2.

Extensive Properties Those properties that depend on There are two types of heat capacities based on the conditions
Concept of Work First Law of Thermodynamics Entropy Change (∆S ) Carnot Engine
DAY SIX quantity of the matter present in the system, e.g.
internal energy, heat, total moles, volume, enthalpy,
entropy, free energy etc.
l The work is said to be done when gas expands or
contracts against the external pressure. Work done is a
According to this law, energy can neither be created nor
destroyed although it may be converted from one form to
such as volume and pressure.
1. Heat Capacity at Constant Pressure (C p) The heat Entropy is the measurement of randomness or disorder of the
molecules. A process which proceeds at its own without any
Carnot in 1824 gave an imaginary reversible cycle which
demonstrates the maximum conversion of heat into
capacity of a substance measured when the gaseous work. He actually proposed a theoretical heat engine to
Force is extensive property but pressure is intensive path function not a state function as depends upon the another. outside help is termed as spontaneous process. The total entropy
system is at constant pressure. show that its efficiency was based upon the
property. path followed. l Mathematical form of first law of thermodynamics, change (∆S total ) for the system and surrounding of a spontaneous
 q  dH temperatures, between which it operated.
W = − pext × ∆V ∆E =q +W Cp =   or C p = process is always positive,

Chemical
 ∆T  p dT
State and Path Functions For expansion W = − pext (V2 − V1 ) [Here, V2 > V1 ] l Both W and q are not state functions but quantity W + q is ∆S total = ∆Ssystem + ∆Ssurrounding > 0. A Carnot cycle comprises four operations or processes:

1. State Functions Those functions which depend only For compression W = − pext (V2 − V1 ) [Here, V2 < V1 ] a state function. 2. Heat Capacity at Constant Volume (CV ) The heat capacity l Entropy is a state function and depends only on initial and (i) Isothermal reversible expansion
on the state of the system and not on how it is reached. of a substance measured when the gaseous system is at final states of the system. (ii) Adiabatic reversible expansion
l Maximum work done for reversible isothermal process
e.g. pressure, volume, temperature, ∆H, ∆E etc. constant volume.
V
Wrev = −2.303 nRT log 2
Enthalpy i.e. ∆S = S final − S initial (iii) Isothermal reversible compression

Thermodynamics
2. Path Functions The functions that depend upon the  q  dV (iv) Adiabatic reversible compression
V1 The total heat content of a system at constant pressure is CV =   or CV = l Unit of entropy is joule per Kelvin per mole.
 ∆T  V
l
path followed are called path functions, e.g. work done, dT
where, V2 = final volume, V1 = initial volume called the enthalpy of the system. It is the sum of internal For a reversible change at constant temperature
heat etc. l
Isothermal
p energy and the product of pressure-volume work. l Relationship between C p and CV is given as q
A(p1,V1)
Also, Wrev = −2 . 303 nRT log 1 C p − CV = R (R is the molar gas constant.) ∆S = rev = S final − S initial expansion
p2 l It is an extensive quantity, state function and T B(p2,V2)
Types of Processes Maximum work done for irreversible isothermal expansion
represented by the symbol H. C p − CV =
R 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
The equation is M Adiabatic
Learning & Revision for the Day The state of a variable can be changed by means of a (i) Intermediate expansion
For monoatomic gas the molar heat capacity at
compression
expansion
thermodynamic process. These are of the following types : H = E + pV
l
V2 l For a spontaneous isothermal expansion
pext < pgas, Wirr = ∫ pext dV  3 D(p4,V4)
1. Adiabatic Process In which system does not ∆H = ∆E + p∆V constant volume, CV =   R V C (p3,V3)
Fundamental of First Law of Thermodynamics Third Law of
V1
 2 ∆S = 2.303 nR log 2 Isothermal
exchange heat with its surrounding, i.e. dQ = 0.
u u u
V1
Thermodynamics u Entropy Change (∆S) Thermodynamics W = − pext (V2 − V1 ) ∆H = ∆E + ∆ng RT
compression
2. Isothermal Process In which temperature remains l For monoatomic gas molar heat capacity at constant Volume
u Types of Processes u Second Law of u Gibb’s Free Energy ( ∆G ) (ii) Free expansion If gas expands in vacuum, pext = 0, where, ∆H = enthalpy change
l The change of matter from one state to another is called phase
fixed, i.e. dT = 0. pressure,
transition. Carnot cycle
u Concept of Work Thermodynamics therefore, W = 0
∆ng = gaseous moles of products − gaseous  3  5
u Heat 3. Isobaric Process In which change of state is brought Cp =   R + R =   R The entropy changes at the time of phase transition are as Net work done in 1 cycle is
about at constant pressure, i.e. dp = 0. moles of reactants  2  2 l

Sign Convention follows:

The laws of thermodynamics deal with the energy changes of macroscopic systems If ∆ng = 0, then ∆H = ∆U; If ∆ng > 0 then ∆H > ∆U and V2 V
4. Isochoric Process In which volume of the system (i) If W is positive — work done on the system
l Cp  5 ∆H fusion W = RT2 ln + RT1 ln 4
involving a large number of molecules rather than microscopic systems containing a Poisson’s ratio, γ = =   = 1.66 (i) ∆S melting = ; (Tm = melting point of substance)
if ∆ng < 0 then, ∆H < ∆U.
l
remains constant, i.e. dV = 0. CV  3 V1 V3
(ii) If W is negative — work done by the system Tm
few molecules.
5. Cyclic Process This is the process in which a system l For reaction involving solids and liquids only, ∆H = ∆E . γ = 1.66 for monoatomic gases (like He, Ar) Net heat absorbed in the whole cycle is
∆H vaporisation
l

