BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE-PILANI, K. K.

BIRLA GOA CAMPUS

FIRST SEMESTER 2015-16

COMPREHENSIVE EXAMINATION (SOLUTION)

Course Title: GENERAL CHEMISTRY Course No: CHEM F111

 
1(a)
  :            


 1
   
 2 
6.626 ! 10#$% &' ! 3 ! 10) ' # 1
  ! 9.11 ! 10#$ -. ! /1.24 ! 101 ' # 2
165 ! 10 
#+ 2
= 1.2047 ! 10#) &  7 ! 10#+&  0.5053 ! 10#) & 4 5.053 ! 10#+ & (3)
 

    


1.11!5678 9:!$!5; <:6=

  5.053 ! 10#+&  2.448 ! 10#+ &
1>!56? <

2.448 ! 10#+ ! 2&

   5.374 ! 10  ' #
9.11 ! 10#$ -.

A  B. CCD ! DEF G/I 4 BCC. DJG/I (3)

Note: Without J unit -1 mark.

RS T U
(b) K.L  LM.K  N', P Q  
VU

1.11!5678 9:!$!5; <: 6= !5+1WW!55!+

 (2)
+

= -2.18 10-18 J (2)

Note: Without J unit -1 mark. No negative sign -1 mark

(c) Number of radial nodes is (n-l-1) and number of angular nodes is equivalent to l quantum
number.

No. of Radial No. of Angular nodes

nodes
2p 0 1
3d 0 2
5s 4 0
(3)

1
2(a)

Molecule Total No. of No. of valence Total no. of Bond Order

electrons electrons in each Molecular
atom orbitals using
valence atomic
orbitals (BASED
ON Linear
combination of
atomic orbitals)
F2 18 7 8 1
N2 14 5 8 3
B2 10 3 8 1
(3 2 = 6)

  
(b) X  Y Z [ \]  Y Z [ \] ^ here \]  793.2# NKM ^  0.0125 (1)

Overtones are transitions with v = +2, +3,..

The first vibrational overtone corresponds to the transition v = 0
2. The wave number of this
transition is therefore: (1)

a aU #ab
First overtone: \]_5   (1)
 

= = U = = U
cYQ [d
e#YQ [ e
dfg h#cY5Q [d
e#Y5Q [ e
dfg h

U U U U


> >  
 iY[ \]  Y % [ \] ^ j  iY[ \]  Y%[ \] ^ j = 2\]  6\] ^  2 ! \] /1  3^ ) (1)

 2 ! 793.2# ! k1  /3 ! 0.01252l = 1526.9 cm-1 (2)

3(a) Given Reaction:

CO (g) + H2O (g) CO2 (g) + H2 (g)

Reqd. to find rH at 1500 K

rH (298 K) = [(0 + 393.51) (110.52 241.82)] kJ/mol = 41.17 kJ/mol

rCp = [(44.22 + 0.00879T) + (27.28 + 0.003267T)] [(28.41 + 0.0041T) + (30.54 +

0.0102T)] = 12.55 2.25 10-3T JK-1mol-1 (2)

2
 >55o
rH (1500 K) = -41170 J/mol + m+)o /12.55  2.25 ! 10#$ n2Mn J/mol

(Kirchoff Eqn.) (2)

>55o
.>!567
= 41170 Z p12.55n  n q J/mol
 +)o

.>!567
= 41170 Z i12.55/1500  2982  /1500  298 2j


)>1.>9
 41170 Z 15085.1  2431.35   <rs
4 tu. FDvJw/Gxy (2)

Note: Calculating formation enthalpy for each reactant and product usingz { | /298 } 2 Z
/
m ~ Mnand then calculating rH (1500 K) is also correct.(Integration method should be used)

(b) Reqd. to find rS at 1500 K

rS at 298K = (130.68 + 213.74) (197.67 +188.83) Jmol-1K-1 = 42.08 JK-1mol-1

(2)

/ |
rS (T/) = rS (T) + m
Mn

>55o .>>#.>!567
rS (1500K) = rS (298K) JK-1mol-1 + pm+)o Mnq JK-1mol-1

(2)
>55o
 42.08 Z i12.55K +)o
 2.25 ! 10#$ /1500  2982}j

= 24.502 JK-1mol-1 (2)

|/ /
For rS (1500 K ): < 298} 2 Z m |/
Mn < 1500} 2 can be calculated for each reactant

and productand then calculating rS (1500 K) is also correct. (Integration method should be
used)

