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UNIT 1 LESSON 1 CONTENTS 1.0 1.1 1.2 AIMS AND OBJECTIVES INTRODUCTION INORGANIC RINGS CHAINS CAGES 1.2.1 HETERO CATENATIONS 1.2.2 ISOPOLY AND HETEROPOLY ANOINS 1.2.3 CAGES 1.3 1.4 1.5 Let us Sum Up Points for Discussion

References

1.0

AIMS AND OBJECTIVES

The aims and objectives of this lesson are to learn and to discuss the structural features of different types of inorganic chains and cage structures.

1.1

INTRODUCTION

S o m e n o n - metals have

the

tendency

to

resemble

carbon

in

certain

properties. This chapter discusses one such property of nonmetals. Nonmetals other than carbon have also the tendency to form chains, rings and cages. Most metals show less tendency to form compounds of this type, length of the chains and size of the rings thus formed are and the

restricted.

However, the ease with which both metals and nonmetals and combinations of the two form clusters has only been recognized in the last decade. This branch of chemistry has seen a rapid growth.

Carbon has the tendency to form extensive stable chains and hence we study the organic chemistry, as a separate branch. This phenomenon is not common in the remainder of the periodic table. Silicon and related nonmetals

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2 have the tendency of form chains, to a limited extent. There is no

thermodynamic barrier to the formation of long chain silanes, Si( n ) H ( 2 n + 2 ) . Their synthesis ad characterizations are difficult tasks. Si Si bonds are weaker than C- C bonds. Silanes are very highly reactive. At 400o C , S i 2 H6 decomposes much faster than C2 H6 .

2 S i 2 H 6 + 7O2 favoured. including Compounds both straight of chain

4 SiO2 + 6 H2 O. silanes and from n=1

This to

reaction n=8 have

is been A

kinetically isolated, of

branched- chain

compounds.

number

Polysilane polymers have been isolated. The chemistry of germanes is similar t o s i l a nes. Nitrogen, phosphorous and Sulphur form chains. Chain length up to 8 atoms of nitrogen are known. They are highly explosive. In the case of sulphanes, chains up to 8 sulphur atoms have been obtained. P2 H6 is well known P 3 H5 is well characterized. (perfluoroalkyl) trioxides such as Oxygen forms no chains longer than three a t o m s , O 3 and its anion O3 and a few compounds are known, for e.g., bis F3 C000C F3 . Allotropes of both 'S' and (Cyclic). The chain form of 'Se' is

'Se', are known in which helical chains of great length are present. Sulphur chains are instable with respect to S8

stable. Red 'P' is polymeric and is thought to have chains of pyramidal 'P' atoms. Polyhalide ions are stable, for e.g., I 3 .

1.2.1 HETERO CATENATION:

The atoms of

phenomenon different

of hetero catenation or chains built up of alternating elements, is are well known. Silicons, (R SiO) n a n d 2 those formed by

polyphosphazenes (PN(OR) 2 ) n application. The simplest hetero

hetero catenated polymers, having wide compounds (P2 O 7 ) - 4 . are

catenated

the dehydration of acids or their salts. Simple acid phosphate salts on heating give rise to pyrophosphates, may be given for as : e.g., The ; general it is formula known of as
(n+2)-

polyphosphate

(Pn O 3 n + 1 )

n=2,

diphosphate, n=3-

triphosphate

etc., 3 Na 5 P 3 O 1 0

melt/100l 5 Na 3 P O 4 + P4 O 1 0

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condensed poly phosphates such as sodium triphosphates, are largely used as detergents.

Silicate Minerals

Silicon heterocatenated

forms anions.

a The

very

large

number make up

of of

compounds various

containing About

silicates

minerals.

three fourths of the earth crust is silicon and oxygen. The majority of silica te minerals are insoluble, because they have an infinite ionic structure and

because of the Si- O bond. Silicate structures have been solved by X- ray crystallographic methods:

i)

The electro negatively difference between 'Si' and 'O' is equal to 1.7. This suggests that the bonds are 50% ionic and 50% covalent.

ii)

The structure may be considered both by ionic and covalent methods. The radius ratio of Si+ 4 : O - 2 is 0.29, which suggests that 'Si' is four co ordinate. It is surrounded by four oxygen atoms at the corners of a tetrahedron. 'Si' in (Si O4 ) - 4 may be assumed to be SP3 and three 3P orbitals) and hence silicates are based hybridized on (si (3s O )- 4 4

tetrahedral units.

iii)

The SiO 4 tetrahedra may exists as discrete units or may polymerize into larger units by sharing corners, i.e., by sharing oxygen atoms.

iv)

The 'O' atoms are often close packed or nearly close packed. Close packed structures have tetrahedral and octahedral holes and metal ions can occupy either tetrahedral or octahedral sites depending on their size. Al 3 + can

fit into either octahedral or tetrahedral site. Thus Al can

replace either octahedral or tetrahedral site. Thus Al can replace either a metal in one of the holes or a silicon atom in the lattice. This is particularly important in the aluminosilicates.