undergoes a number of different states and finally Enthalpy also changes, when a substance undergoes (ii) ∆S vaporisation = ; (Tb = boiling point of substance) V
γ = 1.40 for diatomic gases (like H2 , O2 , CO) q = R (T2 − T1 ) ln 2
Fundamentals of Thermodynamics returns to its initial state. For such a process, change in Heat phase transition. Tb
V1
internal energy and enthalpy is zero, i.e. dE = 0 and γ = 1.33 for triatomic gases (like H2O, O3 ) ∆Hsublimation
Some basic terms and concepts commonly used in thermodynamics are briefly It is defined as the quantity of energy, which flows between (iii) ∆Ssublimation = ; (Tsub = sublimation temperature)
dH = 0. Work done in reversible adiabatic expansion Efficiency of a heat engine (denoted by η ) in a
explained below: system and surroundings on account of temperature difference. Heat Capacity l
Tsub
l

Carnot cycle is given

6. Reversible Process In this process, (quasistatic system),
It is also a path function, i.e. depends upon the path followed. Work done = CV ∆T = CV × (T2 − T1 )
Heat capacity (C) of a system is defined as the amount of heat
System and Surroundings change taken place is infinitesimally slow and their
required to raise the temperature of the system by 1 ° C. NOTE η=
W T2 − T1
=
T
=1 − 1
System is a part of universe under observation and the part of the universe except
direction at any point can be reversed by infinitesimal
change in the state of the system. Reversible process is
Sign Convention The molar heat capacity for any process is given by
Second Law of Thermodynamics q2 T2 T2
q R
system is called surroundings. System basically a specific portion which is considered (i) If q is positive — heat is supplied to the system C= C = CV + The second law of thermodynamics tells us whether a given The above relation was stated in the form of Carnot
an ideal process and here, every intermediate state is in ∆T 1− γ
l

under thermodynamic studies. equilibrium with others, if any. (ii) If q is negative — heat is lost by the system when, pV γ = constant process can occur spontaneously and to what extent, it also helps theorem by Carnot, i.e. “Every perfect engine
l If the system consists of a single substance or a solution us to calculate maximum fraction of heat that can be converted working reversibly between the same temperature
Thus, system and the surrounding together constitute the universe, i.e. 7. Irreversible Process This process, is the one which and weighs 1 mol, the heat capacity of the system is
universe = system + surroundings cannot be reversed. In this process, amount of energy Internal Energy (E or U) referred as molar heat capacity (Cm).
Kirchhoff’s Equation 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.”
On the basis of exchange of mass and energy, systems are of three types: increases. All natural processes are irreversible in According to Kirchhoff’s equation, the partial derivatives of
l It is the total energy within the substance. It is equal to the maximum.
nature. l If the system consists of a single substance or a solution the change of enthalpy (or of internal energy) during a
1. Open System In which energy and matter both can be exchanged with sum of translational energy, vibrational energy, potential For an irreversible process,
and weights 1 g, the heat capacity of the system is
surroundings. • If macroscopic properties like temperature, pressure, etc., energy etc. We can only determine the change in internal
referred as specific heat of the system (Cs ).
reaction, with respect to temperature at constant pressure
(or volume) equals to the change in heat capacity at constant dq Third Law of Thermodynamics
NOTE do not change with the time, the system is said to be in energy. dS >
2. Closed System In which only energy can be exchanged with surroundings. pressure (or volume). T l This law was proposed by German chemist Walther
thermodynamic equilibrium. q = C × m × ∆T Nernst. According to this law, ‘‘The entropy of a
3. Isolated System In which neither matter nor energy can be exchanged with i.e. ∆U = U2 − U1 ∆H2 − ∆H1 ∆E2 − ∆E1 dq
• If the two systems are in thermal equilibrium with a where, m = mass of substance, ∆C p = and ∆CV = ∴ dS ≥ perfectly crystalline substance approaches zero as
surroundings. third system, they must be in thermal equilibrium l At constant temperature, internal energy change (∆E) will T2 − T1 T2 − T1 T
the absolute zero of temperature is approached’’.
with each other. This law is known as zeroth law of be zero. Internal energy depends on temperature, C = specific heat capacity This is the mathematical statement of the second law of
Extensive and Intensive Properties thermodynamics. pressure, volume and quantity of matter. where, ∆C p = ΣC p of products − ΣC p of reactants l It forms the basis from which entropies at other
and ∆T = temperature difference. thermodynamics.
∆CV = ΣCV of products − ΣCV of reactants temperatures can be measured, lim S = 0
Properties used to define the state of a system are extensive and intensive properties. The law defines the temperature as the property T→ 0
which determines, whether the body is in thermal
1. Intensive Properties Those properties that depend on nature of matter but do not
equilibrium or not.
depend on quantity of the matter, e.g. pressure, temperature, specific heat, melting
point etc.

