Birla Institute of Technology & Science, Pilani, Rajasthan-333 031

II Semester 2018-2019
Subject: GENERAL CHEMISTRY CHEM F111 Mid-Semester Examination (Closed Book)
Max. Marks: 90 Model Solutions Date: March 15, 2019
Q1. (a) Sol: The emissive power (energy emitted per unit time per unit surface area) is given as

P = T4 , Therefore total energy emitted per second, E = P.a, where a = total surface area

E = a.T4 = 4× (7×105×103)2 m2 × 5.67×10-8 Wm-2K-4 × (6000)4 K4

= 4.52 ×1026 W [4M]

(b) Sol: (i) we know, p=h/

ℎ ℎ
Hence, 𝜆 = 𝑝 = 𝑚𝑣 [1M]

6.626×10−34 𝑘𝑔𝑚2 𝑠 −2 .𝑠
Or, 𝜆 = 6.62×10−24 ×10−3 𝑘𝑔 ×3.4×107 𝑚.𝑠−1 = 2.94 × 10−15 𝑚 [2M]

(ii) p.x = h/4

ℎ ℎ
Hence, ∆𝑥 = 4𝜋∆𝑝 = 4𝜋𝑚∆𝑣 [1M]

6.626×10−34 𝑘𝑔𝑚2 𝑠 −2 .𝑠
Or, ∆𝑥 = 4×3.141×6.62×10−24 ×10−3 𝑘𝑔×0.1×107𝑚𝑠−1 = 1 × 10−13 𝑚 [2M]

(c) Sol: Let N be the normalization constant

𝑎
Then, 𝑁 2 ∫0 𝜓2 (𝑥)𝑑𝑥 = 1 [1M]
𝑎
Or, 𝑁 2 ∫0 [𝑎(𝑎 − 𝑥)]2 𝑑𝑥 = 1
𝑎
Or, 𝑁 2 𝑎2 ∫0 (𝑎2 − 2𝑎𝑥 + 𝑥 2 )𝑑𝑥 = 1
𝑎
𝑥3
Or, 𝑁 2 (𝑎4 𝑥 − 𝑎3 𝑥 2 + 𝑎2 ) =1 [1M]
3 0

𝑎5 3
Or, 𝑁 2 = 1, 𝑡ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒, 𝑁 = √𝑎5 [1M]
3

3
Hence the normalized function is √𝑎5 𝑎(𝑎 − 𝑥) [1M]

(d) Sol: The transition is from n=3 to n=4 level [1M]

(𝑛𝑓 2 −𝑛𝑖 2 )ℎ2 (42 −32 )ℎ𝜆

Therefore, 𝐿 = √ =√
8𝑚∆𝐸 8𝑚𝑐

(42 −32 )(6.626×10−34 𝐽𝑠)(375×10−9 𝑚)

=√ [2M]
8(9.1×10−31 𝑘𝑔)(2.998×108 𝑚𝑠−1 )

= 892 pm [1M]
Q2. (a) Sol:
1/2
𝑍 3/2 −𝑍𝑟/𝑎 1 𝑍3
𝜳𝟏𝒔 = 2[ ] 𝑒 0 𝑋 =[ ] 𝑒 −𝑍𝑟/𝑎0
𝑎0 2𝜋1/2 𝜋𝑎0 3

𝟐 𝟐 𝑍3
𝟒𝝅𝒓 𝜳𝟏𝒔 = 4𝜋 [ ] 𝒓𝟐 𝑒 −2𝑍𝑟/𝑎0
𝜋𝑎0 3
𝟐
𝒅 4𝜋𝑍 3 𝟐𝒁 𝟐 −2𝑍𝑟/𝑎
𝟒𝝅𝒓𝟐 𝜳𝟏𝒔 = [ ] [𝟐𝒓 − ( )𝒓 ] 𝑒 0 = 0
𝒅𝒓 𝜋𝑎0 3 𝒂𝟎

