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THERMODYNAMICS (ENERGETICS)
SYNOPSIS Cv , m dT  
RT
dv
v
1. Thermodynamic changes in adiabatic dT T2 v2 dv
changes in volume of an ideal gas Cv , m   R 
T1 T v1 v

E  q  w 1st law T  V 
Cv , m ln  2    R ln  2 
q  0 in adiabatic process  T1   V1 
E  w
Cv ,m R
we know that T  V 
ln  2   ln  2 
 T1   V1 
Cv ,m R
 E  n cvm  T  T2  V 
 w  n cvm  T    2 
 T1   V1 
C pm  C v m  R Cv ,m R
 T2  V 
C pm    1 

Cv,m  T1   V2 
Cv ,m
 Cv .m  C v ,m  R T v R  cons tan t
R / Cv ,m
R TV  cons tan t
Cv , m 
 1 TV r 1
 cons tan t
R
wn T 3. Relation between T and P
 1
nR Cv ,m
w T2  T1  T V R  cons tan t  R C p,m  cv ,m  
 1 R  
1 Cv ,m  RT   C p,m C p,m 
w  nRT2  nRT1  T    cons tan t  
 1  P   Cv,m 
  1 
T v ,m P  R  cons tan t  
(C  R )
1 C p,m
w  P2V2  PV1 1  
 1 C
T p . m P  R  cons tan t  1 
  1 
 T   R/C 
w   nC v , mT1 1  2  T P p ,m  cons tan t  
 T1   1   
1 
  

T P  cons tan t   

2. Adiabatic reversible process

Relation between P and V
dE  dw C v ,m
T V R  cons tan t
dE  n Cv ,m dT and dw   pext dv C v ,m
 PV 
Pext  PInt  R  V R  cons tan t
 
nRT P
C v ,m
V
C p ,m
 cons tan t
PInt 
V C p ,m
C v ,m
nRT PV  cons tan t
nCv ,m dT   dv 
v PV  cons tan t
THERMODYNAMICS (ENERGETICS)
4. Entropy change in terms of temperature 6. Entropy changes in Isothermal process
and volume changes Isothermal reversible process In Expan
1st law sion system takes q heat from surround
dU  dq  w ings
 dqrev  ( Pdv) qRe v   w
dqrev  dU  PdV V2
w   nRT ln
dq rev dU PdV V1
 
T T T
nc dT nR V2
dS  vm  dV n R T ln
q V1
T v  S S YS  re v 
T T
S2 dT
T2 V2 dv
 S S YS
V
 n R ln 2
S1 dS  nC v , m T1 T  nR V1 v V1
 q Re v
T V  S s u r ro u n d in g 
S  nCv ,m ln 2  nR ln 2 T
T1 V1
For Isothermal change T1  T2  S s u rr .   n R ln
V2
V1
V2   S T o ta l ( o r )  S u n iv e r s e   S S Y S   S s u rr .
S  nR ln
V1 V2 V
 n R ln  n R ln 2
V1 V1
For Isochoricprocess V1  V2
 0
T
 S  n C v ,m ln 2 In compression, system gives Q heat to
T1
surroundings
5. Entropy change in terms of temperature
and pressure changes V2
  S sys   nR ln
V2 PT V1
 1 2 V2
V1 P2T1  S su rro  nR ln
V1
T2 V
 S  n cv , m ln  n R ln 2  S To tal  0
T1 V1
7. Isothermal Irreversible prosses
T2 V (A) Free Expansion w = 0 q = 0
S  ncv , m ln  nR ln 2
T1 V1 since Entropy is a state function, the
T2 PT entropy changes of a system in going
 nc v ,m ln  nR ln 1 2 from volume V1 toV2 by any path will be
T1 P2T1
T2 P same as that of reversible porcess
 n  Cv, m  R  ln  nR 1
T1 P2
V2
T2 P SSYS  nRln
S  nc p , m ln  nR ln 1 V1
T1 P2
Ssurro  o
For Iso baric process P1  P2
T
V2
S  nC p , m ln 2 Stotal  nRln
T1 V1
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(B) Irriversible expansion (B) . Irreversible adiabatic free Expansion
qrev is the amount of heat the system
would have absorbed. In the P resent w  O , T  O T2  T1 
case Expansion done against constant T2 P
Ssys  nC p ,m ln  nR ln 1
pressure T1 P2
P1
Qrev  w S SYS  nR ln
P2
 Pext (V2 V1 ) (or )
S SYS is  ve
 qIrr  Pext (V2  V1 ) STotal  S SYS  Ssurro
S surrounding  
T T V2
 nR ln o
V P (V  V ) V1
STotal  nR ln 2  ext 2 1
V1 T STotal  nR ln
V2
V1
S SYS is  ve and S surro is  ve STotal is  ve
STotal is  ve
C. Irriversible Compression (C) Intermediate Expansion
T2 V
 S SYS  n C v ,m ln  n R ln 2
V T1 V1
S SYS  nR ln 2 (o r )
V1
T2 P
 S SYS  n C ln  nR 1
p (V  V ) p ,m
T1 P2
S surro   ext 2 1
T In Expansion the increase in entropy due
S SYS  S surro to volume change is larger than the de
S SYS is  ve and S surrois  ve crease in cntropy due to temp change
S SYS is  ve
V2 Pext  (V2  V1 ) STotal is also  ve
STotal   nR ln 
V1 T In copression, the decrease in entropy
STotal is  ve due to volume change is smaller than the
8. Entropy changes in adiabtic process increase in entropy due teperature
q = o S surro  o S SYS is  ve
(A) Reversible process STotal is also  ve
T2 V H vap
 S S YS  nC v , m ln  nR in 2
T1 V1 9. Trouton’s rule is Svap 
Tb
T2 P
S SYS  nC p , m ln  nR ln 1
T1 P2 i.e Svap  10.5R at boiling point
in Expansion, the increase entrcpy due
10. For Hg l  , H 2O l  , NH 3 l  have high Svap
to volume change just compensate the
decrease in entropy due to the fall in and doesn’t follow trouton’s rule
temperature 11. s Gisothermal (in isolated gaseous system)
 S SYS  o
V 
 The process is known as “Isoentropic  Wmax .  2.303nRT log  2 
process.  o  V1 
 THERMODYNAMICS (ENERGETICS)
12. 3rd low of T.D equation is 2. No heat is absorbed by the system from the
ST  2.303 ncv log T surroundings, but work (w) is done on the
system. What type of wall does the system
Cv , m
ST  have?
3
13. Criterion of spontaneity (A)  U = Wad ; wall is insulated
I. (B)  U = - q, thermally conducting walls
 0 : Spon tan eous( Irreversible)
(C)  U = q - w, closed system.
Stotal  0 
  0 :Re versible Pr ocess
 0 : Non spon tan eous (D)  U = q - w, open system
II. 3. Which one of the following bonds has the
 0: Spon tan eous(Irreversible) highest average bond energy (kcal/mol)
(A) S = S (B) C  C (C) C  N (D) N  N
 G  system T ,P  0 
  0:Re versible Pr ocess
 0: Nonspon tan eous 4. For the reaction
III.  3O 2 H f  16 KJ / mole .
2O 3 
 0 : Spon tan eous( Irreversible) We can say that
 E 
system S ,V  0 
  0 :Re versible Pr ocess (A) ozone is more stable than oxygen
 0 : Non spon tan eous (B) ozone is less stable than oxygen and ozone
IV. decomposes forming oxygen readily
 0 : Spon tan eous( Irreversible) (C) oxygen is less stable than ozone and oxygen
 H 
system S , P  0 
  0 :Re versible Pr ocess readily forms ozone
 0 : Non spon tan eous (D) none of the above
V. 5. Which reaction either endothermic or
 0 : Spon tan eous( Irreversible) exothermic characteristics has the greater
chance of occuring spontaneously?
 A 
system T ,V  0 
  0 :Re versible Pr ocess
 0 : Non spon tan eous (A) One in which entropy change is positive
VI. (B)One in which entropy change is negative
 0 : Spon tan eous ( Irreversible) (C) One in which free energy change is negative
(D) One in which equilibrium has been established
 S 
system E ,V  0   0 :Re versible Pr ocess
6. S for the reaction,
 0 : Non spon tan eous
MgCO3  s   MgO  s   CO 2  g  will be
SINGLE ANSWER QUESTIONS (A) zero (B) –ve (C) +ve (D) 
7. Change in entropy is negative for:
1. The work done by a weightless piston in (A) Bromine (l)  Bromine (g)
causing an expansion V (at constant
temperature), when the opposing pressure, (B) C  s   O 2  g   CO2  g 
P is variable, is given by: (C) N 2  g,10atm   N 2  g,1atm 
(A) W    PdV (B) W = 0
(D) Fe 1mol, 400 K   Fe 1mol,300K 
(C) W   PV (D) None of these
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8. Identify the correct statement for change of 13. A heating coil is immersed in a 100g sample
Gibb’s energy for a system  G system  at of H 2O  l  at 1 atm and 1000 C in a closed
constant temperature and pressure: vessel.In this heating process, 60% of the
(A) if G system  0 , the system is still moving in a liquid is converted to the gaseous form at
constant pressure of 1 atm. The densities
particular direction
of liquid and gaseous water under these
(B) if G system   ve , the process is not
conditionsare 1000 k g / m 3 and
spontaneous
0.60 k g / m 3 respectively. Magnitude of
(C) if G system   ve , the process is spontaneous
the work done for the process is
(D) if G system  0 , the system has attained A) 4997 J B) 4970 J
equilibrium C) 9994J D)1060J
9. The internal energy when a system goes 14. What is the value of change in internal
from state A to B is 40 kJ/mol. If the system energy at 1 atm in the process?
goes from A to B by a reversible path and H 2O  l ,323 K   H 2O  g , 423K 
returns to state A by an irreversible path.
What would be the net change in internal Given : CV , m  H 2O, l   75.0 JK 1 mol 1 ;
energy?
(A) 40 kJ (B) > 40 kJ H vap at 373K  40.7 KJ / mol
(C) < 40 kJ (D) zero C p,m  H 2O, g   33.314 JK 1 mol 1
10. One mole of an ideal gas
A) 42.91 kJ / molB) 43086kJ / mol
C V  20 J K 1 mol 1  initially at STP is
C) 42.6 kJ / mol D) 49.6kJ / mol
heated at constant volume to twice the initial 15. The standard enthalpy of formation of
temperature. For the process, W and q will
be octane  C8 H18  is -250kJ/mol. The enthalpy
(A) W  0;q  5.46 kJ of combustion of C8 H18 . If the enthalpy of
(B) W  0;q  0 formation of CO2  g  and H 2O  l  are -394
(C) W  5.46 kJ; q  5.46 kJ kJ/mol and -286kJ/mol respectively
(D) W  5.46 kJ;q  5.46 kJ A) -5200 kJ/mol B) -5726 kJ/mol
11. Calculate Q and w for the isothermal C) -5476 kJ/mol D) -5310kJ/mol
reversible expansion of one mole of an ideal 16. Consider the following reactions:
gas from an initial pressure of 1.0 bar to a C  s   O2  g   CO2  g   xkJ
final pressure of 0.1 bar at a constant
temperature of 273 K respectively. 1
CO  g   O2  g   CO2  g   y kJ
(A) 5.22kJ, - 5.22kJ (B) -5.22 kJ, 5.22 kJ 2
(C) 27.3kJ, -27.3 kJ (D) -27.3 kJ, 27.3 kJ
The heat of formation of CO  g  is
12. When 1 mole of gas is heated at constant
volume. Temperature is raised from 298 to A)   x  y  kJ / mol B)  x  y  kJ / mol
308 K. Heat supplied to the gas is 500 J.
Then which statement is correct? x 
C)  y  x  kJ / mol D)   y  kJ / mol
(A) q = –W=500 J, U  0 2 
(B) q  U  500J, W  0 The value of H f of PCl5 is
(C) q  W  500J, U  0 (A) 454.5 kJ mol–1 (B) –454.5 kJ mol-1
(D) U  0,q  W  500J (C) –772 kJ mol–1 (D) –498 kJ mol–1
 THERMODYNAMICS (ENERGETICS)
17. The enthalpy of combustion at 25°C of H2,
cyclohexane (C 6 H 12 ) and cyclohexene
(C6H10) are –241, –3920 and –3800 kJ/mol
respectively. The heat of hydrogenation of
cyclohexene is:
(A) –121 kJ mol–1 (B) +121 kJ mol–1
(C) –242 kJ mol–1 (D) +242 kJ mol–1
18. Calculate the enthalpy change when 50 mL
of 0.01 M Ca(OH)2 reacts with 25 mL of 0.01
M HCl . Given that Ho neutralization of a
strong acid and a strong base is 140 kcal
mol–1
(A) 14 kcal (B) 35 cal
(C) 10 cal (D) 7.5 cal
19. If  f H 0  C2 H 4  and  f H 0  C2 H 6 
a and b kcal mol 1 , the heat of
hydrogenation of C2 H 4 is
A) ab B) a  b C) b  a D) a  2b
20. Stearic acid [CH 3  CH 2 16 CO2 H ] is a fatty
acid, the part of fat that stores most of the
energy. 1.0g of stearic acid was burnt in a
bomb calo rimeter. The bomb had a heat
capacity of 652 J /0 C . If the temprature of
22. At 250 C , 1 mole of MgSO4 was dissolved
in water, the heat evolved was found to be
91.2 kJ. One mole of MgSO4 7H 2O on
dissolution gives a solution of the same
composition accompained by an absorption
of 13.8kJ. H for the reaction
MgSO4  s   7 H 2O  l   MgSO4 7 H 2O  s 
is
A) -105 kJ/mol B) 77.4kJ / mol
C) 105kJ / mol D) 77.4kJ/mol
23. The enthalpies of neutralization AOH and a
strong base BOH by HCl are -12250 cal/mol
and -13000cal/mol respectively. When one
mole of HCl is added to a solution containing
are
1 mole of AOH and 1 mole of BOH, the
enthalpy change was-12500 cal/ mol. In what
ratio is the acid distributed between AOH
and BOH respectively.
A) 2:1 B) 2:3 C) 1:2 D) 3:2
24. Substance A2 B  g  can undergo
decomposition to form two set of products
A2  g   B  g  ;  H 0  40 kJ / mol
A2 B  g 
A  g   AB  g  ; H 0  50kJ / mol