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5 Classification of Silicates

i)

Ortho Silicates: A wide variety of minerals contain discrete (SiO4 ) 4 tetrahedra. They have the general formula M2 ( S i O 4 ) (M=Be, Mg, Fe, Mn or Zn). M(SiO4 ) M - Zr. These silicates share no cormers.

I n Z n 2 SiO 4

(Willemite) and Be2 S i O 4 (Phenacite) Zn and Be have a

'CN' of 4; Zn and Be occupy tetrahedral holes. In Mg2 S i O 4 , Mg has a CN of 6 and occupies octahedral holes. Zr SiO4 is a gem stone. Zr has a CN of 8. The structure is not close packed. The garnents are minerals with discrete tetrahedra; are used as red gem stones. Its formula is M 3 M 2 ( S i O 4 ) 3 M(II) = Mg, Ca or Fe (II); Me(III) may be Fe(III), Cr or Al. These are 8 coordinate.

ii)

Pyrosilicates

Two tetrahedral units are joined by sharing the 'O' at one corner and the unit is (Si2 O 7 ) ions. The name like pyrophosphates
6-

. This is the simplest of the condensed silicate comes from the similarity in structure with

pyro

Na4 P 2 O 7 .

Pyrosilicates

are

rare, for e.g., Thortveitite (Sc2 ( S i 2 O 7 ) S i - O- S i b o n d

angle is 180o in this compound and it changes upto 133o .

The co ordination number of the metal changes from 6 to 7 and then to 8, with increase in size of the metal. Structural studies show no

difference in the lengths of the bridging and terminal Si- O bonds.

Cyclic Silicates

If

two

oxygen

atoms

per

tetrahedron

are

shared,

ring

structures

of

formula (Si O3 )n 2 n -

may be formed. Rings containing, three, four, six and Ca3 ( S i 3 O 9 ). The Si6 O 1 8 1 2 -

eight tetrahedral units are known. But those with three and six are the most. The cyclic ion Si3 O 9 6 occurs in wollastonite,

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6 occurs in beryl, Be3 A l 2 ( S i 6 O 1 8 ). In beryl the Si6 O 1 8 units are aligned one found in

above the other, leaving channels. Na+ , L i + and Cs+ are commonly

these channels, and because of the channels the mineral is permeable to gases consisting of small atoms or molecules e.g., helium. Beryl and emerald are

gemstones. Beryl is found with granite and usually forms pale green crystals, w h i c h a r e six sided prisms. Emerald has the same formula as beryl, but it

contains 1- 2%Cr, which gives it a strong green colour.

Chains Silicates:

Pyroxenes are simple chain silicates. These are formed by the sharing of oxygen atoms on two corners of each tetrahedron, with other tetrahedra. This gives the formula (Si O3 ) n 2 n - . A large number of important minerals form chains, but there of are a variety in of different may vary structures and formed affect because the the arrangement tetrahedra space thus repeat

distance along the chain. The most common arrangement repeats after every second tetrahedron for e.g., in spodumene, Li Al [(Si O ) 2 ], enstatite 3 repeat of

Mg2 [(Si O3 ) 2 ] and diopsite, Ca Mg

[(Si O3 ) 2 ] . C a 3 [(Si O3 ) 3 ] has a

three, and others are known with repeat units 4,5,6,7,9 and 12.

Double together by

chains shared

can

be

formed These

when

two are

simple

chains

are They

joined have

oxygens.

minerals

amphiboles.

different formulae, due to several ways of forming double chains, for e.g., [(Si 2 O 5 ) n 2 n - , [ ( S i 4 O 1 1 ) n 6 n - , [ ( S i 6 O 1 7 ) n 1 0 n - etc., Asbestos minerals are the best known amphiboles . These have the structural units (Si4 O 1 1 ) n 6 n - . Amphiboles always contain OH groups, which are attached to the metal ions. The Si- O bonds together in the by chains metal are strong present. and directional. and Adjacent amphiboles chains are held

ions

Pyroxenes

cleave

readily

parallel to the chains, forming fibres. For this reason, they are called fibrous minerals. The cleavage angles for pyroxenes Example are tremolite and amphiboles are different. and crocidolite Na2 F e 3

Ca2 M g 5 ( [ ( S i 4 O 1 1 ) 2 ] (OH) 2

Fe 2 ([(Si 4 O 1 1 ) 2 ] (OH) 2 (. (blue asbestos).