3 An ideal gas expands in volume from1 × 10−3 m 3 to 27 In view of the signs of ∆ r G ° for the following reactions Direction (Q.Nos. 39 and 40) In the following questions
Gibbs Free Energy (∆G ) ∆S ∆H ∆G Spontaneity of a Process
1 × 10−2 m 3 at 300 K against a constant pressure of
12 The combustion of benzene (l ) gives CO2(g ) and H2O(l ). 21 Which of the following does not have zero entropy even
PbO2 + Pb → 2PbO, ∆rG ° < 0
36 The value of log10 KC for a reaction A = B is assertion followed by a reason is given. Choose the correct
+ − Negative at all Spontaneous at all Given that heat of combustion of benzene at constant at absolute zero? ° K = − 54.07 kJ mol −1,
[Given, ∆rH298
l The maximum amount of energy available to a system, temperatures. temperatures. 1 × 105 N/ m 2. The work done is volume is −3263.9 kJ mol −1 at 25° C; heat of combustion CO, CO 2 , NaCl, NO SnO2 + Sn → 2SnO, ∆rG ° > 0 answer out of the following choices.
during a process that can be converted into useful (a) −900 J (b) −900 kJ (in kJ mol −1) of benzene at constant pressure will be (a) CO, CO 2 (b) CO, NO (a) For lead + 4, for tin + 2 (b) For lead + 2 , for tin + 2
° 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
− − Negative at all Spontaneous at low
work is called free energy or Gibbs free energy. (c) 270 kJ (d) 900 kJ (R = 8.314 JK −1 mol−1) ª JEE Main 2018 (c) For lead + 4, for tin + 4 (d) For lead + 2, for tin + 4 Reason is correct explanation of Assertion.
temperatures. temperature but (c) CO 2 , NaCl (d) NaCl and 2.303 × 8.314 × 298 = 5705]
l Under standard conditions of temperature non-spontaneous at high 4 When 1 mole of a gas is heated at constant volume, (a) 4152.6 (b) −452.46 (b) Both Assertion and Reason are correct statements but
22. The enthalpy of vaporisation of liquid diethyl ether 28 When the heat of a reaction at constant pressure is (a) 5 (b) 10
(i.e. at 298 K) and pressure (i.e. 1 atm), the free energy temperature. (c) 3260 (d) −3267.6 Reason is not correct explanation of Assertion.
temperature is raised from 298 K to 308 K. Heat supplied (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 (c) 95 (d) 100
change for a process in which reactants in their + + to the gas is 500 J. Then, which statement is correct? (c) Assertion is correct statements but Reason is wrong
Positive at low Spontaneous at high 13 Heat required to raise the temperature of 1 mole of a 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 37 For a spontaneous reaction, the ∆G, equilibrium constant statement.
standard state is converted into products in their temperature and negative temperature. (a) q = −W = 500 J, ∆E = 0 substance by 1°C is called
standard state is called standard free energy change at high temperature.
and vapour to liquid respectively? (a) reversible (b) spontaneous (K ) and E °cell will be respectively (d) Both Assertion and Reason are wrong.
(b) q = W = 500 J, ∆E = 0 (a) specific heat (b) molar heat capacity (a) + 84 .41 and − 84 .41 JK −1 mol −1
(i.e. ∆G°). (c) q = ∆E = 500 J, W = 0
(c) non-spontaneous (d) irreversible (a) − ve, > 1, − ve (b) − ve, < 1, − ve
+ + Positive at all temperature. Non-spontaneous at all (c) water equivalent (d) specific gravity 39 Assertion (A) Spontaneous process is an 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) + ve, > 1, − ve (d) − ve, > 1, + ve
l The changes in the Gibbs energy of a system as a temperature. (d) ∆E = 0, q = W = −500 J process and may only be reversed by some external
14 The molar heat capacity of water at constant pressure is (c) − 84 .41 and + 90 .63 JK −1 mol −1 The temperature of the reaction at equilibrium is 38 In a fuel cell, methanol is used as fuel and oxygen gas is agency.
function of temperature can be calculated by the 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 (d) + 68 .83 and − 84 .41 JK −1 mol −1 (a) 400 K (b) 330 K (c) 200 K (d) 110 K used as an oxidiser. The reaction is
equation known as Gibbs Helmholtz Equation.
Relation between Gibbs Energy Change between system and surroundings. Choose the correct water, which is free to expand, the increase in 3
Reason (R) Decrease in enthalpy is a contributory factor
∆G = ∆H − T∆S option for free expansion of an ideal gas under adiabatic temperature of water is 23 The direct conversion of A to B is difficult, hence it is 30 For a particular reversible reaction at temperature T, ∆H CH3OH(l ) + O2(g ) → CO2(g ) + 2H2O(l ) for spontaneity.
where, ∆G = Gibbs free energy (measurement of useful
and Equilibrium Constant condition from the following. (a) 1.2 K (b) 2.4 K
