) '

7. The reaction of cyanamide, NH2CN(s) with oxygen was

run in a bomb calorimeter and AU was found to be- 742.24

First Law .and Basic Fundamentals

\ kJ mol- 1• The magnitude of A8i98 for the reaction

of Thermodynamics . NHzCN(s)+ io2 (g) Nz (g)+ CO2 (g) + HzO(l)

2
1
I. 200 mL of0:2 M HCl is mixed with 300 mL of0.l M NaOH. is -- · kJ. (Rounded off to the nearest integer)
The molar heat ofneutralization of this reaction is-57.1 kJ. [Assume ideal gases and R = 8.314 J mo1- 1 K- 11
The increase in temperature in °C of the system on mixing [NV, Feb. 25, 2021 (1)1
isx x 10-2• , S. Five moles of an ideal gas at 1 bar and 298 K is expanded
The value ofx is _ _ _ . (Nearest integer) into vacuum to double the volume. The work done is :
[Given: Specific heat of water= 4.18 J g- 1 K- 1 - (Sep. 04, 2020 (U))
Density of water= 1.00 g cni-3] (a) Cv(T2 -T 1) (b) -:--RT (V2 -V 1)
(Assume no volume change on mixing) (c) -RTln V1N 1 ~,(d) zero
1
[NV,Aug. 27, 2021 (I)] 9. The magnitude of work done by a gas that undergoes a
2. For water~ H= 41 kJ mol- 1 at 373 Kand 1 bar pressure. rev.ersibl.e+xpansion along the path ABC shown in the
Assuming that water vapour is an ideal gas that occupies figure i s _ _ _ [NV, Jan. 08, 2020 (1)1
a much larger volume than liquid water, the internal energy
change during evaporation-of water is_ ·_' _kJ mo1- 1 Pressure
(Pa)
.[Use: R= 8.3 Jmo1- 1 K- 1] 1-NV,Aug. 26, 2021 (II)] 10
3. For water at 100°C and l bar, A B
Avap H-A U= ____ x 10 2 Jmol- 1• • 8

(Round off to the Nearest Integer) 6 &'1 )

[Use : R= 8.31 J mo1- 1 K- 11
[Assume volume ofHiO(l) is much smaller than volume 4
of HiO(g). Assume HiO(g) treated as an ideal gas] C
. · . [NV,July27,2021 (l)] (2, 2)
-t A system does 200) of work and at the same tiroe-al:>sorbs 4 6 8 10 12 Volume
(ml)
150 J of.heat. The magnitude of the change in internal energy
fs : ,v\ J. (Nearest integer) [NV,J uly 25, 2021 (11)1 10. At constant volume, 4 mol of an ideal gas when heated
5. If the standard molar enthalpy change for combustion of from 300 K to 500 K changes its internal energy by 5000 J.
graphite powder is -2.48 x 10 2 kJ mo1- 1, the amount of The molar heat capacity at constant volume is 1 '-
heat generated on combustion of 1 g of graphite powder\ [NV, Jan. 08, 2020 (II))
is _ _ _ kJ. (NearestintegQ") [NV, July 22, 2021 (11)1 11. An ideal gas is allowed to expand from 1 L to l0Lagainst ·
6. At i 5°C, 50 g of iron reacts with HCl to form FeC12. The .__/ n a constant external pressure of 1 bar. The work done in kJ
evolved hydrogen gas expands against a constant is: !April 12, 2019 (1)1
-' pressure of 1 bar. Th~ 1
work done by the gas during this (a) -9.0 (b) + 10.0 (c) -0.9 (d) -2.0
expansion is '' J. ' 12. Among the following, the set of parameters that represents
(Round off to the Nearest Integer). path functions, is: IApril 9, 2019 (1)1
[NV, March 16, 2021 (Il) I (A) q + w (B) q (C) w (D) H- TS
1 1
[Given : R = 8.314 J mo1- K- • Assume, hydrogen is ~n (a) (B) and (C) (b) (B), (C) and (D)
ideal gas] " (c) (A) and (D) (d) (A), (B) and (C)
[Atomic mass ofFe is 55.85 u]
 ,----
13. During compression of a spring the work done is lO kJ temperature of I mole of Al. If molar heat capacity of Al is
and 2 kJ escaped to the surroundings as heat. The change 24 J moI- 1 K- 1, the temperature of Al increases by:
in internal energy, "U (in kJ) is: !April 9, 2019 (11)1 !Jan. 10, 2019 (11)1
_ (a) -12 (b) -8 (c) 8 (d) 12
14. - Which one of the following equations does not correctly _ (a) I2 K (b) 2 K
.
__,(t)
3
K (d) I K
represent the first law of thermodynamics for the given
19. Consider the reversible isothermal expansion of an ideal
processes involving an ideal gas ? (Assume non-
gas in a closed system at two different temp.er~tures, T 1
expansion work is zero) !April 8, 2019 (1)1
and T (T < T2). The correct graphical dep1ct10n of t?e
(a) Cyclic process : q = -w 2 1
dependence of work done (w) on the final volume (V) 1s:
(b) Adiabatic process : AU= -w [Jan. 9, 2019 (f)J
(c) Isochoric process: AU= q
(d) Isothermal process: q = - w . lwl
1S. 5 moles of an ideal gas at 100 K are allowed to undergo
reversible compression till its temperature becomes 200 K.
/; lwl /~
(a)
If Cv = 28 J K- 1 mol- 1, calculate AU and APV for this
process. (R = 8.0 J K =-1 mol- 1) [April 8, 2019 (Il))
(a) AU= 14 kJ; A(PV)= 18 kJ

H?T, yT,
0 /nV 0 /n V
(b),, AU= 14 kJ; ti(PV) = 0.8 kJ
\ (-c) AU= 14kJ; ti(PV)=4kJ
(d) AU= 14kJ;ti(PV)=8.0kJ
1.6. For a diatomic ideal gas in a closed system, which of the (c) (d) l•I
/ following plots does not correctly describe the relation
between various thermodynamic quantities?

