DAY SIX

Chemical
Thermodynamics
Learning & Revision for the Day

u Fundamental of u First Law of Thermodynamics u Third Law of

Thermodynamics u Entropy Change (∆S) Thermodynamics
u Types of Processes u Second Law of u Gibb’s Free Energy ( ∆G )
u Concept of Work Thermodynamics
u Heat

The laws of thermodynamics deal with the energy changes of macroscopic systems
involving a large number of molecules rather than microscopic systems containing a
few molecules.

Fundamentals of Thermodynamics
Some basic terms and concepts commonly used in thermodynamics are briefly
explained below:

System and Surroundings

System is a part of universe under observation and the part of the universe except
system is called surroundings. System basically a specific portion which is considered
under thermodynamic studies.
Thus, system and the surrounding together constitute the universe, i.e.
universe = system + surroundings
On the basis of exchange of mass and energy, systems are of three types:
1. Open System In which energy and matter both can be exchanged with
surroundings.
2. Closed System In which only energy can be exchanged with surroundings.
3. Isolated System In which neither matter nor energy can be exchanged with
surroundings.

Extensive and Intensive Properties

Properties used to define the state of a system are extensive and intensive properties.
1. Intensive Properties Those properties that depend on nature of matter but do not
depend on quantity of the matter, e.g. pressure, temperature, specific heat, melting
point etc.
 2. Extensive Properties Those properties that depend on
quantity of the matter present in the system, e.g.
Concept of Work
internal energy, heat, total moles, volume, enthalpy, l The work is said to be done when gas expands or
entropy, free energy etc. contracts against the external pressure. Work done is a
Force is extensive property but pressure is intensive path function not a state function as depends upon the
property. path followed.
W = − pext × ∆V
State and Path Functions For expansion W = − pext (V2 − V1 ) [Here, V2 > V1 ]
1. State Functions Those functions which depend only For compression W = − pext (V2 − V1 ) [Here, V2 < V1 ]
on the state of the system and not on how it is reached. l Maximum work done for reversible isothermal process
e.g. pressure, volume, temperature, ∆H, ∆E etc.
V
2. Path Functions The functions that depend upon the Wrev = −2.303 nRT log 2
V1
path followed are called path functions, e.g. work done,
heat etc. where, V2 = final volume, V1 = initial volume
p
Also, Wrev = −2 . 303 nRT log 1
p2
Types of Processes Maximum work done for irreversible isothermal expansion
The state of a variable can be changed by means of a (i) Intermediate expansion
thermodynamic process. These are of the following types : V2
pext < pgas, Wirr = ∫ pext dV
1. Adiabatic Process In which system does not V1
exchange heat with its surrounding, i.e. dQ = 0.
W = − pext (V2 − V1 )
2. Isothermal Process In which temperature remains
(ii) Free expansion If gas expands in vacuum, pext = 0,
fixed, i.e. dT = 0.
therefore, W = 0
3. Isobaric Process In which change of state is brought
about at constant pressure, i.e. dp = 0. Sign Convention
4. Isochoric Process In which volume of the system (i) If W is positive — work done on the system
remains constant, i.e. dV = 0.
(ii) If W is negative — work done by the system
5. Cyclic Process This is the process in which a system
undergoes a number of different states and finally
returns to its initial state. For such a process, change in Heat
internal energy and enthalpy is zero, i.e. dE = 0 and
It is defined as the quantity of energy, which flows between
dH = 0.
system and surroundings on account of temperature difference.
6. Reversible Process In this process, (quasistatic system),
It is also a path function, i.e. depends upon the path followed.
change taken place is infinitesimally slow and their
direction at any point can be reversed by infinitesimal Sign Convention
change in the state of the system. Reversible process is
an ideal process and here, every intermediate state is in (i) If q is positive — heat is supplied to the system
equilibrium with others, if any. (ii) If q is negative — heat is lost by the system
7. Irreversible Process This process, is the one which
cannot be reversed. In this process, amount of energy Internal Energy (E or U)
increases. All natural processes are irreversible in
l It is the total energy within the substance. It is equal to the
nature.
sum of translational energy, vibrational energy, potential
• If macroscopic properties like temperature, pressure, etc., energy etc. We can only determine the change in internal
NOTE do not change with the time, the system is said to be in energy.
thermodynamic equilibrium.
• If the two systems are in thermal equilibrium with a i.e. ∆U = U2 − U1
third system, they must be in thermal equilibrium l At constant temperature, internal energy change (∆E) will
with each other. This law is known as zeroth law of be zero. Internal energy depends on temperature,
thermodynamics. pressure, volume and quantity of matter.
The law defines the temperature as the property
which determines, whether the body is in thermal
equilibrium or not.
 There are two types of heat capacities based on the conditions
First Law of Thermodynamics such as volume and pressure.
According to this law, energy can neither be created nor 1. Heat Capacity at Constant Pressure (C p) The heat
destroyed although it may be converted from one form to
capacity of a substance measured when the gaseous
another.
system is at constant pressure.
l Mathematical form of first law of thermodynamics,
 q  dH
∆E =q +W Cp =   or C p =
 ∆T  p dT
l Both W and q are not state functions but quantity W + q is
a state function. 2. Heat Capacity at Constant Volume (CV ) The heat capacity
of a substance measured when the gaseous system is at
constant volume.
Enthalpy
 q  dV
The total heat content of a system at constant pressure is CV =   or CV =
 ∆T  V
l
dT
called the enthalpy of the system. It is the sum of internal
energy and the product of pressure-volume work. l Relationship between C p and CV is given as
l It is an extensive quantity, state function and C p − CV = R (R is the molar gas constant.)
represented by the symbol H. R
C p − CV =
The equation is M
H = E + pV
l For monoatomic gas the molar heat capacity at
 3
∆H = ∆E + p∆V constant volume, CV =   R
 2
∆H = ∆E + ∆ng RT l For monoatomic gas molar heat capacity at constant
where, ∆H = enthalpy change pressure,
∆ng = gaseous moles of products − gaseous  3  5
Cp =   R + R =   R
moles of reactants  2  2
l If ∆ng = 0, then ∆H = ∆U; If ∆ng > 0 then ∆H > ∆U and Cp  5
Poisson’s ratio, γ = =   = 1.66
if ∆ng < 0 then, ∆H < ∆U.
l