carried out by the following shown path and ∆S were found to be both positive. If Te is the 2
At 298 K standard Gibb’s energies of formation for 40 Assertion (A) The thermodynamic function which
work) Relation between Gibbs free energy with reaction quotient and (a) q = 0, ∆T ≠ 0, W = 0 (c) 4.8 K (d) 6.8 K C D temperature at equilibrium, the reaction would be
CH3OH(l ), H2O(l ) and CO2 (g ) are –166.2, –237.2 and determines the spontaneity of a process is the free
equilibrium constant are as follows : (b) q ≠ 0, ∆T = 0, W = 0 spontaneous when ª AIEEE 2010
l The following cases are considered for ∆G. 15 For two moles of an ideal gas −394.4 kJ mol−1, respectively. If standard enthalpy of energy. For a process to be spontaneous, the change in
(c) q = 0, ∆T = 0, W = 0 (a) T e > T (b) T > T e
(i) ∆G > 0, for non-spontaneous process l ∆G = ∆G °+ 2.303 RT log Q (d) q = 0, ∆T < 0, W ≠ 0 (a) (Cp − CV ) = 2R (b) (Cp − CV ) = 0 combustion of methanol is –726 kJ mol−1, efficiency of the free energy must be negative.
A B (c) T e is 5 times T (d) T = T e
(ii) ∆G < 0, for spontaneous process where, Q = reaction quotient (c) (Cp − CV ) = R (d) (Cp − CV ) = R /2 fuel cell will be ª AIEEE 2009 Reason (R) The change in free energy is related to the
6 1 mole of an ideal gas at 300 K is expanded isothermally ∆S (A → C ) = 50 eu 31 For the process,
(iii) ∆G = 0, at equilibrium At equilibrium, ∆G = 0 16 The heat of sublimation of iodine is 24 cal g −1 at 50°C. If Given, (a) 80% (b) 87% change in enthalpy and change in entropy. The change
l
from an initial volume of 1 L to 10 L. The ∆E for this
∆S (C → D ) = 30 eu H 2O(l ) (1 bar, 273 K) → H 2O ( g ) (1 bar, 373 K), (c) 90% (d) 97% in entropy for a process must be always positive if it is
∴ ∆G ° = −2.303 RT log K process is (R = 2 cal K −1 mol −1 ) specific heat of solid iodine and its vapours are 0.055
Criteria for Spontaneity and 0.031 cal g −1 respectively, the heat of sublimation of The correct set of thermodynamic parameters is spontaneous.
K = equilibrium constant (a) 270 cal (b) zero (c) 10 L atm (d) 181.7 cal ∆S (B → D ) = 20 eu
iodine at 100°C is (a) ∆G = 0, ∆S = + ve (b) ∆G = 0, ∆S = − ve
l In the determination of spontaneity, Gibbs energy l ∆G ° = − n Ecell
° F 7 ∆U is equal to ª JEE Main 2017 (a) 22.8 cal g −1 (b) 25.2 cal g −1 where, eu is entropy unit, then ∆S (A → B ) is (c) ∆G = + ve, ∆S = 0 (d) ∆G = − ve , ∆S = + ve
criteria is better than entropy criteria because Gibbs (a) isochoric work (b) isobaric work (c) –22.8 cal g −1 (d) –25.2 cal g −1
energy refers to the system only while entropy refers to where, n = number of electrons lose or gained, (a) + 100 eu (b) + 60 eu 32 Considering entropy (S) as a thermodynamic parameter,
(c) adiabatic work (d) isothermal work (c) − 100 eu (d) − 60 eu
both system and surroundings. °
Ecell = standard electrode potential,
8 A piston filled with 0.04 mole of an ideal gas expands
17 What will be the change of entropy ∆rS ° at 298 K for the the criterion for the spontaneity of any process is DAY PRACTICE SESSION 2
l For negative value of ∆G several conditions exist 1F = 96500 C
reaction, in which urea is formed from NH 3 and CO 2 ? 24 Match the following and choose the correct option. (a) ∆Ssystem + ∆Ssurrounding be +ve
reversibly from 50.0 mL to 375 mL at a constant 2NH 3 (g ) + CO 2 (g ) → NH 2CONH 2 (aq ) + H 2O (l ) (b) ∆Ssystem be zero
which plays an important role in deciding the
spontaneity of the process.
l Efficiency of the fuel cell = ∆ G / ∆ H × 100 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 ), A.
Column I
Entropy of vaporisation 1.
Column II
decreases
(c) ∆Ssystem − ∆Ssurrounding be + ve
(d) ∆Ssurrounding be zero
PROGRESSIVE QUESTIONS EXERCISE
[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 B. K for spontaneous process 2. is always + ve 1
(a) q = − 208 J, W = − 208 J 69.9 JK mol −1 respectively] 33 For a reaction, M 2O(s ) → 2M (s ) + O 2(g ), 1. An ideal gas is allowed to expand both reversibly and 3. Water is brought to boil under a pressure of 1.0 atm.
(b) q = − 208 J, W = + 208 J
C. Crystalline solid state 3. lowest entropy 2 irreversibly in an isolated system. If Ti is the initial When an electric current of 0.50 A from a 12 V supply is
DAY PRACTICE SESSION 1 (a) 200 JK −1 mol −1 (b) –35.44 JK −1 mol −1 ∆E in adiabatic expansion of ∆Hvap ∆H = 30 kJ mol −1 and ∆S = 0.07 kJ K −1 mol −1 at 1 atm. The temperature and Tf is the final temperature, which of the passed for 300 s through a resistance in thermal contact
