Tutorial on properties of Transition Metal and Magnetism.

Prepared by
Lawrence Kok
awrencekok.blogspot.com
 Periodic Table of elements divided into s, p, d, f block

s block
s orbital partially fill

p block
d block
p orbital partially fill
d orbital partially filled
transition element

f block
f orbital partially fill
 s block element Periodic Table s, p d, f block element p block element
s orbitals partially fill p orbital partially fill

5 B [He] 2s2
1 H 1s1 2p1
2 H 1s2 n = 1 peri
od 1 6 C [He] 2s2
e n = 2 period 2
2p2
3 Li [He] 2s1 2
p eriod 7 N [He] 2s2
4 Be [He] 2s2 n=2
2p3
d3
eri o n
= 8 O [He] 2s2
p 3
11 Na [Ne] 3s =3 2p4
1
pe
n rio
d
4
12 Mg [Ne] 3s2 d 3 9
13 F
Al [He]
[Ne] 2s
3s2 3p1
ri o
2p5
pe

14 Si [Ne] 3s2 3p2

4

10 N [He] 2s2
=

19 K [Ar] 4s 1
n

15 P
e [Ne]
2p6 3s2 3p3
20 Ca [Ar] 4s2 16 S [Ne] 3s2 3p4
17 CI [Ne] 3s2 3p5
4

f block element 18 Ar [Ne] 3s2 3p6

d
rio

d block element f orbitals partially fill

pe

d orbitals partially fill

4

transition elements
=
n

21 Sc [Ar] 4s2 3d1

22 Ti [Ar] 4s2 3d2
Video on electron configuration
23 V [Ar] 4s2 3d3
24 Cr [Ar] 4s1 3d5
25 Mn [Ar] 4s2 3d5
26 Fe [Ar] 4s2 3d6
27 Co [Ar] 4s2 3d7
28 Ni [Ar] 4s2 3d8
29 Cu [Ar] 4s1
3d10
Click here electron structure Click here video on s,p,d,f notation Click here video s,p,d,f blocks,
30 Zn [Ar] 4s2
 Periodic Table s, p d, f blocks element

Electron structure Electron structure Electron structure

Chromium d block (Period 4) Germanium p block, Gp 14 (Period 4) Iodine p block, Gp 7 (Period 5)

1s2 2s2 2p6 3s2 3p6 4s1 3d5 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2 1s2 2s2 2p6 3s2 3p6 3d104s2 4p6 5s2 4d10 5p5

[Ar] 4s1 3d5 [Ar] 4s2 3d10 4p2 [Kr] 5s2 4d10 5p5

d block d partially filled Gp 14 -4 valence electron Gp 17 - 7 valence electron

Electron structure Electron structure Electron structure

Cadmium d block (Period 5) Mercury d block (Period 6) Lead p block, Gp 14 (Period 6)

2
2s2 2p6 3s2 3p6 3d104s2 4p6 5s22
1s 4d
2s102 2p6 3s2 3p6 3d104s2 4p6 5s2 4d10 5p6 6s2 1s
4f14
2
2s
5d 2p 3s2 3p6 3d104s2 4p6 5s2 4d10 5p6 6s2 4f14 5d10
2 10 6

r] 5s2 4d10 [Xe] 6s 4f2 14
5d10
[Xe] 6s 4f14 5d10 6p2
2

d block d partially filled d block d partially filled Gp 14 -4 valence electron

 IE Transition metal Ionization Energy Transition metal Why IE increases slowly across ?

Nuclear charge increase IE increase slowly

3d elec added to 3d sub level

3d elec shield the outer 4s elec from nuclear charge

Period 4

Sc Ti V Cr Mn Fe Co Ni Cu

4s

3d

Shielding nuclear charge by 3d electron

+21 +22 +23 +24 +25 +26 +27 +28 +29

Shielding by 3d electron
Shielding by 3d electron
Balance increase in nuclear charge

Small increase in IE
Sc Ti V Cr Mn Fe Co Ni Cu Zn

Easier to lose outer electron Nuclear pull

Variable oxidation state
+21 +22 +23 +24 +25 +26 +27 +28 +29 +30
 Transition Metal (d
block )