(a) c,~ ut
[Jan. 12, 2019 (I)) 0 In V O /n V --
·20. An ideal gas undergoes a cyclic process as shown in
Fjgure.
(b)

,lSJ:
cl.Lr . . cvt
p T

V
tiUBC =-5 kJmol- 1, n'1AB =2kJmo1- 1
.

(c) (d) . WA8 =-5 kJ mo1- 1, WcA = 3 kJ mo1- 1

Heat absorbed by the system during process CA is:
T V [Online April 15, 2018 (l))
17. The combination of plots which does not represent (a) -5KJ mo1- 1 (b) +5 kJ mo1- 1
isothermal expansion ofan ideal gas is: (c) · 18 kJ mo1- 1 (d) -18 kJ mo1- 1
IJan.12, 2019 (II)) 21. tiU is equal to [20171

'l
(a) Isochoric work (b) Isobaric work
(c) Adiabatic work · (d) Isothermal work
22. A gas undergoes change from state A to state B: In this
(A)p~ ~) process, the heat absorbed and work done by the gas is 5
J and 8 J, respectively. Now gas is brought back to A by
another process during which 3 J of heat is evolved. In

,v.L "L
0 IN m O Vm
this reverse process ofB to A: !Online April 9, 20171
(a) 10 J of the work will be done by the gas.
(b) 6 J of the work will be done by the gas.
(q OJ) (c) 10 J of the work will be done by the surrounding on gas.
(d) 6 J of the work will be done by the surrounding ori gas.
23. If 100 mole ofH.,O., decomposes at I bar and 300 K, the
0 p O vm work done (kJ) by one mole of O,(g) as it expands against
(a) (B) and (D) (b) (A) and (C) l bar pressure is: ! On line April 10, 20161
(c) (B)and(C) . (d) (A)and(D) 2H.,Oi/) H.,0(/) + Oig)
An ideal gas undergoes isothermal compression from 5 m3 (R = 83 JK- 1 m~1-i) - -
18. to 1 m3 against a constant external pressure of 4 Nm--.'
(a) 124.50 ·(b) 249.00 (c) 498.00 (d) 62.25
Heat released in this process is used to increase th e
 24. A piston filled with 0.04 mol of an ideal gas expands
reversibly from 50.0 mL to 375 mL at a constant temperature
of 37.0 °C. As it does so, it absorbs 208 J of heat. The ~ Mt+
values of q and w for the process will be: 120131
(R= 8.314 J/mol K) (ln 7.5 =2.01) Laws of Thermochemistry
(a) q=+208J, w=-208J
(b) q=-208J, w=-208J 31. Oata given for the following reaction is as follows :
(c) q=-208J, w=+208J
(d) q=+208J,w=+208J 1 1
Substance ~H 0 (kJ mol- ) ~S 0 (J mol K- )
1
25. Which of the following statements/relationships is not correct \
.in thermodynamic changes? !Online April 23, 2013] FeO(s) -266.3 57.49
(a) ~U = 0 (isotherma,l reversible expansion·ofa gas) C(graphite) 0 5.74
V Fees) 0 27.28
(b) w = - nRT 1n -2 (isothermal reversible expansion of
V1 CO(g) -110.5 197 .6
an ideal gas)
' The minimum temperature/ in KI at which the re,\ction
V •

(c) w=nRTln -2 (isothermalreversibleexpansionofan becomes spontaneous is · . (Integer answer)

V1 . .. !NV, Aug. 27, 2021 (fl)I
ideal gas) 32. These are physical properti<JS of an element
(d) For a system of constant volume heat involved directly · (A) Sublimation enthalpy
j changes to internal energy. (B) J pnisation enthalpy
26. An ideal gas is allowed to expand both reversibly and (:.(C) Hydration enthalpy
irreversibly in an isolated system. If Ti is the initial (D) Electron gain enthalpy . 1
temperature and Tr is the final temperature, which of the The total number of above properties that affect the
following statements is correct? (2006] reduction potential is _ _ _ _ (Integer answer)
(a) (T r\ev = (Tf)in-ev (N V,Aug. 26, 2021 (1) 1
(b) T f = Ti for both reversible and irreversible pro~esses 33. The Born-Haber cycle for KCI is evaluated with the
(c) (T f)irrev > (T f)rev . following data : - · ·
(d) T f> Ti for reversible process but Tr= Ti for irreversible
~_µ9for KCt =-436.7 kJ mot- 1;
process
27. An ideal gas expands in volume from 1x 10-3 to 1 x 10-2 m 3 sub
He for K = 89 .2 kJ mo1-1.'
at 300 K against a constant pressure of l x 10 5 Nm- 2 • The
- . 1·10n He for K = 419.0 kJ mo1-1; ~electron gain
~ 1omza ' w> for
work done is 12004]
(a) 270kJ (b) - _9 00kJ Cl(g) = -348.~ kJ mot-1; ~bonJie for Ct 2
= 243.01<.J mo1~1
(c) -900 J (d) 900kJ The magnitude of lattice eajhatpy ofKCl in kJ mo1- 1 is
28. The internal energy change when a system goes from state _ _ _ (Near est integer) [NV, Aug. 26, 2021 (I) I
A to B is 40 kJ/mole. If the system goes from A to B by a 34. At 298 K, the enthalpy of fusion of a solid (X) is 2.8 kJ
1
reversible p~th and returns to state A by an irreversible path mo1- and the enthalpy of vaporisation of the liquid (X) is
1
what would be the net change in internal energy? (20031 98.2 kJ mo1- • The enthalpy of sublimation of the substance.
(a) ~ 40kJ (b) <40kJ (X) in kJ mo1- 1 is _ _ _ _ . (in nearest integer)

