Thermodynamics IInd Law ResoSir With Ans GJGBSBL

Thermodynamics & Thermochemistry
THERMODYNAMICS IInd & IIIrd LAW

Å"ekxfrdh f}rh; rFkk r`rh; fu;e (Thermodynamics IInd & IIIrd Law)
PART - I : SUBJECTIVE QUESTIONS

Hkkx - I : fo"k;kRed iz'u ¼SUBJECTIVE QUESTIONS½
Section (A) : Introduction about entropy
[k.M (A) : ,UVªksih ifjp;
A-1. The entropy of a gas increases on its expansion. Why ?
izlkj ds nkSjku xSl dh ,UVªkWih eas o`f) gksrh gS] D;ksa ?
Sol. Because larger space creates more disorder. (D;ksafd vf/kd LFkku eas vf/kd ;kn`fPNdrk mRiUu gksrh gSA )
A-2. Entropy of the solutions is higher than that of pure liquid. Why ?
'kq) nzo dh rqyuk eas foy;uksa dh ,UVªkWih vf/kd gksrh gS] D;ksa?
Sol. Dissolution of solute makes the motion of solute particles free. Also the increased number of particles in
mixed state increases disorderness.
foys; ds foyk;du ls foys; d.kksa dh eqDr xfr gksrh gSA fefJr voLFkk eas d.kksa dh la[;k eas o`f) ls ;kn`fPNdrk
esa o`f) gksrh gSA
A-3. What are the signs of S for the system and for the surrounding in each of the following processes ?
(a) Water boils in a teakettle on a hot stove.
(b) Ice in an ice cube tray, left an a table melts.
(c) A cup of coffee is reheated in a microwave oven.
izR;sd izØe eas fudk; o ifjos'k ds fy;s S dk fpUg crkb;s ?
(a) xeZ LVkso ij pk; dh dsryh esa ty dk mcyukA
(b) ,d cQZ dh Vªs esa mifLFkr cQZ dks ,d est ij j[ks jgus ij xfyr gksukA
(c) ,d ekbØksoso vksou esa ,d di dkWQh dks iqu% xeZ djukA
Sol. (a) Ssys is positive ; Ssurr is negative, (Sfudk; /kukRed gS ; Sifjos'k _.kkRed gSA)
(b) Ssys is positive, Ssurr is negative; (Sfudk; /kukRed gS ; Sifjos'k _.kkRed gSA)
(c) Ssys is positive, Ssurr is negative. (Sfudk; /kukRed gS ; Sifjos'k _.kkRed gSA)
A-4. State the second law of thermodynamics.
Å"ekxfrdh dk f}rh; fu;e crkb;sA
Ans. Entropy of the universe is constantly increasing. Suniverse = Ssystem + Ssurrounding > 0 for a spontaneous
process.
czák.M dh ,UVªkWih fu;r :i ls c<+rh gSA ,d Lor% izØe ds fy;s Sczák.M = Sfudk; + Sifjos'k > 0
A-5. Write statement of IIIrd law of thermodynamics ?
Å"ekxfrdh ds r`rh; fu;e dk dFku crkb,A
Sol. At 0 K, entropy of a perfect crystalline pure substance is taken to be zero.
Sol. 0 K ij fdlh iw.kZr% fØLVyh; 'kq) inkFkZ dh ,UVªkWih 'kwU; yh tkrh gSA
A-6. State the thermodynamic condition of spontaneous occurance of a process ?
fdlh izØe ds Lor% ?kfVr gksus ds fy, m"ekxfrdh ifjfLFkfr crkb,sA
Ans. GT,P = (–)ve or Stotal > 0
Ans. GT,P = (–)ve ;k Sdqy > 0
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ADVTDS - 1
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A-7. If H for a reaction has a positive value, how would you know the sign requirement of S for it so that
the reaction is spontaneous ?
;fn fdlh vfHkfØ;k ds fy, H dk eku /kukRed gks rks vki fdl iz dkj S dk fpUg fu/kkZfjr djsxsa ftlls
vfHkfØ;k Lor% gks lds \
Ans. G = H – TS
For spontaneous reaction G = (–) ve 
S Should be positive
Ans. G = H – TS
Lor% vfHkfØ;k ds fy;s G = (–) ve
vr% S /kUkkRed gksuk pkfg;saA
Section (B) : Entropy Calculation
[k.M (B) : ,UVªksih x.kuk
B-1. The entropy of vaporization of benzene is 85 JK–1 mol–1. When 117 g benzene vaporizes at it’s normal
boiling point, calculate the entropy change of surrounding.
casthu ds ok"iu dh ,UVªkWih 85 JK–1 mol–1 gSA tc 117 g casthu dks blds lkekU; DoFkukad ij okf"ir fd;k tkrk
gS] rks ifjos'k dh ,UVªkWih ifjorZu dks ifjdfyr dhft,A
Ans. – 1.5 × 85 J/K
117
Sol. nC6H6 = = 1.5
78
Ssystem = 1.5 × 85 J/K
 Ssurrounding = – 1.5 × 85 J/K
117
Sol. nC6H6 = = 1.5
78
Sfudk; = 1.5 × 85 J/K
 Sifjos'k = – 1.5 × 85 J/K
B-2. Calculate standard entropy change in the reaction

Fe2O3 (s) + 3H2 (g)  2Fe (s) + 3H2O ()
Given : Sºm(Fe2O3, S) = 87.4 , Sºm(Fe, S) = 27.3, Sºm(H2, g) = 130.7, Sºm(H2O, ) = 69.9 JK–1 mol–1.
fuEu vfHkfØ;k] Fe2O3 (s) + 3H2 (g)  2Fe (s) + 3H2O ()
esa ekud ,UVªkWih ifjorZu ifjdfyr dhft;s
fn;k x;k gSa % Sºm(Fe2O3, S) = 87.4 , Sºm(Fe, S) = 27.3, Sºm(H2, g) = 130.7, Sºm(H2O, ) = 69.9 JK–1 mol–1.
Ans. – 215.2 JK–1 mol–1
Sol. rSº =  v pSº(Products)–  vRSº(Reactants)
= (2×27.3+ 3 × 69.9) – (87.4 + 3 × 130.7) = – 215.2 JK–1 mol–1
Sol. rSº =  v pSº(mRikn) –  v RSº(fØ;kdkjd)
= (2×27.3+ 3 × 69.9) – (87.4 + 3 × 130.7) = – 215.2 JK–1 mol–1
B-3.^ One mole of liquid iron at its boiling point was vaporized in an oven at 3500 K. If iron boils at 3133 K
and enthalpy of vaporization is 349 KJ mol –1, determine Ssystem, Ssurrounding and Suniverse.(Oven is
considered as surroundings).
3500 K ij ,d vksou esa ,d eksy nzo vk;ju dks blds DoFkukad ij okf"ir fd;k x;kA ;fn vk;ju 3133 K ij
mcyrk gS rFkk ok"ihdj.k dh ,UFkSYih 349 KJ mol–1gS] rks Sfudk;, Sifjos'k vkSj Sczãk.M dh x.kuk dhft,A (vksou
dks ifjos'k ekuk x;k gSA)
Ans. Ssystem = 111.4 JK–1, Ssurr = –99.71 JK–1, Suniv = +11.69 JK–1
Ans. Sfudk; = 111.4 JK–1, Sifjos'k = –99.71 JK–1, Sczãk.M = +11.69 JK–1
ADVTDS - 2
Hvap 349  103
Sol. At boiling point, Ssystem =  = 111.4 JK–1
Tb 3133
Heat change in surrounding = – 349 KJ
349  1000
Ssurr = – = – 99.71 JK–1
3500
  Suniv = Ssys + Ssurr = 111.4 – 99.71 = +11.69 JK–1
Hvap 349  103
gy- DoFkukad fcUnq ij, Sfudk; =  = 111.4 JK–1
Tb 3133
ifjos'k esa Å"ek ifjorZu = – 349 KJ
349  1000
Sifjos'k = – = – 99.71 JK–1
3500
 Sczãk.M = Sfudk; + Sifjos'k = 111.4 – 99.71 = +11.69 JK–1
B-4. Calculate the entropy change in surroundings when 1.00 mol of H2O() is formed under standard
conditions at 298 K. Given rHº = – 286 kJ mol–1.
tc 1.00 eksy H2O() dks ekud ifjfLFkfr;ksa esa 298 K ij fojfpr fd;k tkrk gS] rc ifjos'k dh ,UVªkWih esa
ifjorZu dh x.kuk dhft,A fn;k x;k gS ] rHº = – 286 kJ mol–1.
Ans. Entropy change in surroundings = 959.73 JK–1.
Ans. ifjos'k esa ,UVªkWih ifjorZu = 959.73 JK–1.
1
Sol. Given : H2(g) + O2(g)  H2O(l); fHº=–286 kJ mol–1
2
T = 298 K
Asked : The entropy change for the reaction.= ?
q
Formula : Ssurr = surr
T
Explanation : S = Entropy change
T = Temperature in K [T = 298 K under standard conditions]
qsurr = Heat absorbed by the surrounding (qsurr = + 286 kJ mol–1)
Substitution & Calculation :
286000
Ssurr = = 959.73 JK–1.
298
Ans. Entropy change in surroundings = 959.73 JK–1.
1
Sol. fn;k x;k gS : H2(g) + O2(g)  H2O(l); fHº = –286 kJ mol–1
2
T = 298 K
iwNk gS : vfHkfØ;k ds fy;s ,UVªkWih ifjorZu ?
q
lw=k : Sifjos'k = surr
T
O;k[;k : S = ,UVªkWih ifjorZu
T = rkieku K esa [ekud ifjfLFkfr;ksa eas T = 298 K]
qifjos'k = ifjos'k }kjk vo'kksf"kr Å"ek (qifjos'k = + 286 kJ mol–1)
eku j[kus ij rFkk x.kuk djus ij :
286000
Sifjos'k = = 959.73 JK–1.
298
Ans. ifjos'k esa ,UVªkWih ifjorZu = 959.73 JK–1.
B-5. Order of increasing of entropy among given condition of substance is :
(I) 1 mole of H2O(l) at 298 K and 0.101 M Pa (II) 1 mole of ice at 273 K and 0.101 M Pa
(III) 1 mole of H2(g) at 298 K and 1 atm (IV) 1 mole of C2H6(g) at 298 K and 1 atm
inkFkZ dh fn xbZ fLFkfr;ksa esa ,UVªkWih dh o`f) dk Øe gksxk gS&
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(I) 298 K ij 1 eksy H2O(l) rFkk 0.101 M Pa (II) 273 K ij 1 eksy cQZ rFkk 0.101 M Pa
(III) 298 K ij 1 eksy H2(g) rFkk 1 atm (IV) 298 K ij eksy C2H6(g) rFkk 1 atm
Ans. II < I < III <IV
B-6. Oxygen & ozone are gases at standard temperature. Their molar entropies are in the sequence O2 <
O3. Using molecular properties, explain why ozone is more disordered than oxygen.
ekud rkieku ij vkWDlhtu o vkstksu xSlsa gSaA budh eksyj ,UVªkWih O2 < O3 ds Øe esa gSA vkf.od xq.kksa dk iz;ksx
djrs gq;s O;k[;k dhft;s fd vkstksu] vkWDlhtu ls vf/kd ;kn`fPNd (disordered) gSA
Sol. Ozone has three atoms per molecule, whereas O2 has only two.
vkstksu ds izR;sd v.kq esa rhu vkWDlhtu ijek.kq gksrs gSa tcfd O2 esa dsoy nks vkWDlhtu ijek.kq gksrs gSaA
Section (C) : Free energy
[k.M (C) : eqDr ÅtkZ
C-1.^ What will be the states of a chemical reaction occuring at constant pressure and temperature conditions
when :
(i) G = 0 (ii) G > 0 (iii) G < 0
leku rki o nkc dh ifjfLFkfr;ksa esa jklk;fud vfHkfØ;k fdl voLFkk esa gksxh tc:
(i) G = 0 (ii) G > 0 (iii) G < 0
Ans. (i) Chemical reaction in equilibrium state (jklk;fud vfHkfØ;k lkE;koLFkk esa gksxh )
(ii) non-spontaneous (vLor% gksxh)
(iii) Spontaneous. (Lor% gksxh)
C-2. A gaseous reactant A forms two different product, in parallel reaction, B and C as follows :
A  B; Hº = –3kJ, Sº = 20JK–1 ; A  C; Hº = –3.6 kJ, Sº = 10 JK–1
Discuss the relative stability of B and C on the basis of Gibb’s free energy change at 27ºC.
A xSlh; vfHkdkjd fuEu izdkj ls lekukUrj vfHkfØ;k }kjk nks fHkUu&fHkUu mRikn B rFkk C cukrk gSA
A  B; Hº = –3kJ, Sº = 20JK–1 ; A  C; Hº = –3.6 kJ, Sº = 10 JK–1
27ºC ij fxCl eqDr ÅtkZ ifjorZu ds vk/kkj ij B rFkk C ds lkis{k LFkkf;Ro ds lanHkZ esa crkb;sA
Ans. Gº indicates that B is more stable than C.
Gº crkrk gS fd B, C dh vis{kk T;knk LFkk;h gSA
Sol. A  B H° = – 3kJ S° = 20 J/kJ
A  C H° = – 3.6 kJ S° = 10 J/kJ
300  20
(i) For A  B(A  B ds fy;s)  G = H – TS = – 3 – = – 9 kJ = – 9000 J
1000
300  10
(ii) For A  C (A  C ds fy;s) ; G = – 3.6 – = – 6.6 kJ = – 6600 J
1000
Gº Indicate that B is more stable than C.
 Gº crkrk gS fd B, C dh vis{kk T;knk LFkk;h gSA
C-3. With the following informations, determine standard Gibb’s free energy of formation of N2O4(g).
fuEu tkudkjh ds lkFk N2O4(xSl) ds lEHkou dh ekud fxCl eqDr ÅtkZ Kkr dhft,
1 1
N2(g) + O2(g)  NO(g) Gº = 86.6 kJ .....(i)
2 2
1
NO(g) + O2(g)  NO2(g) Gº = –34.82 kJ .....(ii)
2
2NO2(g)  N2O4(g) Gº = –5.77 kJ .....(iii)
Ans. 97.79 kJ
Sol. Multiplying both Eqs (i) and (ii) by 2 and finally adding them yields
N2 (g) + 2O2 (g)  2NO2 (g) Gº = 103.56 kJ
2NO2(g)  N2O4 (g) Gº = –5.77 kJ ....(iii)
______________________________________________________________
Adding N2 (g) + 2O2 (g)  N2O4 (g) Gº = 97.79 kJ
ADVTDS - 4
gy- lehdj.k (i) rFkk (ii) dks 2 ls xq.kk djsa vkSj fQj mUgsa tksM+us ij
N2(g) + 2O2(g)  2NO2(g) Gº = 103.56 kJ
2NO2(g)  N2O4(g) Gº = –5.77 kJ ....(iii)
______________________________________________________________
tksMs+ N2(g) + 2O2(g)  N2O4(g) Gº = 97.79 kJ
C-4. For the equilibrium : PCl5(g) PCl3(g) + Cl2(g) at 298 K, equilibrium constant, K = 1.8 × 10–7. What
is G0for the reaction ?
298 K ij lkE; PCl5(g) PCl3(g) + Cl2(g) dk lkE; fLFkjkad] K = 1.8 × 10–7 gSA vfHkfØ;k ds fy, G0
D;k gksxkA
Ans. Gº of reaction is 38477 J/mol.
Ans. vfHkfØ;k dk Gº = 38477 J/mol gSA
Sol. Given : Keq = 1.8 × 10–7
T = 298 K
Asked : Gº = ?
Formula : Gº = – 2.303 RT log Keq
Explanation : Gº = Standard Gibb’s free energy change
R = Gas constant (R = 8.314 JK–1 mol–1)
T = Temperature in K
Keq = equilibrium constant
Substitution & calculation :
Gº  – 2.3030 × 8·314 × 298 × log 1·8×10–7 J/mol
 38477 J/mol
Ans. Gº of reaction is 38477 J/mol
Sol. fn;k x;k gS : Keq = 1.8 × 10–7
T = 298 K
iwNk gS : Gº = ?
lw=k : Gº = – 2.303 RT log Keq
O;k[;k : Gº = ekud fxCl eqDr ÅtkZ ifjorZu
R = XkSl fu;rkad (R = 8.314 JK–1 mol–1)
T = rkieku K eas
Keq = lkE; fu;rkad
eku j[kus ij rFkk x.kuk djus ij %
Gº  – 2.3030 × 8·314 × 298 × log 1·8×10–7 J/mol
 38477 J/mol
Ans. vfHkfØ;k dk Gº = 38477 J/mol gSA
PART - II : ONLY ONE OPTION CORRECT TYPE

