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Pilani Campus

CHEM F111 : General Chemistry

Lecture 19
18 Sep 2019
AY 2019-20, Sem-I
Crystal Field Theory
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Notice

Section: 3
Instructor: Saumi Ray
Room number: 6104
Day: 20.9.19, Friday
Time: 5:00 pm

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Summary of lecture 18
____ e
g

6 Dq
__ 10 Dq = ΔO
E __
_
4 Dq
____ How to estimate ΔO
__ t2g electronic spectroscopy

6 Dq = 0.6 ΔO and 4 Dq = 0.4 ΔO

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Summary of lecture 18
(1) Nature of the Ligands:
Spectrochemical Series: Strength of the Ligands
Halide donors < O donors < N donors < C donors
Weak Field Ligands Strong Field Ligands
(2) Nature of Metal cation:
Different Charges on the cation of the same metal:
Δo for [Fe(H2O)6]2+ = 10,400 cm-1
Δo for [Fe(H2O)6]3+ = 13,700 cm-1
Metal cation with a higher oxidation state has a larger value of Δo
than that with lower oxidation state.
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Summary of lecture 18

Different charges on the cation of different metal:

Two different cation with the same number of d-electrons
but with different charge (metals within a same period):

Δo for [V(H2O)6]2+ = 12,400 cm-1

Δo for [Cr(H2O)6]3+ = 17,400 cm-1

Oxidation state α ΔO

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Tetrahedral complex

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Tetrahedral complexes
The direction of approaching ligands coincides with neither eg nor
t2g orbitals.

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Tetrahedral complexes
axial orbital –metal-ligand = 109o28’/2 =
54o44’
Distance between axial orbital and ligand =
0.707a (a=edge length) (Face of the cube)
54o44’
 non-axial orbital –metal-ligand
= 35o16’
distance between non axial orbital
& ligand = 0.5a (a= edge length)
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Splitting in tetrahedral complex
d-orbital energy level diagram dxy dxz dyz
_ _ _

_ _ 
E dz2 dx2- y2
isolated
metal ion only high spin
_____
metal ion in tetrahedral
d-orbitals complex
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Tetrahedral complexes
____
__ t2
__ 2/5 Δt
E __
_
3/5 Δt
____ e
• t2 orbitals are in higher energy as opposed to octahedral field.
• Since there is no centre of symmetry in tetrahedron the parity subscript g is
omitted.
• The total tetrahedral splitting is t
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Tetrahedral complexes
In general t < o ,
• Since there are only 4 ligands compared to 6 in octahedron; this
gives 2/3 reduction from the octahedral crystal field splitting.
• d-orbitals do not coincide with the direction of M-L bonds; this gives
another 2/3 reduction.
So for the same ligand and same metal ion
t = (4/9)o (approximately)
Due to this low t values almost all the tetrahedral complexes are
High Spin (No pairing).
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Octahedral vs. tetrahedral
Tetrahedral Octahedral ____ eg
____
t2 __ 0.6 ΔO
E 0.4 Δt __
__
_
-0.6 Δt -0.4 ΔO
Free ion ____
_
___ __ t2g
e
So for the same ligand and same metal ion
t = (4/9)o (approximately)
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d6 configuration
Weak Strong
eg t2g6eg0
t2g4eg2 eg
E o E o Octahedron
t2g t2g

e3t23 e3t23
E E
Tetrahedron

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Crystal Field Stabilization Energy
In the d1 system, one electron is 0.4 o below Bari Centre. OR this
electron is stabilized wrt spherically symmetric field.
For an octahedral geometry:
Crystal Field Stabilization Energy = CFSE = (-0.4nt2g + 0.6neg) o ;
n = no. of electrons
[Ti(H2O)6]3+ : CFSE = -0.4 x 1 x o =-0.4x243 = -97 kJmol-1 eg
NOTE: This stability is w.r.t. Bari Centre.
E t2g

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CFSE for d-electron
eg
Similarly, V3+ = d2 = t2g So CFSE = - 0.8 o
2

E
t2g
Cr3+ = d3 = t2g3 CFSE = - 1.2 o eg
E
t2g

Due to Hund’s rule of maximum multiplicity the electrons are going to

different orbitals
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CFSE of d4 configuration
Case I Case II
eg eg
E o E ’o
t2g t2g

Case I: involves pairing which requires energy input

Case II: electron is placed in high energy eg orbital
Note: In both the cases the fourth electron placement raises the
energy of the system
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CFSE of d4 configuration
Case I Case II
eg eg
E o E ’o
t2g t2g
o >> ’o
Case I Case II
Pairing energy << o o’ << Pairing energy;
Low spin complex; high spin Complex;
Spin paired complex; spin free complex;
Strong ligands Weak ligands
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CFSE for Octahedral complexes
Weak Field Ligand Strong Field Ligand
dn Configuration Unpaired CFSE Configuration Unpaired CFSE
electrons o electrons o
d1 t2g1 1 -0.4 t2g1 1 -0.4
d2 t2g2 2 -0.8 t2g2 2 -0.8
d3 t2g3 3 -1.2 t2g3 3 -1.2
d4 t2g3eg1 4 -0.6 t2g4 2 -1.6
d5 t2g3eg2 5 0.0 t2g5 1 -2.0
d6 t2g4eg2 4 -0.4 t2g6 0 -2.4
d7 t2g5eg2 3 -0.8 t2g6eg1 1 -1.8
d8 t2g6eg2 2 -1.2 t2g6eg2 2 -1.2
d9 t2g6eg3 1 -0.6 t2g6eg3 1 -0.6
d10 t2g6eg4 0 0.0 t2g6eg4 0 0.0
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Tetrahedral complexes

Octahedral CFSE = (-0.4nt2g + 0.6 neg) o

Tetrahedral CFSE = (-0.6ne + 0.4 nt2) t

In octahedral cases, CFSE = 0 for d0, d5(weak) and d10 cases;

In Tetrahedral cases, CFSE =0 for d0, d5 and d10 cases irrespective of

strong or weak field ligands.

