2 NO g 
and the work done on the system is 10 Joules.
What is the change in internal energy of the 2) N 2 g   3H 2 g   92k .J  2 NH 3 g 
system in Joules ? 3) C graphite  H 2O g   CO g   H 2 g   131.3kJ
1) 60 2) 40 3) 50 4) 10
Heat Capacity and Specific Heat 4) C graphite  2S s   CS 2l   91.9k .J
6. The  for inert gases is 13. Which of the following is an exothermic
1) 1.33 2) 1.66 reaction?
3) 2.13 4) 1.99 1) H 2 g   Cl2 g   2 HCl g  ; H  184.6 KJ
7. The molar heat capacity of water is
1) 4.184 JK-1 2) 75.3 JK-1 2) N 2 g   O2 g   2 NO g  ; H  180.8KJ
-1
3) 185 JK 4) 1 JK-1
Measurement of H And E 3) C graphite  H 2O g   CO2  H 2 g   131.4KJ
8. For a reaction 2 A  s   2 B  g   2C  g   D  g  . 4) C graphite  2S g   91.9 KJ  CS2l 

If heat of reaction at constant pressure is -28
Enthalpy of Reaction
K.cal. The heat of reaction at constant volume
at 270C is (Enthalpy of Phase Transitions)
1) -27.4 K.cal 2) 27.4 K.cal 14. The H for the conversion of C(diamond) to
3) 28.4 K.cal 4) 28 K.cal C(graphite) when the following reactions are given
9. A sample of CH4 of 0.08g was subjected to C(diamond)+O2(g)  CO2 (g); H = -94.5 K.cal.
combustion at 270C in a bomb calorimeter. The C(graphite)+O2(g)  CO2(g); H = -94.0 K.cal.
temperature of the calorimeter system was 1) -188.5 K.cal 2) +188.5 K.cal
found to be raised by 0.250C. If heat capacity 3) +0.5 K.cal 4) -0.5 K.cal
of calorimeter is 18KJ, H for combustion of 15. H 2 g   I 2 s   2 HI g ; H = 51.9 KJ/mole
CH4 at 270C is
1) -900 KJ/mole 2) -905 KJ/mole H 2  g   I 2  g   2 HI  g  ; H = -9.2 KJ/mole.
3) -895KJ/mole 4) -890KJ/mole The heat of reaction of I 2 s   I 2 g 
10. 100ml of water at 200C and 100ml of water at
1) -61.1 KJ 2) +61.1 KJ
400C are mixed in calorimeter until constant
3) +31.1 KJ 4) 50.1 KJ
temperature reached. Now temperature of the
16. If heats of combustion of red phosphorus and
mixture is 28 0 C. Water equivalent of
calorimeter is yellow phosphors are - 8.78KJ and - 9.19 Kj
1) 50J 2) 104.5 J 3) -24.2J 4) 209J respectiely then heat of transition of yellow
11. Heat of combustion of benzoic acid (C6H5 phosphorus to red phosphrus will be
COOH) at constant volume at 250C is - 1)17.97 KJ 2) -17.97 Kj
3233KJ/mole. When 0.5g of benzoic acid is 3) -1.13 Kj 4) +1.13KJ
burnt in bomb calorimeter, the temperature of Enthalpy of Formation
calorimeter increased by 0.530C. Now in the 17. The heats of combustion for C, H2 and CH4
same bomb calorimeter 1g of C2H6 burnt then are -349, -241.8 and -906.7 KJ respectively.
temperature increased by 2.040C. H for The heat of formation of CH4 is
combustion of C2H6 is 1) 174.1 KJ 2) 274.1 KJ
1) -1530KJ/mole 2) -1536.2 KJ/mole
3) 374.1 KJ 4) 74.1 KJ
3) -1522.8KJ/mole 4) +1536.2KJ/mole

18. From the thermo chemical reactions, What is H f of H 2 S
1 1) 2.7 Kcal 2) -2.7 Kcal
C graphite   O 2  CO;  H  110.5 KJ.
2 3) 5.4 Kcal 4) -5.4 Kcal
1 3
CO  O 2  CO 2 ; H  283.2 KJ. H for 25. A  O2  AO3  3x KJ
2 2
the reaction, C graphite   O 2  CO 2 is 1
AO2  O2  AO3  2 y KJ
1) -393.7 KJ 2) +393.7 KJ 2
3) -172.7 KJ 4) +172.7 KJ The heat of formation of AO2 is
19. The heats of combustion of carbon, hydrogen 1) 2y - 3x 2) 2x + 3y 3) 2x + y 4) 3x/2y
and ethane are 94, 68.3 and 373 Kcal/mole 26. The heat evolved during the formation of 24.95
respectively. The heat of formation of ethane grams of hydrated copper sulphate from
in K.cals/mole is anhydrous copper sulphate (mol.wt=159.5) is
1) +19.9 2) -19.9 3) +39.8 4) -39.8
20. If the heats of formation of C2H2 and C6H6 are CuSO4  5 H 2O  CuSO4 .5H 2O
-1 -1
230 KJ mol and 85 KJ mol respectively, the H  78.2 KJ
H value for the trimerisation of C H
2 2
is 1) -78.21 KJ 2) 78.21 KJ
1) -605 KJ 2) -205 KJ 3) 7.82 KJ 4) -7.82 KJ
3) 205 KJ 4) 605 KJ 27. The molar enthalpies of combustion of
21. At 298 K, the heats of formation of CCl4 (g),
C2 H 2 g  , C(graphite) and H2(g) are -1300,-394, -
H2O (g), CO2 (g) and HCl (g) are -25, -57, -94
and -22 K.cal mol-1 respectively. The H of 286 kJmol-1 respectively. The standard
the reaction: enthalpy of formation of C2 H 2 g  is
CCl4 g   2H 2 O  CO2 g   4 HClg  1) -226 kJmol–1 2) -626 kJmol–1
1) -43 K.cal 2) +72 K.cal 3) 226 kJmol–1 4) 626 kJmol–1
3) 14 K.cal 4) -125 K.cal 28. For a given reaction ,
22. The standard heats of formation of NO2 (g) C7 H 8  l   9O2 ( g )  7CO2 ( g )  4 H 2O  l 
and N 2O4 (g) are 33.5 and 8.4 KJ mol-1
respectively. The heat of dimerisation of NO2 the calculated and observed heats of reaction
in KJ is are respecively 232 and 50.4Kj mol  . The
1) 41.9 2) -25.1 3) -52.2 4) -58.6 resonance energy for it will be
23. The enthalpies of formation of CO2 g  , H 2O l  1) 160KJmol 1 2) 172.2KJmol 1
3) 182.2KJmol 1 4) 182.2Kjmol 1
and C2 H 4 g  are respectively -393.5, -286 and
+52.3 kJ mol-1 the enthalpy change for the
Hess Law
29. Hess’s law states that
combustion of C2 H 4 g  is 1) The standard enthalpy of an overall reaction is
l) –1306 kJ mol–1 2) –1411.3 k J mo|–1 the sum of the enthalpy changes in individual
3) -509.7 kJ mol-1 4) -731.5 kJmol–1 reactions.
2) Enthalpy of formation of compound is same as
3 the enthalpy of decomposition of the compound
24. If H 2 S  O2  H 2O  SO2 ,
2 into constituent elements, but with opposite sign
H  136.7 Kcal 3) At constant temperature the pressure of a gas in
inversely proportional to its volume
1 4) The mass of a gas dissolved per lit of a solvent
H2  O2  H 2O, H  68.4 Kcal
2 is proportional to the pressure of the gas in
S  O2  SO2 , H  71 Kcal equilibrium with the solution.

SR-MAIN-CHEM-VOL-II
30. Heat of reaction  H  is given by MgO s   C s   Mg  s   CO g 
1) H = (Ea)f - (Ea)b 2) H = BER - BEP 1) S1+S2+S3+S4 2) (S1+S4)-(S2+S3)
3) H = HP - HR 4) All the above 3) (S2+S3)-(S1+S4) 4) (S4-S3)
Enthalpy of Combustion Gibbs Free Energy (or) Gibbs
31. The values of heat of combustion of graphite Function
and H2 are -395 and -269 KJ respectively. If 37. The value  S for the process
heat of formation of glucose is -1169 KJ the H2O(s) ——> H2O(l) at 1 atm pressure and
heat of combustion of glucose is 273K is greater than zero. The value of  G
1) -2815 KJ/mole 2) -1169 KJ/mole will be
3) 1169 KJ/mole 4) 2815 KJ/mole 1) = 0 2)<0
32. At constant volume and at 298K, the heat of 3) >0 4) lies between-1 and 0
combustion of sucrose  C12 H 22O11 (s ) is - 38. On the basis of reaction,
1348.9 Kcal mol  . If steam is produced during 4 2

Al  O2  Al2O3 , G  827 KJ mol 1 of
the combuston, the heat of reaction at constant 3 3
pressure will be O2 , the minimum emf required to carryout
1) -1355.46Kcal 2) +1355.46Kcal
Electrolysis of Al2 O3 is
3) -1342.34Kcal 4) +1342.344 cal
1) 6.42 V 2) 8.56V 3) 2.14V 4) 4.28V
Enthalpy of - Atomisation, Bond
39. Consider the following reactions at 1000C .
Dissociation, Solution, Dilution And
Hydration 1 0
A) ZnS s  O2 g   ZnO s  G  360 KJ / mol
33. AT 298 K, the heat of solution of MgSO4 (s) is 2
-91.21 KJ mol-1 and that of MgSO4. 7 H2O (s) 1 0
is 13.81 KJ mol-1. Calculate heat of hydration B) C gra   O2 g   CO g  G  460 KJ / mol
2
of MgSO4 (s) i.e., H for the reaction
correct statement at 1000C is
MgSO4 s   7 H 2O l   MgSO4 .7H 2 O s  1) Zn can be oxidised by CO
1) -105.02 KJ mol-1 2) 105.02 KJ mol-1 2) ZnO can be reduced by “C”
3) -77.40 KJ mol-1 4) 77.40 KJ mol-1 3) CO can be reduced by “Zn”
Spontaneous Process-Entropy 4) Both (1) , (2) true
34. The entropy change for cooling 1.6g of an 40. Acetic acid forms dimer in vapour phase. The
organic compound ( mol.wt.32, molar heat dimer is held together by two hydrogen bonds
capacity at constant pressure, with a total strength of 66.5 KJ per mole of
59J K  mol  ) from 1000 K to 800 K is: dimer. if at 25C , the equilibrium constant for
1) 0.7375JK  2) 1.4750JK  the dimerisation is 1.3  103 . S 0 for the
3) 0.3688JK  4) none of these reaction 2CH 3COOH  CH 3COOH 2 will
35. The entropy change during heating of 50g be ( log1.3  0.1139 )
water (sp.heat = 4200 Jkg –1 K –1 ) from
1) 0.163KJ 2) 0.236KJ
200 C to 400 C will be 3) 0.342KJ 4) 0.456KJ
1) 13.83 JK–1 2) –13.83 JK–1
–1
41. The temperature in K at which G  0 for a
3) 27.66 JK 4) 55.32 JK–1
36. Standard molar entropies of given reaction with H  20.5kJ mol 1 and
Mg s  , C s  , MgO s  & CO g  respectively are S  50.0 JK 1 mol 1 is (EAM-2014)
S1,S2,S3&S4J/K/mol. Then S sys for 1) -410 2) 410 3) 2.44 4) -2.44

Key Level -II (C.W) H  H R  H P
01) 2 02) 3 03) 1 04) 2 05) 1 06) 2 25. A  O2  AO2 H  H P  H R
07) 2 08) 1 09) 2 10) 4 11) 2 12) 2
13) 1 14) 4 15) 2 16) 3 17) 4 18) 1 H  Eq 1  Eq  2 
19) 2 20) 1 21) 1 22) 4 23) 2 24) 2 26. 249.5 gm CuSO4 .5H 2 O  -78.5 KJ
25) 1 26) 3 27) 3 28) 4 29) 1 30) 4 24.95 gm  ? x
31) 1 32) 3 33) 1 34) 1 35) 1 36) 2 27. 2C  H 2  C2 H 2 ; H  H R  H P
37) 1 38) 3 39) 2 40) 1 41) 2
Hints Level -II (C.W) 28. R.E   R.Ecal    R.Eobs 
29. Hess’s law
V2
1. W  2.303nRT log 30. Standard definition
V1
31. C6 H12O6 s   6O2  6CO2  6 H 2O
2. W  PV
3. U   q  w H  H P  H R
4. 22 gm  U 32. C12 H 22O11 s  12O2 g   12CO2 g   11H 2O g 
x?  4U
H  U  nRT
5. U  q  w
33. H  H P  H R , H  H MgSO4  H MgSO4 .7 H 2O
5
6. Inert gases are mono atomic so   q q
3 34. C P  S 
T T
7. CP , m  4.18  18
H
8. H  U  nRT 35. S 
T
M
9. U  Z    ; H  U  nRT 36. S  S P  S R
W
37. ice and water at equilibrium
 m2  t2  t3   38. G   nFEcell0
10. W   t  t  m1 
 3 1  39. More G  ve value substance acts as reductant
M in the reaction.
11. U  Z    ; H  U  nRT
W 40. G  2.303RT log K c
12&13. H  ve , exothermic 41. G  H  T S
14. H  H Graphite  H Diamond
Level -II (H.W)
15. H  H I2  g   H I2  S 
Internal Energy, Enthalpy and Work
16. H  H Re d P  H Yellow P Done, First Law
17. H  H R  H P C  2 H 2  CH 4 41. A gas is allowed to expand reversibly under
adiabatic conditions. What is zero for such a
18 & 21. H  H P  H R process ?
19. 2C  3H 2  C2 H 6 ; H  H R  H P 1) G 2) T
20. 3C2 H 2  C6 H 6 ; H  H P  H R 3) S 4) None of these
Heat Capacity and Specific Heat
22. 2NO2  N 2 O4
42. One mole of an ideal diatomic gas absorbs
23. C2 H 4  3O2  2CO2  2 H 2O 1831.4J of heat and does 1000J of work at
270C. What is the change in temperature
24. H 2  S  H 2 S
observed ?
1) 250C 2) 400C 3) 370C 4) 670C
SR-MAIN-CHEM-VOL-II
43. Calculate the change in enthalpy for he 3) 72.8 KJ/mole 4) -72.8 KJ/mole
following process at 1 atm Enthalpy of Formation
H 2O  l ,50 0 C   H 2O  g ,1500 C  48. Given the enthalpy of formation of CO2 (g) is
–94.0 KJ, of CaO (s) is -152 KJ, and the
given that H v at 1000C is 40.7 kJ mol-1 enthalpy of the reaction CaCO3 (s)  CaO
(s) + CO2 (g) is 42 KJ, the enthalpy of
C p  H 2O, l   75.0 Jmol 1K 1
formation of CaCO3 (s) is
C p  H 2O, g   33.3 Jmol 1K 1 1) -268 KJ 2) +202 KJ
3) -202 KJ 4) -288 KJ
1) 64.8 KJ 2) 52.4 KJ
3) 48.6 KJ 4) 46.1KJ 49. C  O 2  CO2 ; H  94 K.cal;
Measurement of H and E 1
CO  O 2  CO 2 ; H  67.7 K.cal. On the
44. 16 g of O2 at 280C is compressed to half of its 2
initial volume under reversible isothermal basis of the above data, the heat of formation
conditions. If this gas behaves ideally, the of ‘CO’ is
workdone and change in internal energy in this 1) -26.3 K.cals 2) +26.3 K.cals
process are 3) +52.6 K.cals 4) +13.2 K.cals
1) U  0 and w=-1247.1 ln 2 J Hess Law
2) U  0 and w = +1247.1 ln 2J 50. What is the heat of formation of C6H6, given
3) w = U  = +1247.1 ln 2J that the heats of combustion of Benzene,
4) U  -1247.1 ln 2J and carbon and Hydrogen are 782, 94 and 68 K.Cal
w = +1247.1 ln 2J respectively
1) +14 K.Cal 2) -14 K.Cal
45. In the following process/es H  U
3) +28 K.Cal 4) -28 K.Cal
(A) C  s   O2  g   CO2  g  51. How much energy is released when 6 mole of
octane is burnt in ? Given that the heat of
1
(B) CO  g   O2  g   CO2  g  formation of CO2, H2O and C8H18 respectively
2 are -390, -240, and +160 KJ/mole.
(C) N 2  g   3H 2  g   2 NH 3  g  1) -32.6 MJ 2) -37.4 MJ
3) -35.5 MJ 4) -20.0 MJ
(D) CaCO3  s   CaO  s   CO2  g  Enthalpy of Combustion
The correct answer is 52. The heat of combustion of methane is -880 KJ
1) A,B 2) B,C,D 3) A,B,C 4) B,C mol-1. The quantity of heat liberated in the
Exothermic and Endothermic Reactions combustion of 3.2 g methane is
46. Which of the following will involve evolution 1) -88 KJ 2) +88 KJ
of heat ? 3) +176 KJ 4) -176 KJ
1) Dissolution of conc. H2SO4 in water 53. When 6 g carbon is burnt in a sufficient amount
2) Formation of NO in atmosphere of oxygen, the heat evolved is x KJ. The heat
3) Conversion of molecular hydrogen to atomic of combustion of carbon is
hydrogen 1) –x KJ 2) –2x KJ
4) Formation of water gas from coal and steam 3) –4x KJ 4) –8x KJ
Enthalpy of Reaction 54. The heats of combustion of C2H4 , C2H6 and H2
gases are –1409.5 KJ, –1558.3 KJ and –285.6
(Enthalpy of Phase Transitions) KJ respectively. The heat of hydrogenation of
47. The sublimation energy of I2 (solid) is 57.3 KJ/ ethene is
mole and enthalpy of fusion is 15.5 KJ/mole. 1) -136.8 KJ 2) -13.68 KJ
The enthalpy of vapourisation of I2 is 3) 273.6 KJ 4) 1.368 KJ
1) 48.1 KJ/mole 2) -48.1 KJ/mole
55. The enthalpies of formation of CO and CO2 62. In which of the following reactions the entropy
are -110.5 KJ mol-1 and -393.5 KJ mol-1 change is positive? (EAMCET-2013)
respectively. The enthalpy of combustion of
1
carbon monoxide is 1) H 2 g   O2 g   H 2Ol 
1) -110.5 KJ mol-1 2) -283.0 KJ mol-1 2
-1
3) 504.0 KJ mol 4) 221.2 KJ mol-1 2) Na

 Cl  g   NaCl s 
g
56. When 14 grams of ethene is completely burnt
in oxygen, the heat evolved is 705 kJ. What 3) NaCl g   NaCl s 
is the heat of combustion (in kJ.mol–1) of
ethene? 4) H 2O l   H 2O g 
1) 1410 2) 2820 3) -1410 4) -2820 Gibbs Free Energy (or) Gibbs
Enthalpy of - Atomisation, Bond Function
Dissociation, Solution, Dilution And 63. Calculate the free energy change for the
Hydration following reaction at 300K.
57. H 2O( g )  H  g   OH  g  H  x1 ; 1
2CuO s   Cu2O s   O2 g  Given
OH  g   H  g   O g  H  x2 2
Based on these value,BE of O-H bond is H  145.6 kJ mol 1 and S  116. JK 1 mol 1
x1  x2 1) 110.8 kJ mol-1 2) 221.5 kJ mol-1
1) 2) x1  x2 3) 55.4 kJ mol-1 4) 145.6 kJ mol-1
2
64. For the reduction of lead oxide by coke
x1  x2 (PbO+C  Pb+CO), H and S are found to
3) 4) 2( x1  x2 )
2 be 108.8 kJ mol -1 and 190 JK -1 mol - 1
58. Heat evolved in the reaction respectively. The minimum temperature above
H 2  Cl2  2 HCl is 182kJ Bond energies H- which the reaction will be spontaneous will be
H=430 kJ/mole, Cl-Cl=242kJ/mole. The H-Cl 1) 1000C 2) 2000C 3) 3000C 4) 4000C
bond energy is Key Level -II (H.W)
1) 763 kJ/mole 2) 427 kJ/mole 41) 3 42) 2 43) 4 44) 2 45) 4 46) 1
3) 336 kJ/mole 4) 154 kJ/mole 47) 1 48) 4 49) 1 50) 1 51) 1 52) 3
59. C6 H 6  C6 H12 H  204 KJ heat of 53) 2 54) 1 55) 2 56) 3 57) 1 58) 2
hydrognentaion of each C=C bond in benzene 59) 1 60) 2 61)2 62) 4 63) 1 64) 3
1) -68 kJ 2) - 93kJ 3) -56kJ 4) -88 kJ Hints Level -II (H.W)
Spontaneous Process-Entropy
60. The direct conversion of A to B is difficult. q
41. q  0 S  0
Hence it is carried out by the following shown T
path: 42. H  U  PV
S  A  C   50e.u., S  C  D   30e.u, U  0
S  B  D   20e.u where e.u is entropy unit. H   PV
qP
Then S  A  B  ; CP 
T
1) +100e.u 2) +60e.u 3) -100e.u 4) -60e.u
43. H 2 0 l   500 C   H 2Ol  1000 C   H 2O g  1500 C 
61. CaCO3 s   CaO s   CO2 g  H  180 KJ
If entropies of limestone ,lime and carbon H  H1  H 2  H 3
dioxide are 93,39 and 213 J/mol/K. Then H
CP 
Stotal in JK–1 at 300K is T
1) 441 2) -441 3) 700 4) -650 44. U  Q  W
SR-MAIN-CHEM-VOL-II
45. H  U  nRT energy is available for muscular work. If 100
46. Dissolution of sulphuric acid in water is exothermic KJ of muscular work is needed to walk one
kilometer, what is the maximum distance that
47. I 2  S   I 2  l   I 2  g 
a person will be able to walk after consuming
H SE  H Fusion  H Eva 120 gm of glucose?
1) 4.8 km 2) 9.6 km 3) 2.4 km 4) 7.2 km
48. CaCO3  CaO  CO2 ; H  H P  H R
2. Three statements are given below
1 i) The enthalpy of any element is zero in their
49. C  O2  CO ; standard state
2
ii) The heat of neutralisation for any strong
H  H P  H R
acid and strong base at 25ºC is -13.7 kJ/mole
50. 6C  3H 2  C6 H 6 ;
iii) Q  E  W is a mathematical form of first
H  H P  H R law of thermodynamics if work is done by the
25 system according IUPAC
51. C8 H18  O2  8CO2  9 H 2O 1) i only correct 2) ii and iii are correct
2
3) i and iii are correct 4) all are correct
H  H P  H R
3. I: H 2O s  II: H 2O l  III: H 2O g 
52. 16 gm  -880
3.2 gm  ? For the above compounds the correct of
53. 6 gm  x internal energy content is
12 gm  ? 1) I  II  III 2) I  II  III
54. C2 H 4  H 2  C2 H 6 3) I  II  III 4) III  II  I
4. A gas contained a cylinder fitted with a friction
H  H P  H R less piston expands against a constant
1 pressure 1atm from a volume of 4litre to
55. CO  O2  CO2 volume of 14litre. In doing so, it absorbs 800J
2
thermal energy from surrounding. then the
H  H P  H R
E for the process is
56. 14 gm  705 1) - 213.7 J 2) - 112 J
28 gm  ? 3) - 50J 4) - 25 J
57. H  H R  H P 5. The amount of work done by 2mole of an ideal
gas at 298K in reversible isothermal expansion
58. H  H R  H P
from 10litre to 20litre is
59. for three C=C bonds in benzene is -204KJ 1) -120J 2) - 2452J 3) -3434.9J 4) 2200J
for one C=C bond is ...............? 6. 5moles of an ideal gas at 27 0C expands
60. S  S1  S2  S3 isothermally and reversibly from a volume of
6L to 60L. The work done in KJ is
61. S  S P  S R
1) –14.7 2) -28.72 3) +28.72 4) –56.72
63. G  H  T S 7. 1mole of a gas is heated at constant pressure
64. G  H  T S to raise its temperature by 10C. The work done
in Joules is
Level -III
1) -4.3 2) -8.314
Internal Energy, Enthalpy, Work 3) -16.62 4) Unpredictable
Done And First Law Of Thermo 8. 3.0 moles of ideal gas is heated at constant
pressure from 270C to 1270C. then the work
Dynamics expansion of gas is
1. The enthalpy change involved in the oxidation 1) - 2.494KJ 2) + 2.494KJ
of glucose is -2880 KJ mol-1 25% of this 3) - 10.5KJ 4) + 10.5KJ
3
9. An ideal gas occupying a volume of 2 dm and Enthalpy of Reaction
a pressure of 5 bar undergoes isothermal and 16. When a certain amount of ethylene was burnt
irreversible expansion against external 622 KJ heat was evolved. If heat of combustion
pressure of 1 bar. The final volume of the of ethylene is 1411 KJ, the volume of O2 (at
system and the work involved in the process NTP) that entered into the reaction is
is 1) 296.5 ml 2) 29.62 litre
1) 10 dm3, 1000 J 2) 8 dm3, –800 J 3) 6226  22.4 litre 4) 22.4 litre
3) 10 dm3, –800 J 4) 10 m3, –1000 J 17. When 100 ml of 0.2 M HCl is mixed with 100
10. A position filled with 0.04 mol of an ideal gas ml of 0.2M NaOH, the rise in temperature is
expands reversibly from 50.0 mL to 375 mL T1. When the experiment is repeated using
at a constant temperature of 37.00C . As it does 200 ml each of the same solutions, the rise in
so, it absorbs 208J of heat. The values of q temperature is T2. Then
and w for the process will be:(R=8.314J/molK) 1) T1 = T2 2) 2T1 = T2
(ln 7.5=2.01) (AIEEE-2013) 3) T1 = 4T2 4) T1 = 2T2
1) q = +208 J, w = +208 J 18. When 20 ml of 0.1 M HCl is mixed with 20 ml
2) q = +208 J, w = -208 J of 0.1 M NaOH, the rise in temperature is T1.
3) q = -208 J, w = -208 J When the experiment is repeated using 20 ml
4) q = -208 J, w = +208 J of 0.2 M HCl and 0.2 M NaOH solutions, the
11. A heat engine absor bs heat Q1 at temperature rise in temperature is T2. Then
T1and heat Q2 at temperature T2. Work done 1) T1 = T2 2) T1 = 2T2
by the engine is (Q1+Q2). This data 3) T1 = 4T2 4) 2T1 = T2
1) Violates 1st law of thermodynamics 19. Three statements are given below
2) Violates 1st law of thermodynamics if Q1 is -ve i) The amount of heat evolved when 500 ml of
3) Violates 1st law of thermodynamics if Q2 is -ve 1 M H2SO4 is mixed with 250ml of 1 M NaOH
4) Does not violate 1st law of thermodynamics solution is -28.65 k.j
ii) The amount heat evolved when 1 L of 1 M
12.  H  U  for the formation of
CH3COOH is neutralised with l L of 1 M
carbonmonoxide from its elements at 298K is NaOH solution -13.3k.cals. The heat of
1) -2477.57 J mol-1 2) 2477.57 J mol-1 dissociation of acetic acid is 0.4k.cal
3) -1238.78 J mol-1 4) 1238.78 J mol-1
iii) The standard heat of combustion of
13. The gas in a refrigerator causes cooling on
graphite is equal to standard heat of formation
expansion becuase:
of CO2
1) Work done by the gas is converted into heat
1) All are correct 2) i and ii are correct
2) Heat of the gas is lost as work is done by the
3) i,ii and iii are correct 4) ii and iii are correct
gas
20. 500 ml of 0.1M HCl is neutralised with 500 ml
3) The heat is spread over a large space
of 0.1M KOH solution. The raise in
4) None of the above
temperature is noted as T 1 . Again the
Heat Capacity and Specific Heat experiment is repeated by addition of 1 litre
14. 5moles of oxygen are heated at constant of each solution. Then the raise in
volume from 100 C to 200 C . the change in temperature is noted as T2. Then.
internal energy of a gas. i) T1 = T2
CP  7.03calmol 1 deg 1 and R  8.31Jmol 1 deg 1  ii) The amount of heat liberated in first
experiment is half to the amount of heat
1) 125cal 2) 252cal 3) 50cal 4) 500cal
liberated in the second experiment.
15. The molar heat capacity of water is 75 JK-1
iii) in both experiments the weight of salt
mole-1. What is the amount of heat required
formed in the solution is same
to raise the temperature of 100g of water from
1) All are correct 2) i and ii are correct
300K to 302.4 K ?
3) ii and iii are correct 4) i and iii are correct
1) 10J 2) 1000 J 3) 375 J 4) 10 J
SR-MAIN-CHEM-VOL-II
21. How much heat is produced when 2.63g of 28. For which of these process is the value of
phosphorous and 40g of Bromine is allowed to H negative
react according to following equation
i) N2  O2  2 NO
P  6 Br  4 PBr ; H  486 KJ
4(s ) 2(l ) 3( g ) Fe  Mo
ii) N 2  3H 2   2 NH 3
1) 10.30KJ 2) 20.6KJ 3) 40.12KJ 4) 5.63KJ
V2O5
22. A coffee cup calorimeter initially contains 125g iii) 2SO2  O2   2SO3
of water at a temperature of 24.20C. After pt
iv) H 2  I 2   2 HI
adding 10.5gm KBr temperature becomes
21.10C.The heat of solution is 1) i and ii are correct 2) ii and iii are correct
1) 85J/g 2) 110J/g 3) 270J/g 4) 167J/g 3) iii and iv are correct 4) i and iv are correct
23. The lattice energy of solid NaCl is 29. 2 H 2( g )  2Cl2( g )  4 HCl ( g ), H 0  92.3kJ
180 K .cal mol 1 .The dissolution of the solid in i) If the equation is reversed, the H 0 value
water in the form of ions is endothermic to the equal to  92.3kJ
extent of 1K .cal mol 1 .If the hydration energies ii) The four H  Cl bonds are stronger than
+ –
of Na and Cl are in the ratio 6:5, what is the the four bonds in 2H 2 and 2Cl2
enthalpy of hydration of Na+ ion
1) - 85.6K.cal mol-1 2) - 97.5K.cal mol-1 iii) The H 0 value will be 92.3 k.J if the HCl
3) - 182.6K.cal mol-1 4) +100K.cal mol-1 is produced as a liquid
24. The change in enthalpy when HF reacts with 1) All are correct 2) i only correct
NaOH in dilute conditions is 3) i and ii are correct 4) iii only correct
1) 57.32KJ 2) >57.32KJ 30. The correct statement among the following
3) <57.32KJ 4) None of these i) heat of reaction depends on the temperature
at which the reaction is carried
1 1
25. If X 2O( s )  X ( s )  O2( g ) ; H  90 KJ then heat ii) heat of neutralisation depends on the
2 4
temperature at which the experiment is
change during reaction of metal X with 1mole
carried.
O2 to form oxide to maximum extent is
iii) experimentally heat of combustion is E .
1) - 360KJ 2) - 180KJ 1) i only correct 2) ii only correct
3) + 360KJ 4) + 180KJ 3) iii only correct 4) All are correct
26. The bond energy of H2 is 104.3K.cal mol–1. It 31. The data given below are for vapour phase
means that reactions at constant pressure
1) 104.3K.cal heat is released during breaking up 
‘N’ bonds in N molecules of H2 C2 H 6  C2 H 5  H ; H  420K .Jmol 1
2) 104.3K.cal heat is needed to break up 6.023  

