Chemistry of the Elements

5

TRANSITION ELEMENTS
Copyright Pooran Appadu
Chemistry of the Elements
Zn
Sc
Ti
V
Cr
Mn
Fe
Ci
Ni
Cou
FIGURE 5.1 First Row Transition Elements
Copyright Pooran Appadu
Chemistry of the Elements
`
Copyright Pooran Appadu
Sc [Ar]
Ti [Ar]
V [Ar]
Cr [Ar]
Mn [Ar]
Fe [Ar]
Chemistry of the Elements
FIGURE 5.2 Electronic Configuration Of The Elements
FIGURE 5. Electronic !tructure Of The Common Ions Of Iron "n# $anganese
Copyright Pooran Appadu
Co [Ar]
Ni [Ar]
Cu [Ar]
Zn [Ar]
Fe [Ar]
Fe
2+
[Ar]
Fe
3+
[Ar]
Mn [Ar]
Mn
2+
[Ar]
Mn
3+
[Ar]
Chemistry of the Elements
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic No. 3d
1
4s
2
3d
2
4s
2
3d
3
4s
2
3d
5
4s 3d
5
4s
2
3d
6
4s
2
3d
7
4s
2
3d
8
4s
2
3d
10
4s 3d
10
4s
2
1
st
I.E / KJ mol
-1
630 660 650 650 720 760 760 740 750 910
At. Radius / m 0.164 0.147 0.135 0.129 0.137 0.126 0.125 0.125 0.128 0.137
!." /
0
# 1540 1680 1900 1890 1240 1540 1500 1450 1080 420
$." /
0
# 2730 3260 3400 2480 2100 3000 2900 2730 2600 910
%&sit' (/cm
-3
3.00 4.50 6.1 7.2 7.4 7.9 8.9 8.9 8.9 7.1
#ommo )*
+tat& / Eo
,3 ,4- ,3 ,5- ,3 ,6- ,3 ,7- ,4-
,2
,3- ,2 ,3- ,2 ,2 ,2- ,1 ,2
!
2,
/ ! -1.20 -0.91 -1.19 -0.44 -0.28 -0.25 -0.34 -0.76
!
3,
/ ! -2.1 -1.2 -0.86 -0.74 -0.28 -0.04 ,0.40
FIGURE 5.% &h'sical &ro(erties Of The Transition Elements )First Row*
Copyright Pooran Appadu
Chemistry of the Elements
THE TRANSITION ELEMENTS
These are elements that could be considered
!a" #ositioned $ithin the d or % bloc&
!b" Formin' atleast one ion $ith a (artiall) %illed d * subshell+
COMMON PROPERTIES
The) are all hard metals $ith hi'h meltin' (oints and boilin' (oints+
The) sho$ more than one o,idation state in their com(ounds+
The) tend to %orm coloured com(ounds and ions+
Man) sho$ catal)tic acti-it)+
The) %orm com(le, ions in $hich molecules called li'ands %or dati-e bonds $ith the metal ion+
For the %irst ro$ the elements ran'e %rom scandium to .inc+ T$o elements do not sho$ multi(le
o,idation state !Sc and Zn" and the) %orm $hite rather than coloured com(ounds and the) do not
act as a catal)st+ The reason bein'
Scandium atom loses three electrons to 'i-e Sc3+ $hich has the same electronic con%i'uration as
Ar'on+
Zinc atom loses onl) the outer /s electrons to 'i-e Zn
2+
ions $ith an electronic structure [Ar] 3d
01
+
2n neither case is an ion %ormed $ith an incom(lete d * subshell and so Sc and Zn are not
considered true transition elements+
The %irst ro$ elements ha-e small and relati-el) similar atomic radius due to the increasin'
number o% electrons bein' used to %ill d * subshell rather than to add ne$ shells+ The atomic
radius is -er) little a%%ected until the (oint is reached $here all the d orbital contain one electron
$hen a second electron is (it into a d orbital3 the re(ulsion %orces bet$een the t$o electrons cause
the radius o% the atom to increase sli'htl)+
For chromium and co((er hal% %illed and %illed subshells are %a-ourable ener'eticall)3 so electrons
%rom /s are trans%erred to 3d+
TRENDS ACROSS PERIOD OF TRANSITION ELEMENTS
4et$een sodium to ar'on electrons are bein' added to the outershell and the nuclear char'e is