CV  3
l For reaction involving solids and liquids only, ∆H = ∆E . γ = 1.66 for monoatomic gases (like He, Ar)
Enthalpy also changes, when a substance undergoes
γ = 1.40 for diatomic gases (like H2 , O2 , CO)
phase transition.
γ = 1.33 for triatomic gases (like H2O, O3 )
Work done in reversible adiabatic expansion
Heat Capacity l

Work done = CV ∆T = CV × (T2 − T1 )

Heat capacity (C) of a system is defined as the amount of heat
required to raise the temperature of the system by 1 ° C. NOTE The molar heat capacity for any process is given by
q R
C= C = CV +
∆T γ 1− γ
when, pV = constant
l If the system consists of a single substance or a solution
and weighs 1 mol, the heat capacity of the system is
referred as molar heat capacity (Cm).
Kirchhoff’s Equation
According to Kirchhoff’s equation, the partial derivatives of
l If the system consists of a single substance or a solution the change of enthalpy (or of internal energy) during a
and weights 1 g, the heat capacity of the system is reaction, with respect to temperature at constant pressure
referred as specific heat of the system (Cs ). (or volume) equals to the change in heat capacity at constant
pressure (or volume).
q = C × m × ∆T
where, m = mass of substance, ∆H2 − ∆H1 ∆E2 − ∆E1
∆C p = and ∆CV =
T2 − T1 T2 − T1
C = specific heat capacity
where, ∆C p = ΣC p of products − ΣC p of reactants
and ∆T = temperature difference.
∆CV = ΣCV of products − ΣCV of reactants
Entropy Change (∆S ) Carnot Engine
Entropy is the measurement of randomness or disorder of the Carnot in 1824 gave an imaginary reversible cycle which
molecules. A process which proceeds at its own without any demonstrates the maximum conversion of heat into
outside help is termed as spontaneous process. The total entropy work. He actually proposed a theoretical heat engine to
change (∆S total ) for the system and surrounding of a spontaneous show that its efficiency was based upon the
process is always positive, temperatures, between which it operated.
∆S total = ∆Ssystem + ∆Ssurrounding > 0. A Carnot cycle comprises four operations or processes:
l Entropy is a state function and depends only on initial and (i) Isothermal reversible expansion
final states of the system. (ii) Adiabatic reversible expansion
i.e. ∆S = S final − S initial (iii) Isothermal reversible compression
l Unit of entropy is joule per Kelvin per mole. (iv) Adiabatic reversible compression
l For a reversible change at constant temperature
A(p1,V1) Isothermal
q
∆S = rev = S final − S initial expansion
T B(p2,V2)
q rev = heat absorbed or evolved at absolute temperature T. If
Adiabatic
∆S > 0, heat is absorbed and if ∆S < 0, heat is evolved.

Pressure
compression Adiabatic
expansion
l For a spontaneous isothermal expansion
D(p4,V4)
V C (p3,V3)
∆S = 2.303 nR log 2 Isothermal
V1 compression
l The change of matter from one state to another is called phase Volume
transition. Carnot cycle

The entropy changes at the time of phase transition are as l Net work done in 1 cycle is
follows:
V2 V
∆H fusion W = RT2 ln + RT1 ln 4
(i) ∆S melting = ; (Tm = melting point of substance) V1 V3
Tm
Net heat absorbed in the whole cycle is
∆H vaporisation
l

(ii) ∆S vaporisation = ; (Tb = boiling point of substance) V

Tb q = R (T2 − T1 ) ln 2
V1
∆Hsublimation
(iii) ∆Ssublimation = ; (Tsub = sublimation temperature) l Efficiency of a heat engine (denoted by η ) in a
Tsub
Carnot cycle is given
W T2 − T1 T
η= = =1 − 1
Second Law of Thermodynamics q2 T2 T2
The second law of thermodynamics tells us whether a given l The above relation was stated in the form of Carnot
process can occur spontaneously and to what extent, it also helps theorem by Carnot, i.e. “Every perfect engine
us to calculate maximum fraction of heat that can be converted working reversibly between the same temperature
into work in a given process. The second law states that the limits has the same efficiency, whatever be the
entropy of the universe is continuously increasing and tends to a working substance.”
maximum.
For an irreversible process,
dq Third Law of Thermodynamics
dS >
T l This law was proposed by German chemist Walther
dq Nernst. According to this law, ‘‘The entropy of a
∴ dS ≥ perfectly crystalline substance approaches zero as
T
the absolute zero of temperature is approached’’.
This is the mathematical statement of the second law of
thermodynamics.
l It forms the basis from which entropies at other
temperatures can be measured, lim S = 0
T→ 0
Gibbs Free Energy (∆G ) ∆S ∆H ∆G Spontaneity of a Process
+ − Negative at all Spontaneous at all
l The maximum amount of energy available to a system, temperatures. temperatures.
during a process that can be converted into useful
− − Negative at all Spontaneous at low
work is called free energy or Gibbs free energy.
temperatures. temperature but
l Under standard conditions of temperature non-spontaneous at high
(i.e. at 298 K) and pressure (i.e. 1 atm), the free energy temperature.
change for a process in which reactants in their + + Positive at low Spontaneous at high
standard state is converted into products in their temperature and negative temperature.
standard state is called standard free energy change at high temperature.
(i.e. ∆G°). + + Positive at all temperature. Non-spontaneous at all
l The changes in the Gibbs energy of a system as a temperature.
function of temperature can be calculated by the
equation known as Gibbs Helmholtz Equation.
Relation between Gibbs Energy Change
∆G = ∆H − T∆S
where, ∆G = Gibbs free energy (measurement of useful
and Equilibrium Constant
work) Relation between Gibbs free energy with reaction quotient and
equilibrium constant are as follows :
l The following cases are considered for ∆G.
(i) ∆G > 0, for non-spontaneous process l ∆G = ∆G °+ 2.303 RT log Q
(ii) ∆G < 0, for spontaneous process where, Q = reaction quotient
(iii) ∆G = 0, at equilibrium l At equilibrium, ∆G = 0
∴ ∆G ° = −2.303 RT log K
Criteria for Spontaneity K = equilibrium constant
l In the determination of spontaneity, Gibbs energy l ∆G ° = − n Ecell
° F
criteria is better than entropy criteria because Gibbs
energy refers to the system only while entropy refers to where, n = number of electrons lose or gained,
both system and surroundings. °
Ecell = standard electrode potential,
l For negative value of ∆G several conditions exist 1F = 96500 C
which plays an important role in deciding the l Efficiency of the fuel cell = ∆ G / ∆ H × 100
spontaneity of the process.

