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Crystal Field Theory and Coordination Complexes

Description: GATE Valence Bond and Crystal Field TheoryGeometry and Magnetic PropertiesGeneral Characteristics of 3d ElementsCoordination Complexes
Number of Questions: 15
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Tags: GATE Valence Bond and Crystal Field Theory Geometry and Magnetic Properties General Characteristics of 3d Elements Coordination Complexes
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Which of the following pairs does not form active positive ions in chemical reactions?

  1. As and Sb

  2. Ga and Po

  3. Tl and In

  4. As and Ga

  5. Sb and In


Correct Option: A
Explanation:

Both As and Sb, belong to groupb15 and are metalloids which have the properties of metals as well as non-metals. Metalloids do not form positive ions in chemical reactions. Metals and poor metals form active positive ions during the chemical reactions.

Which of the following statements is/are correct? P. Bell metal consists of Cu, Sn and little Zn. Q. Wood metal is used in the making of automatic sprinklers. R. Duralumin is used in the manufacturing of aeroplane parts and consists of Al, Cu, Mg and Mn.

  1. Only P

  2. Only Q

  3. Only R

  4. P and Q

  5. Q and R


Correct Option: E
Explanation:

Bell metal is an alloy and consists of Cu = 80%, Sn = 20%. Wood metal consists of Bi = 50%, Pb = 25%, Sn = 12.5% & Cd = 12.5% and is used in the making of automatic sprinklers as it melts in hot water (m.p.= 68 oC). Duralumin is used in the manufacturing of aeroplane parts and consists of Al = 95.5%, Cu = 4%, Mg = 0.5% and Mn = 0.5%.

The CFSE for octahedral complexes of Fe3+ in a weak field and strong field ligand systems are ____________ respectively.

    • 4Dq, - 20 Dq
  1. 0, - 20 Dq

    • 4Dq, - 20 Dq+2P
    • 12Dq, - 20 Dq+2P
  2. 0, - 20 Dq+2P


Correct Option: E
Explanation:

In a weak field ligand system, the electron filling of splitting of d-orbital corresponds to Hund’s rule, followed by pairing. In strong field ligand system, the electron filling of splitting of d-orbital corresponds to pairing at initial stage. For Fe3+ electronic configuration is d5. For d5 in weak field ligand system, CFSE = 3 (- 4) + 2 (6) = - 12 + 12 = 0 Dq (All electrons is unpaired, 3 in t2g and 2 in eg) For d5 in strong field ligand system, CFSE = 5 (- 4) + 0 = - 20 Dq + 2P
(two paired electrons and one electron is unpaired in t2g and 0 electron in eg orbital) Hence, the CFSE for octahedral complexes of Fe3+ in a weak field and strong field ligand systems are 0 and -20 Dq+2P respectively.

Which of the following copper minerals is the least pure?

  1. Azurite

  2. Cuprite

  3. Malachite

  4. Covellite

  5. Chalcocite


Correct Option: A
Explanation:

The percentage of copper in azurite, (2CuCO3.Cu(OH)2) is 55.1%. Hence, azurite is the least pure among all the given minerals.

The ground state free ion term of V2+ for weak field ligand is ________.

  1. 3D3/2

  2. 3F3/2

  3. 4D3/2

  4. 4F3/2

  5. 4F9/2


Correct Option: D
Explanation:

V2+ has d3 electronic configuration and it is empowered in a weak field ligand. The term symbol is calculated by the formula- 2s+1 LJ For d3, n = 3 s = n/2 = 3/2 2s + 1 = 4 L = 3 = F J = (L + s) to (L - s) = 2, 1, 0 term symbols = 2s + 1 LJ = 4F9/2, 4F7/2, 4F5/2, 4F3/2 The ground state term for V2+ is 4F3/2.

Which of the following metal ions has/have 5D4 as ground state term(s)? A. Mn4+ B. Fe2+ C. Co3+

  1. Only A

  2. Only B

  3. Only C

  4. Only A and B

  5. Only B and C


Correct Option: E
Explanation:

Ground state term for Mn4+ is 6S5/2. Ground state term for Fe2+ is 5D4. Ground state term for Co3+ is 5D4.

The ground state term symbols of Fe3+ and Fe2+ in a high spin ligand system are __________.

  1. 6S5/2 and 5D4

  2. 6S3/2 and 5D3

  3. 5S5/2 and 5D4

  4. 6S3/2 and 4D3/2

  5. 6S5/2 and 5D3/2


Correct Option: A
Explanation:

Fe3+ and Fe2+ have d5 and d6 electronic configurations and both are in high spin ligand system. The term symbol is calculated by the formula- 2s+1 LJ For d5, n = 5 s = n/2 = 5/2 2s + 1 = 6 L = 0 = S J = (L + s) to (L - s) = 5/2 Possible term symbol for Fe3+ = 2s + 1 LJ = 6S5/2 Similarly, possible term symbols for Fe2+ = 5D4, 5D3, 5D2, 5D1, 5D0 The ground state term for Fe3+ is 6S5/2. The ground state term for Fe2+ is 5D4.

Which of the following sandwich compounds has a diamagnetic nature?

  1. (η-C5H5)2Ti

  2. (η-C5H5)2V

  3. (η-C5H5)2Cr

  4. (η-C5H5)2Fe

  5. (η-C5H5)2Co


Correct Option: A
Explanation:

(η-C5H5)2Ti has zero number of unpaired electrons and possesses a diamagnetic nature.

Match the List-A (electronic configurations) with the items in List-B (ground state terms).