3 (a)

3
For a solid or liquid,
Pf

G = VdP = V ( Pf Pi )
Pi

Gm (C , s,100 bar) = Gm (C , s,1 bar) + Vm ( Pf Pi ) = Gm (C , s,1 bar) + (P Pi )

M
f

12.011 10-3 kg
=0+ -3
99.0 105 Pa = 52.8 J
2250 kg m (2)

Treating He as an ideal gas,

Pf

Gm ( He, g ,100 bar ) = Gm ( He, g ,1 bar ) + VdP

Pi

Pf 100 bar
= 0 + RT ln = 1 mole 8.314 J mol-1 K -1 298.15 K ln =11.4 103J
Pi 1 bar (2)

This result is a factor of 216 greater than that for graphite. (1)

(b) The stoichiometry of the reaction is such that for every reactant molecule that decays (x), two
acetone (2x) and one ethane (x) are produced. Using this, the extent of reactant decomposition
when the total pressure is 1.8 atm can be determined as follows:

1.8 atm = (1 atm x ) + 2x + x

1.8 atm = 1 atm + 2x
x = 0.4 atm

Thus, Preactant = 1 atm 0.4 atm = 0.6 atm

(2)

Using the integrated rate law expression for a first-order reaction (as indicated by the units of the
rate constant), the time is determined as follows:
[ Reactant ] = [ Reactant ]0 e kt
( 0.6 atm ) = (1 atm ) e ( )
1.9103 s1 t

(2)
( )
1.9103 s 1 t
0.6 = e
ln ( 0.6 )
=t
1.9 103 s 1
269 s = t (1)

(c )

4
 Applying the steady state approximation to the intermediate NO3 and substituting back
into the differential rate expression for N2O5 yields:

d [ NO3 ]
= 0 = k1 [ NO2 ][ O3 ] k2 [ NO 2 ][ NO3 ] (2)
dt
k2 [ NO 2 ][ NO3 ] = k1 [ NO 2 ][ O3 ]
k
[ NO3 ] = 1 [ O3 ] (1)
k2

d [ N 2 O5 ]
= k2 [ NO 2 ][ NO3 ] (1)
dt
k
= k2 [ NO 2 ] 1 [ O3 ]
k2
= k1 [ NO2 ][ O3 ]
(1)

The mechanism predicts that the reaction is first order in NO2 and O3, second order overall.

5(a) (i) [Rh(py)3Cl3] (ii) [Rh(bpy)2Cl2]

Cl

N N
Rh
N N (1)

Cl trans

N
N
Cl
(1)
Rh
NN Cl

N
Cis and its optical
isomer
Mer-isomer Fac-isomer

(1)
(1)

5
 N

Cl N
(1)
Rh

Cl N

(b) - 2- 2-
Cl Cl
CN CN

Ni
Ni
Cl
CN CN Cl

[Ni(Cl)4]2- (3)
2-
[Ni(CN)4] (3) 6
(c) o > P in [FeY6]2+ o < P in [FeX6]2+ pairing takes place in [FeY6]2+ (less spin only
magnetic moment). Highest spin only magnetic moment in [FeX6]2+ (3)

Note: 5. a) 0.5 marks each reduced if py and bpy structures are wrong or not given

1 mark reduced if optical isomer of cis is not drawn

If so many isomers structures are given (same structure, but different drawing), 1 mark reduced

b) Marks deducted for crystal field splitting diagram without electrons.

6 (a) (i) (ii) (iii) (iv) (v)

O
O
(5 2 = 10)
AcO

6 (b)
Cl (3)
Cl
Cl
1 2 3
3>1>2

6 (c) 2>3>4>1 (1)

Note: Q. 6(a) 1 mark for missing stereo; 6(a) (v) Only 1 mark for showing

6(b) If order is correct, then (+1 mark), if two chair forms are correct, then (+1), if all are correct
(+3). If axial and equatorial and and are not shown clearly then no marks.

6(c) Full credit or zero credit.

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