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

1 Which of the following statement is correct? 2 The pressure-volume work for an ideal gas can be
Vf
(a) The presence of reacting species in a covered calculated by using the expression W = − ∫ pexdV . The
beaker is an example of open system Vi

(b) There is an exchange of energy as well as matter
between the system and the surroundings in a closed
system
(c) The presence of reactants in a closed vessel made
up of copper is an example of a closed system
(d) The presence of reactants in a thermos flask or any
other closed insulated vessel is an example of a
closed system
work can also be calculated from the pV − plot by using the
area under the curve within the specified limits. When an
ideal gas is compressed (a) reversibly or (b) irreversibly
from volume Vi to Vt . Choose the correct option.
(a)W(reversible) = W(irreversible )
(b)W(reversible) < W(irreversible )
(c)W(reversible) > W(irreversible )
(d) W(reversible) = W(irreversible ) + pex ∆V
 3 An ideal gas expands in volume from1 × 10−3 m 3 to 12 The combustion of benzene (l ) gives CO2(g ) and H2O(l ).
1 × 10−2 m 3 at 300 K against a constant pressure of Given that heat of combustion of benzene at constant
1 × 105 N/ m 2. The work done is volume is −3263.9 kJ mol −1 at 25° C; heat of combustion
(a) −900 J (b) −900 kJ (in kJ mol −1) of benzene at constant pressure will be
(c) 270 kJ (d) 900 kJ (R = 8.314 JK −1 mol−1) ª JEE Main 2018
4 When 1 mole of a gas is heated at constant volume, (a) 4152.6 (b) −452.46
temperature is raised from 298 K to 308 K. Heat supplied (c) 3260 (d) −3267.6
to the gas is 500 J. Then, which statement is correct? 13 Heat required to raise the temperature of 1 mole of a
(a) q = −W = 500 J, ∆E = 0 substance by 1°C is called
(b) q = W = 500 J, ∆E = 0 (a) specific heat (b) molar heat capacity
(c) q = ∆E = 500 J, W = 0 (c) water equivalent (d) specific gravity
(d) ∆E = 0, q = W = −500 J
14 The molar heat capacity of water at constant pressure is
5 In an adiabatic process, no transfer of heat takes place 75 J K −1 mol −1. When 1.0 kJ of heat is supplied to 100 g of
between system and surroundings. Choose the correct water, which is free to expand, the increase in
option for free expansion of an ideal gas under adiabatic temperature of water is
condition from the following. (a) 1.2 K (b) 2.4 K
(a) q = 0, ∆T ≠ 0, W =0 (c) 4.8 K (d) 6.8 K
(b) q ≠ 0, ∆T = 0, W =0
15 For two moles of an ideal gas
(c) q = 0, ∆T = 0, W =0
(d) q = 0, ∆T < 0, W ≠0 (a) (Cp − CV ) = 2R (b) (Cp − CV ) = 0
(c) (Cp − CV ) = R (d) (Cp − CV ) = R /2
6 1 mole of an ideal gas at 300 K is expanded isothermally
from an initial volume of 1 L to 10 L. The ∆E for this 16 The heat of sublimation of iodine is 24 cal g −1 at 50°C. If
process is (R = 2 cal K −1 mol −1 ) specific heat of solid iodine and its vapours are 0.055
and 0.031 cal g −1 respectively, the heat of sublimation of
(a) 270 cal (b) zero (c) 10 L atm (d) 181.7 cal
iodine at 100°C is
7 ∆U is equal to ª JEE Main 2017 (a) 22.8 cal g −1 (b) 25.2 cal g −1
(a) isochoric work (b) isobaric work (c) –22.8 cal g −1 (d) –25.2 cal g −1
(c) adiabatic work (d) isothermal work
17 What will be the change of entropy ∆rS ° at 298 K for the
8 A piston filled with 0.04 mole of an ideal gas expands reaction, in which urea is formed from NH 3 and CO 2 ?
reversibly from 50.0 mL to 375 mL at a constant 2NH 3 (g ) + CO 2 (g ) → NH 2CONH 2 (aq ) + H 2O (l )
temperature of 37.0°C. As it does so, it absorbs 208 J of
heat. The values of q and W for the process will be [Given, the standard entropy of NH 2CONH 2 (aq ),
[R = 8.314 J/mol K) (ln 7.5 = 2.01) ª JEE Main 2013 CO 2 (g ), NH 3 (g ) and H 2O(l ) are 174.0, 213.7, 192.3 and
(a) q = − 208 J, W = − 208 J 69.9 JK mol −1 respectively]
(b) q = − 208 J, W = + 208 J
(a) 200 JK −1 mol −1 (b) –35.44 JK −1 mol −1
(c) q = + 208 J, W = + 208 J
(c) –354.4 JK −1 mol −1 (d) 425.2 JK −1 mol −1
(d) q = + 208 J, W = − 208 J
18 2 moles of an ideal gas at 27°C are expanded reversibly
9 Latent heat of vaporisation of a liquid at 500 K and 1 atm
from 2 L to 20 L. Find entropy change (in cal/mol K).
pressure is 10.0 kcal/mol. What will be the change in
internal energy ( ∆E ) of 3 moles of liquid at same (R = 2 cal/mol K)
temperature? (a) 0 (b) 4
(a) 30 kcal (b) –54 kcal (c) 27.0 kcal (d) 50 kcal (c) 9.2 (d) 92.0

