CLIP * THERMODYNAMICS AND THERMOCHEMISTRY *

FIITJEE - CRR
Q.1 C2H4 (g) + HCl (g) → C2H5Cl (g) ; ∆H = – 72.3 kJ/mol Tc(cold piece) are brought into contact into thermal contact
and isolated from its surrounding. The total change in
What is the value of ∆U(in kJ), if 70 g of ethylene and 73 g entropy of system is given by
(A) C ln  Tc  Th  (B) C ln  Tc 
of HCl are allowed to react at 300K.
(A) – 69.8 (B) –180.75 (C) –174.5 (D) –139.6    
 2Tc   Th 
(C) C ln  (Tc  Th )  (D) C ln  (Tc  Th ) 
2 2
Q.2 The heat capacity of liquid water is 75.6 J/mol-K, while
the enthalpy of fusion of ice is 6.0 kJ/mol . What is the    
 2ThTc   4ThTc 
smallest number of ice cubes at 0°C, each containing 9.0 g
of water, needed to cool 500 g of H2O(l) from 20°C to 0°C ? Q.13 The molar heat capacity of a diatomic ideal gas
(A) 1 (B) 7 (C) 14 (D) 28 subjected to a process , such that absolute temperature is
proportional to cube of its volume , is given by:
Q.3 Molar heat capacity of water in equilibrium with ice at 5R 7R 17R 15R
(A) (B) (C) (D)
constant pressure is ( in kJ K–1mol–1 ) 2 2 6 6
(A) zero (B) ∞ (C) 40.45 (D) 75.48
Q.14 Enthalpy of neutralization of H3PO3 acid is –106.68
Q.4 For the reaction at 300K : A(g) + B(g) → C (g) ;
kJ/mol using NaOH. If enthalpy of neutralization of HCl
∆U = –3.0 kcal and ∆S = – 10.0 cal/K . Value of ∆G is by NaOH is –55.84 kJ/mol. Calculate ∆Hionization of
(A) –600 cal (B) –6600 cal (C) –6000 cal (D) –6660 cal H3PO3 into its ions (in kJ/mol) .
(A) 50.84 (B) 5 (C) 2.5 (D) 60.84
Q.5 What is the free energy change (∆G) when 1.0 mole of Q.15 ∆Hlattice value for salts P , Q and R are +50, +120 and
water at 100°C and 1 atm pressure is converted into steam +150 kJ/mol respectively and ∆Hhydration value for salts P,
at 100°C and 2 atm pressure? [ ln 2 = 0.693 ] Q and R are –70, –135 and –200 kJ/mol respectively at
(A) zero cal (B) 540 cal (C) 517.13 cal (D) 510 cal 1 atm and 25℃. Correct order of solubility in water is
(A) Q < P < R (B) P < Q < R (C) R < Q < P (D) Q < R < P
Q.6 One mole of monoatomic ideal gas expands
adiabatically at initial temperature T against a constant Q.16 Study the following thermochemical equations:
external pressure of 1 atm from one litre to two litre. Find
(i) A → B ; ∆H = + 100 Kcal (ii)B → C ; ∆H = – 80 Kcal
out the final temp. (R = 0.0821 litre. atmK–1mol–1)
T 2 2 Correct order of enthalpies of formation of A, B and C is
(A) T (B) 5 (C) T – (D) T +
(2)3
− 1 3 x 0.0821 3 x 0.0821 (A)A< B < C (B)A< C < B (C) C <A < B (D) B < C <A
Q.7 Ethanol can undergoes decomposition to form two sets
of products Q.17 For the allotropic change represented by the equation
C (graphite) → C (diamond), ∆H= 1.9 kJ.
If 6g of diamond and 6 g of graphite are separately burnt
to yield CO2 , the enthalpy liberated in first case is
If the molar ratio of C2H4 to CH3CHO is 8 : 1 in a set of (A) < second case by 1.9 kJ (B) > second case by 11.4 kJ
product gases, then the enthalpy involved in the (C) > second case by 0.95 kJ (D) < second case by 11.4 kJ
decomposition of 1mole of ethanol is
(A) 65 kJ (B) 48 kJ (C) 49 kJ (D) 57 kJ Q.18 Given that: C + O2  CO2 ; H° = –x KJ and
2CO + O2  2CO2 ; H° = –y KJ .
Q.8 Which of the following will have +ve value of ∆Hf° ? The enthalpy of formation of carbon monoxide will be
+ 2𝑥 − 𝑦 𝑦 − 2𝑥
(A) Br2(l) (B) O3(g) (C) ZnO(s) (D) H (aq) (A) (B) (C) 2x – y (D) y = 2x
2 2
Q.9 ∆Hf° of water is –285.8 kJmol–1. If enthalpy of
neutralisation of monoacidic strong base is –57.3 kJmol–1, Q.19 The enthalpy of combustion at 25°C of H2,cyclohexene
∆Hf° of OH − ion will be (in kJmol–1) (C6H10), and cyclohexane (C6H12) are –241 KJ/mole,
(A) – 228.5 (B) 228.5 (C) 114.25 (D) –114.25 –3800 KJ/mole, and –3920 KJ/mole respectively. The heat
Q.10 Which of the following reactions defines ∆Hf° ? of hydrogenation of cyclohexene is (in KJ mole–1)
1 1 (A) –121 (B) +121 (C) –242 (D) +242
(A) Cdiamond + O2(g) → CO2(g) (B) H2(g) + Cl2(g) → HCl(g)
2 2
(C) N2(g) + 3H2(g) → 2NH3 (D) CO(g) + 1/2O2(g) → CO2(g) Q.20 Work done in process CB
for 1 mol of an ideal gas if
Q.11 The standard enthalpies of formation of CO2(g), H2O(l) total 600 cal heat is released
and glucose(s) at 25°C are – 400 kJ/mol, – 300 kJ/mol and by the gas in whole process is:
–1300 kJ/mol, respectively. The standard enthalpy of (A) 800 cal (B) 400 cal
combustion per gram of glucose at 25°C is : (C) –800 cal (D) –400 cal
(A) + 2900 kJ (B) –2900 kJ (C) – 16.11 kJ (D) + 16.11 kJ
ANSWERS.
1. D 2. C 3. B 4. A 5. C 6. C 7. B
Q.12 When two equal sized pieces of the same metal(heat 8. B 9. A 10. B 11. C 12. D 13. C 14. B
capacity = C) at different temperatures Th (hot piece) and 15. A 16. B 17.C 18. B 19. A 20.A