increasin' b) addition o% (rotons+ The added electrons shield each other onl) $ea&l) %rom the
e,tra nuclear char'e3 so the atomic radii decrease shar(l) %rom Na to Ar+ At the same time the
electrone'ati-ities and ioni.ation ener'ies steadil) rise+
2n mo-in' %rom Sc to Zn3 the nuclear char'e is also increasin'3 but electrons are bein' added to
an inner d sub shell+ These inner d electrons shield the outer /s electrons %rom the increasin'
nuclear char'e much more e%%ecti-el) than the outer electrons can shield each other+
Conse5uentl)3 the atomic radii decrease much less ra(idl)+
Similarl)3 electrone'ati-ities and ioni.ation ener'ies increase %rom Sc to Zn3 but onl) mar'inall)
com(ared $ith Na to Ar+ The increasin' electrone'ati-ities %rom Sc to Zn mean that the element
becomes sli'htl) less metallic+ This is re%lected in the increasin' (ositi-e electrode (otential6 7
o
+
Copyright Pooran Appadu
Chemistry of the Elements
2% a salt o% -anadium !V"3 %or e,am(le3 ammonium -anadate3 N8/V93 is dissol-ed in acid
solution and then sha&en $ith a (iece o% 'ranulated .inc3 a stri&in' series o% colour chan'es
occur+ The -anadium chan'es %rom an o,idation state o% +: $hen it is )ello$ to o,idation state o%
+/ $hen it is blue to o,idation state o% +3 $hen it is 'reen to o,idation state o% +2 $hen it is
-iolet+
V92
+
V9
2+
V
3+
V
2+
COLOUR
;hen li'ht ener') is absorbed b) a substance3 an electron in the substance is (romoted %rom an
orbital o% lo$er ener') to one o% a hi'her ener')+ 2% the absorbed %re5uenc) is in the -isible re'ion
o% the li'ht s(ectrum3 then the materials a((eared coloured+
Transition metal ions are o%ten coloured+ The %i-e d * orbitals are de'enerate3 i+e+3 the) all ha-e
the same ener') le-el+ 2n a com(le, ion3 the d * orbitals di%%er sli'htl) in ener') as a result
o-erla((in' di%%erentl) $ith the li'ands+ 7lectrons can <um( %rom one d orbital to another i% the)
absorb ener')+ The colour o% the ion is com(lementar) to the colour absorbed+ 7+'+
Absorbed =e%lected
>ello$ 'reen Violet
>ello$ oran'e 4lue
>ello$ 4lue -iolet
?reen =ed Violet
4lue ?reen 9ran'e
?reen 4lue =ed
The Sc
3+
!a5" ion has no d * electrons and is colourless+ 2n the ion Cu+ and Zn2+3 $ith a d01
con%i'uration3 no d * d transition is (ossible3 and these ions are colourless+ @i%%erent li'ands
a%%ect the ener') le-els o% the d * orbitals+
For e,am(le3 [Cu!829"/]
2+
is blue $here as [Cu!N83"/]
2+
is -er) intense dee( blue+
Cr)stal %ield theor) su''ests that the %i-e d orbitals be s(lit into t$o 'rou(s3 t$o o% the orbitals
!d.2 and d,2)2" ha-in' a hi'her ener') and three o% the orbitals !d,)3 d). and d,." ha-in' a lo$er
ener')+ The e,tent o% s(littin' is 'i-en the s)mbol Ao+ The t$o orbitals $ith the hi'her ener')3
e+'+ set and the three $ith the lo$er ener') are the t2' set+
Copyright Pooran Appadu
Chemistry of the Elements
Bi'ands at the ends o% ,3 )3 . a,es ha-e electron densit) that $ill interact stron'l) $ith electrons
in the d.2 and d, * )2+ These $ill ha-e hi'her ener'ies+ The lie directl) o((osite the lobe+
Copyright Pooran Appadu
d
,
2
* )
2
d
.
2
d
,.
d
,)
Chemistry of the Elements
FIGURE 5.5 +igan#s "ttaching To , Or-itals
FIGURE 5..