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7 The mineral chrysatile Mg3 ( O H ) 4 ( S i 2 O 5 ) is white asbestos and is a

sheet silicate. Asbestos causes lung cancer.

Sheet Silicates

When SiO 4 units share three corners the structure formed is an infinite two dimensional sheet of empirical formula (Si2 O 5 ) n 2 n - within the Si- O s h e e t bonds are strong but much weaker forces hold each sheet to the next one. These sheets cleave into thin sheets. These consist of two or three layers joined together. Examples are

(i) (ii) (iii) (iv)

Clay

minerals

(Kaolinite)

White asbestos Micas (Muscovite) Montmorillonites (fullers earth, bentonite).

consider the formation of a two layer structure. If a Si2 O 5 layer is placed along side a layer of Al(OH)3 , then many of the 'O' atoms will coincide. The 'OH' groups in Al(OH)3 can be removed and an electrically neutral two layer structure is formed. These double layers stacked parallel give the mineral kaolinite, which has the formula Al2 (OH) 4 ( S i 2 O 5 ). It is a white solid and formed by the decomposition of granite.

Al (OH)3 Sheet Silicate Sheet (Two Layer Structure)

Three

Dimensional

Silicates

Sharing all four corners of a Si O4 dimensional These lattice no of formula ions, Si O2

tetrahedron tridymite,

results

in

three etc.,). in

(quartz, three

cristobalite

contain

metal

but

dimensional

silicate

structures

which some of the Si + 4 ions are replaced by Al3 + , plus an additional metal

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8 ion. This gives an infinite three dimensional lattice and the additional cations occupy holes in the laltice. The cations are usually the larger metal ions like K + , N a + , C a + 2 or Ba+ 2 . The smaller ions Fe 3 + , C r 3 + and Mn2 + common in chain and sheet silicates do not occur in three which are dimensional

silicates because the cavities in the lattice are too large. Replacement of one quarter or one half of the 'Si' atoms are quite M [ A l S i 3 O 8) minerals. and M[Al2 S i 2 O 8 ). Such common. These give structures, replacements gives rise to the

i) ii) iii)

Feldspars Zeolites Ultramarines

Granite is made up of feldspars. We have orthoclase a) b) Orthoclase K[Al Si3 O 8 ) Celsian Ba[Al 2 Si 2 O 8 ) Clase: Albite Na[Al Si3 O 8 ] Anorthite Ca [Al2 S i 2 O 8 ].

feldspars:

Plagio a) b)

The ortho clases are more symmetrical than are Plagio Clases. K+ a n d B a 2 + are just the right size to fit into the lattice while Na+ & Ca2 + cause distortion. being smaller,

Zeolites:

Zeolites

have

much

more

open

structure,

than

the

feldspars.

The

anion skeleton is penetrated by channels, giving a honeycomb like structure. These channels are large enough to allow them to exchange certain ions. They can also absorb or lose water, and other small molecules without the structure being broken. Zeolities are often used as ionexchange materials

and as molecular sieves. Nat r o l i t e , N a 2 [Al 2 S i 3 O 1 0 ] 2 H 2 O is a natural ion

2 exchanger. Permutit water softeners use sodium zeolites. Zeolites take Ca +

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9 from water and replace them by Na+ . Zeolites can absorb CO2 , N H 3 and Et OH, Zeolites have been employed to separate branched chain hydrocarbons from straight chain hydrocarbons.

The mineral lapis lazuli has a fine blue colour. It contains ultramarine Na8 [(Al Si O4 )6]S 2 , in which the colour is produced by the polysulphide ion. Ultra marines do not contain water.

The

ultramarines

are now produced synthetically is obtained by heating

kaolinite, Na 2 C O 3 and S in the absence of air.

1.2.2 ISOPOLY

AND

HETEROPOLYANIONS

Transition

metals

in

their

higher

oxidation

states

are

similar

to

nonmetals with corresponding group numbers. For e.g., V and P in VO3 - 4 a n d PO 3 - 4 , C r O 2 - 4 and SO2 - 4 , M n O 4 - and ClO4 - . The analogy may be extended to poly anions, such as Cr2 O 2 - 7 . P o l y m e n s a t i on of some metal anions occurs spontaneously, Cr 2 O 2 - 7 . When upon acidification. treated At low with P1+ CrO4 - is converted into sulphuric acid red Cr2 O 2 - 7 is concentrated

chromium (VI) oxide, chromium acid is formed.

n Cr2 O 2

2+ nH + 7 (CrO 3 ) n +

n H2 O 2

The structure of CrO3 consists of infinite linear chains of Cr O4 tetrahedra. The vanadate ion, VO3 - 4 c o n c e n t r a t e d ( V 2 O 7 )4 polymerization anions have of been vanadate, exists in extremely basic
+

solution.

