1 answer

Consider the spectrum of [V(H2O).]3+ in aqueous solution below and answer the questions that follow 17,000...

Question:

Consider the spectrum of [V(H2O).]3+ in aqueous solution below and answer the questions that follow 17,000 cm 24,500 cm Absor

Consider the spectrum of [V(H2O).]3+ in aqueous solution below and answer the questions that follow 17,000 cm 24,500 cm Absorbance Warenumber cm (a) What is the free-ion term for the electronic arrangement of the metal-ion? Use the appropriate Tanabe-Sugano diagram to assign the absorbance bands in the spectrum above Which transition is not observed in the spectrum? Suggest a reason why only two absorption bands are observed Determine the B Racah parameter Show all calculations. (e) Determine the Ao parameter Show all calculations.

Answers

CmpinVC. a) The The xidatim shate of Vs3 ls 0 3 = 3 V ir The outer cludmi Cona (AJ 3d 45 Thus Vt W ecomme of 2 CA J 3d Thu ththe L Valur Cwin be and 1-313/ 1-2-11 ahe L 0 S L: PA L 2 D Gre L3 F 1 Thu th term Cund shak for V3 Cd is Paid dxt+L F Caand

  1. The given complex is [V(H2O)6]3+.

Since H2O is a neutral ligand the oxidation state of V will be +3.

The outer electronic configuration of V is [Ar] 3d3 4s2, hence for V3+ it is [Ar] 3d2. Thus it is a d2 system.

The simplified tanabe sugano diagram is shown below for d2 configuration (g notations are used in calculations since we are considering a octahedral molecule which is centrosymmetric. The TB diagram shown below is a general one and thus the terms doesn't have g or u representations).

E A, T 60 T2 3T1 S 50 3T2 40 A, 30 G 20 E P T2 D 10+ 3T, 3 3F 2 1 A/B

From the diagram we can see that the four possible electronic transitions are

  1. 3T1g    3T2g (17000 cm-1)
  2. 3T1g      3T1g (P) (24500 cm-1)
  3. 3T1g     3A1g

The energy order of the transitions are 3>2>1.

c. The spin allowed transition that is not observed in the spectrum is 3T1g   3A1g .

This is because the energy separation between these states is very high and the absorption occurs at very high frequencies or wave number (in other word at very small wavelengths in UV region). It has a low intensity and since it is in the high energy portion of the spectrum where it is masked by many totally allowed transitions, it is not observed.

frm the specharum 000 cm 24500 cm-1 Cp) the rah of these dwo wav Ringhs a4500 -7 144 17000 -7 The ratie of 1hese twe transitifranshon t 70 00 m 3hey 2 Capp) 13 13 B 17000 em 586 20 (m l Bavary 583.3 58 6.20 584 75 m 31 e Simce Do (s 6, Bx 31 584.75 x

.

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