D and f block

●​ Transition elements are called so because their chemical properties are transitional between those of

s and p block

●​ Transition metals are defined as metals which have incomplete d subshells either in neutral atom or in

their ions with exceptions zinc cadmium and mercury which are not transition metals

●​ These transition metals have full d10 configuration in the ground state as well as their common

oxidation states. Electron vary in s subshell and d subshell because of very little energy difference

between (n-1) d and ns Orbitals

●​ Chromium and copper have partially filled subshell and fully filled subshell respectively and have one

electron less in their s subshell. Chromium is 4s1 3d5 and copper is 4s1 3d10

●​ The d orbitals of the transition elements protrude to the periphery of an atom more than the other

orbitals hence they are more influenced by the surroundings as well as affect the atoms or molecules

surrounding them.

●​ Transition elements display variety of oxidation States, formation of coloured ions and entering into

complex formation with a variety of ligands

●​ Silver atom has completely filled D orbital in its ground state but it is still a Transition Element as it

exist as AG+ which has incomplete D orbital (intext question)

●​ Zinc, cadmium, mercury and manganese have low volatility. Their melting points and boiling points

are high and there an exception

●​ Complexes are attributed to the involvement of greater number of electrons from (n - 1) d and

addition to the ns electrons in the interior atomic metallic bonding

●​ In any row the melting points if these metals rise to a maximum of d5 accept for Anomalous

values of mn and tc and fall regularly as a atomic number increases (jee mains 2025)

●​ They have high and help is of atomisation. Greater the number of Valence Electrons stronger is the

result and bonding

●​ Since the enthalpies of atomization is an important factor in determining the standard electrode

potential of a metals with very high enthalpy of atomization tends to be Noble in their reactions and

they have high standard electrode potential

●​ Ions of the same charge in the given series show progressive decrease in radius with increasing atomic

number this is because new electrons enter a d orbital is time then nuclear charge increases by Unity

●​ The filling of 4f before 5D orbital results in a regular decrease in atomic radii called Lanthanide

contraction which compensate for the expected increase in atomic size with increasing atomic number

●​ Second and third D series exhibit similar radii and have very similar physical and chemical properties

such as zr and hf
●​ Filling of 14 f electron by another is less than that one of the electron by another as the nuclear

charge increases along the series

●​ There is not much change in the ionisation energy of 3d series as the increasing nuclear charge is

counterbalanced by the shieling of (n-1) d electrons

●​ Chromium has unpaired electrons which result in strong metallic bonding which results in it being a

hard solid and the absence of unpaired electrons in Hg results in it being a liquid.

●​ The decrease in metallic radius coupled with increase in atomic mass results in a General increase in

density

Thus from Titanium to Copper the significant increase in the density is noted

●​ Why do the transition elements exhibit higher enthalpies of atomization?

Because of large number of unpaired electrons in their atoms they are stronger enter the atomic

interaction and hands stronger bonding between atoms resulting in high and enthalpies of atomization

●​ Zinc have the lower enthalpy of atomization due to absence of unpaired electron as they have D 10

configuration

●​ Successor enthalpy of transition elements ionization do not increase as chiefly as an case of non

transition elements. The first ionization enthalpy, in general increases but the magnitude of increase

in the second and third ionization enthalpies is much higher along a series the air regular trend in the

first ionization enthalpy of metals of 3D series can be accounted for my considering that the removal

of one electron alters the relative energy of 4S and 3d orbitals.

●​ However, the trend of study increase in second and third ionization enthalpy brakes for the formation

of mN + 2 and fe + 3 respectively because the ions have D5 configuration

●​ The three terms responsible for the value of ionization enthalpy are attraction of each electron

towards nucleus, repulsion between the electrons and the exchange energy

●​ Exchange energy is responsible for the stabilization of energy state. Exchange energy is

approximately proportional to the total number of possible pair of parallel spence in the degenerate

orbitals. You the loss of exchange energy increases the stability as the stability increases ionization

becomes more difficult.