Under

dilution

and low pH, protonation yields monomers (VO 2 ). When solutions are more and higher vanadates and In tungstates the are ions obtained. forming The molybdate studied. iso poly the

extensively

condensation

process,

coordination number changes from 4 to 6 and the basic building block in the polymerization surrounding process metal becomes atom. The an octahedron resulting of six may oxygen link atoms, by

each

octahedra

either

sharing an apex or edge (rarely a face) due to the relaxation of electrostatic

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10 repulsion, in the larger octahedra. As a result, the structures tend to be small clusters of octahedra, in the discrete poly anions, culminatin g in infinite

structures in the oxides. When the edge sharing occurs, the structure may be stabilized, if some distortion occurs such that the metal ions move away from each other. It might be expected that the smaller the metal ion, the less the repulsion and the larger the number of edge sharing octahedra per unit. This is found to be true V5 + (68pm), Mo6 + (73pm), W6 + (74 pm), Nb5 + (78pm) Ta5 + (78pm) and the most common edge shared poly anions are, (V 0 O 2 8 ) 6 - , 1 (Mo 7 O 2 4 ) 6 - , (Mo 8 O 2 6 ) 4 - ( W 6 O 1 9 ) 2 - , ( W 7 O 2 4 ) 6 - , ( N b 6 O 1 9 ) 8 - and (Ta6 O 1 9 ) 8 - . To form larger polyanions such as (W12 O 4 2 ) 1 2 apex sharing. edge sharing must give to rise to

The isopoly an ions may be considered to be portions of a closest packed array of oxide ions with metal ions occupying the oc t a h e d r a h o l e s . The edge sharing This with represent is array the found largest in (V1 0 O stacked
28) 6-

consists

of

ten

octahedral cluster shaped

stacked. compatible structures

octahedra and the

isopoly remaining

anion edge

metal- metal

repulsions,

portions of this unit.

Elements other than V, Nb, Ta, Mo and W do not form isopoly anions. Al 3 + , G a 3 + , I 7 + may have appropriate radii for isopoly anion formation. But they form, sheets or three dimensional frame works. The reason given is as follows. The terminal oxygen atom in the isopoly anion is strongly b o n d e d

to a transition metal such as Mo(VI) or W(VI). The metal ion is displaced in the direction of the terminal oxygen; due to this effect. Metal ions such as Al 3 + and Ga3 + a r e poor acceptors. Thus their terminal oxygen atoms are not stabilized, and this leads to chain structures. Due to bonding the terminal

oxygen atoms of the transition metal polyanions are stabilized and have less affinity for adjacent metal units.

In aprotic media, new poly anions have been obtained for e.g., When [(n- Bu) 4 N] OH and [(n- Bu) 4 N ] [ H 3 V 1 0 O 2 8 ] are mixed in acetonitrile, a new isopoly vanadate, [V5 O 1 4 ] 3 - is formed. It is the first example of a poly

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11 oxoanion cage that is built from corner shared tetrahedra. When [n Bu 4 N] [H 2 V1 0 O 2 8 ] is refluxed in acetonitrile, CH3 CN is found to be suspended in a (V 1 2 O 3 2 ) - 4 basket. Heteropolyanions

It has been found that there is a cavity in the center of a metatungstate ion. This cavity is surrounded by a tetrahedron of four oxygen atoms. This cavity is sufficiently large to accommodate a relatively small atom like P(v), As(V), Si (IV), Ge(IV), Sn (IV) or Zr (IV). The 12- tungs to heteropoly anions are of general formula [Xn + W 1 2 O 4 0 ] ( 8 - n ) are also known. For e.g., when a molybdate is similar solution molybdo heteropoly anions and

containing

phosphate

acidified, the ion (PMo1 2 O 4 0 ) 3 - is formed P- O b o n d s are not

broken in this process. The product anion contains the PO3 - 4 in the MO1 2 O 3 6 cage. Between 35 and 40 hetero atoms are known to form heteropoly anions and their corresponding acids. Large hetero atoms such as Ce (IV) and Th (IV) are found icosahedrally coordinated in salts such as (NH4 ) 2 H6 Ce Mo1 2 O 4 2 . It is unique in as much as pairs of MoO6 octahedra share faces to form Mo 2 O
9

groups

which

are

corner

connected

to

each

other

molybdo

heteropoly acids form with hetero atoms Te(VI), I(VII) and tri p o s i t i v e m e t a l ions such as Rh(III). All these heteroatoms prefer an octahedral coordination sphere, which can be provided by a ring of six Mo O 6 octahedral. The isopoly

and heteropoly anions may be considered small chunks of metal oxide lattice. F o r s e l e ctive oxidation of organic molecules, these may be used as catalysts. As anions they show very low surface charge densities and low basicities. Hence molybdate
6-

(- 2) ion and 12- tungsto

2+

phosphate

(- 3)

ion

have

lower

basicities than perchlorate ion. Mn of (H 2 W1 2 O

40)

b i n d s weakly to a terminal oxygen atom

and the anion functions as a monodentate ligand.