K
4s1

Ca
4s2

Across period

Cr - 4s13d5 Cu - 4s13d10
half filled more stable fully filled more stable

Transition metal have partially fill 3d orbital

3d and 4s electron can be lost easily
electron fill from 4s first then 3d
electron lost from 4s first then 3d
4s
3d and 4s energy level close together (similar in energy)
3d

Filling electron- 4s level lower, fill first Losing electron- 4s higher, lose first
 Transition Metal (d
block )
d block element with half/partially fill d orbital / sublevel in one or more of its oxidation states

Lose electron

Formation ions

Sc3+ Zn 2+
4s03d0 4s03d10

NOT NOT
Transition Partially fill d orbital Transition
element. element.

Sc Sc Zn Zn2+

3+
4s 3d
2 10
4s0
4s23d1 3d10
4s0 3d0 fully fill d orbital
empty d
orbital
 Transition Metal

Physical properties Chemical properties

Element properties Atomic properties

Formation of complex ion
Formation coloured complexes
High electrical/thermal Ionization energy Variable oxidation states
conductivity Atomic size Catalytic activity
High melting point Electronegativity
Malleable
Ductile Formation
Formation complex
complex ion
ion Formation
Formation coloured
coloured complexes
complexes
Ferromagnetic
Transition
Transition Metal
Metal (( d
d block)
block)

Ionization Atomic size Electronegativity

energy
Decrease EN increase
IE increase slowly slowly
slowly
Shielding of
Shielding of outer electron
nuclear charge from nuclear
by 3d elec charge by 3d
elec
Electrostatic
Gp 1 Gp 17
force attraction Physical Catalytic
Catalytic activity
activity Variable
Variable Oxidation
Oxidation states
states
Properties
V Cr Mn Fe Co Ni

Sc +2 +2 +2 +2 +2 +2
IE increase
Zn
+3 +3 +3 +3 +3 +3
EN increase
+4 +4 +4 +4 +4 +4
Atomic size decrease
+5 +5 +5 +5 +5

molecule adsorp on
surface catalyst +6 +6 +6

+7
 Transition Metal Variable Oxidation States
+7 (MnO4)-
oxides
oxyanion
+6 Cr2O 7
2-
(MnO4) 2- Highest oxidation states bind to oxygen

+5 V2O5 MnCI4
+4 TiCI4 (VO2)2+ MnCI3
chlorides
+3 ScCI3 TiCI3 VCI3 CrCI3 MnCI2 FeCI3 CoCI3
+2 CrCI2 FeCI2 CoCI2 NiCI2 CuCI2 ZnCI2

reas
es +7
r inc
on n
um be
+6 +6
Ox i d
at i
+5
+4 +4
+3 +3 +3 +3 +3 +3 +3
+2 +2 +2 +2 +2 +2 +2

+3 oxidation state more common +2 oxidation state more common

Oxidation state +3 common (Sc Oxidation state Mn highest Oxidation state +2 common (Co
Fe) +7 Zn)
Highest oxidation state
Easier to lose electron exist Harder to lose electron

Nuclear charge (NC ) from Sc Element bond to oxygen Nuclear charge (NC ) from Co
- Fe - Zn
Ionic bond more common for lower oxi Transition metal variable
(oxide/oxyanion)
states oxidation state
TiCI2 Ionic bonding
Covalent bond more common for higher 4s and 3d orbital close in
oxi states energy
TiCI4 Covalent bonding
 Transition Metal

Formation
Formation coloured
coloured complexes
complexes Variable
Variable Oxidation
Oxidation states
states

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+
1

+ + + + + + + + + +
2 2 2 2 2 2 2 2 2 2
+ + + + + + + +
3 3 3 3 3 3 3 3

+ + + + + + +
Colour formation 4 4 4 4 4 4 4

+ + + + +
Diff ligand
+3- most common5 5 + 7- 5
Highest
5 5 + 2- most common
Nature of Oxidation Shape
transition metal state Stereochemistry
oxi state oxi state oxi state
+ + +
6 6 6