10 ( ∆H − ∆E ) for the formation of carbon monoxide (CO) 19 For an isolated system, ∆E = 0, then
from its elements at 298 K is (R = 8.314 JK −1 −1
mol ) (a) ∆S = 0
(b) ∆S < 0
(a) −2477.57 J mol −1 (b) 2477.57 J mol −1
(c) ∆S > 0
(c) –1238.78 J mol −1 (d) 1238.78 J mol −1
(d) the value of ∆S cannot be predicted
11 Consider the reaction,
20 When 1.8 g of steam at the normal boiling point of water is
N2 + 3H2 → 2NH3 carried out at constant
converted into water, at the same temperature, enthalpy
temperature and pressure. If ∆H and ∆E are the
and entropy changes respectively will be
enthalpy and internal energy changes for the reaction,
[Given, ∆Hvap for water = 40.8 kJ mol −1]
which of the following expressions is true?
(a) −8.12 kJ, 11.89 JK −1 (b) 10.25 kJ, 12.95 JK −1
(a) ∆H > ∆E (b) ∆H < ∆E
(c) −4.08 kJ, − 10.93 JK −1 (d) 10.93 kJ, −4.08 JK −1
(c) ∆H = ∆E (d) ∆H = 0
21 Which of the following does not have zero entropy even 27 In view of the signs of ∆ r G ° for the following reactions
at absolute zero? PbO2 + Pb → 2PbO, ∆rG ° < 0
CO, CO 2 , NaCl, NO SnO2 + Sn → 2SnO, ∆rG ° > 0
(a) CO, CO 2 (b) CO, NO (a) For lead + 4, for tin + 2 (b) For lead + 2 , for tin + 2
(c) CO 2 , NaCl (d) NaCl (c) For lead + 4, for tin + 4 (d) For lead + 2, for tin + 4
22. The enthalpy of vaporisation of liquid diethyl ether 28 When the heat of a reaction at constant pressure is
(C 2 H 5 )2O, is 26.0 kJ mol −1 at its boiling point (35°C). − 2.5 × 10 3 cal and entropy change for the reaction is
What will be the ∆S for conversion of liquid to vapour 7.4 cal deg −1, it is predicted that the reaction at 25°C is
and vapour to liquid respectively? (a) reversible (b) spontaneous
(a) + 84 .41 and − 84 .41 JK −1 mol −1 (c) non-spontaneous (d) irreversible
(b) + 80 .90 and − 68 .83 JK −1 mol −1 29 At 1 atm pressure, ∆S = 75 J K −1 mol −1; ∆H = 30 kJ mol −1.
(c) − 84 .41 and + 90 .63 JK −1 mol −1 The temperature of the reaction at equilibrium is
(d) + 68 .83 and − 84 .41 JK −1 mol −1 (a) 400 K (b) 330 K (c) 200 K (d) 110 K
23 The direct conversion of A to B is difficult, hence it is 30 For a particular reversible reaction at temperature T, ∆H
carried out by the following shown path and ∆S were found to be both positive. If Te is the
C D temperature at equilibrium, the reaction would be
spontaneous when ª AIEEE 2010
(a) T e > T (b) T > T e
A B (c) T e is 5 times T (d) T = T e
Given, ∆S (A → C ) = 50 eu 31 For the process,
∆S (C → D ) = 30 eu H 2O(l ) (1 bar, 273 K) → H 2O ( g ) (1 bar, 373 K),
The correct set of thermodynamic parameters is
∆S (B → D ) = 20 eu
(a) ∆G = 0, ∆S = + ve (b) ∆G = 0, ∆S = − ve
where, eu is entropy unit, then ∆S (A → B ) is (c) ∆G = + ve, ∆S = 0 (d) ∆G = − ve , ∆S = + ve
(a) + 100 eu (b) + 60 eu 32 Considering entropy (S) as a thermodynamic parameter,
(c) − 100 eu (d) − 60 eu the criterion for the spontaneity of any process is
24 Match the following and choose the correct option. (a) ∆Ssystem + ∆Ssurrounding be +ve
(b) ∆Ssystem be zero
Column I Column II
(c) ∆Ssystem − ∆Ssurrounding be + ve
A. Entropy of vaporisation 1. decreases (d) ∆Ssurrounding be zero
B. K for spontaneous process 2. is always + ve 1
33 For a reaction, M 2O(s ) → 2M (s ) + O 2(g ),
C. Crystalline solid state 3. lowest entropy 2
D. ∆E in adiabatic expansion of ∆Hvap ∆H = 30 kJ mol −1 and ∆S = 0.07 kJ K −1 mol −1 at 1 atm. The
ideal gas 4. temperature upto which the reaction would not be
Tb
spontaneous is
Codes (a)T < 400.08 K (b)T < 273.15 K
A B C D A B C D (c)T < 428.57 K (d)T < 473.50 K
(a) 2,4 2 3 1 (b) 3 1,2 4 2 34 For the process, H2O (l ) → H2O (g ) atT= 100 °C and 1
(c) 2 4 1 3 (d) 3,4 2 1 2 atmosphere pressure, the correct choice is ª JEE Main 2014
25 The entropy change involved in the isothermal reversible (a) ∆Ssystem > 0 and ∆SSurrounding > 0
expansion of 2 moles of an ideal gas from a volume of (b) ∆Ssystem > 0 and ∆SSurrounding < 0
10 dm 3 to a volume of 100 dm 3 at 27°C is ª AIEEE 2011 (c) ∆Ssystem < 0 and ∆SSurrounding > 0
(a) 38.3 J mol −1 K −1 (d) ∆Ssystem < 0 and ∆SSurrounding < 0
(b) 35.8 J mol −1 K −1 35 The incorrect expression among the following is ª AIEEE 2012
(c) 32.3 J mol −1 K −1 ∆G system
(a) = −T
(d) 42.3 J mol −1 K −1 ∆S total
26 A Carnot engine operates between temperatureT and Vf
(b) In isothermal process,W reversible = − nRT ln
400 K (T > 400 K ). If efficiency of engine is 25%, the Vi
temperature T is ∆ H ° − T∆ S °
(c) ln K =
(a) 666.0 K (b) 498.5 K RT
(c) 533.3 K (d) 500.0 K (d) K = e −∆G ° / RT
36 The value of log10 KC for a reaction A = B is Direction (Q.Nos. 39 and 40) In the following questions
° K = − 54.07 kJ mol −1,
[Given, ∆rH298 assertion followed by a reason is given. Choose the correct
answer out of the following choices.
° K = 10 JK −1 mol −1 and
∆rS 298 R = 8.314 JK −1 mol −1 (a) Both Assertion and Reason are correct statements and
Reason is correct explanation of Assertion.
and 2.303 × 8.314 × 298 = 5705]
(b) Both Assertion and Reason are correct statements but
(a) 5 (b) 10
Reason is not correct explanation of Assertion.
(c) 95 (d) 100
(c) Assertion is correct statements but Reason is wrong
37 For a spontaneous reaction, the ∆G, equilibrium constant statement.
(K ) and E °cell will be respectively (d) Both Assertion and Reason are wrong.
(a) − ve, > 1, − ve (b) − ve, < 1, − ve
39 Assertion (A) Spontaneous process is an irreversible
(c) + ve, > 1, − ve (d) − ve, > 1, + ve
process and may only be reversed by some external
38 In a fuel cell, methanol is used as fuel and oxygen gas is agency.
used as an oxidiser. The reaction is Reason (R) Decrease in enthalpy is a contributory factor
3
CH3OH(l ) + O2(g ) → CO2(g ) + 2H2O(l ) for spontaneity.
2
At 298 K standard Gibb’s energies of formation for 40 Assertion (A) The thermodynamic function which
CH3OH(l ), H2O(l ) and CO2 (g ) are –166.2, –237.2 and determines the spontaneity of a process is the free
−394.4 kJ mol−1, respectively. If standard enthalpy of energy. For a process to be spontaneous, the change in
combustion of methanol is –726 kJ mol−1, efficiency of the free energy must be negative.
fuel cell will be ª AIEEE 2009 Reason (R) The change in free energy is related to the
(a) 80% (b) 87% change in enthalpy and change in entropy. The change
(c) 90% (d) 97% in entropy for a process must be always positive if it is
spontaneous.