23 24
10 molecules into 1.2046  10 atoms of H C 2 H 5  C 2 H 4  H ; H  168K .Jmol 1
3) 104.3K.cal heat is evolved during combination The enthalpy change for the reaction
of 2N atoms of H to form N molecules of H2 
2C 2 H 5  C2 H 6  C2 H 4 is
4) Both 2 and 3.
27. Calculate the heat of combustion (in KJ) of 1) + 250KJ mol-1 2) + 588KJ mol-1
-1
methane from the following data 3) - 252KJ mol 4) - 588KJ mol-1
i) C (graphite) + 2H2 (g)  CH4 (g), 32. The enthalpy of neutralisation of a weak acid
in 1M solution with a strong base is - 56.1 KJ
H = -74.8 KJ
mol-1 . If the enthalpy of ionisation of acid is
ii) C (graphite) + O2 (g)  CO2 (g),
1.5 KJ mol-1 and enthalpy of neutralisation of
H = -393.5 KJ the acid with a strong base is -57.3KJ.eq-1
iii) H2(g) + 1/2O2(g)  H2O(l), H = -286.2 KJ.
.what is the % ionisation of the weak acid
1) –891.1 2) –816.3 initially in molar solution
3) –965.9 4) –1040.7 1) 25 2) 20 3) 15 4) 10
33. One mole of an ideal gas undergoes a change 38. The enthalpy changes for the following
of state (2.0atm, 3.0L, 95K)  (4.0atm, 5.0L, processes are listed below:
245K) with change in internal energy Cl2 ( g )  2Cl ( g ), 242.3kJ mol–1
E  30.0 L atm .The change in enthalpy of the I 2 ( g )  2 I ( g ), 151.0kJ mol–1
process in L atm is ICI ( g )  I ( g )  Cl ( g ), 211.3kJ mol–1
1) 40.0 2) 44.0 3) 42.3
I 2 (s )  I 2 ( g ), 62.76kJ mol–1
4) Not defined, because it is not constant.
34. The enthalpy of combustion of H2(g) to give H2O(g) Given that the standard states for iodine and
is -249KJ mol-1 and bond enthalpies of H – H chlorine are I 2 ( s) and Cl2 ( g ) , the standard
–1 -1 enthalpy of formation for ICI ( g ) is:
and O = O are 433KJ mol and 492KJ mol
respectively, The bond enthalpy of O – H is 1) +16.8 kJ mol-1 2) +244.8kJ mol-1
–1 –1
1) 464KJ mol 2) - 464KJ mol 3) -14.6kJ mol-1 4) -16.8kJ mol-1
–1 –1
3) 232KJ mol 4) - 232KJ mol 39. Assuming that water vapour is an ideal gas,
35. If at 298K the bond energies of C–H, C – C, C the internal energy change (U ) when 1 mol
= C and H – H bonds are respectively 414, of water is vapourised at 1 bar pressure and
347, 615 and 435KJmol–1, the value of enthalpy 1000C, (given: molar enthalpy of vapourisation
change for the reaction of water at 1bar and 373 K=41 kJ mol-1 and
H 2C  CH 2( g )  H 2( g )  H3C  CH 3( g ) R=8.3 Jmol-1 K-1) will be [AIEEE 2007]
-1
at 298 K will be 1) 41kJ mol 2) 4.1kJ mol-1
1) - 250 kJ 2) + 125 kJ 3) 3.7904kJ mol-1 4) 37.904kJ mol-1
3) - 125 kJ 4) + 250 kJ 40. Oxidising power of chlorine in aqueous
36. The formation of the oxide ion O(2g) requires solution can be determined by the parameters
indicated below:
first an exothermic and then an endothermic
step as shown below 1 Δ HΘ Δeg H Θ
1
Cl 2 diss
  Cl   Cl -
O(g) + e - = O(g)
-
, ΔH 0 = -142 kJmol -1 2 2(g) (g) (g)
O -(g) + e - = O(g)
2-
, ΔH 0 = 844 kJmol -1 Δ HΘ
hyd
 Cl -
This is because (aq)
–
1) O ion will tend to resist the addition of another Θ = 240kJmol -1 ,
electron. using the data Δdiss HCl
2
2) Oxygen has high electron affinity
Θ
Δ eg H Θ = -349kJmol -1 , Δhyd H Cl - = -381kJmol ,
-1
3) Oxygen is more electronegative Cl
4) O– ion has comparatively larger size than oxygen
H will be [AIEEE 2008]
atom. 1) + 152 kJ mol -1
2) - 850 kJ mol-1
37. An ideal gas is allowed to expand both 3) - 610 kJ mol-1 4) + 120 kJ mol-1
reversibly and irreversibly in an isolated 41. The standard enthalpy of formation of NH is
3
system. If Ti is the initial temperature and T f is 1
46.0kJ mol . If the enthalpy of formation of
the final temperature, which of the following
statements is correct? H2 from its atoms is 436kJ mol 1 and that of
1) T f rev  T f irrev N2 is 712kJ mol 1 , the average bond enthalpy
2) T f  Ti for both reversible and irreversible of N - H bond in NH3 is [AIEEE2010]
processes 1) 964kJ mol 1 2) 352kJ mol 1
3) T f irrev  T f rev 3) 1056 kJ mol 1 4) 1102 kJ mol 1
4) T f  Ti for reversible process but T f  Ti for
irreversible process.
SR-MAIN-CHEM-VOL-II
Spontaneous Process-Entropy 48. Identify the correct statement regarding a
42. In conversion of lime stone to lime, spontaneous process: [AIEEE 2007]
CaCO3( s )  CaO( s )  CO2( g ) the values of H 0 and 1) Lowering of energy in the process is the only
-1
criterion for spontaneity.
S 0 are + 179.1 kJmol and 160.2J/K 2) For a spontaneous process in an isolated system,
respectively at 298K and 1 bar. Assuming that the change in entropy is positive.
H 0 and S do not change with temperature,
0
3) Endothermic process are never spontaneous.
temperature above which conversion of 4) Exothermic process are always spontaneous.
limestone to lime will be spontaneous is 49. The standard Gibb’s energy change for the
[AIEEE 2007] formation of propane. C3 H 8 ( g ) at 298K is
1) 1118 K 2) 1008 K 3) 1200 K 4) 845 K
43. Standard entropy of X 2 , Y2 and XY3 are 60, 40 [  f H  for propane   103.85 K . J mole  1 ,
and 50JK 1mol 1 , respectively.For the S  mC3 H 8 ( g )  270.2 J .K 1mol 1,

reaction,
S  m H 2 ( g )  130.68 J .K 1mol 1.
1 3
X 2  Y2  XY3 H  30 K . J to be at
2 2 and S  mC( graphite)  5.74 JK 1mol 1 ]
equlibrium the temperature will be 1) -23.4 K.J 2) -44.4 K.J
(AIEEE 2008) 3) -54.4 K.J 4) -104.5 KJ.
1) 1250K 2) 500K 3) 1000K 4) 750K 50. Which correctly represents the physical sig-
44. The entropy change involved in the isother- nificance of Gibbs energy change?
mal reversible expansion of 2 mole of an ideal
1) G  WCompression 2) G  Wexpansion
gas from a volume of 10dm3 to a volume of
3) G  Wexpansion  Wnon-expansion
100dm3 at 270 C is [AIEEE 2011]
1) 35.8J mol 1 K 1 2) 32.3J mol 1 K 1 4) G  Wexpansion
51. The incorrect expression among the following
3) 42.3J mol 1 K 1 4) 38.3J mol 1 K 1
is [AIEEE2012]
45. The molar heat capacity (CP) of CD2O is 10
cals at 1000K. The change in entropy Gsystem
1)  T
associated with cooling of 32g of CD2O vapour S total
form 1000K to 100K at constant pressure will
be : (D = deuterium, at mass = 2u) Vf
(AIEEE-2014) 2) In isothermal process W   nRT in
reversible Vi
–1 –1
1) 23.03 cal deg 2) -23.03 cal deg
3) 2.303 cal deg–1 4) -2.303 cal deg–1 H 0  T S 0
3) In K 
Gibbs Free Energy (or) Gibbs Function RT
0
46. At 60 N 2O4 is 50% dissociated at this 0
4) K  e G / RT
temperature and one atmosphere pressure the
52. For a particular reversible reaction at tem-
standard free energy change is
perature T, H and S were found to be both
1) -863.8 Jmol-1 2) -963.8 Jmol-1
3) -973.8 Jmol-1 4) -796.9 Jmol-1 +ve. If Te is the temperature at equilibrium,
47. For a spontaneous reaction the G , the reaction would be spontaneous when
equilibrium constant (K) and ECell will be
0
[AIEEE-2010]
respectively 1) Te  T 2) T  Te
1) -ve,>1,-ve 2) -ve,<1,-ve
3) +ve,>1,-ve 4) -ve,>1,+ve 3) Te is 5 times T 4) T  Te

53. In a fuel cell methanol is used as fuel and 12. H  U  nRT
oxygen gas is used as an oxidizer. The reaction 13. Heat of the gas is lost as work is done by the gas
3 14. C P  CV  R ; q  CV T
is CH 3OH l   O2  g   CO2  g   2H 2O l  At 298K
2
Since W =0 U  q  W ; U  q
standard Gibb’s energies of formation for
q
CH 3OH  l  H 2O  l  and CO2  g  are -166.2, 15. C P 
T
-237.2 and 394.4kJ mol 1 respectively. If 16. C2 H 4  3O2  2CO2  2 H 2O
standard enthalpy of combustion of methanol is 28 gm  1411 KJ
726kJ mol 1 , efficiency of the fuel cell will be ? 622 KJ
17. The rise in temperature depend on numbers of
[ AIEEE2009] equivalents of acid and base
1) 80% 2) 87% 3) 90% 4) 97% 18. 2m mol - T1 4m mol - 2T1
54. On the basis of the following thermochemical 19. 0.25 x 57.3 kJ
20. 0.05 mol H++0.05 mol OH-
data :  fG 0 H   aq   0  [AIEEE2009]
21. P4  6 Br2  4 PBr3 H  486KJ
H 2O  l   H   aq   OH   aq  ; H  57.32kJ
Limiting Reagent = P4 excess reagent = Br2
1 124 gm  -486 KJ
H 2  g   O2  H 2 O  l  ; H  286.20kJ 2.63 gm  ?
2
22. H  msT
The value of enthalpy of formation of OH  ion
23. H sol n  H L.E  H H . E
at 250 C is
24. H  57.3KJ because of more hydration energy
1) -22.88kJ 2) -228.88kJ
3) +228.88kJ 4) -343.52kJ of F  ion
Key Level -III 1
25. mole of O2  90 KJ
01) 1 02) 3 03) 4 04) 1 05) 3 06) 2 4
07) 2 08) 1 09) 3 10) 2 11) 4 12) 4 1 mole  ?
26. Definition of bond enthalpy
13) 2 14) 2 15) 2 16) 2 17) 1 18) 4
19) 4 20) 2 21) 1 22) 4 23) 2 24) 2 27. CH 4  2O2  CO2  2 H 2 O ; H  H P  H R
25) 1 26) 4 27) 1 28) 2 29) 3 30) 4 28. ii, iii are exothermic
29. Enthalpy change is dependent on physical state
31) 3 32) 2 33) 2 34) 1 35) 3 36) 1 30. Standard definition
37) 3 38) 1 39) 4 40) 3 41) 2 42) 1 31. -420 + 168
43) 4 44) 4 45) 2 46) 4 47) 4 48) 2 0.3
49) 1 50) 4 51) 3 52) 2 53) 4 54) 2 32. H ioni  HWA/ SB  H SA/ SB  100
1.5
Hints Level -III H  U  ( PV
33. 2 2  PV
1 1)
2880 25 120
1.   34&35. H  H R  H P
180 100 100 36. O- will resist the addition of another electrons
2. The heat of neutralization for any strong acid and 37. Wrev > Wirr
strong base is -13.7 k Cal/mole at 250C
3. Gas > liquid > solid 1 1
38. I 2  Cl2  ICl ; H  H R  H P
V2 2 2
4 to 6. W  2.303nRT log V 39. H  U  nRT
1
40. 120 - 349 - 381
8. W  nRT
41. N 2  3H 2  2 NH 3
7,9. W  PV
42. G 0  H 0  T S 0
10. U  Q  W
11. First law of thermodynamics
SR-MAIN-CHEM-VOL-II
H 1. Process, A  B represents
43. S  S P  S R ; S 
T 1) Isobaric 2) Isochoric
V2 3) Isothermal 4) Adiabatic
44. S  2.303nR log V 2. The pressure at C is
1
T2 1) Zero 2) 1.642 atm

45. S  2.303nC p log T 3) 0.0821 atm 4) 0.821 atm
1
46. N 2O4 2 NO2 3. Work done in the process C  A is

1 0 1) Zero 2) 8.21 L atm
1-0.5 2  0.5 3) 16.2 L atm 4) Unpredictable
Total Moles = 1.5 ; G 0  2.303RT log K p 4. The process which occurs in going from,
47. G  GP  GR B  C is
48. II Law 1) Isothermal 2) Adiabatic
49. G 0  H 0  T S 0 3) Isobaric 4) Isochoric
50. G  Wmax II. PASSAGE : Work is the mode of transfrence
0
of energy. If the system involves gaseous
51. G   RT ln K  eq  substance and there is difference of pressure
52. G  0 at equilibrium between system and surroundings, such a
G work is referred to as pressure - volume work
53. G  GP  GR ,Efficiency of fuelcell   100
H WPV   Pext V  . It has been observed that
1   reversible work done by the system is the
54. H 2  O2  H  OH H  228.88KJ
2 maximum obtainable work. wrev  wirr
Level -IV The works of isothermal and adiabatic
processes are different from each other. For
Exercise On Passages isothermal reversible proces,
Read the following passage and answer
the question V 
Wisothermal reversible=2.303nRT log10  2 
I. PASSAGE : Graph for one mole gas is given  V1 
below
Wadiabatic reversible  CV  T1  T2 
A B 5. If w1 , w2 , w3 and w4 are work done in
20L
isothermal, adiabatic, isobaric and isochoric
reversible processes, then the correct
Vo l u m e
sequence (for expansion) would be:

1) w1  w2  w3  w4 2) w3  w2  w1  w4
10L 3) w3  w2  w4  w1 4) w3  w1  w2  w4
6. Calculate work done when 1 mole of an ideal
gas is expanded reversibly from 20 L to 40 L
at a constant temperature of 300 K.
200K 400K
1) 7.78 KJ 2) -1.73 KJ
Temperature
3) 11.73 KJ 4) -4.87 KJ

7. A thermodynamic system goes in acyclic IV PASSAGE : The change in Gibbs free energy
process as represented in the following P-V of the system alone provides a criterion for
diagram: the spontaneity of a process at constant
temperature and pressure. A change in the
free energy of a system at constant
temperature and pressure will be:
Pressure
Gsystem  H system  T S system

11. The free energy for a reaction having
H  31400 cal , S  32cal K 1 mol 1 at 10000 C
1) 9336 cal 2) 7386 cal
3) 1936 cal 4) 9336 cal
Volume
12. For a spontaneous reaction G , equilibrium
0
' K ' and Ecell will be respectively:
The net work done during the complete cycle
is given by the area: 1) ve,  1,  ve 2) ve,  1,  ve
1) Cycle ACBDA 2) AA1 B1 BDA 3) ve,  1, ve 4) ve,  1, ve
3) AA2 B2 B 4) Half of area bonded by curve. 13. For a system in equilibrium, G  0, under
conditions of constant....
III. PASSAGE : G is a thermodynamic prop erty
the decrease in which value is the measure of 1) Temperature and pressure
useful work done at constant temperature and 2) Temperature and volume
pressure : 3) Pressure and volume
4) Energy and volume
Gsystem  0  spon tan eous  ;
Match the Following Equations
Gsystem  0  equilibrium  ; 14. LIST - I LIST - II
Gsystem  0  non  spon tan eous  ; A) H P  H R 1) Exothermic
Free energy is related to the equilibrium B) PV 2) Total heat content
constant, as G 0  2.0303RT log10 Kc C) E  PV 3) H is positive
8. If both H and S are negative, the reaction D) H R  H P 4) Zero at constant
will be spontaneous: volume
1) At high temperature 2) At low temperature The correct match is
3) At all temperature 4) At absolute zero A B C D A B C D
9. A reaction has positive values of H and S 1) 3 4 2 1 2) 2 3 1 4
3) 1 3 4 2 4) 1 3 4 2
from this you can deduce that the reaction:
15. LIST - I LIST - II
1) Must be spontaneous at any temperature
2) Cannot be spontaneous at any temperature A) HNO3  KOH 1. 55.22 KJ
3) Will be spontaneous only at low temperature B) NH 4 OH  CH 3COOH 2. 58.7 KJ
4) Will be sponatneous only at high temperature
10. For a reaction to be spontaneous at all C) CH 3COOH  NaOH 3. 57.3 KJ
tempeautres: 4. - 51.46 KJ
1) G  ve, H  ve and S  ve The correct match is
A B C A B C
2. G  ve, H  ve and S  ve
1) 1 2 3 2) 4 3 2
3. G  ve, H  ve and S  ve 3) 3 4 1 4) 3 2 1
4. G  ve, H  ve and S  ve
SR-MAIN-CHEM-VOL-II
16. LIST - I LIST - II LIST-II
A) Work 1) Extensive proopety 1) Spontaneous only at low temperature
B) Enthalpy 2) Intensive property 2) Spontaneous only at high temperature
C) Temperature 3) State variable 3) Spontaneous at all temperature
D) P,V,T and n 4) Path function 4) Non-Spontaneous at all temperature
The correct match is The correct match is
A B C D A B C D A B C D A B C D
1) 4 1 2 3 2) 1 2 3 4 1) 1 3 2 4 2) 2 1 3 4
3) 4 3 2 1 4) 4 3 1 2 3) 2 3 1 4 4) 1 2 3 4
17. LIST - I LIST - II Assertion & Reasoning
(melting of ice) (condition) 1) Both (A) and (R) are true and (R) is the
A) Ice at 100 C 1. G  O correct explanation of (A)
2) Both (A) and (R) are true and (R) is not the
B) Ice at 100 C 2. G  Ve
correct explanation of (A)
C) Ice at 00 C 3. G   Ve 3) (A) is true but (R) is false
The correct match is 4) (A) is false but (R) is true
A B C A B C 20. Assertion (A): Internal energy change in a cyclic
1) 1 2 3 2) 3 2 1 process is zero
3) 2 3 1 4) 1 3 2 Reason (R): Internal energy is a state function.
18. LIST-I 21. A: Heat of neutralization of HClO4 with NaOH is
A) C ( s, graphite)  O2  g   CO2  g  same as that of HCl with NaOH
B) C (s, graphite)  C  g  R: Both HCl and HClO4 are strong acids

22. A: The enthalpy of formation of H 2O  l  is greater
1
C) CO  g   O2  g   CO2  g 
2 than that of H 2O  g 
D) CH 4  g   C  g   4 H  g  R: Enthalpy change is negative for the condensa-
List-II tion reaction H 2O  g   H 2O  l 
1) H 0 combustion 23. A: Absolute values of internal energy cannot be
determined
2) H 0 formation R: It is impossible to determine the exact values of
3) H 0 atomization constituent energies of the substances.
24. A: Mass and volume are extensive properties.
4) H 0 sub lim ation R: Mass / volume is also an extensive property.
The correct match is Key Level -IV
A B C D A B C D 01) 2 02) 2 03) 3 04) 3 05) 4 06) 2
1) 1 2 3 4 2) 2 4 1 3 07) 1 08) 2 09) 4 10) 4 11) 1 12) 1
3) 2 3 1 4 4) 1 3 2 4 13) 1 14) 1 15) 3 16) 1 17) 3 18) 2
19. LIST-I (sign of H and S ) 19) 1 20) 1 21) 1 22) 1 23) 1 24) 3
A) &
B) &
C) &
D) &