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SUBJECTIVE

Q.1 Predict sign of work done in following reactions at

constant pressure.
(i) H2O (g) →H2O (l) (ii) H2O (s) →H2O (g)
(iii) H2O (l) →H2O (s) (iv) CaCO3 (s) → CaO (s) + CO2 (g)

Q.2 The gas is cooled such that it loses 65 J of heat. The

gas contracts as it cools and work done on the system
equal to 20 J is exchanged with the surroundings.
What are q, w and ∆U? Q.10 A monoatomic ideal gas of two moles is taken through
a reversible cyclic process starting from A as shown in
Q.3 Two moles of a monoatomic ideal gas undergoes a 𝑉 𝑉
thermodynamic process such that cube of its volume figure. Given : 𝐵 = 2 and 𝐷 = 4 . If the temperature TA
𝑉𝐴 𝑉𝐴
is directly proportional to square of its absolute
temperature. If the temperature is raised by 300K, at A is 27°C, calculate:
then find molar heat capacity of gas , work done ,
change in internal energy and heat transferred (in
terms of R).
Q.4 Two mole of ideal diatomic gas (CV,m =5/2R) at
300K and 5 atm expanded irreversibly &
adiabatically to a final pressure of 2 atm against a
constant pressure of 1 atm. Calculate q,w, ∆U & ∆H. (a) The temperature of the gas at point B.
(b) Heat absorbed or released by the gas in each process.
Q.5 Calculate the work done by the system in an
irreversible (single step) adiabatic expansion of (c) The total work done by the gas during complete cycle.
1mole of a polyatomic gas (γ = 4/3) from 400K and
pressure 10 atm to 1 atm. Q.11 Five moles of an ideal gas at 300K, expanded
isothermally from an initial pressure of 4 atm to a final
Q.6 1 mole of SO2 gas at 300K is expanded under
reversible adiabatic condition such that its volume pressure of 1 atm against a cont. ext. pressure of 1 atm.
becomes 27 times. (a) What is final temperature? Calculate q, w, ∆U & ∆H. Calculate the corresponding
(b) What is work done?
(Given γ = 1.33 and CV = 25.08 J mol–1K–1 for SO2 ) value of all if the above process is carried out reversibly.