29.
t'
(c) ero (d) 40 kJ
Ah at engine abosrbs heat Q 1 at temperature T 1.and heat 35. For the reaction
' t ._ •
(NV, July 25,202 l (l)J

Q 2 t temperature T2 • Work done by the engine is C2~4+Hz

J (Q 1 + Q2 ) . This data (2002) the reaction enthalpy ~,H = _ _ _ _ kJ mo1- 1•
(a) I violates 1st law of thermodynamics · (Rounded off to the Nearest Integer). 1 ..,J.
)I
(b violates 1st law of themodynami_cs if Q I i~ -ve [Given: Bond enthalpies in kJ mot- : 1
.-
(c) violates 1st law of thermodynamics of Q 2 1s -ve C-C: 347, C=C: 611 ; \
(d) does not violate 1 law ofthemodynamics.
st
C-H: 414, H-H: 436] !NV, March 18, 2021(1) 1 -
30. The heat required to raise the temperature ofl,ody by 1 K 36. \:rhe average S-F bond energy in kJ mo1- 1 of SF 6 is
is .c alled (2002)
_ _ _ _ _ . (Rounded off to the nearest integer)
(a) specific heat
[Given : The values of standard enthalpy of formation of
(b) thermal capacity
~F 6(g)' S(g) and F(g) are - 1100, 275 and 80 kJ mo1- 1
(c) water equivalent
respectively.] INV, Feb. 26, 202 1 (fl) I
(d) none of these.

T
 45. The standard heat of formation ( d'JH; 98 ) of ethane (in kl/
37. The ionization enthalpyofNa+ formation from Na(&) is 495.8
1
.
kJ mo1-- , while the electron gain enthalpy o Br 1s f mo!), if the heat of combustion of ethane, hydrogen_and
1
-325.0 kJ mo1-- • Given the lattice enthalpy of NaBr is graphite are-1560, -393.5 and-286 kJ/mol, respectively
-728.4 kJ mo1-- 1. The energy for the formation ofNaBr ionic /'is _ _ _ . I NV, Jan. 07, 2020 (IO I
solid is (-) _ _ _ x 10-- 1kJmo1-- 1. jNV, Feb. 25, 2021 (1)1 A6
Enthalpy of sublimation ofiodine is 24 cal g- 1at 200°C. If
38. Lattice enthalpy and enthalpy of solution of NaCl · specific heat oflz(s) and Iz(vap) are 0.055 an~ 0.031_ ca~ fr
788 kJ mo1-- 1 and 4 kJ mo1-- 1, respectively. The hydration - 1 • 1 K--1 respectively, then enthalpy of sublimation of 1odme
enthalpy ofNaCl is: !Sep. 05, 2020 (U)I at 250 oc in cal g-l is: !April 12, 2019 <DI
(a) -780kJmo1-- 1 (b) 780kJmo1-- 1 (a) 2.85 (b) 5.7 \ (c) 22.8 (d) 11.4
(c) -784kJmo1-- 1 (d) 784kJmo1-- 1 47. ThedifferencebetweendttanddU(dtt-dU), wbenthe
39. For one mole of an ideal gas, which of these statements combustion of one mole of heptane (I) is carried out at a
must be true? [Sep. 04, 2020 (1)1 temperatureT, is equal to: (April IO, 2019 (U)I
(1) UandHeachdependsonlyontemperature (a) -4RT (b) -3RT (c) 4ltr (d) 3RT
(2) Compressibility factor z is not equal to 1 48. For silver, C (JK- 1 mo!-- 1) = 23 + 0.01 T. If the temperature
(3) C - r =R (T) of3 mol:s of silver is raised from 300 K to l 000 Kat 1
(4) dO~ c'):T for any process atm pressure, the value of dH will be close to: ·
(a) (l)and(3) (b) (2),(3)and(4) / 1Apri18, 2019 (1)1
(c) (3)and(4) (d) (l),(3)and(4) (a) 62kJ (b) 16kJ (c) 2lkJ· (d) 13kJ
40. The intermolecular potential energy for the molecules A,
B, C and D given below suggests that: 49. (i) C (graphite)+ Oz(g) COz(g); drHo = x kJ mo1- 1
[Sep. 04, 2020 (I) I
(ii) C(graphite) + Oz(g) ½ CO(g); drHo = y kJ mo1- 1
Interatomic distance (pm)