Bi'and %ield theor) be'ins b) constructin' molecular orbitals %rom the -alenc) d3 s and ( orbitals
o% the central metal atom and %rom the si, li'and orbitals that (oint alon' the metal li'and bonds
in the octahedral com(le,+ The li'and orbital $ill be so3 orbital containin' a lone (air in N833 or
(. orbital %rom a Cl
C
ion on the . a,is+ There are three t)(es o% h)bridi.ation %ound in transition
metal com(le,es+
Copyright Pooran Appadu
d
).
t
2'
e
'
d
,.
d
).
d
,)
A
o
d
.
2
*
)
2
d
.
2
7ner')
Chemistry of the Elements
Tetrahedral * d
3
s S5uare #lanar * ds(
2
9ctahedral * d
2
s(
3
FIGURE 5./ Energ' +e0el Filling For " 1CoF
.
2
3
ion.
A
t
A
0
A
0
Copyright Pooran Appadu
7ner') D
(
E
A
o
FF
C
[CoF
F
]
3C
Co
4ondin' 9rbitals
D
s
D
(
D
d
d
,)
nb
d
,)
nb
d
,)
nb
D
d
E
D
s
E
3d
/s
/(
Bi'and D !si'ma"
Anti * 4ondin' 9rbitals
Tetrahedral
A
3
d
,
2
C )
2
d
.
2
d
,)
d
,.
d
).
ds(
2
S5uare #lanar d
).
d
,)
d
.
2
d
,)
d
,
2
C )
2
A
o
d
2
s(
3
9ctahedral d
.
2
d
,
2
C )
2
d
,.
d
).
d
,)
Chemistry of the Elements
FIGURE 5.4
Octahe#ral !tructure )Ca)56

*
.
7
FIGURE 5.8 !9uare &lanar !tructure
1&t)56

*
2
Cl
2
2
Copyright Pooran Appadu
Co
N8
3 N8
3
N8
3
N8
3 N8
3
N8
3
N8
3
N8
3
Cl
N8
3
"t
N8
3
Cl
Chemistry of the Elements
Cl
Cl Cl
Cl
FIGURE 5.1: Tetrahe#ral 1FeCl
%
2
3
STABILITY CONSTANT K
stab
Co((er !22" sul(hate is blue due to the (resence o% h)drated Cu
2+
ions+ A standard test %or these
ions is to add dilute ammonia solution $hich (roduce a clear ro)al blue solution3 the
tetraammineco((er !22" ion3 Cu!N83"/
2+
+ The chan'e is an e,am(le o% e5uilibrium reaction
Cu!829"/
2+
!a5" + /N83 !a5" Cu!N83"/
2+
!a5" + /829 !l"
?i-en that the reaction is done in $ater3 $hose concentration remains constant3 the e5uilibrium
constant is
[Cu!N83"/
2+
!a5"]
G H
[Cu!829"/
2+
] [N83 !a5"]/
H 0+2 E 01
03
dm
02
mol
C/
at 2:
o
C
2% chloride ions are added !e+'+ %rom 8Cl" to co((er 22 ions in solution3 a )ello$ colour is
(roduced+
Cu!829"/
2+
+ /Cl
C
!a5" CuCl/
2C
!a5" + /829
[CuCl/ !a5"]
Gstab H
[Cu!829"/
2+
!a5"] [ClC !a5"]/
H /+2 E 01
:
dm
02
mol
C/
4) com(arin' the t$o constants )ou could tell $hat the reaction $ill be i% both substances $ere
in the reactin' -essel+
Gstab [Cu!N83"/]
2+
H 03+0 !lo' 0+/ E 01
03
"
Copyright Pooran Appadu
.&
Chemistry of the Elements
Gstab [CuCl/]
2C
H :+F1 !lo' /+1 E 01
:
"
So the blue ammine com(le, $ill %orm o-er the )ello$+
For the %ormation o% CuCl/
2C
3 the e5uilibrium is
[Cu!829"F]
2+
!a5" + /Cl
C
!a5" CuCl/
2C
!a5" + F829 !l"
The concentration o% $ater bein' ta&en as constant3 so the stabilit) constant is $ritten
[CuCl/ !a5"]
Gstab H
[Cu!829"/
2+
!a5"] [ClC !a5"]/
The lar'er the -alue o% this constant3 the more stable the com(le, ion+ A li'and ma) be dis(laced
%rom a metal ion in the (resence o% another li'and that can %orm a com(le, $ith a lar'er stabilit)
constant+ For e,am(le3 $ater ma)be be dis(laced as the li'and %rom [Cu!829"F]
2+
ion b)
ammonia %ormin' [Cu!829"2!N83"]
2+
ion+ This in turn ma) be dis(laced b) the (ol)dentate li'and
edta
/C
to %orm [Cuedta]
2C
+ Finall)3 edta
2C
ma) be dis(laced b) c)anide %orm o% [Cu!CN"/]
2C
+ This
series o% dis(lacement is as %ollo$s
[Cu!829"F]
2C
[Cu!829"2!N83"/]
2+
Cu!edta"
2C
Cu!CN"/
2C
Ligand Equilibrium
M
m+
+ XL
L
MLx
(m-xL+
S!abili!" Con#!an!