+
7

Diff oxidation states Diff metal Shape/ Diff ligand

Stereochemistry

V5+/ VO2+ - MnCI2 - Pink Cr2O3 - Tetrahedral Octahedral

NiCI2 -
yellow MnSO4 - Red Green Yellow
V4+/ VO2+ - MnO2 - Black CrO4 2- - NiSO4 -
blue MnO4 - - Yellow Green
V3+ - Purple CrO3 - Red Ni(NO3)2 -
green Cr2O72- -
V2+ - Violet
Orange NiS -
violet
Black

Yellow Blue
Click here vanadium ion complexes Click here nickel ion complexes
 Formation
Formation complex
complex ion
ion
Ligand
Transition Metal
ion Ligand
Neutral/anion species that donate lone pair/non bonding electron pair to metal ion
Transition Metal ion
Lewis base, lone pair donor dative bond with metal ion
High charged density
metal ion
Partially fill 3d orbital Monodentat Bidentate
Attract to ligand e
Form dative/co-ordinate C2O42- C2H4(NH2)2
bond
(lone pair from ligand)
Neutral Anion ligand
ligand

.
H2O CI : CI :

:
Polydentat
CN e

NH3 O2-

OH
CO
SCN
Transition metal + ligand =
Complex Ion
Drawing complex ion
Overall charged on complex ion
Metal ion in center (+ve charged)
Ligand attach +3
+2 Dative bond from ligand

4 water ligand attach 6 water ligand attach

4 dative bond 6 dative bond
Coordination number = 4 Coordination number = 6
 Complex ion with diff metal ion, ligand, oxidation state and overall charge Coordination number
number of ligand
Coordinatio Shape Complex ion Ligand Metal ion Overall
around central ion
n number (metal + ligand) (charged) (Oxidation charge on
#) complex ion
linear [Cu(CI2)]- CI = -1 +1 -1

2 [Ag(NH3)2]+ NH3 = 0 +1 +1 L: Mn+ :L

[Ag(CN)2]- CN = -1 +1 -1

Square [Cu(CI)4]2- CI = -1 +2 -2
L: :L
4 planar
[Cu(NH3)4]2+ NH3 = 0 +2 +2 L:
M n+

:L
[Co(CI)4]2- CI = -1 +2 -2
:L

4
Tetrahedr [Cu(CI)4]2- CI = -1 +2 -2
al Mn+
[Zn(NH3)4]2+ NH3 = 0 +2 +2 :L :L
:L
[Mn(CI)4]2- CI = -1 +2 -2
:L
Octahedr [ Cu(H2O)6] 2+
H 2O = 0 +2 +2

6 al
[Fe(OH)3(H2O)3] OH = -1
H 2O = 0
+3 o
:L
:L
Mn+
:L
:L
[Fe(CN)6]3- CN = -1 +3 -3 :L

[Cr(NH3Types
)4CI2]+ of ligand:
NH3 = 0 +3 +1
onodentate 1 lone pair electron donor H 2O, F-, CI CI=
-
, NH
-1 3, OH , SCN CN
- - -

dentate 2 lone pair electron donor 1,2 diaminoethane H 2NCH2CH2NH2, ethanedioate (C2O4)2-
lydentate 6 lone pair electron donor EDTA 4- (ethylenediaminetetraacetic acid)
 Ligand displacement

Ligand
Neutral/anion species that donate lone pair/non bonding electron pair to metal ion
Lewis base, lone pair donor dative bond with metal ion

Monodentat
e
Neutral Anion ligand Bidentate Polydentat
ligand e

.
C2O42- C2H4(NH2)2
H2O CI : CI :

:
CN

O2-
NH3
OH

CO SCN Spectrochemical series

Co/CN > en > NH3 > SCN- > H2O > C2O42- > OH- > F- > CI- > Br- > I-

Stronger ligand displace weaker ligand

2+ Chelating agent
EDTA for removal of Ca2+
Prevent blood clotting
Detoxify by removing heavy
H2O displace CI- displace metal poisoning
by CI- by NH3

Tetraaqua
copper(II) ion
Tetrachloro
copper(II) ion
Tetraamine

copper(II) ion
Stronger
Stronger
ligand ligand
 Magnetic properties of transition metals