Hkkx - II : dsoy ,d lgh fodYi çdkj (ONLY ONE OPTION CORRECT TYPE)
A-1.^ In which state, matter have highest entropy
(A) Solid (B) Liquid (C*) Gas (D) Equal in all
dkSulh voLFkk esa inkFkZ lokZf/kd ,UVªksih j[krk gSA
(A) Bksl (B) nzo (C*) xSl (D) lHkh esa leku
A-2. Predict which of the following reaction (s) has a positive entropy change ?
I. Ag+(aq) + Cl–(aq)  AgCl(s)
II. NH4Cl(s)  NH3(g) + HCl(g)
III. 2NH3(g)  N2(g) + 3H2(g)
(A) I and II (B) III (C*) II and III (D) II
ADVTDS - 5
crkb;s fd fuEu eas ls dkSulh vfHkfØ;k /kukRed ,UVªkWih ifjorZu j[krh gSaA
I. Ag+(aq) + Cl–(aq)  AgCl(s)
II. NH4Cl(s)  NH3(g) + HCl(g)
III. 2NH3(g)  N2(g) + 3H2(g)
(A) I rFkk II (B) III (C*) II rFkk III (D) II
Sol. ng is +ve.
ng /kukRed gSA
A-3. Mixing of non-reacting ideal gases is generally accompanied by
(A) Decrease in entropy (B*) Increase in entropy
(C) Change in enthalpy (D) Increase in free energy
vfØ;k'khy (non-reacting) xSlksa ds fefJr djus ij
(A) ,UVªkWih esa deh gksrh gSA (B*) ,UVªkWih esa o`f) gksrh gSA
(C) ,UFkSYih esa ifjorZu gksrk gSA (D) eqDr ÅtkZ eas ifjorZu gksrk gSA
Sol. Mixing of non-reacting gases increases randomness and so increase entropy .
(vfØ;k'khy xSlksa dks fefJr djus ij ;kn`fPNdrk esa o`f) gksrh gS rFkk blfy, ,UVªkWih esa o`f) gksrh gSA )
A-4. Which of the following reactions is associated with the most negative change in entropy ?
(A) 2SO2(g) + O2(g)  2SO3(g) (B) C2H4(g) + H2(g) C2H6(g)
(C) C(s, graphite) + O2  CO2(g) (D*) 3C2H2(g)  C6H6( )
fuEu esa ls dkSulh vfHkfØ;k ds fy;s ,UVªkWih esa lcls _.kkRed ifjorZu gksrk gS %
(A) 2SO2(g) + O2(g)  2SO3(g) (B) C2H4(g) + H2(g) C2H6(g)
(C) C(s, xzsQkbV) + O2  CO2(g) (D*) 3C2H2(g)  C6H6( )
Sol. ng is most – ve (ng vf/kd _.kkRed gSA½
A-5. For the gas - phase decomposition, PCl5(g) PCl3(g) + Cl2(g) :

xSl&izkoLFkk fo?kVu PCl5(g) PCl3(g) + Cl2(g) ds fy, %
(A) H < 0, S < 0 (B*) H > 0, S > 0 (C) H > 0, S < 0 (D) H < 0, S > 0
Sol. Reaction is endothermic and no. of moles increases on decomposition.
vfHkfØ;k Å"ek'kks"kh gS o fo?kVu ij eksyks dh la[;k esa o`f) gksrh gSA
A-6. Which one of the following has Sº greater than zero.
fuEu esa ls fdl vfHkfØ;k ds fy;s Sº dk eku 'kwU; ls vfèkd gSA
(A) CaO (s) + CO2(g) CaCO3 (s) (B) NaCl (aq) NaCl (s)
(C*) NaNO3(s) Na+ (aq) + NO3– (aq) (D) N2 (g) + 3H2 (g) 2NH3 (g)
Sol. NaNO3 is a solid, which is converted to liquid ions. (NaNO 3 Bksl gS] tks fd nzo vk;uksa esa ifjofrZr gks tkrk
gSA)
A-7. For which reaction from the following, will be maximum entropy change :
fuEu esa ls dkSulh vfHkfØ;k ds fy, ,UVªksih ifjorZu vf/kdre gS %
1
(A) Ca(s)  O2 (g)  CaO(s) (B*) CaCO3 (s)  CaO(s)  CO2 (g)
2
(C) C(s)  O2 (g)  CO2 (g) (D) N2 (g)  O2 (g)  2NO(g)
A-8. Which of the following statement is true. The entropy of the universe
(A*) Increases and tends towards maximum value
(B) Decreases and tends to be zero
(C) Remains constant
(D) Decreases and increases with a periodic rate
fuEu esa ls dkSulk dFku lgh gSA ;fn czEgk.M dh ,UVªksih
(A*) c<rh gS rFkk vf/kdre eku dh vksj c<+rh gSA (B) ?kVrh gS rFkk 'kwU; dh vksj c<+rh gSA
(C) fLFkj jgrh gSA (D) vkorhZ nj ds e/; ?kVrh o c<+rh gSA
ADVTDS - 6
B-1. An isolated system comprises the liquid in equilibrium with vapours. At this stage the molar entropy of
the vapour is :
(A) Less than that of liquid (B*) more than that of liquid
(C) Equal to zero (D) Equal to that of liquid
,d foyfxr ra=k esa nzo dks ok"i ds lkFk lkE; esa lEihfMr fd;k tkrk gSA bl voLFkk ij ok"i dh eksyj ,UVªkWih
D;k gSA
(A) nzo ls de (B*) nzo ls vf/kd (C) 'kwU; ds cjkcj (D) nzo ds leku
 5 
B-2. When two mole of an ideal gas  Cp,m  R  heated from 300 K to 600 K at constant pressure. The
 2 
change in entropy of gas (S) is :
tc fu;r nkc ij ,d vkn'kZ xSl  Cp,m  R  ds 2 eksy dks 300 K ls 600 K rki rd xeZ fd;k tkrk gSA rc
5
 2 
xSl dh ,UVªkWih esa ifjorZu (S) fuEu gSs %
3 3 5
(A) R ln 2 (B) – R ln 2 (C*) 5R ln 2 (D) R ln 2
2 2 2
T 5 600
Sol. S = nCp, m In 2 = 2 × R In = 5 R In 2
T1 2 300
B-3. The entropy change when two moles of ideal monoatomic gas is heated from 200 to 300ºC reversibly
and isochorically ?
tc vkn'kZ ,dyijek.oh; xSl ds nks eksyksa dks ÅRØe.kh; o levk;rfud :i ls 200 ls 300ºC rd xeZ fd;k
tkrk gS] rks ,UVªkWih ifjorZu fuEu gksrk gS \
3  300  5  573   573  3  573 
(A) R ln   (B) R ln   (C*) 3R ln   (D) R ln  
2  200  2  273   473  2  473 
T 3 573  573 
Sol. Sgas = n CV,m ln 2 = 2 × R ln = 3R ln  .
T1 2 473  473 
 5 
B-4. If one mole of an ideal gas  Cp,m  R  is expanded isothermally at 300 K until it’s volume is tripled,
 2 
then change in entropy of gas is :
5
(A) zero (B) infinity (C) R ln 3 (D*) R ln 3
2
;fn ,d eksy vkn'kZ xSl  Cp,m  R  dks 300 K ij lerkih; :i ls rc rd çlkfjr fd;k tkrk gSa tc rd fd
5
 2 
bldk vk;ru frxquk ugha gks tkrk gS rc xSl dh ,UVªkWih esa ifjorZu fuEu gSa %
5
(A) 'kwU; (B) vuUr (C) R ln 3 (D*) R ln 3
2
V2
Sol. Sgas = nR ln = R ln 3
V1
B-5.^ Calculate the total entropy change for the transition at 368 K of 1 mol of sulphur from the monoclinic to
the rhombic solid state and H = – 401.7 J mol–1 for the transition. Assume the surroundings to be an
ice-water bath at 0ºC :
(A) – 1.09 JK–1 (B) 1.47 JK–1 (C*) 0.38 JK–1 (D) None of these
368 K ij ,dUkrk{k ls fo"keyEck{k Bksl voLFkk eas 1 eksy lYQj ds laØe.k ds fy, dqy ,UVªkWih ifjorZu dh x.kuk
dhft,A bl laØe.k ds fy, H = – 401.7 J mol–1 gSA ;g ekudj fd ifjos'k eas ty&cQZ ckFk 0ºC ij gSA
(A) – 1.09 JK–1 (B) 1.47 JK–1 (C*) 0.38 JK–1 (D) buesa ls dksbZ ugh
ADVTDS - 7
1 401.7
Sol. S(system) = = – 1.09 JK–1
368
The ice-water both absorbs the 401.7 J mol–1 at temperature 273 K
1 401.7
 Ssurrounding = = 1.47 JK–1 and S(universe) = – 1.09 + 1.47 = 0.38 JK–1
273
1 401.7
Sol. S(fudk;) = = – 1.09 JK–1
368
273K rki ij cQZ&ty nksuksa 401.7 J mol–1 Å"ek vo'kksf"kr djrs gSA
1 401.7
 Sifjos'k = = 1.47 JK–1 rFkk S(czãk.M) = – 1.09 + 1.47 = 0.38 JK–1
273

C-1. Which of the follwing is incorrect regarding Gibbs free energy
(A) it is a state function (B) it is extensive property
(C) it is macroscopic property (D*) it is intensive property
fxCl eqDr ÅtkZ ds lanHkZ esa dkSulk fodYi lgh ugha gS
(A) ;g voLFkk Qyu gSA (B) ;g ek=kkRed xq.k/keZ gSA
(C) ;g esØksLdksfid xq.k gSA (D*) ;g ek=kk LorU=k xq.k/keZ gSA
C-2. Which of the following conditions regarding a chemical process ensures its spontaneity at all
temperature ?
fuEu esa ls dkSulh ifjfLFkfr jklk;fud vfHkfØ;k ds lUnHkZ esa lHkh rki ij blds Lor% gksus dks lqfuf'pr djrh gS\
(A) H > 0, S < 0 (B*) H < 0, S > 0 (C) H < 0, S < 0 (D) H > 0, S < 0
Sol. For spontaneity G < 0, which is possible when H < 0, S > 0.
Lorrk% ds fy, G < 0, ;g rc laHko gksxk] tc H < 0, S > 0 gksxkA
C-3.^ When reaction in standard state is at equilibrium, then :

(A) Hº = 0 (B) Sº = 0
(C) equilibrium constant K = 0 (D*) equilibrium constant K = 1
tc vfHkfØ;k ekud ifjfLFkfr esa dh tkrh gS rc %
(A) Hº = 0 (B) Sº = 0 (C) lkE; fLFkjkad K = 0 (D*) lkE; fLFkjkad K = 1
Sol. Equilibrium at standard state means equilibrium constant is 1.
ekud voLFkk ij lkE; ls rkRi;Z gS fd lkE; fLFkjkad 1 gksrk gSA
C-4. What is the free energy change (G) when 1.0 mole of water at 100ºC and 1 atm pressure is converted
into steam at 100ºC and 1 atm pressure ?
(A) 80 cal (B) 540 cal (C) 620 cal (D*) Zero
tc 100ºC o 1 atm nkc ij 1.0 eksy ty dks 100ºC o 1 atm nkc ij Hkki esa ifjofrZr fd;k tkrk gSA eqDr
ÅtkZ ifjorZu (G) Kkr dhft, \
(A) 80 cal (B) 540 cal (C) 620 cal (D*) 'kwU;
Sol. At equilibrium, G = 0
lkE; ij, G = 0
C-5. A reaction has H = – 33 kJ and S = – 58 J/K. This reaction would be :

(A) spontaneous at all temperatures (B) non-spontaneous at all temperatures
(C) spontaneous above a certain temperature (D*) spontaneous below a certain temperature
,d vfHkfØ;k ds fy;s H = – 33 kJ rFkk S = – 58 J/K gSA ;g vfHkfØ;k gksxhA
(A) lHkh rki ij Lor% (B) lHkh rki ij vLor%
(C) dsoy fuf'pr rki ds Åij Lor% (D*) dsoy fuf'pr rki ls de rki ij Lor%
ADVTDS - 8
Sol. G = (H) – T(S)
 
 –ve –ve
33000
since both are –ve, the reaction would have a –ve G below a temperature of K ( = 569K)
58
33000
pwafd nksuksa _.kkRed gSa] blfy, G _.kkRed K ( = 569K) rki ls uhps gksxkA
58
C-6. For a reaction A(g) B(g) at equilibrium. The partial pressure of B is found to be one fourth of the
partial pressure of A. The value of G° of the reaction A  B is
,d vfHkfØ;k A(g) B(g) lkE;koLFkk ij gSA ;fn B dk vkaf'kd nkc] A ds vkaf'kd nkc dk ,d pkSFkkbZ nkc
ik;k tkrk gS rks vfHkfØ;k A  B ds fy, G° ds eku dh x.kuk djksA
(A*) RT n 4 (B) – RT n 4 (C) RT log 4 (D) – RT log 4
1
Sol. A (g) B (g) PB = PA PA = 4PB
4
PB P /4 1
Kp = = A =
PA PA 4
At equilibrium (lkE;koLFkk ij), G = 0.
1
Gº = – RT nKP = – RTlnKP = –RT ln = RT ln 4
4
3
C-7. If Gº = – 177 K cal for (1) 2 Fe(s) + O2 (g)  Fe2O3 (s)
2
and Gº = – 19 K cal for (2) 4 Fe2O3 (s) + Fe(s) 3 Fe3O4 (s)
What is the Gibbs free energy of formation of Fe3O4(s) ?
3
;fn Gº = – 177 K cal (1) 2 Fe(s) + O2 (g)  Fe2O3 (s)
2
rFkk Gº = – 19 K cal (2) 4 Fe2O3 (s) + Fe(s) 3 Fe3O4 (s)
rc Fe3O4(s) ds lEHkou dh fxCl eqDr ÅtkZ D;k gS ?
(A) + 229.6 kcal/mol (B*) – 242.3 kcal/mol (C) – 727 kcal/mol (D) – 229.6 kcal/mol
Sol. G for 3Fe(s) + 2O2 (g)  Fe3O4 (s) can be obtained by taking
1
[(2) + 4 × (1)] ×
3
1
Hence, we get Gf = [– 19 + 4 × (– 177)] × = – 242.3 k cal for 1 mole Fe3O4
3
Sol. vfHkfØ;k 3Fe(s) + 2O2 (g)  Fe3O4 (s) ds fy, G bl izdkj izkIr fd;k tk ldrk gSA
1
[(2) + 4 × (1)] ×
3
1
vr% gesa 1 eksy Fe3O4 ds fy;s izkIr gksrk gS Gf = [– 19 + 4 × (– 177)] × = – 242.3 k cal
3
C-8. For a paticular reaction H° = – 76.6 KJ and S° = 226 JK–1. This reaction is :
(A*) Spontaneous at all temperatures (B) Non spontaneous at all temperatures
(C) Spontaneous at temperature below 66°C (D) Spontaneous at temperature above 66°C
,d fof'k"V vfHkfØ;k ds fy, H° = – 76.6 KJ rFkk S° = 226 JK–1 gSA ;g vfHkfØ;k gS%
(A*) lHkh rkiksa ij Lor% izØe (B) lHkh rkiks ij vLor% izØe
(C) 66°C ls de rki ij Lor% izØe (D) 66°C ls vf/kd rki ij Lor% izØe
Sol. Gº = Hº – TSº
For spontaneous process Gº < 0
So, Hº – TSº < 0
ADVTDS - 9
Lor% izØe ds fy,] Gº < 0
blfy,, Hº – TSº < 0
PART - III : MATCH THE COLUMN