(c) q = + 208 J, W = + 208 J D.
(c) –354.4 JK −1 mol −1 (d) 425.2 JK −1 mol −1 4. temperature upto which the reaction would not be
(d) q = + 208 J, W = − 208 J ideal gas Tb following statement is correct? with it, it is found that 0.798 g of water is vaporised.
18 2 moles of an ideal gas at 27°C are expanded reversibly spontaneous is (a) (Tf ) irrev > (Tf ) rev Calculate the molar internal energy change at boiling
FOUNDATION QUESTIONS EXERCISE 9 Latent heat of vaporisation of a liquid at 500 K and 1 atm
pressure is 10.0 kcal/mol. What will be the change in
from 2 L to 20 L. Find entropy change (in cal/mol K). Codes (a)T < 400.08 K
(c)T < 428.57 K
(b)T < 273.15 K
(d)T < 473.50 K
(b)Tf > Ti for reversible process, butTf = Ti for irreversible point (373.15 K).
(a) 37.5 kJ mol −1 (b) 3.75 kJ mol −1
internal energy ( ∆E ) of 3 moles of liquid at same (R = 2 cal/mol K) A B C D A B C D process
(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) (Tf ) rev > (Tf ) irrev (c) 42.6 kJ mol −1 (d) 4.26 kJ mol −1
1 Which of the following statement is correct? 2 The pressure-volume work for an ideal gas can be temperature? (a) 0 (b) 4
Vf (c) 9.2 (d) 92.0 (c) 2 4 1 3 (d) 3,4 2 1 2 atmosphere pressure, the correct choice is ª JEE Main 2014 (d)Tf = Ti for both reversible and irreversible processes 4. 1 mole of CO 2 gas at 300 K is expanded under adiabatic
(a) The presence of reacting species in a covered calculated by using the expression W = − ∫ pexdV . The (a) 30 kcal (b) –54 kcal (c) 27.0 kcal (d) 50 kcal
beaker is an example of open system Vi 19 For an isolated system, ∆E = 0, then 25 The entropy change involved in the isothermal reversible (a) ∆Ssystem > 0 and ∆SSurrounding > 0 2. When one mole of monoatomic ideal gas at T K conditions such that its volume becomes 27 times. What
10 ( ∆H − ∆E ) for the formation of carbon monoxide (CO) (b) ∆Ssystem > 0 and ∆SSurrounding < 0 is work done? (γ = 1.33 and CV = 6 cal mol −1 for CO 2 )
work can also be calculated from the pV − plot by using the (a) ∆S = 0
expansion of 2 moles of an ideal gas from a volume of
(b) There is an exchange of energy as well as matter from its elements at 298 K is (R = 8.314 JK −1 mol −1 ) 10 dm 3 to a volume of 100 dm 3 at 27°C is ª AIEEE 2011 (c) ∆Ssystem < 0 and ∆SSurrounding > 0
undergoes adiabatic change under a constant external
area under the curve within the specified limits. When an (b) ∆S < 0 pressure of 1 atm, changes volume from1 L to 2 L.The (a) 900 cal (b) 1000 cal (c) 1200 cal (d) 1400 cal
between the system and the surroundings in a closed (a) −2477.57 J mol −1 (b) 2477.57 J mol −1 (d) ∆Ssystem < 0 and ∆SSurrounding < 0
ideal gas is compressed (a) reversibly or (b) irreversibly (c) ∆S > 0 (a) 38.3 J mol −1 K −1 final temperature in Kelvin would be
system (c) –1238.78 J mol −1 (d) 1238.78 J mol −1 5. A monoatomic ideal gas undergoes a process in which
from volume Vi to Vt . Choose the correct option. (d) the value of ∆S cannot be predicted (b) 35.8 J mol −1 K −1 35 The incorrect expression among the following is ª AIEEE 2012 (a)
T
Z (b) T +
2 the ratio of p to V at any instant is constant and equals
(c) The presence of reactants in a closed vessel made
(a)W(reversible) = W(irreversible ) 11 Consider the reaction,
20 When 1.8 g of steam at the normal boiling point of water is (c) 32.3 J mol −1 K −1 ∆G system 22/ 3 3 × 0.0821 to 1. What is the molar heat capacity of the gas?
up of copper is an example of a closed system N2 + 3H2 → 2NH3 carried out at constant (a) = −T
(b)W(reversible) < W(irreversible ) converted into water, at the same temperature, enthalpy (d) 42.3 J mol −1 K −1 ∆S total (c)T (d) T −
2 (a) 4R / 2 (b) 3R / 2
(d) The presence of reactants in a thermos flask or any temperature and pressure. If ∆H and ∆E are the 3 × 0.0821 (c) 5R / 2 (d) Zero
(c)W(reversible) > W(irreversible ) and entropy changes respectively will be 26 A Carnot engine operates between temperatureT and Vf
other closed insulated vessel is an example of a enthalpy and internal energy changes for the reaction, (b) In isothermal process,W reversible = − nRT ln
(d) W(reversible) = W(irreversible ) + pex ∆V [Given, ∆Hvap for water = 40.8 kJ mol −1] 400 K (T > 400 K ). If efficiency of engine is 25%, the Vi
closed system which of the following expressions is true?
(a) −8.12 kJ, 11.89 JK −1 (b) 10.25 kJ, 12.95 JK −1 temperature T is (c) ln K =
∆ H ° − T∆ S °
(a) ∆H > ∆E (b) ∆H < ∆E
(c) −4.08 kJ, − 10.93 JK −1 (d) 10.93 kJ, −4.08 JK −1 (a) 666.0 K (b) 498.5 K RT
(c) ∆H = ∆E (d) ∆H = 0
(c) 533.3 K (d) 500.0 K (d) K = e −∆G ° / RT