500g water  c  4.18 J / g 0 C  rise from 25.0 If the molar ratio of A2  g  to A  g  is 5:3 in a
to 39.30 C , how much heat was released set of product gases , then the energy involved in
when the stearic acid was burned ? [Given the decomposition of 1 mole of A 2 B  g  is:
C p  H 2O   4.18 J / g 0C ] A)48.75 kJ/mol B) 43.73 kJ/mol
C) 46.25 kJ/mol D) 64.2 kJ/mol
A) 39.21 kJ B) 29.91kJ 25. Calculate the enthalpy for the following
C) 108kJ D) 9.32 kJ reaction using the given bond energies (kJ/
21. A 0.05 L sample of 0.2 M aqeous mol)
hydrochloric acid is added to 0.05 L of 0.2
M aqeous ammonia in a calorimeter. Heat  C  H  414; H  O  463; 
capacity of entire calorimeter system is 480  
 H  Cl  431, C  Cl  326; 
J/K. The temperature increase is 1.09 K.  C  O  335 
 
 r H 0 in kJ/mol for the following reaction
CH 3  OH  g   HCl  g 
is:
 CH 3  Cl  g   H 2O  g 
HCl  aq.  NH 3  aq.  NH 4Cl  aq 
A) -23 kJ /mol B) -43 kJ/mol
A) -52.3 B) -61.1 C)-55.8 D) -58.2
C) -59 kJ/mol D) -511kJ/mol
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26. What is the bond enthalpy of Xe  F bond 31. Using given standard enthalpies of formation
if Ionization energy of Xe =279 kcal/mol (in kJ/ mol) determine the enthalpy of the
following reaction ?
B.E.  F  F   38 kcal / mol , electron affinity
NH3  g 3F2  g   NF3  g   3HF  g
of F=85kcal/mol
A) 24kcal/mol B) 34kcal/mol H 0f  NH 3 , g   46.2;
C) 8.5 kcal/mol D) 16.2 kcal/mol
27. In the conversion of lime stone to lime: H 0f  NF3 , g   113.0;
CaCO3  s   CaO  s   CO 2  g  The values of H 0f  HF , g   269.0 kJ / mol
–1
Ho and So are 179.1 kJ mol and 160.2 A) 335.8kJ / mol B) 873.8 kJ / mol
JK–1 mol–1 respectively at 298 K and 1 bar.
C) 697.2 kJ / mol D) 890.4 kJ / mol
Assuming Ho and So remains constant 32. One mole of an ideal gas is subjected to a
with temperature, at which minimum reversible cyclic process as shown in figure.
temperature conversion of lime stone to lime the max. temperature attained by the gas
will be spontaneous: during the cycle
(A) 1118 K (B) 1008 K
(C) 1200 K (D) 845 K B
4bar
C p.m
28. For an ideal gas C   . The molecular P
v ,m

mass of the gas is M, its specific heat 1bar

capacity at constant volume is : A
R M
A) M    1 B) R    1 1 litre 2 litre
V
 RM R
C) D) M    1 A) 7/6R B) 12/ 49R
 1 C) 49/12R D) 12/7R
29. 1 mole of an ideal gas A  Cv , m  3 R  and 2  5 
33. A gas  Cv ,m  R  behaving ideally was
 2 
 3 
mole of an ideal gas B are  Cv ,m  R  allowed to expand reversibly and
 2  adiabatically from 1 litre to 32 litre. It’s
taken in a container and expanded reversible initial temperature was 327 0 C . The molar
and adiabatically from 1 litre to 4 litre
enthalpy change (in J/mol) for the process
starting from initial temperature of 320K. is :
E for the process is : A) -1125R B) -675
A) -240R B) 240R C) -1575R D) 1012R
C) 480R D) -960R
34. For polytropic process PV n  constant , C m
30. When 1.0g of oxalic acid  H 2C2O4  is burnt (molar heat capacity ) of an ideal gas is
in a bomb calorimeter whose heat capacity given by:
is 8.75 kJ/K, the temperature increases by R R
0.312 K. The enthalpy of combustion of A) Cv , m   n  1 B) Cv , m  1  n 
oxalic acid at 270 C is
A) -245.7 kJ/mol B) -2.43.45 kJ/mol R
C) -246.95 kJ/mol D) -122.5kJ/mol C) Cv , m  R D) C p, m   n  1
 THERMODYNAMICS (ENERGETICS)
35. 2 mole of an ideal monoatomic gas 39. 3 mole of a diatomic ideal gas which is
undergoes a reversible process for which heated and compressed from 298 K and 1
PV 2  C . The gas is expanded from initial bar to 596 K and 4 bar S is
volume of 1L to final volume of 3L starting
5
from initial temprature of 300K. H for [Given : Cv , m  gas   R;
2
the process is :
A) -600R B) -1000R ln  2   0.70; R  2 cal K 1 mol 1 ]
C) -3000R D)-2000R
A) 14.7 cal K 1 B) 14.7 cal K 1
36. The enthalpy of neutralization of a weak
monoprotic acid (HA) in 1 M solution with a C) 4.9 cal K 1 D) 6.3 cal K 1
strong base is -55.95 kJ/mol. If the unionized 40 One mole of an ideal monoatomic gas at
acid requires 1.4 kJ/mol heat for its
complete ionization and enthalpy of 270 C is subjected to a reversible isoentropic
neutralization of the strong monobasic acid compression until final temperature reached
with a strong monoacidic base is -57.3 kJ/ to 327 0 C . If the initial pressure was 1.0 atm
mol. What is the % ionization of the weak then find the value of ln P2 : (Given :
acid in molar solution?
A) 1% B) 3.57% C) 35.7% D) 10% ln 2  0.7 )
37. Consider the following data: A) 1.75atm B) 0.176atm
C) 1.0395 atm D) 0atm
 f H 0  N 2 H 4 , l   50kJ / mol , 41. For a perfectly crystalline solid
f H 0
 NH , g   46kJ / mol
3 C p,m  aT 3  bT , where a and b are constant

B.E.  H  H   436 kJ / mol , If C p ,m is 0.40 J/K mol at 10 K and 0.92 J/

K mol at 20 K , the molar entropy at 20K is
vap H  N 2 H 4 , l   18kJ / mol
A) 0.92J/K mol B) 8.66 J/K mol
BE  N  H   393KJ / mol C) 0.813 J/K mol D) 8.314 J/K mol
42. Calculate  f G 0 for  NH 4Cl , s  at 310 K.
The N-N bond energy in N 2 H 4 is
A) 226 kJ/mol B) 154kJ/mol  f H 0  NH 4Cl , s   314.5 KJ / mol ;
C) 190kJ/mol D) 182kJ/mol
rC p  0
38. If enthalpy of hydrogenation of
C6 H 6  l  int o C6 H12  l  is  205 kJ a n d S 0 N 2( g )  192 JK 1mol 1
resonance energy of
S 0 H 2 ( g )  130.5 JK 1mol 1
C6 H 6  l  is  152kJ / mol then enthalpy of
S 0Cl2( g )  233JK 1mol 1
hydrogenation of is Assume S 0 NH 4Cl ( s )  99.5 JK 1mol 1

Hvap of C6 H6  l  , C6H8  l  , C6H12  l  are equal All given data at 300 K.