Hkkx - III : dkWye dks lqesfyr dhft, (MATCH THE COLUMN )
1. Match the column:

Columm-I Columm-II
(A) (Gsystem)T,P = 0 (p) Process is in equilibrium
(B) Ssystem + Ssurrounding > 0 (q) Process is nonspontaneous
(C) Ssystem + S surrounding < 0 (r) Process is spontaneous
(D) (Gsystem)T,P > 0 (s) System is unable to do useful work
dkWye lqesfyr dhft,A
dkWye-I dkWye-II
(A) (Gfudk;) T,P = 0 (p) izØe lkE; esa gSA
(B) Sfudk; + Sifjos'k > 0 (q) izØe vLor% gSA
(C) Sfudk; + Sifjos'k < 0 (r) izØe Lor% gSA
(D) (Gfudk;) T,P > 0 (s) fudk; mi;ksxh dk;Z ugha dj ldrk gSA
Ans. (A)  (p, s); (B)  (r) ; (C)  (q, s) ; (D) (q, s).
Sol. (A) Gsys = 0  equilibrium and free energy is zero. So, no useful work.
(B) Suniverse > 0  Spontaneous process and able to do useful work.
(C) Suniverse < 0  Nonspontaneous process and unable to do useful work.
(D) Gsys > 0  Nonspontaneous process and unable to do useful work.
gy (A) Gsfudk; = 0  lkE; o eqDr ÅtkZ 'kwU; gS vr% fudk; dksbZ mi;ksxh dk;Z ugha dj ldrkA
(B) Sczãk.M > 0  Lor% izØe o mi;ksxh dk;Z gks ldrk gSA
(C) Sczãk.M < 0  vLor% izØe o mi;ksxh dk;Z ugha gks ldrk gSA
(D) Gfudk; > 0  vLor% izØe o mi;ksxh dk;Z ugha gks ldrk gSA
2. Match the column:
Columm-I Columm-II
(A) Reversible adiabatic compression (p) Ssystem > 0
(B) Reversible vaporisation of liquid (q) Ssystem < 0
(C) 2N(g) N2(g) (r) Ssurrounding < 0
(D) MgCO3(s)  
 MgO(s) + CO2(g) (s) Ssurrounding = 0
dkWye lqesfyr dhft,A
dkWye-I dkWye-II
(A) mRØe.kh; :)ks"e laihMu (p) Sfudk; > 0
(B) nzo dk mRØe.kh; ok"ihdj.k (q) Sfudk; < 0
(C) 2N(g) N2(g) (r) Sifjos'k < 0
(D) MgCO3(s)  
 MgO(s) + CO2(g) (s) Sifjos'k = 0
Ans. (A)  (s); (B)  (p, r); (C)  (q); (D)  (p, r)
Sol. (A) For reversible process Suniverse = 0 and for adiabatic process Ssystem = 0
(B) For reversible process Suniverse = 0, and in vaporisation entropy of system increases
(C) Number of gaseous moles decreases. So, entropy of system decreases and N2 is more stable. So,
process is spontaneous. For spontaneous process Suniverse > 0
(D) Number of gaseous moles increases. So, entropy of system increases.
ADVTDS - 10
Sol. (A) mRØe.kh; izØe ds fy;s Sczãk.M = 0 o :)ks"eh; izØe ds fy;s Sfudk; = 0
(B) mRØe.kh; izØe ds fy;s Sczãk.M = 0 o ok"ihdj.k esa fudk; dh ,UVªkWih c<+rh gSA
(C) xSlh; eksy ?kVrs gSa vr% fudk; dh ,UVªkWih ?kVrh gS o N2 vf/kd LFkk;h gS blfy;s izØe Lor% gSA Lor% izØe ds
fy;s Sczãk.M > 0.
(D) xSlh; eksy c<+rs gSa vr% fudk; dh ,UVªkWih c<+rh gSA
PART - I : ONLY ONE OPTION CORRECT TYPE

Hkkx-I : dsoy ,d lgh fodYi çdkj (ONLY ONE OPTION CORRECT TYPE)
1. Which of the following option the first compound has less entropy than second :
(A) (i) aqueous solution of 1 M of MgCl2 (ii) aqueous solution of 1 M of NaCl
(B) (i) Br2 liquid at 25ºC (ii) Br2 liquid at 20ºC
(C*) (i) HgO solid (ii) HgS solid
(D) (i) Br2 liquid (ii) I2 solid
fuEu esa ls fdl fodYi esa igyk ;kSfxd] nwljs ;kSfxd dh rq yuk esa de ,UVªksih j[krk gS :
(A) (i) 1 M MgCl2 dk tyh; foy;u (ii) 1 M NaCl dk tyh; foy;u
(B) (i) 25ºC ij nzo Br2 (ii) 20ºC ij nzo Br2
(C*) (i) Bksl HgO (ii) Bksl HgS
(D) (i) nzo Br2 (ii) Bksl I2

2. Isentropic process is
(A) adiabatic and irreversible process (B) isothermal and reversible process
(C*) adiabatic and reversible process (D) isothermal and reversible for which Q = 0
le,UVªksih izØe gS %
(A) :)ks"eh; o vuqRØe.kh; izØe (B) lerkih; o mRØe.kh; izØe
(C*) :)ks"eh; o mRØe.kh; izØe (D) lerkih; o mRØe.kh; izØe (ftlds fy, Q = 0)
3.^ Third law of thermodynamics states that :

(A*) the entropy of a perfectly crystalline pure substance at zero K is zero.
(B) absolute entropy of hydrogen ion is zero at zero K.
(C) net change in entropy in coverssion H2(g) (130 K)  H2(g) (200K) is zero.
(D) entropy generally decrease in combustion reactions.
m"ekxfrdh dk r`rh; fu;e crkrk gS fd %
(A*) 'kwU; K ij iw.kZ 'kq) fØLVyh; inkFkZ dh ,UVªksih 'kwU; gSA
(B) 'kwU; K ij gkbMªkstu vk;u dh ije ,UVªksih 'kwU; gSA
(C) H2(g) (130 K)  H2(g) (200K) esa :ikUrj.k dh dqy ,UVªksih ifjorZu 'kwU; gSA
(D) ,UVªksih lkekU;r% vfHkfØ;k ds ngu esa de gksrh gSA

ADVTDS - 11
4. Select correct statements :
S1 : For every chemical reaction at equilibrium, standard gibbs energy of reaction is zero
S2 : At constant temperature and pressure, chemical reactions are spontaneous in the direction of
decreasing gibbs energy.
S3 : Spontaneity is related to change in entropy of universe.
lgh dFku dk pquko dhft, &
S1 : lkE; ij izR;sd jklk;fud vfHkfØ;kvksa ds fy,] vfHkfØ;k dh ekud fxCl ÅtkZ 'kwU; gSA
S2 : fu;r rki o nkc ij jklk;fud vfHkfØ;k fxCl ÅtkZ esa deh dh fn'kk esa Lor% gksrh gSA
S3 : Lor% izØe czãk.M dh ,UVªksih esa ifjorZu ls lEcfU/kr gSA
(A) S1 S2 S3 (B) only S1 (C*) S2, S3 (D) S1, S3
PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

Hkkx - II : ,dy ,oa f}&iw.kk±d eku izdkj ¼SINGLE AND DOUBLE VALUE INTEGER TYPE½
1. The equilibrium constant for a reaction is 10. What will be the magnitude value of Gº ?
R = 8.31 JK–1 mol–1, T = 314 K. (Approximate integer value in KJ mol –1)
,d vfHkfØ;k ds fy, lkE; fLFkjkad 10 gSA Gº dk eku D;k gksxk\ R = 8.31 JK–1 mol–1, T = 314 K. (KJ mol–1
esa yxHkx iw.kkZd eku)
Ans. 6
Sol. Given : Keq = 10
T = 314 K
Gº = – 2.303 RT log Keq = – 2.303 × 8.31 × 314 log 10 J = – 6 kJ mol–1.
Ans. The value of Gº is –6 kJ mol–1.
Sol. fn;k x;k gS : Keq = 10

T = 314 K
iwNk gS : G0 = ?
lw=k : Gº = – 2.303 RT log Keq = – 2.303 × 8.31 × 314 log 10 J= – 6 kJ mol–1.
Ans. Gº dk eku –6 kJ mol–1 gSA
2.^ For the reaction at 298 K