SR-MAIN-CHEM-VOL-II
6. What is the value of change in internal energy
LEVEL-V at 1 atm in the process?
SINGLE ANSWER TYPE QUESTIONS H 2O  l ,323 K   H 2O  g , 423K 
1. Identify the correct statement for change of Given : CV , m  H 2O, l   75.0 JK 1 mol 1 ;
Gibb’s energy for a system  G system  at H vap at 373K  40.7 KJ / mol
constant temperature and pressure:
A) if G system  0 , the system is still moving in a C p,m  H 2O, g   33.314 JK 1 mol 1
particular direction A) 52.91 kJ / mol B) 43086kJ / mol
B) if G system   ve , the process is not C) 42.6 kJ / mol D) 49.6kJ / mol
spontaneous 7. The standard enthalpy of formation of octane
C) if G system   ve , the process is spontaneous (C8H18) is -250kJ/mol. Find the enthalpy of
combustion of C8H18. Given the enthalpy of
D) if G system  0 , the system has attained formation of CO2(g) and H2O(l) are -394 kJ/
equilibrium mol and -286kJ/mol respectively
2. One mole of an ideal gas  C V  20 J K 1 mol 1  A) -5200 kJ/mol B) -5726 kJ/mol
C) -5476 kJ/mol D) -5310kJ/mol
initially at STP is heated at constant volume 8. The enthalpy of combustion at 25°C of H2,
to twice the initial temperature. For the cyclohexane (C6H12) and cyclohexene (C6H10)
process, W and q will be are –241,–3920 and –3800 kJ/mol respectively.
A) W  0;q  5.46 kJ B) W  0;q  0 The heat of hydrogenation of cyclohexene is:
C) W  5.46 kJ;q  5.46 kJ A) –121 kJ mol–1 B) +121 kJ mol–1
D) W  5.46 kJ;q  5.46 kJ C) –242 kJ mol–1 D) +242 kJ mol–1
9. Calculate the enthalpy change when 50 mL of
3. Calculate Q and w for the isothermal
reversible expansion of one mole of an ideal 0.01 M Ca(OH)2 reacts with 25 mL of 0.01 M
gas from an initial pressure of 1.0 bar to a final HCl . Given that Ho neutralization of a strong
pressure of 0.1 bar at a constant temperature acid and a strong base is 14 kcal mol–1
of 273 K respectively. A) 14 cal B)3.5 cal C)10 cal D)7.5 cal
A) 5.22kJ, - 5.22kJ B) -5.22 kJ, 5.22 kJ 10. Stearic acid [CH 3  CH 2 16 CO2 H ] is a fatty
C) 27.3kJ, -27.3 kJ D) -27.3 kJ, 27.3 kJ
4. When 1 mole of gas is heated at constant acid, the part of fat that stores most of the
volume. Temperature is raised from 298 to energy. 1.0g of stearic acid was burnt in a bomb
308K. Heat supplied to the gas is 500 J. Then calo rimeter. The bomb had a heat capacity of
which statement is correct? 652 J/0C. If the temprature of 500g water
A) q=–W=500 J, U  0  c  4.18 J / g C 
0
rise from 25.0 to 39.30C,
B) q  U  500J, W  0 how much heat was released when the stearic
C) q  W  500J, U  0 acid was burned ? [Given CP(H2O)=4.18J/g0C]
D) U  0,q  W  500J A) 39.21 kJB) 29.91kJ C) 108kJ D) 9.32 kJ
5. A heating coil is immersed in a 100g sample 11. A 0.05 L sample of 0.2 M aqeous hydrochloric
of H2O(l)at 1 atm and 1000C in a closed vessel. acid is added to 0.05 L of 0.2 M aqeous
In this heating process, 60% of the liquid is ammonia in a calorimeter. Heat capacity of
converted to the gaseous form at constant entire calorimeter system is 480 J/K. The
pressure of 1 atm. The densities of liquid and temperature increase is 1.09 K.  r H 0 in kJ/
gaseous water under these conditions are
1000kg/m 3 and 0.60kg/m 3 respectively. mol for the following reaction is:
Magnitude of the work done for the process HCl  aq.  NH 3  aq.  NH 4Cl  aq 
is A) -52.3 B) -61.1 C)-55.8 D) -58.2
A) 4997 J B) 4970 J C) 9994J D)1060J
SR-MAIN-CHEM-VOL-II
12. At 250 C , 1 mole of MgSO4 was dissolved in 17. 1 mole of an ideal gas A  Cv , m  3 R  and 2
water, the heat evolved was found to be 91.2
 3 
kJ. One mole of MgSO4 7H 2O on dissolution mole of an ideal gas B are  Cv ,m  R  taken
 2 
gives a solution of the same composition
accompained by an absorption of 13.8kJ. H in a container and expanded reversible and
for the reaction adiabatically from 1 litre to 4 litre s t a r t i n g
from initial temperature of 320K. E for
MgSO4  s   7 H 2O  l   MgSO4 7 H 2O  s  is the process is :
A) -105 kJ/mol B) 77.4kJ / mol A) -240R B) 240R C) 480R D) -960R
C) 105kJ / mol D) 77.4kJ/mol 18. When 1.0g of oxalic acid (H2C2O4) is burnt in
13. The enthalpies of neutralization AOH and a a bomb calorimeter whose heat capacity is
strong base BOH by HCl are -12250 cal/mol 8.75 kJ/K, the temperature increases by 0.312
and -13000cal/mol respectively. When one K. The enthalpy of combustion of oxalic acid
mole of HCl is added to a solution containing at 270 C is
1 mole of AOH and 1 mole of BOH, the A) -245.7 kJ/mol B) -2.43.45 kJ/mol
enthalpy change was-12500 cal/ mol. In what C) -246.95 kJ/mol D) -241.95 kJ/mol
ratio is the acid distributed between AOH and 19. One mole of an ideal gas is subjected to a
BOH respectively. reversible cyclic process as shown in figure.
A) 2:1 B) 2:3 C) 1:2 D) 3:2 the max. temperature attained by the gas
14. Substance A2 B  g  can undergo during the cycle
decomposition to form two set of products 4bar
B
0
A2(g) + B(g); DH = 40kJ | mole
A2B(g) P
A(g) + AB(g); H0 = 50kJ | mole
1bar
If the molar ratio of A2  g  to A  g  is 5:3 in A
a set of product gases , then the energy
involved in the decomposition of 1 mole of
1 litre 2 litre
A2 B  g  is: V
A)48.75 kJ/mol B) 43.25 kJ/mol A) 7/6R B) 12/ 49R C) 49/12R D) 12/7R
C) 46.25 kJ/mol D) 64.2 kJ/mol
15. What is the bond enthalpy of Xe  F bond if  5 
20. A gas  Cv ,m  R  behaving ideally was
Ionization energy of Xe =279 kcal/mol  2 
B.E.  F  F   38 kcal / mol , electron affinity allowed to expand reversibly and adiabatically
from 1 litre to 32 litre. It’s initial temperature
of F=85kcal/mol
A) 24kcal/mol B) 34kcal/mol was 327 0 C . The molar enthalpy change (in J/
C) 8.5 kcal/mol D) 16.2 kcal/mol mol) for the process is :
16. In the conversion of lime stone to lime: A) -1125R B) -675 C) -1575R D) 1012R
CaCO3  s   CaO  s   CO 2  g  The values of 21. For polytropic process PV n  constant , C m
–1 (molar heat capacity ) of an ideal gas is given
Ho and So are 179.1 kJ mol and 160.2
JK–1 mol–1 respectively at 298 K and 1 bar. by:
Assuming H o and So remains constant with R R
temperature, at which minimum temperature A) Cv , m   n  1 B) Cv , m  1  n 
conversion of lime stone to lime will be
spontaneous: R
A) 1118 K B) 1008 K C) 1200 K D) 845 K C) Cv , m  R D) C p, m   n  1

SR-MAIN-CHEM-VOL-II
22. 2 mole of an ideal monoatomic gas undergoes
a reversible process for which PV2=C. The gas 28. Calculate  f G 0 for  NH 4Cl , s  at 310 K.
is expanded from initial volume of 1L to final  f H0  NH4Cl, s  314.5 KJ / mol, rCp  0
volume of 3L starting from initial temprature
of 300K. H for the process is : S0N2(g) 192JK1mol 1, S0H2 (g) 130.5JK1mol1
A) -600R B) -1000R C) -3000R D)-2000R
23. The enthalpy of neutralization of a weak S0Cl2(g)  233JK1mol1 , S0NH4Cl(s) 99.5JK1mol1
monoprotic acid (HA) in 1 M solution with a All given data at 300 K.
strong base is -55.95 kJ/mol. If the unionized A) 198.56 kJ / mol B) 426.7 kJ / mol
acid requires 1.4 kJ/mol heat for its complete C) 202.3 kJ / mol D) -84-5 kJ /mol
ionization and enthalpy of neutralization of the
strong monobasic acid with a strong 29. Calculate  f H 0  in kJ / mol  for Cr2 O3 from
monoacidic base is -57.3 kJ/mol. What is the
the  r G 0 and the S 0 values provided at 270 C
% ionization of the weak acid in molar
solution? 4Cr  s   3O2  g   2Cr2O3  s  ;
A) 1% B) 3.57% C) 35.7% D) 10%
24. If enthalpy of hydrogenation of C6H6(l) and  r G 0  2093 kJ / mol
C6H12(l) is -205kJ and resonance energy of
S 0  J / K mol  : S 0  Cr , s   24;
C 6 H 6 (l) is -152kJ/mol then enthalpy of
J K 1 mol 1
S 0  O2 , g   205; S 0  Cr2O3 , s   81
hydrogenation of is Assume A)-2258.1 kJ /mol B) -1129.05 kJ/mol
C) -964.35 kJ/mol D) 3462kJ/mol
Hvap of C6 H6  l  , C6H8  l  , C6H12  l  are equal
A) -535.5 kJ /mol B) -238 kJ/mol MULTIPLE ANSWER TYPE QUESTIONS
C) -357 kJ/mol D) -119 kJ/mol 30. The value of
25. 3 mole of a diatomic ideal gas which is heated
and compressed from 298 K and 1 bar to 596 H transition of C  graphite   C (diamond)
K and 4 bar S is is 1.9 kJ/mol at 250C entropy of graphite is
higher than entropy of diamond. This implies
5 that
[Given : Cv , m  gas   R;
2 A) C (diamond) is more thermodynamically stable
ln  2   0.70; R  2 cal K 1 mol 1 ] than C (graphite ) at 250C
B) C (graphite) is more thermodynamically stable
A) 14.7 cal K 1 B) 14.7 cal K 1 than C (diamond ) at 250C
C) diamond will provide more heat on complete
C) 4.9 cal K 1 D) 6.3 cal K 1
combution at 250C
26. One mole of an ideal monoatomic gas at 270C is D)
subjected to a reversible isoentropic compression
until final temperature reached to 327 0 C . If the Gtransition of C  diamond 
is -ve
initial pressure was 1.0 atm then find the value of  C  graphite 
ln P2 : (Given : ln 2  0.7 ) 31. Select the correct statements:
A) 1.75atm B) 0.176atm C)1.0395 atm D) 0 atm A) temperature can be raised in an insulated
27. For a perfectly crystalline solid system by doing electrical or mechanical work
B) temperature can be lowered in an insulated
C p,m  aT 3  bT , where a and b are constant , system by doing electrical or mechanical work
C) temperature cannot be lowered in an insulated
If C p ,m is 0.40 J/K mol at 10 K and 0.92 J/K
system by doing electrical or mechanical work
mol at 20 K , the molar entropy at 20K is D) temperature cannot be raised in an insulated
A) 0.92J/K mol B) 8.66 J/K mol system by doing electrical or mechanical work
C) 0.426 J/K mol D) 8.314 J/K mol

SR-MAIN-CHEM-VOL-II
32. Select the correct statements: 38. A 250 W electric heater raised the temperature
A) State of a system is assumed to be in internal of a calorimeter by 4.22°C in 55s. When the
equilibrium and the temperature and pressure are oxidation of a methanol sample was carried out
uniform throughout the system in the same calorimeter, the temperature rose
B) Thermal drift ina system with time is more in from 22.49°C to 26.77°C. Then,
Dewar flask than in insulated system. A) The amount of heat supplied by the electric
C) Thermal drift in a system with time is more in heater is 13.75 kJ
non-insulated system than in in1sulated system. B) The amount of heat supplied by the electric
D) Thermal drift in a system with time is more in heater is 4.6 kJ
insulated system than in non-insulated system C)The enthalpy of change for the oxidation is 1.39 kJ
33. Which are not correct representation at D) The enthalpy of change for the oxidation is 13.9 kJ
equilibrium: 39. Choose the correct statements:
V
1 S/ R
A) The enthalpy of combustion of a fuel per gram
A) V  e B) K  eG o
/ RT (expressed without a negative sign) is called its
2
specific enthalpy
V2 S / RT P2 H / RT B) The enthalpy of combustion of a fuel per gram
C) V  e D) P  e (expressed without a negative sign) is called its
1 1
34. Which of the following statements is/are enthalpy density

correct C) The enthalpy of combustion of fuel per litre
A) Absolute value of internal energy can’t be determined (expressed without a negative sign) is called its
B) Absolute value of heat content can be determined specific enthalpy
C) Absolute value of entropy can be determined D) The enthalpy of combustion of fuel per litre
D) All the three E, H and S are extensive properties (expressed without a negative sign) is called its
35. Predict in which of the following, entropy enthalpy density
increases: 40. 200 g of water is contained in a beaker of mass
A) A liquid crystallizes into a solid. 150 g at 20°C. The temperature of water is
B) Temperature of a crystalline solid is raised required to be raised to 80°C. It is given that
from 0 K to 115 K. the specific heat of water is 4.184J/(g°C) and
C) 2NaHCO3(s)  Na2CO3(s)+CO2(g)+H2O(g) of glass is 0.78J/(g°C). Then
D) H2(g)  2H(g) A) Heat required by water is 50.2 kJ
B) Heat required by glass is 7.0 kJ
36. The vapour pressure of solid benzoic acid has
C) Heat required by glass 9.4 kJ
been found to obey the relationship (in the
D) Total heat required is 57.2 kJ
P b 41. Which one of the following is correct for a
neighbourhood of 298 K) as: ln o
a ;
P T cyclic process as shown in figure?
where a = 22.88 and b = 1.07×104K Which of
the following values are correct at 298 K for
the sublimation of benzoic acid?
A) G o  32.34 kJ mol1 B) Ho  88.96kJ mol1 30
o 1 1 o 1
C) S  190 JK mol D) H  88.96kJ mol
37. Select the incorrect statements about the plots P 10
of ln K vs 1/T
G o kPa
A)Linear with slope equal to and intercept H
R
B) Curve 10 3 30
o o
V in m
H S
C) Linear with slope and intercept A) dU  0 B) q   w
R R
D) none of these C)W =314 J D)W = 31.4 J

SR-MAIN-CHEM-VOL-II
42. Select the correct statements for the 46. He, N2 and O3 are expanded adiabatically and
equilibriun under standard conditions their expansion curvesbetween P and V are
H 2O( s )   H 2O( l ) ; S1  plotted under similar conditions.About the ratio
of the slopes, which one is correct;
H 2O( l )   H 2O( v ) ;  S 2 A)the ratio of slopes of P-V curves for He and O3
is 1.25
H 2O( s )   H 2O( v ) ; S3 B)the ratio of slopes of P-V curves for He and N2
A) S1  S 2 B) S 2  S1 is 1.20
C)the raio of slopes of P-V curves for N2 and O3 is
C) S3  S 2 D) S3  S1 1.05.
D)the slope of He is least steeper and for O3 is most
2 Fe2O3 s   4 Fe s   3O2 g  ; steeper.
43. Given 0  , 47. Heat of neutralisation of strong acid and
 G1  1487kJ mol
strong base under I atm and 250C is -13.7 kcal.
6CO g   3O2 g   6CO2 g  ; If standard Gibbs energy change for
dissociation of water to H+ and OH- is -
 r G20  1543.2kJ mol 1
19.14kcal,the change is standard entropy for
correct statement is:
dissociation of water in cal K 1 mol 1 is;
0
A)  r G for reduction of iron oxide by CO is A)18.25 B)110.2 C)-18.25 D) none of these.
+56.2 kJ mol-1 48. One mole of CH3COOH undergo dimerization
B) Fe2O3 can be reduced by CO spontaneously in vapour state at 127 0 C as
C) Fe2O3 cannot be reduced by CO spontaneously
D) The reduction of Fe2O3 takes part in higher part
2CH3COOH  g   CH3COOH 2  g  if dimer
of blast furnace formation is due to two H-bonds involved in
44. Whic of the following is correct for the change dimer, each of 33kJ strength and the degree
shown below? of dimersation of acetic acid 98.2% which is
 r S 1
correct
aA  bB   cC  dD A) S 0 for dimerization is negative
(298 K ) (298)
B) S 0 for dimerization is positive
 r S 2    r S 4
C) S 0 for dimerization is -104.1J/mol

3
aA  bB  S
 cC  dD D) S 0 for dimerization is + 1.04J/mol
(0 K ) (0 K )
49. Work done in expansion of an gas from 4 litre
    
A)  r S1  cSC  dS D  (aS A  bS B ) to 6 litre against a constant external pressure
of 2.5 atm was used to heat up 1 mole of water
B)  r S2    aS A  bS B  at 293 K. If specific heat of water is 4.184Jg-
1 -1
k , the final temperature of water is nearly ?
C)  r S3  0. 4)  r S 4   cSC  dS D  A)300K B)456K C)278K D)600K
45. Which of the following figures given below 50. 2 mole of a perfect gas at 27 0 C if is
shows adiabatic process; compressed reversibly and isothermally from
III a pressure of 1.01105 Nm2 to 5.05 106 Nm2
compression which is correct among the following
A) work done on the gas is 1.9518x104J
expansion IV B) Free energy change for the process is
P P -1.9518x104J
I C) work done on the gas is 1.19  107 J
II D) Free energy change for the process is -
V V 1.19x107J
A) II,III B) I,III C) II,IV D) I,IV

SR-MAIN-CHEM-VOL-II
3 A) HA aq  BOH  aq BA aq  H2O -42.3

51. If one mole of an ideal gas with Cv  R is
2 B) HA g   BOH  g   BA aq  H2O -93.0
heated at a constant pressure of 1 atm 250 c
C) HA  g   H   aq   A  aq  -55.7
to 1000 C. Which is correct
A) U during the process is 223.51cal D) B   aq   OH   aq   BOH  aq  -20.0
B)  H during the process is 372.56 cal COMPREHENSION TYPE QUESTIONS
C) entropy change during the process is Comprehension–1
1.122 cal k mol 1 1 The bond dissociation energy of a diatomic molecule
is also called bond energy. However, the bond
D) U , H are same for the process dissociation energy depends upon the nature of
52. One mole of an ideal gas is subjected to a two bond and also the molecule in which the bond is
step reversible process as shown in figure. present. The bond energy of N — H bond in NH3
is equal to one-third of the energy of dissociation
 A  Band B C the pressure at A and C is of NH3 because there are three N-H bonds and
same. The correct statement(s) is/are those of C — H bond in CH4 is equal to one-
(1,100) fourth of the energy of dissociation of CH4. H e a t
of a reaction = Bond energy of reactants - Bond
A B(3,600) energy of products
P(atm)
55. The enthalpy changes for the reaction

H 2 O (g)  H (g)  OH (g) and
C(13,00)
OH (g)  O(g)  H(g) are 501.87kJmol1 and
T(K)
423.38kJmol1 . The bond enthalpy of O-H bond
A) Work involved in the path AB is zero is
B) In the path AB work will be done on the gas by A) –462.625 kj mol–1 B) 462.625 kJ mol–1
the surroundings C) -713.54 kJ mol–1 D) 713.54 kJ mol–1
C) Volume of gas at C= 3 volume of gas at A 56. In which of the following , the bond enthalpy
and bond dissociation enthalpy are identical?
D) Volume of gas at B is 16.42 litres A) H- H bond enthalpy in H2 (g)
53. The normal boiling point of a liquid ‘X’ is 400K. B) O-H bond ehthalpy in H2O (g)
Which of the following statement is true C) C- H bond enthalpy in CH4(g)
about the process X  l   X  g  ? D) N- H bond enthalpy in NH3 (g)
57. Find the bond ehthalpy of S-S bond from the
A) At 400 K and 1 atm pressure G  0 following data.
B) At 400K and 2 atm pressure G  ve C2H5 - S-C2H5 (g) H0f = -147.23 kJ mol–1
C) at 400K and 0.1 atm pressure G  ve C2H5 - S-S-C2H5 (g) H0f = -201.92 kJ mol–1
D) at 410 K and 1 atm pressure G  ve 0
S (g) Hf = 222.80 kJ mol–1
54. From the following data, mark the option (s) A) –277.49 kJ mol–1 B) 277.49 kJ mol–1
where H is correctly written for the given C) –349.15 kJ mol D) 349.15kJmol–1
–1
reaction. Given
H   aq   OH   aq   H 2O  l  ; Comprehension–2
The first law of thermodynamics was gives as q = U
H  57.3 kJ + (-w); where q is heat given to a system and U
H of HA  g   70.7kJ / mol represents increase in internal energy and -w is work
solution
done by the system. Various processes such as
 H solution of BOH  g   20kJ / mol isothermal, adiabatic, cyclic, isobaric and isochoric
process in terms of first law of thermodynamics leads
H ionization of HA  15kJ / mol and BOH is a for important results. The molar heat capacity for 1
mole of monoatomic gas is 3/2R at constant volume
strong base Reaction H r  kJ / mol  and 5/2R at constant pressure.

SR-MAIN-CHEM-VOL-II
58. Which of the following statements are correct: Comprehension–3
1) Both work and heat appears at the Enthalpy of neutralization is defined as the enthalpy
boundaries of system. change when 1 mole of acid/base is completely
2) Heat given to a system is given +ve sign. neutralized by base/acid in dilute solution. For strong
3) Heat given to a system is equal to increase acid and strong base neutralization net chemical
in internal energy under isothermal conditions
4) Heat given to a system is used to increase H   aq   OH   aq 
internal energy under isochoric conditions change is
 H 2 O  l  ;  r H 0  55.84kJ / mol
5) Both work and heat are not state functions
but their sum (q + w) is state function. H 0 ionization of aqueous solution of strong acid and
A) 1,2,4,5 B) 1,3,4,5 C) 1,2,3,4 D) 2,3,4,5 strong base is zero. When a dilute solution of a
59. A system is allowed to move from state A to B
weak acid or base is neutralized, the enthalpy of
following path ACB by absorbing 80 J of heat
neutralization is some what less because of the
energy. The work done by the system is 30J.
The work done by the system in reaching state absorption of heat in the ionization of the weak acid
B from A is 10 J through path ADB which or base for weak acid /base
statements are correct: H 0 neutralization  H 0 ionization   r H 0
H 
 OH   H 2O 
61. If enthalpy of neutralization of
CH 3COOH by HCl is -49.86 kJ /mol then
enthalpy of ionization of CH 3COOH is
1. Increase in internal energy from state A to
A) 5.98 kJ/mol B) 5.98kJ / mol
state B is 50 J.
2. If path ADB is followed to reach state B, C) 105.7kJ / mol D) 10.57kJ/mol
U  50 J 62. What is H for complete neutralization of
0
3. If work done by the system in path AB is 20

strong diacidic base A  OH  2 by HNO3
J, the heat absorbed during path AB = 70J.
4. The value UC - UA is equal to UD - UB. A) -55.84 kJ B) -111.68 kJ
5. Heat absorbed by the system to reach B C) 55.84kJ / mol D) -49.86kJ/mol
from A through path ADB is 60 J. 63. Under the same conditions how many mL of
A) 1, 5 B) 1, 3, 5 C) 1, 2, 3, 5 D) 1, 4, 5
60. 1 mole of a monoatomic gas is expanded 0.1 M NaOH and 0.05 M H 2 A (strong diprotic
through path ABC as shown in figure. acid) solution should be mixed for a total
volume of 100 mL produce the highest rise in
temprature
A) 25: 75 B) 50:50 C) 75: 25 D) 66. 66:33.33
Comprehension–4
Work done by the system in isothermal reversible
V2
Select the correct statements : process is : wrev. = -2.303 nRT log V . Also in
1) If specific heat of gas are 0.125 and 0.075 1
cal/g, the mol. wt. of gas = 40. case of adiabatic reversible process work done by
2) Temperature at point A, B, C are 273, 546 nR
and 273 K respectively. the sytem is given by : wrev. = [T2  T1 ] . During
3) U for the process A to B is 2.27 kJ.  -1
4) U for the process B to C is 3.44 kJ. expansion disorder increases and the increase in
5) U for the overall cycle A  B  C  A disorder is expressed in terms of change in entropy
is 3.4 kJ.
A) 1,2,3,4 B) 3,4,5 C) 1,3,4 D) 1,2,5

SR-MAIN-CHEM-VOL-II
q rev. MATRIX MATCHING

S  . The entropy changes also occurs
T 68. Match the following
during transformation of one state to other and
Column – I
H A) Free energy change G of a reaction
expressed as T  . Both entropy and
T B) Enthalpy change of a reaction in standard state H0
enthalpy changes obtained for a process were taken C) Entropy change S of a reaction
as a measure of spontaniety of process but finally D) Free energy change of a reaction in standard state
it was recommended that decrease in free energy Column – II
is responsible for spontaniety and  d G 
2  d ln K 
G  H  T S . p) - RTlnK q) RT   r) – nFE s)   
 dT  P  dT  P
64. Which of the following statements are correct:
1) The expansion work for a gas into vacuum is 69. Match the column:
equal to zero. Column – I
2) 1 mole of a gas occupying 3 litre volume on A) Joule Thomson coefficient for ideal gas
expanding to 15 litre at constant pressure of 1 atm B) Svap , m for liquids which does not undergo
does expansion work 1.215 kJ. association and dissociation
3) The maximum work done during expansion of C) Work done in adiabatic irreversible expansion
16 g O2 at 300 K from 5 dm3 to 25 dm3 is 2.01 of an ideal gas
kJ. D) Work done in adiabatic reversible expansion
4) The S for S  L is almost negligible in of an ideal gas
Column – II
comparison to S for L  G .
p) 88 J mol-1 K-1 q) nCv m  T2  T1 
V
5) S = 2.303 nR log 2 . (at constant T)
V1  T2 P2 
A) 2,3,4,5 B) 1,2,3,4,5 r) 0 s) nRT1  T  P 
 1 1 
C) 1, 2 D) 4, 5
70. Columm - I
65. The heat of vaporisation and heat of fusion of
A) Heating of an ideal gas at constant pressure
H2O are 540 cal/g and 80 cal/g. The ratio of
B) Compression of liquid at constant temperature
Svap . C) Reversible process for an ideal gas at constant
for water is:
S fusion temperature
D) Adiabatic free expansion of an ideal gas
A) 6.75 B) 9.23
Columm - II
C) 4.94 D) 0.2
p) H = nCp,m T q) U = 0
1
66. Ag2O(S)  2Ag(S) +
 O2 (g) ; attains  P2 
2 r) G = V P s) G = nRT In  P 
 1
equilibrium at temperature...K is: (The H
71. Columm - I
and S for the reaction are 30.5 kJ/ mol and
A) H+ (aq)
66 J/ mol/ K)
B) H(g)
A) 462.12 B) 237 C) 373 D) 273
C) H2(g)
67. A chemical change will definitely be
D) C (s, diamond)
spontaneous if :
Columm - II
A) H = -ve, S = -ve and low temperature p)  fHº = 0
B) H = +ve, S = -ve and high temperature q)  fHº > 0
C) H = -ve, S = +ve and any temperature r)  fGº = 0
D) H = +ve, S = +ve and T S<H s)  fSº < 0