A) -535.5 kJ /mol B) -238 kJ/mol A) 198.56 kJ / mol B) 426.7 kJ / mol
C) -357 kJ/mol D) -119 kJ/mol C) 202.3 kJ / mol D) -84-5 kJ /mol
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43. Calculate  f H 0  in kJ / mol  for Cr2 O3 47. Select the correct statements:
(A) temperature can be raised in an insulated
from the  r G 0 and the S 0 values provided
system by doing electrical or mechanical work
at 270 C (B) temperature can be lowered in an insulated
4Cr  s   3O2  g   2Cr2O3  s  ; system by doing electrical or mechanical work
(C) temperature cannot be lowered in an
 r G 0  2093 kJ / mol
insulated system by doing electrical or mechanical
S 0  J / K mol  : S 0  Cr , s   24; work
S 0  O2 , g   205; S 0  Cr2O3 , s   81 (D) temperature cannot be raised in an insulated
system by doing electrical or mechanical work
J K 1 mol 1 48. Which statements are correct?
A)-2258.1 kJ /mol B) -1129.05 kJ/mol (A) A spontaneous chemical reaction has
C) -964.35 kJ/mol D) 3462kJ/mol
maximum total entropy
MULTI ANSWER QUESTIONS (B) The entropy increases in an irreversible
adiabatic process
44. In an isothermal ideal gas expansion (C) The entropy decreases in a reversible
A) w  0 B) U1  U 2 adiabatic process
V
(D) The entropy does not change in a reversible
2
C) H1  H 2 D) q  nRT ln V adiabatic process
1
49. The enthalpy of reaction depend upon:
45. In an adiabatic process, the work involved
during expansion or compression of an ideal (A) The manner by which the reaction is carried
gas is given by out
nR (B) Temperature at which the reaction is carried
A) nCV T B) T2  T1  out
 1
(C) Physical state of reactants and products
 T2 P1  T1 P2  (D) Whether the reaction is carried out at
C) nRPext  P P  constant pressure or at constant volume
 1 2 
50. Select the correct statements:
V2
D) 2.303 RT log V (A) State of a system is assumed to be in internal
1 equilibrium and the temperature and pressure
46. The value of are uniform throughout the system
H transition of C  graphite   C (diamond) (B) Thermal drift ina system with time is more in
is 1.9 kJ/mol at 250 C entropy of graphite Dewar flask than in insulated system.
is higher than entropy of diamond. This (C) Thermal drift in a system with time is more
implies that in non-insulated system than in in1sulated system.
A) C (diamond) is more thermodynamically (D) Thermal drift in a system with time is more
stable than C (graphite ) at 250 C in insulated system than in non-insulated system
B) C (graphite) is more thermodynamically stable 51. Which are not correct representation at
than C (diamond ) at 250 C equilibrium:
C) diamond will provide more heat on complete
V
1 S/ R
combution at 250 C (A) V  e (B) K  eG o
/ RT
2
Gtransition of C  diamond 
D) is -ve V S / RT P
 C  graphite  2
(C) V  e
2
(D) P  e
H / RT

1 1
 THERMODYNAMICS (ENERGETICS)
52. Select the correct statements:
(A) Dissolution of KCl in water shows an
increase in entropy
(B) Acetic acid in benzene shows a decrease in
entropy
(C) The benzene solution containing acetic acid
is more ordered than molecular acetic acid.
(D) The solution containing ionised acitic acid is
less ordered than molecular acetic acid.
53. Which of the following expression may be
represents for the spontaneous reaction
(A)  G T.P   ve (B)  G T.P.   ve
(C)  H P.T   ve (D)  SE.V   ve
54. Choose the correct statements:
(A) There is net reduction in energy when a large
number of gas phase K+ and Cl– ions come
together to form a bulk ionic solid
(B) There is a net increase in energy when a
large number of gas phase K+ and Cl– ions come
together to form a bulk ionic solid
(C) The net effect of all the ion interactions in
the solid KCl lattice, is attraction, because the
cation or anion is the closest to ions of opposite
charge
(D) The net effect of all the ion interactions in
the solid KCl lattice, is repulsion, because the
anion and cation is the closest to ions of same
charge.
55. Choose the correct statements:
(A) The enthalpy change for the reverse of any
process is the negative of the enthalpy change
for the original process
(B) The enthalpy change for the reverse of any
process is not the negative of the enthalpy change
for the original process and depends on the path
taken from the initial state of the final state
(C) Generally, the higher the freezing point, the
higher the enthalpy of melting
(D) Generally, the higher the freezing point, the
lower the enthalpy of melting
56. During the formation of an ion pair, say
between a gaseous K atom and a gaseous
Cl atom, as they approach each other, one
contribution to energy is the energy.
(A) Needed to form the K ions from a K atom
in the gas phase, which is the electron affinity of
potassium
(B) Needed to form the K+ ions from a K atom
in the gas phase, which is the ionisation energy
of potassium
(C) Released when the Cl- ion forms from a Cl
atom in the gas phase which is the electron affinity
of chlorine
(D) Needed to form the Cl- ion from a Cl atom
in the gas phase which is the ionisation energy of
chloride
57. Which of the following statements is/are
correct for bond enthalpies in case of
general diatomic molecules?
(A) Bond enthalpy increases with the increase
in the number of bonds between the atoms
(B) Bond enthalpy decreases with the increase
in the number of bonds between the atoms
(C) Bond enthalpy increases with the increase
in the size of the neighbouring atoms
(D) Bond enthalpy decreases with the increase
in the size of the neighbouring atoms
58. Which of the following statements is/are
correct
(A) Absolute value of internal energy cannot be
determined
(B) Absolute value of heat content can be
determined
(C) Absolute value of entropy can be determined
(D) All the three E, H and S are extensive
properties
59. In the reaction, 2H 2  g   O 2  g   2H 2 O  l 
H   x kJ
(A) x kJ is the heat of formation of H2O
(B) x kJ is the heat of reaction
(C) x kJ is the heat of combution of H2
(D) x/2 kJ is the heat of formation of H2O
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60. Predict in which of the following, entropy 64. Choose the correct statements:
increases/decreases: (A) The enthalpy of combustion of a fuel per
(A) A liquid crystallizes into a solid. gram (expressed without a negative sign) is called
(B) Temperature of a crystalline solid is raised its specific enthalpy
from 0 K to 115 K. (B) The enthalpy of combustion of a fuel per
(C) 2NaHCO3(s) gram (expressed without a negative sign) is called
  Na2CO3(s) + CO2(g) + H2O(g) its enthalpy density
(D) H2(g)  2H(g) (C) The enthalpy of combustion of fuel per litre
61. The vapour pressure of solid benzoic acid (expressed without a negative sign) is called its
has been found to obey the relationship (in specific enthalpy
the neighbourhood of 298 K) as: (D) The enthalpy of combustion of fuel per litre
(expressed without a negative sign) is called its
P b
ln o
a ; where a = 22.88 and b = enthalpy density
P T
65. 200 g of water is contained in a beaker of
1.07×104K Which of the following values are
mass 150 g at 20°C. The temperature of
correct at 298 K for the sublimation of
water is required to be raised to 80°C. It is
benzoic acid?
given that the specific heat of water is
(A) G o  32.34 kJ mol1 4.184J/(g°C) and of glass is 0.78J/(g°C).
(B) Ho  88.96kJ mol1 Then
(A) Heat required by water is 50.2 kJ
(C) So  190 JK 1 mol1
(B) Heat required by glass is 7.0 kJ
(D) Ho  88.96kJ mol1 (C) Heat required by glass 9.4 kJ
62. Select the incorrect statements about the (D) Total heat required is 57.2 kJ
plots of ln K vs 1/T 66. Which statements are correct?
(A) A spontaneous chemical reaction which starts
G o
(A) Linear with slope equal to and far from equilibrium always gives irreversible
R
process.
intercept H
(B) The entropy increases in an irreversible
(B) Curve
adiabatic process
H o S (C) The entropy decreases in reversible adiabatic
(C) Linear with slope and intercept
R R process
(D) none of these (D) The entropy does not change in a reversible
63. A 250 W electric heater raised the adiabatic process
temperature of a calorimeter by 4.22°C in 67. Select the correct statements:
55s. When the oxidation of a methanol (A) Gibbs energy plays the same role for a
sample was carried out in the same chemical system as the gravitational energy plays
calorimeter, the temperature rose from for a purely mechanical systems
22.49°C to 26.77°C. Then, (B) Gibbs energy is minimum at definite pressure
(A) The amount of heat supplied by the electric and temperature for a chemical system at
heater is 13.75 kJ equilibrium
(B) The amount of heat supplied by the electric
(C) A positive value of G o does not mean that
heater is 4.6 kJ
(C) The enthalpy of change for the oxidation is the reaction does not occur spontaneously.
1.39 kJ (D) A negative value of G o means for the
(D) The enthalpy of change for the oxidation is spontaneous conversion of reactants into
13.9 kJ products, if both are in standard states
 THERMODYNAMICS (ENERGETICS)
68. Point out the correct statements: 72. Given
(A)Oxides of nitrogen are thermodynamically
2 Fe2O3 s   4 Fe s   3O2 g  ;
unstable with respect to decomposition into
,
elements  G10  1487kJ mol 
(B) A spontaneous process does not necessarily
6CO g   3O2 g   6CO2 g  ;
reduce internal energy or enthalpy of a system
(C) For thermodynamic equilibrium Stotal  0  r G20  1543.2kJ mol 1

(D) Entropy can not decrease in an isolated correct statement is:

system A)  r G 0 for reduction of iron oxide by CO is
69. Which of the following statements are +56.2 kJ mol 1
correct?
B) Fe2O3 can be reduced by CO
(A) The entropy of an isolated system increases
spontaneously
in an irreversible process
C) Fe2O3 cannot be reduced by CO
(B) The entropy of an isolated system remains
unchanged in a reversible process spontaneously
(C) Entropy can never decrease D) The reduction of Fe2O3 takes part in higher
(D)  s(system) as well as  s (surroundings) part of blast furnace
are negative quantities 73. Whic of the following is incorrect for the
change shown below?
70. Which one of is not correct for a cyclic 1
r S
process as shown in figure? aA  bB   cC  dD
(298 K ) (298)

 r S 2    r S 4

S 3
aA  bB   cC  dD
(0 K ) (0 K )

A)  r S1  cSC  dS D  (aS A  bS B )

B)  r S2    aS A  bS B 

C)  r S3  0.
A) dU  0 B) q   w D)  r S 4   cSC  dS D 
C)W =314 J D)W = 31.4 J 74. Which of the following figures given below
71. Select the correct statements for the shows adiabatic process;
equilibriun under standard conditions
 H 2O( l ) ; S1
H 2O( s ) 