●​ There is no loss of exchange energy at B6 configuration thus ionization enthalpy of mn+ is lower than

CR +

●​ And the ionization enthalpy of fe2+ is lower than that of mn2+

●​ The lowest common Oxidation state of these metals is +2

●​ To form the M + 2 ions from the gaseous atoms the first and second ionization enthalpy is required in

addition to the enthalpy of atomization unit

chromium where M + ions have the D5 and date and configurations respectively

●​ And general, the third ionization enthalpy is a quite high.

●​ Which have the greatest number of oxidation States occur in or near the middle of the series

manganese exhibit all oxidation States from +2 to + 7

●​ The lesson number of oxidation States at the extreme ends stems from either to few electrons to

share or lose or too many D electrons for higher valance.

●​ scandium(+2) is virtually unknown

●​ Only Oxidation state of zinc is +2

●​ The variability of Oxidation State, a characteristic of transition elements, arises out of incomplete

filling FD orbitals in such a way and there oxidation States differ from each other by Unity. This is in

contrast with the variability of oxidation states of non transition elements were oxidation States

normally differ by a unit of 2. Although in the P block the lower oxidation states of favoured by the

heavier members due to inert pair effect, the opposite is true in the groups of D block

●​ Chromium + 4 in the form of dichromate in acidic medium is a strong oxidizing agent

●​ Low oxidation states of found When a complex compound has ligands capable of pi- acceptor character

in addition to the Sigma bonding

●​ The unique behaviour of copper having positive electrode potential accounts for its inability to

liberate H2 from acids. Only oxidizing acid such as nitric and hot concentrated sulphuric acid react

with copper the acids being reduced. The high energy to transform copper solid to Copper + 2 aquaous

is not balanced by its hydration enthalpy

●​ Chromium +2 is reducing as its configuration changes from D4 to d3, the letter having a half field t2g

level. On other hand, the change from MN + 3 to mn + 2 results in the half field configuration which is

extra stability

●​ Copper has low hydration enthalpy

●​ The stability of half field of disruption in MN + 2 and the completely filled the 10 configuration and zn

+ 2 are related to their electrode potential values where as electrode potential for Nickel is related

to the highest negative hydration enthalpy

●​ The ability of fluorine to stabilize the Highest Oxidation state is either due to hire lattice energy as

n case of co X3 or higher Bond enthalpy terms for the higher covalent compounds. The another

feature of fluorides in there in stability in low oxidation States

●​ The ability of oxygen to civilize these high oxidation States exceed that of fluorine the ability of

oxygen to form multiple bonds to metals explain its superiority. It is interesting to know that the
 electrod potential values for manganese Nickel and zn are more negative than the expected from the

general Trend.

●​ MN + 3 and Co + 3 ions are the strongest oxidizing agents in aqueous solutions. Titanium plus two

venadium + 2 and chromium +2 are strong reducing agents and will liberate hydrogen from a dilute acid.

●​ The electrode potential of M + 2 to M values are not regular which can be explained from the irregular

variation of ionization enthalpy and also the sublimation ethalpies which are relatively much less for

manganese and vanadium

●​ Electrode potential value from M + 3 to M + 2 is more positive because of much larger third ionization

energy of Manganese

●​ Diamagnetic substances are repelled by applied feel while paramagnetic substances are attracted

●​ Substances which are attracted very strongly or said to be ferromagnetic. Ferromagnetism is an

extreme form of paramagnetism.

●​ The unit of magnetic moment is bohr magneton BM

●​ The magnetic moment increases with the increasing number of unpaired electrons the magnetic

moments calculate it from the spin only formula

●​ When an electron from a lower energy D orbital is excited to a higher energy De orbital the energy of

excitation correspons to a frequency of light absorbed which generally lies in the visible region. The

colour observed corresponds to the complementary colour of the light absorbed.

●​ Complex compounds are those in which the metal iron bind a number of anions on neutral molecules

giving Complex species with characteristic properties. The transition metals form a large variety of

complex compounds. This is due to the comparatively smaller sizes of metal ions their high ionic

availability of the orbitals for Bond formation.