DAY PRACTICE SESSION 2

PROGRESSIVE QUESTIONS EXERCISE

1. An ideal gas is allowed to expand both reversibly and 3. Water is brought to boil under a pressure of 1.0 atm.
irreversibly in an isolated system. If Ti is the initial When an electric current of 0.50 A from a 12 V supply is
temperature and Tf is the final temperature, which of the passed for 300 s through a resistance in thermal contact
following statement is correct? with it, it is found that 0.798 g of water is vaporised.
(a) (Tf ) irrev > (Tf ) rev Calculate the molar internal energy change at boiling
(b)Tf > Ti for reversible process, butTf = Ti for irreversible point (373.15 K).
process (a) 37.5 kJ mol −1 (b) 3.75 kJ mol −1
(c) (Tf ) rev > (Tf ) irrev (c) 42.6 kJ mol −1 (d) 4.26 kJ mol −1
(d)Tf = Ti for both reversible and irreversible processes 4. 1 mole of CO 2 gas at 300 K is expanded under adiabatic
2. When one mole of monoatomic ideal gas at T K conditions such that its volume becomes 27 times. What
undergoes adiabatic change under a constant external is work done? (γ = 1.33 and CV = 6 cal mol −1 for CO 2 )
pressure of 1 atm, changes volume from1 L to 2 L.The (a) 900 cal (b) 1000 cal (c) 1200 cal (d) 1400 cal
final temperature in Kelvin would be 5. A monoatomic ideal gas undergoes a process in which
T 2
(a) Z (b) T + the ratio of p to V at any instant is constant and equals
22/ 3 3 × 0.0821 to 1. What is the molar heat capacity of the gas?
2 (a) 4R / 2 (b) 3R / 2
(c)T (d) T −
3 × 0.0821 (c) 5R / 2 (d) Zero
6. CaCO3 exists in two forms calcite and aragonite. The 11 A reaction is non-spontaneous at the freezing point of
conversion of 1 mole of calcite to aragonite is water but is spontaneous at the boiling point of water,
accompanied by internal energy change equal to then
+ 0.21 kJ. Given that the densities of calcite and ∆H ∆S
aragonite are 2.71 cm −3 and 2.73 g cm −3 respectively. (a) + ve + ve
The enthalpy change at the pressure of 1.0 bar will be (b) − ve − ve
(a) 200.72 J mol −1 (b) 309.72 J mol −1 (c) − ve + ve
(d) + ve − ve
(c) 209.72 J mol −1 (d) 315.00 J mol −1
7 Identify the correct statement regarding a spontaneous 12 One mole of a liquid (1 bar, 100 mL) is taken in an
process. adiabatic container and the pressure increases steeply
to 100 bar. Then at constant pressure of 100 bar, volume
(a) For a spontaneous process in an isolated system, the
decreases by 1 mL. ∆U and ∆H will be respectively.
change in entropy is positive
(b) Endothermic processes are never spontaneous (a) 10 J, 10 J
(c) Exothermic processes are always spontaneous (b) 10 J, 0
(c) 0, 10 J
(d) Lowering of energy in the reaction process is the only
(d) 5 J, 10 J
criteria for spontaneity
13 Standard entropy of X 2, Y2 and XY3 are 60, 40 and
8 The reversible expansion of an ideal gas under adiabatic
50 JK −1 mol −1 respectively. For the reaction,
and isothermal conditions is shown in the figure. Which 1 3
of the following statement is incorrect? X 2 + Y2 → XY3, ∆H = − 30 kJ
2 2
(p1, V1, T1)
to be at equilibrium, the temperature will be
(a) 750 K (b) 1000 K
ad isothermal (c) 1250 K (d) 500 K
p
iab
at (p2, V2, T2) 14 For an isomerisation reaction A 3 B, the temperature
ic
(p3, V3, T3) dependence of equilibrium constant is given by
V 2000
loge K = 4.0 −
(a)T1 = T2 (b)T3 > T1 T
(c)W(isothermal) > W(adiabatic ) (d) ∆ E (isothermal) > ∆ E (adiabatic) The value of ∆S ° at 300 K is therefore,
9 A gas present in a cylinder, fitted with a frictionless (a) 4R (b) 5 R
(c) 400 R (d) 2000 R
piston, expands against a constant pressure of 1 atm
from a volume of 2 litre to a volume of 6 litre. In doing so, 15 1 kg block of ice at 0°C is placed into a perfectly
it absorbs 800 J heat from surroundings. The increase in insulated, sealed container that has 2 kg of water also at
internal energy of process is 0°C. The water and ice completely fill the container is
(a) 305.85 J (b) 394.95 J flexible. After sometime one can except that
(c) 405.83 J (d) –463.28 J (a) the water will freeze so that the mass of the ice will
increase
10 In an irreversible process taking place at constantT and
(b) the ice will melt so that the mass of ice will decrease
p and in which only pressure volume work is being done,
(c) both the amount of water and the amount of ice will
the change in Gibbs free energy ( ∆G ) and change in
remain constant
entropy ( ∆S ), satisfy the criteria
(d) both the amount of water and the amount of ice will
(a) (∆S)V , E < 0, (∆G)T , p < 0 (b) (∆S)V , E > 0, (∆G)T , p < 0 decrease
(c) (∆S)V , E = 0, (∆G)T , p = 0 (d) (∆S)V , E = 0, (∆G)T , p > 0