 H 2O( v ) ;  S 2
H 2O( l ) 

 H 2O( v ) ; S3
H 2O( s ) 

A) S1  S 2 B) S 2  S1

A) II,III B) I,III
C) S3  S 2 D) S3  S1 C) II,IV D) I,IV
JEE
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75. He, N 2 and O3 are expanded adiabatically
and their expansion curves between P
and V are plotted under similar
conditions.About the ratio of the slopes,
which one is not correct;
A)the ratio of slopes of P-V curves for He and
O3 is 1.25
B)the ratio of slopes of P-V curves for He and
N 2 is 1.20
C)the raio of slopes of P-V curves for
N 2 and O3 is 1.05.
D)the slope of He is least steeper and for O3 is
most steeper.
76. Heat of neutralisation of strong acid and
strong base under I atm and 25 C is -13.7
kcal. If standard Gibbs energy change for
dissociation of water to
H  and OH  is  19.14 kcal,the change is
standard entropy for dissociation of water
in cal K 1 mol 1 is;
A)18.25 B)110.2
C)-18.25 D) none of these.
77. An ideal gas is allowed to expand both
reversily and irreversibly in an isolated
system. If T1 is the initial temperature,which
of the following statement is correct?
A) (T f )irrev  (T f )rev
B) (T f  Ti for reversible process but T f  Ti for
irreversible process.
C) (T f ) rev  (T f )irrev
D) T f  Ti for both reversible and irreversible
process
78. One mole of CH 3COOH undergo
dimerization in vapour state at 1270 C
as 2CH3COOH  g    CH3COOH 2  g  if
dimer formation is due to two H-
bonds involved in dimer, each of 33kJ
strength and the degree of dimersation of
acetic acid 98.2% which is correct
A) S 0 for dimerization is negative
B) S 0 for dimerization is positive
C) S 0 for dimerization is -104.1J/mol
D) S 0 for dimerization is + 1.04J/mol
79. Work done in expansion of an gas from 4
litre to 6 litre against a constant external
pressure of 2.5 atm was used to heat up 1
mole of water at 293 K. If specific heat of
water is 4.184J g 1 K 1 , the final
temperature of water is nearly ?
A)300K B)456K C)278K D)600K
80. 2 mole of a perfect gas at 27 0 C if is
compressed reversibly and isothermally
from a pressure of
1.01  105 Nm 2 to 5.05  106 Nm 2 which is
correct among the following
A) work done on the gas is 1.9518  104 J
B) Free energy change for the process is
1.9518  104 J
C) work done on the gas is 1.19  107 J
D) Free energy change for the process is -
1.19  107 J
3
81. If one mole of an ideal gas with Cv  R is
2
heated at a constant pressure of 1 atm 250 c
to 1000 C. Which is correct
A) U during the process is 223.51cal
B)  H during the process is 372.56 cal
C) entropy change during the process is
1.122 cal k 1 mol 1
D) U , H are same for the process
82. One mole of an ideal gas is subjected to a
two step reversible process as shown in
figure.  A  Band B C the pressure at A
and C is same. The correct statement(s) is/
are
(1,100)
B(3,600)
A
P(atm )
C(1,300)
T K
A) Work involved in the path AB is zero
B) In the path AB work will be done on the gas
by the surroundings
C) Volume of gas at C= 3 volume of gas at A
D) Volume of gas at B is 16.42 litres
 THERMODYNAMICS (ENERGETICS)
83. For a process to be spontaneous
A)  Gsystem T , P  0
B) S system  S surrounding 0
C) S system  S surrounding 0
D)  Gsystem T , p  0
84. The normal boiling point of a liquid ‘X’ is
400K. Which of the following statement
is true about the process X  l   X  g  ?
A) At 400 K and 1 atm pressure G  0
B) At 400K and 2 atm pressure G  ve
C) at 400K and 0.1 atm pressure G  ve
D) at 410 K and 1 atm pressure G  ve
85. Which of the following statements (s) is/are
false?
A) all adibatic process are isoentropic (or
isentropic) processes
B) When  Gsystem T , p  0; the reaction must
be exothermic
C) dG  VdP  SdT is applicable for closed
system, both PV and non-PV work
D) The heat of vaporisation of water at 1000 C
is 40.6 kJ/mol. When 9gm of water
vapour condenses to liquid at 1000 C of 1 atm,
then Ssystem  54.42 J / K
86. From the following data, mark the option
(s) where H is correctly written for the
given reaction. Given
 
H  aq   OH  aq   H 2O  l  ;
H  57.3 kJ
H solution of HA  g   70.7kJ / mol
 H solution of BOH  g   20kJ / mol
H ionization of HA  15kJ / mol and BOH is a
strong base Reaction H r  kJ / mol 
A) HA  aq   BOH  aq   BA  aq   H 2O -42.3
B) HA  g   BOH  g   BA  aq   H 2O -93.0
C) HA  g   H   aq   A  aq 
D) B   aq   OH   aq   BOH  aq  -20.0
COMPREHENSION TYPE QUESTIONS
Comprehension–1
The bond dissociation energy of a diatomic
molecule is also called bond energy. However,
the bond dissociation energy depends upon the
nature of bond and also the molecule in which
the bond is present.
The bond energy of N — H bond in NH3 is
equal to one-third of the energy of dissociation
of NH3 because there are three N-H bonds and
those of C — H bond in CH4 is equal to one-
fourth of the energy of dissociation of CH4.
Heat of a reaction = Bond energy of reactants -
Bond energy of products
87. The enthalpy changes for the reaction
H 2 O (g)  H (g)  OH (g) and
OH (g)  O(g)  H(g) are 501.87kJmol1 and
423.38kJmol1 . The bond enthalpy of O-H bond
is
(A) –462.625 kj mol–1 (B) 462.625 kJ mol–1
(C) -713.54 kJ mol–1 (D) 713.54 kJ mol–1
88. In which of the following , the bond enthalpy
and bond dissociation enthalpy are identical?
(A) H- H bond enthalpy in H2 (g)
(B) O-H bond ehthalpy in H2O (g)
(C) C- H bond enthalpy in CH4(g)
(D) N- H bond enthalpy in NH3 (g)
89. Find the bond ehthalpy of S-S bond from
the following data.
C2H5 - S-C2H5 (g) H0f = -147.23 kJ mol–1
0
C2H5 - S-S-C2H5 (g) Hf = -201.92 kJ mol–1
0
S (g) Hf = 222.80 kJ mol–1
-55.7
(A) –277.49 kJ mol–1 (B) 277.49 kJ mol–1
(C) –349.15 kJ mol–1 (D) 349.15kJmol–1
JEE
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COMPREHENSION -2
Two vessels A and B are connected via a
stopcock. The vessel A is filled with a gas at a
certain pressure and the vessel B is completely
evacuated. The entire assembly is immersed in a
large vat of water and is allowed to come to
thermal equilibrium with the water. The stopcock
is opened and the gas is allowed to expand till
both the vessels are uniformly occupied. After
sometime when the vessel has again come to
thermal equilibrium, temperature of the water is
recorded. The result shows that the temperature
of water after the experiment is the same as that
before.
90. For the expansion referred to above, which
of the following is true?
(A) du = 0 (B) du >0 (C) du < 0 (D) dq > 0
91. Taking ‘U’ as a function of T and V, under
the given conditions of the experiment.
Choose the correct statement.
(A) The change in energy of a gas with change
of volume at constant temperature is a positive
quantity.
(B) The energy of the gas is a function of
temperature only.
(C) The change in energy of a gas with change
of volume at constant temperature is a negative
quantity.
(D) The result is applicable to both ideal and real
gases.
92. The expansion that occurred is
(A) isothermal reversible expansion
(B) isothermal irreversible expansion
(C) adiabatic reversible expansion
(D) isothermal free expansion
Comprehension–3
The first law of thermodynamics was gives as q
= U + (-w); where q is heat given to a system
and U represents increase in internal energy
and -w is work done by the system. Various
processes such as isothermal, adiabatic, cyclic,
isobaric and isochoric process in terms of first
law of thermodynamics leads for important
results. The molar heat capacity for 1 mole of
monoatomic gas is 3/2R at constant volume and
5/2R at constant pressure.
1. Increase in internal energy from state A to state
B is 50 J.
93. Which of the following statements are
correct :
(1) Both work and heat appears at the boundaries
of system.
(2) Heat given to a system is given +ve sign.
(3) Heat given to a system is equal to increase in
internal energy under isothermal conditions
(4) Heat given to a system is used to increase
internal energy under isochoric conditions
(5) Both work and heat are not state functions
but their sum (q + w) is state function.
(A) 1, 2, 4, 5 (B) 1, 3, 4, 5
(C) 1, 2, 3, 4 (D) 2, 3, 4, 5
94. A system is allowed to move from state A to
B following path ACB by absorbing 80 J of
heat energy. The work done by the system
is 30J. The work done by the system in
reaching state B from A is 10 J through path
ADB which statements are correct:
1. Increase in internal energy from state A to state
B is 50 J.
2. If path ADB is followed to reach state B,
U  50 J
3. If work done by the system in path AB is 20
J, the heat absorbed during path AB = 70J.
4. The value UC - UA is equal to UD - UB.
5. Heat absorbed by the system to reach B from
A through path ADB is 60 J.
(A) 1, 5 (B) 1, 3, 5
(C) 1, 2, 3, 5 (D) 1, 4, 5
95. 1 mole of a monoatomic gas is expanded
through path ABC as shown in figure.
Select the correct statements :
(1) If specific heat of gas are 0.125 and 0.075
cal/g, the mol. wt. of gas = 40.
(2) Temperature at point A, B, C are 273, 546
and 273 K respectively.
(3) U for the process A to B is 2.27 kJ.
(4) U for the process B to C is 3.44 kJ.
(5) U for the overall cycle A  B  C  A
is 3.4 kJ.
(A) 1, 2, 3, 4 (B) 3, 4, 5
(C) 1, 3, 4 (D) 1, 2, 5
 THERMODYNAMICS (ENERGETICS)
Comprehension–4 q rev.
Enthalpy of neutralization is defined as the change in entropy S  . The entropy
T
enthalpy change when 1 mole of acid/base is changes also occurs during transformation of one
completely neutralized by base/acid in dilute
solution. For strong acid and strong base H
state to other and expressed as T  . Both
neutralization net chemical change is T
entropy and enthalpy changes obtained for a
H   aq   OH   aq 
process were taken as a measure of spontaniety
 H 2 O  l  ;  r H 0  55.84kJ / mol of process but finally it was recommended that
decrease in free energy is responsible for
H 0 ionization of aqueous solution of strong acid spontaniety and G  H  T S .
and strong base is zero. When a dilute solution 99. Which of the following statements are
of a weak acid or base is neutralized, the enthalpy correct:
of neutralization is some what less because of (1) The expansion work for a gas into vacuum is
the absorption of heat in the ionization of the equal to zero.
weak acid or base for weak acid /base (2) 1 mole of a gas occupying 3 litre volume on
H 0 neutralization  H 0 ionization   r H 0 expanding to 15 litre at constant pressure of 1
atm does expansion work 1.215 kJ.
H 
 OH   H 2O  (3) The maximum work done during expansion
96. If enthalpy of neutralization of of 16 g O2 at 300 K from 5 dm3 to 25 dm3 is
2.01 kJ.
CH 3COOH by HCl is -49.86 kJ /mol then
(4) The S for S  L is almost negligible in
enthalpy of ionization of CH 3COOH is comparison to S for L  G .
A) 5.98 kJ/mol B) 5.98kJ / mol V
C) 105.7kJ / mol D) 10.57kJ/mol (5) S = 2.303 nR log 2 . (at constant T)
V1
97. What is H 0 for complete neutralization of (A) 2, 3, 4, 5 (B) 1, 2, 3, 4, 5
strong diacidic base A  OH  2 by HNO3 (C) 1, 2 (D) 4, 5
A) -55.84 kJ B) -111.68 kJ 100. The heat of vaporisation and heat of fusion
of H2O are 540 cal/g and 80 cal/g. The ratio
C) 55.84kJ / mol D) -49.86kJ/mol
98. Under the same conditions how many mL of Svap .
of for water is:
0.1 M NaOH and 0.05 M H 2 A (strong S fusion
diprotic acid) solution should be mixed for a (A) 6.75 (B) 9.23 (C) 4.94 (D) 0.2
total volume of 100 mL produce the highest 1
rise in temprature 101. Ag2O(S)   2Ag(S) + O2 (g) ; attains
A) 25: 75 B) 50:50 2
C) 75: 25 D) 66. 66:33.33 equilibrium at temperature . . . K is:
Comprehension–5 (The H and S for the reaction are 30.5 kJ/
Work done by the system in isothermal reversible mol and 66 J/ mol/ K)
(A) 462.12 (B) 237
V2
process is : wrev. = -2.303 nRT log V . Also in (C) 373 (D) 273
1 102. A chemical change will definitely be
case of adiabatic reversible process work done spontaneous if :
nR (A) H = -ve, S = -ve and low temperature
by the sytem is given by : wrev. = [T2  T1 ] .
 -1 (B) H = +ve, S = -ve and high temperature
During expansion disorder increases and the (C) H = -ve, S = +ve and any temperature
increase in disorder is expressed in terms of (D) H = +ve, S = +ve and T S<H
JEE
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106. Match the column:
MATRIX MATCHING Column – I
A) Joule Thomson coefficient for ideal gas
103. Match the following
B) Svap , m for liquids which does not
Column – I
A) Free energy change G of a reaction undergo association and dissociation
B) Enthalpy change of a reaction in standard C) Work done in adiabatic irreversible
state H0 expansion of an ideal gas
C) Entropy change S of a reaction D) Work done in adiabatic reversible
D) Free energy change of a reaction in expansion of an ideal gas
standard state
Column – II Column – II
P) - RTlnK P) 88 J mol-1 K-1
2  d ln K  Q) nCv m  T2  T1 
Q) RT  dT  R) 0
 P
R) – nFE
 T2 P2 
 d G  S) nRT1  T  P 
S)     1 1 
 dT  P
104. Match the following 107. Columm - I
Column – I (A) (DGsystem) T,P = 0
A) G (B) DSsystem + DSsurrounding > 0
B) G 0 (C) DSsystem + DS surrounding < 0
C) W or Wmax (D) (DGsystem) T,P > 0
D) S 0
Column – II Columm - II
P) nFE or  nFE 0 (P) Process is in equilibrium
(Q) Process is nonspontaneous
Q) H  T S
R) – RT logeK (R) Process is spontaneous
(S) System is unable to do useful work
V2  108. Columm - I
S) 2.303 nR log10  V 
 1 (A) (DGsystem) T,P
(B) Work done in reversible isothermal ideal
105. Match the list – I with list - II gas expansion
List – I (Thermodynamic properties) (C) DG for reversible isothermal expansion of
A) Free energy change of a reaction (G) an ideal gas
B) Enthalpy change of a reaction in a
standard state (H0) (D) DSgas for isothermal expansion of an ideal
gas
C) Entropy change  S 0  Columm - II
D) Free energy change of a reaction in a
V2 
standard state  G 0  (P) nR In  V 
 1 
List – II (Equation)
P) –RTlnK P2 
(Q) nRT In  P 
 1 
2  d ln K 
Q) RT 
 dT  P (R) – nFE
R) – nFE
P1 
 d G  (S) nR In  P 
S)    
 dT  P
2
 THERMODYNAMICS (ENERGETICS)
109. Columm - I 113. The feasibility of a chemical reaction can
(A) Heating of an ideal gas at constant pressure be explained based on DH, DS and DG, so
(B) Compression of liquid at constant answer the following :
temperature Column-I
(C) Reversible process for an ideal gas at (A) 2O3(g)  3O2(g)
constant temperature (B) 3O2(g)  2O3(g)
(D) Adiabatic free expansion of an ideal gas (C) NH2COONH4(s)    2NH3(g) + CO2(g)
Low temp.
Columm - II
(D) Ice H2O (l) at room temperature 25ºC
(P) DH = nCp,m DT ¹ 0
Column–II
(Q) DU = 0(R) DG = V DP (p) DH = +ve, DS = –ve