50 : JOO (iii) CO(g) + _!_ Oz(g) COz(g); drHo = z kJ mo1- 1

0 2
' -JOO Based on the above thermochemical equations, find out
which one of the following algebraic relationships is
-200 correct? (Jan.12, 2019 (ll)I
Potential ·
Energy -300
(a) x=y+z (b) z=x+y
-- l (c) y= 2z-x (d) x = y-z
(kJ mol .)
--400 : The combustion ofbenzene (1) gives CO 2 (g) and HzO ([).
A-A A-C Given that heat of combustion of benzene at constant
-500
volume is-3263.9.kJmol- 1 at25°C;heatofcombustion(in ·
-600 A-B kJ mol- 1) ofbenzene at constant pressure will be:
(R=8:314JK-1 mol-- 1) (201 8 1
(a) 4152.6 (b) --452.46
(c) 3260 (d) -3267.6
(a) A-D has the shortest bond length ·
51. For which of the following reactions, dH is equal to dU?
(b) A-A has the largest bond enthalpy
[Online April 15, 2018 (1)1
(c) Dis more electronegative than other atoms
(d) A-B has the stiffest bond (a) N 2 (g)+3H 2 (g) 2NH 3 (g)
41. The internal energy change (in J) when 90 g of water /
(b) 2Hl(g) Hz(g)+ lz(g)
undergoes complete evaporation at 100°C is _ __
(Given: dl\.a/or water at 373 K= 41 kJ/ mol, R = 8.314 (c) 2SO 2 (g) +O 2 (g) 2SO 3 (g)
JK,- 1 mot- 1) [NV, Sep. 02, 2020 (l)I
(d) 2NOz(g) NzO4(g)
42. The heat of combustion of ethanol into carbon dioxids
and water is - 327 kcal at constant pressure. The heat
·s2. Given
evolved (in cal) at constant volume and 27°C (if all gases C(graphite) + O 2(g) COz(g); d)I 0 = -393.5 kJ mol- 1
behave ideally) is (R = 2 cal mo1-- 1 K-- 1) _ _ __ 1 .
INV, Sep. 02, 2020 (11)1 Hz (g) + 0 2 (g) HzO(l); d)I 0 =-285.8 kJ mol-- 1
2
43. If enthalpy of atomisatio.n for Br z( £) is x kJ/mol and bond
COi(g) + 2HzO(1) CHig) + 2Oi(g);
enthalpy for Br2 is y kJ/mol, the relation between them:
Li)I = + 890.3 kJ mo1- 1
0