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Uses of CFSE values

Stabilization of oxidation state

(i) [Co(H2O)6]3+ : 3d6 system, t2g4eg2, CFSE: -0.4 ΔO

(ii) [Co(H2O)6]2+ : 3d7 system, t2g5eg2, CFSE: -0.8 ΔO

(iii) [Co(NH3)6]3+ (CFSE: -2.4 ΔO) and [Co(NH3)6]2+ (CFSE: -1.8 ΔO)

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Crystal Field Theory: lattice energy
CRYSTAL FIELD THEORY in explaining variation of Lattice Energy for
transition metal chlorides (1st row transition metals)

Excess stabilization (-ve) energy

above the line can be from CFSE

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
Sc2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+
-0.4o -0.8o -1.2o -0.6o 0 -0.4o -0.8o -1.2o -0.6o 0
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Crystal Field Theory: hydration energy
CRYSTAL FIELD THEORY in explaining variation of Hydration Energy

M2+(g) + H2O(excess)  [M(H2O)6]2+ H= -ve

Zero CFSE cases (Spherically

symmetric field cases) are d0, d5
(weak) and d10 i.e. Ca2+, Mn2+, and
Zn2+
All other ions have additional
stability which is CFSE
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Crystal Field Theory: ionic radii
CRYSTAL FIELD THEORY in explaining variation of Ionic Radii of M2+
ions in Octahedral environment

 Ca2+  Zn2+ nuclear charge increases

 Additional electrons are going to the same shell
 d electron shielding is poor
 Therefore the size of the ions should decrease smoothly
 However, as seen in the following graph the radius change is not
smooth
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Crystal Field Theory: ionic radii
Ionic radii of the dihalides of
the 1st transition series
Dark circles represents low spin
anions

t2g electrons : not oriented in the direction of metal-ligand bonds.

Less repulsion between the ligand and metal d electrons; closer
bonding and the ionic radius decreases.
V2+  d3  t2g3 ; nuclear charge is increased, but the additional
electron goes to t2g only; hence radius further decreases.
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Explanation
Cr2+  d4  t2g3eg1 (weak field); The fourth electron is now placed in an
orbital directly in M-L bond; repulsion and ionic radius increases

Mn2+  d5  t2g3eg2 ; one more electron in eg; hence radius further

increases
Similarly for Fe2+, Co2+, Ni2+ (d6, d7, d8) the additional electrons go to
t2g orbitals and hence the radius decreases
For Cu2+ and Zn2+ the 9th and 10th d electrons go to eg orbital and the
radius increases
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Crystal structure of spinels
Explanation of Crystal Structure of Spinels using CFT:
Spinels, AB2O4: A(II); B(III); O2-
Structure: Cubic Close Packed
Structure of Anions and
cations occupy the empty sites
(holes/ voids)

No. of Tetrahedral sites: 2N

(N= no. of anions per unit cell)
No. of Octahedral sites: N

In normal Spinel: (A2+[B3+2]O42-)

A(II) occupy the tetrahedral sites
B(III) occupy the octahedral sites
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Crystal structure of spinels
Crystal Structure of Spinels:
In Inverse Spinel: (B3+[A2+B3+]O42-)
A(II) occupy the Octahedral sites
B(III) occupy the Octahedral and Tetrahedral sites
Compare the structures of Mn2+Mn23+O4 and Fe2+Fe23+O4
Mn3+ (d4) Mn2+ (d5) Fe3+ (d5) Fe2+ (d6)

CFSE -0.60 Δo 0 0 -0.40 Δo

(Octahedral weak field)
CFSE (Tetrahedral weak field) -0.18 Δo 0 0 -0.27 Δo

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Crystal structure of spinels
Identify the preferred spinel structure for NiFe2O4
Ni is in +2 oxidation state, d8 configuration
In tetrahedral void, configuration: e4t24, CFSE = -0.8 Δt (0.4 ΔO)
In an octahedral void, configuration: t2g6eg2, CFSE = -1.2 ΔO
Fe is in +3 oxidation state, d5 system
In tetrahedral void, Configuration: e2t23, CFSE = 0
In octahedral void, configuration: t2g3eg2, CFSE = 0
Hence, Ni2+ prefer to stay in the octahedral void
Therefore, inverse spinel structure, FeIII[NiIIFeIII]O4
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Discussed topics……

 Factors affecting the magnitude of ΔO

 Tetrahedral complexes
 Crystal field stabilization energy in Octahedral geometry
 CFSE calculation of tetrahedral complexes
 Uses of CFSE: stabilization of oxidation state, lattice energy,
hydration energy, and ionic radii
 Crystal structure of spinel
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CFSE comparison (supporting slide)
When the CFSE is comparable both in octahedral and tetrahedral
geometries.
d0, d5, d10 no CFSE in oct. and tet.

d1 and d6 (weak) has Oct and Tet CFSE difference

= -0.4 o –(-0.6t) = (-0.4-(-0.6 x(4/9))) o
= (-0.4-(-0.27))o = -0.13 o

Similarly for d2 and d7 cases the difference is

Only – 0.17 o
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