P2  (q) DH = –ve, DS = +ve
(S) DG = nRT In  P  (r) DG = +ve
 1 
(s) DH = –ve
110. Columm - I (t) DG = –ve
(A) Reversible adiabatic compression 114. Match the following :
(B) Reversible vaporisation of liquid Column-I
(C) 2N(g) ® N2(g) (A) H2(g)
 (B) H2O(l)
(D) MgCO3(s)  MgO(s) + CO2(g)
(C) C(diamond)
Columm - II (D) NO(g)
(P) DSsystem > 0 Column–II
(Q) DSsystem < 0 (p) DHfº = 0
(R) DSsurrounding < 0 (q) DGfº = 0
(S) DSsurrounding = 0 (r) Entropy at absolute zero = 0
111. Columm - I (s) Entropy at absolute zero  0
(A) H+ (aq) (T) DGFº  0
(u) DSfº = 0
(B) H(g)
(C) H2(g) STATEMENT TYPE QUESTIONS
(D) C (s, diamond)
Columm - II 115. Statement – 1: For a process to be
(P) DfHº = 0 spontaneous, G as well as S has to be
(Q) DfHº ¹ 0 less than zero.
(R) DfGº = 0 Statement – 2: For spontaneous change,
(S) DfSº < 0 Stotal  0
112. Column - I a) Statement-1 is true, Statement-2 is true,
(A) An ideal gas Statement-2 is a correct explanation for
(B) A real gas at inversion temperature statement-1
(C) H2 gas at STP b) Statement-1 is true, Statement-2 is true,
(D) NH3 gas at STP Statement-2 is not a correct explanation for
Column - II[Under adiabatic free expansion] statement-1
(p) Temperature increases c) Statement-1 is true, Statement-2 is false
d) Statement-1 is false, Statement-2 is true
(q) Temperature decreases
116. Statement – 1: Phase transition involves
(r) Temperature remains constant change in internal energy only.
(s)Temperature first increases and then Statement – 2: Phase transition occurs at
decreases constant pressure.
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117. Statement – 1: The work done in an open
container at 300 K, when 112 g of iron
reacts with dil. HCl is
1200 cal.
Statement – 2: Work done = Pext V2  V1  ,
where V1 and V2 are initial and final
volume of reaction mixture &
Pext is external applied pressure.
118. Statement – I: Many endothermic
reactions that are not spontaneous at
room temperature become spontaneous at
high temperatures.
Statement – II : Energy of the system
increases with increase in temperature.
119. Statement – 1: In the case of an ideal gas
the change in Gibbs free energy and
Helmholtz free
energies are equal to each other
 G  A for isothermal reversible
process.
Statement – 2:?There is no change in
internal energies and enthalpies for ideal
gas at constant
temperature.
120. Statement – I: The heat absorbed during
the isothermal expansion of an ideal gas
against vacuum is zero.
Statement – II : The volume occupied by
the molecules of an ideal gas is zero.
121. Statement – 1: For a reaction at
equilibrium, the free energy for the
reaction is minimum.
Statement – 2: The free energy for both
reactants and products decreases and
become equal.
122. Statement – I: CP – CV = R for ideal gas.
 dU 
Statement – II :    0 for ideal gas
 dV T
CP – CV = R is correct statement
 dU 
   0 is also correct
 dV T
 dU 
But because   0
 dV T
Therefore, to say CP – CV = R is not a
correct reasoning.
123. Statement – 1: The amount of heat change
during the isothermal free expansion of an
ideal gas is zero.
Statement – 2: There are no
intermolecular forces of attraction among
the gas molecules, in case of real gas at a
given pressure.
124. Statement – 1 : The enthalpy of formation
of H2O(l) is greater than of H2O (g).
Statement – 2: Enthalpy change is nega-
tive for the condensation reaction
H2O (g)  H2O(l)
125. Statement – 1 : Heat of neutralisation of
H3PO4 with NaOH is more than that of
HCl with NaOH.
Statement – 2 : H3PO4 is a triprotic acid
and hence releases more heat on complete
neutralization, while HCl is a monoprotic
acid.
126. Statement – 1: Work done by the sur-
rounding on the system of an ideal gas to
do a particular isothemal compression
reversibly is less than that done irrevers-
ibly.
Statement – 2: Isothermal reversible
compression takes place through infinite
number of infinetesimally small steps.
127. Statement – 1 : The magnitude of the work
involved in an isothermal reversible
expansion is greater than that involved
in an adiabatic reversible expansion.
Statement – 2 : Adiabatic expansion is
associated with fall in temperature of the
system which in turn decreases the
pressure of the system to a lower value
than that in isothermal process.
128. Statement – 1 : For every chemical reac-
tion at equilibrium, standard Gibbs energy
of reaction is zero.
and
Statement – 2: At constant temperature and
pressure, chemical reactions are spontane-
ous in the direction of decreasing Gibbs en-
ergy.      
 THERMODYNAMICS (ENERGETICS)
129. Statement – 1 : There is a natural asym-
metry between converting work to heat
and converting heat to work.
and
Statement – 2 : No process is possible in
which the sole result is the absorption of
heat form a reservoir and its complete
conversion into work.
130. Statement – 1 : Entropy change in revers-
ible adiabatic expansion of an ideal gas is
zero.
Statement – 2: The increase in entropy
due to volume increase just componsate
the decrease in entropy due to fall in
temperature.
131. Statement – 1 : The standard free energy
changes of all spontaneously occuring
reactions are negative.
Statement – 2: The standard free energies
of the elements in their standard states at
1 bar and 298 K are taken as zero.
132. Statement – 1 : Enthalpy and entropy of
any elementary substance in the standard
states are taken as zero.
Statement – 2 : At absolute zero, particles
of the perfectly crysalline substance
become completely motionless.
133. Statement – 1: A reaction which is
spontaneous and accomapnied by
decrease of randomness must be
exothermic.
Statement – 2: All exothermic reactions
are accompanied by decrease of
randomness.
134. Statement – 1 : Many endothermic
reactions that are not spontaneous at
room temperatures become spontaneous
at high temperature.
Statement – 2 : DHº of the endothermic
reaction increases with increase in
temperature.
135. Statement – 1 : Decrease of free energy
during the process under constant
temperature and pressure provides a
measure of its spontaneity.
Statement – 2 : A spontaneous change
must have + ve sign of DSsystem.
136. Statement – 1 : All combustion reactions
are exothermic.
Statement – 2 : Enthalpies of products
greater than enthalpies of reactants
(SvpDfH(P) > SvRDfH(R))
137. Statement – 1 : Due to adiabatic free
expansion temperature of real gas may
increase
Statement – 2 : In adiabatic free expan-
sion, temperature is always constant
irrespective of real or ideal gas
138. Statement – 1: Under adiabatic free
 dU 
expansion ,  dV  is + ve when attractive
 T
forces are dominant between gas mol-
ecules [U, V, T respresent internal energy,
volume and temperature of gas respec-
tively]
Statement – 2 : Internal energy is a state
function.
139. Statement – 1 : At low temperatures, DH
is the dominant factor for spontaneity of a
reaction.
Statement – 2: At low temperatures, the
opposing factor TDS remains very small.
140. Statement – 1 : A reaction which is sponta-
neous and accompanied by decrease of
randomness must exothermic.
Statement – 2 : All exothermic reactions
are accompanied by decrease of random-
ness.
INTEGER TYPE QUESTIONS
141. Temperature of one mole of helium gas is
increased by 10 C, find the
increase in internal energy in cal.
142. An ideal gas is taken through the cycle
A  B  C  A As shown in figure. If
net heat supplied to the gas in the cycle is
5 j . Find the work done by the gas in the
process C  A in Joule (taken mole
value)
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143. If 2kcal heat is given to a system and 6
kcal work is done on the system then the 62.(A, B) 63.(A, D)
internal energy of system will increase by 64.(A, D) 65.(A, B)
how many kcal? 66.(A, B, D) 67.(A, B, D)
144. The constant volume molar heat capacity 68.(A, B, C, D) 69.(A, B)
of an ideal gas is expressed by 70.(a,b,c) 71.(b,c,d)
Cv , m  16.5  102 T (All values are in SI 72.B 73.(d)
units) 74.(a) 75.(d)
If 2.5 mol of this gas at constant valume is 76.(b) 77.(a)
heated from 270 C to1270 C , the internal 78.(c) 79.(a)
energy increases by “x” kJ. Hence, x is 80.A,B 81.(a,b,c)
145. Molar enthalpy of vaporization of a liquid 82(c,d) 83(B,D) 84.(A,B,C)
is 2.6 kJ. If boiling point of this liquid is 85.(A,B,C,D) 86.(A,B,C)
1770c, the molar entropy of vaporization COMPREHENSION TYPE QUESTONS
(in JK-1) unit is 87.(B) 88.(A) 89.(B) 90.(A)
146. The echemical reaction 91. (A) 92.(D) 93.(A) 94.(C)
: A  P H  2.8kJ is spontaneous only 95.(A) 96.(A) 97.(B) 98.(B)
above 400 K. Therefore,  S of reaction 99.(B) 100.(C) 101.(A) 102.(C)
MATRIX MATCHING
must be at least  JK 1 
103. A-R,B-Q,C-S,D-P
104.A – P,Q ; B – P,R ; C – P; D- S
KEY 105. A – R ; B – Q ; C – S ; D – P
LEVEL (V)
SINGLE ANSWER QUESTIONS 106.A – R ; B – P ; C – S ; D - Q
1. A 2. A. 3. D 4. B 107.A -P, S;B - R;C - Q, S; D - Q, S;
5. C 6. C 7. D 8. D
108.A - R;B - Q;C - Q;D - P,S
9. D 10. A 11. A 12. B
109. A - P; B- R;C - Q, S;D - Q, S;
3. C 14. C 15. C 16.C
17.A 18B 19.C 20.A 110.A - S;B - P, R;C -Q;D - P, R;
21.A 22.A 23.A 24.B 111.A - P, R;B - Q;C - P, R; D - Q, S
25.B 26.B 27.A 28.A 112.(A - r) ; (B – r) ; (C - p); (D - q).
29.D 30.D 31.B 32.C 113.(A - q, t) ; (B - p, r) ; (C - r) ; (D - t)
33.C 34.B 35.B 36.B 114.A – p, q, s, u ,B – s, t, u,C – r, t,D – s, t
37.C 38.D 39.D 40.A STATEMENT TYPE QUESTIONS
41.C 42.A 43.B
115.(D) 116. (D) 117. (A) 118 (C)
ONE OR MORE ANSWER QUESTIONS
119 (A) 120 (B) 121 (A) 122 (B)
44.(B,C,D) 45.(A,B,C)
46.B 47.(A, C) 123 (C) 124 (A) 125 (D) 126 (A)
48.(A, B, D) 49.(B, C, D) 127 (A) 128 (D) 129 (A) 130 (A)
50.(A, C) 51.(A, C, D) 131 (B) 132 (D) 133 (C) 134 (C)
52.(A, B, C) 53(A, C, D) 135 (C) 136 (C) 137 (C) 138 ( B)
54.(A, C) 55.(A, C) 139 (A) 140 (C)
56(B, C) 57.(A, D) INTEGER TYPE QUESTIONS
58.(A, D) 59.(B, D) 141 (3) 142 (5) 143 (8) 144 (5)
60.(A, B , C, D) 61.(A, B, C) 145 (8) 146 (7)
 THERMODYNAMICS (ENERGETICS)
12. (B)
LEVEL(V) At constant volume PV  0 , Q  U
HINTS & SOLUTIONS 13. (c)
w   Pext V f  Vi 
SINGLE ANSWER QUESTIONS
 60 103 40 103 100 103 
1. (A)  105    
 0.60 1000 1000 
Wrev    PdV or   PV ; note that
opposing pressure is not constant throughout.  105 100  103  0.04  10 3  0.1 10 3 
2. This is possible for adiabatic wall and thus
U  Wadiabatic ; w  9994 J
3. (D) 14. (c)
B.E. of S = S, C  C , C  N and N  N are U1
H 2O  l ,323 K     H 2O  l ,373K 
523, 839, 891 and 941 kJ mol–1 respectively.
4. (B)  U 2
O3 possesses more energy than O2 U
H 2 O  g , 323 K  3
 H 2 O  g , 373 K 