Q.7 3 moles of a ideal gas at 200K and 2.0 atm undergo Q.12 Oxygen is heated from 300K to 600K at a constant
reversible adiabatic compression until the pressure of 1 bar. What is the increases in molar entropy?
temperature becomes 250K . For the gas CV is 27.5
JK–1mol–1 in this temperature range. Calculate q, w, The molar heat capacity in JK–1mol–1 for the O2 is :
∆U & ∆H and final V and final P. CP = 10 + 10–2 T – 10–6 T2 (Given ln 2 = 0.7)
{(5/4)1/0.3 = 2.1, (5/4)13/3 = 2.61}
Q.13 A real gas obeys the equation P(Vm – b ) = RT, where
Q.8 2 mole of an ideal gas undergoes isothermal
compression along three different paths (b = 0.1 L/mol), if 2 moles of gas is slowly compressed
(i) reversible compression from Pi = 2 bar and Vi = 4 L to from 1.2 litre to 0.6 litre at constant temperature of 300K .
Pf = 20 bar Find work done in the process .
(ii) a single stage compression against a constant external
pressure of 20 bar, and Q.14 Derive a mathematical expression for the work done on
(iii) a two stage compression consisting initially of the surrounding when a gas that has the equation of state
compression against a constant external pressure of 10 𝑎𝑛2
bar until Pgas = Pext, followed by compression against a PV = nRT– expands reversibly from Vi to Vf at
𝑉
constant pressure of 20 bar until P gas = Pext . constant temperature.
Calculate the work (in bar. L) for each of these processes .
For which of the irreversible processes is the magnitude of the Q.15 1 mole of ideal monoatomic gas was taken through
work greater ? [Given : R = 0.08 bar.L/mole.K] isochoric heating from 100 K to 1000 K. Calculate
Q.9 1 mole of an ideal monoatomic gas is carried through ∆Ssystem , ∆Ssurr , and ∆Stotal in
the reversible cycle of the given figure consisting of step (i) when the process carried out reversibly
A, B and C and involving state 1,2 and 3. Fill in the (ii) when the process carried out irreversibly (one step)
blank space assuming reversible steps for both cases
Q.16 The enthalpy of atomization of PH3 is 954 KJ-mol–1
Case(i) Case(ii) and that of P2H4 is 1.485 MJ-mol–1.What is the bond
enthalpy of the P–P bond ?

Q.17 Calculate enthalpy change when infinitely dilute

solution
of CaCl2 and Na2CO3 are mixed.
∆Hf° for Ca2+(aq), CO32– (aq) and CaCO3(s) are – 130,
– 161.5, – 288.5 kCal mol–1 respectively.

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Q.18 The enthalpies of neutralization of NaOH & NH4OH
ANSWERS
by HCl are –13680 Cal and –12270 Cal respectively. 1. i = +ve , ii = – ve , iii = – ve iv = – ve
What would be enthalpy change if one g-eq of NaOH is
added to one g-eq of NH4Cl in solution ? Assume that 2. q = – 65 J , w = 20 J , ∆U = – 45 J
NH4OH and NaCl are quantitatively obtained. 3. CM = 13/6 R , w = – 400R , ∆U = 900R, q = 1300R
4. ∆U = w = – 1247.1 J ; ∆H = – 1745.94 J
Q.19 If the enthalpy of formation of HCl (g) and Cl – (aq) are
–92.3 kJ/mole and –167.3 kJ/mol, find enthalpy of 5. – 2.245 kJ
solution of HCl(g).
6. T2=100K, w = –5.016 kJ
7. q = 0; w =∆U= 4.12 kJ; ∆H = 5.37 kJ; Vf = 11.8 dm ;
3
Q.20 Calculate electron gain enthalpy of fluorine atom by
given data . Make Born-Haber's cycle. All values are in P = 5.21 atm
kJmol–1 at 25º C. Given : ∆Hdiss (F2) = 160, ∆Hf (NaF(s)) 8. (i) 18.424 bar.L; (ii) 72 bar.L; (iii) 40 bar.L . Single
stage compression
= –570, I.E. [Na(g)] = 495, ∆HSub [Na(s)] = 100. Lattice 9. Case(i)
enthalpy of NaF(s) = 895.