72 40 DAYS ~ JEE MAIN CHEMISTRY DAY SIX

As, ∆G = − ve − [− ∆Gf (CH3OH, l ) = 1800 J = + 1.8 kJ

6. CaCO3 exists in two forms calcite and aragonite. The
conversion of 1 mole of calcite to aragonite is
accompanied by internal energy change equal to
11 A reaction is non-spontaneous at the freezing point of
water but is spontaneous at the boiling point of water,
then
Hints and Explanations 16 Using Kirchhoff’s equation,
∆C p =
∆H2 − ∆H1
24 A → (2, 4), B → (2 ), C → (3), D → (1)
A → Entropy of vaporisation is always
Hence, the process is spontaneous.
35 (a) ∆G = ∆H − T∆S
For a system, total entropy change −
3
2
∆Gf (O 2 , g )] Molar enthalpy of vaporisation,
∆H ∆H
T2 − T1 ∆Hvap 29 ∆G = ∆H − T∆S = ∆S total ∆Hm = =
+ 0.21 kJ. Given that the densities of calcite and ∆H ∆S SESSION 1 Thus, no external work is done for the For the reaction, positive, i.e. = − 394.4 + 2 (−237.2) − (−166.2) − 0 moles of H2O nH 2O
aragonite are 2.71 cm −3 and 2.73 g cm −3 respectively. (a) + ve + ve separation of gaseous molecules. N2 (g ) + 3H2 (g )→ 2NH3 (g ) ∆H2 − ∆H1 = ∆C p (T2 − T1 ) Tb At equilibrium, ∆G = 0 ∆Htotal = 0 = − 394.4 − 474.4 + 166.2
1 For a closed vessel made up of copper, 1.8 kJ
The enthalpy change at the pressure of 1.0 bar will be (b) − ve − ve ∆ng = 2 − 4 = −2 ∆H2 − 24 = (0.031 − 0.055) (100 − 50) ∴ ∆Gsystem = − T ∆S total = −702.6 kJ mol −1 = = 40.6 kJ mol −1
(c) − ve no matter can exchange between the 6 For isothermal process, ∆T = 0, then B → ∆ G ° = − RT In K ∆H 30 × 103 0.798
(a) 200.72 J mol −1 (b) 309.72 J mol −1 + ve T= = = 400 K
(d) + ve − ve system and the surrounding but energy ∆E = 0 Thus, ∆H = ∆E − 2 RT ∆H2 = 22.8 cal g −1 ∆S 75 ∆Gsystem
(c) 209.72 J mol −1 (d) 315.00 J mol −1 If K is +ve, then, ∆G° = −ve, i.e. ∴ = −T Percentage efficiency 18
exchange can occur through its walls. ⇒ ∆H < ∆E spontaneous process. ∆S total 702.6 ∆Hm = ∆Em + ∆ng RT
7 Identify the correct statement regarding a spontaneous 12 One mole of a liquid (1 bar, 100 mL) is taken in an 7 According to first law of 17 For the given change, 30 ∆G = ∆H − T∆S = × 100 = 9678
. % ≈ 97%
Presence of reaction species in a Numerical value of ∆H < ∆E in 726 ∆Hm = ∆Em + RT
adiabatic container and the pressure increases steeply thermodynamics, C → Crystalline state is most orderly At equilibrium, ∆G = 0 (b) For isothermal reversible process,
process. covered beaker-closed system and exothermic reaction and when ∆ng < 0. ∆ r S ° = ΣnPS P° − ΣnRS R°
to 100 bar. Then at constant pressure of 100 bar, volume ∆U = q + W = q − p∆V arranged state of particles, thus lowest [∆ng = 1for H2O (l ) 1 H2O (g )]
(a) For a spontaneous process in an isolated system, the exchange of matter as well as ∴ Te = ∆H/∆S ∆E = 0 39 Spontaneous processes are
decreases by 1 mL. ∆U and ∆H will be respectively. energy-open system. Presence of In isochoric process (∆V = 0),
12 Calculate the heat of combustion with °
= SNH + SH° 2 O entropy. accompanied by decrease in energy Molar internal energy change,
change in entropy is positive 2 CONH 2 For a reaction to be spontaneous By first law of thermodynamics
(a) 10 J, 10 J the help of following formula,
(b) Endothermic processes are never spontaneous reactant in a closed vessel is a closed ∆U = q ° ] D → During adiabatic expansion of an ∆G should be negative, so this implies
and increase in randomness. ∆Em = ∆Hm − RT
(b) 10 J, 0 ∆Hp = ∆U + ∆ng RT − [2 × SNH
° + SCO ∆E = q + W
(c) Exothermic processes are always spontaneous system and presence of reactant flask In isobaric process (∆p = 0), 3 2 ideal gas, q = 0 thus, ∆E = W i.e. ∆H < T∆S. 40 Reason is the correct explanation for = 40.6 − 8.314 × 10−3 × 37315
.
(c) 0, 10 J is an isolated system. where, ∆Hp = Heat of combustion at Vf '
(d) Lowering of energy in the reaction process is the only
criteria for spontaneity
(d) 5 J, 10 J ∆U = q = 174.0 + 69.9 − [2 × 192.3 + 2137
. ] Work done at the cost of internal energy ∆H
< T;Te < T
∴ Wreversible = − q = − ∫V p dV Assertion. = 37.5 kJ mol −1
constant pressure = − 354.4 JK −1 mol −1
i
2 In adiabatic process (q = 0) which decreases when q = 0. ∆S γ −1
13 Standard entropy of X 2, Y2 and XY3 are 60, 40 and ∆U = Heat at constant volume Vf SESSION 2 T2  V1 
8 The reversible expansion of an ideal gas under adiabatic ∆U = W Therefore, T should be greater than Te . Wreversible = − nRT ln 4 For adiabatic condition, = 
50 JK −1 mol −1 respectively. For the reaction, (It is also called ∆E) 18 ∆S = 2.303 nR log
V2 25 Entropy change for n moles of Vi T1  V2 
and isothermal conditions is shown in the figure. Which 1 3 Irreversible In isothermal process ∆T = 0 and V1 1. The pV diagram for the reversible and
X 2 + Y2 → XY3, ∆H = − 30 kJ compression ∆ng = Change in number of isothermal expansion of an ideal gas 31 H2O(l ) and H2O (g ) both exist together at 1.33 − 1
of the following statement is incorrect? p ∆U = 0 (c) ∆G = ∆H° − T∆S ° = −RT log K T2  1 
0.33
⇒  
20 from volume V1 to volume V2 is irreversible expansion of an ideal gas 1
2 2 moles (In gaseous state = 2.303 × 2 × 2 log = 9.2 same temperature and pressure, = 
∴ ∆U is equal to adiabatic work. ∆H° − T∆S °  T1  27   27 
log K = − 
to be at equilibrium, the temperature will be 2 V is shown below :
(p1, V1, T1) R = Gas constant ∆S = 2.303 nR log 2 H2O(l ) q H2O (g ) 
 