Therefore,
𝒁 𝒂𝟎
[𝟏 − (𝒂 ) 𝒓 ] = 𝟎  𝒓𝒎𝒑 = (2)
𝟎 𝒁

𝒂𝟎 52.9 𝒂 52.9
𝒓𝒎𝒑 (𝑩) = = = 𝟏𝟎. 𝟔 𝒑𝒎 𝒓𝒎𝒑 (𝑼) = 𝟗𝟐𝟎 = = 𝟎. 𝟓𝟖 𝒑𝒎 (1+1)
𝟓 𝟓 𝟗𝟐

As per announcement made during exam:

𝟐
𝒅 𝟐
(4√2)𝜋𝑍 3 𝟐𝒁
𝟒𝝅𝒓 𝜳𝟏𝒔 = [ 3
] [𝟐𝒓 − ( ) 𝒓𝟐 ] 𝑒 −2𝑍𝑟/𝑎0 = 0
𝒅𝒓 𝜋𝑎0 𝒂𝟎

Will not make any difference in the solution.

−𝒉𝒄𝑹𝑯 𝒁𝟐 −𝒉𝒄𝑹𝑯 −𝒉𝒄𝑹𝑯

(b) Sol: 𝑬𝒏 = = =
𝒏𝟐 𝒏𝟐 𝟗

Therefore, n = 3 and l = 0, 1, 2. (1)

n l ml degeneracy Marks
3 0 0 1 (1)
3 1 +1, 0, -1 3
3 2 +2, +1, 0, -1, -2 5
Total degeneracy 9 (1)

(c) Sol: (i) For fluorine Z = 7; electronic configuration is 1s22s22p5;

This can be considered as “one hole” in p – orbital case, and hence will have the same levels as that of p1.

+1 0 -1

l = 1; ml = +1; therefore L =1.

S = +1/2; 2S+1 = 2 ; J = 1+1/2 and 1-1/2 ; J =3/2 and ½. (1)

Therefore the term is 2P and the levels are 2P3/2 ; 2P1/2 (1)
For ground level the J will depend on the filling; In this case it is more than half filled. The ground level will
correspond to highest J value.

The ground level is 2P3/2 (1)

(ii) 4F9/2 F L = 3 (Only possible with d and f orbital electrons. Since atomic number is less than 31, f orbitals
are ruled out) (1)

2S + 1 = 4; therefore S= 3/2 and three unpaired electrons are expected. (1)

The valence shell configuration is either d3 or d7. (1)

L = 3 and S = 3/2; therefore J = | 3+3/2|,…….., |3-3/2|; J = 9/2,……3/2

Since the highest value of J is given the shell is more than half filled and hence the configuration is d7.

The electronic configuration of the atom is 1s22s22p63s23p64s23d7 (Co) (1)

(d) Sol: N2 molecular orbital configuration is 1σg21σu21πu42σg2 (core electrons are neglected);

N2+ will have one unpaired electron in 2σg (The ionization is from HOMO). Therefore, the

μso (N2+) = √n(n+2) = √1(1+2) = 1.732 BM. (2)

N22- will have two unpaired electrons in 1πg2 ( added electrons will go to the LUMO).

μso (N22-) = √n(n+2) = √2(2+2) = 2.449 BM (2)

1𝑢×35𝑢
Q3. (a) Sol: (i) 𝜇 = (1𝑢+35𝑢) × 1.67 × 10−27 𝑘𝑔 = 1.623 × 10−27 𝑘𝑔 (1)

I = r2 = 1.623 10-27 kg  (1.30 10-10)2 = 2.74 10-47 kg m2 (1)

ℎ 6.626 ×10−34 𝐽𝑠
𝐵 = (8𝜋2𝐼) = (8(3.14)2 (2.74 ×10−27 𝑘𝑔 𝑚2 ) = 3.06 × 1011 𝐻𝑧 (2)

II line will be observed at 4B

4(3.06  10-11) = 12.24 x 1011 Hz (1+1)
(ii) = (3.0 x 1010 cm/s)(2988.9 cm-1)= 8.966 x 1013 s-1 (1)
𝑘 = 4𝜋 2 𝜈 2 μ = 4(3.14)2(8.966 x 1013 s-1)2(1.623 x 10-27 kg) = 515 N/m (1+1)
(b) Sol: Separation between the first and third anti-Stokes lines = 8B = 7.06 cm–1
B = (1/8) (7.06) = 0.8825 cm–1 (1+1)
1/2
ℎ 6.626 ×10−34 𝐽𝑠
𝑟 = (8𝜋2 𝜇𝑐𝐵) = (8(3.14)2 (1.577 ×10−26 𝑘𝑔)(3.0 ×1010𝑐𝑚 𝑠−1 (0.8825𝑐𝑚−1 )) (2)
= 1.417 x 10-12 m (1)
(c) Sol:

IR stretching frequencies (cm-1) Compound

3500 (broad), 1710 (strong), 1200

3400, 3300, 1690 (strong)

 1735 (strong), 1200, 1000

2850, 2750, 1725 (strong)

1+ 1+1+1

Q4. (a) Sol: The stable complex is Cr(CO)6 [1M]

EAN for Cr(CO)6 = 24+12 = 36e- = Kr configuration [2M]
EAN for V(CO)6 = 23+12 = 35e- ≠ Kr configuration
EAN for Mn(CO)5 = 25+10 = 35e- ≠ Kr configuration

(b) Sol: (i) coordination isomer. [1M]

(ii) Ionization isomer [1M]
(iii) Linkage isomer [1M]
(c) Sol: VCl2 < CrCl2 < MnCl2 [1M]

t2g electrons are not oriented in the direction of metal-ligand bonds, whereas, eg electrons are oriented directly.

V2+ d3 t2g3 ; electrons are in t2g only; hence radius decreases. [1M]

Cr2+ d4 t2g3eg1; The fourth electron is now placed in an orbital directly in M-L bond; repulsion and ionic
radius increases [1M]

Mn2+ d5 t2g3eg2 ; one more electron in eg; hence radius further increases [1M]

(d) Sol: Cu is in +2 oxidation state, d9 configuration

(i) In an octahedral, configuration: t2g6eg3, CFSE = -0.6 ΔO = -0.6 × 162 = -97.2 kJ/mol. [2M]

(ii) In tetrahedral, configuration: e4t25, CFSE = -0.4 Δt = -0.2 ΔO = -0.2 × 162 = -32.4 kJ/mol [3M]

(e) Sol:
Primary Structure Molar Cryoscopic
valence conductivity measurement
(charges) (particles)
3 3K+[Co(NO2)6]3- 6 4

Q5. (a) Sol: [Co(NO2)6]4- and [Cr(CN)6]4- will exhibit the Jahn-Teller distortion [1M]

Ni(CO)4 and[Fe(H2O)6]3+will not exhibit Jahn-Teller distortion [1M]

(ii) Co(II), d7 the electronic configuration in Oh geometry, t2g6eg1 (nitrite is a strong field ligand);
unsymmetrical distribution of electrons in eg orbitals and hence will exhibit Jahn-Teller distortion [1.5M]

Cr(II), d4, the electronic configuration in Oh geometry, t2g4eg0 (cyanide is a strong field ligand); unsymmetrical
distribution of electrons in t2g orbitals and hence will exhibit Jahn-Teller distortion [1.5M]

Ni(0), d10, the electronic configuration in Td geometry, e4t26; so symmetrical distribution of electrons in e and t2
orbitals and hence will not exhibit Jahn-Teller distortion [1.5M]

Fe(III), d5, the electronic configuration in Oh geometry, t2g3eg2; so symmetrical distribution of electrons in t2g
and eg orbitals and hence will not exhibit Jahn-Teller distortion [1.5M]
(iii) (A) Magnetic moment = √n(n+2) = 0 [1M]

n = no of unpaired es;

(B) Magnetic moment = √n(n+2) = √3; n = 1 [1M]

(C) Magnetic moment = √n(n+2) = √8 = 2√2 (approx); n = 2 [1M]

(D) Magnetic moment = √n(n+2) = √35; n = 5 [1M]

(b) Sol: Platinum(II) is 5d8 system

For d-orbitals in appropriate splitting form will get [2M] and filling up with es will get [1M]

(c) Sol: The Beer-Lambert law is, log(I/I0) = -Ɛcl; so, l = (1/Ɛ x c) log(I/I0)

I = 1/(30dm3mol-1cm-1) x (1moldm-3) log(1/2) [2M]

= 0.01cm [1M]

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