$ %&
o
C ' mol dm
-(
N/3 A(
,
, 2N/3 0 1A(2N/3324
,
#u
2,
, 4N/3 01#u2N/3344
2,
1.7 5 10
7
1.4 5 10
13
#l
-
#)
3,
, 6N/3 0 1#o2N/3364
3,
#u
2,
, 6#l
-
0#u#l4
2-
/(
2,
, 4#l
-
0/(#l4
2-
4.5 5 10
33
4.0 5 10
5
1.7 5 10
16
#N
-
#d
2,
, 4#N
-
0 1#d2#N434
2-
.&
2,
, 6#N
-
01.&2#N434
2-
/(
2,
, 4#N
-
01/(2#N344
2
7.1 5 10
16
1.0 5 10
24
2.5 5 10
41
T";+E 5.11 Reactions Of Common +igan#s
Copyright Pooran Appadu
IS
C)anide
IS
7dta
IS
N83
Chemistry of the Elements
The lar'e stabilit) constants %or com(le,es $ith c)anide ions !CN
C
" as li'ands sho$ $h) c)anide
is such as (o$er%ul (oison+ 2t binds irre-ersibl) to Fe
2+
ions are essential %or the trans(ort o%
o,)'en in the blood+ C)anide binds more stron'l) than o,)'en to the Fe
2+
ion in haemo'lobin
and this sto(s the carria'e o% o,)'en in the blood+
The same e,(lanation 'oes %or carbon mono,ide $hich is a (oisonous 'as and has a hi'h stabilit)
constant+
The electronic structure o% carbon mono,ide is re(resented
C 9
The lone (air o% electrons on the carbon atom enables it to act as a li'and in the %ormation o%
carbon)l com(le,es e+'+ [Cr!C9F"]3 C[FeC9]3 N !C9"/ etc+
Carbon mono,ide is a neutral molecule and there%ore has no char'e+ The metal3 it combines $ith
has o,idation state o% 2++
.&
.&
92
829
Copyright Pooran Appadu

N
N
N N
N N
NN
N N
N8
Chemistry of the Elements
FIGURE 5.12 Reactions Of Common +igan#s
The mode o% o,)'en carria'e b) haemo'lobin $ith a $ater molecule $hich is re-ersibl) re(laced
b) an o,)'en molecule+
.&
FIGURE 5.1 6aemoglo-in ;in#ing <ith Car-on $ono=i#e
L)*+
N,
N+ME
6 No
2-
Nit7o
6
)#)2
2-
#a78oat&
6 )N)
-
Nit7at&
6 #N
-
#'ao
6 +#N
-
9:ioc'aato
6 N#+
-
Isot:ioc'aa
to
6 )/
-
/'d7o*o
6)/2 A;ua
6 N/3 Ami&
6 #) #a78o'l
Copyright Pooran Appadu
Bone (air %rom
carbon attach to
Fe
2+
on =4C
C J 9
N N
:
N N
N
Chemistry of the Elements
6 N)
2-
Nit7os'l
T";+E 5.1% Common +igan#s
Carbon mono,ide re(laces both 829 and 92 and %orm a stable bond !li'and"+
FIGURE 5.15 Formation Of " !ta-le ;on# <ith Car-on $ono=i#e
VARIABLE OXIDATION STATES
d * subshells are -er) close in ener') le-el to the /s subshell3 and so it is relati-el) eas) lose
electrons+ This means that se-eral di%%erent ions o% the same element are (ossible b) losin'
di%%erent numbers o% electrons * all o% these di%%erent ions are a((ro,imatel) e5uall) stable+ The
inter con-ersions bet$een one o,idation state and another are an im(ortant as(ect o% transition
metal chemistr)3 and the intercon-ersions are %re5uentl) re%uted b) colour chan'es in solutions o%