Sc Ti V Cr Mn Fe Co Ni Zn

4s

3d
Spinning electron in atom behave like tiny magnet

Paired electron spin cancel NO net magnetic effect Unpaired electron net spin Magnetic effec

Material

Diamagnetic Paramagnetic Ferromagnetic

Zn2+ Mn2+ Iron

Cobalt
Nickel
Spin cancel
Spin cancel Net spin
Diamagnetism
Paramagnetism


Paired electron
Unpaired electron

No Net magnetic effect Strong Attraction
Weak Repulsion Weak Attraction
Net magnetic effect
(Repel by magnetic field)
(Attract by magnetic field)

Click here paramagnetism Click here paramagnetism Click here levitation bismuth Click here levitation
 Magnetic properties of transition metals

Sc Ti V Cr Mn Fe Co Zn

4s

3d

Paramagnetic Diamagnetic

Click here paramagnetism measurement

Vs
Spin cancel Net spin Spin cancel Spin cancel
Paramagnetism Diamagnetism

Unpaired electron Paired electron

Net magnetic effect No Net magnetic effect
(Attract by magnetic field) (Repel by magnetic field)
Click here paramagnetism

Strong diamagnetic materials

pyrolytic graphite Bismuth

Click here levitation bismuth Click here levitation

 Transition Metal Catalytic
Activity
Catalytic Properties of Transition metal
Variable oxidation state - lose and gain electron easily.
Use 3d and 4s electrons to form weak bond.
Act as Homogeneous or Heterogenous catalyst lower activation energy
Homogeneous catalyst catalyst and reactant in same phase/state
Heterogeneous catalyst catalyst and reactant in diff phase/state
Heterogenous catalyst- Metal surface provide active site (lower Ea )
Surface catalyst bring molecule together (close contact) -bond breaking/making easier

molecule adsorp on
surface catalyst
Bond break
Bond making

Pt/Pd
Pt/Pdsurface
surface

How catalyst work ?

Fe2+ catalyst Nickel catalyst

Transition metal as catalyst with diff

oxidation states CH2 = CH2 + H2 CH3 - CH3
Activation energy
2H2O2 + Fe2+ 2H2O+O2+Fe3+
Without
recycle
catalyst, Ea
H2O2+Fe2+H2O + O2 + Fe3+
3+ CH2= CH2 + H2
Fe3+ + I - Fe2+ + I2 CH3 - CH3
Fe2+ Fe3+ With catalyst, Ea

adsorption adsorption bond breaking desorption

Rxn slow if only I- is added H2O2 + I- I2 + H2 C2H4 making C2H6
H2 O + O 2
Surface of catalyst for adsorption
Rxn speed up if Fe2+/Fe3+ added
Fe2+ change to Fe3+ and is change back to Fe2+
again
 Uses of transition metal as catalyst in industrial process

Haber Process Production ammonia for fertiliser/ agriculture Hydrogenation Process- Margerine and trans fat
3H2 + N2 2NH3 C2H4 + H2 C2H6

Iron , Fe Nickel, Ni

NH3
Contact Process Sulphuric acid/batteries Vitamin B12 RBC production Catalytic converter Convertion to CO2 and N2
2SO2 + O2 2SO3 2CO + 2NO 2CO2 + N2

Vanadium (V) oxide, V2O5 Cobalt, Co3+ Platinum/Palladium, Pt/Pd

Co3+

Biological enzyme Hydrogen peroxide decomposition O2 production

Hemoglobin transport oxygen 2H2O2 2H2O + O2

Iron , Fe2+ ion Manganese (IV) oxide, MnO2

Fe2+ O2
 Acknowledgements
Thanks to source of pictures and video used in this
presentation

http://crescentok.com/staff/jaskew/isr/tigerchem/econfig/electron4.htm
http://pureinfotech.com/wp-content/uploads/2012/09/periodicTable_20120926101018.png

Thanks to Creative Commons for excellent contribution on

licenses
http://creativecommons.org/licenses/

Prepared by Lawrence Kok

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