C o in [(Si W1 1 O 3 9 ) Co (H2 O)] 6 - is 6 coordinate, the heteropoly anion functions as a pentadentate ligand. (W6 O 1 9 ) 2 for has been studied using O1 7

N M R s p e c troscopy. The spectm gives three signals corresponding to twelve bridging oxygen atoms, one signal encapsulated oxygen and one for

terminal oxygens.

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12 Fig.1.2(a) Mutterties, York, and E.L. (b) The Bonding and structure of and tetraborane, Its B4H10. Wiley: (From New

Chemistry with

of Boron

compound;

1967.

Reproduced

permission.]

1.2.3 CAGES

The bonding and structures of boranes are of great interest. They are different from all other hydrides. These compounds are electron deficient.

D i b o r a n e ( B 2 H6 ) h a s 12 valency electrons (3 from B and 6 from H atoms). Electron diffraction studies indicate that the compound has B- H- B b r i d g e s . The two bridging H- atoms are in a plane perpendicular to the rest of the molecule, and prevent rotation between the two 'B' atoms. Specific heat

measurements confirm that the rotation is hindered. Four of the H- a t o m s a r e in a different environment than the other two. This is confirmed by Raman spectra and by the fact that diborane cannot be methylated beyond Me4 B 2 H2 , without breaking the molecule into B Me3 . The terminal B- H d i s t a n c e s are the same. These are assumed to be normal covelant bonds. These are (2C2e) two centre- two electron bonds. The structure is shoen in fig 1. Each of the bridging B- H- B linkages then involves a delocalised Each 'B' is SP3 hybridised. three centre bonds.

The appropriate combinations of three orbital wave functions, j B1 , j B2 ( S P 3 hybrid (M O ) orbitals) and j H ('s' orbitals), give rise to three molecular orbitals

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13

1 Yb = 2 1 Yn = 2 j B1 j B1 +

1 j B2 2 1 j B2 2 +

1 jH 2

1 Ya = 2 j B1 +

1 j B2 2 +

1 jH 2

Yb= bonding Mo, Y a = antibonding MO and Y n = nonbonding. Each bridging bond thus consists of a bonding Mo containing two electrons. Thus all the twelve electrons in B2 H 6 qualitative description
14

have been accounted for fig,1.1(a) and (b) give atomic orbitals and three
10

of

centre is

Mo by

orbitals slow

respectively B10 H decomposition of

is quite stable in air. B4 H

formed

B2 H6 . In addition to terminal and bridging of B- H b o n d s undergoes both symmetric

B4 H1 0 contains a direct B- B bond. Tetraborane

and unsymmetric cleavage. Fig 1.2(a) and (b). Fig 1.3 gives bonding and structure of B4 H1 0 . Larger bases spit off BH3 groups: B4 H 1 0 + 2 Me3 N BH 2 + Me 3 N B 3 H 7 + Me3 N BH3 .

small hard Lewis bases (NH3 ) result in unsymmetr i c a l c l e a v a g e splits of

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14 B4 H 1 0 + 2 NH3 [H 2 B(NH 3 ) 2 ]
+

+ [B3 H 8 ] -

Fig 1.2 Symmetric (a) and Unsymmetric (b) Cleavage of Tetraborane [B 1 2 H1 2 ] 2 - is a highly symmetric borohydride. It is obtained from B3 H8 - ion. 5[B 3 H8 ] [B 1 2 H1 2 ] 2 - + 3[BH4 ]- + 8H2

T h e [ B 1 2 H 1 2 ] 2 - is a regular icosahedron of atoms, each of the twenty faces being an equilateral triangle. All of the H atoms are external t the o bonds. The structure boron icosahedron and are attached by terminal B- H involves several

canonical forms. Both two electron, two centre B B a n d fragments of a B1 2 icosahedron (or of the [B1 2 H1 2 ] 2 - ion) in

two electron, three centre B- B- B bondings are involved. Several boranes may be considered as

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15 which extra hydrogen atoms are used to "sew up" the unused valences around the edge of the fragment. For e.g., decaborane (B10 H1 4 ), may be considered as a B1 2 H 1 2 frame work from which B1 and B6 have been "dangling" three centre f o r m B - H- B bridges. (B6 H1 0 (hexaborane) is a removed, leaving bonds that are completed with hydrogen atoms to pentagonal prism.