A (g) + B (g) C (g) + D (g)
If Hº = – 29.8 Kcal and Sº = – 0.1 Kcal K–1 then calculate equilibrium constant (K) :
298 K ij vfHkfØ;k ds fy,
A (g) + B (g) C (g) + D (g)
;fn Hº = – 29.8 Kcal o Sº = – 0.1 Kcal K–1 gS] rks lkE; fu;rkad (K) ds eku dh x.kuk djks :
Ans. 1
= – 29.8 – 298 × (– 0.1)
= – 29.8 + 29.8 = 0 = nRTln(K)
K=1
3. Calculate the magnitude of free energy in KJ mol–1 when 1 mole of an ionic salt MX (s) is dissolved in
water at 27°C. Given
Lattice energy of MX = 780 kJ mol–1
Hydration energy of MX = – 775.0 kJ mol–1
Entropy change of dissolution at 27°C = 40 J mol –1 K–1
27ºC ij tc 1 eksy vk;fud yo.k MX (s) dks ty esa ?kksyk tkrk gS] rks eqDr ÅtkZ dh x.kuk djksA
fn;k x;k gS fd MX dh tkyd ÅtkZ = 780 kJ mol–1
MX dh ty;kstu ÅtkZ = – 775.0 kJ mol–1
27°C ij foyk;du dh ,UVªkWih ifjorZu = 40 J mol–1 K–1 gSA
Ans. 7 kJ mol–1.
ADVTDS - 12
Sol. Hdissolution = Hionisation + Hhydration = 780 – 775 = 5 kJ mol–1
Gdissolution = Hdissolution – TSdissolution = 5000 – 300 × 40 = – 7000 J = – 7 kJ mol–1
Sol. Hfo;kstu = Hvk;uu + Hty;kstu = 780 – 775 = 5 kJ mol–1
Gfo;kstu = Hfo;kstu – TSfo;kstu = 5000 – 300 × 40 = – 7000 J = – 7 kJ mol–1
4. For the formation of C (g) at 300 K.
A (g) + 3 B (g)  2C (g)
Calculate the magnitude of Gº (Kcal) if given data :
A B C
Hfº (Kcal mol-1) 0 0 –10
Sfº (Cal K mol )
–1 -1 40 30 45
300 K ij C (g) ds fuekZ.k dh vfHkfØ;k %
A (g) + 3 B (g)  2C (g)
fn;s x;s vk¡dM+ks dks iz;qDr djds Gº (Kcal) ds eku dh x.kuk djksA
A B C
Hfº (Kcal mol-1) 0 0 –10
Sfº (Cal K–1 mol-1) 40 30 45
Ans. 8
Sol. Hfº = 2 × (– 10) = – 20
S = 90 – (40 + 90) = – 40
G = H – TS = – 20 + 12 = – 8
5. The entropies of H2(g) and H(g) are 60 and 50 J mole–1 K–1 respectively at 300 K. Using the data given
below calculate the bond enthalpy of H2 (g) in Kcal mole–1.
H2 (g)  2H (g) ; Gº = 21.6 KJ mole–1
300 K ij H2(g) rFkk H(g) dh ,UVªksih Øe'k% 60 o 50 J mole–1 K–1 gSA fuEu vk¡dM+ks dks iz;qDr djds H2(g) dh
ca/k ,UFkSYih dk eku Kcal mole–1 esa Kkr dhft,A
H2 (g)  2H (g) ; Gº = 21.6 KJ mole–1
Ans. 8
21.6 = HH–H – 300 (2 × SºH – SºH2)
HH–H = 33.6 KJ mole–1 = 8 Kcal mole–1
6. The free energy change for a reaction is –213.3 kJ mol–1 at 25ºC. If the enthalpy change of the reaction
is –217.77 kJ mole–1. Calculate the magnitude of entropy change for the reaction in Joule mole –1.
25ºC ij fdlh vfHkfØ;k ds fy;s eqDr ÅtkZ ifjorZu – 213.3 kJ mol–1 gSA ;fn vfHkfØ;k ds fy, ,UFkSYih ifjorZu
–217.77 kJ mole–1 gS rks vfHkfØ;k ds fy, ,UVªkWih ifjorZu dh x.kuk dhft,A
Ans. 15
Sol. Given : H = – 217.77 kJ K–1 mol–1
G = – 213.3 kJ mol–1
T = 273 + 25 = 298 K
Asked : The entropy change for the reaction.= ?
Formula : G = H – TS
Explanation : G = Gibb’s free energy change
H = Enthalpy change
T = Temperature in K
S = Entropy change
Substitution & Calculation :
–213.3 × 103 = – 217.77 × 103 – 298 × S
(217.77  103  213.3  103 )
or S =
298
S = – 15 J / mol K
Ans. Entropy change for the reaction is – 15 J / mol K
ADVTDS - 13
Sol. fn;k x;k gS : H = – 217.77 kJ K–1 mol–1
G = – 213.3 kJ mol–1
T = 273 + 25 = 298 K
iwNk x;k gS : vfHkfØ;k ds fy, ,UVªksih ifjorZu = ?
lw=k : G = H – TS
O;k[;k :  G = fxCl eqDr ÅtkZ
H = ,UFkSYih ifjorZu
T = K esa rkieku
S = ,UVªksih ifjorZu
–213.3 × 103 = – 217.77 × 103 – 298 × S
(217.77  103  213.3  103 )
;k S =
298
S = – 15 J / mol K
Ans. vfHkfØ;k ds fy, ,UVªksih ifjorZu – 15 J / mol K gSA
7. Calculate the magnitude of standard entropy change for reaction X Y if Hº = 25 KJ and Keq is
10–7 at 300 K.
300 K rki ij vfHkfØ;k X Y ds fy;s ekud ,UVªkWih ifjorZu dh x.kuk djks ;fn Hº = 25 KJ rFkk
KlkE;=10–7 gSA
Ans. 51
Sol. Given :  Hº = 25 KJ
T = 300 K
Keq = 10–7
Asked : standard entropy change
Formula :  Gº = Hº – TSº
Since  Gº = – 2.303 RT log Keq
 – 2.303 RT log Keq = Hº – TSº
Explanation :  Gº = Standard free energy change
 Hº = standard enthalpy change
T = Temperature
 Sº = standard entropy change
R = Gas constant
Keq = equlibrium constant
Substitution & calculation :
– 2.303 × (25/3) × (300) log10–7 = 25000 – (300) Sº
 Sº = – 51 J/K.
Ans. Standard entropy change in reaction is – 51 J/K.
gy % (a) fn;k x;k gS: Hº = 25 KJ
T = 300 K
Keq = 10–7
iwNk gS : ekud ,UVªkWih ifjorZu
lw=k :   Gº = Hº – TSº
  pwafd Gº = – 2.303 RT log Keq
 – 2.303 RT log Keq = Hº – TSº
O;k[;k :  Gº = ekud eqDr ÅtkZ ifjorZu
  Hº = ekud ,UFkSYih ifjorZu
T = rkieku
  Sº = ekud ,UVªkWih ifjorZu
R = xSl fu;rkad
Keq = lkE; fu;rkad
ADVTDS - 14
– 2.303 × (25/3) × (300) log10–7 = 25000 – (300) Sº
 Sº = – 51 J/K.
Ans. vfHkfØ;k esa ekud ,UVªkWih ifjorZu – 51 J/K gSA
8. Calculate the magnitude of standard free energy of formation of ammonium chloride at 25ºC
(approximate integer in Kcal mol –1), the equation showing the formation of NH4Cl from its elements is
½N2(g) + 2H2(g) + ½Cl2(g)  NH4Cl(s)
For NH4Cl, Hºf is – 313 kJ mol–1, Also given that
SN0 2  191.5 JK 1 mol1 SH0 2  130.6 JK 1 mol1
S0Cl2  223.0J K 1 mol1 0
SNH4 Cl
 94.6 JK 1 mol1
25ºC ij veksfu;e DyksjkbM ds fuekZ.k dh ekud eqDr ÅtkZ dh x.kuk dhft,A (Kcal mol–1 esa yXkHkx iw.kkZd eku)
lehdj.k ½N2(g) + 2H2(g) + ½Cl2(g)  NH4Cl(s), NH4Cl dk fuekZ.k blds rRoksa ls n'kkZrh gSA
NH4Cl ds fy;s Hºf = – 313 kJ mol–1 gSA
;g Hkh fn;k x;k gS fd SN0 2  191.5 JK 1 mol1 SH0 2  130.6 JK 1 mol1
S0Cl2  223.0J K 1 mol1 0
SNH4 Cl
 94.6 JK 1 mol1
Ans. 48
Sol. For the formation reaction above (mijksDr lEHkou vfHkfØ;k ds fy;s )
1 1 0 
S0f  SNH0
  SN0 2  2SH0 2  SCl
4 Cl
2 2 2 
 94.6  [½ (191.5)  2 (130.6)  ½ (223.0)]
= – 373.85 J K–1 mol–1
Now that we have H and S, we can find G, (vc ge H o S ls G dk eku Kkr dj ldrs gSaA )
G0f  H0f  TS0t
= – 313 × 103 J mol–1 – (298 K) × (– 373.85 J K–1 mol–1)
= – 201.6 × 103 Jmol–1 or ¼;k½ – 201.6 kJ mol–1
= – 48 Kcal mol–1.
1 3
9. For the reaction N2(g) + H2(g)NH3(g) ; H = – 30 kJ to be at equilibrium at 477ºC. If standard
2 2
entropy of N2 (g) and NH3 (g) are 60 and 50 J mole–1 K–1 respectively then calculate the standard
entropy of H2(g) in Jmole–1K–1.
1 3
vfHkfØ;k N2(g) + H2(g) NH3(g) ds fy,; 477ºC o lkE; ij H = – 30 kJ ; ;fn N2 (g) o NH3 (g) dh
2 2
ekud ,UVªksih Øe'k% 60 o 50 J mole–1 K–1 gS] rks H2(g) dh ekud ,UVªksih dh x.kuk Jmole–1K–1 esa dhft,A
Ans. 40
1 3
Sol. N2 (g) + H2 (g) NH3 (g)
2 2
3
Srxn = 50 – 30 – X JK–1
2
Hrxn = – 30000 J
at equilibrium lkE; ij
Grxn = 0 = Hrxn – TSrxn
 3 
750 ×  20 – x  = – 30000
 2 
120
x= = 40.
3
ADVTDS - 15
PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE
Hkkx - III : ,d ;k ,d ls vf/kd lgh fodYi çdkj
1.^ In which of the following entropy increases :
(A) Fe(s) + O2(g)  Fe2O3(s). (B*) Melting of ice
(C) Crystallisation of sugar from solution (D*) Vaporisation of camphor
fuEu esa ls fdu izØeksa esa ,UVªkWih esa o`f) gksrh gS %
(A) Fe(s) + O2(g)  Fe2O3(s). (B*) cQZ dk fi?kyuk
(C) foy;u ls 'kdZjk dk fØLVyhdj.k (D*) diwj dk ok"ihdj.k
2. When a liquid solidifies, generally, there is :

(A*) Decrease in enthalpy (B*) Decrease in entropy
(C) Increase in enthalpy (D) Increase in entropy
tc nzo dk Bkslhdj.k (solidifies) gksrk gS rc%
(A*) ,UFkSYih esa deh gksrh gSA (B*) ,UVªkWih esa deh gksrh gSA
(C) ,UFkSYih esa o`f) gksrh gSA (D) ,UVªkWih esa o`f) gksrh gSA
3. Which of the following is false about molar entropy ?

(A*) It is same for all type of gases
(B*) For the gas of comparable mass. It decreases with the increase in atomicity.
(C) Under identical condition, it is greater for heavier gas.
(D*) For ideal gas of comparable molar mass it decreases with the increase in thermo molecular
attractions.
eksyj ,UVªksih ds lanHkZ esa dkSulk dFku xyr gSA
(A*) ;g lHkh izdkj dh xSlks ds fy, leku gSA
(B*) rqyukRed nzO;eku dh xSl ds fy, ;g ijek.kqdrk esa o`f) ds lkFk deh n'kkZrh gSA
(C) leku fLFkfr;ksa ds vUrxZr ;g Hkkjh xSlksa ds fy, vf/kd gksrh gSA
(D*) rqyukRed eksyj nzO;eku dh vkn'kZ xSl ds fy, ;g rkih; v.kq vkd"kZ.k esa o`f) ds lkFk deh n'kkZrh gSA
4. Which of the following statements is/are correct

(A*) Reversible adiabatic process is iso entropic process
(B*) Ssystem for irreversible adiabatic compression is greater than zero
(C) Ssystem for free expension in zero
(D*) Ssurrounding for irreversible isothermal compression is greater than zero
fuEu esa ls dkSulk@dkSuls dFku lgh gS@gSa
(A*) mRØe.kh; :)ks"e izØe le,UVªksih izØe gSA
(B*) vuqRØe.kh; :)ks"eh; lEihMu ds fy, Sfudk; 'kwU; ls vf/kd gSA
(C) eqDr izlkj ds fy, Sfudk; 'kwU; gSA
(D*) vuqRØe.kh; lerkih; lEihMu ds fy, Sfudk; 'kwU; ls vf/kd gSA
5. The normal boiling point of a liquid `X` is 400 K. Which of the following statement is true about the
process X(l)  X(g)?
(A*) at 400 K and 1 atm pressure G = 0 (B*) at 400 K and 2 atm pressure G = + ve
(C*) at 400 K and 0.1 atm presure G = – ve (D) at 410 K and 1 atm pressure G = + ve
,d nzo `X` dk lkekU; DoFkaukd 400 K gSA X(l)  X(g) ds lanHkZ esa fuEu esa ls dkSulk dFku lR; gS ?
(A*) 400 K vkSj 1 ok;qe.My nkc ij G = 0 (B*) 400 K vkSj 2 ok;qe.My nkc ij G = + ve
(C*) 400 K vkSj 0.1 ok;qe.My nkc ij G = – ve (D) 410 K vkSj 1 ok;qe.My nkc ij G = + ve
Sol. Boiling of a liquid at normal boiling point is a equilibrium process and on decreasing the pressure
equilibrium will go forward and G will be negative and vice versa.
ADVTDS - 16
nzo dk mcyuk lkekU; DoFkukad ij ,d lkE; izØe gS ftlesa nkc dks de djus ij izØe vxz fn'kk dh vkSj tkrk
gS ,oa G _.kkRed gksxkA
6. For isothermal expansion in case of an ideal gas :