tJan. 09, 2020 (l)I

Based on the above thermochemical equations, the value
( ) is x =y (b) does not exist
of Li rH0 at 298 K for the reaction
(:) isx>y . (d) isx<y C(graphitel + 2Hz(g) CHig) will be: 120171
44. For the react10n; A(l) 2B(g) (a) + 74.8 kJ mo1- 1 (b) + 144.0 kJ mo1-- 1
AU= 2 _1 kcal, AS= 20 cal K- at 300
1
K (c) -74.8kJmot- 1 (d) -144.0kJmol-- 1
. kcal is INV, Jan. 07, 2020 (l}I
HenceA G m
 · · · f water will be·
- 53. For a reaction, A(g) A(I); ~H= -3RT. The correct The molar enthalpy ofvapounsat1on o . A ·19 20.131
fOnlm e · pn ,
statement for the reaction is: IOn line April 8, 20171
(a) ~H=~U:t:O (b) ~H=~U=O (a) 241.8kJmol- 1 (b) 22.0 kJ mo1- 1
(c) l~I< l~Ul _(d) 1Aff1> l~Ul (c) 44.lk.Jmol- 1 (d) 527.7 kJ mol- '
54. The enthalpy change on freezing of J mol of water at 5 °C 61. Given
to ice at-5 °C is: IOnline April 8, 20171 Reaction Energy Change
(Given ~fusH = 6 kJ moJ- 1 at o.°C, '(in kJ)
C/8iO, I) =75 .3 J moJ-1 K-1 , Li(s) Li(g) 161 .
C~(HiO, s) = 36.8 J m0J-I K-1) Li(g) Lt(g) 520
(aJ 5.44kJmo1- 1 (b) 5.81 kJmol- 1 1
1 77
(c) 6.56 kJ mo1- (d) 6.00 kJ mot- 1
55. The heats of combustion of carbon and carbon monoxide
2Fi(g) F(g)
F(g) + e- P-(g) (Electron gain
are-393.5 and-283.5 kJ mol- 1, respec!!_vely. The heat of enthalpy)
formation (in kJ) of carbon monoxide per mole is: [20161 Li+(g)+F-(g) LiF(s) -1047
(a) -076.5 (b) -110.5 (c) 110.5 (d) 676.5
56. The heat of atomization of methane and ethane are 360 kJ/ Li(s)+ .!_Fi(g) LiF(s)-617
mo! and 620 kJ/mol, respectively. The longest wavele~gth 2
oflight capable ofbreaking the C -C bond is (Avogadro Based on data provided, the value of electron gain enthalpy
number = 6.02 x 1023 , h = 6.62 x 10-34 J s): · offluorine would be: (Online April 22, 20131
[Online April 10, 2015] (a) -300kJmo1- 1 (b) -350kJmoI- 1
(a) 2.48 x 104nm -(b) 1.49 x 103 nm (c) -3281_<lmoI- 1 (d) -228kJmoI- 1
(c) 2.48 x 103 nm (d) 1.49 x 104nm. 62. In which of the following exothermic reactions, the heat
57. For complete combustion of ethanol, liberated per mole is the highest? (Online April 25, 20131
C2H5OH(l)+3O 2 (g)~2C0 2 (g)+3H 2O(l), (a) CaO + 8i0 Ca(OH)2
the amount of heat produced as measured in bomb (b) SrO+ 8i0 Sr(OH)2
calorimeter, is 1364.47 kJ mo1- 1 at 25 °C. Assuming ideality
the enthalpy of combustion, ~cH, for the reaction will be: (c) BaO+ Ba(OH)2
(R=8.314kJmoI- 1) . [2014]
(d) MgO + 8i0 Mg(OH) 2
(a) -1366.95 kJ moi- 1 (b) -1361.95 kJ moi- 1 63. Given that: [OnlineApril 25, 20131
(c) -1460.95 kJ mol- 1
(d) -1350.50 kJ mo1- 1 1
(i) ~rH°~fN 2O is82kJmo1-
58. The standard enthalpy of formation ofNH3 is - 46.0 kJ/ (ii) Bond energies ofN =~. N = N, 0 = 0 and N = 0 are
mo!. If the enthalpyofformation ofH2 from its atoms is- 946, 418, 498 and 607 kJ mo1-1 respectively,
436 k.J/mol and that ofN2 is- 712 kJ/mol, the average bond The resonance energy ofN 2O is :
enthalpyofN - Hbond in~ is: [Online April 9, 20141 (a) ~8kJ (b) --o6kJ
(a) - 1102 kJ/mol (b) - 964 kJ/mol (c) -o2kJ (d) -44kJ
(c) +352kJ/mol (d) +1056kJ/mol 64. The difference between the reaction enthalpy change (~)I)
59. The standard enthalpy of formation (~1H0 298 ) for methane, and reaction internal energy change(~,U) for the reaction:
CH4 is - 74.9 kJ moJ- 1• In order to calculate_the average
energy given out in the formation of a C - H bond from 2C6H6 (1) + 1502 (g)-----+ l 2CO2 (g) + 6H 20(1)
this it is necessary to know which one of the following? at 300 K is (R = 8.314 J mol- 1K- 1) - (Online May 12, 20121
[Online April 12, 20141 (a) 0Jmo1- 1 (b) 2490Jmo1- 1
(a) The dissociation energy of the hydrogen molecule, Hi- (c) -2490Jmo1- 1 (d) -7482Jmo1-1
(b) The first four ionisation energies of carbon. 65. The enthalpy of neutralisation of NHpH with HCl is
(c) The dissociation energy of H2 and enthalpy· of -51.46 kJ mo1- 1 and the enthalpy ofneutralisation ofNaOH
sublimation of carbon (graphite). with HCl is .:_55_90 kJ mo1- 1• The enthalpy ofionisation of
(d) The first four ionisation energies of carbon and
NH4OH is {Online May 19, 20121
electron affinity of hydrogen.
(a) -107.36kJmol- 1 (b) -4.44kJmo1- 1
60. Given:
(c) +107.36kJmol- 1 (d) +4.44kJmo1- 1
l 66. The value of enthalpy change (~H) for the reaction
(I) H 2 (g) + 02 (g) H2O(l);
2 C2H5OH(l) + 302 (g) 2CO 2(g) + 3H2O(l)
~w 298 K = -285.9kJmo1-1 at27 °C is-1366.S-k J mol- 1. The value ofinternal energy
1 change for the above reaction at this temperature will be :
(II) (a) -1369.0kJ (b) -1364.0kJ f2011RSJ
2
(c) -l361.5kJ (d) -1371.Skl
~ o298K = -241.8kJ mol-1
67. Consider the reaction: 73. The enthalpy changes for the following processes are listed
below : [20061
4NO2(g) +O 2(g) 2N2O 5 (g), Cli(g) = 2Cl(g), 242.3 kJ mo1- 1
11,H=-l.llkJ. Ii(g) = 2l(g), 151 .0 kJ moI- 1
If N2Os(s) is formed instead of Nps(g) in the above ICl(g) = l(g) + Cl(g), 211.3 kJ mot- 1
reaction, the 11,H value will be : Iz(s)=lz(g), 62.76kJmoI- 1
(given, MI of sublimatio.n for Np 5 is 54 kJ mol- 1) Given that the standard states for iodine and chlorine are
· [2011RSI Iz(s) and Clz(g), the standard enthalpy of formation for
(a) + 54 kJ (b) + 219 kJ (c) - 219 J (d) - 165 kJ ICl(g) is : f2006J
68. The standard enthalpy of formation of NH 3 (a) +16.8kJmoI- 1
is - 46.0 kJ mo1- 1• If the enthalpy of formation ofH 2 from (b) +244.8kJmoI- 1
its atoms is-436 kJ mol- 1 and thatofN 2 is- 712 kJ mo1- 1, (c) -14.6 kJ moI- 1
the average bond enthalpy ofN - H bond in NH 3 is [2010) (d) -16.8kJmoI- 1
(a) -%4kJmo1-1 (b) +352kJmol-:- 1 74. (11H-11U) for the formation ofcarbon monoxide (CO) from
(c) +1056kJmol- 1 (d) -1102kJmol- 1 its elements at 298 K is [2006)
69. On the basis of the following thermochemical data : (R = 8.314 JK- 1 moI- 1)
(11fG 0 H~q) = 0) [2009) , (a) -2477.57 J moJ- 1
(b) 2477.57 J moI- 1
~20(/) H+ (aq) + OH-(aq);11H = 57.32 kJ (c) -1238.78Jmof· 1
. (d) 1238.78Jmo1-1
H2(g)+.!..02(g)~H20(/); MI=.:...286.20 kJ 75. Consider the reaction: N 2 + 3H 2 2NH 3 ·carried out
2 . . .
The value of enthalpy of formation of OH- ion at 25° C is: at constant temperature and pressure. If 11H and ~U are
(a) -228.88kJ (b) +228.88kJ the enthalpy and internal energy changes for the reaction,
(c) -343.52kJ (d) -22.88kJ which of the following expressions is true? [2005]
70. Oxidising power of chlorine in aqueous solution can be
determined by the parameters indicated below: (a) m > ~u (b) m <- ~u

