Thermodynamics: Synopsis
Thermodynamics: Synopsis
Thermodynamics: Synopsis
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
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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.
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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 pV
' 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
V1 V2
V
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,,
= -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
G 0 147.2 0 0 65
= -212.2 kJ mol–1.
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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 2.4710–29 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
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.
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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 ,
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
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
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.
5. w Pext V f Vi
LEVEL -V - KEY
SINGLE ANSWER TYPE QUESTIONS 60 103 40 103 100 103
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)
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 TSo ; H o TSo
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
25 105 ; 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
50 105
1000 1000
n OH 2 50 105 10 3
U n1CV ,m1 n2CV , m2 T 960 R
2258.1
f H 0 Cr2O3 , s
205 152 357 2
1129.05kJ / mol .
Enthalpy of hydrogenation of 357
119 kJ / mol
3
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
2.3038.314 400log 1515.4 66103 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 msT 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 1003.14 314 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 )
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 PV , 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 ****
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
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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
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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
216
VELAMMAL BODHI IIT ACADEMY
JEE-MAIN & ADV CHEMISTRY-VOL-II
SR-MAIN-CHEM-VOL-II THERMODYNAMICS
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 TSº– Hº Hº– T S º RT c) Clausius Clepeyron eq.d) Gibbs-Helmholtz eq.
A) – RT B) 2.303 RT C) RT D) TSº– 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
217
VELAMMAL BODHI IIT ACADEMY
THERMODYNAMICS JEE-MAIN & ADV CHEMISTRY-VOL-II
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 399kcalmol1 ;
(C) Statement-1 is True, Statement-2 is False
(D) Statement -1 is False, statement-2 is True H f Fe2 O3 195.92kcalmol1
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 2288Jmol1
trans
minimum (Wmin)
218
VELAMMAL BODHI IIT ACADEMY
JEE-MAIN & ADV CHEMISTRY-VOL-II
SR-MAIN-CHEM-VOL-II THERMODYNAMICS
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 1.5310 Nm at
87. How much of the following are extensive 303K and 5.2 104 Nm2 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
VELAMMAL BODHI IIT ACADEMY
THERMODYNAMICS JEE-MAIN & ADV CHEMISTRY-VOL-II
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
4.24 102 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
221
VELAMMAL BODHI IIT ACADEMY
THERMODYNAMICS JEE-MAIN & ADV CHEMISTRY-VOL-II
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
222
VELAMMAL BODHI IIT ACADEMY
JEE-MAIN & ADV CHEMISTRY-VOL-II
SR-MAIN-CHEM-VOL-II THERMODYNAMICS
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 yz 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
VELAMMAL BODHI IIT ACADEMY
THERMODYNAMICS JEE-MAIN & ADV CHEMISTRY-VOL-II
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
VELAMMAL BODHI IIT ACADEMY
JEE-MAIN & ADV CHEMISTRY-VOL-II
SR-MAIN-CHEM-VOL-II THERMODYNAMICS
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
VELAMMAL BODHI IIT ACADEMY
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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 mol1
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 mol1
2
work. If 100 kJ of muscular work is needed to
iii) H 2 O l H 2 O g ; H 44 kJ mol1
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 mol1
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
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VELAMMAL BODHI IIT ACADEMY
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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 1 100 103 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 2.76 103 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
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VELAMMAL BODHI IIT ACADEMY
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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
230
VELAMMAL BODHI IIT ACADEMY
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SR-MAIN-CHEM-VOL-II THERMODYNAMICS
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
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 Hionisation 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
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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 95.4 103
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. H2l 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 kJmol1 =41.2 kJ mol–1
Final temperature = T1 + T = 290 + 0.81 = 290.81K Hence (B) is correct option
233
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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.
HH2 H1 E2 P2V2 E1P1V1 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 12.31.67V
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 AC 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 TSo
(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 TSo
225 2 H 1 BEH H 2 BEC H 1 BEC C
o o C s C g
2.303RT log10 K TS H
225 1410 1 330 2 350 1 BEC C
TSo Ho 29810 54.071000
log10 K 10 225 1410 330 700 BEC C
2.303RT 2.3038.314 298
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
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SR-MAIN-CHEM-VOL-II THERMODYNAMICS
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 : PT 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
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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 3Csg 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 3H 4 5H1 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 809kJmol1 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
VELAMMAL BODHI IIT ACADEMY
JEE-MAIN & ADV CHEMISTRY-VOL-II
SR-MAIN-CHEM-VOL-II THERMODYNAMICS
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 mol1
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 mol1
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 Cs Cg 2H H H H O O To get the required equation carry out the following
2
3H CH H CO 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 mol1
6
237
VELAMMAL BODHI IIT ACADEMY
THERMODYNAMICS JEE-MAIN & ADV CHEMISTRY-VOL-II
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 VP ; V 0 ; U H VP
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 TSo 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