Q.21 The enthalpy of formation of ethane, ethylene and

benzene from the gaseous atoms are –2840, –2280 and
–5544 kJmol–1 respectively. Calculate the resonance
energy of benzene. The bond enthalpy of C–H bond is Process q w ∆E ∆H
given as equal to +410 kJ/mol. A isochoric 3/2 R(273) 0 3/2 R(273) 5/2 R(273)
B isothermal 546 R ln2 -546 R ln2 0 0
C isobaric -5/2R(273) R(273) -3/2R(273) -5/2R(273)
Q.22 The enthalpy of formation of C2H5OH(l) is 546 R ln2 -546 R ln2 0 0
cyclic
–66kCal/mol . The enthalpy of combustion of - R(273) + R(273)
CH3–O–CH3 is –348 k Cal/mol . Given that the
enthalpies of formation of CO2(g) and H2O(l) are Case(ii)
–94kCal/mol & –68 kCal/mol respectively, calculate ∆H
for the isomerisation of ethanol to methoxymethane . All
data are at 25ºC.

Q.23 Find the Bond enthalpy (in kJ/mol) of one "3c-2e bond" Process q w ∆E ∆H
A isobaric 5/2 R(273) -R(273) 3/2 R(273) 5/2 R(273)
in B2H6 , i.e.{B–H–B → 2B(g) +H(g)} from given data. B isochoric -3/2R(273) 0 -3/2R(273) -5/2R(273)

∆Hf° [BH3(g)] = 100 kJ/mole , ∆Hf° [B2H6(g)] = 36 kJ/mole, C isothermal -273R ln2 +273R ln2 0 0
cyclic R(273) - -R(273) 0 0
∆Hatm [B(s)] = 565 kJ/mole , ∆Hatm [H2(g)] = 436 kJ/mole. 273R ln2 +273R ln2

10. (a) 600 K

Q.24 For the reaction at 298 K, A (g) + B(g) → C(g) + D(g) ; (b) qAB = 3000 cal; qBC =1663 cal; qCD = –1800 cal;
∆H° = – 29.8 kcal ; ∆S° = –0.1 kcal / K. Calculate ∆G° qDA= –1663 cal; Total q = 1200 cal (c) w = –1200 cal
and Keq. 11. w(irr.)= – 9353.25 J ,w(rev.)= – 17288.47 J , ∆U=∆
H= 0
Q.25 Water expands when it freezes. Determine amount of
work done in joules, when a system consisting of 1.0 L of 12. ∆S = 9.865 JK–1 mol–1 13. 4.59 kJ
liquid water freezes under a constant pressure of 1.0 atm 𝑉𝑓 2 1 1
and forms 1.1 L of ice. 14. w= – nRT ln – n a{ − }
𝑉𝑖 𝑉𝑓 𝑉𝑖

Q.26 One mole of solid Zn is placed in excess of dilute 15. (i) Rev. Process ∆Ssys =(3/2)R ln 10 ;
H2SO4 at 27 °C, in a cylinder fitted with a piston. Find
the value of ∆U, q and w for the process if the area of piston ∆Ssurr = – (3/2)R ln 10 ; ∆Stotal =0
is 500 cm2 and it moves out by 50 cm against a pressure of (ii) Irr. Process ∆Ssys = (3/2)R ln 10 ;
1 atm during the reaction. The heat given to surrounding is
36.5 kJ. Zn(s) + 2H+ (aq) → Zn2+ (aq) + H2(g) ∆Ssurr = – (3/2)R (0.9) ; ∆Stotal = (3/2)R (1.403)]
16. 213 kJ /mol 17. 3 kCal
18. –1410 Cal 19. – 75 kJ/mole
Q.27 Two solutions initially at 25°C were mixed in an
adiabatic constant pressure Calorimeter. One contains 20. –350 kJ mol–1 21. – 24 kJ/mol
400ml of 0.2 M weak monoprotic acid solution. The 22. 22 kCal mol–1 23. EB-H-B = 455kJ/mol
other contain 100ml of 0.80 M NaOH . After mixing
temperature increased to 26.2 °C. How much heat is 24. ∆G° = 0 ; Keq = 1 25. – 10 J
evolved in the neutralization of 1 mole of acid? 26. ∆E = – 39.03 kJ/mole; q = – 36.5 kJ; w = – 2.53 kJ
Assume density of solution 1.0 g/cm3, and specific
heat of solution 4.0 J/g-K. Neglect heat capacity of 27. –30 kJ/mole
the Calorimeter.

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