1/ 3
=  
(a) 750 K (b) 1000 K 8 As the process is carrying out at V1 RT 1 1
T = Temperature 19 For an isolated system, In the state of equilibrium, ∆G = 0 and (pI)irr,(pI)rev =
isothermal (c) 1250 K (d) 500 K constant temperature, therefore this 100  27  3
p ad Vf Vi From the equation, = 2.303 × 2 × 8.3143 log conversion of liquid into gas increases (d) ∆G ° = − RT log K
iab
Volume type of expansion is called isothermal ∆H = ∆E + p∆V or T∆S = ∆E + p∆V 10
1
T2 = 300 × = 100 K
ati (p2, V2, T2) 14 For an isomerisation reaction A 3 B, the temperature 15 the disorderness. ∆G °
c reversible expansion, for which, C 6H6 (l ) + O 2 (g )→ 6CO 2 (g )+ 3H2O(l ) But ∆E = 0 ∴ log K = − 3
(p3, V3, T3) dependence of equilibrium constant is given by 2 = 38.296 J mol −1 K −1 Hence, entropy ∆S = + ve RT
Irre
∆U = 0. Hence, q = − W ∴ T∆S = p∆V
ve
rsib Thus, T2 < T1, hence cooling takes
2000 T2 − T1
V loge K = 4.0 − i.e. heat absorbed by the system is Change in the number of gaseous 26 η (efficiency) = 32 For a spontaneous process, ∴ K = e − ∆G ° / RT le place due to expansion under
(a)T1 = T2 (b)T3 > T1 Reversible p∆V
T p moles, i.e. ∆S = >0 T2 (pF)irr adiabatic condition.
compression equal to the work done by the system. ∆S total = ∆Ssystem + ∆Ssurroundings
(c)W(isothermal) > W(adiabatic ) (d) ∆ E (isothermal) > ∆ E (adiabatic) The value of ∆S ° at 300 K is therefore, q = + 208 J 15 3 T 36 ∆G ° = ∆H° − T∆S ° = −2.303 RT log10 K reversible
∆E = q + W = W
Thus, ∆ng = 6 − = − or −15
. T − 400 be positive.
(pF)rev
9 A gas present in a cylinder, fitted with a frictionless (a) 4R (b) 5 R W = − 208 J 2 2 20 ∆Hcondensation for 1.8 g of steam ⇒ 0.25 = (Qq = 0 for adiabatic change.)
T (VI)rev, irr (VF)rev, irr
(c) 400 R (d) 2000 R Now, we have ∆ng and other values 33 For a non-spontaneous reaction,
piston, expands against a constant pressure of 1 atm ∴ − 2.303 RT log10 K = ∆H° − T∆S ° Sign of W is negative because the gas
Vf Vi 9 ∆H = ∆E + ∆ng RT given in the question are = (−40.8) ×
1.8
= − 4.08 kJ ∴ T = 533.3 K ∆G = + ve
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 i.e. −2.303 × 8.314 × 298 × log10 K From ideal gas equation expands.
18
it absorbs 800 J heat from surroundings. The increase in insulated, sealed container that has 2 kg of water also at Volume Given, ∆H = 30 kcal for 3 mol ∆U = − 3263.9 kJ/mol PbO 2 + Pb → 2PbO ∆G = ∆H − T∆S nRT W = − ∆ E = − C V (T2 − T1 )
∆H −4.08 × 10 3 27 = [−54.07 × 1000] − [298 × 10] p=
internal energy of process is 0°C. The water and ice completely fill the container is As the area under the curve is more in ∆ng = 3 T = 25° C ∆S = = ∴ ∆H − T∆S should be + ve or ∆H > T∆S V = − 6 (100 − 300) = 1200 cal
irreversible compression than the area Tb .
37315 Oxidation state +4 0 +2
(a) 305.85 J (b) 394.95 J flexible. After sometime one can except that because, liquid 0 vapour = 273 + 25 = 298 K ∆H For final condition of temperature,
Since, ∆G° < 0, i.e. it is negative. which is possible if T < −5705 log10 K = − 54070 − 2980 5. The molar heat capacity for any process
(c) 405.83 J (d) –463.28 J (a) the water will freeze so that the mass of the ice will under curve of reversible compression.
R = 8.314 JK −1mol −1 = − 10.93 JK −1 ∆S pressure and volume
Thus, W irreversible > W reversible . 30 = ∆E + 3 × 2 × 500 × 10−3 Therefore, the reaction is spontaneous −5705 log10 K = − 57050 is given by following expression,
increase nRTf
10 In an irreversible process taking place at constantT and ∆E = 27 kcal So, ∆Hp = (−3263.9) + (−15
. ) × 8.314 21 CO and NO molecules in solid states at in the forward direction. This suggest Given, ∆H = 30 × 103 J mol −1 pF = C = CV +
R
when pV γ = constant
(b) the ice will melt so that the mass of ice will decrease or log10 K = 10 Vf
p and in which only pressure volume work is being done, 3 Work done due to change in volume that Pb 2+ is more stable than Pb 4+ . 1− γ
(c) both the amount of water and the amount of ice will against constant pressure is 1 × 10−3 × 298 0 K adopt a nearly random arrangement ∆S = 70 JK −1 mol −1 From the curve it is seen that
the change in Gibbs free energy ( ∆G ) and change in 10 C(s ) + O 2 (g ) → CO(g ) indicating a positive value of entropy. It SnO 2 + Sn → 2SnO
37 The standard free energy related to and C p / C V = γ
