Inorganic chemistry

Periodicity in properties
(1) Atomic radius (or size)
Radii ↓ ZeH↑ (no. if shell same)

Zeff = Effective nudear force

Down, the group Zeff↓ no. of sheels↑

(2) Ionization Enthalpy

I.E (△Ih)

The energy required to remove e - from valence shell of an

isolated gaseous in the gaseous state.

Na( △) △ Na+ +e-

Sublimation
enthalpy

Na (g) △
→ Factors affecting △iH
(i) Zeff α △iH

(ii) Radius or size α _1_

△iH

(iii) No. of shell α 1_

△iH

(iv) Shielding effect α 1_

△ih
 (v) Stable configuration increases △iH

P3, d5, f7 → hay filled

P6, d10, f14 → fully filled

n3, np6 → closed shell

(n-1) d10 ns2, → pseudo inert gas configuration

→ In period
△iH↑, Zeff↑, size↓
 D- block elements (transition metols)

The elements having incomplete d-orbitals in ground state or

in their common oxidation state (+2)

SC = 23 = 3d1 452 Cr24 = 3d5 451 cu29 = 3d10 451 x

Cu+2 = 3d9

Zu30 = 3d10 us2 X

Zu+2 = 3d10 X
cd = 4d10 5s2 X
Hg = 5d10 6s2 X

Q:- Se shares only + 3 state. How can you that is a transition

elements

→ Sc + 3 = 3d14s2

Sc + 3 = 3d0
Incomplete d-shell, so a transition element.

Q:- why d-block elements are e/a transition elements?

Ans:-Reasons are below, some can be listed below:-
(i) It connects main group s and p-block elements.
(ii) It shows various OXdn state as non-metal of p-block
(iii) The pen – ultimate shell (n-1)d subshell filled after as.
(iv) They show catalytic properties.
(v) Transition elements have more periodic similarities then group
similarities.

There are 4 series of transition metals.

(1) 1st series:-3d series → The elements in which 3d-subshell is

getting filled one by one.

(2) 2nd series :- 4-d series → The elements in which 5d subshell is

getting filled one by one.

(3) 4th series→ 6d series :- The elements in which 6d subshell is

getting filled one by one.

3-D Series (1st Transition state)

3d1 4s2 3d2 4s2 3d3 4s2 3d4 4s1 3d5 4s2
Sc Tp V Cr Mn

Fe Co Ni Cu Zn
3d6 4s2 3d 4s2
7
3d 4s2
8
3d 4s1
10
3d 4s2
10

↑ Cr
Melting Cu
Point Sc Fe
Zn
Mn
Z→
(1) Melting point depends on the strength of metallic bond as
the no. of unpaired e- increases metallic bond becomes
stronger and mp increases.

(2) Cr- has largest mp because it has mazm no. of unpaired e-

 (3) Mn has lower mp because of hay filled d-and completely
filled & due to which metallic bond weakens.

(4) Zn has the lowest mp of all d-series (3d-series) because it

has completely filled d1 and d1s1 orbitals so metallic bond is
very weak.

→ Enthalpy of atomization (sublimation enthalpy)

e-

e- 4s
- -
e e
3d

e-
 Atomisation enthalpy is higher because of larger no. of valence e- metallic bonding is strong.

 It generally increases in the series because no. of e- increases which make metallic bond.

 It generally varies irregularly in series because with increase in Z shielding effect and nuclear
force very irregularly.

 Zn has lowest atomization ‘d’ and ‘s’ orbital so, metallic bond is poor.

Metallic Radii/ Size

(1) Size of d-block elements is very small because of very poor shielding of d-orbitals (and
stronger metallic bond)

(2) In the series, it decrease because with increase with increase in Z shielding effect
variation.

(3) It various irregular variation.

(4) Zn has largest size of au 3-D series because it doesn’t participate in metallic bonf due to
completely filled ‘d’ and ‘s’ subshell.

(5) The size of metal atoms from iron to copper is virtually some because with increase in Z
the increased nuclear force is balanced by increased shielding effect perelectrom.
→ Lanthanoid Contraction

The completely filled uf orbitals have poor shielding extended to some next elements after
lanthanoid series. Therefore this is c/o lanthanoid contraction.

→ The size of s-d series elements is almost similar because of Lanthanoid contraction due to
completely filled uf orbitals or because of very poor shielding of complete of orbitals.

(i) △iH (ionization Enthalpy)

(ii) △iH of transition metal is very high because of very poor shielding of penultimate d-
orbitals.