●​ The transition metals and their compounds are known for their catalytic activity this activity is a

scribed to there ability to form variable Oxidation State, surface area and ability to form complexes

●​ Vanadium + 5 oxide in contact process, finally divided iron in habers process, and Nickel and catalytic

hydrogen

●​ Catalyst at a solid surface involve the formation of bonds between react and molecules and atoms of

the surface of the catalyst first row transition metals utilise 3D and 4S electrons for bonding. This

has affect the increasing the concentration of reactant at the catalyst surface and also we Canning of

the bonds in the reacting molecules does the activation energy is lowerred.

●​ Interstitial compounds are those which are formed when small atoms of hydrogen carbon or nitrogen

or trapped inside the crystal lattice of metals

●​ They have high melting points higher than those of pure metals
●​ They are very hard some borides approach diamond in hardness

●​ They retain metallic conductivity

●​ They are chemically inert

●​ An alloy is a blend of metals prepared by mixing the components alloys may be homogeneous solid

solutions and which the atoms of 1 metals are distributed randomly among the atoms of the other.

Lawyers of formed by atoms when metallic radii that are within about 15% of each other.

●​ Because of similar radii and other characteristics of transition metals alloys are readily formed by

these metals. There are so formed are hot and often have high melting points

●​ alloys of transition metals with non transition metals such as brass which is made of Copper and Zinc

and bronze which is made of Copper and tin. Some known ferrous alloys are chromium vanadium

tungsten molabdinum and manganese which are used for the production of variety of Steels and

stainless steel.

●​ The oxides a generally formed by reaction of metals with oxygen at high temperatures. all the metals

except scandium form mo oxides which are ionic.

●​ As the oxidation number of a metal increases, ionic character decreases

●​ In case of MN, mn2o7 is a covalent green oil

●​ Even cro3 and v2o5 have low melting points. In these higher oxides, the acetic character is

predominant

●​ We need to check which of sides are amphoteric basic and acidic

●​ Potassium dichromate

●​ Potassium dichromate is a very important chemical used in leather industry and as anoxidant for

preparation of many azo compounds

●​ 4 fecr2o4 + 8 na2co3 + 7 o2 -----> 8 na2 cro4+ to fe2o3+ 8C02

●​ Yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a solution from

which Orange sodium dichromate can be crystallized

●​ 2 na2cro4+ 2 h+ -------> na2 cr2o7+ 2 na + + h2O

●​ Sodium dichromate is more soluble than potassium dichromate

●​ Na2cr2o7 + 2 KCL gives k2cr2o7 + 2 NaCl

solution the oxidation state of chromium in chromate and dichromate is same

●​ The chromate ion is tetrahedral where as the dichromate Ion consist of two tetrahedra sharing one

corner with CR-o-cr bond angle of 126

●​ Sodium and potassium dichromates are strong oxidizing agent, the sodium salt has a greater solubility

in water and is extensively used as an oxidizing agent in organic chemistry. Potassium dichromate is

used as a primary standard in volumetric analysis.

●​ Potassium permanganate

●​ Potassium permanganate is prepared by fusion of mno2 with an alkali metal hydroxide and oxidizing

agents like kno3. This produces the dark green k2mno4 which disproportionates in a neutral or acidic

solution to give permanganate.

●​ 2 mno2 + 4Koh + O2 gives 2 k2mno4 + 2h2o

●​ 3 mno42 - + 4 H+ gives 2 mno4— + mno2 + 2h2o

●​ Commercially it is prepared by alkaline oxidative fusion of mno2 followed by the electrolytic oxidation

of manganate

●​ Mno2 (fused with KOH oxidized with air or kno3) gives mno4 2 - manganate ion

●​ MNo42 - manganate (electrolytic oxidation in alkaline solution) gives mno4 - permanganate ion

●​ 2 MN+ 2 + 5s2o82 - + 8 H2O gives 2 mno4— + 10 so42 - + 16 H+

●​ Potassium permanganate forms dark purple crystals which are ISO structures with those of kclo4

●​ Tetrahedral manganate ion mno42 - is green

●​ Tetrahedral permanganate Ion mno4— is purple

●​ Potassium permanganate has intense colour and its diamagnetism along with temperature dependent

weak paramagnetism. The magnet and permanganate ions are tetrahedron; the pi bonding takes place

by overlap of P orbitals of Oxygen and D orbitals of Manganese.