l
1
-t:.dissH
0
t:. H0 (c) m = ~u (d) m =o.
· eg Cl-(g)
2 76. If the bond dissociation energies ofXY, X 2 and Y2 (all
t:. Ho diatomic molecules) are in the ratio of 1 : 1 : 0.5 and M4for
Cl-(aq)
hyd
The energy envolved in the conversion of the formation of XY is - 200 kJ mole- 1• The bond
dissociation energy of X2 will be [2005]
.!_Cl2 (g) to Cl-I (aq) (a) 400kJ mol- 1
2
(using the data, (b) 300kJ mol- 1
o -I o -1
i1dissHc1t 240 kJ mol , ~egH ci= -349 kJ mol , (c) 200kJ mol- 1
~hydH c1- = -381 kJ moC\ will be
0
[2008] (d) · 1ookJ mol- 1
1
(a) .+ 152kJinol- 1 (b) -6l0kJmo1- 77. The enthalpies of combustion of carbon and carbon
(c) -850 kJ mo1- 1 (d) + 120 kJ mol- 1 monoxide are- 393 .5 and - 283 kJ mo1- 1 respectively. The
71. Assuming that water vapour is an ideal gas, the internal enthalpy of formation of carbon monoxide per mole is
energy change (~U) when 1 moJ of water is vapourised at (a) -676.SkJ (b) 676.SkJ [20041
(c) 110.5 kJ (d) -110.5 kJ
1 _bar pressure and 100 °C, (given : molar enthalpy of
78. lfat 298 K the bond energies of C- H, C-C, C = C and
vapourisation of water at 1 bar and 373 K = 41 kJ mo1- 1 and
H-Hbondsarerespectively414, 347, 615 and435 kJ mo1- 1,
R= 8.3 Jmo1- 1 K- 1)will be [2007]
the value of enthalpy ch~nge for the reaction
(a) 41.00kJmol- 1 (b) 4.l00kJmoI- 1
(c) 3.7904kJ mo1- 1 (d) 37.904kJ mo1- 1 H 2 C ;= CH 2 (g)+H 2 (g) H 3C-CH 3 (g)at298Kwillbe
72. The standard enthalpy of formation (~!1°) at 298 K for (a) - ·25okJ (b) + 125kJ 120031
methane, CH4 (g) is -74.8 kJ.moJ- 1. The additional (c) -125kJ (d) +250kJ
information required to determine the average energy for 79. The enthalpy chang~ for a reaction does not depend upon
c-H bond formation would be . [2006) . [20031
(a) the first four ionization energies of carbon and electrqn (a) use of different reactants for the same product
gain enthalpy ofhydrogep (b) the nature of intermediate reaction steps
(b) the dissoci~tio_n energy of hydrogen molecule, H2 (c) the differences in initial or final temperatures of
(c) the _dissociat10n energy of H2 and enthalpy of involved substances
(d) the physical states of reactants and products
sublimation of carbon
(d) latent heat ofvapourization of methane
 ~ ')Uo)Q@ > . 87. The entropy change associated with the conversion of l
kg of ice at 273 K to water vapours at 383 K is:

Entropy and Second Law of

\ (Specific beat of water liquid and water vapour are 4.2 kJ
K- 1 kg- 1 and 2.0 kJ K- 1 kg- 1; heat of liquid fusion an~
' Thermodynamics vapourisation of water are 334 kJ kg- 1 and 2491 kJ kg- ,
respectively). !Jan. 9, 2019 (H)I
80. For a given chemical reaction A B at 300 K the free (log 273 = 2.436, log 373 = 2.572, log 383 = 2.583)
(b) 2.64 kJ kg- 1 K-
1
~nergychange is-49.4 kJ mol- 1 and the enthalpyofreaction (a) 7.90 kJ kg- 1 K- 1
1
is 51.4 kJ mo1- 1• The entropy change of the reaction is (c) 8.49 kJ kg- K-
1 1 (d) 9.26 kJ kg- K- 1
___ JK-1 moJ- 1• INV, July 20,2021 (11)1 88. For which of the following processes, LiS is negative?
(Online April 16, 20181
81. ForachemicalreactionA+B C+D
0
(L\H = 80 kJ moJ-l) the entropy change Li S0 depends on (a) C(diamond) C(grapbite)
the temperature T (in K) as Li S0 =2T (JK-~ mol- 1). (b) N 2 (g,latm) N 2 (g,5atm)
Minimum temperature at whi~h it will become spontaneous
is _ _ _ _ _ K. (Integer) [NV, Feb. 26, 2021 (1)1 (c) N 2 (g,273K) N 2 (g,300K)
82. For the reaction A(g) B(g), the value of the equilibrium (d) H 2 (g) 2H(g)
constant at 300 Kand 1 atm is equal to 100.0. The value of 89. The molar heat capacity (C~ ?fCDp is l 0 ~ls at l 000 K.
LirG for the reaction at 300 Kand l atm in J mol- 1 is-xR, The change in entropy associated wtth coolmg of32 g of

ln
where xis _ _ _ _ (Rounded off to the nearest integer)
(R = 8.31 J mo1- 1 K- 1 and 10.= 2.3)
[NV, February 24, 2021 (I))
CD O vapour from l 000 K to 100 Kat constant pressure
will\e: (D = deuterium, atomic mass= 2 u)
(Online April 11, 20141
83. Assuming ideal behaviour, the magnitude oflog K for the (a) 23.03 cal d·eg- 1 (b) -23.03 cal deg- 1
following reaction at 25°C is xx io- 1. The value ofx-is (c) 2.303 cal deg- 1 (d) - 2.303 cal deg- 1
_ _ _ _ . (Integer answer). 90. The (S ) of the following substances are:
0