(A*) H = 0 (B*) E = 0 (C*) G = –T.S (D*) Tfinal = Tinitial
vkn'kZ xSl dh fLFkfr esas lerkih; çlkj ds fy;s %
(A*) H = 0 (B*) E = 0 (C*) G = –T.S (D*) TvfUre = TvkjfEHkd
Sol. For isothermal expnasion, H = 0, E = 0 , G = –T.S, Tfinal = Tinitial
lerkih; izlkj ds fy,] H = 0, E = 0 , G = –T.S, TvfUre = TvkjfEHkd
PART - IV : COMPREHENSION
Hkkx - IV : vuqPNsn (COMPREHENSION)
Read the following passage carefully and answer the questions.
fuEu vuqPNsn dks /;kuiwoZd if<+;s rFkk iz' uksa ds mÙkj nhft,A
Comperhension # 1
Entropy is a state function and its value depends on two or three variables temperature (T), Pressure
(P) and volume (V). Entropy change for an ideal gas having number of moles (n) can be determined by
the following equation.
T  V 
 S = 2.303 nCV log  2  + 2.303 nR log  2 
 1
T  V1 
T  P 
S = 2.303 nCp log  2  + 2.303 nR log  1 
 T1   P2 
Since free energy change for a process or a chemical equation is a deciding factor of spontaneity,
which can be obtained by using entropy change (S) according to the expression, G = H – TS at a
temperature T.
vuqPNsn # 1
,UVªkWih ,d voLFkk Qyu gS rFkk bldk eku nks ;k rhu pjks] rki (T), nkc (P) rFkk vk;ru (V) ij fuEkZj djrk gSA
,d vkn'kZ xSl ds fy, ,UVªkWih esa ifjorZu j[kus okys eksyksa dh la[;k fuEu lehdj.k }kjk fu/kkZfjr dh tk ldrh
gSA
T  V 
 S = 2.303 nCV log  2  + 2.303 nR log  2 
 T1   V1 
T   P1 
 S = 2.303 nCp log  2  + 2.303 nR log  
 T1   P2 
pwafd ,d izØe ;k jklk;fud lehdj.k ds fy, eqDr ÅtkZ ifjorZu Lorrk% (spontaneity) dks fu/kkZfjr djus dk
dkjd gS] tSls ,UVªkWih esa ifjorZu (S) ] rki T ij fuEu lehdj.k, G = H – TS }kjk fu/kkZfjr djrs gSA
1. What would be the entropy change involved in thermodynamic expansion of 2 moles of a gas from a
volume of 5 L to a volume of 50 L at 25°C [Given R = 8.3 J/mole – K]
25°C ij xSl ds 2 eksy dk vk;ru 5 yhVj ls 50 yhVj rd Å"ekxfrdh; :i ls izlkfjr djus esa iz;qDr ,UVªkWih
ifjorZu gksuk pkfg,A [fn;k gS R = 8.3 J/mole – K]
(A*) 38.23 J/K (B) 26.76 J/K (C) 20J/K (D) 28.23J/K
 50 
Sol. S = 2.303 x 2 x 8.3 log   = 38.23 J/K
 5 
2. An isobaric process having one mole of ideal gas has entropy change 23.03 J/K for the temperature
range 27°C to 327°C. What would be the molar specific heat capacity (CV) ?
,d eksy vkn'kZ xSl ds lenkch; izØe esa ,UVªkWih ifjorZu 23.03 J/K gS rFkk blds fy, rki esa o`f) 27°C ls
327°C rd gksrh gSA fof'k"V eksyj Å"ek èkkfjrk (CV) D;k gksxh \
ADVTDS - 17
10 10
(A) J/K mol (B*) – 8.3 J/ K mol
log2 log2
(C) 10 × log2 J/K mol (D) 10 log2 + 8.3 J/K mol
 600  10
Sol. S = 2.303 × 1 × CP log   = 23.03  CP =
 300  log2
10
CV = CP – R = – 8.3
log2
1
3. For a reaction M2O(s)  2M(s) + O2(g); H = 30 kJ/mol and S = 0.07 kJ/K-mol at 1 atm. Calculate
2
upto which temperature the reaction would not be spontaneous.
1
1 atm ij vfHkfØ;k M2O(s)  2M(s) + O2(g) ds fy, H = 30 kJ/mol rFkk S = 0.07 kJ/K-eksy gSA fdl
2
rki rd vfHkfØ;k Lor% ugha gksxhA
(A) T > 428.6 K (B) T > 300.8 K (C) T < 300.8 K (D*) T < 428.6 K
Sol. For reaction to be spontaneous, (Lor% vfHkfØ;k ds fy;s)
G < 0  H – TS < 0
H
 T>  T > 428.6 K.
S
If T < 428.6 K so, reaction is non spontaneous.
;fn T < 428.6 K blfy, vfHkfØ;k vLor% gSA
Comprehension # 2
Dependence of spontaneity on temperature :
For a process to be spontaneous, at constant temperature and pressure, there must be decrease in
free energy of the system in the direction of the process, i.e. GP, T < 0. GP, T = 0 implies the
equilibrium condition and GP, T > 0 corresponds to non-spontaneity.
Gibbs-Helmholtz equation relates the free energy change to the enthalpy and entropy changes of the
process as : G P,T = H – TS ...(1)
The magnitude of H does not change much with the change in temperature but the entropy factor TS
changes appreciably. Thus, spontaneity of a process depends very much on temperature.
For endothermic process, both H and S are positive. The energy factor, the first factor of equation,
opposes the spontaneity whereas entropy factor favours it. At low temperature the favourable factor
TS will be small and may be less than H, G will have positive value indicating the nonspontaneity of
the process. On raising temperature, the factor TS increases appreciably and when it exceeds H, G
would become negative and the process would be spontaneous.
For an exothermic process, both H and S would be negative. In this case the first factor of
eq. 1 favours the spontaneity whereas the second factor opposes it. At high temperature, when TS >
H, G will have positive value, showing thereby the non-spontaneity of the process. However, on
decreasing temperature, the factor TS decreases rapidly and when TS < H, G becomes negative
and the process occurs spontaneously. Thus, an exothermic process may be spontaneous at low
temperature and non-spontaneous at high temperature.
vuqPNsn # 2
rkieku ij Lorrk% dh fuHkZjrk :
fu;r rki rFkk nkc ij fdlh izØ e ds Lor% gksus ds fy, izØe dh fn'kk esa fudk; dh eqDr ÅtkZ esa deh gksuk
vko';d gSA tSls GP, T < 0. GP, T = 0 lkE;koLFkk dh ifjfLFkfr ij rFkk GP, T > 0 vLorrk% dh ifjfLFkfr;ksa ls
lEcfUèkr gSA
fxCl gSYehYVkst lehdj.k ,sUFkSYih esa eqDr ÅtkZ ifjorZu rFkk izØe dh ,UVªkWih ifjorZu dks lEcfU/kr djrh gS %
G P,T = H – TS ...(1)
H dk ifjek.k] rki esa ifjorZu ds lkFk ugh cnyrk ysfdu ,UVªkWih] dkjd TS esa ifjorZu ls dqN cnyrk gSA
blfy, fdlh izØe dk Lor% gksuk cgqr gn rd rki ij fuHkZj djrk gSA
ADVTDS - 18
Å"ek'kks"kh (endothermic) izØe ds fy,] H rFkk S /kukRed gksrh gSA lehdj.k dk izFke dkjd ÅtkZ dkjd
Lorrk% ds foifjr gS tcfd ,UVªkWih dkjd blds i{k esa gSA fuEu rki ij izHkkoh dkjd TS NksVk gksxk rFkk H ls
Hkh NksVk gks ldrk gSA G dk /kukRed eku izØe ds vLor% gksus dks n'kkZrk gSA rki c<+kus ij dkjd TS c<+rk gS
rFkk tc ;s H ls T;knk gks tkrk gS] G _.kkRed gks tkrk gS rc izØe Lor% gks tk;sxkA
Å"ek{ksih (exothermic) izØe ds fy,] H rFkk S nksuksa _.kkRed gksaxsA bl ifjfLFkfr esa izFke dkjd lehdj.k ds
i{k esa gS tcfd nwljk dkjd blds foijhr gksxkA mPp rki ij tc TS > H, G dk eku /kukRed gksxk tks fd
izØe ds vLor% gksus dks n'kkZrk gSA tcfd rki ?kVkus ij TS dkjd rsth ls ?kVrk gSa rFkk tc TS < H, G dk
eku _.kkRed gksxk rFkk izØe Lor% gks tk;sxkA vr% ,d Å"ek{ksih (exothermic) izØe fuEu rki ij Lor% rFkk
mPp rki ij vLor% gksxkA
4. When CaCO3 is heated to a high temperature, it undergoes decomposition into CaO and CO 2 whereas
it is quite stable at room temperature. The most likely explanation of it, is
(A) The enthalpy of reaction (H) overweighs the term TS at high temperature.
(B*) The term TS overweighs the enthalpy of reaction at high temperature.
(C) At high temperature, both enthalpy of reaction and entropy change become negative.
(D) None of these.
tc CaCO3 dks mPp rki ij xeZ djrs gS] ;g CaO rFkk CO2 esa fo?kfVr gks tkrk gSA tcfd ;g dejs ds rki ij
LFkk;h gSA bldh lgh O;k[;k gksxhA
(A) mPp rki ij TS dk eku vfHkfØ;k dh ,sUFkSYih (H) ls de gksrk gSA
(B*) mPp rki ij TS dk eku vfHkfØ;k dh ,sUFkSYih (H) ls T;knk gksrk gSA
(C) mPp rki ij vfHkfØ;k dh ,sUFkSYih rFkk ,UVªkWih nksuksa esa ifjorZu _.kkRed gkssaxsA
(D) buesa ls dksbZ ughaA
Sol. G = H – TS
If TS dominates H at high temperature then G < 0 hence CaCO3 decomposes at high temperature.
;fn mPp rki ij TS, H ls izHkkoh gksxk rc G < 0 vr% mPp rki ij CaCO3 fo?kfVr gksxkA
5. For the reaction at 25°C, X2O4()  2XO2(g)
H = 2.1 Kcal and S = 20 cal K–1. The reaction would be
(A*) spontaneous (B) non-spontaneous (C) at equilibrium (D) unpredictable
25°C ij, vfHkfØ;k X2O4()  2XO2(g) ds fy, H = 2.1 Kcal rFkk S = 20 cal K–1 gS] rc vfHkfØ;k
(A*) Lor% (B) vLor% (C) lkE; ij (D) x.kuk ugha dh tk ldrhA
Sol. G = H – TS = 2.1 × 103 – 20 × 298 < 0.
6. For the reaction at 298 K, 2A + B C
H = 100 kcal and S = 0.050 kcal K–1. If H and S are assumed to be constant over the temperature
range, above what temperature will the reaction become spontaneous ?
298 K ij, vfHkfØ;k 2A + B C ds fy, H = 100 kcal rFkk S = 0.050 kcal K–1 gSA ;fn H rFkk•S dks
fdlh rki ijkl ij fu;r eku ys rks fdl rki ds Åij vfHkfØ;k Lor% gks tk;sxhA
(A) 1000 K (B) 1500 K (C*) 2000 K (D) 2500 K
Sol. Reaction to be spontaneous (vfHkfØ;k Lor% gksxhA)
H 100  103
G < 0  H – TS < 0  T >  T >  T > 2000 K.
S .05  103
7. A reaction has a value of H = – 40 kcal at 400K. Above 400 K, the reaction is spontaneous, below this
temperature, it is not. The values of G and S at 400 K are respectively
400 K rki ij ,d vfHkfØ;k ds fy, H = – 40 kcal gSA 400K rki ds Åij vfHkfØ;k Lor% rFkk blds uhps ;g
Lor% ugh gSA 400 K ij G rFkk S dk eku Øe'k% gksxk %
(A) 0, – 0.1 cal K–1 (B) 0,100 cal K–1
(C) – 10 kcal, – 100 cal K–1 (D*) 0, – 100 cal K–1
ADVTDS - 19
H 40000
Sol. Clearly at 400 K, reaction is in equilibrium  G = 0  S = – = – 100 cal K–1
T 400
H 40000
Li"V gS fd 400 K, ij vfHkfØ;k lkE; ij gS  G = 0  S = – = – 100 cal K–1
T 400
8. The enthalpy change for a certain reaction at 300 K is – 15.0 K cal mol–1. The entropy change under
these conditions is – 7.2 cal K–1 mol–1. The free energy change for the reaction and its
spontaneous/non-spontaneous character will be
(A*) – 12.84 kcal mol–1, spontaneous (B) 12.84 kcal mol–1, non-spontaneous
(C) – 17.16 kcal mol–1, spontaneous (D) None of these
300 K ij fdlh vfHkfØ;k ds fy, ,sUFkSYih esa ifjorZu – 15.0 K cal mol–1 gSA bu ifjfLFkfr;ksa esa ,UVªkWih ifjorZu –
7.2 cal K–1 mol–1 gSA vfHkfØ;k ds fy, eqDr ÅtkZ ifjorZu D;k gksxk rFkk vfHkfØ;k ds Lor%@vLor% xq.k gksxsaA
(A*) – 12.84 kcal mol–1, Lor% (B) 12.84 kcal mol–1, vLor%
–1
(C) – 17.16 kcal mol , Lor% (D) buesa ls dksbZ ugha
Sol. Use G = H – TS  
300  ( 7.2)
 G = – 15 – = – 12.84 Kcal mol–1
1000
PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)

Hkkx - I : JEE (ADVANCED) / IIT-JEE ¼fiNys o"kksZ½ ds iz'u
* Marked Questions may have more than one correct option.
* fpfUgr iz'u ,d ls vf/kd lgh fodYi okys iz'u gS -
1. The direct conversion of A to B is difficult, hence it is carried out by the following shown path:
S(A  C) = 50 ; S(C  D) = 30; S(B D) = + 20

The entropy change for the process A B is [JEE 2006, 3/184]
A dk B esa lh/kk ifjorZu dfBu gS blfy, ;g fuEu n'kkZ;s x;s iFk }kjk lEiUu gksrk gS
S(A  C) = 50 ; S(C  D) = 30; S(B  D) = + 20

izØe A  B ds fy, ,UVªkWih ifjorZu D;k gS \ [JEE 2006, 3/184]
(A) 100 (B) – 60 (C) – 100 (D*) + 60
Sol. A  C ; S = 50; C  D; S = 30; D  B; S = – 20
For A  B: (A  B ds fy,) S = 50 + 30 – 20 = 60
2.^ N2 + 3H2 2 NH3 K = 4 × 106 at 298

K = 41 at 400 K
Which statements is correct ? [JEE 2006, 3/184]
(A) If N2 is added at equlibrium condition, the equilibrium will shift to the forward direction because
according to IInd law of thermodynamics the entropy must increases in the direction of spontaneous
reaction.
(B*) The condition for equilibrium is 2GNH3 = 3GH2 + GN2 where G is Gibbs free energy per mole of the
gaseous species measured at that partial pressure.
(C) Addition of catalyst does not change Kp but changes H.
ADVTDS - 20
(D) At 400 K addition of catalyst will increase forward reaction by 2 times while reverse reaction rate will
be changed by 1.7 times.
N2 + 3H2 2 NH3 298 ij K = 4 × 106

400 K ij K = 41
dkSulk dFku lgh gS \ [JEE 2006, 3/184]
(A) ;fn lkE;oLFkk ij N2 dks Mkyk tk,] rks lkE; vxz fn'kk esa ifjofrZr gksxk D;ksafd Å"ekxfrdh ds f}rh; fu;e
ds vuqlkj ,UVªkih dk eku Lor% vfHkfØ;k dh fn'kk esa c<+rk gSA
(B*) lkE; ds fy, 'krZ 2GNH3 = 3GH2 + GN2 tgk¡ G fdlh vkaf'kd nkc ij xSlh; Lih'kht ds fy, fxCl eqDr
ÅtkZ dk eku izfr eksy gSA
(C) mRizsjd dks Mkyus ij Kp esa ifjorZu ugha gksxk tcfd H ifjofrZr gksrk gSA
(D) 400 K ij mRizsjd Mkyus ij vxz vfHkfØ;k dh vksj 2 xquk c<+sxk tcfd foijhr vfHkfØ;k dh nj 1.7 xquk ls
ifjofrZr gksxhA
Sol. When nitrogen is added at equilibrium condition, the equilibrium will shift according to Le-chatelier
principle at equilibrium G = 0 and catalyst changes the rate of forward and backward reactions by
equal extent. KP of reaction is a function of temperature only.
gy- lkE; ifjfLFkfr ij tc ukbVªkstu dks feykrs gS rc yh 'kkrsfy; fl)kUr ds vuqlkj lkE; LFkkukUrfjr gksrk gSA
lkE; ij G = 0 o mRizsjd vxz rFkk i'p vfHkfØ;k dh nj dks cjkcj ek=kk ls ifjofrZr djrk gSA vfHkfØ;k dk KP
ek=k rki dk Qyu gSA
3. The value of log10K for a reaction A B is :
(Given : rHº298 K = –54.07 kJ mol , rSº298 K = 10 JK–1 mol–1 and R = 8.314 JK–1 mol–1 ; 2.303 × 8.314 ×
–1
298 = 5705) [JEE 2007, 3/162]

vfHkfØ;k A B ds fy, log10 K dk eku gS
(fn;k gS % rHº298 K = –54.07 kJ mol–1, rSº298 K = 10 JK–1 mol–1 vkSj R = 8.314 JK–1 mol–1 ; 2.303 x 8.314
x 298 = 5705) [JEE 2007, 3/162]
(A) 5 (B*) 10 (C) 95 (D) 100
Sol. Gº = Hº – TSº = – 54.07 × 1000 – 298 × 10 = – 54070 – 2980 = – 57050
 Gº = – 2.303 RT log10 K
– 57050 = – 2.303 × 298 × 8.314 log10K = – 5705 log10 K
log10 K = 10
4. For the process H2O() (1 bar, 373 K)  H2O(g) (1 bar, 373 K), the correct set of thermodynamic
parameters is : [JEE 2007, 3/162]
izØe H2O() (1 bar, 373 K)  H2O(g) (1 bar, 373 K), ds fy;s Å"ekxfrdh iSjkehVj dk lgh leqPp; gS %
[JEE 2007, 3/162]
(A*) G = 0, S = +ve (B) G = 0, S = –ve (C) G = +ve, S = 0 (D) G = –ve, S = +ve
Sol. H2O(,1bar, 373K)  H2O(g, 1bar, 373 K)
S > 0 ; H > 0 ; G = 0
5. Statement-1 : For every chemical reaction at equilibrium, standard Gibbs energy of reaction is zero.
Statement-2 : At constant temperature and pressure, chemical reactions are spontaneous in the
direction of decreasing Gibbs energy. [JEE 2008, 3/163]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D*) Statement-1 is False, Statement-2 is True
ADVTDS - 21
dFku-1 : lkE;koLFkk (equilibrium) ij izR;sd jklk;fud vfHkfØ;k dh ekud fxCl ÅtkZ (standard Gibbs
energy) 'kwU; gksrh gSA
dFku-2 : fLFkj rki rFkk nkc ij fxCl ÅtkZ ds de gksus dh fn'kk esa jklk;fud vfHkfØ;k,¡ Lor% izofrZr
(spontaneous) gksrh gSA [JEE 2008, 3/163]
(A) dFku&1 lR; gS] dFku&2 lR; gS ; dFku&2, dFku&1 dk lgh Li"Vhdj.k gSA
(B) dFku&1 lR; gS] dFku&2 lR; gS ; dFku&2, dFku&1 dk lgh Li"Vhdj.k ugha gSA
(C) dFku&1 lR; gS] dFku&2 vlR; gSA
(D*) dFku&1 vlR; gS] dFku&2 lR; gSA
Sol. At equilibrium G (Gibbs energy) = 0 but G° (standard Gibbs energy)  0.
As G (Gibbs energy) is more negative reaction will be more spontaneous.
Sol. lkE; ij G (fxCl ÅtkZ) = 0 ysfdu G° (ekud fxCl ÅtkZ)  0.
G (fxCl ÅtkZ) vf/kd _.kkRed gS rks vfHkfØ;k fd Lor% izofrZrk vf/kd gksxhA
6. Statement-1 : There is a natural asymmetry between converting work to heat and converting heat to
work.
Statement-2 : No process is possible in which the sole result is the absorption of heat form a reservoir
and its complete conversion into work. [JEE 2008, 3/163]
(A*) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
dFku-1 : dk;Z dks Å"ek esa cnyus rFkk Å"ek dks dk;Z esa cnyus esa ,d izkd`frd vlefefr gSA
dFku- 2 : ,slk dksbZ izØe lEHko ugha gS ftlesa Hk.Mkj (reservoir) ls 'kksf"kr Å"ek dk dk;Z esa lEiw.kZ :ikUrj.k
fd;k tk ldsA [JEE 2008, 3/163]
(A*) dFku&1 lR; gS] dFku&2 lR; gS; dFku&2, dFku&1 dk lgh Li"Vhdj.k gSA
(B) dFku&1 lR; gS] dFku&2 lR; gS; dFku&2, dFku&1 dk lgh Li"Vhdj.k ugha gSA
(C) dFku&1 lR; gS] dFku&2 vlR; gSA
(D) dFku&1 vlR; gS] dFku&2 lR; gSA
Sol. Statement 2 is IInd law of thermodynamics which concludes that total heat can never be converted into
equivalent amount of work.
dFku 2 Å"ekxfrdh dk IInd fu;e gS ftlls fu"d"kZ fudyrk gS fd lEiw.kZ Å"ek dks leku ek=kk ds dk;Z esa ifjofrZr
ugha fd;k tk ldrkA
7.* For an ideal gas, consider only P-V work in going from an initial state X to
the final state Z. The final state Z can be reached by either of the two paths
shown in the figure. Which of the following choice(s) is (are) correct? [take
S as change in entropy and w as work done].
[JEE 2012, 4/136]
(A*) Sxz =Sxy + Syz
(B) wxz = wxy + wyz
(C*) wxyz = wxy
(D) Sxyz =Sxy
7.* ,d vkn'kZ xSl ds fy,] vkjfEHkd voLFkk X ls vafre voLFkk Z rd tkus ds fy,
dsoy P-V dk;Z dk fopkj djsaA fp=k esa n'kkZ;s vuqlkj vafre voLFkk Z rd ig¡qpus
ds fy, nks iFk gSA fuEufyf[kr esa ls dkSulk@dkSuls fodYi lgh gS@gSaA (S dks
,UVªkWih ifjorZu vkSj w dks fd;k x;k dk;Z ekusa) [JEE 2012, 4/136]
(A*) Sxz =Sxy + Syz
(B) wxz = wxy + wyz
(C*) wxyz = wxy
(D) Sxyz =Sxy
ADVTDS - 22
Sol.
(A) Sxz = Sx–y + Syz (Correct) (lR;)