Experimental work has shown that the icosahedrons of [B1 2 H 1 2 ] 2 - is merely the upper limit of a series of deltahedra (Bn Hn)2 - (from n=4 to n=12). If all the vertices of the deltahedron are occupied, as in the [BnHn]2 series, the

structure is called a 'closo' (closed structure). The number of vertices in the deltahedron framework. will This be one is less than the 'wades number rules'. of For bonding the pairs in the the

theory

called

closo

series

number of frame work electrons equals 2n+2. Consider (B1 2 H 1 2 ) 2 - to count framework electrons. Each 'B' has one of its valence electrons tied up with the 'exo' B- 4 bond and it has thus two to contribute to the framework, giving a total of 2n (in this case 24 electrons) from the 'B' atoms. No neutral Bn Hn species are known, but an array of dianions, obeying the 2n+2 are known.

The 26 electrons (2 x 12 + 2) are just the number required to fill all the bonding molecular orbitals in [B1 2 H 1 2 ) 2 - and this corresponds to 13 (n+1,

n=12) electron pairs as expected for an icosahedrons. If a B atom is removed from a vertex of the closo structure, a cup- like or nest like structure remains. Such structures are called 'nido' (nest). The nido structures obey the

framework formula 2n+4. Consider B5 H9 . Five exo B- H groups will contribute two electrons each, and the four extra 'H' atoms will contribute 4 electrons and thus the total will be 10+4=14 electrons (2n+4, n=5). This corresponds to 7 pairs (n+2) and the geometry will be derived from an octahedron (n- 1 vertices). The structure is thus a square pyramid nido form derived from the closo octahedron. If two vertices are missing, the resulting framework is called "arachno" (spiders web). these

obey the formula 2n+6 (n+3 electron pair). B5 H 1 1 (ponta borane) has arachno structure. In arachno series the extra H atoms form endo B- H bonds. In hypho (net) series the rule is 2n+8. Some borane derivatives, fit it into this scheme. For a regular deltahedron having 'n' vertices there will be n+1 bonding

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16 molecular orbitals. The number of electrons that can occupy these Mos will be 2n+2. This gives the highly symmetric closo structure.

Carboranes: [B1 2 H 1 2 ) 2 - and can be

The

systems

C2 B1 0 H1 2

is

isoelectronic

with

synthesized from decarborane and alkynes using diethyl sulphide as solvent.

B1 0 H 1 4 + R- C X C - R

R2 C 2 B 1 0 H1 0 + 2H2

The acetylene may be unsubstituted or substituted, in which case, the compound is known as 1,2 dicarba- closo- dodeca borane or orthocarborane and is isoelectronic and iso structural with [B1 2 H 1 2 ) 2 - . It is stable to both heat and air, but it isomerises at high temperatures to the 1,7 (meta or 'neo' isomer) and the 1,12 (Para isomer). The mono carboranes are known in closo, nido and arachno structures. Thus closo C 2 B 9 H1 1 + 2e [nido C 2 B 9 H1 1 ] 2 [nido C 2 B 9 H1 1 ) 2 [closo C 2 B 9 H 1 1 ) + 2e

In the anion [C2 B 9 H 1 1 ] 2 - , each of the three 'B' atoms and the two carbon atoms on the open face of the cage directs an orbital (SP3 ) toward the apical position occupied formerly by the 12th boron atom. Further these

orbitals contain a total of six electrons. H1 1 ] 2 be as

Hence C 5 H5 -

this

anion This be

[C2 anion of

B9 could

has

resemblence isoelectronic in

to with

cyclopentadiendeanion. and should

considered aP ligand

capable succeeded

acting

metallocene

compounds.

Hawthorne

in

synthesizing

metalla

carboranes.

2[C 2 B 9 H 1 1 ] 2 - + Fecl 2

[(C 2 B 9 H1 1 ) 2 F e ] 2 - + 2cl-

This has structure similar to ferrocene.

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17 Self Check Exercise m- 1

1) b)

What

is

heterocatenation?

Discuss the different types of silicates and their structures.

2)

Describe with examples, the isopoly anions.

Self

Check

Exercise 2

1) 2) 3)

Discuss the structures of molybdates and tungstates Elucidate the structure of diborane Discuss in detail the structures of boranes and explain the terms, closo, nido and arachno with examples.

