XIII (XYZ) PHYSICAL CHEMISTRY REVIEW TEST-1

PART-A
Select the correct alternative. (Only one is correct) [26 × 3 = 78]
Q.1 Find f H° for HCl(g) from the following data:
NH3(g) + HCl(g)  NH4Cl(s); rH° = –176 kJ/mole
N2(g) + 3H2(g)  2NH3(g); rH° = –92 kJ/mole
N2(g) + 4H2(g) + Cl2(g)  2NH4Cl(s); rH° = –629 kJ/mole
(A) 536.5 kJ/mol (B) –361 kJ/mol (C*) –92.5 kJ/mol (D) None
[Sol. NH4Cl(s) NH3(g) + HCl(g) rH° = 176 kJ/mole
1 3
NH3(g)  N2(g) + H2(g) rH° = 46 kJ/mole
2 2
1 1
N2(g) + 2H2(g) + Cl2(g)  NH4Cl(s) rH° = –314.5 kJ/mole
2 2
______________________________________________________
1 1
H2(g) + Cl2(g)  HCl(g) f H° = –92.5 kJ/mole
2 2

Q.4 With what minimum pressure (in kPa) must a given volume of nitrogen, originally at 400 K and 100 kPa
pressure, be adiabatically compressed in order to raise its temperature to 700 K.
7
Given : Cp,m(N2) = R.
2
(A*) 362.5 kPa (B) 12.5 kPa (C) 437.5 kPa (D) None
[Sol. For an adiabatic irreversible compression, U = w,
 nCv,m(T2 – T1) = –Pext(V2 – V1); here Pext = P2
 nRT2 nRT1 
nCv,m(T2 – T1) = –P2  P  P 
 2 1 

5  T2 T1 
R (T2 – T1) = –P2 × R   
2  P2 P1 

5  700 400 
(700 – 400) = –P2  P  100 
2  2 
750 = –700 + 4P2
4P2 = 1450
P2 = 362.5 kPa ]

5
Q.7 A gas (Cv,m = R) behaving ideally was allowed to expand reversibly and adiabatically from 1 litre to
2
32 litre. It's initial temperature was 527°C
Molar Enthalpy Change (Hm) for the process is
(A) –1500 R Joule (B*) –2100 R Joule (C) 2100 Joule (D) None
 1 7 2
T2  V1   1 5
1
 1 5
[Sol. =    T 2 = T 1·   = 800·  5  = 800(0.5) 2 = 200K
T1 V 
 2  32  2 
7
Hm = R × (200 – 800) = –2100 R Joule ]
2
Q.13 For a perfectly crystalline solid Cp,m = aT3 + bT, where a & b are constant. If Cp,m is 0.40 J/K-mol at
10 K and 0.92 J/K-mol at 20 K, then molar entropy at 20 K is
(A) 0.92 J/K-mol (B) 8.66 J/K-mol (C*) 0.813 J/K-mol (D) None
[Sol. 3
0.40 = aT1 + bT1  0.40 = a × (1000) + b × 10
 0.4 = 1000a + 10 b ...(1)
0.92 = aT23 + bT2  0.92 = a × 8000 + 20b ...(2)
On solving
0.12 = 6000 a
a = 2 × 10–5
0.40 = 2 × 10–5 × 1000 + b × 10
 b = 0.038
aT 3  bT a[T23  T13 ]
Sm =  T ·dT 
3
+ b[T2 – T1]

2  10 5  (8000  0)
  b(20)
3

2 10 5  8000
  0.038  (20)
3
 0.053 + 0.76  0.813 J/K-mol ]

Q.15 The molar heat capacities at constant pressure (assumed constant with respect to temperature) of A, B
and C are in ratio of 1.5 : 3.0 : 2.5 . If enthalpy change for the exothermic reaction A + 2B  3C at
300 K and 310 K is H1 and H2 respectively then
(A) H1 > H2 (B) H1 < H2 (C*) H1 = H2
(D) If T2 > T1 then H2 > H1 & if T2 < T1 then H2 < H1
[Sol. rCp = 3 × 2.5 – 1 × 1.5 – 2 × 3  0
 H1 = H2 ]

Q.18 The enthalpy changes of the following reactions at 27°C are

1
Na(s) + Cl (g)  NaCl (s) rH = –411 kJ/mol
2 2
H2(g) + S (s) + 2O2 (g)  H2SO4 (l) rH = –811 kJ/mol
2Na(s) + S(s) + 2O2 (g)  Na2SO4 (s) rH = –1382 kJ/mol
1 1
H2(g) + Cl2(g)  HCl (g) rH = –92 kJ/mol; R = 8.3 J/K-mol
2 2
from these data, the heat change of reaction at constant volume ( in kJ/mol) at 27°C for the process
2NaCl (s) + H2SO4 (l)  Na2SO4 (s) + 2HCl (g) is
(A) 67 (B*) 62.02 (C) 71.98 (D) None
[Sol. 2NaCl(s)  2Na(s) + Cl2(g) rH = 411 × 2 kJ/mole
H2SO4(l)  H2(g) + S(s) + 2O2(g) rH = 811 kJ/mole
2Na(s) + S(s) + 2O2(g)  Na2SO4(s) rH = –1382 kJ/mole
H2(g) + Cl2(g)  2HCl(g) rH = –184 kJ/mole
____________________________________________________________
2NaCl(s) + H2SO4 (l)  2HCl(g) + Na2SO4(s) rH = 67 kJ/mole
2  8.3  300
67 = rU + ; rU = 62.02 kJ/mole ]
1000
 One or more than one is/are correct

Q.28 Which of the following statement(s) is/are false?