ANSWERS
SESSION 1 1 (c) 2 (b) 3 (a) 4 (c) 5 (c) 6 (b) 7 (c) 8 (d) 9 (c) 10 (d)
11 (b) 12 (d) 13 (b) 14 (b) 15 (a) 16 (a) 17 (c) 18 (c) 19 (c) 20 (c)
21 (b) 22 (a) 23 (b) 24 (a) 25 (a) 26 (c) 27 (d) 28 (b) 29 (a) 30 (b)
31 (a) 32 (a) 33 (c) 34 (b) 35 (c) 36 (b) 37 (d) 38 (d) 39 (b) 40 (a)

SESSION 2 1 (a) 2 (d) 3 (a) 4 (c) 5 (a) 6 (c) 7 (a) 8 (b) 9 (b) 10 (b)
11 (a) 12 (b) 13 (a) 14 (a) 15 (b)
72 40 DAYS ~ JEE MAIN CHEMISTRY DAY SIX

Hints and Explanations

SESSION 1 Thus, no external work is done for the For the reaction,
1 For a closed vessel made up of copper,
separation of gaseous molecules. N2 (g ) + 3H2 (g )→ 2NH3 (g )
no matter can exchange between the 6 For isothermal process, ∆T = 0, then ∆ng = 2 − 4 = −2
system and the surrounding but energy ∆E = 0 Thus, ∆H = ∆E − 2 RT
exchange can occur through its walls. ⇒ ∆H < ∆E
7 According to first law of
Presence of reaction species in a Numerical value of ∆H < ∆E in
thermodynamics,
covered beaker-closed system and exothermic reaction and when ∆ng < 0.
exchange of matter as well as ∆U = q + W = q − p∆V
energy-open system. Presence of In isochoric process (∆V = 0),
12 Calculate the heat of combustion with
reactant in a closed vessel is a closed the help of following formula,
∆U = q
system and presence of reactant flask ∆Hp = ∆U + ∆ng RT
In isobaric process (∆p = 0),
is an isolated system.
∆U = q where, ∆Hp = Heat of combustion at
In adiabatic process (q = 0) constant pressure
2
∆U = W ∆U = Heat at constant volume
(It is also called ∆E)
Irreversible In isothermal process ∆T = 0 and
p compression ∆U = 0 ∆ng = Change in number of
moles (In gaseous state
∴ ∆U is equal to adiabatic work.
R = Gas constant
8 As the process is carrying out at T = Temperature
Vf Vi constant temperature, therefore this
From the equation,
Volume type of expansion is called isothermal
15
reversible expansion, for which, C 6H6 (l ) + O 2 (g )→ 6CO 2 (g )+ 3H2O(l )
∆U = 0. Hence, q = − W 2
i.e. heat absorbed by the system is Change in the number of gaseous
p Reversible
compression equal to the work done by the system. moles, i.e.
q = + 208 J 15 3
Thus, ∆ng = 6 − = − or −15
.
W = − 208 J 2 2
Now, we have ∆ng and other values
Vf Vi 9 ∆H = ∆E + ∆ng RT given in the question are
Volume Given, ∆H = 30 kcal for 3 mol ∆U = − 3263.9 kJ/mol
As the area under the curve is more in ∆ng = 3 T = 25° C
irreversible compression than the area
because, liquid 0 vapour = 273 + 25 = 298 K
under curve of reversible compression.
Thus, W irreversible > W reversible . 30 = ∆E + 3 × 2 × 500 × 10 −3
R = 8.314 JK −1mol −1
∆E = 27 kcal So, ∆Hp = (−3263.9) + (−15
. ) × 8.314
3 Work done due to change in volume
against constant pressure is 1 × 10−3 × 298
10 C(s ) + O 2 (g ) → CO(g )
W = − p (V2 − V1 ) 2 = − 3267.6 kJ mol −1
= − 1 × 105 N /m2 (1 × 10−2 − 1 × 10−3 ) m3 1 1
∆ng = 1 − =
2 2 13 The amount of heat required to raise the
= − 900 Nm = − 900 J
∆H − ∆E = ∆ng RT temperature of one mole of substance
4 At constant volume, p∆V = 0, i.e. W = 0 1 through 1°C is called molar heat
= × 8.314 JK −1 mol −1 × 298 K capacity.
From first law of thermodynamics, 2
q
∆E = q + W = 1238.78 J mol −1 C=
T2 − T1
∴ q = ∆E
11 According to relationship of ∆H and ∆E, 14 Q = mC∆T
5 In free expansion, W = 0 while in ∆H = ∆E + ∆ng RT 100
adiabatic process, q = 0. 1000 = × 75 × ∆T
∆H = enthalpy change (at constant 18
∆U = q + W = 0 pressure) ∆T = 2.4 K
This suggests that internal energy ∆E = internal energy change (at
remains constant. Therefore, ∆T = 0. constant volume) 15 The equation, C p − C V = nR
Expansion of an ideal gas under (given reaction is exothermic) 2 moles of an ideal gas is equal to
adiabatic conditions in a vacuum leads
( ∆ng = moles of gaseous products Cp − CV = 2 R
to no absorption/evolution of heat. – moles of gaseous reactants)
16 Using Kirchhoff’s equation, 24 A → (2, 4), B → (2 ), C → (3), D → (1) As, ∆G = − ve
∆H2 − ∆H1 Hence, the process is spontaneous.
∆C p = A → Entropy of vaporisation is always
T2 − T1 ∆Hvap 29 ∆G = ∆H − T∆S
positive, i.e.
∆H2 − ∆H1 = ∆C p (T2 − T1 ) Tb At equilibrium, ∆G = 0
∆H2 − 24 = (0.031 − 0.055) (100 − 50) B → ∆ G ° = − RT In K ∆H 30 × 103
T= = = 400 K
∆H2 = 22.8 cal g −1 ∆S 75
If K is +ve, then, ∆G° = −ve, i.e.