(2) △iH increases in the series because with increase in Z nuclear force increases and e - in
getting filled in the same 3-d orbitals.

(3) It varies irregularly in the series.

 △iH
(4) △iH of 2nd transition series (4-D series) is smaller than that of 2nd series because with
increase in shell nuclear shielding effect inreases and nuclear force decreases.

(5) △iH of 5-d series element is generally higher than that of 4-d series because of Lanthanoid
contraction due to complete uf orbitals.

△iH for Cr < △iH of Mm

3d54s1 3d54s2
Cr+ Mn+
△iH 3d54 > 3d54s1

Cr+2 Mn+2
3d4 < 3d5

 Oxidation State
+2 ----------------------------------+7
↓ ↓
e- donar e- ganiner
↓ ↓
Reducing agent oxidizing agent
MnO4-

+2 +4
MnO MnO2 MnO4

both ed4 as well as oxidation

+4 +2 +7
MnO2 MnO + MnO1
Redn (Disproportionation rean)
 Oxidation same element undergo oxdn as well as Red11

0 (-3) (+2)
P4 PH3 + HPO2-

(Oxidation)

Se Ti v Cr Mn
+3 +2 +2 +2 +2
+3 +4 +4 +4
+4 +5 +5 +5
+6 +6
+7

Fe co Ni Cu Zn
+2 +2 +2 +1 +2
+3 +3 +3 +2
+4 +4 +4 +3
+5 +5
+6

 Oxidation States
Reasons for the sterility of a particular OXdn State

(i) d˚ (vacant d-orbital), d5 (hay filled), d10 (complete)

(ii) t2g (hay filled t2g level), t2g (complete) in octahedral complex only.
(iii) Higher hydration energy than the sum of atomization and ionization enthalpies.
(iv) O and f also stabilizes higher oxdn states.

(3d14s2) (3d24s2) (d0) (3d4s1) (d0) (d5) (d0)

SC+3 T1+3 V +5
Cr +3
Cr +6
Mn+2 Mn+7

Fe+2 Fe+3 Co+2 Co+3 Ni+2 Cu+1 Cu+2 Zn+2

(3d6) (d2) (3d7) 6
(d ) (d0) (d10) (d9)

→ Hydration Energy
The energy released when ionic compd. Is dissolved into water.

7L 7L 7L
dxy dyz dzx dx2-y2 dz2

Bond

Col (l) co (g) △iH1 + △iH2 co+2

 △
= +ve

CuSO4, (△) Cu2 SO4 (white) + 5H2O ↑

△

5H2O

 Cr+3 → stable only in octahedral complex because of t2g+ configuration.

 Fe+2 stable in octahedral complex due to t2g+

 Co+2 is stable in ag soln due to its higher hydration energy which can compensate the
sum of atomization and ionization enthalpies.

 Co+3 t2g+

 Ni+2

 Co+1 stable in dry state (anhydrous from) only due to d10

E˚M2+/m values = SRP value

 If SRP is +ve, the metal can displace H from acid or base and form m+2 ion.

 +ve, can’t displace, can’t from

Cu + Ha X Cu+2 Zn + Hcl Zna2 + H2 ↑

E˚ w+2/cu = 0.34 V E˚ zn /zn = 0.76 v-
+2

→ The lower is the SRP, the higher is the reactivity, its above example cu is more reactive
than Ag

→ The higher is the mobility of ion, the lower is the Eo values (usually –ve)

Eo m+3/ m+2

E˚ fe+2/fe = -0.44 V
E˚ fe+3/fe +2 = 0.77 V

Q :- Why E˚ ai/ cu is +ve?

It is very higher hydration energy of cu+2 ion due to which its mobility decreases and Eo
Value becomes +ve
→ Aalthough E˚ fe+3/fe = +ve, is stable because its acquires d5 configuration.

Q :- fecl3 when kept in acid soln , it become fea2 why?