SR-MAIN-CHEM-VOL-II
72. Column - I 76. Statement – 1: Phase transition involves change
A) An ideal gas in internal energy only.
B) A real gas at inversion temperature Statement – 2: Phase transition occurs at constant
C) H2 gas at STP pressure.
D) NH3 gas at STP 77. Statement – 1: The work done in an open container
Column - II at 300 K, when 112 g of iron reacts with dil. HCl is
[Under adiabatic free expansion] 1200 cal.
p) Temperature increases
q) Temperature decreases Statement – 2: Work done = Pext V2  V1  ,
r) Temperature remains constant where V 1 and V2 are initial and final volume of
s)Temperature first increases and then decreases reaction mixture & Pext is external applied pressure.
73. The feasibility of a chemical reaction can be 78. Statement – I: Many endothermic reactions that
explained based on DH, DS and DG, so an- are not spontaneous at room temperature become
swer the following : spontaneous at high temperatures.
Column-I Statement – II : Energy of the system increases
A) 2O3(g)  3O2(g) with increase in temperature.
B) 3O2(g)  2O3(g) 79. Statement – 1: In the case of an ideal gas the
change in Gibbs free energy and Helmholtz free
C) NH2COONH4(s)  2NH3(g) + CO2(g)
Lowtemp

.
D) Ice(s) H2O (l) at room temperature 25ºC energies are equal to each other  G  A for
Column–II isothermal reversible process.
p)  H = +ve,  S = –ve Statement – 2: There is no change in internal
q)  H = –ve,  S = +ve energies and enthalpies for ideal gas at constant
r)  G = +ve s)  H = –ve t)  G = –ve temperature.
80. Statement – I: The heat absorbed during the
74. Match the following :
isothermal expansion of an ideal gas against vacuum
Column-I
is zero.
A) H2(g) B) H2O(l) C) C(diamond) D) NO(g)
Statement – II : The volume occupied by the
Column–II
molecules of an ideal gas is zero.
p)  Hfº = 0 q)  Gfº = 0
81. Statement – 1: For a reaction at equilibrium, the
r) Entropy at absolute zero = 0
free energy for the reaction is minimum.
s) Entropy at absolute zero  0
Statement – 2: The free energy for both reactants
t)  GFº  0 (u)  Sfº = 0
and products decreases and become equal.
STATEMENT TYPE QUESTIONS 82. Statement – I: CP – CV = R for ideal gas.
75. Statement – 1: For a process to be  dU 
Statement–II :    0 for ideal gas CP–CV
spontaneous, G as well as S has to be less  dV T
than zero.  dU 
Statement – 2: For spontaneous change, = R is correct statement  dV   0 is also correct
 T
Stotal  0
a) Statement-1 is true, Statement-2 is true,  dU 
But because    0 Therefore, to say CP –
Statement-2 is a correct explanation for statement-  dV T
1 CV = R is not a correct reasoning.
b) Statement-1 is true, Statement-2 is true, 83. Statement – 1: The amount of heat change during
Statement-2 is not a correct explanation for the isothermal free expansion of an ideal gas is zero.
statement-1 Statement – 2: There are no intermolecular forces
c) Statement-1 is true, Statement-2 is false of attraction among the gas molecules, in case of
d) Statement-1 is false, Statement-2 is true real gas at a given pressure.

SR-MAIN-CHEM-VOL-II
84. Statement – 1 : The enthalpy of formation of 93. Statement – 1: A reaction which is spontaneous
H2O(l) is greater than of H2O (g). and accomapnied by decrease of randomness must
Statement – 2: Enthalpy change is negative for be exothermic.
the condensation reaction H2O (g)  H2O(l) Statement – 2: All exothermic reactions are
85. Statement – 1 : Heat of neutralisation of H3PO4 accompanied by decrease of randomness.
with NaOH is more than that of HCl with NaOH.
94. Statement – 1 : Many endothermic reactions that
Statement – 2 : H3PO4 is a triprotic acid and hence
releases more heat on complete neutralization, while are not spontaneous at room temperatures become
HCl is a monoprotic acid. spontaneous at high temperature.
86. Statement – 1: Work done by the surrounding on Statement – 2 : DHº of the endothermic reaction
the system of an ideal gas to do a particular isothemal increases with increase in temperature.
compression reversibly is less than that done 95. Statement – 1 : Decrease of free energy during
irreversibly. the process under constant temperature and
Statement – 2: Isothermal reversible compression pressure provides a measure of its spontaneity.
takes place through infinite number of infinetesimally
small steps. Statement – 2 : A spontaneous change must have
87. Statement – 1 : The magnitude of the work involved + ve sign of DSsystem.
in an isothermal reversible expansion is greater than 96. Statement – 1 : All combustion reactions are
that involved in an adiabatic reversible expansion. exothermic.
Statement – 2 : Adiabatic expansion is associated Statement – 2 : Enthalpies of products greater
with fall in temperature of the system which in turn than enthalpies of reactants (SvpD fH(P) >
decreases the pressure of the system to a lower
SvRDfH(R))
value than that in isothermal process.
97. Statement–1: Due to adiabatic free expansion
88. Statement – 1 : For every chemical reaction at
temperature of real gas may increase.
equilibrium, standard Gibbs energy of reaction is
zero. Statement – 2 : In adiabatic free expansion,
Statement – 2: At constant temperature and temperature is always constant irrespective of real
pressure, chemical reactions are spontaneous in the or ideal gas
direction of decreasing Gibbs energy. 98. Statement – 1: Under adiabatic free expansion ,
89. Statement – 1 : There is a natural asymmetry
between converting work to heat and converting  dU 
  is + ve when attractive forces are dominant
heat to work.  dV  T
Statement – 2 : No process is possible in which between gas molecules [U, V, T respresent internal
the sole result is the absorption of heat form a energy, volume and temperature of gas respectively]
reservoir and its complete conversion into work. Statement – 2: Internal energy is a state function.
90. Statement – 1 : Entropy change in reversible
adiabatic expansion of an ideal gas is zero. 99. Statement–1 : At low temperatures, DH is the
Statement – 2: The increase in entropy due to dominant factor for spontaneity of a reaction.
volume increase just componsate the decrease in Statement – 2: At low temperatures, the opposing
entropy due to fall in temperature. factor TDS remains very small.
91. Statement – 1 : The standard free energy changes 100.Statement–1 : A reaction which is spontaneous
of all spontaneously occuring reactions are negative. and accompanied by decrease of randomness must
Statement – 2: The standard free energies of the
exothermic.
elements in their standard states at 1 bar and 298
K are taken as zero. Statement–2 : All exothermic reactions are
92. Statement – 1 : Enthalpy and entropy of any accompanied by decrease of randomness.
elementary substance in the standard states are INTEGER TYPE QUESTIONS
taken as zero.
101. Temperature of one mole of helium gas is
Statement – 2 : At absolute zero, particles of the
perfectly crysalline substance become completely increased by 10 C, find the increase in internal
motionless. energy in cal.

SR-MAIN-CHEM-VOL-II
102. An ideal gas is taken through the cycle MATRIX MATCHING TYPE QUESTIONS
A  B  C  A As shown in figure. If net 68. (A-r),(B-q),(C-s),(D-p)
heat supplied to the gas in the cycle is 5j. Find 69. (A – r) ; (B – p) ; (C – s) ; (D - q)
the work done by the gas in the process C  A 70. (A - p);(B- r);(C -q,s); (D - q,s );
in Joule (taken mole value) 71. (A - p, r);(B - q);(C - p,r);(D - q,s)
Vm3 72. (A - r) ; (B – r) ; (C - p); (D - q).
C B
73. (A - q, t) ; (B - p, r) ; (C - r) ; (D - t)
V
74. (A – p,q,s,u);(B – s, t, u);(C – r, t);(D–s,t)
STATEMENT TYPE QUESTIONS
A 75.(D) 76. (D) 77. (A) 78(C) 79.(A) 80.(B) 81.(A)
P 10 N/m2 82 (B) 83 (C) 84 (A) 85 (D) 86 (A) 87 (A) 88 (D)
103. If 2kcal heat is given to a system and 6 kcal 89 (A) 90 (A) 91 (B) 92 (D) 93 (C) 94 (C) 95 (C)
work is done on the system then the internal 96 (C) 97 (C) 98 ( B) 99 (A) 100 (C)
energy of system will increase by how many INTEGER TYPE QUESTIONS
kcal? 101 (3) 102 (5) 103 (8) 104 (5) 105 (8) 106 (7)
104. The constant volume molar heat capacity of an ideal
LEVEL(V) - HINTS
gas is expressed by Cv , m  16.5  102 T (All values
SINGLE ANSWER TYPE QUESTIONS
are in SI units). If 2.5 mol of this gas at constant
valume is heated from 270 C to 1270C, the 1. G system   ve , the syst em is spontaneous
internal energy increases by “x” kJ. Hence, x process, G system  0 , the system has attained
is
105. Molar enthalpy of vaporization of a liquid is equilibrium G system   ve , the system is non
2.6 kJ. If boiling point of this liquid is 1770c, spontaneous.
the molar entropy of vaporization (in JK-1) unit 2. W  PV  P  0  0
is Q  CV  T   20  273  5460 J  5.46 kJ
106. The echemical reaction : A  P H  2.8kJ 3. In isothermal process change in internal energy is
is spontaneous only above 400 K. Therefore, 0, so q=-w
4. At constant volume PV  0 , Q  U
 S of reaction must be at least  JK  .
1
5. w   Pext V f  Vi 
LEVEL -V - KEY
SINGLE ANSWER TYPE QUESTIONS  60 103 40 103 100 103 
 105    
1. D 2. A 3. A 4. B 5. C 6. C 7. C  0.60 1000 1000 
8.A 9. B 10.A 11.A 12.A 13.A 14.B
15.B 16.A 17.D 18.D 19.C 20.C 21.B  105 100  10 3  0.04  10 3  0.1  10 3  ;
22.B 23.B 24.D 25.D 26.A 27.C 28.A w  9994 J
29.B
U1
MULTIPLE ANSWER TYPE QUESTIONS 6. H 2O  l ,323 K     H 2O  l ,373K 
30.(B,C) 31.(A, C) 32.(A, C) 33.(A, C, D)
34.(A,D) 35.(B,C,D) 36.(A,B,C) 37.(A, B)  U 2
38.(A) 39.(A,D) 40.(A,B,D) 41.(A,B,C) U
H 2 O  g , 323 K  3
 H 2 O  g , 373 K 
42.(B,C,D) 43.(B) 44.(A,B,C) 45.(A)
46.(A,B,C) 47.(A) 48.(C) 49.(A) CV , m  H 2O, g   33.314  8.314
50.(A,B) 51.(A,B,C) 52.(C,D) 53.(A,B,C) 54.(A,B,C) U 2  H 2  ng RT  37.6 ;
COMPREHENSIVE TYPE QUESTIONS
55.(B) 56.(A) 57.(B) 58.(A) 59.(C) 60.(A) U total  U1  U 2  U 3
61.(A) 62.(B) 63.(B) 64.(B) 65.(C) 66.(A)  Cv, m  l  T  U vap  Cvap  Cvm  g  T
67.(C)

SR-MAIN-CHEM-VOL-II
75  50 25  50 x 2
  37.6   42.6 kJ / mol 13. 750 x  500  x  2 / 3 and y  1 / 3 So, 
1000 1000 y 1
7.  r H 0  8   394   9   286    250  14. 40 x 5/8 + 50 x 3/8=43.25
 5476kJ / mol 15.  r H   Heat supplied    Heat evolved 
1
H 2  g   O 2  g   H 2 O  l   H  241kJ  .(i) 292   4 x  279  38  85
8.
2
 x  34kcal / mol
17 16. For spontaneous reaction G o   ve
C6 H10  O 2  g   6CO2  g   5H 2 O  l 
2
G o  H o  TSo ;  H o  TSo
 H  3800 kJ  ...(ii)
H o 179.10  103
C 6 H12  9O2  g   6CO 2  g   6H 2 O  l  or T    1118K
So 160.2
 H  3920 kJ  ...(iii) n1CV m1  n2 Cv.m2
Eq. (i) + eq. (ii) – eq. (iii) gives 17. Aev. Cv , m   2R
n1  n2
H  241  3800   3920   121kJ For adiabatic process dU=dW
for C 6 H10  H 2  C6 H12 dT R  dV 

9. Number of moles of HCl T Cv ,m  V 
MV 0.01 25
   25  105 ; HCl  H   Cl dV
1000 1000 n1CV , m1 dT  n2 CV , m2 dT   n1 RT  n2 RT  
n H  25  10 5
V
1/ 2
Number of moles of Ca(OH) 2 T2 1  V2   1 
ln   ln    T2  320    =160K
MV 0.01 50 T1 2  V1   4
   50  105
1000 1000
n OH   2  50  105  10 3
 
U  n1CV ,m1  n2CV , m2 T  960 R
In the process of neutralisation 25×10–5 mole H+ 1

18. H 2C2O4  l   O2  g   H 2O  l   2CO2  g  ;
will be completely neutralised 2
5
 H  140  25  10 kcal  0.035kcal  35cal 0.312  8.75
ng  3 / 2 ; U c    90
10. qreaction  qbomb  qwater 1
 245.7 kJ / mol ;
 qreaction   C  bomb    m water  c    T
H  U  ng RT
  652  500  4.18   14.3  39210 J or 39.21kJ
3 8.314  300
11. m mole of acid  0.05  0.2  0.01  245.7     241.95 KJ / mol
2 1000
480  1.09 19. Max temp attained by gas in between B to C.
r H 0   52.32 kJ / mol
0.01 1000 Accroding to equation of straight line
12. Given that ;  r H1  91.2kJ / mol .......(i) P  4 V 1

1  4 2 1
 P  4  3V  3
MgSO4 7 H 2O  s    n  7  H 2O  P  7  3V For 1 mole gas
 MgSO4  nH 2 O  RT
 7  3V ; RT  7V  3V 2 ;
 r H 2  13.8 kJ / mol ....... (ii) V
dT 7
Equation (i) -(ii) or H hyd   r H1   r H 2 R  7  6V  0 ; V
dV 6
 91.2kJ / mol  13.8kJ / mol
 7 7 49
 105kJ / mol substituting in eq (1) RT   7  3  6   6  T  12 R
 

SR-MAIN-CHEM-VOL-II
 1 7
T2  V1   1 5
1
1 
2/5
T2 P1
20.  
T1  V2 
; T2  T1   = 600  5  25. S  nC p m ln T  nR ln P
 32  2  1 2
2 7
 600  0.5   150K ; H m  2 R  150  600   1575R 7  596  1
 3  R ln    3R ln 1
21. dU  dp  dw ; nCv, m .dT  nCm dT  P.dV ; 2  298  4  6.3 cal K
P.dV 26. For isoentropic process S system  0

Cm  Cv , m  ....... (1)
n.dT T2 P
 nC p m ln  nR ln 1  0
PV n  K and PV  nRT  KV 1 n  nRT T1 P2
K 1  n  V  n .dV  nRdT 5  600 
 ln  P2    ln   ;=1.75 atm
2  300 
dV nR

dT K 1  n V  n ............ (2) ; 27. 0.40  aT13  bT1 ; 0.40  a  1000   b  10
R 0.4  1000a  10b ........(1)

From Eqs (1) and (2) Cm  Cv , m  1  n  0.92  aT23  bT2  0.92  a  8000  20b ..(2)
2 2 from Eqs (1) and (2) a  2 105 , b  0.038
22. PV
2 2  PV
1 1
2 aT 3  bT
P2  V1  T PV V 1 Sm   .dT
   Now, 2  2 2  1  T
P1  V2  T1 PV1 1 V2 3
a T23  T13 
300   b T2  T1 
 T2   100 K ; H  nC p , m T 3
3
 0.426 J / K  mol
5
 2  R   200K   1000R 28.  f S 0  NH 4Cl , s  at 300 K
2
23. HA  H   A ;  r H  1.4kJ / mol 0 1 1 
 SNH 4 Cl  s 
  SN0 2  2S H0 2  SCl0 2 
H neutralization  H ionization   r H 2 2 
 374JK 1 mol 1   rC p  0
H 
 OH   H 2 O 
0 0
55.95  H ionization  57.3   f S310   f S300  374 JK 1 mol 1
0 0
H ionization for 1M HA=1.35 kJ/mol % heat  f H 310   f H 300  314.5
utilizsed by 1M acid for ionization 0
 f G310   f H 0  310S 0
1.35
  100  96.43% 310  374 
1.4  314.5   198.56kJ / mol
so, acid is 100-96.3 =3.57% ionizsed 1000
29.  r G 0   r H 0  T   r S 0
 r S 0  2  81  4  24  3  205 J / mol
R.E
H Hyd(Theoretical)   r H 0  2258.1 kJ / mol
24. .  r H 0  2   f H 0  Cr2O3 , s 
H Hyd(Actual)
2258.1
  f H 0  Cr2O3 , s   
 205  152  357 2
 1129.05kJ / mol .
Enthalpy of hydrogenation of 357
 119 kJ / mol
3

SR-MAIN-CHEM-VOL-II
MULTI ANSWER QUESTIONS  for gas 1

30. C  graphite   C  diamond  46. (d)Ratio of slope   for gas II ; slope for
H   ve; S  ve, So, the transition is non He, N 2 and O3 are 7/5,5/4 and 4/3 respectively..
spontaneous at all temperatures.
31. Temperature can be raised in an insulated system. G 0  H 0  T S 0 H 0
47.
32. (a) definition of state for H 2 o H   OH  is  13.7 kcal
(c) thermal drift is more in non-insulated system
H   G 
0
33. G  G  RT ln K eq At equillibrium S  
T
G  0  G 0   RT ln K eq 48. 2CH 3 COOH  g  CH 3COOH 2  g 
v2 T 1 0
 S  sys  nR ln  nCv ln 2 0.982
v1 T1 1-0.982
34. Internal energy depends upon large no. of factors, 2
U = Etra + Erot + Enuclear + Evib...... The exact  CH3COOH 2 0.982
calculation is not possible. K0  2
 2
 1515.4
35. Increase in randomness increases the entropy.  CH3COOH  2   0.018
36.  P 0  1 atm Now, H 0 for dimerization
1 1  2  33kJ  66kJ
ln P  b.  a  ln K p  b.  a Thus, G 0  H 0  T S 0
T T
Peq  P benzoic acid   K p 2.303 RT log K 0  H 0  T S 0
2.3038.314 400log 1515.4  66103  400 S 0
0 0
H 1 S
37. ln K eq  .   24359.2   66000  400  S 0
R T R
38. Heat supplied by electric heater is = 250 J/sec x 41640.8
S 0    104.102 J / mol
55 sec = 13.75 kJ 400
39. refer to standard definition 49. Since, work is done against constant pressure
40. q  msT for water and glass process is irreversible.
41. For a cyclic process dU=0 Given, V  (6  4)  2 litre, p = 2.5 atm
 q  U    w  q  w w   pext  V  2.5  2  5 litre-atm
Also, w= area covered by sphere 5 1.987 5 1.987  4.187
 cal   J  506.31J
2
 (V V   (20)2 0.0821 0.0821
 r 2   2 1   1003.14 314 J
 2  22 C=4.184J/g/Kor4.184J/mol
Now this work is used in heating 1 mole water
42. H 2O( s ) has more ordered arrangement.Also
W  n  C  T 506.31
   
 S 2  S H  SH 1
;  S0  S H 2o( l )  S H 2o( s )
2o( v ) 2o( l )  1 4.184  T  T  6.723

 SH is maximum and thus S 2  S1 Final temp = T1  T  293  6.723  299.723K
2 o( v )
43. G for 2Fe2O3  600  4Fe  6CO2  rG1 rG2 p1

50. reversible process: Wrev  2.303nRT log10 p
2
=+1487-1543.2=-56.2 kJmol 1 . The reduction
occurs spontaneously in lower part of blast furnace. 1.01 105
 2.303  2  8.314  300 log10
5.05 106
44.  r S4   S p   S R  CSc  dS D  0  0  1.9518 104 joule
45. Adiabatic slope are more steeper than isothermal. Since W reversible is a measure of free change
Slope of adiabatic process=   slope of isothermal
process  G  Wrev  Wmax  1.9518 10 4 J

SR-MAIN-CHEM-VOL-II
3 3 5 each refers the reaction H2(g)  2H(g); BE

51.  Cv  R  C p  Cv  R  R  R  R
(H - H) = 433.93 kJ mol-1
2 2 2
 Heat given at constant pressure  m.C p .T 57. BE (S - S); Hvap (s)  { H0f (C2H5S  SC 2H5 )}
or Now work done in the process   PV = Hvap (s)  H0f = H0f (C2H5  S  C2H5 )
5 5
H or q p 1  R 373 298  or H 1 1.98775 372.56 cal
2 2 = 222.80-{-201.92-(-147.23)}=277.49 kJ mol-1
 nRT2 nRT1  58. (A) q = U + PV at T=constant, q= PV
w   p V2  V1    p   
 p p  59. ACB=AC+ BC, ADB=AD+BD Heat absorbed
 pv  nRT  80 J. Work done by the system = 10 Jw  10 J
 w = -30 Also w=-10J  UB-UA = 50 J
  nR  T2  T1   1 1.987   373  298 
 q = 50 + 10 = 60 J
 149.225cal
R
 from I law of thermodynamics 60. Cp - Cv = At A, P = 1 atm. V = 22.4 L
U  q  W  372.56  149.05 M
 U  223.51 cal Also, dqrev  nC p .dt 2
 0.125 - 0.075 =  273  T = 273 K
M
dqrev nC p .dt
ds   ds   M=40 At B, P=1atm. V=44.8 L  T=546K
T T At C, P = 0.5 atm., V = 44.8 L  T = 273 K
T2 nCp .dT T Also At constant V
or S  T1  nCp loge 2
T T1 U  P  V U  Cv  T
T2 1 22.4
 s  2.303 nC p log10 T = 1  22.4 L atm =  8.314 J
1 0.0821
5 373 = 0.075  40  4.12
 2.303  1 R  log10  1.122 cal k 1 mol 1
2 298 = 2268.37 J= 3.44 kJ = 2.27 kJ
1 R  100 1 R  600 61. 55.84  x  49.86
52. At VA   100 R VB   200 R
1 3 62. A  OH 2  2 HNO3  2 H 2O  A  NO3  2 ;
VB  VA so expansion of gas takes place
 55.84  2
VB  200  0.0821  16.42 L
63. For max rise in temp; max neutralization of
400 k
53 X  liq  1atm
X  g  ; G  0 H  and OH  required if we take equal volume,
54 (a) 57.3   15  (b) 70.7  20  15  57.3 all H  ( 5 m-mole) will react with all OH  (5m -
(c) 70.7  15 mole)
COMPREHENSION TYPE QUESTIONS 64. 1) In free expansion Pext  0  w  0
55. The enthalpy of dissociation of the O-H bond
depends on the molecular species from which 2) W  115  3  12lit  atm
H-atom is being separated.  12 101.3J
H2O(g)  H(g) + OH (g); H0 = 501.87
16 25
k J mol -1 . However to break O-H bond in 3) Wrev  2.303   8.314  300  log
hydroxyl a different quant it y o f heat 32 5
(423.38 kJ mo l -1 ) is BE ( O-H)= 4) S for L  G is more
01.87kJmol1  423.38kJmol1
=462.625 kJ mol-1 v2
2
5)  S T  2.303 nR log v
56 In case of diatomic molecules, bond enthalpy and 1
bond dissociation enthalpy are identical because

SR-MAIN-CHEM-VOL-II
72. Ideal gas has no molecular attractions so no heating
540
65.  vap S  or cooling during expansion or contraction.
373
Above inversion temperature a real gas shows
80 heating effect.
f S 
273 73. (a) O2 is more thermodynamically stable than O3
66. At eq; G  0  H  T S  0 (c) 0 mol  3 mol
H (d) 00C is the melting point of ice so its melting is
T spontaneous at room temperature.
S
67. Conditions for spontaniety 74.  f H 0 and  f G 0 are zero for species in their
68 Refer to Important relation standard states.
69. (a) For an ideal gas inter molecular forces are zero from III law entropy of a perfectly crystalline solid
so no heating or cooling during expansion or is zero at 0 K.
contraction 75-100 Statement type questions.
(b) Trouton’s rule
 E 
(c) W  U  q  0  101.    CV
 T V
 nCv  T2  T1  E  CV T
 T2 P2  3
(d) W  nRT1  T  P  CV  R for monatomic gas
 1 1 2
70. (a) H  nC p T T  1K
3 3
(b) G  V P  S T  V P E  R   2  3 cal
2 2
(c) For an ideal gas U  f  T 
102. WAB  PV , WBC  0
at constant temperature U  0
q  U   WT 
dG  vdP  sdT  vdP
 U  0
nRT
dG  .dP
P  q  WT   WAB  WBC  WCA 
dP  5   10  0  WCA 
 dG  nRT 
P
or WCA  5 j
(d) q  0  adiabatic 
103.  E  W
Pext =0  w=0  Q free expansion  104. E  n  CV T
From I law; q  U  W  0  U  0 H
105. S 
0 0
71.  f H and  f G are zero for species in their T
standard states 106. G  H  T S
Graphite is more thermodynamically stable than
diamond ****