5. (C) CV , m  H 2O, g   33.314  8.314

If G   ve , process is spontaneous.  25J / K mol
6. (C)
U 2  H 2  ng RT  37.6 ;
n  1 and thus, entropy increases.
U total  U1  U 2  U 3
7. (D)
The gaseous phase have more entropy and  Cv, m  l  T  U vap  Cvap  Cvm  g  T
thus, S is +ve in (A) and (B). Also decrease in 75  50 25  50
pressure increases disorder and thus, S is +ve   37.6  ;
1000 1000
in (C). In (D) the disorder decreases in liquid
 42.6 kJ / mol
state due to decrease in temperature. Thus, S =
15. (c)
–ve.
 r H 0  8   394   9   286    250 
8. (D)  5476kJ / mol
G system   ve , the system is spontaneous (C – H)6 = 6 × 90 = 540 ;
620 = 540 + C – C
process, G system  0 , the system has attained C – C = 80.
equilibrium G system   ve , the system is non 16. (c)
spontaneous. C  s   O2  g   CO2  g  ;
 r H1   xkJ / mol .... (1)
9. (D)
In a cyclic process E  0 CO  g   1/ 2O2  g   CO2  g 
10. (A) W  PV  P  0  0  r H 2   y kJ / mol Equation (1) -(2)
Q  CV  T   20  273  5460 J  5.46 kJ 1
C s  O2  g CO g ;
11. (A) DU = 0 ; -q = w 2
vapour equilibrium n  3  0  3 than
 f H   y  x  kJ / mol
U  30000  3  2  500  27kcal .
JEE
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17. (A)  MgSO4  nH 2 O 
1
H2  g   O2  g   H2O  l   r H 2  13.8 kJ / mol ....... (ii)
2
Equation (i) -(ii) or H hyd   r H1   r H 2
 H  241kJ  ..(i)
17  91.2kJ / mol  13.8kJ / mol
C6 H10  O 2  g   6CO2  g   5H 2 O  l   105kJ / mol
2
 H  3800 kJ  ...(ii) 23. (a) 12250 x  13000 1  x   12500
C 6 H12  9O2  g   6CO 2  g   6H 2 O  l  750 x  500  x  2 / 3 and y  1 / 3 S o ,
 H  3920 kJ  ...(iii) x 2

Eq. (i) + eq. (ii) – eq. (iii) gives y 1
H  241  3800   3920   121kJ 24. (b)
for C 6 H10  H 2  C6 H12 5 3
18. (B)  r H   40   50  43.75 kJ / mol
8 8
Number of moles of HCl 25. Conceptual
MV 0.01 25 26. (b)
   25  105
1000 1000
 r H   Heat supplied    Heat evolved 
HCl  H   Cl n H  25  10 5
Number of moles of Ca(OH) 292   4 x  279  38  85
MV 0.01 50  x  34kcal / mol
   50  105
1000 1000 27. (A)
n OH   2  50  105  10 3 For spontaneous reaction G o   ve
In the process of neutralisation 25×10–5 mole G o  H o  TSo
H+ will be completely neutralised  H o  TSo

H o 179.10  103
H  140  25  105 kcal  0.035kcal  35cal or T   1118K
So 160.2
19. Conceptual
28. (a)
20. (a) qreaction  qbomb  qwater
Cpm
 qreaction   C  bomb    m  c    T    and C p.m  Cv.m  R
water
C vm

