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Course Handout
Course No. : CHEM F111
Course Title : GENERAL CHEMISTRY
Scope and Objective of the Course: The course provides a
comprehensive survey of the concepts involved in the study of the
transition metal coordination complexes, VB and CFT for inorganic
complexes, stereochemistry and reactivity of organic compounds,
electronic structure of atoms and molecules, spectroscopy, chemical
equilibrium, chemical kinetics,
Text Books:
T1: P.W. Atkins, Elements of Physical Chemistry: 6th Edition, Oxford
University Press, 2015.
T2: T. W. Graham Solomons and Craig B. Fryhle, Organic Chemistry,
10th Edition, John Wiley & Sons, Inc. New York, 2011.
T3: J. D. Lee, Concise Inorganic Chemistry, 5th Edition, Blackwell
Science, Oxford, 1999.
Course Handout
First ~7 Lectures will be on Inorganic
Chemistry: Coordination Compounds
Next ~8-20 Lectures will be on Organic
Chemistry: Stereochemistry, Substitution,
Elimination, Addition, Aromaticity.
Physical Chemistry: ~21 Lectures: Quantum
Theory, Atomic Structure, Chemical Bonding,
Spectroscopy, Thermodynamics and Chemical
Kinetics.
Course Handout
Evaluation Scheme:
Component
Test I
Duration Weightage
Date, Day &Time
%
20/09/16, Tuesday
60 min
30%
2.00 pm-3.00 pm
Remarks
Closed Book
Test II
60 min
30%
25/10/16, Tuesday
2.00 pm-3.00 pm
Comprehensive
Examination
3 hrs.
40%
Open Book
Coordination Compounds
To explain
Structure
Color
and Magnetic properties of Transition metal
compounds using concepts of Valence Bond
Theory (VBT) and Crystal Field Theory (CFT)
Coordination Compounds:
Problem I: Identifying Primary and
secondary valency
CRYOSCOPIC
MEASUREMENT
MOLAR
CONDUCTIVITY
STRUCTURE
CoCl3.6NH3
CoCl3.5NH3
4
3
6
4
?
?
CoCl3.4NH3
2
CoCl3.3NH3
1
Co(NO2)3.KNO2.2NH3 2
2
0
2
?
?
?
Atomic Complex
number
Electrons Electrons
EAN
lost in ion gained by
formation coordination
Cr
24
[Cr(CO)6]
36 (Kr)
Fe
26
[Fe(CN)6]4-
12
36 (Kr)
Fe
26
[Fe(CO)5]
10
36 (Kr)
Co
27
[Co(NH3)6]3+
36 (Kr)
Ni
28
[Ni(CO)4]
36 (Kr)
Cu
29
[Cu(CN)4]3-
Pd
46
[Pd(NH3)6]4+
12
54 (Xe)
Pt
78
[PtCl6]2-
12
Fe
26
[Fe(CN)6]3-
12
Ni
28
[Ni(NH3)6]2+
12
Pd
46
[PdCl4]2-
52
Pt
78
[Pt(NH3)4]2+
84
(Kr)
(Rn)
Trans isomer
Cis isomer
Examples:
[Pt(NH3)4Cl2]2+,
[Co(NH3)4Cl2]+
Meridianal
Facial
Trans
Example: Pt(NH3)2Cl2
Optical isomers
[Co(en)]33+
3d
4s
4p
d2sp3hybridization
Octahedral shape
Inner orbital complex
Low spin complex
Type of question: Using VBT theory diamagnetic or paramagnetic
nature of a octahedral coordination complex
4d
VBT (Contd.)
Formation of a tetrahedral complex from
d6 system
3d
4s
4p
sp3hybridization
Tetrahedral shape
Outer orbital complex
High spin complex
4d
Color Wheel
[CrCl6]3-
13640
163
[Cr(H2O)6]3+
17830
[Cr(NH3)6]3+
21680
259
[Cr(CN)6]3-
26280
kJ/mol
[Co(NH3)6]3+
24800
296
[Rh(NH3)6]3+
34000
406
[Ir(NH3)6]3+
41000
490
Config. 0 (cm-1)
P (cm-1)
Predicted
Found
[Fe(H2O)6 ]2+
d6
10400
17600
High
spin
[Fe(CN)6 ]4-
d6
32850
17600
Low
spin
[CoF6 ]3-
d7
13000
21000
High
spin
[Co(NH3)6 ]3+
d7
23000
21000
Low
spin
Electronic
configuration
CFSE
d1
-0.4 0
d2
-0.8 0
d3
-1.2 0
d4 (High spin)
-1.2 0 + 0.6 0
d4 (Low spin)
-1.6 0
eg
CFSE
t2g
eg
CFSE
-0.4
1.73 1
-0.4
1.73
-0.8
2.83 2
-0.8
2.83
-1.2
3.87 3
-1.2
3.87
-0.6
4.90 4
-1.6
2.83
5.92 5
-2.0
1.73
-0.4
4.90 6
-2.4
-0.8
3.87 6
-1.8
1.73
-1.2
2.83 6
-1.2
2.83
-0.6
1.73 6
-0.6
1.73
10
t = (4/9)O
(Tetrahedral
CFSE scaled
for
comparison
with
octahedral
values)
Weak
field
(Oct.)
Strong
field
(Oct.)
1.73
-0.6
-0.27
-0.4
-0.4
d2
2.83
-1.2
-0.53
-0.8
-0.8
d3
3.87
-0.8
-0.36
-1.2
-1.2
d4
4.90
-0.4
-0.18
-0.6
-1.6
d5
5.92
d6
4.90
d7
d8
d9
d10
No. of delectrons
d1
t2
eg
Nature of
ligand field
Examples
d0
Strong or
weak
d3
Strong or
weak
[Cr(Ox)3]3-, [Cr(H2O)6]3+
d5
Weak
[MnF6]4-, [FeF6]3-
d6
Strong
[Fe(CN)6]4-, [Co(NH3)6]3+
d8
Weak
[NiF6]4-, [Ni(H2O)6]2+
d10
Strong or
weak
[Zn(NH3)6]2+,
[Zn(H2O)6]2+
eg
Nature of
ligand field
Examples
d4
Weak (HS)
Cr(II), Mn(III)
d7
Strong (LS)
Co(II), Ni(III)
d9
Strong or
weak
Cu(II)
eg
Nature of
ligand field
Examples
d4
Weak (HS)
Cr(II), Mn(III)
d7
Strong (LS)
Co(II), Ni(III)
d9
Strong or
weak
Cu(II)
d (z2)
d (xy)
d (xz) d (yz)
Question: Draw the splitting pattern if ligands are compressed along z-axis
dx2-y2
dxy
d-orbital
splitting in
square planar
coordination
dz2
dxz dyz