Ans- f˚ fe+2/fe is –ve ; fe+2 ion is more stable in acid soln

 Stability of higher oxidation state

→ O and F can stabilize higher oxdn state (K2G+6O2, Kmn+7O4) because these 2 elements are
highly electro negative.
 → Oxygen is more efficient to oxidise metals to higher oxdn state than f because O can form
dΠ - PΠ bond.
f

f f o o

T2o Mn 109.281( Mn
f f o
o
f
f

 Magnetic character → Electronic concept

(1) Paramagnetic Diamagnetic

 Unpaired e- * Paired unpaired e-
 Attracted weakly * Repelled weakly in
In magnetic field magnetic field

H = magnetic
moment
√ n(n+ 2)BM
n = no. of unpaired e-

eg:- Cr > Cr+2

↓ ↓
3d54s1 3d4

n= 6 n=4

H= √ 6(8) H = 4.7

= 6.7

→ Cr+2 = Mn+3
↓ ↓
3d4 3d4

→ H = 4.7 H=4.7

Q:- Cr+2 and Mn+3 both same d4 configuration (and magnetic moment) but Cr+2 →reducing, mn+3
Is oxidizing why?

Ans:- → Cr+2 → Cr+3 + e-

→ mn+3 +e- → mn+2

→ Cr+6 → d0 + dia

→ mn+7 → d0 + dia
 → zn+2 → dia

Q:- Cr+2 Cu+2 + cu (ag .SO1n) why ?

Ans:- Cu+1 → Cu+2 + e-

Cu+1 +e- → Cu

Because cu+2 has higher hydration energy than Cr+1

Q:- +4
MnO2 disproportionates why ?

Ans:- because Mn+4 lies b/w oxidation state of mn = +2 +O +7.

 Colour of Transition metals

→ unpaired e- → d-d transition

B
v G
t2g → eg
Maushell
Colour
whell
R y

→ The unpaired e- d-d transition by absorbing the colour of visible region and complementary
colour is observed

 Sc → Sc+3 → X
 mn → mn+3 → mn+7
(exception)
(kmno4)
 Cr → Cr → Cr+4 → Cr+6
+3

(K2G2O7)
(exception)

→ change Transfer (Resonance)

o
⃝ ‖
mn
mn o o-

o o o
o

Kmno4 ia colour ed due to momentarily charge transfer to mm (central atom) (due to resonance)

o o
 o Cr ----- Ӧ̤ Cr o

o- o-

 Catalytic Properties

holes

It is due to variable oxdn s state and large surface of Transition metals and their
compounds.

Intestinal Compounds

When smaller atoms like H, N C etc are trapped inside host (or interstices). The new
compounds formed are c/d interstitial compounds.

 Alloy formation (substitution compounds).

→ transition metals form alloy, because they have very less difference in sizes or similar in
sizes so, they can be substituted at place of one another.

 Oxyanions

Cr0 O72- and mno4

(Dichromate ion) (Permagnet ion)

K2Cr2O7
Commercial (industrial preparation)

(sodium dichromate)
Chromite are feo.Cr2o3 Nd2Co3 Nd2Cra1 H2SO4 Na2 Cr2O7
O2/△ (acid ify)

feCrO4 iron Black (Roasting) (yellow sodium chromate)

(potassium Dichromate0 (oxidising agent)

K 2Cr2O7 kcl Not a primary
(yellow) reagent
Orange ↓
because hygroxepic nature
Cr0 O72- + fe+2 Cr+3 +fe+3
+H+
Acid medium H-H+ O = H2O Basic medium H= OH-
(i) Add H2O to the side having less no. of O- (i) Add H2O to the side having more O and
A term and add double H+ to the opposite add double OH- to the opposite side
Sides.

(ii) If H remains unbalanced add H+ do the (ii) If H remain unbalanced add OH- to the
Side having less H. side having more H and same no. of H2O
to the opposite side.

 Charge balancing
 -ve charge less + e-
+ve charge more + e-

Cr2 O72- + fe+2 Cr+3 +fe+3

Cr2 O72- + 14H++6e- 2Cr+3 + 7H2O

fe+2 fe+3 + e-
Cr2 O72- + 14H+ + 6e- 2Cr+3 + 7H2O

6fe+2 6 fe+3 + 6e-

Cr2 O72- + 6fe+2 14H+ 2Cr+3 + 6fe+3 + 7H2O
→ MeO2 KOH k2 mno4 electrolysis kmnoH
↓ ↓
Magnate Potassium Potassium
Ore Mangnate per mangnate

I – block elements → Inner Transition metals 3rd group metals.

Uf – Lanthanoid → Belong to Lanthanoid group → 38-81

Sf – Actinoid series → belongs to actinium group → 89-103

Lanthanoid contraction → The size of Lanthanoid decreased along the series in a regular
pattern.

→ Oxidation state
(n-2) f 1-14 (n-a)d0-1 ns2

Ce +4 → In this case it has noble gas configuration stable

Common oxidn state → +2 and +3 because ‘f’ orbital gas very poor shielding.