  652  500  4.18   14.3

R
 39210 J or 39.21kJ  CV .m 
 1
21. (a) m mole of acid  0.05  0.2  0.01
CV
480  1.09
0
CV .m  and CV  m.cV
r H   52.32 kJ / mol n
0.01 1000
22. (a) R m.cv
   M and
 1 m
Given that ;  r H1  91.2kJ / mol .......(i)
R
MgSO4 7 H 2O  s    n  7  H 2O  Cv 
  1 M
 THERMODYNAMICS (ENERGETICS)
29. (d)  7 7
substituting in eq (1) RT   7  3   
n1CV m1  n2 Cv.m2  6 6
A ev. Cv , m   2R For
n1  n2 49
T
adiabatic process dU=dW 12 R
dT R  dV   1 7
1
 T2  V1   1 5
T Cv ,m  V  33. (c)   ; T2  T1   =
T1  V2   32 
n1CV , m1 dT  n2 CV , m2 dT
2/5
 1 
dV 600  5 
   n1 RT  n2 RT   ; 2 
V
2
1/ 2  600  0.5   150K ;
T2 1 V  1
ln   ln  2   T2  320   
T1 2  V1   4 7
H m  R  150  600   1575 R
=160K 2
34. (b) dU  dp  dw
 
U  n1CV ,m1  n2CV , m2 T  960 R
nCv, m .dT  nCm dT  P.dV ;
30. (d)
1 P.dV
H 2C2O4  l   O2  g   H 2O  l   2CO2  g  ; Cm  Cv ,m  ....... (1)
2 n.dT
ng  3 / 2 PV n  K and PV  nRT

0.312  8.75  KV 1 n  nRT

U c    90
1 K 1  n  V  n .dV  nRdT
 245.7 kJ / mol
dV nR

H  U  ng RT dT K 1  n V  n ............ (2) ; From

3 8.314  300 Eqs (1) and (2)

 245.7  
2 1000 R
Cm  Cv , m 
 246.95KJ / mol 1  n 
31. (B)Conceptual
35. (b)
32. (c)
2 2
Max temp attained by gas in between B to C 2 2  PV
PV 1 1
Accroding to equation of straight line 2
P2  V1  T2 PV2 2 V1 1
P  4 V 1   Now, T  PV  V  3
  P  4  3V  3 P1  V2  1 1 1 2
1  4 2 1
 P  7  3V For 1 mole gas
RT
 7  3V ; RT  7V  3V 2 ; 300
V  T2   100 K ; H  nC p , m T
3
dT 7
R  7  6V  0 ; V 5
dV 6  2  R   200 K   1000 R
2
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36. (b) 39. (d)
 
HA  H  A ;  r H  1.4kJ / mol T2 P
S  nC p m ln  nR ln 1
T1 P2
H neutralization  H ionization H
 r HOH   H 2 O  7  596  1
 3  R ln    3R ln
55.95  H ionization  57.3 2  298  4
H ionization for 1M HA=1.35 kJ/mol  6.3cal K 1
% heat utilizsed by 1M acid for ionization 40. (a)
1.35 For isoentropic process S system  0
  100  96.43%
1.4 T2 P
so, acid is 100-96.3 =3.57% ionizsed  nC p m ln  nR ln 1  0
37. (c) T1 P2
1 3 5  600 
N 2  g   H 2  g   NH 3  g   ln  P2    ln  ; =1.75 atm
2 2 2  300 
Let B.E of N  N is x 41. (c)
x 3 0.40  aT13  bT1
46    436  3  393  x  958
2 2 0.40  a  1000   b  10
N 2 H 4  l   N2  g   2H 2  g 
0.4  1000a  10b ........(1)
 r H  50kJ / mol 0.92  aT23  bT2
  
 r H    va p H N 2 H 4 ,l  4 B . E ( N  H )  B . E ,( N  N ) 
  0.92  a  8000  20b ......(2) from
 B. E  N  N   2 B. E  H  H   Eqs (1) and (2)
50  18  4  393  y    958  2  436  a  2 105 , b  0.038

50  1590  y   1830  aT 3  bT

Sm   .dT
T
B.E .  N  N  or y  190kJ / mol
38. a T23  T13 
  b T2  T1 
3
 0.813 J / K  mol
42. (a)
R.E  f S 0  NH 4Cl , s  at 300 K

HHyd  Theoretical  0 1 1 
.  SNH 4 Cl  s 
  SN0 2  2SH0 2  SCl0 2 
2 2 
HHyd  Actual 
 374JK 1 mol 1   rC p  0
  f S310
0 0
  f S300  374 JK 1 mol 1
 205  152  357 0
 f H 310 0
  f H 300  314.5
0
Enthalpy of hydrogenation of  f G310   f H 0  310S 0

357 310  374 

 119kJ / mol  314.5   198.56kJ / mol
3 1000
 THERMODYNAMICS (ENERGETICS)
43. (b) 66. (A, B, D); factual
0 0
rG   r H  T  r S 0 67. (A, B, D); factual
70. (a,b,c)
 r S 0  2  81  4  24  3  205 J / mol For a cyclic process dU=0
  r H 0  2258.1 kJ / mol  q  U    w  q  w
 r H 0  2   f H 0  Cr2O3 , s  Also, w= area covered by sphere
2
 (V V   (20)2
2258.1  r 2   2 1   1003.14 314 J
  f H 0  Cr2O3 , s     2  22
2
71. (b,c,d) H 2O( s ) has more ordered
 1129.05kJ / mol .
arrangement.Also
 
MULTI ANSWER QUESTIONS  S 2  S H  SH ;
2o( v ) 2o( l )

 
44. (b,c,d)  S 01  S H  SH
2o( l ) 2o( s )

U  0  U 2  U1  0 
 SH is maximum and thus S 2  S1
2o( v )
similary , H  0
V 72. G for 2Fe2O3  600 4Fe  6CO2  rG1 rG2
q  w  nRT ln 2
V1 =+1487-1543.2=-56.2 kJmol 1
45. (A,B,C) Conceptual The reduction occurs spontaneously in lower
51. (A, C, D); defined at equilibrium part of blast furnace.
52. (A, B, C); conceptual 73.
53. (A, C, D); For spontaneous process, (d)  r S4   S p   S R  CSc  dS D  0  0
 G T,P  ve ;  SE, V   ve and 74. (a) Adiabatic slope are more steeper than iso-
thermal.
 H P.T.   ve Slope of adiabatic process=   slope of iso-
54. (A, C); factual thermal process
55. (A, C); factual  for gas 1
56. (B, C); defined 75. (d)Ratio of slope   for gas II ; slope for
57. (A, D)
58. (A, D)  Internal energy depends upon large He, N 2 and O3 are 7/5,5/4 and 4/3
no. of factors, U = Etra + Erot + Enuclear + Evib...... respectively.
The exact calculation is not possible. 76.
59. (B, D); defined
60. (A, B, C, D); Increase in randomness increases G 0  H 0  T S 0 H 0
the entropy. b)
for H 2 o  H   OH  is  13.7 kcal
61. (A, B, C)
62. (A, B) H   G 
63. (A, D) S  
T
Heat supplied by electric heater is = 250 J/sec
13.7  19.14
x 55 sec = 13.75 kJ   0.1102
64. (A, D); defined 298
65. (A, B)
kcal mol 1
q  msT for water and glass
 11.2 cal k 1 mol 1
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77.(a) Work done in (-ve) reversible process is maxi- 80. Ans (A,B) reversible process:
mum. Thus, in reversible pro cess
p1
Wrev  2.303nRT log10
T f rev  T f irrev p2
78. C.
1.01105
2CH 3COOH  g   CH 3COOH 2  g   2.303  2  8.314  300 log10
5.05 106
1 0  1.9518  104 joule
0.982
1-0.982 Since W reversible is a measure of free change
2
 G  Wrev  Wmax  1.9518 10 4 J
81. Ans A,B,C
 CH 3COOH 2 0.982
K0  2
 2
 1515.4  Cv 
3 3 5
R  C p  Cv  R  R  R  R
 CH 3COOH  2   0.018 2 2 2
Now, H 0 for dimerization  Heat given at constant pressure  m.C p .T
 2  33kJ  66kJ or
Now work done in the process   PV
Thus, G 0  H 0  T S 0
5 5
H or q p 1  R 373 298  or H 1 1.98775 372.56 cal
0 0 0 2 2
2.303 RT log K  H  T S
2.3038.314 400log 1515.4  66103  400 S 0
 nRT2 nRT1 
w   p V2  V1    p   
 p p 
 24359.2   66000  400  S 0
 pv  nRT 
0 41640.8
S    104.102 J / mol
400   nR  T2  T1   1 1.987   373  298 
79. .Ans (A)  149.225cal
Solution: Since, work is done against constant  from I law of thermodynamics
pressure process is irreversible. U  q  W  372.56  149.05
Given, V  (6  4)  2 litre, p = 2.5 atm  U  223.51 cal
w   pext  V  2.5  2  5 litre-atm Also, dqrev  nC p .dt

dqrev nC p .dt
ds   ds 
5 1.987 5 1.987  4.187 T T
 cal   J  506.31J
0.0821 0.0821 nCp.dT
T2 T
C=4.184J/g/Kor4.184J/mol or S    nCp loge 2
T1 T T1
Now this work is used in heating 1 mole water
T2
W  n  C  T 506.31  s  2.303 nC p log10
T1
 1 4.184  T  T  6.723
5 373
 Final temperature  2.303  1 R  log10  1.122 cal k 1 mol 1
2 298
= T1  T  293  6.723  299.723K
 THERMODYNAMICS (ENERGETICS)
1 R 100 u = f(T, V)
82 (c,d) At VA   100 R
1
 u   u 
du    dT    dV
 T  v  V  T
1 R  600
VB   200 R
3 Since dT = 0; du = 0
VB  VA so expansion of gas takes place  u 
  dV  0
VB  200  0.0821  16.42 L  V T
83 (B,D) Since dV  0, follows that
84 (A,B,C)
85 (A,B,C,D)  u 
  0
86 (A,B,C)  V T
since it is a free expansion, it is applicable to
COMPREHENSION TYPE QUESTIONS
only ideal gases.
87. (B) The enthalpy of dissociation of the O-H 92. (D)
bond depends on the molecular species from If the external pressure is only infinitesimally
which H-atom is being separated. smaller than the pressure of the gas, the
H2O(g)  H(g) + OH (g); H0 = expansion is said to take place reversibly. If,
501.87 kJ mol-1 however, the external pressure is much smaller
However to break O-H bond in hydroxyl a than the gas pressure, the expansion occurs
different quantity of heat (423.38 kJ mol-1) is
irreversibly. If the external pressure is zero, the
BE (O - H) =
expansion is known as free expansion.
01.87kJmol1  423.38kJmol1
= 462.625 93. (A) q = U + PV
2
kJ mol-1 at T = constant q = PV
88 (A) 94. (C)
In case of diatomic molecules, bond enthalpy ACB = AC + BC ADB = AD + BD
and bond dissociation enthalpy are identical Heat absorbed 80 J Work done by the
because each r efer s t o t he react ion
system = 10 J
H2(g)  2H(g); BE (H - H) = 433.93
kJ mol-1 w  10 J
89. (B)  w = -30 Also w = -10 J
BE (S - S)  UB-UA = 50 J
Hvap (s)  {H0f (C 2H5S  SC 2H5 )}  q = 50 + 10 = 60 J
= Hvap (s)  H0f 95. (A)