5. Given the following values for the standard molar
LEVEL-VI Gibbs free energy changes. ΔG 0 , at 250C
SINGLE ANSWER QUESTIONS Ag   aq   2 NH 3  l 

Ag  NH 3 2  aq 
1. A certain mass of gas is expanded from (1L,
1
10atm) to (4L, 5atm) against a constant ΔG 0  41.0 kJ  mol Ag  
external pressure of 1 atm. If initial
temperature of gas is 300 K and the heat Ag   aq   Cl   aq  AgCl  s 
capacity of process is 50 J/°C. Then the 1
ΔG 0  55.6 kJ  mol Ag  
enthalpy change during the process is (1L atm
~ 100 J) Calculate the value for the thermodynamic
equilibrium constant. K, at 250C for the reaction:
A)  H = 15 kJ B)  H = 15.7 kJ

C)  H = 14.4 kJ D)  H = 14.7 kJ AgCl  s 2NH3  l Ag NH32  aq Cl  aq
2. A sample containing 2.000 mol of helium gas A) 3.62x102 B) 1.00 C) 9.94x10-1 D) 2.76x10-3
originally at 298.15 K and 1.000 bar is coled 6. Consider a classroom that is roughly 5 m × 10m ×
to its normal boiling temperature of 4K, 3m. Initially t = 27°C and P = 1 atm. There are 50
condensed to a liquid and then cooled further people in an insulated class loosing energy to the
room at the average rate of 150 watt per person.
to 2K, where it undergoes another phase
How long can they remain in class if the body
transition to a second liquid form, called liquid
temperature is 42°C and person feels
helium II. A beam of laser light suddenly uncomfortable above this temperature. Heat
vaporizes this liquid phase, and the helium is capacity of air = (7/2) R. (in minutes)
brought to a temperature of 298.15 K and a A) 4.34 B) 5.91 C) 6.86 D) 7.79
pressure of 0.500 bar. The entropy change for 7. Consider the reaction:
the above process is 2 H 2  g   O2  g  2 H 2O  g 
A) 11.5 JK-1 B) -11.5 JK-1
When hyudrogen is ignited in the presence of
C) 23 JK-1 D) Insufficient information oxygen, a lot of heat is released and water is
3. An athelete is given 100 g of glucose (C6H12O6)
produced.At room temperature, the H r0n is about
of energy equivalent to 1560 kJ. He utilises 50
percent of this gained energy in the event. In -484 kJ/mol and Sr0n is about -87 kJ/mol. Given
order to avoid storage of energy in the body, this datahow wouldyouinterpretthis thermodynamic
the weight of water he would need to perspire process? Select the correct answer.
is- (The enthalpy of evaporation of water is 44 A) The reaction is exothermic (heat is released)
kJ/mole.) and it is becoming more ordered
B) The reaction is endothermic (heat is absorbed)
A)319 gm B)422 gm C)293 gm D) 378 gm
and it is becoming more disordered.
4. Consider the reactions C) The reaction is exothermic (heat is released)
(i)S (rhombic) + 3/2 O2(g)  SO3(g),  H1 (ii)S and it is becoming more disordered.
(monoclinic) + 3/2O2(g)  SO3(g),  H2 D) The reaction is endothermic (heat is absorbed)
(iii) S (rhombic) + O3(g)  SO3(g),  H3 and it is becoming more ordered.
8. A reaction from unknown reactants
(iv) S (monoclinic) + O3(g)  SO3(g),  H4
(R): R  P is molar entropy of the products
incorrect statement is (P) is measured to be 460 J/mol K, and 71.3kJ
A)  H1 <  H2 <  H4 (magnitude only) of heat was given off in the process to the
B)  H1 <  H3 <  H4 (magnitude only) surroundings when 1mol reacted, then the
C)  H1 <  H2 =  H3 <  H4 (magnitude only) molar entropy of the reactants has to be
A) at least -230 J/mol K B) at the most 690 J/mol K
D)  H1 +  H4 =  H2 +  H3
C) at the most 230 J/mol K D) at the least 690 J/mol K
211
VELAMMAL BODHI IIT ACADEMY
SR-MAIN-CHEM-VOL-II
9. One mole of a monatomic ideal gas initially 14. Given the following reactions :
at a pressure of 2.00 bar and a temperature I : N2(g) + 2O2 (g)  2NO2 (g),  H1 = 16.18 kcal
of 273 K is taken to a final pressure of 4.00 II : N2(g) + 2O2(g)  N2O4 (g),  HII = 2.31 kcal
bar by a reversible path defined by p/ Based on the above facts :
V=constant. Taking CV to be equal to 12.5 J A) NO2 is more stable than N2O4 at low temperature
B) N2O4 is more stable than NO2 at low temperature
U
mol-1 K -1 , the value of for this process C) both are equally stable at low temperature
w D) none of the above
is calculated to be 15. Enthalpy of polymerisation of ethylene, as
A) -3.0 B) -1.5 C) +1.5 D) +3.0 represented by the reaction,
10. A popular game is “splatball”, where people nCH2=CH2  (-CH2-CH2-)n is -100 kJ per
use pressurized CO2 cartridges to shoot paint- mole of ethylene. Given bond enthalpy of C=C
filled plastic balls at targets and at each other. bond is 600 kJ mol-1, enthalpy of C-C bond (in
A typical splatball gun takes a 1.00 L CO2 kJ mol) will be :
cartridge filled to 300 PSI pressure. How much A) 116.7 B) 350 C) 700 D) indeterminate
work is done as this cartridge is discharged 16. Haber's process for production of ammonia
(to atmospheric pressure) when the gun is (N 2 + 3 H 2  NH 3 ) requires 500º C
fired? (14.7 PSI=1 atm) temperature and 300 atmospheric pressure,
A) -20.41 J B) +19.41 J C) -1970 J D) -2070 J while blue - green algae (a type of vegetation)
11. The heat of formation of C2H5OH(l) is - 66 carry out the same reaction at ambient
kcal/mole. The heat of combustion of temperature & pressure by breaking down the
CH3OCH3 (g) is – 348 kcal/mole.  Hf for H2O activation energy barrier in many small
and CO2 are -68 kcal/mole and -94 kcal/mole interlinked steps. If  H1 &  H2 represent
respectively. Then the  H for the the enthalpy change for indicated reaction at
isomerisation reaction C 2 H 5 OH (l)  same reaction conditions by Haber's process
CH3OCH3(g), and  E for the same are & by blue - green algae respectively then :
A)  H = 18 kcal/mole,  E = 17.301 kcal/mole A)  H1 <  H2 B)  H1 =  H2
B)  H = 22 kcal/mole,  E = 21.408 kcal/mole C)  H1 >  H2 D)  H2 =  H1 + (  Cp) dT
17. A substance is carried through the following
C)  H = 26 kcal/mole,  E = 25.709 kcal/mole
transformations:
D)  H = 30 kcal/mole,  E = 28.522 kcal/mole
S1 S2
12. In the reaction AB2(l) + 2X2(g) AX2(g) + A B C
BX2(g)  H = – 270 kcal per mol. of AB2(l)
the enthalpies of formation of AX2(g) & BX2(g) S4 S3
are in the ratio of 4 : 3 and have opposite sign.
The value of  Hf0 (AB2(l)) = + 30 kcal/mol. D E
S5
Then
A)  Hf0 (AX2) = – 96 kcal /mol The equation S1  S2  S3  S 4  S5
B)  Hf0 (BX2) = + 480 kcal /mol A) Is true only if the steps are carried out reversibly
C) Kp = Kc &  Hf0 (AX2) = + 480 kcal /mol B) Is always true because entropy is a state function
D) Kp = Kc RT &  Hf0 (AX2) +  Hf0 (BX2) = C) May be true but need more information on the
–240 kcal /mol processes
13. When a certain amount of ethylene was D) Is incorrect
combusted, 6226 kj heat was evolved. If heat   5
18. At 27 0 C a gas    3  is compressed
of combustion of ethylene is 1411 kJ, the  
volume of O2 (at NTP) that entered into the reversible adiabatically so that its pressure
reaction is - becomes 1/8 of original pressure. Final
A) 296.5 ml B) 296.5 litres temperature of gas would be
C) 6226 × 22.4 litres D) 22.4 litres A) 420 K B) 300 K C) – 1420 C D) 3270 C
212
19. Select correct statement (s) 25. One mole of a non-ideal gas undergoes a
A) by trouton’s rule, entropy of vaporization of most change of state (2.0 atm, 3.0 L, 95 K)  (4.0
liquids is 88  5 J mol-1 K-1 at normal boiling point atm, 5.0 L, 245 K) with a change in internal
B) due to excessive H – bonding H2O (l) is most energy,  U = 30.0 L atm. The change in
ordered hence its entropy of vaporization is usually enthalpy (  H) of the process in L atm is
high A) 40.0 B) 42.3 C) 44.0
D) not defined, because pressure is not constant
0
 

C) H f H  aq .  0 D) all of the above 26. The reaction CH4(g) + Cl2(g)  CH3Cl(g) +
20. How many of the following variables can be HCl(g) has  H = –25 kCal.
used to specify the state of the system.
Internal energy, Composition, Pressure, Bond
Temperature, Volume, Work Bond Energy
A) three B) four C) five D) six kCal
21. A system undergoes two cyclic processes 1 and
2. Process 1 is reversible and process 2 is  C—Cl 84
irreversible. The correct statement relating to  H—Cl 103
the two processes is
 C—H x
A) S (for process 1) = 0, while S (for process
2)  0  Cl—Cl y
B) qcyclic = 0 for process 1 and qcyclic  0 for process 2 x:y= 9 :5
C) More heat can be converted to work in process
From the given data, what is the bond energy
1 than in process 2
of Cl—Cl bond (in k.cal)
D) More work can be converted to heat in process
A) 70 B) 80 C) 67.75 D) 57.75
1 than in process 2
27. The standard molar enthalpies for formation
22. A piece of zinc at a temperature of 20.0°C
weighing 65.38 g is dropped into 180 g of boiling of cyclohexane (l) & benzene (l) at 25°C are -
water (T = 100°C). The specific heat of zinc is 156 & + 49 kJ/mol respectively . The standard
0.400 J g–1 C–1 and that of water is 4.20 J g– enthalpy of hydrogenation of cyclohexene(l) at
1°C–1. What is the final common temperature 25º is - 119 kJ mol-1. The resonance energy of
reached by both zinc and water? benzene is
A) 97.3 °C B) 33.4 °C C) 80.1 °C D) 60.0°C A) 152 kJ mol–1 B) -240 kJ mol–1
23. Determine which of the following reactions at C) -152 kJ mol-1 D) 240 kJ mol-1
constant pressure represent systems that do 28. The value of log10K for a reaction A B
work on the surrounding environment
I.CaO (s) + CO2 (g)  CaCO3 (s) is :(Given : rH298K = –54.07 kJ mol –1 ,
II.NH4Cl (s)  NH3 (g) + HCl (g) r S 298K = 10 JK–1 mol–1 and R = 8.314 JK–1
III.2NH3 (g)  N2 (g) + 3H2 (g) mol–1 ; 2.303 x 8.314 x 298 = 5705)
A) I B) III C) II & III D) I and II A) 5 B) 10 C) 95 D) 100
24. The P-V diagram for the shown cyclic process 29. Find  G° and  H° for that the reaction
is a circle. The magnitude of the work done is: 1
V CO(g) + O (g)  CO 2 (g) at 300 K
2 2
V2 respectively are, when the standard entropy
change is – 0.094 kJ mol–1 K–1. The standard
V1 Gibbs free energies of formation for CO2 and
CO are – 394.4 and – 137.2 kJ mol –1 ,
P
P1 P2 respectively.
2 2 A)  G° = 257.2 kJ/mol,  H° = 285.4 kJ/mol
 V2  V1 
A)   P2  P1  B)    B)  G° = 514.4 kJ/mol,  H° = – 570.8 kJ/mol
 2   2 
C)  G° = +514.4 kJ/mol,  H° = 570.8 kJ/mol
 D)  G° = – 257.2 kJ/mol,  H° = – 285.4 kJ/mol
C) (P2 – P1) (V2 – V1) D) p (V2 – V1)2
4
213
SR-MAIN-CHEM-VOL-II
30. In conversion of lime-stone to lime, 34. One mole of an ideal monoatomic gas
CaCO3 (s)  CaO(s) + CO2 (g) the values of expands isothermally against constant
0 0 –1
 H and  S are + 179.1 kJ mol and 160.2 J/ external pressure of 1 atm from initial
K respectively at 298 K and 1 bar. Assuming volume of 1L to a state where its final
that  H° and  S° do not change with pressure becomes eq ual to external
temperature, temperature above which pressure. If initial temperature of gas is 300
conversion of limestone to lime will be K then total entropy change of system in the
spontaneous is above process is :
A) 845 K B) 1118 K C) 1008 D) 1200 K [R = 0.082 L atm mol–1 K–1 = 8.3 J mol–1K–1].
31. The change in free energy accompanied by A) 0 B) Rln (24.6)
the isothermal reversible expansion of 1 mol 3
of an ideal gas when it doubles its volume is C) R ln (2490) D) Rln (24.6)
2
 G1. The change in free energy accompanied 35. At 1000 K water vapor at 1atm has been found
by sudden isothermal irreversible doubling to be dissociated into H2 and O2 to the extent
volume of 1 mole of the same gas is G2. Ratio of 3 × 10–5 %. Calculate the free energy
of G1 and G2 is decrease of the system, assuming ideal
1 1 behaviour.
A) 1 B) 2
C) – 1 D) 
2 A) –G = 90,060 cal B) –G = 20 cal
32. The following curve represents the variation C) –G = 480 cal D) –G = – 45760 cal
of Gibbs function `G` with pressure at constant 36. Which of the following graphs best illustrates
temperature. the variation of entropy of a substance with
temp.
G c
svap
Sfus
S
b A)
a
tf tb T(K)
pressure (P)
Svap
Correct match of given plots with the physical B) S sfus
state of a substance is
A) c – solid , a – gas , b – liquid
B) c – gas , b – liquid , a – solid tf tb t(°C)
C) a – liquid , b – solid , c – gas
D) c – gas , b – solid , a – liquid
33. Which correctly represents the entropy (s) of Svap
an isolated system during a process. C) S Sfus
S
S
Tf Tb T(K)
B)
A) equilibrium equilibrium
Time Time
Svap
S S
equilibrium D) S Sfus
D)
C)
equilibrium
Tf Tb T(K)
Time Time
214
37. During winters, moisture condenses in the Path (A) represents a reversible isothermal
form of dew and can be seen on plant leaves expansion from P1V1 to P2V2. Path (B + C)
and grass. The entropy of the system in such represents a reversible adiabatic expansion
cases decreases as liquids possess lesser (B) from P1, V1, T1 to P3, V2, T2 followed by
disorder as compared to gases. With reference reversible heating the gas at constant volume
to the second law, which statement is correct, (C) from P3, V2 , T2 to P2, V2, T1. Path (D + E)
for the above process? represents a reversible expansion at constant
A) The randomness of the universe decreases pressure P1 (D) from P1, V1, T1 to P1, V2, T3
B) The randomness of the surroundings decreases followed by reversible cooling at a constant
C) Increase in randomness of surroundings equals volume V2 (E) from P1, V2, T3 to P2, V2, T1.
the decrease in randomness of system 41. What is qrev. for path (A)?
D) The increase in randomness of the surroundings
V2 V2 V2
is greater as compared to the decrease in A) zero B) nR ln V C) nRT1 ln V D) nRT1 ln V
randomness of the system. 1 1 1
38. A reactions is spontaneous if 42. What is qrev for path (B + C)?

A) H  0 B)  S(total) > 0 V2 V2 V2
C)  G<0 D)  U<0 A) zero B) nR ln V C) nR ln V D) nRT1 ln V
1 1 1
39. Which of the following expressions are correct
43. What is S for path (D + E)?
for an ideal gas?
T2
CV  T  V V
 U   U  A) zero B)  , dT C) nR ln 2 D) nR ln 2
A)  V   0 B)  P   0 T V1 V1
 T  T T1
 Cv   Cv  Paragraph – 2

C)  V   0 D)  P   0 Standard Gibb’s energy of reaction (rGº) at a
 T  T
certain temperature can be computed as rGº
40. Which of the following expressions are = rHº – T.rSº and the change in the value of
incorrect for a perfect gas ?  rHº and  rSº for a reaction with temperature
 Cv   U  can be computed as follows :
A)  T   0 B)  T   0  rHºT –  rHºT =  rCºP (T2 – T1)
 v  p 2 1

T 
 U   U   rSºT –  rSºT =  rCºP ln  2 
2 1  T1 
C)  P   0 D)  P   0
 T  T  rGº=rHº – T . rSº and by  rGº=– RT ln Keq.
COMPREHENSIVE TYPE QUESTIONS Consider the following reaction :
CO(g) + 2H2(g) CH3OH(g)
Paragraph–1
Given :  ƒHº (CH3OH, g) = – 201 kJ/mol ;
For an ideal gas, an illustration of three  ƒHº (CO, g) = – 114 kJ/mol Sº (CH3OH, g) =
different paths, A, (B + C) and (D + E) from 240 J/mol-K ; Sº (H2, g) = 29 JK–1 mol–1
an initial state P1, V1, T1 to a final state P2, V2, Sº (CO, g) = 198 J/mol-K ;
T1 as shown in the given figure. Cºp, m (H2) = 28.8 JK–1 mol–1
Cºp, m (CO) = 29.4 J/mol-K ;
P1,V1,T1 D P1,V2,T3  320 
Cºp, m (CH3OH) = 44 J/mol-K andln   =
 300 
E
A 0.06, all data at 300 K.
P
B P2,V2,T1 44. rSº at 300 K for the reaction is :
C
P3,V3,T2 A) 152.6 J/K-mol B) 181.6 J/K-mol
C) –16 J/K-mol D) None of these
45. rHº at 300 K for the reaction is (in kJ/mol)
V A) –87 B) 87 C) –315 D) –288
215
SR-MAIN-CHEM-VOL-II
46. rSº at 320 K is : Paragraph – 5
A) 155.18 J/mol-K B) 150.02 J/mol-K
J.W. Gibbs and H.Von Helmoltz had given two
C) 172 J/mol-K D) None of these
equation and are known as Gibbs-Helmholtz
47. rHº at 320 K is : equation. One equation can be expressed in
A) –288.86 kJ/mol B) –289.1 kJ/mol terms of change in free energy ( G) and
C) –87.86 kJ/mol D) None of these enthalpy (H) while other can be expressed in
48. rGº at 320 K is : terms of change in internal energy (E) and
A) –48295.2 kJ/mol B) –240.85 kJ/mol work function (W)
C) 240.85 kJ/mol D) –81.91 kJ/mol
 G 
Paragraph – 3 G = H + T . d   .......... (1)
 dT P
9.0gmice at0oCis mixedwith 36 gmofwaterat 50oCin  W 
athermallyinsulatedcontainer.usingthefollowingdata, W = E + T . d   .......... (2)
 dt  V
answerthequestionthatfollow: Where T is temperature equation (1) is
Cp (H2O) = 4.18 Jg–1 K–1; Hfusion (ice) = 335 J g–1 obtained at constant pressure while equation
49. Final temperature of water is (B) is obtained at constant volume system. It
A) 304.43 K B) 296.97 K is observed that for the reaction.
C) 303.93 K D) 287 K N2(g) + 3H2(g)  2NH3(g)
50.  Sice is Free energy change at 25°C is –33 kJ
A) 11.04 JK–1 B) 3.16 JK–1 while at 35°C is –28 kJ which are at a constant
C) 14.2 JK–1 D) 7.84 JK–1 pressure.
51.  Swater is 55. What would be the difference between enthalpy
A) –12.64 JK–1 B) –0.34 JK–1 change at 25°C and 35°C for a given reaction :
C) –5.42 JK–1 D) 12.64 JK–1 A) 4 kJ B) 5 kJ C) 3 kJ D) zero
52. What is the total entropy change in the 56. What would be the free energy change at 30°C-
process? A) 30.5 kJ B) 33 kJ C) –28 kJ D) –30.5 kJ
A) –1.56 JK–1 B) –1.60 JK–1 57. Internal energy change at 25°C is E1 while at
–1
C) 1.56 JK D) 1.60 JK–1 35°C is E2 then
Paragraph – 4 A) E1 = E2 B) E2 > E1 C) E1>E2 D) None of these
Liquid water freezes at 273 K under external Paragraph – 6
pressure of 1 atm. The process is at equilibrium For a reversible reaction at constant
H2O (l) H2O (s) at 273 K & 1 atm. temperature and at constant pressure the
However it was required to calculate the equilibrium composition of reaction mixture
corresponds to the lowest point on Gibbls
thermodynamic parameters of the fusion
energy Vs progress of reaction diagrams as
process occuring at same pressure & different
shown. At equilibrium Gibbs energy of reaction
temperature. Using the following data, answer
is equal to Zero.
the question that follow.
dice=0.9gm/cc ; dH2O(l)=1gm/cc ; CP[H2O(s)]=
36.4 JK–1mol–1; CP [H2O (l)] = 75.3 JK–1 mol–1; G
–1
 Hfusion = 6008.2 Jmol .
53. The value of "Hfusion" at 263 K & 1 atm will
be :
A) +6008.0 J mole–1 B) 5619.2 J mole–1 A
C) – 5619.2 J mole–1 D) 6619.2 JK–1 mol–1
54. " Sfusion " at 263 K & 1 atm will be : Reactants Products
A) 22.01 JK–1 mol–1 B) 22.84 JK–1 mol–1 Equilibrium