●​ fe2+ ion is green and fe3+ ion is yellow

●​ Permanganate titrations in presence of hydrochloric acid are unsatisfactory sins hydrochloric acid is

oxidized to chlorine

●​ Besides it's use in analytical chemistry potassium permanganate is used as favourable oxidant in

propritive organic chemistry it uses for the bleaching of wool cotton silk and other textile fibres and

for decolarization of oils are also dependent on its strong oxidizing power.
 Inner transition elements F block

●​ The chemistry of actinoids is much more complicated owing to the occurrence of wide range of

oxidization states in these elements and partly because of their radioactivity

Lanthanide

●​ The electronic configuration of all tripositive ions is the most stable

●​ The decrease in atomic radii is not quite regular. This contraction is similar to that observed in an

ordinary transition series and it is attributed to the same cause, the imperfect shielding of one

electron by another in the same subshell. The shielding of 1 4f electron by another is less than that of

1D electron by another with the increase then nuclear charge along the series

●​ The most identical radii of zR and HF are consequence of Lanthanide contraction

●​ Ce+4 is paved by its noble gas configuration but it is a strong oxidant revolting to its common + 3 state

it can oxidize water

●​ Ce+4 is a good analytical reagent

●​ Eu+2 is a strong reducing agent changing to the common + 3 state similarly yb+2 which has f14

configuration is a reductant tB+4 has half field of Orbital and is an oxidant all length and its a silvery

white of metals and rapidly in air neither La+3 not lu+3 Iron show any colour but rest do so

●​ The Lanthanide ions other than f0 type la+3 and 3 + 4 and the f14 type yb+2 and lu+3 are all

paramagnetic

●​ The first ionization enthalpys of Lanthanide are around 600 kj mol-1,the second about 1200 compable

with those of calcium

●​ They have abnormally low value of third ionization enthalpy of lanthanum gadolinium and leuticium

●​ The earlier members of the series are quiet reactive similar to calcium but with increasing atomic

number they behave more like aluminium

●​ The best single use of lanthanides is for production of alloy Steel for plates and pipes. A well known

alloy is Miss metal which contains lanthanide metals 95% and iron 5% and traces of s, c,ca and al. Deal

of missed metal is used in MG based alloy to produce bullets shell and lighter Flint. It mixed oxides of

lanthanides are employed as crystals in petroleum cracking. Some individual Alan oxides are used in

Phosphorus and television screens and similar fluorescent surfaces

Actinoids
●​ All actinoids are radioactive elements and the earlier members have relatively long half life but the

letter ones have half life stranging from a day to 3 minutes for laurenceum

●​ All those the five f orbitals resembled the 4f orbitals in their angular part of the wave function they

are not as buried as poor f orbitals and hence 5 f orbitals can participate in bonding to a far greater

extent.

●​ They show actinoid contraction resulting from poor shielding by 5f electrons.

●​ The actinoid show in general + 3 Oxidation State. In the first half of the series frequently exhibit

higher Oxidation State. However + 3 and + 4 ions tend to hydrolyse

●​ The structural variability is obtained due to irregularities in metallic radii which of per greater than in

lanthanides. The actinoids are highly reactive metals a specially when the finally divided

●​ Actinoid contraction is Greater from element to element then Lanthanide contraction because

shielding effect of 5f is less than 4D subshell.

●​ T i o is used for the pigment industry and MI NO2 is used in dry battery cells. The battery industry

also requires zn and Ni and CD.

●​ Group 11 elements are called coinage metals

●​ V2o5 catalyzes the oxidation of SO2 in the manufacture of sulphuric acid. Ticl4 with al(ch3)3 forms

the basis of Ziggler catalyst used to manufacture polythene. Iron catalyst are used in the habers

process for the production of ammonia from N2 and H2 mixtures. Nickel catalyst enable the

hydrogenation of fats to proceed. In the wackers process oxidation of ethyne to ethanol is catalysed

by pdcl2. Nickel complexes are useful in the polymerisation of alkynes and other organic compound

such as Benzene. The photographic industry realize on the special light sensitive properties of agbr