= H0f (C2H5  S  C2H5 ) R

Cp - Cv = At A, P = 1 atm. V = 22.4 L
= 222.80 - {-201.92 - (-147.23)} M
= 277.49 kJ mol-1
2
90. (A) The gas expands against a zero opposing  0.125 - 0.075 =  273
pressure. Since dw = -Popp dv, it is obvious that M
the work involved in the expansion is zero.  T = 273 K
du = dq + dw  M = 40 At B, P = 1 atm. V = 44.8 L
Hence du = dq  T=546K
Since there is no change in temperatuare dq = 0
At C, P = 0.5 atm., V = 44.8 L
Hence du = 0
91. (A)  T = 273 K
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Also At constant V
13
 3  volumeof C4 H10
U  P  V U  Cv  T 2
13
 3   0.281 X   5.48  X  litreO 2
1 22.4 2
= 1  22.4 L atm =  8.314 J
0.0821 104. The polymersiation reaction
= 0.075  40  4.12 is nCH 2  CH 2   CH 2  CH 2 n
= 2268.37 J = 3.44 kJ
In this process, one double bond (C= C)
= 2.27 kJ
breaks and two –CO2 groups are linked with
98. (b) For max rise in temp; max neutralization of
single bonds thus forming three single bonds
H  and OH  required (two single bonds are formed when each CH2
if we take equal volume, all H  ( 5 m-mole) group of ethylene (CH2 = CH2) links with
will react with all OH  (5m -mole) another CH2 - group of another ethylene
molecule).
99. (B) all are correct
Therefore, in polymerisation reaction one C =
H v 540 C is replaced by two C – C bonds or one
100. (C) Sv   ;
373 373 mole of C = C bonds are replaced by 2 moles
; H  809kJmol1 of C – C bonds
Energy Released = Energy due to formation of
Let the temperature be T and assume volume
2 single bonds.
of 1 mle of a gas is V litre at this condition.
= (2×331) kJ = 662 kJ
V litre of 1 mole of CH4 gives energy
Energy needed to dissociate one mole of C =
on combustion = 809 kJ
C bonds = 590 kJ
X litre of CH4 gives energy on
H pot or enthalpy of polymerisation = (590–
808  X 
combustion  kJ 662) kJ = –72 kJ moles
V
105. C 6 H10  H 2  C6 H12 ; H  119kJ
2878 kJ energy is obtained by 1 mole
of V litre C4H10 (involves breaking up of three double bond and
additional of three H2 molecule)
809  X 
 kJ energy is obtained  C6 H 6  3H 2  C 6 H12 ;
V
H  3   119   357 kJ
809  X   V
 litre C4H10 = 0.281 (X) (involves breaking up of three double bond and
V  2878
additional of three H2 molecule)
litre C4H10
Thus, butane sullpied for the same calorific Also given 6C  6H 2  C 6 H12  l  ; H  156
output = 0.281 (X) litre We have C6 H 6  3H 2  C6 H12  l  ;
13 H  357
 C4 H10  O 2  4CO 2  5H 2 O ;
2 6C  3H 2  C6 H 6 ; H  201kJ
H  2878kJ / mol Therefore, resonance energy = 49– 201
Volume of O2 required = 3 volume of O2 for = – 152 kJ
combustion of C4H10
 THERMODYNAMICS (ENERGETICS)
106. Energy available for muscular work by 1 mole
AlCl3  aq  AlCl3  aq 
2880  25 ; H  ?
of glucose   720 kJ
100
= (Energy released during
H
Thus, 180 g (1 mole ) of glucose (C6H12O6) hydration) – (Energy used during hydration)
supplies energy = 720 kJ = (–4665)–(3×381) + 5137 =
–1
720 –671 kJ mol
Will supply 120 g glucose   120  480 kJ
180 Thus, formation of ions will take place.
Distance covered by 100 kJ energy = 1km or 109. Following equation can be obtained from the
100 kJ is need to walk 1 km available data
 Distance covered by 480 kJ energy (i) C  s   O 2  g   CO2  g  ;
1 H  393.5kJ
 480  4.8km
100
1
107. The concerned thermochemical reaction is (ii) H2  g   O2  g   H2O  l  ;
2
H  2858kJ
H
| (iii) 3C  s   3H 2  g   C 2 H 6  g  ;
C  g   4H  g   O  g   H  C  O  H
| ; H  20.42 kJ
H CH2 CH2
(iv) (g)  C3 H 6  g  ;
H  ? CH2
H  33.0 kJ
 1 
H f   H Cs Cg   2H H  H  H O O  The desired equation is
 2 
 3H CH  H CO  H O H  H Vap CH3OH   CH2 CH2
CH2
= [715+2 ×436+249] –[3×415 +365 +463
+38] = –275 kJ mol–1 9
(g)  O2  g   3CO2  g   3H 2O  l  ;
108. Total hydration energy of Al3+ and 3 Cl– ions of 2
AlCl3 H  2091.32 kJ mol1
 H Hydration   = Hydration energy of Al3+ + 3 To get the desired equation compute as follows
× Hydration energy of Cl– [3×(i)+3×(ii)] + [(vi)–(iii)]
= [–4665 + 3 ×(–381)] kJ mol–1 = –5808 kJ CH2 CH2
(g)
mol–1 CH2
This amount of energy exceeds the energy
9
needed for the ionisation of Al to Al3+ (i.e., 5808  O2  g   3CO2  g   3H 2 O  l  ;
2
> 5137). Because of this AlCl3 becomes less ionic
in aqueos solution. H  2091.32 kJ mol1
In aqueous solution AlCl3 exists in ionic form 110. Given : SF6  g   S  g   6F  g  ;
as [Al(H2O)6]3+ and 3 Cl–
H  ?
3
AlCl3  6H 2 O   Al  H 2 O 6   3Cl From the available data, we can write the
following equation
JEE
JEE ADVANCED
MAINS - CW -- VOL
VOL -- III

(i) S  s   3F2  g   SF6 ; H  1100.0 kJ 257.2  H o  300  0.094   H o

 285.4 kJ mol1
(ii) S  s   S  g  ; H  275.0 kJ
Since the value of H is negative so the reaction
1 is exothermic.
(iii) F2  g   F  g  ; H  80.0 kJ
2
iv  (i)  3(iii)  3(ii)
To get the required equation carry out the 113.
36  (1273)  3(44)  3(286)
following computation [6×(iii) +(ii)]–(i)
i.e. Substracting given equation (iv)) from
(vi), we get
H   6  80  2745    1100.0   1855kJ
B2 H 6  g   3O 2  g   B2 O3  s   3H 2 O  g 
Now, in SF6 we find S–F bonds, therefore the
bond energy H  2035.0 kJ
Thus average bond energy for S – F bond 114. Calculation of G
1855  Product 
  309.16 kJ mol1 G o  2.303RT log
6  Reactant 
111. For adiabatic expansion of a gas, we have
For the equilibrium reaction B  A , we get
T R V2
ln 1  ln
T2 CV V1
and for the reaction B  C , we get
300 8.31 2.50  1.3 
or ln  ln G1o   2.303  8.314  448log
T2 12.48 1.25 
 95.2 
1
Solving the above equation, we get T2 = 188.5  15.992 kJmol
K
 3.5 
Number of moles of argon gas, G o2   2.303  8.314  448log 
 95.2 
1
PV 1  1.25  12.312 kJmol
n   0.05
RT 0.082  300
Again, for the reaction A  C
Now, we know that H  n.Cp .T
 3.5 
H  0.05  20.8 188.5  300  [Cp = G o3   2.303  8.314  448log 
  1.3 
1
CV+R=(12.48+8.314)  20.8]  3.688kJmol
= –115.96 J Fromthe above calculations, we have
112. Following reaction takes place B  A , G1o  15.992 kJ mol1
1
CO  g   O 2  CO 2  g  B  C , G o2  12.312 kJ mol1
2
o o o
A  C , G o3  3.688kJ mol1
We know, G  G  Pr oduct   G  Re ac tan t 
Thus, the correct order of stability B > C > A
= –394.4–[–137.2 + 0] = –257.2 kJ mol–1 115. H  U  VP
Since G o is negative so the reaction is feasible
V  0 
i.e., spontaneous,
U  H  VP
Again, G o  Ho  TSo
= –560 – [0.1 (40–70)×0.1] = –557 kJ
So, the magnitude is 557 kJ mol–1
 THERMODYNAMICS (ENERGETICS)
116. In case of helium (monoatomic gas) we have
G o  2.303RT log K p  0 ; KP = 1
only three degrees of freedom which correspond
to three translational motion so the total heat Initially, PN O  PNO  10 bar
2 4 2

capacity will increase. The contributors by

2
vibrational motion is not appreciable at low

P NO2

100
 10
temperature but increases from 0 to R when Reaction quotient
PN2O2 10
temperature increases.
R G o  2G of  NO2   G of N 2O 4   100  100  0
CV  f , where f is the degree of freedom.
2 Initial Gibbs free enrgy of the above reaction,
At low temperature only translational motion is G  G o  2.303RTlog QP
3R G  0  2.303  8.314  298log10
considered and f = 3.  CV 
2  5.0705  103 kJ mol 1
At moderate temperature both translational and (ii) Since initial Gibbs free energy change of
rotational motions are considered. the reaction is positive, so the reverse reaction
f = 3+2 (3-translational and 2 rotational) will take place.
5R
 CV   E 
2 141.    CV
 T V
At still high temperature translational, rotational
and vibrational motions are considered.  E  CV T
f= 3+2+2 (3-translational, 2-rotational,
3
2-vibrational) CV  R for monatomic gas
2
7R
 CV  T  1K
2
117. Here, P1 = 1 bar P2 = 100 bar ; 3 3
E  R   2  3 cal
V1 = 100 ml , V2 = 99 ml 2 2
For adiabatic process, q  0 , 142. WAB  PV , WBC  0
U  W
q  U   WT 
Since, U  q  W (first law of
thermodynamics)  U  0
 q  P  V2  V1  [W= P(V2–V1)]  q  WT   WAB  WBC  WCA 
= 0–100(99–100) = 100 bar mL  5   10  0  WCA 
Also, H  U    PV 
or WCA  5 j
 U  P2 V2  P1V1 ;
143.  E  W
 100   99  100  100  1  9900bar mL
144. E  n  CV T
118. (i)Standard Gibbs free energy change for
the reaction, H
145. S 
N 2 O 4  g   2NO 2  g  T
146. G  H  T S
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