–1 –1 state
C) 21.36 JK mol D) 20.557 JK–1 mol–1
Progress of reaction
216
58. The value of log10 keq is equal to [keq is the 63. Column - I
equilibrium coustant] a) Van’t Hoff isochore b) Kirchhoff’s eq.
 Gº TSº– Hº Hº– T S º RT c) Clausius Clepeyron eq.d) Gibbs-Helmholtz eq.
A) – RT B) 2.303 RT C) RT D) TSº– Hº
Column - II
59. Which diagram represents the large value of
equilibrium constant for the reversible reaction P2 Hv  1 1 
p) ln P  R  T  T 
G G 1  1 2
B)   ( G ) 
q) G  H  T  T 
A)
 P
Reactants Products Reactants Products d ln K P H 0   ( G ) 
Progress of reaction Progress of reaction r)  2 s)  T   C p
dT RT  P
64. Column-I (Process for ideal gas)
G G A) Reversible isothermal expansion
B) Reversible adiabatic compression
C) D) C) Adiabatic free expnansion
D) Irreversible isothermal compression
Column-II (Entropy change)
Reactants Products Reactants Products
Progress of reaction Progress of reaction p) S surrounding  0 q) S surrounding  0
60. For a reaction
1 r) S surrounding  0 s) S system  0
M2O(s) ¾  2M(s) + 2 O2 (g)  H = 30 KJ/mol 65. Column-I
and  S = 0.07 KJ/mol /K at 1atm. The reaction A) heating of an ideal gas at constant pressure
would not be spontaneous at temperatures B) Compression of liquid at constant temprature
A) > 428 K B) < 428 K C) < 100 K D) > 100 K C) Reversible process for an ideal gas at constant
MATRIX-MATCHING QUESTIONS temperature
D) Adiabatic free expnasion of an ideal gas
61. Match Column - I with Column - II Column-II
Column - I
p) H  nC p.m T  0 q) U  0
A) C6 H12 O 6   aq  C6 H12 O 6  aq  ; H
 P2 
B) CaO   aq  Ca  OH 2  aq  ; H
r) G  V P s) G  nRT ln  P 
C) C  O 2  CO 2 ; H 298K  1
66. Column-I
D) Cgraphite  O 2  CO 2 ; H 298K
Column - II A) O2  g 
p) Exothermic q) Endothermic B) O3  g 
r) H is heat of reaction
s) H is heat of formation of CO2 C) Br2  g 
t) H is standard heat of fomration of CO2
62. Match Column - I with Column - II D) H 2O  l 
[SR - Rohmbic, SM - Monoclinic] Column-II
Column - I Column - II
p)  f H 0  ve;  f S 0  ve
A)  f H o  O 2 ,g  p) Zero
q)  f H 0  ve;  f S 0  ve
B)  f H o SR  q) Not equal to zero
C)  f H o SM  r) Most stable form r)  f H 0  ve;  f S 0  ve
D)  f H o  PWhite  s) Less stable form s)  f H 0  0  f S 0  0
217
SR-MAIN-CHEM-VOL-II
67. Column-I 71. Statement – 1 : Heat of neutralization of HCl by
NaOH is more than that by NH4OH
A)  Gsystem T , P Statement – 2: NaOH is stronger base than
B) Work done in reversible isothermal ideal NH4OH.
gas expansion 72. Statement – 1 : The change in internal energy and
C) G for reversible isothermal change in enthalpy does not depend upon path by
expansionof an ideal gas which change are brought in.
Statement – 2: Both are path independent and E
D) S gas for isothermal expansion of an
and H are state function
ideal gas 73. Statement – 1 : Entropy change of a process is
Column-II different when it is carried out reversibly and
V  P 
2
irreversibly..
q) nRT ln  P 
2
p) nR ln  V  Statement – 2: Entropy change is the amount of
 1   1 
heat absorbed at a given temperataure.
 P1  INTEGER TYPE QUESTIONS
r) nFE s) nR ln  P 
 2 74. The enthalpy change involved in the oxidation
68. Column-I
of glucose is 2880 kJ mol 1 . Twenty five
(Partial derivative)
percent of this energy is available for
 U   H   G   G  muscular work. If 100 kJ of muscular work is
A)  T  B)  T  C)  T  D)  P 
 V  P  P  T needed to walk one kilometer, what is the
Column-II maximum distance that a person will be able
(Thermodynamic varible) to walk after eating 125 g of glucose?
p) C p q) CV r) -S s) V 75. Calculate the enthalpy change when infinitely
dilute solutions of CaCl2 and Na2 CO3 are
ASSERTION & REASON QUESTIONS
mixed. H 0f for Ca2+ (aq), CO23   aq  and
Each question contains STATEMENT – 1
(Assertion) and STATEMENT – 2 (Reason). CaCO 3 (s) are 129.80,  161.65
Each question has 4 choices (A), (B), (C) and 1
and 288.45 kcal mol respectively..
(D) out of which ONLY ONE is correct.
76. An intimate mixture of ferric oxide and
(A) Statement-1 is True, Statement-2 is True;
aluminium is used as solid fuel in rockets.
Statement-2 is a correct explanation for
Statement-1 Calculate the fuel value per cm3 of the
(B) Statement-1 is True, Statement-2 is True; mixture. Heats of formation and densities are
Statement-2 NOT a correct explanation for as follows:
Statement-1. H f  Al2 O3   399kcalmol1 ;
(C) Statement-1 is True, Statement-2 is False
(D) Statement -1 is False, statement-2 is True H f  Fe2 O3   195.92kcalmol1
69. Statement – 1:The heat absorbed during the
isothermal expansion of an ideal gas against Density of Fe2O3  5.2 g / cm3 ;
vacuum is zero. Density of Al  2.7 g / cm3
Statement – 2: The volume occupied by molecule
77. Calculate the entropy change for the following
of an ideal gas is assume to be zero.
reversible process:
70. Statement – 1: For isothermal reversible expansion
the work done will be the maximum (Wmax)   Tin   Tin at 130 C
Statement – 2: The work done for the isothermal 1 mol at 1 atm 1 mol at 1 atm
reversible compression is taken as work done  H  2288Jmol1 
trans
minimum (Wmin)
218
78. Heat of neutralization between HCl and NaOH SUBJECTIVE TYPE QUESTIONS
is 13.7 k .cal . If heat of neutralization 89. One mole of an ideal gas is heated at constant
between CH3COOH and NaOH is 11.7 k .cal . pressure from 00C to 1000C
Calculate heat of ionization of CH3COOH. A)Calculate work done. B) If the gas were
79. A gas occupies 2 litre at STP. It is provided expanded isothermally and reversibly at 00C
58.63 joule heat so that its volume becomes from 1 atm to some other pressure P1 , what
2.5litre at 1 atm. Calculate change in its internalmust be the final pressure if the maximum
energy. work is equal to the work involved in (a)?
80. A sample of ideal gas    1.4  is heated at 90. Water is boiled under a pressure of 1.0
atm.When an electric current of 0.50A from a
constant pressure. If an amount of 85J of heat
12V. supply by passed for 300 s through a
is supplied to gas, find U . resistance in thermal contact with it. it is found
81. The free energy change when 1 mole of NaCl that 0.789 g of water is vaporized. Calculate
is dissolved in water at 298 K. is –x KJ find the molar internal emergy and enthalpy
out value of ‘x’ given– changes and enthalpy changes at boiling
(a) Lattice energy of NaCl  778 kJ mol 1 point(373.15K).
91. 14g oxygen at 00C and 10 atm are subjected
(b) Hydration energy of NaCl  775 kJ mol 1 to reversible adiabatic expansion to a pressure
(c) Entropy change at 300 K  40 J mol 1 of 1 atm.Calculate the work done in;
82. Calculate the maximum work done in kJ A) Litre atm. B) Calorie (Given, Cp / C v  1.4 )
expanding 16 g of oxygen at 300 K and 92. Calculate the equilibrium consthant for the
occupying a volume of 5 dm3 isothermally until reaction given below at 400 K if
0 1 0 1 1
H  77.2 kJ mol and S 122 JK mol
the volume becomes 25 dm3 . (Ignoring the sign
of value) PCl5  g   PCl3  g   Cl2  g 
83. What is the entropy change for the conversion 93. Calculate the free energy change when I mole
of one gram of ice to water at 167 K and one of NaCl is dissoved in water at 298 K .
1
atmospheric pressure?  H fusion  6.025 kJ mol  Given. A) Lattice energy of
84. The enthalpy of transition of crystalline boron NaCl  778 kJ mol 1 . B) Hydration energy of
to amorphous boron at 15000C is 0.4 kcal mole- NaCl  774.3 kJ mol 1
1
. Assuming at.wt of boron 10, the change in
enthalpy of transition 50g boron from C) Entropy change at 298 K=43 J mol 1. .
crystalline to amorphous form is 94. How much heat is required to change 10 g ice
0
85. At 0 C, if enthalpy of fusion of ice is 1365 kcal/ at 0 C to steam at 1000C? Heat of fusion and
mol. The molar entropy, change for melting of heat of vaporization for H2O are 80 and 540
ice at 00C is cal/g respectively.Specific heat of water is
86. A reaction becomes spontaneous only 1cal/g.
at 500K. If H at 500K is 3.0 kJ, the change 4 2
in entropy at 500K 95. The vapour pressure of benzene is 1.5310 Nm at
87. How much of the following are extensive 303K and 5.2  104 Nm2 at 333K. Calculate the
properties? Resistance, Electromotive force, mean latent heat of evaportion of benzene over this
Heat enthalpy, Dipole moment, Heat capacity, temprature range
Specific Heat, Denisity specific volume 96. Molar heat capacity of CD 2 O (deutero
88. How much of the following are intensive formaldehyde) at constant pressure is
properties? Vapour pressure , Molarity ,
Refractive index, Dielectric constant, Osmotic 14 cal mol 1 K 1 at 1000K. Calculate the
pressure, Molarity, Specific gravity, Molar entropy change associated with cooling of
volume 3.2g of CD2O vapour from 1000K to 900K
219
SR-MAIN-CHEM-VOL-II
97. I mole of an ideal gas at 250C is subjected to 103. The standard enthalpy of combustion at 25°C
expand reversibly ten times of its initial of hydrogen, cyclohexene (C 6 H 10 ) and
volume. Calculate the change in entropy of cyclohexane (C6H12) are –241, – 3800 and
expansions. –3920 kJ/mole respectively. Calculate the
98. The standard enthalpy and entropy changes heat of hydrogenation of cyclohexene.
for the reaction in equlibrium for the forward 104. Calculate enthalpy change of the following
direction are given as reaction:
CO( g )  H 2O( g ) CO2 ( g )  H 2 ( g ) H2C = CH2(g) + H2(g)   H3C - CH3(g).
The bond energy of C – H, C – C, C = C, H –
H   41.16 kJ mol 1
300 k H are 414,347,615 & 435kJ/mol respectively.
H 
 4.24  102 kJ mol 1 105. For the reaction, N 2 (g) + 3H 2 (g)  
300 k
2NH3(g); H = -95.4 kJ and S = -198.3J/K.

H  32.93 kJ mol 1 
Calculate the maximum temperature at which
1200 k S 1200k  32.93kJ mol 1
Caculate K P at each temperature and predict the reaction will proceed in forward direction.
106. Assume that for a domestic hot water supply
the direction of reaction at 300K and 1200
150 kg of water per day must be heated from
K,when PCO  PCO2  PH 2  PH 2O  1 atm at 10°C to 65°C and gaseous fuel propane C3H8
initial state. is used for this purpose. What moles & volume
99. At 300 K, the standard enthalpies of formation of propane ( in litre at STP ) would have to be
of C6H5COOH(s), CO2(g) and H2O(l) are -408, used for heating domestic water. ΔH for
-393 and -286 kJ/ mol respectively. Calculate combustion of propane is –2050 kJ/mol &
the heat of combustion of benzoic acid at 300 specific heat of water is 4.184 ×10–3 kJ/g.
(i) Constant pressure (ii) constant volume 107. A gas expands from 3dm3 to 5dm3 against a
100. The heat of combustion of glycogen is about constant pressure of 3atm. The work done
476 kJ/mol of carbon. Assume that average during expansion is used to heat 10 mole of
heat loss by an adult male is 150 watt. If we water of temperature 290 K. Calculate final
were to assume that all the heat comes from temperature of water. Specific heat of water
oxidation of glycogen, how many units of = 4.184 J/ g/K.
glycogen (1mole carbon per unit) must be 108. Diborane is a potential rocket fuel which
oxidised per day to provide for this heat loss? undergoes combustion according to the
101. Calculate H 0f for chloride ion from the reaction,
following data: B2H6(g) + 3O2(g)   B O (s) + 3H O(g)
2 3 2
1 1
From the following data, calculate the enthalpy
 HCl( g ) ; H 0f  92.4 kJ
H 2 ( g )  Cl2 ( g )  change for the combustion of diborane :
2 2
  3
 
 H ( aq )  Cl( aq ) ;
HCl (g) + nH2O  i) 2 B(s) +   O2(g) 
 B O (s) ;
 2 2 3
H 0  74.8 kJ H 0f H (aq )  0.0 kJ

ΔH=-1273 kJ/ mol
102. A constant pressure calorimeter consists of
an insulated beaker of mass 92 g made up of 1
 
ii) H2(g) +   O2(g) 
 H O(l) ;
glass with heat capacity 0.75 J/K/g. The  2 2
beaker contains 100 mL of 1 M HCl of 22.6°C ΔH = -286 kJ/ mol

to which 100 mL 1M NaOH at 23.4°C is added. iii) H2O(l) 
 H O(g) ;
2
The final temperature after the reaction is
complete is 29.3°C. What is ΔH per mole for ΔH = 44 kJ/ mol
this neutralization reaction ? Assume that the iv) 2B(s) + 3H2(g) 
 B H (g) ;
2 6
heat capacities of all solutions are equal to ΔH = 36 kJ/ mol
that of same volumes of water.
220
PREVIOUS IIT QUESTIONS 115. In thermodynamics, a process is called

reversible when [IIT JEE 2001]
SINGLE ANSWER TYPE QUESTIONS (A) surroundings and system change into each other
109. For the complete combustion of ethanol, (B) there is no boundary between system and
C2 H 5OH  l   3O2  g   2CO2  g   3H 2O  l  surroundings
amount of heat produced as measured in bomb (C) the surroundings are always in equilibrium with
calorimeter, is 1364.47 kJ mol-1 at 250 C. the system
Assuming ideality the enthalpy of combustion, (D) the system change into the surroundings
spontaneously
C H , for the reaction will be (R=3.314 JK-1 116. Which one of the following statements is false?
mol-1) [MAINS -2014 ] [IIT JEE 2001]
(A) -1366.95 kJ mol-1 (B) -1361.95 kJ mol-1 A) Work is a state function
(C) -1460.50 kJ mol-1 (D) -1350.50 kJ mol-1 B) Temperature is a state function
110. For the process H 2O  l   H 2O  g  C) Change in the state is completely defined when
the initial and final states are specified
at T=1000C and 1 atmosphere pressure, the
D) Work appears at the boundary of the system
correct choice is [IIT-ADV- 2014] 117. One mole of a non-ideal gas undergoes a
(A) S system  0 and S surroundings  0 change of state (2.0 atm, 3, 0 L,95(K)  (4.0
atm, 5.0 L, 245 K) with a change in internal
(B) S system  0 and S surroundings  0
energy, U  30.0L atm is [IIT JEE 2002]
(C) S system  0 S surroundings  0 A) 40.0 B) 42.3C) 44.0
D) not defined, because pressure is not constant
(D) S system  0 S surroundings  0
118. Which of the reaction defines Hof ?
111. For which change H  E ? [IIT JEE 1995]
[IIT JEE 2003]
A) H 2  I 2  2HI B) HCl  NaOH  NaCl
A) C  diamond   O2  g   CO 2  g 
C) C  s   O 2  g   CO2  g 
1 1
D) N 2  3H 2  2NH 3 B) H 2  g   F2  g   HF  g 
2 2
112. Molar heat capacity of water in equilibrium
with ice at constant pressure is[IIT 1997] C) N 2  g   3H 2  g   2NH 3  g 
A) zero B) infinty    1
D) CO  g   O 2  g   CO 2  g 
C) 40.54 kJ–1 Mol–1 D)75.48 kJ–1Mol–1 2
113. Standard molar enthalpy of formation of CO2 119. Two moles of an ideal gas is expanded
is equal to [IIT JEE 1997] isothermally and reversibly from 1 litre to 10
A) zero litre at 300 K.The enthalpy change (in kJ) for
B) the standard molar enthalpy of combustion of the process is [IIT JEE 2004]
gaseous carbon A) 11.4 kJ B) –11.4 kJ C) 0 kJ D) 4.8 kJ
C) the sum of standard molar enthalpies of 120. The enthalpy –1
of vapourisation of liquid is 30
formation of CO and O2 kJ mol and entropy of vapourisation is 75 kJ
–1
D) the standard molar enthalpy of combustion of mol K. The boiling point of the liquid at 1
carbon (graphite) atm is [IIT JEE 2004]
A) 250 K B) 400 K C) 450 K D) 600 K
114. The Ho f forCO2(g) and H2O(g) are –393.5, –110.5
121. The value of log10 K for a reaction A B is
and –241.8 kJ mol–1 respectively. The standard
enthalpy change (in kJ) for reaction (Given Hor 298K  54.07 kJ mol1 ,
CO2  g   H 2  g   CO 2  g   H 2 O  g  is Sor 298K  10JK 1 mol1 and R =8.314 JK–1 mol–1,
A) 524.1 B) 41.2 [IIT 2000] 2.303×8.314×298=5705) [IIT JEE 2007]
C) –262.5 D) –41.2 A) 5 B) 10 C) 95 D) 100
221
SR-MAIN-CHEM-VOL-II
122. For the process 128. For which change H  E (1995)
H 2 O  l 1bar,373K   H 2 O  g 1bar,373K  , A) H 2  I 2  2 HI B) HCI  NaOH  NaCI
the correct set of thermodynamic parameters
is [IIT JEE 2007] C) C s   O2 g   CO2 g  (D) N 2  3H 2  2 NH 3
A) G  0, S   ve B) G  0, S   ve 129. Which of the following is correct for an ideal
C) G   ve, S  0 D) G   ve, S   ve gas?
123. Which of the following equations correctly  E   E   E 
represents the standard heat of formation (A)  T   0 (B)  p   0 (C)  T   0
 v  T  p
 H  of methane?
0
f (1992) (D) All of these
130. The rusting of iron takes place as follows:
A) C  diamond   2H 2  g  CH 4  g 
  1 0
B) C  graphite  2 H2  g  CH4  l  (2005) 2 H  2e  O2  H 2 O  l  ; E  1.23V
2
C) C  graphite  2H2  g  CH4  g  Fe 2  2e   Fe  s  ; E 0  0.44V
D) C  graphite  4H  g  CH4  g  Calculate G 0 for the net process
124. The products of combustion of an aliphatic A) 322kJ mol 1 B) 161kJ mol 1
thiol (RSH) at 298 K are: (1992)
C) 152 kJ mol 1 D) 76 kJ mol 1
A) CO2  g  , H 2O  g  and SO2  g 
131. The direct conversion of A to B is difficult ,
B) CO2  g  , H 2O  l  and SO2  g  hence it is carried out by the following show
path (2006)
C) CO2  l  , H 2O  l  and SO2  g  C D
D) CO2  g  , H 2O  l  and SO2  l  S AC   50e.u.,

125. At a given temperature, the energy of S C  D   30e.u.,
activation of two reactions is same if : Given :
A) the specific rate constant for the two reactions S B  D   20e.u
A B
is the same (1993)
B) the temperature coefficient for the specific rate Where e.u is the entropy unit, then S A B  is
constant for the two reactions is the same
A) +60e.u B) +100e.u C) -60e.u D) -100e,u
C) H of the reactions is the same but not zero
132. In thermodynamics, a process is called
D) H of the two reactions is zero
reversible when (2001)
126. The enthalpy of vaporisation of liquid water
A) the surrounding and system change into each
using the data : (1993)
other
1 B) there is no boundary between system and
i) H 2 g    O 2  g   H 2 O  l  ,
2 surroundings
H  285.77kJ / mol C)the surroundings are always in equilibrium with
the system
1 D) the system changes into the surroundings
ii) H 2  g     O 2  g   H 2 O  g  ,
2 spontaneously
H  241.84kJ / mol 133. Which of the following statements is false
in kJ/mol is A) Work is a state function
A) + 43.93 B) -43.93 C) +527.61 D) -527.61 B) Temperature is a state function
127. Identify the state function among the C) Change in the state is completely defined when
following: (1993) the initial and fianl states are specified
(A) q (B) q-w (C) q / w (D) q + w D) Work appears at the boundary of the system
222
134. The species which by definition has zero 139. Among the following which are /is state
standard molar enthalpy of formation a t function(s) (2009)
298 K is A) Internal Energy
B) Irreversible Expansion Work
A) Br2  g  B) Cl2  g  C) H 2O  g  D) CH 4  g  C) Reversible Expansion work
135. Using the data provided, calculate the multiple D) Molar Enthalpy
140. The reversible expansion of an ideal gas under
bond energy  kJ mol 1  of a C  C bond in
adiabatic and isothermal conditions is shown
C2 H 2 . That energy is (take the bond energy in the figure. Which of the following
statement(s) is (are) correct? (IIT-2011)
of a C  H bond as 350 kJ mol 1 ) (2012)
2C  s   2C  g  ; H  1410 kJmol 1 P1,V1,T1
H 2  g   2H  g  ; H  330 kJmol 1 p
P2,V2,T2
A) 1165 B) 837 C) 865 D) 815
adiabatic
136. The standard enthalpies of formation of
P3,V2,T3
CO2(g), H2O(l) and glucose (s) at 250C are -
400 kJ/mol, -300 kJ/mol and -1300 kJ/mol, v
respectively The standard enthalpy of
A) T1  T2 B) T3  T1
combustion per gram of glucoses at 250C is
(2013) C) wisothermal  wadiabatic
A) +2900 kJ B) -2900 kJ C) -1611 kJ D) +1611 kJ D) U isothermal  U adiabatic
MULTIPLE ANSWER TYPE QUESTIONS 141. For an ideal gas, consider only P-V work in
137. An ideal gas in thermally insulated vessel at going from an initial state X to thefinal state
internal pressure=p1, volume=v1, and absolute Z . The final state Z can be reached by either
temperature=T1 expands irreversibly against of the two paths shown in the figure. Which of
zero external pressure, as shown in the the following choice (s) is(are) correct ?[Take
diagram.The final internal pressure, volume S as change in entropy and as work done
and absolute temperature of the gas are p2, [2012]
V2 and T2, respectively. For this expansion.
[ IIT-ADV -2014 ] X Y
p(atmosphere)
Pext = 0
Irreversible Z
Pext = 0
[[201 V (litre)
P1,V1,T1 P2,V2,T2
A) S x z  S x y  S y  z
Thermal insulation
B) Wx z  Wx  y  Wy  z
(A) q=0 (B) T2=T1
(C) p2V2=p1V1 (D) p2 V2 =p1 V1 C) Wx y  z  Wx y D) Sx yz  Sx y
138. The following is (are) endothermic reaction (s) 142. Benzene and naphthalene form an ideal solution
at room temperature For this process, the true
[IIT JEE 1999]
statement(s) is(are) (2013)
A) Combustion of methane
B) Decomposition of water A) Gsystem is positive B) S system is positive
C) Dehydrogenation of ethane to ethylene C) Ssurroundings 0 D) H  0
D) Conversion of graphite to diamond
223
SR-MAIN-CHEM-VOL-II
COMPREHENSIVE TYPE QUESTIONS 146. Match the transformations in Column-I with
Passage-1 appropriate options in Coumn-II
A fixed mass ‘m’ of a gas is subjected to Column-I
transformation of states from K to L to M to A) CO2  s   CO2  g 
N and back to K as shown in the figure (2013)
B) CaCO3  s   CaO  s   CO2  g 
C) 2H .  H2  g  D) P white, solid   P r e d , solid 
K L Column-II
p) phase transition q) allotropic change
Pressure r) H is positive s) S is positive
t) S is negative
ASSSERTION & REASON TYPE
N M QUESTIONS
Direction: This section contains reasoning type
Volume questions. Each question has 4 choice (A), (B),
143. The succeeding operations that enable this (C) & (D), out of which ONLY ONE is correct.
transformation of states are (A) Statement 1 is true; statement 2 is true;
A) Heating, cooling, heating, cooling statement 2 is a correct explanation for
B) Cooling, heating, cooling, heating statement 1.
C) Heating, cooling, cooling, heating (B) Statement 1 is true; statement 2 is true;
D) Cooling, heating, heating, cooling statement 2 is NOT a correct explanation for
statement 1.
144. The pair of isochoric processes among the
(C) Statement 1 is true; statement 2 is false
transformation of states is
(D) Statement 1 is false ; statement 2 is true
A) K to L and L to M B) L to M and N to K 147. Statement 1: The endothermic reactions are
C) L to M and M to N D) M to N and N to K favoured at lower temperature and the
MATRIX MATCHING TYPE exothermic reactions are favoured at higher
145. One mole of a monoatomic ideal gas is taken temperature.
through a cycle ABCDA as shown in the PV Statement 2: When a system in equilibrium is
diagram. Column-II gives the characterstics distrubed by changing the temperature, it will
involved in the cycle. Match them with each of tend to adjust itself so as to overcome the
effect of change. [IIT JEE 1991]
the processes given in Coloumn-I (2011)
148. Statement 1: The heat absorbed during the
P isothermal expansion of an ideal gas against
3P vacuum is zero. [IIT-JEE 2000]
Statement 2: The volume occupied by the
1P
molecules of an ideal gas is zero.
C D 149. Statement 1: For every chemical reaction at
0 1V 3V 9V V
equilibrium, standard Gibbs energy of
reaction is zero. [IIT JEE 2008]
Column-I Column-II Statement 2: At constant temperature and
A) Process A  B p) Internal energy pressure, chemical reactions are spontaneous
decreases in the direction of decreasing Gibbs energy.
B) Process B  C q) Internal energy 150. Statement 1: There is a natural asymmetry
increases between converting work to heat and
C) Process C  D r) Heat is lost converting heat to work.
Statement 2: No process is possible in which
D) Process D  A s) Heat is gained
the sole result is the absorption of heat from
t) Work is done on a reservoir and its complete conversion into
the gas work. [IIT JEE 2008]
224
INTEGER TYPE QUESTIONS 160. Using the data (all value are in kcal mol–1 at
151. One mole of an ideal gas is taken from a to b 25°C) given below, calculate the bond energy
along two paths denoted by the solid and the of C –C and C – H bonds. [IIT JEE 1990]
dashed lines as shown in the graph below. If H ocombustion  ethane   372.0 ;
t he wor k done along t he solid line pat h is Ws H ocombustion  propane   530.0 ;
and that along the dotted line path is Wd then Hocombustion  graphite   C  g   172.0 ; Bond
the integer closest to the ratio Wd / Ws is energy of H–H = 104.0;
4.5 Hof of H2O (l) = 68.0, Hof of CO2 (g) = 94.0
4.0
a
3.5
161. A gas mixture of 3.67 litres of ethylene and
3.0 methane on complete combustion at 25°C
2.5
2.0 produces 6.11 litres of CO2. Find out the
1.5 IIT-JEE2010 amount of heat evolved on burning one litre
1.0 b
0.5
0.0
of the gas mixture. The heats of combustion
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
of ethylene and methane are 1423 and 891 kJ
152. For a liquid the vapour pressure is given by mol–1at 25°C. [IIT JEE 1991]
400 162. Determine the enthalpy change of the
log10 P   10 . Vapour pressure of the
T reaction. C3H8  g  H2  g C2H6  g  CH4 (g) at
liquid is 10 x mm Hg. The value of x will be----- 25°C, using the given heat of combustion value
under standard conditions: Compound H2(g)
FILL IN THE BLANKS TYPE CH4(g) C2H6(g) C(graphite)
153. A system is said to be ............... if it can neither
H o  kJ / mol  –285.8 –890.0 –1560.0 –393.5
exchange matter nor energy with the
surroundings. [IIT JEE 1997] The standard heat of formation of C3H8(g) is –103.8
154. The heatcontent of the products is more than [IIT JEE 1992] kJ/mol
that of the reactants in an ............... reaction. 163. In order to get maximum calorific output, a
[IIT JEE 1993] burner should have an optimum fuel to oxygen
155. Enthalpy is an ......... property. [IIT JEE 1997] ratio which corresponds to 3 times as much
oxygen as is required theoretically for
TRUE / FALSE complete combustion of the fuel. A burner
156. First law of thermodynamics is not adequate which has less adjusted for metahne as fule (
in predicting the direction of a process. with x litre/hour of CH4 and 6x litre/hour of
[IIT JEE 1982] O2) is to be readjusted for butane, C4H10. In
157. Heat capacity of a diatomic gas is higher than order to get the same calorific output, what
that of a monoatomic gas. [IIT JEE 1985] should be the rate of supply of butane and
SUBJECTIVE TYPE QUESTIONS oxygen? Assume that losses due to
incomplete, etc. Are the same for both fuels
158. An athlete is given 100 g of glucose (C6H12O6)
and the gases behave ideally. (Heats of
of energy equivalent to 1560 kJ. He utilizes
combustion: CH4 = 809 kJ /mol; C4H10 = 2878
50 per cent of this gained energy in the event,
kJ/mol) [IIT JEE 1993]
in order to avoid storage of energy in the body,
164. The polymerisation of ethylene to linear
calculate the weight of water he would need to
polyethylene is represented by the reaction
perspire. The enthalpy of evaporation of water
is 44 kJ/mole. [IIT JEE 1989] nCH 2  CH 2   CH 2  CH 2 n where n has a
159. The standard enthalpy of combustion at 25°C large integral value. Given that the average
of hydrogen, cyclohexene (C 6 H 10 ) and enthalpies of bond dissociation for C = C and
cyclohexane (C6H12) are –241, –3800 and – C – C at 298K are + 590 and +331 kj mol–1
3920 kJ mole respectively. Calculate the heat respectively, calculate the enthalpy of
of hydrogenation of cyclohexene. [IITJEE-89] polymerisation per mole of ethylene at 298 K.
225
SR-MAIN-CHEM-VOL-II
165. The standard molar enthalpies of formation 173. Diborane is a potential rocker fuel which
of cyclohexane (l) and benzene (l) at 25°C are undergoes combustion according to the
–156 and +49 kJ mol–1 respectively. The reaction B2 H 6  g   3O2  B2 O3  s   3H 2 O  g  .
standard enthalpy of hydrogenation of From the following data, calculate the enthalpy
cyclohexene (l) at 25° is –119 kJ mol–1. Use change for the combustion of diborane.
these data to estimate the magnitude of the
resonance energy of benzene [IIT1997] 3
i) 2B  s   O2  g   B2 O3  s  ; H  1273kJ mol1
166. The enthalpy change involved in the oxidation 2
of glucose is –2880 kJ mol–1. Twenty five per 1
cent of this energy is available for muscular ii)H2  g  O2  g  H2  l  ; H  286kJ mol1
2
work. If 100 kJ of muscular work is needed to
iii) H 2 O  l   H 2 O  g  ; H  44 kJ mol1
walk one kilometre, what is the maximum
distance that a person will be able to walk after iv)2B s  3H2  g   B2 H6  g ; H  36 kJ mol1
eating 120 g of glucose? [IIT JEE 1997] 174. When 1-pentyne (A) is treated with 4 N
167. Calculate the heat of formation of liquid methyl alcoholic KOH at 175°C, it is converted slowly
alcohol in kilojoules per mole, using the into an equilibrium mixture of 1.3% 1-pentyne
following data. Heat of vapourisation of liquid (A), 95.2% 2-pentyne (B) and 3.5% of 1, 2-
methyl alcohol = 38 kJ/mol. Heat of formation pentyne (C). The equilibrium was maintained
of gaseous atoms from the elements in their at 175°C. Calculate G o for the following
standard states; H = 218 kJ/ mol; C = 715 kJ/
mol; O = 49 kJ/mol. Average bond energies: equilibria: B A ; G1o  ? ; B C ; G o2  ?
C – H = 415 kJ mol, C –O = 365 kJ/mol , O – From the calculate value of G1o and G o2
H =463 kJ/ mol [IIT JEE 1997] indicate the order of stability of (A), (B) and
168. Anhydrous AlCl3 is covalent. From the data (C). Write a reasonable reaction mechanism
given below, predict whether it would remain showing all intermediates leading to (A), (B)
covalent or become ionic in aqueous solution. and (C). [IIT JEE 2001]
(Ionisation energy for Al = 5137 kJ mol–1 ; 175. For the reaction, 2CO  O2  2CO 2 ;
H hydration for Al3+ = –4665 kJ mol–1; H hydration H  560kJ . Two moles of CO and one mole
for Cl– = –381 kJ mol–1) [IIT JEE 1997] of O2 are taken in a container of volume 1 L.
169. From the following data, calculate the enthalpy They completely form two moles of CO2, the
change for the combustion of cyclopropane at gases deviate appreciablyfrom ideal
298 K. The enthalpy of formation of CO2(g), behaviour. If the pressure in the vessel
H2O(l) and propene (g) are–393.5,–285.8and changes from 70 to 40 atm, find the magnitude
20.42 kJ mol–1 respectively. The enthalpy of (absolute value) of U at 500 K. (1atm=0.1kJ)
isomerisation of cyclopropane to propene is – 176. CV value of He is always 3R/2 butCV value of
33.0 kJ mol–1. [IIT JEE 1999] H2 is 3R/2 at low temperature and 5R/2 at
170. Formation of SF6(g), S(g) and F(g) are : –1100, moderate temperature and morethan 5R/2 at
275 and 80 kJ mol–1 respectively. higher temperature. Explain in two to
Cal- average S-F bond erthalpy ? three lines. [IIT JEE 2003]
171. A sample of argon at 1 atm pressure and 27°C 177. An insulated container contains 1 mol of a
expands reversibly and adiabatically from 1.25 liquid, molar volume 100 ml, at 1 bar. When
dm3 to 2.50 dm3 . Calculate the enthalpy liquid is steeply pressed to 100 bar, volume
change in this process. CV..m for argon is 12.48 decreases to 99 ml. Find H and U for the
JK–1 mol–1. [IIT JEE 2000] process.
172. Show that the reaction 178. In the following equilibrium
C O g  
1
O 2 g   C O 2 g  N 2O4  g  2NO 2  g  . When 5 moles of each
at 300 K, is
2 is taken and the temperature is kept at 298
spontaneous and exothermic and, when the K, the total pressure was found to be 20 bar.
standard entropy change is –0.094 kJ mol–1
K–1 . The standard Gibbs free energies of Given G of  N 2 O 4   100 kJ ; G of  NO 2   50 kJ .
formation for CO2 and CO are –394.4 and – (i) Find G of the reaction at 298 K. (ii) Find
137.2 kJ mol–1, respectively. the direction of the reaction. [IIT JEE 2004]
226
LEVEL-VI - KEY 106. 3.77  102 liter 107. 290.81 K