(B) W xy = W x–y + W yz (Incorrect) (vlR;)
(C) W xyz = W x–y (Correct) (lR;)
(D) Sxyz = Sx–y (Incorrect) (vlR;)
8. For the process, H2O()  H2O(g) at T = 100C and 1 atmosphere pressure, the correct choice is :
[JEE(Advanced) 2014, 3/120]
(A) Ssystem > 0 and Ssurroundings > 0 (B*) Ssystem > 0 and Ssurroundings < 0
(C) Ssystem < 0 and Ssurroundings > 0 (D) Ssystem < 0 and Ssurroundings < 0
rkieku T = 100C rFkk 1 ok;qeaMyh; nkc ij izØe H2O()  H2O(g) ds fy, lgh fodYi gS %
(A) Siz.kkyh > 0 vkSj Sifjos'k > 0 (B*) Siz.kkyh > 0 vkSj Sifjos'k < 0
(C) Siz.kkyh < 0 vkSj Sifjos'k > 0 (D) Siz.kkyh < 0 vkSj Sifjos'k < 0
Sol. For H2O()  H2O(g) at T = 100ºC, 1atm
equilibrium exists. G = 0, H – TS = 0
H = TS > 0 for system, since evaporation is endothermic
q
 (S)system > 0, also (S)surrounding = surr
Tsurr
Heat gained by system = heat lost by surroundings
 qsurr. < 0  (S)surr. < 0
gy T = 100º, 1 atm ij
H2O()  H2O(g) ds fy;s lkE; LFkkfir gksrk gS G = 0, H – TS = 0
rU=k ds fy, H = TS > 0, pwafd ok"iu Å"ek'kks"kh gksrk gSA
q
 (S)ra=k > 0, lkFk gh (S)ifjos'k = ifjos'k
Tifjos'k
ra=k }kjk izkIr Å"ek = ifjos'k }kjk âkflr Å"ek
 qifjos'k < 0  (S)ifjos'k < 0
9. Match the thermodynamic processes given under Column-I with the expressions given under Column-
II. [JEE(Advanced) 2015, 8/168]
Column-I Column-II
(A) Freezing of water at 273 K and 1 atm (P) q=0
Expansion of 1 mol of an ideal gas into a vacuum under isolated
(B) (Q) w=0
conditions
Mixing of equal volumes of two ideal gases at constant
(C) (R) Ssys < 0
temperature and pressure in an isolated container
Reversible heating of H2(g) at 1 atm from 300 K to 600 K,
(D) (S) U = 0
followed by reversible cooling to 300 K at 1 atm
(T) G = 0
ADVTDS - 23
dkWye-I esa fn;s x;s m"ekxfrd (thermodynamic) izØeksa dks dkWye-II esa fn;s x;s O;atdksa ls lqesfyr djsaA
dkWye-I dkWye II
(A) 273 K rFkk 1 atm ij ty dk fgehdj.k (P) q=0
(B) foyfxr (isolated) voLFkkvksa esa ,d eksy vkn'kZ xSl dk fuokZr esa izlj.k (Q) w=0
fLFkj rki rFkk nkc ij ,d foyfxr ik=k esa nks vkn'kZ xSlksa ds leku vk;ruksa dk
(C) (R) Ssys < 0
feJ.k
1 atm ij H2(g) dh 300 K ls 600 K rd mRØe.kh; (reversible) rkiu]
(D) (S) U = 0
rRi'pkr 1 atm ij 300 K rd mRØe.kh; 'khryu
(T) G = 0
Ans. (A-R,T); (B-P,Q,S); (C-P,Q,S); (D-P,Q,S,T)
Sol. (A) H2O( )  H2O(s) at 273 K. & 1 atm
H = – ve = q
 Ssys < 0,  G = 0.
w  0 (as water expands on freezing), U  0
w  0 (pwafd ty] teus ij izlfjr gksrk gSA) U  0
(B) Free expansion of ideal gas. q=0

vkn'kZ xSl dk eqDr izlkj w=0
U = 0
Ssys > 0
G < 0
(C) Mixing of equal volume of ideal gases at constant pressure & temp in an isolated container
,d foyfxr ik=k esa fu;r rki rFkk nkc ij] vkn'kZ xSlksa ds leku vk;ru dks feyk;k tkuk
q = 0, w = 0, U = 0, Ssys > 0, G < 0
(D) H2(g) 300 K 
Re versible
Heating,1atm
 600 K 
Re versible
Cooling,1atm
 300 K.
q = 0, w = 0, U = 0, G = 0, Ssys = 0
mRde.kh;
z mRde.kh;
z
(D) H2(g) 300 K 
xeZ djuk,1atm
 600 K 
B.Mk djuk,1atm
 300 K.
q = 0, w = 0, U = 0, G = 0, Ssys = 0
10. One mole of an ideal gas at 300 K in thermal contact with surroundings expands isothermally from 1.0 L
to 2.0 L against a constant pressure of 3.0 atm. In this process, the change in entropy of surroundings
(Ssurr) in JK–1 is : (1 L atm = 101.3 J) [JEE(Advanced) 2016, 3/124]
,d vkn'’kZ xSl dk ,d eksy 300 K ij ifjos'’k (surroundings) ds lkFk Å"”eh; lEidZ (thermal contact) esa
lerkih; voLFkk esa 3.0 atm ds fLFkj nkc ij 1.0 L ls 2.0 L rd izlkfjr gksrk gSA bl izfØ;k esa ifjos’'k dh ,UVªkW ih
esa ifjorZu (Ssurr) JK–1 ek=kd esa] D;k gksxk \ (1 L atm = 101.3 J) [JEE(Advanced) 2016, 3/124]
(A) 5.763 (B) 1.013 (C*) –1.013 (D) –5.763
qSurr qSys WSys
Sol. SSurr =   ( Isothermal process U = 0) ( lerkih; izØe U = 0)
T T T
Pext ( Vf  Vi)  3(2  1)
SSurr =   101.3 = –1.013 J/K
T 300
11.* For a reaction taking place in a container in equilibrium with its surroundings, the effect of temperature
on its equilibrium constant K in terms of change in entropy is described by
(A*) With increase in temperature, the value of K for endothermic reaction increases because
unfavourable change in entropy of the surroundings decreases
(B*) With increase in temperature, the value of K for exothermic reaction decreases because favourable
change in entropy of the surroundings decreases
(C) With increase in temperature, the value of K for endothermic reaction increases because the
entropy change of the system is negative
ADVTDS - 24
(D) With increase in temperature, the value of K for exothermic reaction decreases because the entropy
change of the system is positive
ifjos'k (surroundings) ds lkFk lkE;koLFkk esa ,d ik=k esa gks jgh ,d vfHkfØ;k ds fy,] ,UVªkih esa cnyko ds
vuqlkj blds lkE;koLFkk fLFkjkad K ij rkieku ds izHkko dk o.kZu ,sls fd;k tkrk gSA
(A*) rkieku c<+us ds lkFk] Å"ek'kks"kh (Endothermic) vfHkfØ;k ds lkE;koLFkk fLFkjkad K dk eku c<+rk gS D;ksafd
ifjos'k dh izfrdwy ,aVªksih esa cnyko ?kVrk gS
(B*) rkieku c<+us ds lkFk] Å"ek{ksih (Exothermic) vfHkfØ;k ds lkE;koLFkk fLFkjkad K dk eku ?kVrk gS D;ksafd
ifjos'k dh vuqdwy ,aVªksih esa cnyko ?kVrk gS
(C) rkieku c<+us ds lkFk] Å"ek'kks"kh (Endothermic) vfHkfØ;k ds lkE;koLFkk fLFkjkad K dk eku c<+rk gS D;ksafd
fudk; dh ,aVªksih esa cnyko _.kkRed gS
(D) rkieku c<+us ds lkFk] Å"ek{ksih (Exothermic) vfHkfØ;k ds lkE;koLFkk fLFkjkad K dk eku ?kVrk gS D;ksafd
fudk; dh ,aVªksih esa cnyko /kukRed gS
– H
Sol. SSurr =
TSurr
For endothermic, if Tsurr. increases, Ssurr will increases.
For exothermic, if Tsurr. increases, Ssurr. will decreases.
– H
gy % Sifjos'k =
Tifjos'k
Å"ek'kks"kh vfHkfØ;k ds fy,, ;fn Tifjos'k o`f) gksrh gS] rc Sifjos'k esa o`f) gksxhA
Å"ek{ksih vfHkfØ;k ds fy,, ;fn Tifjos'k o`f) gksrh gS] rc Sifjos'k esa deh gksxhA
12.* For a reaction, A P, the plots of [A] and [P] with time at temperature T 1 and T2 are given below.
vfHkfØ;k, A P ds fy,, [A] vkSj [P] ds le; ds lkFk rkieku T1 vkSj T2 ij vkys[k uhps fn, x, gSaA
10 10
T1
[P]/(mol L )
-1
[A]/(mol L )
T2
-1
5 5
T2
T1
Time Time
If T2 > T1, the correct statement(s) is (are)
(Assume H and S are independent of temperature and ratio of lnK at T1 to lnK at T2 is greater than
T2
. Here H, S, G and K are enthalpy, entropy, Gibbs energy and equilibrium constant, respectively.)
T1
;fn T2 > T1, rks lgh izdFku gS (gSa)
T2
(H vkSj S dks rkieku fuHkZjrk ls Lora=k ekfu;s vkSj T1 ij ln (K) rFkk T2 ij In (K) dk vuqikr T1
ls
vf/kd gSA ;gk¡ H, S, G vkSj K, Øe'k% ,UFkSYih] ,UVªkih] fxCt (Gibbs) ÅtkZ vkSj lkE;koLFkk fLFkjkad gSaA½
(A*) H < 0, S < 0 (B) G < 0, H > 0 (C*) G < 0, S < 0 (D) G < 0, S > 0
Sol. As temperature increases concentration of product decreases
so reaction is exothermic H° < 0
ADVTDS - 25
lnK T1
 1  lnK T1  lnK T2 so, K T1  K T2
lnK T2
ln K T1 T2
Also, 
ln K T2 T1
or T1 lnK T1  T2 lnK T2  R T1 lnK T1  R T2 lnK T2
or GT1  GT2
or H  T1S  H  T2S
As GT1  GT2 , since as temperature increases G increases this is possible only when S° < 0
Sol. tSls gh rki c<+rk gS rc mRikn dh lkUnzrk ?kVrh gSA
vr% vfHkfØ;k Å"ek{ksih gS H° < 0
lnK T1
 1  lnK T1  lnK T2 so, K T1  K T2
lnK T2
ln K T1 T2
lkFk gh, 
ln K T2 T1
;k T1 lnK T1  T2 lnK T2  R T1 lnK T1  R T2 lnK T2
;k GT1  GT2 ;k H  T1S  H  T2S
GT1  GT2 , pwafd tSls gh rki c<+rk gS G c<+rk gSA ;g dsoy rc lEHko gS tc S° < 0
13. The surface of copper gets tarnished by the formation of copper oxide. N2 gas was passed to prevent
the oxide formation during heating of copper at 1250 K. However, the N2 gas contains 1 mole % of
water vapour as impurity. The water vapour oxidises copper as per the reaction given below :
2Cu(s) + H2O(g)  Cu2O(s) + H2(g)
pH2 is the minimum partial pressure of H2 (in bar) needed to prevent the oxidation at 1250 K. The value
 
of ln pH2 is_______.
(Given: total pressure = 1 bar, R (universal gas constant) = 8 J K –1 mol–1, ln(10) = 2.3, Cu(s) and
Cu2O(s) are mutually immiscible.
1
At 1250 K : 2Cu(s) + O2(g) Cu2O(s) ; G° = –78,000 J mol–1
2
1
H2(g) + O2(g)  H2O(g) ; G° = –1,78,000 J mol–1; G is the Gibbs energy)
2
dkWij dk i`"B] dkWij vkWDlkbM ds cuus ls efyu gksrk gSA dkWij dks 1250 K ij xje djrs le; vkWDlkbM cuus
ls jksdus ds fy, ukbVªkstu xSl dk izokg fd;k x;kA fdUrq ukbVªkstu xSl esa 1 eksy % ty ok"i dk viæO; gSA
tyok"i dkWij dk uhps fn, x, vfHkfØ;k ds vuqlkj vkWDlhdj.k djrk gS %
2Cu(s) + H2O(g) Cu2O(s) + H2(g)
1250 K ij vkWDlhdj.k jksdus ds fy, H2 dk U;wure vkaf'kd nkc (bar esa) pH2 pkfg,A
 
In pH2 dk eku _______ gSA
(fn;k x;k gS] iw.kZ nkc = 1 bar, R (lkoZtfud xSl fu;rkad) = 8 J K–1 mol–1, ln(10) = 2.3, Cu(s) vkSj Cu2O(s)
ijLij vfeJ.kh; gSA
1
1250 K ij : 2Cu(s) + O2(g) Cu2O(s) ; G° = –78,000 J mol–1
2
1
H2(g) + O2(g)  H2O(g) ; G° = –1,78,000 J mol–1; G fxCt mtkZ gSA)
2
ADVTDS - 26
Ans. –14.6
1
Sol. (i) 2Cu(s) + O2(g)  Cu2O(s) : Gº = –78000 J/mol
2
1
(ii) H2(g) + O2 (g)  H2O(g), Gº = –178000 J/mol
2
(i) – (ii) then
2Cu(s) + H2O (g)  Cu2O(s) + H2(g)
Gº = –78000 + 178000 = 100000 J/mol
Now for the above reaction
 P 
G = Gº + RT n  H2 
 PH O 
 2 
To prevent the above reaction :
G  0
 P 
Gº + RT n  H2   0
 PH O 
 2 
104( nPH2  nPH2O ) –105
nPH2 – 10 + nPH2O
– 10 + 2.3 log(0.01)
nPH2 – 10 + 4.6
nPH2 – 14.6
 Minimum nPH2 = –14.6
1
Sol. (i) 2Cu(s) + O2(g)  Cu2O(s) : Gº = –78000 J/mol
2
1
(ii) H2(g) + O2 (g)  H2O(g), Gº = –178000 J/mol
2
(i) – (ii) rc
2Cu(s) + H2O (g)  Cu2O(s) + H2(g)
Gº = –78000 + 178000 = 100000 J/mol
vc mijksDr vfHkfØ;k ds fy,
 PH 
G = Gº + RT n  2