(A*) All adiabatic processes are isoentropic (or isentropic) processes
(B) E = 0 for combustion of C2H6(g) in a sealed rigid adiabatic container
(C*) dG = VdP – SdT is applicable for closed system, both PV and non-PV work
(D*) The heat of vaporisation of water at 100°C is 40.6 kJ/mol. When 9 gm of water vapour condenses
to liquid at 100°C of 1 atm, then Ssystem = 54.42 J/K

Q.31 Which of the following statement(s) is/are true?

(A) When (Gsystem)T,P < 0; the reaction must be exothermic
(B*) f H° (S, monoclinic)  0
(C*) If dissociation energy of CH4(g) is 1656 kJ/mole and C2H6 (g) is 2812 kJ/mole, then value of
C–C bond energy will be 328 kJ/mole
(D) If H+(aq) + OH–(aq)  H2O(l) rH° = –56 kJ/mol
f H°(H2O, g) = –242 kJ/mole; Enthalpy of vaporization of liquid water = 44 kJ/mol
then, f H°(OH , aq) will be –142 kJ/mole
–

PART-C
SUBJECTIVE: [3 × 8 = 24]

Q.1 Calculate f G°| for (NH4Cl, s) at 350 K.

Given: f H°(NH4Cl, s) = –314.5 kJ/mol

SN 2 ( g ) = 192 JK–1mol–1; SH 2 ( g ) = 130.5 JK–1mol–1

SCl2 ( g ) = 223 JK–1mol–1; SNH 4Cl (s ) = 94.5 JK–1mol–1; All given data at 300K.

 350 
rCP = –20 J/mol-K ; ln   = 0.15
 300 

 1  1 
[Sol. f S° (NH4Cl, s) at 300 K = S NH 4Cl(s ) –  S N 2  2SH 2  SCl2 
2 2 
1 1 
= 94.5 –   192  2  130.5   223 
2 2 
= 94.5 – (96 + 261 + 111.5)
f S300 = –374 JK–1mol–1

 350 
 f S =f S300 + rCpln  
310  300 
= –374 – 20 × (0.15) = –377 JK–1mol–1

 f H 310 = f H 300 + rCp[350 – 300]
 20  50
= –314.5 – = –315.5
1000
f G 350 = f H° – T.f S°
350  ( 377)
= –315.5 –  –183.55 kJ/mol
1000
f G 350 | = 183.55 kJ/mol  183 kJ/mol ]

Q.2 Fixed amount of an ideal gas contained in a sealed rigid vessel (V = 24.6 litre) at 1.0 bar is heated
reversibly from 27°C to 127°C. Determine change in Gibb's energy (G | in Joule) if entropy of gas
S = 10 + 10–2 T (J/K)
[Sol. dG = V.dP – S.dT ; at const. volume
P1 P2
2 
G = V.P –  (10  10 T).dT T1 T2  P2 = 1 × 400/300

4    T 2 T 2 
G = 24.6 ×  1 × 100 – 10  100  10  2   2  1 
3    2 2 
 

1  160000 90000 
G = 24.6 × × 100 – [1000 + 10–2 ×   ]
3  2 2 
1
= 24.6 × × 100 – 1000 – 350 = –530 J ]
3

Q.3 One mole of a monoatomic gas behaving ideally is used as

working substance in an engine working in the cycle as shown
in the figure. The process AB, BC, CD and DA are respectively
reversible isobaric, adiabatic, isochoric and isothermal. The ratio
of maximum to minimum volume and temperature during the
cycle is 8 2 and 4 respectively. If the maximum T is 800 K
and  = 5/3. Calculate E ( in kJ) for the process BC.
Given R = 8.3 J/K-mol.
[Ans.E = 2.49 kJ]
[Sol. Let maximum volume is V0
Volume at A = VA = V0
Volume at C = VC = Minimum volume
VA
=8 2 ...(1)
VC
Temp. at D and A is max. temp. = TD = TA = Tmax = T0
Minimum temp. is at point 'B' = TB = Tmin
TA T
TB =4 ...(2)  TB =
4
VB VA TB V0
Volume at B = VB ; =  VB = V0 · =
TB TA TA 4
 V0
also VC =
8 2
Temp. at C: TC VC 1 = TB VB 1
 1
TC  VB 
=  
 = (2 2 ) 2 / 3 = 2
TB V
 C
T0
TC = 2TB =
2
Internal energy change in the process BC:
T T 
E = nCv,m(TC – TB) = n C v,m  0  0 
 2 4 

nC v,m ·T0 3  T0  3 800

H = = R ·  = R  = 300 R  2.49 kJ Ans. ]
4 2  4  2 4