3HC = CH (g) C6H6 (/) CH4 (g) 186.2JK- 1 mol- 1

0 2 (g) 205.2 JK- 1 mo1- 1 .
[Given: Li 1 G0 (Hc=·CH)=-2.04x10 5 J mol- 1; CO 2 (g) 213.6 JK- 1 mo1- 1
HiO (l) 69.9.JK- 1 mo1- 1
Li f G 0 (C 6 H 6 ) = -1.24 x 105 J mol- 1; The'entropy change (LiS 0 ) for the reaction
CH/g) + 2O/g) COi(g) + 28iO(1) is:
R = 8.314 J K- 1 mol- 1] [NV, February 24, 2021 (II)] (Online April 12, 20141
84. The true statement amongst the following is : (a) -312.5 J K- 1 mol- 1 (b) -242.8 J K- 1·mo1- 1
[Jan. 09, 2020 (II)] (c) -108.1 JK- 1 mol- 1 (d) -37 .6 JK~ 1 mo1- 1
(a) Both LiS and Sare functions of temperature. 91. The entropy of a sample of a certain substance increases
(b) Both Sand LiS are not functions of temperature. by 0.836 J K- 1 on adding reversibly 0.3344 J of heat at
(c) Sis not a function of temperature but LlS is a function constant temperature. The temperature of the sample is:
of temperature. · · (Online May 7, 20121
·(d) Sis a function of temperature but LiS is not a function (a) 2.5 K (b) 0.3 K (c) 0.016K (d) 0.4 K
of temperature. 92. One mole of an ideal gas is expanded isothermally and
85. Two blocks of the same metal having same mass and at
temperature T 1, and T 2, respective!~, are brought i~ ~n_tact
with each other and allowed to attam thermal eqmhbnum
in J K- 1 mol- 1 is [ln
reversibly to half of its initial pressure. LiS for the process
2 = 0.693 andR = 8.314, J/(mol K))
[Online May 26, 20121
at constant-pressure. The change in entropy, LiS, for this (a) 6.76 (b) 5.76 (c) 10.76 (d) 8.03

process is[: (T, + T1)'

(a) Cp In 4T1T2
l (b) 2Cp lnr'~:~~;::;119
T1 2 .
(I)]
93. Standard entropy of X 2 , Y 2 and XY 3 are 60, 40 and
50 J K- 1 mo1- 1, respectively. For the reaction,
1
-X 2 +-Y2
2
3
2
XY3 ,Af-I = -30 kJ , to beat eqm·1·b .
1 num,

the temperature will be (2008)

(a) 1250K (b) SOOK (c) 750K (d) 1000K
(c) 2C m(T1+T2) (d) 2Cpln[T1+T2] 94. In conversion oflime-stone to lime,
P 4T1T2 2T1T2 0
CaCO 3 (s) CaO(s) + CO 2 (g) th~ values of Afl and
86. The process with negative entropy change is: · ·
!Jan. 10, 2019 (II)) LiS are+ 179 .1 k.J mol- 1 and 160.2 J/K respectively at 298 K
0

(a) Dissociation ofCaSOis) to CaO(s) and SO/g) and I bar. Assuming that Aff O and LiS0 do not change
(b) Sublimation of dry ice with temperature, temperature above which conversion of
(c) Dissolution ofiodine in water limestone to lime will be spontaneous is 12007 1
(a) 1118K (b) 1008K (c) J200K (d) 845 K.
(d) Synthesis of ammonia from N 2 and_Hz
 l 02. A process has ~H = 200 J moJ- 1 and ~S = 40 JK-Im 0 1-1

O ''*'• Spontaneity and Gibb's Free Energy

\ Out of t"he values given below, choose the minim~
temperature above which the process w i ll be
spontaneous:
(a) 20K (b) 12K
(Jan. 10, 2019(1 )1

(c) 5K (d) 4K
I 03. Which of the following lines correctly show the
95. For the reaction 2NOi(g) Np 4 (g), when ~S = _
1 temperature dependence of equilibrium constant, K, for
176.0 JK- andAfI=-57.8 kJ mo1- 1, themagnitudeof ~G at an exothermic reaction? [201 81
298 K for the reaction is_ _. kJ moI- 1. (Nearest integer)
. . . (NV, Sep. 1, 2021 (H)]
96. Consider the followmg cell reaction :
_l_
9 9 T(K)
Cd(s) +Hg 2S04(s) +
5 H2O(l) ~CdSO 4. 5H 2o(s) +2Hg(l)
The value ofE~ell is 4.315 Vat 25°C. If Afl0 = -825.2 kJ
mo1- 1, the standard entropy change ~S 0 in J K-1 is
(a) AandB (b) BandC
(Nearest integer) --
(c) CandD (d) AandD
[Given: Faraday constant= 96487 C moI- 1]
104. At 320 K, a gas Ai is 20% dissociated toA(g). The standard
(NV,Aug. 31, 2021 (I))
free energy change at. 320 K and 1 atm in J mot- 1 is
97. For a dimerization reaction, 2A(g) A 2 (g),
appr_oximately: [On line April 16, 201 8 )
1
(R = 8.314JK-I moI- ; In 2 = 0.693; In 3 = 1.098) · ·
at 298 K, dU = -20 kJ mo1- 1, ~so= -30 J K-1 moI-1
0