 PH O 
 2 
mijksDr vfHkfØ;k dks jksdus ds fy,
G  0
 PH 
Gº + RT n  2
 0
 PH O 
 2 
104( nPH2  nPH2O ) –105
nPH2 – 10 + nPH2O
– 10 + 2.3 log(0.01)
nPH2 – 10 + 4.6
nPH2 – 14.6
 U;wure nPH2 = –14.6
ADVTDS - 27
PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)
Hkkx - II : JEE (MAIN) / AIEEE ¼fiNys o"kksZ½ ds iz'u
JEE-MAIN OFFLINE PROBLEMS
1. Identify the correct statement regarding a spontaneous process : [AIEEE 2007, 3/120]
(1) Exothermic processes are always spontaneous.
(2) Lowering of energy in the reaction process is the only criterion for spontaneity.
(3*) For a spontaneous process in an isolated system, the change in entropy is positive.
(4) Endothermic processes are never spotaneous.
,d Lor% izØe ds fy, lR; dFku gS % [AIEEE 2007, 3/120]
(1) Å"ek{ksih izØe lnSo Lor% gksrs gaSA
(2) Lor% izØe ds fy, vfHkfØ;k esa ÅtkZ dk de gksuk gh dsoy ,d dlkSVh gSA
(3*) ,d foyfxr fudk; esa Lor% izØe ds fy, ,UVªkWih esa ifjorZu /kukRed gksrk gSA
(4) Å"ek'kks"kh izØe lnSo Lor% ugha gksrs gaSA
Sol. In an isolated system, there is no exchange of energy or matter between the system and surrounding.
For a spontaneous process in an isolated system, the change in entropy is positive, i.e. S > 0.
Most of the spontaneous chemical reactions are exothermic. A number of endothermic reaction are
spontaneous e.g melting of ice (an endothermic process) is a spontaneous reaction.
The two factors which are responsible for the spontaneity of process are
(i) tendency to acquire minimum energy
(ii) tendency to acquire maximum randomness.
Sol. fdlh foyfxr fudk; esa] fudk; o ifjos'k ds chp ÅtkZ ;k inkFkZ dk fofue; ugh gksrk gSA foyfxr fudk; esa ,d
Lor% izØe ds fy;s] ,UVªkWih esa ifjorZu /kukRed gksrk gS vFkkZr~ S > 0.
vf/kdrj Lor% jklk;fud vfHkfØ;k,a Å"ek{ksih gksrh gSa ysfdu dqN Å"ek'kks"kh vfHkfØ;k,a Hkh Lor% gksrh gSa tSls dh
cQZ dk fi?kyuk ¼,d m"ek'kks"kh izØe½ ,d Lor% vfHkfØ;k gSA
izØe dh Lorrk% ds fy;s nks dkjd mRrjnk;h gSa
(i) U;wure ÅtkZ izkIr djus dh izo`fr
(ii) vf/kdre ;kn`fPNdrk izkIr djus dh izo`fr
2. In conversion of lime-stone to lime, CaCO3(s) CaO(s) + CO2(g) the values of Hº and Sº are +
179.1 kJ mol–1 and 160.2 J/K respectively at 298 K and 1 bar. Assuming that H° and S° do not
change with temperature, temperature above which conversion of limestone to lime will be spontaneous
is : [AIEEE 2007, 3/120]
pwuk&iRFkj dk pwus esa ifjorZu CaCO3(s) CaO(s) + CO2(g) gSA 298 K rki o 1 ckj nkc ij Hº o Sº dk
eku Øe'k% + 179.1 fdykstwy eksy–1 rFkk 160.2 twy@dsfYou gSA ;g ekudj fd rki ds lkFk H° o S° ugha
cnyrs] fdl rki ls Åij tkus ij pwuk&iRFkj dk pwus esa ifjorZu Lor% gksxkA
(1) 845 K (2*) 1118 K (3) 1008 (4) 1200 K
for a spontaneous process Go < 0
Ho 179.1 1000
  Ho – TSo < 0  TSo > Ho  T > T >  T > 1117.9 K  1118 K.
S o
160.2
Lor% izØe ds fy, Go < 0
Ho 179.1 1000
 Ho – TSo < 0  TSo > Ho  T >  T>  T > 1117.9 K  1118 K.
S o
160.2
ADVTDS - 28
3. Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1, respectively. [AIEEE 2008, 3/105]
1 3
For the reaction, X2 + Y2  XY3 H = –30 kJ. To be at equilibrium the temperature will be :
2 2
1 3
X2, Y2 rFkk XY3 dh ekud ,UVªkWih Øe'k% 60, 40 rFkk 50 JK–1 mol–1 gSaA vfHkfØ;k X2 + Y2  XY3 ds fy;s
2 2
H = –30 kJ gSA lkE; ij rki gksxk % [AIEEE 2008, 3/105]
(1) 500 K (2*) 750 K (3) 1000 K (4) 1250 K
1 3
Sol. S° reaction = 50 – (60) – (40) = –40 JK–1
2 2
For reaction to be at equilibrium
G = 0
H 30000
H – TS = 0  T = = = 750 K
S 40
1 3
Sol. S° vfHkfØ;k = 50 – (60) – (40) = –40 JK–1
2 2
lkE; ij vfHkfØ;k gksus ds fy;s
G = 0
H 30000
H – TS = 0  T = = = 750 K
S 40
4. For a particular reversible reaction at temperature T, H and S were found to be both +ve. If Te is the
temperature at equilibrium, the reaction would be spontaneous when. [AIEEE 2010, 4/144]
(1) Te > T (2*) T > Te (3) Te is 5 times T (4) T = Te
rki T ij ,d fof'k"V mRØe.kh; vfHkfØ;k ds fy, H vkSj S nksuksa /kukRed ik, x,A ;fn lkE; ij rki Te ik;k
tkrk gS] rks vfHkfØ;k rc Lor% gksxh tc [AIEEE 2010, 4/144]
(1) Te > T (2*) T > Te (3) Te, T dk 5 xquk gS (4) T = Te
Sol. G = H – TS
For spontaneous reaction G must be negative
At equilibrium temperature G = 0
to maintain the negative value of G
T should be greater than Te.
gy % G = H – TS
Lor% vfHkfØ;k ds fy, G _.kkRed gksuk pkfg,
lkE; rki ij G = 0
G ds _.kkRed eku dks cuk;s j[kus ds fy, T dk eku Te dh rqyuk esa vf/kd gksuk vko';d gSA
5. The entropy change involved in the isothermal reversible expansion of 2 moles of an ideal gas from a
volume of 10 dm3 to a volume of 100 dm 3 at 27°C is : [AIEEE 2011, 4/120]
27°C ij] vkn'kZ xsl ds 2 eksy dk lerkih; mRØe.kh; izlkj 10 dm3 vk;ru ls 100 dm3 vk;ru rd gksrk gS]
izØe esa ,UVªkih ifjorZu gksxk % [AIEEE 2011, 4/120]
(1*) 38.3 J mol–1 K–1 (2) 35.8 J mol–1 K–1 (3) 32.3 J mol–1 K–1 (4) 42.3 J mol–1 K–1
V V 100
Sol. S = nR ln 2 = 2.303 nR log 2 = 2.303 × 2 × 8.314 × log = 38.3 J mol–1 K–1
V1 V1 10
6. In view of the signs of rGº for the following reactions :