 
Electronic configurations
Ground state terms
P. d1 1. 4F3/2
Q. d2 2. 2D3/2
R. d3 3. 3F2
S. d4 4. 5D0
  1. P - 2, Q - 3, R - 1, S - 4

  2. P - 2, Q - 1, R - 4, S - 3

  3. P - 4, Q - 3, R - 1, S - 3

  4. P - 2, Q - 1, R - 3, S - 4

  5. P - 1, Q - 2, R - 4, S - 3


Correct Option: A
Explanation:

The ground state terms for d1, d2, d3 and d4 electronic configurations are 2D3/2, 3F2, 4F3/2 and 5D0 respectively. Hence, the representation of codes P - 2, Q - 3, R - 1, S - 4 is the correct answer.

Which of the following statements is/are correct? A. Carborundum is used as a refractory material. B. Blast furnace is used for the smelting of lead ore. C. Calamine and zincite are the ores of zinc.

  1. Only A

  2. Only A and B

  3. Only B and C

  4. Only A and C

  5. A, B and C


Correct Option: E
Explanation:

The substances which are capable of withstanding very high temperatures without melting or becoming soft are called refractory materials like- SiC (carborundum), Al2O3 and SiO2. Blast furnace is used for the smelting of iron, copper and lead ores. Calamine (ZnCO3) and zincite (ZnO) are the ores of zinc.

Which of the following sets represents weak field ligands?

  1. S2-, SCN-, NO3-

  2. NO2-, CN-, PPh3

  3. Cl-, N3-, NO2-

  4. NO3-, NO2-, I-

  5. PPh3, S2-, SCN-


Correct Option: A
Explanation:

On the basis of ligand field theory, the spectrochemical series is an empirically-derived list of ligands ordered by the size of the splitting CFSE that they produce. It can be seen that the low-field ligands are all pi-donors, the high field ligands are pi-acceptors, and ligands such as H2O and NH3, which are neither of the two, are in the middle. The spectrochemical series is give as: I− < Br− < S2− < SCN− < Cl− < NO3 < N3 < F < OH < C2O42− < H2O < NCS < CH3CN < py (pyridine) < NH3 < en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) < NO2 < PPh3 < CN < CO Hence, S2-, SCN- and NO3- are all weak field ligands.

Which of the following pairs represents high spin complexes?

  1. [FeF6]3-and [Mn(H2O)6]3+

  2. [Cr(NH3)6]3+ and [Mn(CN)6]3-

  3. [CoF6]3-and [Cr(NH3)6]3+

  4. [Co(NH3)6]3+and [Mn(CN)6]3-

  5. [Mn(CN)6]3- and [Mn(H2O)6]3+


Correct Option: A
Explanation:

[FeF6]3- and [Mn(H2O)6]3+ both have sp3d2 hybridisation and hence, are outer orbital or high spin complexes.

Which of the following complexes has/have two unpaired electrons? A. (ηi-C5H5)2Ni B. (η-C5H5)2V C. (η-C5H5)2Cr

  1. Only A

  2. Only B

  3. Only C

  4. Only A and B

  5. Only B and C


Correct Option: E
Explanation:

A and B both have a paramagnetic nature with 2 unpaired electrons respectively. Hence, these are identical in the number of unpaired electrons.

Match the coordination complexes in Column-I with corresponding coordination numbers and select the correct answer.

 
Column-I
Column-II
P. [Mn(NH3)6]2+ 1. 7
Q. [(Ph4As)2Mn(NO2)4] 2. 8
R. [Mn(EDTA)(NH3)]2- 3. 5
S. [Mn(S2C6H3Me)2]- 4. 4
5. 6
  1. P - 3, Q - 5, R - 1, S - 2

  2. P - 4, Q - 2, R - 3, S - 5

  3. P - 5, Q - 2, R - 1, S - 4

  4. P - 3, Q - 2, R - 4, S - 1

  5. P - 2, Q - 5, R - 1, S - 3


Correct Option: C
Explanation:

The coordination complexes [Mn(NH3)6]2+, [(Ph4As)2Mn(NO2)4], [Mn(EDTA)(NH3)]2- and [Mn(S2C6H3Me)2]- have the coordination numbers of 6, 8, 7 and 4 respectively. Hence, the representation of the codes P - 5, Q - 2, R - 1, S - 4 is the correct answer.

Match the entries in List-I with List-II and select the correct answer.

 
List-I
List-II
A. (PPh3)3RhCl 1. Monsanto
B. Rh(CO)2I2 2. Wilkinson
C. PdCl4 3. Ziegler-Natta
D. Al(C2H5)3/TiCl4 4. Wacker
  1. A - 2, B - 1, C - 4, D - 3

  2. A - 2, B - 3, C - 4, D - 1

  3. A - 1, B - 2, C - 4, D - 3

  4. A - 3, B - 4, C - 1, D - 2

  5. A - 4, B - 3, C - 2, D - 1


Correct Option: A
Explanation:

(PPh3)3RhCl is a Wilkinson’s catalyst and catalyses the hydrogenation of alkenes, Rh(CO)2I2 is a Monsanto catalyst and is an important process for the manufacture of the acetic acid. PdCl4 is a Wacker catalyst. The Wacker process is originally referred to as the oxidation of ethylene to acetaldehyde by oxygen in water in the presence of a tetrachloropalladate catalyst. Al(C2H5)3/TiCl4 is a Ziegler-Natta catalyst. It is as a catalyst in the synthesis of polymers of alpha-alkenes. Hence, the correct answer using the codes is A - 2, B - 1, C - 4, D - 3.

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