17 For the given change, spontaneous process. 30 ∆G = ∆H − T∆S
C → Crystalline state is most orderly At equilibrium, ∆G = 0
∆ r S ° = ΣnPS P° − ΣnRS R° arranged state of particles, thus lowest
° entropy. ∴ Te = ∆H/∆S
= SNH 2 CONH 2
+ SH° 2 O
For a reaction to be spontaneous
° ] D → During adiabatic expansion of an ∆G should be negative, so this implies
− [2 × SNH
° + SCO ideal gas, q = 0 thus, ∆E = W i.e.
3 2
∆H < T∆S.
= 174.0 + 69.9 − [2 × 192.3 + 2137
. ] ∆H
Work done at the cost of internal energy < T;Te < T
= − 354.4 JK −1 mol −1 which decreases when q = 0. ∆S
V2 Therefore, T should be greater than Te .
18 ∆S = 2.303 nR log 25 Entropy change for n moles of
V1 isothermal expansion of an ideal gas 31 H2O(l ) and H2O (g ) both exist together at
20 from volume V1 to volume V2 is
= 2.303 × 2 × 2 log = 9.2 same temperature and pressure,
2 V
∆S = 2.303 nR log 2 H2O(l ) q H2O (g )
V1
19 For an isolated system, In the state of equilibrium, ∆G = 0 and
100
= 2.303 × 2 × 8.3143 log conversion of liquid into gas increases
∆H = ∆E + p∆V or T∆S = ∆E + p∆V 10 the disorderness.
But ∆E = 0
= 38.296 J mol −1 K −1 Hence, entropy ∆S = + ve
∴ T∆S = p∆V
T −T 32 For a spontaneous process,
p∆V 26 η (efficiency) = 2 1
∆S = >0 T2
T ∆S total = ∆Ssystem + ∆Ssurroundings
T − 400 be positive.
20 ∆Hcondensation for 1.8 g of steam ⇒ 0.25 =
T 33 For a non-spontaneous reaction,
= (−40.8) ×
1.8
= − 4.08 kJ ∴ T = 533.3 K ∆G = + ve
18
27 PbO 2 + Pb → 2PbO ∆G = ∆H − T∆S
∆H −4.08 × 103
∆S = = ∴ ∆H − T∆S should be + ve or ∆H > T∆S
Tb .
37315 Oxidation state +4 0 +2
∆H
Since, ∆G° < 0, i.e. it is negative. which is possible if T <
= − 10.93 JK −1 ∆S
Therefore, the reaction is spontaneous
21 CO and NO molecules in solid states at in the forward direction. This suggest Given, ∆H = 30 × 103 J mol −1
0 K adopt a nearly random arrangement that Pb 2+ is more stable than Pb 4+ . ∆S = 70 JK −1 mol −1
indicating a positive value of entropy. It SnO 2 + Sn → 2SnO
is due to their dipole moment which 30 × 103
Oxidation state +4 0 +2 T<
results in disorder. 70
Since, ∆ r G° > 0, i.e. it is positive,
∆Hvap 26 × 103 therefore, the reaction is T < 428. 57 K
22 ∆S vap = =
T 308 non-spontaneous in the forward 34 Total entropy change of universe is zero.
direction. But it will be spontaneous in
= + 84.41 JK −1 mol −1 At 100°C and 1 atmosphere pressure,
the backward direction. This suggests
∆Hcond that Sn4+ will be more stable than Sn2+ . H2O(l ) r H2O(g )
∆Scond = [Q∆Hcond = − 26 kJ ]
T These facts are also supported by the is at equilibrium.
26 × 103 inert pair effect down the group. For equilibrium, ∆S total = 0
=− = −84.41 JK −1 mol −1
308 28 Heat at constant pressure means and ∆Ssystem + ∆Ssurrounding = 0
enthalpy, i.e. As we know, during conversion of
23 ∆S liquid to gas, entropy of system
∆H = − 2.5 × 103 cal
A → C = 50 eu increases, in a similar manner entropy
C → D = 30 eu ∆S = 7.4 cal deg −1 of surroundings decreases.
D → B = −20 eu T = 298 K ∴ ∆Ssystem > 0
A→ B 60 eu ∆G = ∆H − T∆S and ∆Ssurrounding < 0
= −2.5 × 103 − 298 × 7.4 Hence, (b) is the correct choice.
= − 4705 cal
35 (a) ∆G = ∆H − T∆S − [− ∆Gf (CH3OH, l ) = 1800 J = + 1.8 kJ
3
For a system, total entropy change − ∆Gf (O 2 , g )] Molar enthalpy of vaporisation,
2 ∆H ∆H
= ∆S total ∆Hm = =
= − 394.4 + 2 (−237.2) − (−166.2) − 0 moles of H2O nH 2O
∆Htotal = 0 = − 394.4 − 474.4 + 166.2
1.8 kJ
∴ ∆Gsystem = − T ∆S total = −702.6 kJ mol −1 = = 40.6 kJ mol −1
0.798
∆Gsystem Percentage efficiency 18
∴ = −T
∆S total 702.6 ∆Hm = ∆Em + ∆ng RT
= × 100 = 9678
. % ≈ 97%
726 ∆Hm = ∆Em + RT
(b) For isothermal reversible process,
[∆ng = 1for H2O (l ) 1 H2O (g )]
∆E = 0 39 Spontaneous processes are
accompanied by decrease in energy Molar internal energy change,
By first law of thermodynamics
and increase in randomness. ∆Em = ∆Hm − RT
∆E = q + W
Vf ' 40 Reason is the correct explanation for = 40.6 − 8.314 × 10−3 × 37315
.
∴ Wreversible = − q = − ∫V i
p dV Assertion. = 37.5 kJ mol −1
γ −1
Vf SESSION 2 T2  V1 
Wreversible = − nRT ln 4 For adiabatic condition, = 
Vi T1  V2 
1. The pV diagram for the reversible and
1.33 − 1
(c) ∆G = ∆H° − T∆S ° = −RT log K
0.33
T2  1 
⇒  
irreversible expansion of an ideal gas 1
= 
∆H° − T∆S °  T1  27   27 
log K = − 
is shown below :