entropy ( ∆S ), satisfy the criteria
remain constant W = − p (V2 − V1 ) 2 = − 3267.6 kJ mol −1 30 × 103 equilibrium constant, K as ( pF ) irr > ( pF ) rev or (TF ) irr > (Tf ) rev
is due to their dipole moment which T< p
(d) both the amount of water and the amount of ice will = − 1 × 105 N /m2 (1 × 10−2 − 1 × 10−3 ) m3 ∆ng = 1 − =
1 1 Oxidation state +4 0 +2 Here, = 1, i.e. pV −1 constant
(a) (∆S)V , E < 0, (∆G)T , p < 0 (b) (∆S)V , E > 0, (∆G)T , p < 0 results in disorder. 70 ∆G ° = − 2 .303 RT log Keq 2 For adiabatic change, ∆E = ∆W V
decrease 2 2 13 The amount of heat required to raise the Since, ∆ r G° > 0, i.e. it is positive,
(c) (∆S)V , E = 0, (∆G)T , p = 0 (d) (∆S)V , E = 0, (∆G)T , p > 0 = − 900 Nm = − 900 J ∆Hvap T < 428. 57 K ∆G ° = − nFE °cell
temperature of one mole of substance 26 × 103 therefore, the reaction is ∆ E = nC V (T2 − T ) 3
C = R+
R 3
= R+ = R
R 4
∆H − ∆E = ∆ng RT 22 ∆S vap = =
4 At constant volume, p∆V = 0, i.e. W = 0 through 1°C is called molar heat T 308 non-spontaneous in the forward If a cell reaction is spontaneous ∆W = − p(V2 − Vt ) 2 1 − (−1) 2 2 2
1 34 Total entropy change of universe is zero.
= × 8.314 JK −1 mol −1 × 298 K capacity. direction. But it will be spontaneous in (proceeding in forward side), it means
From first law of thermodynamics, 2
q = + 84.41 JK −1 mol −1 At 100°C and 1 atmosphere pressure, Keq > 1and E°cell = + ve
6 ∆H = ∆U + p ∆V
C= the backward direction. This suggests nC V (T2 − T ) = − p (V2 − Vt ) = −12
( − 1)
ANSWERS ∴
∆E = q + W
q = ∆E
= 1238.78 J mol −1 T2 − T1 ∆Scond =
∆Hcond
[Q∆Hcond = − 26 kJ ] that Sn4+ will be more stable than Sn2+ . H2O(l ) r H2O(g )
is at equilibrium.
Thus, ∆G° = − ve
n×
R
× (T2 − T ) = −1
Here, ∆U = + 0.21kJ mol −1
11 According to relationship of ∆H and ∆E, T These facts are also supported by the
38 Percentage efficiency of the fuel cell (γ − 1) = 0.21 × 103 J mol −1
14 Q = mC∆T inert pair effect down the group. For equilibrium, ∆S total = 0
5 In free expansion, W = 0 while in ∆H = ∆E + ∆ng RT 26 × 103 = 210 J mol −1
100 =− = −84.41 JK −1 mol −1 ∆G For monoatomic gas n = 1,γ =
5
SESSION 1 1 (c) 2 (b) 3 (a) 4 (c) 5 (c) 6 (b) 7 (c) 8 (d) 9 (c) 10 (d) 1000 = × 75 × ∆T and ∆Ssystem + ∆Ssurrounding = 0 = × 100 ,
adiabatic process, q = 0. ∆H = enthalpy change (at constant 18
308 28 Heat at constant pressure means ∆H 3 p = 1bar =105 Pa
11 (b) 12 (d) 13 (b) 14 (b) 15 (a) 16 (a) 17 (c) 18 (c) 19 (c) 20 (c) ∆U = q + W = 0 enthalpy, i.e. As we know, during conversion of R = 0.0821 L atm K −1 mol −1
pressure) ∆T = 2.4 K 23 ∆S liquid to gas, entropy of system The concerned reaction is ∆V = Molar volume of aragonite
21 (b) 22 (a) 23 (b) 24 (a) 25 (a) 26 (c) 27 (d) 28 (b) 29 (a) 30 (b) ∆H = − 2.5 × 10 cal 3
0.0821
This suggests that internal energy ∆E = internal energy change (at A → C = 50 eu increases, in a similar manner entropy 3
CH3OH(l ) + O 2 (g ) → CO 2 (g ) 1× × (T2 − T ) = −1 – Molar volume of calcite
31 (a) 32 (a) 33 (c) 34 (b) 35 (c) 36 (b) 37 (d) 38 (d) 39 (b) 40 (a)
remains constant. Therefore, ∆T = 0. constant volume) 15 The equation, C p − C V = nR ∆S = 7.4 cal deg −1
(5/ 3) − 1
C → D = 30 eu of surroundings decreases. 2 2 100 100
Expansion of an ideal gas under T2 = T − = − cm3 mol −1
(given reaction is exothermic) 2 moles of an ideal gas is equal to D → B = −20 eu T = 298 K ∴ ∆Ssystem > 0 + 2H2O(l ); 3 × 0.0821 2.93 2.71
SESSION 2 1 (a) 2 (d) 3 (a) 4 (c) 5 (a) 6 (c) 7 (a) 8 (b) 9 (b) 10 (b) adiabatic conditions in a vacuum leads
( ∆ng = moles of gaseous products Cp − CV = 2 R A→ B 60 eu ∆G = ∆H − T∆S and ∆Ssurrounding < 0 ∆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 )
to no absorption/evolution of heat.
11 (a) 12 (b) 13 (a) 14 (a) 15 (b) – moles of gaseous reactants) = −2.5 × 103 − 298 × 7.4 Hence, (b) is the correct choice. = 0.50 A × 12 V × 300 s
= − 4705 cal

= 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
 2
2
2 2 
From first law of thermodynamics,
∆S total = ∆Ssys + Ssurr > 0 = 50 −  × 60 + × 40
1 3
q = ∆E − W
For an isolated system ∆Ssurr = 0  2 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) ∆ r H° −30,000 J mol −1
(b) Since, change of state ( p1, V1, T1 ) to T= = = 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.