PbO2 + Pb  2PbO, rGº < 0
SnO2 + Sn  2SnO, rGº > 0,
which oxidation states are more characteristics for lead and tin ? [AIEEE 2011, 4/120]
(1) For lead +2, for tin +2 (2) For lead +4, for tin +4
(3*) For lead +2, for tin +4 (4) For lead +4, for tin +2
PbO2 + Pb  2PbO, rGº < 0
SnO2 + Sn  2SnO, rGº > 0,
ADVTDS - 29
mijksDr vfHkfØ;kvksa esa rGº ds ekuksa dks /;ku esa j[krs gq, Kkr dhft, fd ysM vkSj fVu ds fy;s dkSulh
vkWDlhdj.k voLFkk,a vf/kd vfHkyk{kf.kd gSa\ [AIEEE 2011, 4/120]
(1) ysM ds fy, +2, fVu ds fy, +2 (2) ysM ds fy, +4, fVu ds fy, +4
(3*) ysM ds fy, +2, fVu ds fy, +4 (4) ysM ds fy, +4, fVu ds fy, +2
Sol. Negative rGº value indicates that +2 oxidation state is more stable for Pb2+. Also it is supported by inert
pair effect that +2 oxidation state is more stable for Pb and +4 oxidation state is more stable for Sn.
Sol. rGº, dk _.kkRed eku n'kkZrk gS fd Pb2+ ds fy, +2 vkWDlhdj.k voLFkk vf/kd LFkk;h gSA lkFk gh vfØ; ;qXe
izHkko }kjk Hkh ;g le>k;k tk ldrk gS fd] Pb ds fy,] +2 vkWDlhdj.k voLFkk vf/kd LFkk;h gS] rFkk Sn ds fy,]
+4 vkWDlhdj.k voLFkk vf/kd LFkk;h gSA
7. The incorrect expression among the following is : [AIEEE 2012, 4/120]
Gsystem V
(1) =–T (2) In isothermal process, wreversible = –nRT ln f
S total Vi
Hº TSº
(3*) lnK = (4) K = e–Gº/RT
RT
fuEu esa ls xyr O;atd gS : [AIEEE 2012, 4/120]
Gsystem Vf
(1) =–T (2) lerkih izØe esa, wmRØe.kh; = –nRT n
S total Vi
Hº TSº
(4*) lnK = (4) K = e–Gº/RT
RT
–RTlnK = Hº – TSº
Hº TSº
lnK = –
RT
8. The following reaction is performed at 298 K.
2NO(g) + O2(g) 2NO2(g)
The standard free energy of formation of NO(g) is 86.6 kJ/mol at 298 K. What is the standard free
energy of formation of NO2(g) at 298 K ? (KP = 1.6 × 1012) [JEE(Main) 2015, 4/120]
fuEufyf[kr vfHkfØ;k dks 298 K ij fd;k x;kA
2NO(g) + O2(g) 2NO2(g)
298 K ij NO(g) ds laHkou dh ekud eqDr ÅtkZ 86.6 kJ/mol gSA 298 K ij NO2(g) dh ekud eqDr ÅtkZ D;k
gS\ (KP = 1.6 × 1012) [JEE(Main) 2015, 4/120]
(1) R(298) in (1.6 × 10 ) – 86600
12
(2) 86600 + R(298) ln (1.6 x 1012)
ln (1.6  10 )
12
(3) 86600 – (4*) 0.5 [2 × 86,600 – R (298) ln (1.6 × 1012)]
R (298)
Sol. 2Gºf (NO2) – [2Gºf (NO) + Gºf (O2)] = Gºr = – RTn Kp
2Gºf (NO2) – [2 × 86,600 + 0] = – RTn Kp
Gºf (NO2) = 0.5[2 × 86,600 – R (298) n(1.6 × 1012)]
9. The combustion of benzene (I) gives CO2(g) and H2O(l). Given that heat of combustion of benzene at
constant volume is –3263.9 kJ mol–1 at 25ºC; heat of combustion (in kJ mol –1) of benzene at constant
pressure will be : (R = 8.314 JK–1 mol–1) [JEE(Main) 2018, 4/120]
csathu ds ngu djus ij CO2(g) rFkk H2O(l) izkIr gksrh gSA fLFkj vk;ru ij csathu (I) dh ngu Å"ek 25ºC ij
–3263.9 kJ mol–1 gSA fLFkj nkc ij csathu dh ngu Å"ek (kJ mol–1 esa) dk eku gksxk %
(R = 8.314 JK–1 mol–1) [JEE(Main) 2018, 4/120]
(1) 3260 (2*) –3267.6 (3) 4152.6 (4) –452.46
Sol. C6H6(liq) + 7.5 O2(g) 6CO2(g) + 3H2O(liq) ; n(g) = 6 – 7.5 = –1.5
1.5  8.314  298
H = E + n(g) RT ; H = –3263.9kJ – kJ = –3267.6 kJ
1000
ADVTDS - 30
JEE-MAIN ONLINE PROBLEMS
1. The molar heat capacity (Cp) of CD2O is 10 cals at 1000 K. The change in entropy associated with
cooling of 32 g of CD2O vapour from 1000 K to 100 K at constant pressure will be : (D = deuterium, at.
mass = 2 u) [JEE(Main) 2014 Online (11-04-14), 4/120]
CD2O dh eksyj Å"ek /kkfjrk (Cp) 1000 K ij 10 cals gSA 32 xzke CD2O ok"i dks 1000 K ls 100 K rd fLFkj
nkc ij B.Mk djus ij lEc) ,sUVªkWih ifjorZu gksxk % (D = fM;qVhfj;e vkSj bldk ijek.kq nzO;eku = 2 ek=kd)
[JEE(Main) 2014 Online (11-04-14), 4/120]
(1) 23.03 cal deg–1 (2*) – 23.03 cal deg–1 (3) 2.303 cal deg–1 (4) – 2.303 cal deg–1
2. Then entropy (Sº) of the following substances are :
CH4(g) 186.2 JK–1 mol–1, O2(g) 205.0 JK–1 mol–1
CO2(g) 213.6 JK–1 mol–1, H2O() 69.9 JK–1 mol–1
The entropy change (Sº) for the reaction CH4(g) + 2O2(g)  CO2(g) + 2H2O() is :
[JEE(Main) 2014 Online (12-04-14), 4/120]
(1) –312.5 JK–1 mol–1 (2*) –242.3 JK–1 mol–1 (3) –108.1 JK–1 mol–1 (4) –37.6 JK–1 mol–1
fuEu inkFkksZ ds ,sUVªkih eku gS (Sº) gSa %
CH4(g) 186.2 JK–1 eksy–1, O2(g) 205.0 JK–1 eksy–1
CO2(g) 213.6 JK–1 eksy–1, H2O() 69.9 JK–1 eksy–1
vfHkfØ;k CH4(g) + 2O2(g)  CO2(g) + 2H2O() ds fy;s ,sUVªkWih ifjorZu (Sº) dk eku gksxk %
[JEE(Main) 2014 Online (12-04-14), 4/120]
(1) –312.5 JK–1 eksy–1 (2*) –242.3 JK–1 eksy–1 (3) –108.1 JK–1 eksy–1 (4) –37.6 JK–1 eksy–1
3. For the reaction, A(g) + B(g)  C(g) + D(g), Hº and Sº are, respectively, –29.8 kJ mol–1 and –0.100
kJ K–1 mol–1 at 298 K. The equilibrium constant for the reaction at 298 K is:
[JEE(Main) 2016 Online (09-04-16), 4/120]
jklk;fud vfHkfØ;k, A(g) + B(g)  C(g) + D(g), ds fy, 298 K ij Hº rFkk Sº ds eku Øe'k% –29.8 kJ mol–
1
rFkk –0.100 kJ K–1 mol–1 gSaA bl vfHkfØ;k dk 298 K ij lkE; fLFkjkad gS%:
[JEE(Main) 2016 Online (09-04-16), 4/120]
(1*) 1 (2) 10 (3) 1.0 × 10–10 (4) 1.0 × 1010
Sol.  Gº = Hº – T.Sº = –29.8 + 298 × (0.1) = –29.8 + 29.8
 Gº = 0
apply relation between Gº & Keq
Gº rFkk Keq ds e/; lEcU/k ykxw djus ij
 Gº = –RT n Keq
 Keq = 1
4. A reaction at 1 bar is non-spontaneous at low temperature but becomes spontaneous at high
temperature. Identify the correct statement about the reaction among the following:
[JEE(Main) 2016 Online (09-04-16), 4/120]
(1*) Both H and S are positive. (2) H is negative while S is positive.
(3) H is positive while S is negative. (4) Both H and S are negative.
,d jklk;fud vfHkfØ;k fuEu rki ij vLor% izofrZr gS fdUrq mPp rki ij Lor% izofrZr gks tkrh gSA bl vfHkfØ;k
ds ckjs esa fuEufyf[kr dFkuksa esa ls lgh dFku dks igpkfu;s % [JEE(Main) 2016 Online (09-04-16), 4/120]
(1*) H rFkk S, nksuksa /kukRed gSA (2) H _.kkRed rFkk S /kukRed gSA
(3) H /kukRed rFkk S _.kkRed gSA (4) H rFkk S, nksuksa _.kkRed gSA
Sol. G = H – T.S
If H & S are both positive, then G may be negative at high temperature hence reaction becomes
spontaneous at high temperature.
;fn H rFkk S nksuksa /kukRed gks] rFkk mPp rki ij G _.kkRed gks ldrk gSA vr% vfHkfØ;k mPp rki ij
Lor% gksxhA
ADVTDS - 31
5. fG° at 500 K for substance 'S' in liquid state and gaseous state are +100.7 kcal mol –1 and +103 kcal
mol–1, respectively. Vapour pressure of liquid 'S' at 500 K is approximately equal to :
(R = 2 cal K–1 mol–1) [JEE(Main) 2018 Online (15-04-18), 4/120]
 inkFkZ 'S' ds fy;s] nzo voLFkk rFkk xSlh; voLFkk esa] fG° dk eku 500 K ij Øe'k% +100.7 kcal mol–1 rFkk +103
kcal mol–1 gSaA 500 K ij nzo 'S' dk ok"i nkc yxHkx fuEu ds cjkcj gksxk % (R = 2 cal K–1 mol–1)
[JEE(Main) 2018 Online (15-04-18), 4/120]
(1*) 0.1 atm (2) 1 atm (3) 10 (4) 100 atm
Sol. Sliq Svap
Gvap = Gfp – fGR = 103 kcal – 100.7 kcal
Gvap = 2.3 kcal = – RT In kp = – 2.303 RT log10 KP
2.3 × 1000 = –2.303 × 2 × 500 log10 KP
log kP = – 1
kP = 10–1
kP = vapour pressure = 0.1 atm.
kP = ok"inkc = 0.1 atm.
6. Given
fn;k x;k gS]
(i) 2Fe2O3(s)  4Fe(s) + 3O2(g) ; r G° = + 1487.0 kJ mol–1
(ii) 2CO(g) + O2(g)  2CO2(g) ; rG° = –514.4 kJ mol–1
Free energy change, r G° for the reaction 2Fe2O3(s) + 6CO(g)  4Fe(s) + 6CO2(g) will be
vfHkfØ;k 2Fe2O3(s) + 6CO(g)  4Fe(s) + 6CO2(g) ds fy, eqDr ÅtkZ ifjorZu, rG° gksxk%
[JEE(Main) 2018 Online (15-04-18), 4/120]
(1) –112.4 kJ mol–1 (2*) –56.2 kJ mol–1 (3) –168.2 kJ mol–1 (4) –208.0 kJ mol–1
Sol. Final Reaction = reaction (i) + 3 × reaction (ii)
 vfUre vfHkfØ;k = vfHkfØ;k (i) + 3 × vfHkfØ;k (ii)
Gr° = 1487 kg + 3 × (–514.4kg)
= 1487 kg – 1543.2 kg = – 56.2 kg/mol
7. For which of the following processes, S is negative ? [JEE(Main) 2018 Online (16-04-18), 4/120]
(1) C(diamond)  C(graphite) (2*) N2(g, 1 atm)  N2(g, 5 atm)
(3) N2(g, 273 K)  N2(g, 300 K) (4) H2(g)  2H(g)
fuEu izØeksa esa ls fdlesa S _.kkRed gS \ [JEE(Main) 2018 Online (16-04-18), 4/120]
(1) C(ghjk)  C( xzsQkbV) (2*) N2(g, 1 atm)  N2(g, 5 atm)
(3) N2(g, 273 K)  N2(g, 300 K) (4) H2(g)  2H(g)
Sol. N2 (g, 1 atm)  N2 (g, 5 atm)
 T  V
S =  nCp ln 2  + nR ln 2
 T1  V1
V2 P
for isothermal process ¼lerkih; izØe ds fy,½ T1 = T2 and ¼rFkk½ = 1
V1 P2
P1 1
= 0 + nR ln = nR ln
P2 5
S < 0
8. The entropy change associated with the conversion of 1 kg of ice at 273 K to water vapours at 383 K is:
(Specific heat of water liquid and water vapour are 4.2 kJ K–1kg–1 and 2.0 kJ K–1 kg–1; heat of liquid
fusion and vapourisation of water are 334 kJ kg–1 and 2491 kJ kg–1, respectively). (log 273 = 2.436, log
373 = 2.572, log 383 = 2.583) [JEE(Main) 2019 Online (09-01-19), 4/120]
ADVTDS - 32
273 K ij 1 kg cQZ dks 383 K ds ty Hkki es cnyus ij ,aVªkih es ifjorZu gksxk% ¼ty rFkk Hkki dh fof'k"V Å"ek
Øe'k% 4.2 kJ K–1kg–1 ,oa 2491 kJ kg–1 gSa( laxyu dh Å"ek rFkk ikuh dh ok"ihdj.k Å"ek Øe'k% 334 kJ kg–1 ,oa
2491 kJ kg–1 gS½ (log 273 = 2.436, log 373 = 2.572, log 383 = 2.583)
[JEE(Main) 2019 Online (09-01-19), 4/120]
(1) 8.49 kJ kg–1 K–1 (2*) 9.26 kJ kg–1 K–1 (3) 2.64 kJ kg–1 K–1 (4) 7.90 kJ kg–1 K–1
334 373 2491 383
Sol. S = +4.2 ln + +2ln
273 273 373 373
= 1.2234 + 2.303 × 4.2 (2.572 – 2.436) + 6.678 + 2×2.303 (2.583 – 2.572)
= 7.9014 + 1.315 + 0.05 = 9.267 KJkg–1K–1.
9. A process has H = 200 J mol–1 and S = 40 JK–1 mol–1. Out of the values given below, choose the
minimum temperature above which the process will be spontaneous :
[JEE(Main) 2019 Online (10-01-19), 4/120]
,d izØe esa H = 200 J mol–1 rFkk S = 40 JK–1 mol–1 gSA uhps fn;s x;s vk¡dM+ksa esa ls ml fuEure rki dk
pquko dfj;s ftlds Åij izØe Lor% gksxk& [JEE(Main) 2019 Online (10-01-19), 4/120]
(1*) 5 K (2) 12 K (3) 4 K (4) 20 K
Sol. G = H – TS = 0
H 200
T= = = 5 K.
S 40
10. The process with negative entropy change is: [JEE(Main) 2019 Online (10-01-19), 4/120]
(1) Sublimation of dry ice
(2) Dissolution of iodine in water
(3) Dissociation of CaSO4(s) to CaO(s) and SO3(g)
(4*) Synthesis of ammonia from N2 and H2
_.kkRed ,UVªkih ifjorZu okyk izØe gS: [JEE(Main) 2019 Online (10-01-19), 4/120]
(1) 'kq"d cQZ dk Å/oZikru (2) vk;ksMhu dk ty esa foy;u
(3) CaSO4(s) dk CaO(s) rFkk SO3(g) esa fo;kstu (4*) N2 rFkk H2 ls veksfu;k dk la'ys"k.k
Sol. CO2 (s)  CO2 (g) ; S = +ve
N2 + 3H2  2NH3 ; S = –ve
CaSO4  CaO + SO3 ; S = +ve
dissolution of I2 I2 dk fo;kstu ; S = +ve
11. Two blocks of the same metal having same mass and at temperature T 1 and T2, respectively, are
brought in contact with each other and allowed to attain thermal equilibrium at constant pressure. The
change in entropy, S, for this process is: [JEE(Main) 2019 Online (11-01-19), 4/120]
,d gh /kkrq ds leku lagfr okys nks Cykdksa dks Øe'k% rki T1 rFkk T2 ij ijLij ,d nwljs ds lEidZ esa yk;k x;k
fu;r nkc ij Å"eh; lkE; izkIr djus fn;k x;kA bl izØe esa ,UVªkih ifjorZu S gS %
[JEE(Main) 2019 Online (11-01-19), 4/120]
 1 
 T1  T2   (T1  T2 ) 2 
(1) 2CP In   (2) 2CP In  
 4T1T2   T1T2 
 
 (T  T2 ) 2
 T  T2 
(3*) CP In  1  (4) 2CP In  1 
 4T1T2   2T1T2 
ADVTDS - 33
T1  T2
Sol. TFinal =
2
T 
SI  CP n  f 
 T1 
T 
SII  CP n  f 
 T2 
S  SI  SII
  T  T 2 
 1 2

 T  2  
2
= CP n  f   CP 
n 
 T1T2  T1T2 
   
 
12. For the chemical reaction X Y, the standard reaction Gibbs energy depends on temperature T (in
3
K) as rG°(in kJ mol–1) = 120 – T . The major component of the reaction mixture at T is :
8
[JEE(Main) 2019 Online (11-01-19), 4/120]
(1) Y is T = 280 K (2) Y is T = 300 K (3*) X if T = 315 K (4) X if T = 350 K
jklk;fud vfHkfØ;k X Y ds fy,] ekud vfHkfØ;k fxCl ÅtkZ rki (K esa) ij fuEufyf[kr dh rjg vkfJr
3
gksrh gS% rG°(kJ mol–1 esa) = 120 – T
8
vfHkfØ;k feJ.k dk eq[; la?kVd T ij gS % [JEE(Main) 2019 Online (11-01-19), 4/120]
(1) Y ;fn T = 280 K (2) Y ;fn T = 300 K (3*) X ;fn T = 315 K (4) X ;fn T = 350 K
3
Sol. At 315 K G° = 120 –  315
8
Gº = 1.875
Amount of Y will be greater than its equilibrium amount at 315 K.
Y dh ek=kk] bldh lkE; ek=kk ls vf/kd gSA
13. The standard reaction Gibbs energuy for a chemical reaction at an absolute temperature T is given by
G° = A – BT, where A and B are non-zero constants. Which of the following is TRUE about this
reaction ? [JEE(Main) 2019 Online (11-01-19), 4/120]
(1*) Endothermic if A > 0 (2) Exothermic if B < 0
(3) Exothermic if A > 0 and B < 0 (4) Endothermic if A < 0 and B > 0
ije rki T ij ,d jkl;fud vfHkfØ;k ds fy, ekud vfHkfØ;k fxCt ÅtkZ fuEu ds }kjk vfHkO;Dr dh tkrh gS
G° = A – BT, tgk¡ A rFkk B 'kwU; u gksus okys fLFkjkad gSA bl vfHkfØ;k ds fy, fuEu esa ls dkSu&lk lR; gS \
[JEE(Main) 2019 Online (11-01-19), 4/120]
(1*) Å"ek'kks"kh ;fn A > 0 (2) Å"ek{ksih ;fn B < 0
(3) Å"ek{ksih ;fn A > 0 rFkk B < 0 (4) Å"ek'kks"kh ;fn A < 0 rFkk B > 0
Sol. G = A – BT
= H – TS
A = H
H = A = +ve endothermic Å"ek'kks"kh
14. For the equilibrium 2H2O H3O+ + OH–, the value of G° at 298 K is approximately :
[JEE(Main) 2019 Online (11-01-19), 4/120]
2H2O H3O+ + OH– lkE; ds fy,] 298 K ij G° dk eku yxHkx gS %
[JEE(Main) 2019 Online (11-01-19), 4/120]
(1*) 80 kJ mol–1 (2) –100 kJ mol–1 (3) –80 kJ mol–1 (4) 100 kJ mol–1
ADVTDS - 34
Sol. G° = – 2.303 RT log K
= – 2.303 × 8.314 × 298 log (10–14)
kJ
= + 80
mol
15. The reaction, MgO(s) + C(s)  Mg(s) + CO(g), for which rH° = +491.1 kJ mol–1 and rS° = 198.0 JK–1
mol–1, is not feasible at 298 K. Temperature above which reaction will be feasible is:
[JEE(Main) 2019 Online (11-01-19), 4/120]
vfHkfØ;k] MgO(s) + C(s)  Mg(s) + CO(g), ftldk rH° = +491.1 kJ mol–1 rFkk rS° = 198.0 JK–1 mol–1 gS]
298 K ij lEHko ugha gSA og rki ftlds Åij vfHkfØ;k lEHko gksxh] gS %
[JEE(Main) 2019 Online (11-01-19), 4/120]
(1) 2380.5 K (2) 1890.0 K (3) 2040.5 K (4*) 2480.3 K
Sol. H–TS < O
H
T>
S
491.1 1000
T>
198
T > 2480.3 K
ADVTDS - 35

Thermodynamics IInd Law ResoSir With Ans GJGBSBL

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Thermodynamics IInd Law ResoSir With Ans GJGBSBL

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Thermodynamics & Thermochemistry

THERMODYNAMICS IInd & IIIrd LAW

PART - I : SUBJECTIVE QUESTIONS

B-2. Calculate standard entropy change in the reaction

PART - II : ONLY ONE OPTION CORRECT TYPE

A-5. For the gas - phase decomposition, PCl5(g) PCl3(g) + Cl2(g) :

Section (C) : Free energy

C-3.^ When reaction in standard state is at equilibrium, then :

C-5. A reaction has H = – 33 kJ and S = – 58 J/K. This reaction would be :

PART - III : MATCH THE COLUMN

1. Match the column:

PART - I : ONLY ONE OPTION CORRECT TYPE

Section (B) : Entropy Calculation

3.^ Third law of thermodynamics states that :

Section (C) : Free energy

PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

Sol. fn;k x;k gS : Keq = 10

2.^ For the reaction at 298 K

2. When a liquid solidifies, generally, there is :

3. Which of the following is false about molar entropy ?

4. Which of the following statements is/are correct

6. For isothermal expansion in case of an ideal gas :

PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)

S(A  C) = 50 ; S(C  D) = 30; S(B D) = + 20

S(A  C) = 50 ; S(C  D) = 30; S(B  D) = + 20

2.^ N2 + 3H2 2 NH3 K = 4 × 106 at 298

N2 + 3H2 2 NH3 298 ij K = 4 × 106

298 = 5705) [JEE 2007, 3/162]

(A) Sxz = Sx–y + Syz (Correct) (lR;)

(B) Free expansion of ideal gas. q=0

6. In view of the signs of rGº for the following reactions :

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