the com(le,ions+
Some 'eneral obser-ations are the -ariable o,idation states o% the transition metals titanium to
co((er are 'i-en belo$
0+ +03 +2 or +3 are amon' the most common o,idation states %or each element+ +3 is most common
%rom Ti to Cr3 then %rom Mn on$ards +2 is more common+
2+ Transition metals usuall) sho$ their hi'hest o,idation state $hen combined $ith 92 or F2 or Cl2
the most electrone'ati-e elements+
3+ The hi'hest o,idation states o% all the elements u(to and includin' man'anese com(ounds
corres(ond to the loss in bondin' o% all the electrons outside the ar'on core+ Thus3 the hi'hest
o,idation state o% titanium is +/ $hilst that o% man'anese is +K+ 4e)ond man'anese the d *
electrons are held more stron'l) as a result o% increasin' nuclear char'e3 and so the common
o,idation states in-ol-es the /s shell onl)+
Copyright Pooran Appadu
C J 9
:
:
M
Chemistry of the Elements
/+ ;hen the elements e,hibit hi'h o,idation state !+/ and abo-e" the) do not %orm sim(le ions+
The) either are in-ol-ed in co-alent bondin' e+'+ !Ti923 Ti9/3 Cr933 Mn29K" or the) %orm lar'e
ions such as Cr9/
2C
or Mn9/
C
+
Elemen! Common -xida!ion
S!a!e#
Equa!ion -. Com/ound#
9i ,2- ,3- ,4 9i2)3- 9i)2- 9i#l4
< ,1- ,2- ,3- ,4- ,5 <2)3- <#l3- <2)5
#7 ,1- ,2- ,3- ,4- ,5- ,6 #72)3- #7#l3- #7)3
! ,1- ,2- ,3- ,4- ,5- ,6- ,7 !)- !#l2- !)2- !2)7
.& ,1- ,2- ,3- ,4- ,5 .&)- .&#l2- .&2)3- .&#l3
#o ,1- ,2- ,3- ,4- ,5 #o)- #o2)- #o#l3
Ni ,1- ,2- ,3- ,4 Ni)- Ni#l2
#u ,1- ,2- ,3 #u2)- #u#l2- #u)- #u#l
T";+E 5.1. Common O=i#ation !tates Of The Transition Elements )First Row*
Note that accordin' to Au%ban (rinci(le orbitals are re5uired to be %illed in increasin' order o%
ener')+ 2n the /
th
(eriod it is an e,(erimental %act that the /s orbital actuall) has a lo$er ener')
than the 3d resultin' in con%i'uration+ For G H [Ar]/s
0
and Ca H [Ar] /s
2
+ The ener') o% the 3d
orbitals does decline relati-e to the /s $ith increasin' nuclear char'e+ So %rom Sc the ne,t orbital
that is %illed is the 3d and lies belo$ that o% /s in ener'ies+ 7lectrons are %irst remo-ed %rom the /s
to %orm ions+
7,am(le Sc
+
H [Ar] 3d
0
/s
0

(d Filling
+c 9i < #7
3d
5
4s
1
! .& #o Ni #u
3d
10
4s
1
=
0d Filling
> =7 N8
4d
4
5s1
!o
4d
5
5s
1
9c Ru
4d
7
5s
1
R:
4d
8
5s
1
"8
4d
10
A(
4d
10
5s
1
#d
&d Filling
?u /@ 9a A R& )+ I7 "t
5d
9
6s
1
Au
5d
10
6s
1
/(
1d Filling
?B
T";+E 5.1/ "nomalous Eletronic Configuration Of The Transition Elements
Note the 'rou( $ith Cu3 A'3 Au and Cr and Mo3 so as to account %or com(le, ions+
Copyright Pooran Appadu