1.3 Let us Sum Up Heterocatenations, structures are like heteropoly and isopoly anions and their

discussed various types of silicate minerals and how SO4

tetrahdra could form different types of structure sare indicated. Boron cage compounds, wades rules and cloro nido and arachno spieces are also described.

1.4 Points

for

Discussions

i) ii) iii)

Silicates ad their structures Isopoly and heteropoly Closo nido anions structures and uses & arachno species the different formulae as

Boranes

2n+2, 2n+4, 2n+6 and 2n+8

1.5 References

Concise

Inorganic

chemistry

edition J . D . L e e B l a c k w e l l .

Publishing N o i d a - D e l h i 2 0 0 5 .

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18

LESSON 2

CONTENTS
2.0 2.1 2.2 AIMS AND OBJECTIVES INTRODUCTION METAL CLUSTERS 2.2.1 TYPES OF METAL CLUSTERS 2.2.2 ORGANOMETALLIC CLUSTERS 2.3 2.4 2.5 Let us Sum Up Points for Discussion

References

2.0

AIMS AND OBJECTIVES

The aims and objectives of this lesson are to learn about the different types of metal clusters and their structures.

2.1

INTRODUCTION

Compounds

containing

metal- metal

bonds

are

as

old

as

chemistry

itself. Calomel was known to chemists of India as early as 12th century. The dimeric nature of mercurous ion was confirmed only later. It was only some 30- 35 years ago that the study of other metal- metal bonds began in earnest; yet this branch of inorganic chemistry has grown at a phenomenal rate.

M e t a l c l u s ter classes: i) ii) Polynuclear

compounds

can

be

conveniently

classified

into

two

carbonyls,

nitrosyls

and

related

compounds

Halide and oxide complexes

The second class will be discussed here. The two classes have un related chemistry. Metal atoms in class.

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19 i) ii) Have formal oxidation states 1 to +1, while those in

are found in higher formal oxidation states, +2 to +3.

The transition metals (late transition metals) typically form class i) Clusters, while those on the right side of the periodic table ( e a r l y

second and third row transition metals) tend to form class II clusters. Atoms having large energies of atomization (hence very high m- pts and b- p t s ) f o r m metal clusters. Thus the most refractory metals (Zr, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Os, Ir and Pt) have the greatest tendency to form metal clusters. Effective clusters. overlap Excessive of d- orbitals of appears the 'd' necessary orbitals will for stabilizing the metal metal

contraction

destabilize

clusters. Hence large charges (very high oxidation states) on the metal atoms are unfavourable for the formation of metal clusters. In first row transition metals, the 'd' orbitals are relatively small and metal cluster formation is not favoured.

i)

Dinuclear Compounds

The best studied compound is (Re2 x 8)2 - ion; obtained by reducing Hx Perrhenate with H3 Po 2 in the presence of x= cl, Br, I, NCS.
x-

2 ReO4 H3 Po 2

(Re 2 x 8)2 - ;

It has two unusual features. Re- Re bond distance is 224pm compared with an average of 275pm in rhenium metal, and 248pm in Re3 Cl 9 . T h e unexpected features in this ion is the eclipsed configuration of the chlorine atoms. But chlorine atoms are expected to lie at distances of 330pm, i.e., the staggered configuration would be preferred. According to Cotton, the Z- axis

of the ion is taken a the line joining the two Re atoms. Each Re atom is bonded to four 'Cl' atoms in a square planar array. We may consider the Re Cl bonds to involve dSP2 hybrids on each metal (using dx2 - y2 orbitals). The m e t a l d Z 2 and PZ orbitals lie along the bond axis and may be hybridized to form one orbital directed toward the other rhenium atom and a second orbital

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20 directed in the opposite direction. The former can overlap with the similar orbital on the second 'Re' atom to form a 's' bond, the second dZ2 - p z h y b r i d orbital forms an approximately a non- bonding orbital. The dxZ and dyz

orbitals of each rhenium atom can overlap to form two P

bonds. The dxy bond (delta).

orbitals on each Re atom can overlap "sideways" forming a 'd '

overlap of the dxy orbitals can only occur if the chlorine atoms are eclipsed. If the chlorine atoms are staggered, the dxy orbitals do not overlap. The ei ht g d electrons (Re3 + , d 4 ) from two 'Re' atoms occupy s bonding (2), two P

bonds (4) and delta bond (2) ing orbitals to from the quadruple bond; hence the complex is diamagnetic. The model accounts for the strength of the bond, the short Re- Re distance and the eclipsed configuration. (Mo2 C l 8 ) 2 - is known. Both Re (III) and Mo(III) form

The

isoelectronic

a large series of carboxylate complexes of formula Re2 (RCo 2 ) 2 x 4 etc, and Mo 2 ( R C O 2 ) 4 . Structurally these are related to (Re2 x 8 ) 2 - . [Re 2 C l 8 ] 2 - (having qudruple bond) has all its bonding Mos filled up i.e s 2 P 4 d 2 (bond order = 4). d and d * are nearly non- bonding.