' (a) 1844 (b) 2068 ·

then the dG 0 will be . J.
(c) 4281 (d) 4763
. (NV, Sep. 05, 2020 (II)(
105. dfJ at 500 K for substance 'S' in liquid state and gaseous
0
98. A process will be spontaneous at all temperatures if:
(Apr il 10, 2019 (I)] state are+ 100. 7 kcal moJ- 1 and+ 103 kcal moJ-1, respectively.
(a) Afl<0and~S<0 (b) Afl>0and~S<0 Vapour pressure ofliquid 'S' at 500 K is approximately equal
(c) Afl<0anddS>0 (d) dH>0anddS>0 to:(R'."' 2 cal K- 1moI- 1) . IOnline April 15, 2018 (0))
(a) l00atm (b) 1 atm
99. For the chemical reaction X Y , the standard
reaction Gibbs energy depends on temperature T (in K) (c) IOatm (d) 0.1 atm
106. Given [Online April 15, 2018 (ll)]
as~G 0 (inkJmoI- 1)= 120-i T (i)
r 8
The major component of the reaction mixture at Tis : drG 0 = +1487.0 kJ mol-l
[Jan . 11, 2019 (1) 1
(a) YifT=300K (b) YifT=280K (ii) 2CO(g) + 02 (g) 2CO 2(g);
(c) XifT=350K (d) XifT=315K
100. The reaction ~rG 0 = -514.4 kJ JnOl-l
MgO (s) + C(s) Mg(s) + CO (g), for which Free energy change, dp 0 for the reaction
MI =+491.1 kJmo1- 1 and~S 0 = 198.oJK- 1mol- 1,
0
. 2Fe2O3(s) + 6CO(g) 4Fe(s)+ 6CO 2(g) will be:
is not feasible at 298 K. Temperature above which reac- (a) -112.4kJmoI- 1
tion will be feasible is [Jan. 11, 2019 (H))
(b) -56.2kJmoI- 1
(a) 20405K (b) 1890.0K
(c) -208.0kJmol- 1
(c) 2480.3K (d) 2380.5K
o
1 J. The standard reaction Gibbs energy for a chemical reaction (d) -168.2 kJ mo1- 1
at an absolute temperature Tis given by ~G0 =A - BT where 107. An ideal gas undergoes isothermal expansion at constant
A and Bare non-zero constants. Which of the following pressure. During the process : (Online April 9, 2017)
is true about this reaction? [Jan. 11, 2019 (]])( . (a) enthalpy increases but entropy decreases.
(a) ExothennicifB<O (b) enthalpy remains constant but entropy increases.
(b) EndothennicifA>O (c) enthalpy decreases but entropy increases.
( c) ~ndothermic ifA< 0 and B > 0 (d) Both enthalpy and entropy remain constant.
(d) Exothermic ifA> 0 and B < O
J 08. A reaction at 1 bar is non-spontaneous at low temperature (c) Endothermic processes are never spontaneous.
but becomes spontaneous at high temperature. Identify (d) Exothermic processes are always spontaneous.
the correct statement about the reaction among the 112. In an irreversible process taking place at constant T and P
following : !Online April 9, 20161 and in which only pressure-volume work is being done, the
(a) LiH is negative while LiS is positive change in Gibbs free energy (dG) and change in entropy
(b) Both LiH and LiS are negative (dS), satisfy the criteria 12003 I
(c) LiH is positive while LiS is negative (a) (dS)VE>0,(dG)TP<0
(d) Both LiH and LiS are positive. (b) (dS);E = 0, (dG); p= 0
109. The incorrect expression am~ng the following is: [2012 1 (c) (dS)v, E= 0, (dG)r,P> 0
(d) (dS)vE<0,(dG)TP<0
LiGsystem
(a) - - - = - T 113. The correct relationship between free energy change in a
LiS19tal reaction and the corresponding equilibrium constant Kc is
(b) In isothermal process, 120031
(a) -LiG=RT In Kc
. Vr
W reversible = -nRT Cn - (b) LiG0 = RT In Kc
. vi (c) -LiG0 = RT In Kc
(d) LiG= Rf In Kc
LiH 0 -TLiS0
(c) l n K = - - - - 114. If an endothermic reaction is non-spontaneous at freezing
RT point of water and becomes feasible at its boiling point,
(d) K = e-t.G•fRr then 120021
110. For a particular reversible reaction at temperature T, LlH (a) LiH is -v~, LiS is +ve
and LiS were found to be both +ve. IfTe is the temperature (b) LiH and 11S both are +ve
at equilibrium, the reaction would be spontaneous when (c) LiH and LiS both are-ve
(a) Te>T . (b) T>Te [20 101 (d) LiH is +ve, LiS is -ve
(c) Teis5timesT (d) T=Te 115. For the reactions, [20021
111. Identify the correct statement regarding a spontaneous 2C+O2 LlH =-393J
process: [2007) 2Zn+O2 2ZnO; LlH =-412J
(a) lowering of energy in the process is the only criterion (a) carbon can oxidise Zn
for spontaneity. (b) oxidation of carbon is not feasible
(b) For a spontaneous process in an isolated system, the (c) oxidation of Zn is not feasible
change in entropy is positive. · (d) Zn can oxidise carbon

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