 
1/ 3
=  
RT 1 1
(pI)irr,(pI)rev =
 27  3
(d) ∆G ° = − RT log K 1
∆G ° T2 = 300 × = 100 K
∴ log K = − Irr 3
RT e ve
rsi Thus, T2 < T1, hence cooling takes
ble
∴ K = e − ∆G ° / RT place due to expansion under
(pF)irr adiabatic condition.
36 ∆G ° = ∆H° − T∆S ° = −2.303 RT log10 K (pF)rev
reversible
∆E = q + W = W
(VI)rev, irr (VF)rev, irr (Qq = 0 for adiabatic change.)
∴ − 2.303 RT log10 K = ∆H° − T∆S ° Sign of W is negative because the gas
i.e. −2.303 × 8.314 × 298 × log10 K From ideal gas equation expands.
nRT W = − ∆ E = − C V (T2 − T1 )
= [−54.07 × 1000] − [298 × 10] p=
V = − 6 (100 − 300) = 1200 cal
For final condition of temperature,
−5705 log10 K = − 54070 − 2980 5. The molar heat capacity for any process
pressure and volume
−5705 log10 K = − 57050 is given by following expression,
nRTf
pF = C = CV +
R
when pV γ = constant
or log10 K = 10 Vf 1− γ
37 The standard free energy related to From the curve it is seen that
and C p / C V = γ
equilibrium constant, K as ( pF ) irr > ( pF ) rev or (TF ) irr > (Tf ) rev
p
Here, = 1, i.e. pV −1 constant
∆G ° = − 2 .303 RT log Keq 2 For adiabatic change, ∆E = ∆W V
∆G ° = − nFE °cell ∆ E = nC V (T2 − T ) 3 R 3 R 4
C = R+ = R+ = R
If a cell reaction is spontaneous ∆W = − p(V2 − Vt ) 2 1 − (−1) 2 2 2
(proceeding in forward side), it means
Keq > 1and E°cell = + ve
6 ∆H = ∆U + p ∆V
nC V (T2 − T ) = − p (V2 − Vt ) = −12
( − 1)
Thus, ∆G° = − ve Here, ∆U = + 0.21kJ mol −1
R
n× × (T2 − T ) = −1
38 Percentage efficiency of the fuel cell (γ − 1) = 0.21 × 103 J mol −1
∆G 5 = 210 J mol −1
= × 100 For monoatomic gas n = 1,γ = ,
∆H 3 p = 1bar =105 Pa
R = 0.0821 L atm K −1 mol −1
The concerned reaction is ∆V = Molar volume of aragonite
3 0.0821
CH3OH(l ) + O 2 (g ) → CO 2 (g ) 1× × (T2 − T ) = −1 – Molar volume of calcite
2 (5/ 3) − 1 2
T2 = T − 100 100
+ 2H2O(l ); = − cm3 mol −1
3 × 0.0821 2.93 2.71
∆Gr = [ ∆Gf (CO 2 , g ) + 2 ∆Gf (H2O, l )] 3 ∆H = work done = i × V × t (QMolar mass of CaCO 3 = 100 g mol −1 )
= 0.50 A × 12 V × 300 s
 = 100 
1 1  (correct statement) Further, at constant pressure of 100 bar,
− 
 2.93 2.71 volume has decreased by 1 mL,
9 Work is done against constant pressure therefore, work of contraction
 0.22  and thus, irreversible.
= 100 ×   = p∆V = 100 bar × 1 mL
 2.93 × 2.71 Given, ∆V = 6 − 2 = 4 L and p = 1 atm
= (100 × 105 Nm−2 ) (10−6 m3 )
= 2.77 cm3 mol −1 W = − p × dV
= − 1 × 4 L atm = 10 J
= − 2.77 × 10−6 m3
1 × 4 × 1987
. During adiabatic process, work done
∴ ∆H = 210 × 105 (−2.77 × 10−6 ) =− cal
0.0821 = change in internal energy
= 210 − 0.277 J (Q0.0821 L atm = 1987
. cal) Hence, ∆U = 10 J
= 209.72 J mol −1 = − 96.81 cal
° −  S X° +
13 ∆ r S ° = S XY
1 3 °
SY
7 For spontaneous process
= − 96.81 × 4184
. J = −405.04 J 3
 22
2 2 
From first law of thermodynamics,
∆S total = ∆Ssys + Ssurr > 0 = 50 −  × 60 + × 40
1 3
q = ∆E − W  2 
For an isolated system ∆Ssurr = 0 2
Hence, ∆Ssys > 0. ∆E = q + W = 800 + (−405.04)
= 50 − (30 + 60) = − 40 JK −1 mol −1
= 394.95 J
8 (a) Since, change of state ( p1, V1, T1 ) to ∆ r G ° = ∆ r H° − T∆ r S °
( p2 , V2 , T2 ) is isothermal 10 For an irreversible process to be
(At equilibrium, ∆ r G° = 0)
therefore, T1 = T2 (correct statement) spontaneous,
∴
(∆S )V, E (change in entropy) ∆ H° −30,000 J mol −1
(b) Since, change of state ( p1, V1, T1 ) to T= r = = 750 K
( p3 , V3 , T3 ) is an adiabatic = + ve > 0 ∆ rS ° −40 JK −1 mol −1
expansion, it brings about cooling of ⇒(∆G ) T , p (change in Gibbs free energy) 14 ∆G = ∆H − T∆S
gas, therefore, T3 < T1. Thus, it is = − ve < 0 Also, ∆G = −2.303 RT log K
incorrect.
11 For spontaneity, ∆G = − ve Variation of K with temperature is given
(c) Work done is given by the area ∆ S ° ∆ H°
under the curve of p-V diagram. As ∆G = ∆H − T ∆S by log K = −
R RT
obvious from the given diagram, ∆H, for endothermic process + ve
2000
magnitude of area under the isothermal At lower temperature, Given, log K = 4.0 −
curve is greater than that under T
T∆S = + ve
adiabatic curve, hence ∆S °
At lower temperature, T∆S will be less On comparing, = 4 or
Wisothermal > Wadiabatic (correct R
than ∆H.
statement). ∆S ° = 4 R
Hence, ∆G = + ve
(d) ∆ E = nC V ∆T
But at high temperature, T∆S will be 15 In accordance to second law of
In isothermal process, ∆ E = 0 as greater than ∆H. thermodynamics, if an irreversible
Hence, ∆G = − ve, spontaneous. process occurs in a closed system, the
∆T = 0
entropy of that system always increases,
In adiabatic process, 12 As the process is carried out under it never decreases. As the ice is more
adiabatic conditions, q p = 0. But by ordered then water, i.e. it has less
∆ E = nC v (T3 − T1 ) < 0 as T3 < T1 definition q p = ∆H. entropy. Therefore, the ice will melt so
∆ E isothermal > ∆ E adiabatic Hence, ∆ H = 0 that the mass of the ice will decrease.