SINGLE ANSWER TYPE QUESTIONS 108. -2035 kj / mole
1.B 2.A 3.A 4.C 5.D 6.B 7.A PREVIOUS IIT QUESTIONS
8.B 9.A 10.C 11.B 12.C 13.B 14.B
15.B 16.B 17.B 18.C 19.D 20.C 21.C
SINGLE ANSWER TYPE QUESTIONS
109. A 110.B 111. D 112. B 113.D 114.B 115.C
22.A 23.C 24.C 25.C 26.D 27.C 28.B
116.A 117.C 118.B 119. C 120. B 121. B 122. A
29.D 30.B 31.A 32.B 33.C 34.B 35.D
123. C 124. B 125. A126. A 127. D 128. D 129. B
36.C 37.D
130. A131. A 132. C 133. A 134. B 135. D 136. C
MULTIPLE ANSWER TYPE QUESTIONS
38.B,C 39.ABCD 40.AB
MULTIPLE ANSWER TYPE QUESTIONS
137.A, B, C 138.B, C,D 139. A,D
COMPREHENSION TYPE QUESTIONS
140. A,C,D 141. A,C 142. B,C,D
41.D 42.B 43.D 44.C 45.A 46.D 47.C
48.D 49.B 50.C 51.A 52.C 53.B 54. D
COMPREHENSION TYPE QUESTIONS
143.C 144.B
55.D 56.D 57.C 58.B 59.C 60.B
MATRIX MATCHING TYPE QUESTIONS MATRIX MATCHING TYPE QUESTIONS
61. A -Q,R,B-P,R,C-P,R,S,D-P,R,T,U 145.A-R,T,P,B-P,R ,C-S,Q,D-T,R
62. A - P, R, B - P, R, C - Q, S,D - Q, R 146.A-P,R,S,B-R,S,C-T ,D-Q,T
63. A - R, B - S, C - P, D - Q ASSERTION & REASON
64. A-Q B-P,S ,C-P,D-R 147.(D) 148.(B) 149.(D) 150.(A)
65. A-P ,B-R, C-Q,S,D-Q,S INTEGER TYPE QUESTIONS
66. A-S, B-R,C-P,D-Q 151) 2 152) 9
67. A-R,B-Q,C-Q,D-P,S FILL IN THE BLANKS TYPE
68. A-Q, B-P,C-R,D-S 153. Isolated
ASSERTION – REASON TYPE 154. Endothermic
69.B 70.B 71.A 72.A 73.D 155. Extensive
INTEGER TYPE QUESTIONS TRUE/ FALSE
74) 5 km. 75)3 kcal. 76)4 kcal . 156. True 157. True
77) 8 J K 1 mol 1 78)2 79)8 Joule. SUBJECTIVE TYPE QUESTIONS
158. 319.1 g 159. –121 kJ
80)5J. 81) 9 82)2 kJ. 83).2
160. C–C=82 kcal / C–H = 99 kcal
84) 2 85) 5 86) 6 87) 3 88) 7
161. 5557 kJ
SUBJECTIVE TYPE QUESTIONS 162. –55.7 kJ/mol
89. 0.694atn 163. 5.48(X) litre O2
90. molar internal enegry change= 37.5 kj/mol,molar 164. –72 kJ moles–
enthaply of vapourization = 40.6kj/mol 165. –152 kJ
14 0.0821141.4  273  166. 4.8 km
91. In litre-atm 32 
 167. –275 kJ mol–1
1.4  1 168. IONIC 169.2091.32 kJ mol–1
–1
Wrev  11.82 litre-atm (or) -288 cal 170. 309.16 kJ mol 171.–115.96 joules
172. G o is negative; H is negative
92.  K C  1.958  10 4 93. -9.1555 kj
173. –2035 kJ
94. 7200 cal 95. 31.1kj
96. -0.1555cal/deg 97. 19.15j/k/mol 174. G1o  15.992 kJ mol1 , Go2  12.312 kJ mol1 ,
0 
98. 4
K P  8.94  10 ,at 1200K. K P =0.77 H  O , B > C < A ; G3  3.688 kj mol
99. -3199.75 kj 100. 27.22units 175. 557 kj / mol
101. heat of formation for Cl aq = -167.2 kj 176. Explaining by using vibrasitional modes
177. U  100 bar ml; H  9900 bar ml
102. 57 kj 103. 121 kj / mole
104. 125 kj 105. T > 481 178. 5.0705×103 kJ mol–1; reverse direction
227
SR-MAIN-CHEM-VOL-II
LEVEL-VI - HINTS P p1V1 p2V2
9. Given,  K (constant) also, 
PV
1 1 PV V T1 T2
1.  2 2  T2  600 K ; q  C.T  15KJ
T1 T2  p2V2   p2 
w  Pext .V  1 4  1  0.3KJ U  14.7 KJ  T2  T1  p V   T1  p  .......(i)
 1 1  1
H  14.7   5  4  10  1  100  103  15.7KJ  U  CV t  3CV T1  dw  pdV  kVdV
2. Entropy, a state function, does not depends on path, k 2 p RT
Hence, for  w 
2
V2  V12  ; Also
V
k  2
V
He(g) [2 mol, 398.15 K, 1.00bar]   
He(g) [2 mol, 298 K, 0.50 bar] 2 RT 2 2 R 3T R
V   V2  V1  T2  T1   1
P1 K K K
1
 S  nR ln P  2 R ln 2  11.5 JK K 3T1 R 3RT1
2  w  
2 K 2
50 m  44  103 U 2C
3. 1560  103     V  3
100 18 
w R
4. Rhombic sulphur is more thermodynamically stable
than monoclinic sulphut and also Oxygen is more 10. w   Pext V    20.4  1.0   19.4 L atm
stable than ozone.  19.4 101.4  1967J
5. Reversing the 2nd equation and adding into 1st
1
equation gives 11. 2C  3H 2  O2  C2 H 5OH ; H  66
 2
AgCl  s   2 NH 3  l  Ag  NH 3 2  aq   Cl   aq 
CH 3 .O.CH 3  3O2  2CO2  3 H 2O; H  348
G 0  14.6 kJ Also, G 0  14.6  100 J
 1 
 2.303  298  8.314 log K  K  2.76  103  H 2  O2  H 2 O   3; H  68  3
 2 
6. Volume of room= 5  10  3  15  104 lit
 C  O2  CO2   2; H  94  2
P 3
no of moles of air= V  6.1 10 And H  E  nRT
RT
Heat produced per second by ‘50’ 12. AB2  l   4 X 2  g  AX 2  g   2 BX 2  g 
students=50x150=7500 Watt/sec H  270 ; 270  2  3 x   4 x  30
H air  n.CP .T 6226
13. No.of moles of ethylene combusted =  4.4
7 1411
1500  t  60  6.1 103   8.314  15
2  No.of moles of O2 used = 3  4.4 accroding
0
7. H  484 kJ / mol indicates exothermic nature to balanced eq. C H  3O  2CO  2 H O
2 4 2 2 2
of reaction while S 0  87 J / K   0  indicates  volume of O2 used= 3  4.4  22.4 lit at N.T.P
.P
that the system is becoming more ordered. 14.  f  H 0 for N 2O4 is less
8. Let us solve this at boundary condition of G 0  0
15. nCH 2  CH 2   CH 2  CH 2  n
H 0 71.3  1000 In this process, one mol of double bonds (C=C)
0
S    230 JK 1
T 310 are replaced by 2mol of single bonds (C-C)
 230 JK 1  Sm0  R   460 JK 1  Sm0  R  600   2  C  C   100
 Sm0  R   690 JK 1 . It is the maximum value of 16. Catalyst has no effect on H
17. State functions do not depend on path followed.
entropy which the reactant can have. If 18. In adiabatic process
S m0  690 JK 1mol 1 , G 0  0 . 1   1  
P1 .T1  P2 .T2 =Constant
228
 vap H 41-43 (Comprehension Type)

19. vap S   88 KJ / mol (Troiton’s rule) path (A) : isothermal  U  0 
Tb
In water, molecules are arranged by H-bonding v2
qrev  w  nRT1 ln
f H 0
 H  eq    0

v1
20. Work is ‘NOT’a state function i.e., It has no unique  v2 
value fora state Path (B+C) : qrev  0   nR ln v 
 1 
21. Wrev  Wirrev
Path (D+E):
22. 65.38  0.4  T  293  180  4.2  373  T  v T v
23. I. n  ve ; II. n  ve ; III. n  ve  S sys  nR ln 2  n Cv ln 2  nR ln 2
v1 T1 v1
2
1 
24. Workdone=Area of sphere=  r 2     P2  P1   44. S 0  240  198  2  29   16 J / mol / K
2 
25. H  U  P.V = 30   5  4  3  2  45. H 0  201   114   87 KJ / mol
T2
26. 103  3 x  84   4 x  y   25 .Given x : y  9 : 5 0 0 0
46. S T2  S T1  C p ln T
Solving for x and y, we get Cl-Cl bond energy. 1
27. 6C  6 H 2  C6 H12 ;  156 ....(1) 0 0 T2

S 320  S300  C p ln
T1
6C  3H 2  C6 H 6 ;  49 ....(2)
C6 H10  H 2  C6 H12 ;  119 C p  44   29.4  2  28.8 
0 0
 C6 H 6  3H 2  C6 H12 ;  119  3 .....(3) 47. H 320  H 300  C p T2  T1 
[Observed] from (1) and (2) 0
48. G320 0
 H 320 0
 S 320
C6 H 6  3H 2  C6 H12 ;  205 [Calculated]
49. 9 T  273  335  36  323  T   4.18
 Resonance energy=  H obs ~  H cal 50-52
28. G 0  2.303 RT log K eq  H 0  T S 0 H
S 
T
0 0 0
29. G   GP   GR  394.4   137.2  53. H 2O  l  H 2O  s 
=-257.2 KJ/mol C p  36.4  75.3  38.9 J .K 1.mol 1
30. G  H  T S  0 for Spontaneity
31. free energy is a state function i.e.,independent on H 273  H 263  C p T2  T1 
the path followed
 fussion H
32. S gas  Sliq  S solid 54.  fussion S  Tf
33. S  0 for spontaneity and S  0 at equillibrium
55. H 35  H 25  0
v P
34.  S T  nRT ln 2  nR ln 1 for an ideal gas, d
v1 P2 56. G30  H 30  T .  G  p
dT
PV=RT Given P1 1  R  300 & P2  1atm
57. E1  E2
36.  fusion S   vap S
58. G 0  H 0  T S 0 =-2.303RT log Keq
37.  S surr   S sys 59. K eq is high  Reaction is almost completed
38. G  0 and S  0 for sponteneity towards products side
39. For an ideal gas, (U=f(T)) as P.E=0 60. G 0  H 0  T S 0 >0 for a non-spontaneous
40. For an ideal gas, (U=f(T)) as P.E=0 process
229
SR-MAIN-CHEM-VOL-II
61. A) Dissolution of glucose is endothermic P
2
B) Dissolution of quick lime is exothermic C) G  nRT ln P
1
C) All combustion reactions are exothermic
D) Graphite is the standard state of carbon v P
D)  S T  nR ln v  nR ln P
2 1
62. The most stable allotropes in standard states are 1 2

O2(g); Rhombic sulphur and white phosphorous
 U   H 
d H 0 68.  T   Cv  T   C P
63. Vant Hoff isochore :
dT
 ln K p  
RT 2
 V  P
 G   G 
    T   s  T   v
Kirchoff’s equation:  T  G    C p  P  T
 P 74. Energy available for muscular work
P2  vap H 1 1 2880  25
Clausius-clapeyron: ln P  R T  T    720 kJ / mol .
1  2 1 100
Gibb’s helm holtz’s equation :  Energy available for muscular work from 125
720
   gm glucose =  125  500KJ
G  H  T   G   180
 T p
500
64. Reversible isothermal expansion:  Distance travelled = 100  5km .
 S sys  0   S surr  0 75. On mixing CaCl2  aq. and Na2 CO3
Reversible adiabatic compression:
CaCl2  Na2CO3   CaCO3  2 NaCl
 S sys   S  surr  0 Solutions are very dilute and thus, 100 %
Adiabatic free (Irreversible) expansion: dissociation occurs.
 S sys  0 Ca2  aq. 2Cl  aq. 2Na  aq. CO32  aq. 

Irreversible isothermal compression:  
CaCO3  2 Na  aq.  2Cl  aq. or
 S sys  0   S surr  0 Ca 2  aq.  CO32  aq. 
 CaCO3  s 
65. A) H  nC p , m T  0  0 
 H HPr0 oducts HRe
0 0 0
actants or H Hf CaCO3  Hf ca2 Hf CO32 
B)  dC p T  VdP  SdT  VdP
 H 0 of a compound
C) U  fCT   U  0 at constant 0
 H Formation  288.45   129.80  161.65  3 k cal
nRT 76. The required equation is:
temperature and also  dC p T  Vd p  .dp
P 2 Al  Fe2 O3 
 Al2 O3  2 Fe, H  ?
dP  C  nRT ln P2 H  H f  products   H f  reac tan ts 
 dC p  nRT  P
P P1
D) Adiabatic free expansion: q=0 ( adiabatic)   H f  Al2O3   2H f  Fe    2H f  Al   H f  Fe2O3  
Pext  0  w  0 ( free expansion)
  399  2  0    2  0   195.92  
from I law, U  0
 399  195.92  203.08 .
66. The standard states for oxygen is O2  g 
At. mass of aluminium = 27, Mol. mass of Fe2O3  160
Bromine is Br2  liq 
160 2  27
Volume of reactants   50.77 cm3 ;
67. A) G   nFEcell 5.2 2.7
2v 2 P 203.08
B) Wrev   nRT ln v  nRT ln P Fuel value per cm3   4 kcal .
1 1 50.77
230
H trans 2288 88. Intensive properties are: Vapour pressure, molarity,

77. Strans    8 J K 1 mol 1 . Refractive index, Dielectric constant, molarity,
T 286
specific gravity, molar volume.
78. Q  13.7  11.7  2 89. Solution (a) Work involved in heating of gas
79. Work done   P  dV  1  2.5  2.0  Wa   P.V   P(V2  V1 ) -198.7
 0.5litre  atm 1
0.5  1.987  4.184 =–2.303X1X9.87X 273log to P  P1  0.694 atm
  joule  50.63 J 1
0.0821 90. Solution: The vaporization occurs at consstant
 Work is carried out at constant P and thus pressure therefore the enthalpy change is equal to
irreversible. From I law of thermodynamics the work done by the heater;
 q  U  W ; 58.63  U  50.63 H '  0.50 X 12 X 300  1800 J   1.8kJ
 U  8 joule H ' H
 Molar enthalpy of vaporization  H  
mole ofH 2 O n H 2 o
5
80. Gas is diatomic as   1.4 , thus, Cv  R and
2 1.8
  40.6 kJ mol 1
7  0.798 
Cp  R ; Given, H  85 J at constant pressure  
2  18 
85 140  2 40  U  PV  U  ng RT  U  RT

Also, T   
nC p 7 n  R n Also, (H2o(l) H2o(g), ng  1)
40 U  molar int ernal energy change
Now, W   nRT   n  2   80 J
n   H  R T  4 0 .6  8 .3 1 4 X 1 0  3 X 3 7 3 .1 5  3 7 .5 kJ m o l  1
Also, q p  H  U   W  14
91. p1  10atm at T  273 k for moleO2
U  H  W  85  80 U  5 J . 32
81. Hdissolution  Hionisation  H hydration  778  775 14
p2  1atm at T  T2 k for moleO2
32
 3 kJ mol 1  3000 J mol 1 S dissolution  40 J mol 1 ;
For adiabatic expansion we have T  .P1  cons tan t
Gdissolution   H  T S  3000  300  40  9000 J
 1
G  9 kJ .  T1   P2  T1 p
    or  log  1    log 2
82. Reversible work is maximum work.  T2   P1  T2 p1
V  273 1
 w  2.303 nRT log10  2  or 1.4 log T  1  1.4  log 10  T2  141.4 K
 V1  2
16 25 nR
 2.303 
32
 8.314  300log
5 Work done in adiabatic expansion     1 T2  T1 
 fusion H
6.025  103 1 92. H 0  77.2 mol 1 ; S 0  122 JK 1mol 1
83.  fusion S  Tf
 
167 18 T  400k ; G 0  H 0  T S 0 ;
84. 1 mol - 0.4 K.cal  10 g - 0.4 K.cal ; 50- ?
G 0  77200  400  122  28400 J
 fusion H 1365
85.  fusion S   Also, we have G 0  2.303RT log10 K c
Tf 273
where, kc is equilibrium constant
86. G  0 for spontaneity ; H  T S  0
 28400  2.303  8.314  400 log10 kc
3  103  500  S  0
87. Extensive properties are: Enthalpy, Heat capacity,  kc  1.958  10 4
Resistance
231
SR-MAIN-CHEM-VOL-II
93.  3.7 kJ mol 1  3700 J mol 1 1

H2(g) + O2 (g)   H2O(l)
H dissolution H ( ionisation ) H ( hydration )  778 774.3 2
Sdisolution  43 J mol 1 H 0  286 kJ . . .(iii)
15
G disolution  H  T S  3700  298 X 43  9114 J ; G  9.114kJ C6H5COOH(s) + O2 ( g ) 
 7CO2(g) +
2
94. H total  H fusion  H heating  H vaporization 3H2O(l) ; H  ? . . . .. . . . (iv)
10  80  10 1100  10  540  7200cal By (ii)  7 + (iii)  3 - (i)
95. Using Clausius-Clapeyron equation; 15
C6H5COOH(s)+ O 2 ( g )   7CO2(g) + 3H2O(l)
P2 H v T2  T1  2
2.303log 
P1 R T1T2
H 0  [393  7  286  3  408]
2.303RT1T2 P H  U  ng RT
H v  log 2  H 0  3201kJ Also
(T2  T1 ) P1
 = 3201 = U  (0.5)  8.314 10 3  300
We have
 U  3201  1.2471 = -3199.75 kJ
2 .3 0 3  8 .3 1 4  3 0 3  3 3 3 5 .2 1 0 4 100. Total energy required in the day
H v  lo g to
(333 300 ) 1 .5 3  1 0 4  × 24× 60× 60
 kJ (1 watt = J/ sec) = 12960 kJ
3
 31.1 10 J  31.1 kJ 1000
96. H for the colling of 12960
Units of glycogen required =  27.22 units.
3.2 476
CD2O  mS T   14  100  140 cal 1
32 101. Given, H 2 ( g )  aq.  H  ( aq )  e;
 Cooling is exothermic H  140cal 2
0
H  0 . . . . (i)
H 140
Now, S    0.1555 cal deg 1 1 1
T 900 H 2 ( g )  Cl2 ( g )   HCl ( g );
2 2
V2
2.303nRT log to H 0  92.4kJ . . . . (ii)
97. Sol;-Wehave , S  q1  V1
HCl(g) + nH2O(l)  + -
T T  H (aq) + Cl (aq);
Given,n=1,R=8.314J,T=298K, V1  V ,V2  10V H 0  74.8 kJ . . . . .(iii) Add. eq. (ii) and (iii)
1 1
S  2.3031 8.314logto
10V
 19.15JK 1mol 1 H2 ( g)  Cl2 ( g)  nH2O H(aq )  Cl (aq ) ;
V 2 2
0
98. At equilibrium G 0  H 0  T S 0 H  167.2 kJ . . . . (iv) Subtract eq. (i) from (iv)
1
0
G300 K  41.16  300  4.24  10 
2
 28.44kJ   Cl  ( aq .) ;
 2 Cl2 ( g )  aq.  e  H  167.2 kJ
k  32.93  1200   2.96  10   2.59kJ

0 2
and G1200 Heat of formation for Claq  167.2 kJ
Thus, at 300 K, reaction will process in forward 102. Initial average temperature of the acid and base =
direction and 1000K back ward direction Also, 22.6  23.4
 23.0C
G 0  2.303 RT log K p ;  K p  8.94 10 4 2
Rise in temperature = (29.3 – 23.0) = 6.3°C
Similarly , at 1200K, K P  0.77
Total heat produced = ( 92×0.75+200×4.184) × 6.3
99.Given,7C(s)+ 3H2(g)+O2(g) 
 C6H5COOH(s); = (905.8) × 6.3 = 5706.54 J
H 0  408kJ . . Enthalpy of neutralisation = –
(i) C(s) + O2(g)   CO2(g) 5706.54
 1000  1 = – 57065.4 J = – 57 kJ
100
H 0  393kJ . . .(ii)
232
103. The required reaction is 108. The concerned chemical reaction is
C6 H10  H 2 
 C6 H12 , H  ? .. . . .(i) B 2H6(g) + 3O2(g) 
 B O + 3H O ,  H = ?
2 3(s) 2 (g)
1
Cyclohexene Cyclohexane
The enthalpy change can be calculated in the
1 following way. H  [H B O (s )  3H H O (g) ]  H B H (s) ;
Given H 2  O 2 
 H 2 O, H 2  241 kJ/mole ...(ii) 2 3 2 2 6
2
( H of O2  0) H H 2 O( g ) can be obtained by
0
f
17
C6 H10  O 2   6CO 2  5H 2 O, adding H H O and H H O ,
2 (l) 2 (g)
2
i.e. – 286 + 44 = –242 kJ mol–1
H 3 = – 3800 kJ/mole . . . . . (iii) –1
 H = [–1273 + 3 ´ –242] – 36 kJ mol
C6H12 + 9O2   6CO2 + 6H2O, H 4 = –1273 – 726 – 36 = –2035 kJ mol–1
= – 3920 kJ/mole . . . . . (iv) 109. C 2 H 5 OH  l   3O 2  g   2 CO 2  g   3 H 2 O  l 
add (ii) and (iii)
C6H10+H2+9O2  U =-1364.47 kJ/mol ; H = U + ng RT
 6CO2+6H2O H 5 =404kJ/mole
Substract (iv) from (v) C6H10 + H2   C6O12 1364.47  1 8.314  298
ng =1 ; H 
H = 121 kJ/mole 1000
104. H reaction = Bond energy data for the formation of [Here, value of R in unit of J must be converted
into kJ] =-1364.47-2.4776=-1366.94 kJ/mol
bond + Bond energy data for the dissociation of
110. Plan This problem is based on assumption that total
bond = –[1(C–C)+6(C–H)]+[1(C=C)+4(C–H)+
1(H – H)] = –347 – 2  414 + 615 + 435 entropy change of universe is zero.At 1000 C and
= – 125 kJ 1 atmosphere pressure, H 2O  l  H 2O  g 
Enthalpy change for the reaction = –125 kJ
105. G = H - T S is at equilibrium. For equilibrium, Stotal  0 and
For a reaction to be spontaneous, G = -ve S system  S surrounding  0 . As we know during
H  T S  ve or H  T S or conversion of liquid to gas entropy of system
increases, in a similar manner entropy of surrounding
H 95.4  103
 T or  T or 481.0 > T decreases.  d S system  0 and  S surrounding  0
S 198.3
Thus, if temperature of system is lesser than 481 Hence, (b) is the correct choice.
K, the reaction would be spontaneous. At 481 K, More stable allotrope is being converted to less
the reaction will be in equilibrium. An increase in stable allotrope.
temperature above 481 k will develop non- 111. H     n  RT
spontaneity for the reaction. For H   n  0 Products where n =no. of
106. Heat taken up by water = m SΔT moles of gaseous products – no. of moles of
= 150 × 1000 × 4.184 × 10–3 × 55 = 34518 kJ gaseous reactants.
 2050 kJ heat is provided by 1 mole C3H8 For (A), (B) and (C), n  0
 34518 kJ heat is provided by = 34518/2050 Hence (D) is correct option.
= 16.83 mole of C3H8
H 2 O C  H 2  H1  H  
 Volume of C3H8 at NTP = 16.83 × 22.4 litre 112. H2l O s  ; P (infinity)
= 3.77 × 102 litre T 0
[ T  0 , because two states (liquid and solid) of
107. Work is done aganist constant P
water are in equilibrium]
V  5  3  2dm3  2 litre; P  3 atm. Hence (B) is correct option.
 W =  P.V  3  2 litre atm. 113. Hof for CO 2 is given by
6  4.184  1.987 C  graphite   O2  g   CO 2  g 
 J  607.57 J
0.0821 Hence (D) is correct option.
Now this work is used up in heating water
114. H    H P   H R 
 W = n  C  T
607.57 = 10  4.184  18  T ; T  0.81   110.5  241.8    393.5 kJmol1 =41.2 kJ mol–1
Final temperature = T1 + T = 290 + 0.81 = 290.81K Hence (B) is correct option
233
SR-MAIN-CHEM-VOL-II
115. Since the driving and opposite forces are equal in 128. d) ng for the reaction,
case of a reversible process so in such a process,
the surroundings are always in equilibrium with the N 2  g   3 H 2  g   2 NH 3  g  , is not equal
system. Hence (C) is correct option
to zero hence H  U ; H  U  ng RT
116. Work done depends upon the path adopted so it
is not a state function. Hence (A) is correct option 130. a) Fe  s   Fe 2  2e  E 0  0.44V
117.    
HH2 H1 E2 P2V2  E1P1V1  E2 E1 P2V2 P1V1
1
2 H   2e   O2  H 2O  l  E 0  1.23V
=30 + 4×5–2×3= 44 L atm 2
Hence (C) is correct option. 1
118. Is not correct because C(graphite) and not Fe s   2 H   O2  Fe2   H 2O E 0  0.44 12.31.67V
2
C(diamond) is the standard state.
is correct because in it one mole of HD in its G 0   nFE 0  2  96500  1.67  322kJ
standard state is formed from its elements in their 131. a) S A B  S AC  SC D  S B D
standard states. is incorrect because in it 2 moles  50  30  20  60eu
of NH3 are formed. is incorrect as it involves CO 132. sys surr (equillibrium)
(not an element). Hence (B) is correct option. 133. Work is a path function
119. H  n.C P .T ; Since T  0 134. The standard state of Cl2 is Cl2(g)
Hence, H  0 Hence (C) is correct option.
135. (i) 2C  s  H2  g   H  C  C  H  g 
dq 30  103
120. ds  rev  75   T  400 K H  225 kJmol 1
T T
Hence (B) is correct option. (ii) 2C  s   2C  g  ; H  1410 kJmol 1
121. For the equilibrium, A B ; G o  H o  TSo
(iii) H 2  g   2 H  g  ; H  330kJmol 1
Go  2.303RT log10 K (K is equilibrium constant)
From equation (i):
2.303RT log10 K  Ho  TSo  
225   2 H 1 BEH  H    2 BEC  H 1 BEC C 
o o  C  s  C  g  
2.303RT log10 K  TS  H
225 1410  1 330    2  350  1 BEC C 
TSo Ho 29810  54.071000
log10 K   10 225 1410  330   700  BEC C 
2.303RT 2.3038.314 298
Hence (B) is correct option. 225  1740  700  BEC C
122. The change given is occuring at the boiling point of
the liquid, where, at a given pressure and 225  1040  BEC C
temperature the liquid-vapour system virtually BEC C  1040  225  815 kJ mol 1
remains at equilibrium and hence G  0 . Also due
136. C  O2  CO2 ;  400 ...(1)
to absorption of heat as latent heat of vaporisation,
or due to change from liquid to gaseous state where 1
H 2  O2  H 2O;  300 ...(2)
randomness has also increased, S  0 . 2
Hence (A) is correct option
6C  6 H 2  3O2  C6 H12O6 ;  1300 ...(3)
123. Natural isotopic form of carbon is graphite and that
hydrogen is H 2 . The required equation is C2 H12O6  6O2  6CO2  6 H 2O ; H  ?
138. All combustion reactions are accompained by
C  s   2 H 2  g   CH 4  g  evolution of heat i.e., they are exothermic. Hence
124. The combustion products of RSH are CO2 SO2 (B, C, D) is correct option.
and H2O 139. State functions do not depend on the path followed
125. If K1 = K2, Ea1  Ea2 140. T1  T2 because process is isothermal work done
126. Enthalpy of vaporisation of liquid water = in adiabatic process is less than in isothermal
because area covered by isothermal curve is more
285.77  241.84  43.93kJ mol 1
then the area covered by the adiabatic curve
127. U  q  w, U  State function  U 2  U1 
234
In adiabatic process expansion occurs by using 400 400
internal energy hence it decreases while in isothermal 152. log10 P    10    10  9 ;
T 400
process temperature remains constant that’s why
no change in internal energy. P  109 mm Hg x=9
153. Isolated; when the boundary is both sealed and
141. S x z  S x y  S [Entropy(S) is a state
Y z insulated, no interaction is possible with the
function, hence additive]WX Y Z  WX Y (Work surroundings.
done in Y  Z is zero as it is an isochoric process) 154.Endothermic;SinceHP>HRor H P  H R  H   ve
142. G  ve ; H  0 ; S sys   ve ; S surr  0 155. Extensive; A property which depends upon the
quantity of matter present in the system is called
143. K  L : V T ; L  M : PT an extensive property
144. L  M & N  K are isochoric process 156. (It only tells that if a process occurs the heat gained
145. A  B : Work is done on gas by one end would be exactly equal to lost by the
Heat is lost other. It does not predict the direction).
Internal energy decreases. 157. In case of polyatomic gases, a part of energy
B  C : Internal energy decreases, Heat is lost supplied is used in increasing the internal energy of
C  D : Internal energy increases the system, and thus some additinal energy is
Heat is gained needed to raise the temperature of the gs through
1°C. it means that the heat capacity (amount of
D  A : Heat is lost
heat required to raise the temperature of the system
Work is done on gas
by 1°C) is higher in case of polyatomic gases as
146. A) s  g ; Phase transition,
compared to that for monoatomic gases.
H  ve , S  ve 158. 100 g glucose = 1560 kJ
B) 0 mol  1 mol gas;
50
H   ve, S   ve Energy utilised left in body   1560  780 kJ
100
C) 2 mol  PRead ; Phase transition, Hence energy to be given out = 780 kJ
Allotropic change; S  ve Enthalpy of evaporation of water = 44 kJ / mol =
147. In this case statement-1 is wrong because 44kJ /18 g of water
endothermic reactions are favoured at high Thus 44 kJ energy is given by water = 18 g
temperature and exothermic reacts arefavoured at 1 kJ energy is given by water = 18/44 g
lower temperature in accordance with Le 730 kJ energy will be given by wat er
Chatelier’s principle. Statement-2 is correct as it is 18
in accordance with Le Chatelier’s principle. Hence   780  319.1g
44
(D) is correct option.
148. By first law of thermodynamics dq= dE+ dW. Hence amount water to be perspired to avid
Under isothermal condition for ideal gas dW = 0 storage of energy = 319.1 g
as volume occupied bythe molecules of ideal gas is 159. In this case the required reaction is
zero. Also (dE)T = 0 as for ideal gas there is no C 6 H10  H 2  C6 H12 ; H f  ?
change in internal energy at constant T due to no From the given data, we can write following
force of attraction between the molecules. equations
dq = 0+0 =0 Hence, (B) is correct option 1
149. At equilibrium G  0 , but standard Gibb’s energy (i) H 2  O 2  H 2 O ; H  241kJ
2
 G  of a reaction mayor may not be zero. For
o
17
reaction to be spontaneous G (Gibbs energy) (ii) C6 H10  O 2  6CO 2  5H 2 ; H  3800 kJ
2
should be more negative, i.e. G  0 . (iii) C6 H12  9O 2  6CO 2  6H 2 O ; H  3920 kJ
Hence, (D) is correct option
To get the desired eqaution add (i) and 9ii) and
150. Second law of thermodynamics states that total heat
substract (iii).Then
can never be converted into equivalent amount of
work. Hence, (A) is correct optionxz. H  241   3800    3920   121kJ / mole
235
SR-MAIN-CHEM-VOL-II
160. For formation of C3H8, 3C  4H 2  C3 H8 , H1  ? Since volume of 1 mole of a gas at NTP = 22.4 L
So heat evolved due to combustion of 0.665 L of
For formation of C2H6 2C  3H 2  C 2 H 6 , H 2  ?
Thus 0.665  1423
C2H4    42.32 kJ
22.40
(i) H1  2 C  C  8 C  H  3Csg  4 H  H Hence total heat evolved = 13.32+(–42.25)=–55.57kJ
(ii)  H 2  1  C  C   6  C  H     2C s  g  3  H  H   Total heat evolved = 5557 kJ
Negative sign indicates evolution of heat.
Let the bond energy of C – C and C – H bonds be
162.From the given data, we can get following equations.
x kcal and y kcal respectively. Then, we have
1
(iii) H1    2x  8y   3  1724  104  and (i) H 2  O 2  H 2 O ; H1  285.8kJ
2
(iv) H 2    x  6y    2  172  3  104 Given (ii) CH 4  2O 2  CO 2  2H 2 O ; H 2  890 kJ
(v) C  O 2  CO2 ; H  94.0 kcal 7
1 (iii) C2 H 6  O2  2CO 2  3H 2 O ; H 3  1560 kJ
2
(vi) H 2  O 2  H 2 O ; H  68.0 kcal
2 (iv) C  s   O2  CO2 ; H 4  393.5kJ
7
(vii) C2 H 6  O2  2CO 2  3H 2 O ; H  372.0 kcal (v) 3C  s   4H 2  C3 H8 ; H 4  103.8kJ
2
The required equation is
(viii) C 2 H8  5O 2  3CO 2  4H 2 O ; H  530.0 kcal
C3 H 8  g   H 2  g   C 2 H 6  g   CH 4  g  H  ?
If we multiply (v) by 2 and (vi) by 3 and then from
the sum of these new equation substract We can get the desired equation using the
(vii) we get (ix) manipulations given below
[3×(iv) + 5×(i)] – [(v) + (iii) + (ii)]
(ix) 2C  3H 2  C 2 H 6 ; H 2  20.0 kcal
Again 3–(v) +4×(vi) (viii) gives; H   3H 4  5H1    H 5  H 3  H 2 
(x) 3C  4H 2  C3 H8 ; H1  20.0 kcal =[3×(–393.5)+5×(–285.8)]–[–103.8–1560–590]
Solving equation (iii), (iv), (ix) and (x) we get = –55.7 kJ mole
x + 6y = 676 ; 2x + 8y = 956 163. Combustion of CH4 and C4H10 takes place as
or x = 82 kcal and y = 99 kcal CH 4  2O 2  CO 2  2H 2 O ;
Initial volume (in litre) X 6X
hence bond energy of C–C bond = 82 kcal and
bond energy of C–H bond = 99 kcal H  809kJmol1 Let the temperature be T and
161. Combustion of C2H4 and CH4 takes place as assume volume of 1 mle of a gas is V litre at this
C 2 H 4  3O2  2CO2  2H 2 O condition.V litre of 1 mole of CH4 gives energy
1vol 2 vol on combustion = 809 kJ X litre of CH4 gives
CH 4  2O2  CO 2  2H 2 O 808  X 
1vol 1vol energy on combustion  kJ 2878 kJ
Let the volume of CH4 in the mixture be x litre. V
Then the volume of C2H4 in mixture = (3.67 –x) energy is obtained by 1 mole of V litre C4H10
litre 809  X  809  X   V
Volume of CO2 produced by x L of CH4 = x L  kJ energy is obtained  litre
V V  2878
Volume of CO2 produced by (3.67–x) L of C2H4 C4H10 = 0.281 (X) litre C4H10Thus, butane sullpied
= 2(3.67–x) L for the same calorific output = 0.281 (X) litre
 Total volume of CO2 produced = x + 2(3.67–x) L
or 6.11 = x +2(3.67–x) L  x = 12.3 L 13
 C4 H10  O 2  4CO 2  5H 2 O ;H  2878kJ / mol
Thus, volume of CH4 in mixture = 1.23 L 2
So volume of C2H4 is mixture = ( 3.67–1.23) L = Volume of O2 required = 3 volume of O2 for
2.44 L combustion of C4H10
1.23 13
Volume of CH4/ litre of mixture   0.335L  3  volumeof C4 H10
3.67 2
13
2.44  3   0.281 X   5.48  X  litreO 2
Volume of C2H4/ litre of mixture   0.665L 2
3.67
236
164. The polymersiation reaction is + 3 × Hydration energy of Cl–
nCH 2  CH 2   CH 2  CH 2 n = [–4665 + 3 ×(–381)] kJ mol–1 = –5808 kJ mol–1
This amount of energy exceeds the energy needed
In this process, one double bond (C= C) breaks for the ionisation of Al to Al3+ (i.e., 5808 > 5137).
and two –CO2 groups are linked with single bonds Because of this AlCl3 becomes less ionic in aqueos
thus forming three single bonds (two single bonds solution. In aqueous solution AlCl3 exists in ionic
are formed when each CH2 group of ethylene (CH2 form as [Al(H2O)6]3+ and 3 Cl–
= CH2) links with another CH2 - group of another 3
ethylene molecule). Therefore, in polymerisation AlCl3  6H 2 O   Al  H 2 O 6   3Cl
reaction one C = C is replaced by two C – C
AlCl3  aq  AlCl3  aq  ; H  ?
bonds or one mole of C = C bonds are replaced
by 2 moles of C – C bonds. Energy Released = H = (Energy released during hydration) –
Energy due to formation of 2 single bonds. = (Energy used during hydration)
(2×331) kJ = 662 kJ. Energy needed to dissociate = (–4665)–(3×381) + 5137 = –671 kJ mol–1
Thus, formation of ions will take place.
one mole of C = C bonds=590kJ. H pot or 169. Following equation can be obtained from the
enthalpy of polymerisation=(590–662)kJ=–72 kJ available data
moles
(i) C  s   O 2  g   CO2  g  ; H  393.5kJ
165. C 6 H10  H 2  C6 H12 ; H  119kJ
(involves breaking up of three double bond and 1
(ii) H 2  g   O 2  g   H 2O  l  ; H  2858kJ
additional of three H2 molecule) 2
 C6 H 6  3H 2  C 6 H12 ; H  3   119   357 kJ (iii) 3C  s   3H 2  g   C 2 H 6  g  ; H  20.42 kJ
(involves breaking up of three double bond and CH2 CH2
additional of three H2 molecule) (iv) (g)  C3 H 6  g  ; H  33.0 kJ
CH2
Also given 6C  6H 2  C 6 H12  l  ; H  156 CH2 CH2
The desired equation is
We have C6 H 6  3H 2  C6 H12  l  ; H  357 CH2
6C  3H 2  C6 H 6 ; H  201kJ 9
(g)  O2  g   3CO2  g   3H 2O  l  ;
Therefore, resonance energy = 49– 201=–152 kJ 2
166. Energy available for muscular work by 1 mole of H  2091.32 kJ mol1
2880  25 To get the desired equation compute as follows
glucose   720 kJ
100 CH2 CH2
Thus, 180 g (1 mole ) of glucose (C6H12O6) [3×(i)+3×(ii)] + [(vi)–(iii)]
CH2
supplies energy = 720 kJ will supply 120 g glucose
9

720
 120  480 kJ . Distance covered by 100 (g)  O2  g   3CO2  g   3H 2O  l  ;
2
180
kJ energy = 1km or 100 kJ is need to walk 1 km H  2091.32 kJ mol1
1 170. Given : SF6  g   S  g   6F  g  ; H  ?
Distance covered 480 kJ energy  480  4.8km
From the available data, we can write the following
100
167. The concerned thermochemical reaction is equation
H (i) S  s   3F2  g   SF6 ; H  1100.0 kJ
|
C  g   4H  g   O  g   H  C  O  H (ii) S  s   S  g  ; H  275.0 kJ
| ; H  ?
H 1
(iii) F2  g   F  g  ; H  80.0 kJ
 1  2
H f   H Cs Cg   2H H  H  H O O  To get the required equation carry out the following
 2 
 3H CH  H CO  H O H  H Vap CH3OH   computation [6×(iii) +(ii)]–(i)
i.e. H   6  80  2745    1100.0   1855kJ
= [715+2 ×436+249] –[3×415 +365 +463+38]
= –275 kJ mol–1 Now, in SF6 we find S–F bonds, therefore the bond
168. Total hydration energy of Al3+ and 3 Cl– ions of energy. Thus average bond energy for S – F bond
1855
AlCl3 .  H Hydration   = Hydration energy of Al3+   309.16 kJ mol1
6
237
SR-MAIN-CHEM-VOL-II
171. For adiabatic expansion of a gas, we have Thus, the correct order of stability B > C > A
T1 R V2 300 8.31 2.50 175. H  U  VP ; V  0  ; U  H  VP
ln  ln or ln  ln
T2 CV V1 T2 12.48 1.25 = –560 – [0.1 (40–70)×0.1] = –557 kJ
Solving the above equation, we get T2 = 188.5K So, the magnitude is 557 kJ mol–1
Number of moles of argon gas, 176. In case of helium (monoatomic gas) we have only
three degrees of freedom which correspond to three
PV 1  1.25
n   0.05 translational motion so the total heat capacity will
RT 0.082  300 increase. The contributors by vibrational motion is
Now, we know that H  n.Cp .T not appreciable at low temperature but increases
from 0 to R when temperature increases.
 H  0.05  20.8 188.5  300 
R
[Cp= CV+R=(12.48+8.314)  20.8] = –115.96 J CV  f , where f is the degree of freedom.At low
2
172. Following reaction takes place temperature only translational motion is considered
1 3R
CO  g   O 2  CO 2  g  and f = 3.  CV  2 At moderate temperature
2
o o o both translational and rotational motions are
We know, G  G Pr oduct   G  Re ac tan t  considered. f = 3+2 (3-translational and 2
= –394.4–[–137.2 + 0] = –257.2 kJ mol–1 5R
Since G o is negative so the reaction is feasible rotational).  CV  . At still high temperature
2
i.e., spontaneous, Again, G o  Ho  TSo translational, rotational and vibrational motions are
considered. f= 3+2+2 (3-translational, 2-rotational,
257.2  H o  300  0.094   H o
7R
 285.4 kJ mol 1 2-vibrational).  CV  2
Since the value of H is negative so the reaction 177. Here, P1 = 1 bar P2 = 100 bar ;
is exothermic. V1 = 100 ml , V2 = 99 ml
iv  (i)  3(iii)  3(ii) For adiabatic process, q  0 , U  W
173. Substracting given Since, U  q  W (first law of thermodynamics)
36  (1273)  3(44)  3(286)
equation (iv)) from (vi), we get  q  P  V2  V1  [W= P(V2–V1)]
B2 H 6  g   3O 2  g   B2 O3  s   3H 2 O  g  = 0–100(99–100) = 100 bar mL
H  2035.0 kJ Also, H  U    PV   U  P2 V2  P1V1 ;
o  Product   100   99  100  100  1  9900bar mL
174.Calculation G ; G  2.303RT log Reactant
  178. (i)Standard Gibbs free energy change for the
For the equilibrium reaction B A , we get and reaction, N 2 O 4  g  2NO 2  g 
for the reaction B C , we get G o  2.303RT log K p  0 ; KP = 1
 1.3  Initially, PN O  PNO  10 bar
G1o   2.303  8.314  448log  2 4 2
 95.2  2
 15.992 kJmol 1 P NO2 100

Reaction quotient 
PN2 O2

10
 10
 3.5 
G o2   2.303  8.314  448log
 95.2  G o  2G of  NO2   G of N 2O 4   100  100  0
1
 12.312 kJmol Initial Gibbs free enrgy of the above reaction,
Again, for the reaction A C G  G o  2.303RTlog QP
 3.5  G  0  2.303  8.314  298log10
G o3   2.303  8.314  448log 
 1.3   5.0705  103 kJ mol 1
1
 3.688kJmol (ii) Since initial Gibbs free energy change of the
Fromthe above calculations, we have reaction is positive, so the reverse reaction will take
place.
B A , G1o  15.992 kJ mol1
*****
B C , G o2  12.312 kJ mol1
A C , G o3  3.688kJ mol1
238

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THERMODYNAMICS JEE-MAIN & ADV CHEMISTRY-VOL-II

W = –(P  V); (  V = Vfinal – Vinitial ); In Reversable Processes the changes can be

WAC  No area covered by straight line AC (if

Reactions : b) Molar Enthalpy of Vapourisation

 Solid - Liquid (fusion or melting) Enthalpy of Combustion

Driving Forces for Spontaneous S0

Entropy Change During Phase 6000

Entropy of Fusion 6000

spontaneous at 130.6JK-1mol-1 and 205 JK-1mol-1 respectively.

= 163000 J mol-1 or 163 kJ mol-1

43. For the reaction

VELAMMAL BODHI IIT ACADEMY 169

VELAMMAL BODHI IIT ACADEMY 173

Given that  f G 0 for Cu 2( aq ) and Zn 2(aq) as

VELAMMAL BODHI IIT ACADEMY 175

8. For a reaction 2 A  s   2 B  g   2C  g   D  g  . 4) C graphite  2S g   91.9 KJ  CS2l 

180 VELAMMAL BODHI IIT ACADEMY

VELAMMAL BODHI IIT ACADEMY 181

1348.9 Kcal mol  . If steam is produced during 4 2

182 VELAMMAL BODHI IIT ACADEMY

and 50JK 1mol 1 , respectively.For the S  mC3 H 8 ( g )  270.2 J .K 1mol 1,

190 VELAMMAL BODHI IIT ACADEMY

T2 1) Zero 2) 1.642 atm

46. N 2O4 2 NO2 3. Work done in the process C  A is

sequence (for expansion) would be:

192 VELAMMAL BODHI IIT ACADEMY

Gsystem  H system  T S system

B) C (s, graphite)  C  g  R: Both HCl and HClO4 are strong acids

194 VELAMMAL BODHI IIT ACADEMY

196 VELAMMAL BODHI IIT ACADEMY

VELAMMAL BODHI IIT ACADEMY 197

34. Which of the following statements is/are enthalpy density

198 VELAMMAL BODHI IIT ACADEMY

VELAMMAL BODHI IIT ACADEMY 199

3 A) HA aq  BOH  aq BA aq  H2O -42.3

55. The enthalpy changes for the reaction

200 VELAMMAL BODHI IIT ACADEMY

3. If work done by the system in path AB is 20

VELAMMAL BODHI IIT ACADEMY 201

q rev. MATRIX MATCHING

202 VELAMMAL BODHI IIT ACADEMY

VELAMMAL BODHI IIT ACADEMY 203

204 VELAMMAL BODHI IIT ACADEMY

VELAMMAL BODHI IIT ACADEMY 205

In the process of neutralisation 25×10–5 mole H+ 1

206 VELAMMAL BODHI IIT ACADEMY

21. dU  dp  dw ; nCv, m .dT  nCm dT  P.dV ; 2  298  4  6.3 cal K

P.dV 26. For isoentropic process S system  0

R 0.4  1000a  10b ........(1)

VELAMMAL BODHI IIT ACADEMY 207

MULTI ANSWER QUESTIONS  for gas 1

43. G for 2Fe2O3  600  4Fe  6CO2  rG1 rG2 p1

208 VELAMMAL BODHI IIT ACADEMY

3 3 5 each refers the reaction H2(g)  2H(g); BE

VELAMMAL BODHI IIT ACADEMY 209

210 VELAMMAL BODHI IIT ACADEMY

38. A reactions is spontaneous if 42. What is qrev for path (B + C)?

 Cv   Cv  Paragraph – 2