Tungsten forms a series of compounds W2 C l 4 ( O R ) 4 R 2

(R=Me, Et),

with a W=W double bond. These ditungsten compounds have bond orders 4, 3, 2 and 1 Cu(II) and Cr (II) in the 1st transition complexes. weak single These bond are diamagnetic. from series form acetate

Cu- Cu bond in Cu (II) acetate is only a pairing the odd electron in each copper

resulting

a t o m . C r- Cr bond in its acetate complex, is stronger than Cu- Cu bond. Cr C r d istance is shorter in the complex than in the metal. These suggest that the Cr complex has a qudruple bonds (weak). But the lengths of the qudruple bonds in Mo- Mo and W- W are uniform.

(RO) 6 M2 e.g. W2 ( O R )

are known. WX W i s found in these complexes

(s 2 P 4 ). This undergoes addition reactions with halogens (Cl2 , B r 2 , I 2 ) . W 2 (O- I- Pr) 6 dimerises to W4 (o- i- Pr) 1 2 analogous to cyclobutadiene a

fluxional molecule.

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21

Trinuclear Clusters:

[(ReCl 3 ) 3 contains three metal atoms. Each rhenium atom is bonded to other two 'Re' atoms ligand. directly In by metal- metal each, bonds, and indirectly in the by a binding array is halogen addition rhenium atom triangular

coordinated by two more halide ligands above and below the plane

defined by the three rhenium atoms. Each Re (III) has d4 configuration which would lead to a paramagnetic complex, if only metal- metal single bonds were present. The complexes are diamagnetic, however which implies that each Re

atom is doubly bonded to its Re neighbour. Re3 cluster is persistent in many chemical transformations.

Tetra Nuclear Clusters :

W 4 (OR) 1 2 is a tetra nuclear cluster which is formed by the dimerisation o f W 2 (OR) 6 . is saturated, The tetrameri c W 4 (OR) 1 6 has also been synthesised. containing W- W single bonds. Qudruply bonded W4 (OR) 16 dinuclear

compounds can also dimerise to give tetrameric molecules

(R 3 P) 2K 4 Mo 2 cl 8 Four ring member is not Mo 4 ( R 3 P) 4 c l 8 + Kcl. The resulting four membered indicate, that there are

ring containing Mo is formed. square. and Bond triple length Mo by

measurements Mo bonds. oxygen

alternating

single

Tetranuclear cluster units and forming infinite

( r h o m b o h e d r a l M o 4 ),

connected

atoms

chains, are found in Ba1.1 4 M o 8 O 1 6 .

Hexa

Nuclear

Clusters

Clusters of six, Mo, Nb or Ta atoms are known. There are two types. In the first an octahedron of six metal atoms is coordinated by eight chloride

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22 ligands, one on each face of the octahedran. This is found in "Molybdenum

dichloride", Mo 6 , C l 1 2 , better formulated as [Mo6 cl 8 ] C l 4 . Each Mo (II) atom can use its four electrons to form four bonds with adjacent Mo atoms and can form dative bonds from the four chlide ligands (Mo2 c l 8 ) have a cubicarrangement of chloride ions, Nb and
4-

a nd (Mo6 cl8 ) form

4-

Ta

hexanuclear

clusters. These have octahedron of metal atoms, but they are coordinated by twelve halide ligands, along the edges. The structures are complicated. The metal atoms are surrounded by a distorted square prism of four metal and four helogen atoms. These compounds are electron deficient (as boranes) there are fewer pairs of electrons than orbitals to receive than orbitals and so fractional bond orders of 2 / 3 are obtained. Che v r e l P h a s e s

Ternary phases and

molybdenum are polynuclear

chalcogenides, clusters

Mx

Mo6 x unusual

8,

are

called

chevrel have

having

structures.

Thes

interesting electrical and magnetic properties Pb Mo6 S 8 is a super conductor below 13.3k. This has a octahedral cluster of Mo atoms, surrounded by a cubic cluster of S atoms, which in turn is currounded by a cubic lattice of lead atoms.

2.2.2 Organoi

Metallic

Clusters

Poly nuclear carbonyls such as B3 H7 [Fe(Co) 3 ] 2 and t y p e R h 6 (Co) 1 6 m a y

complexes

of the

be classified as organo metallic clusters. The structures

of these cages or clusters can be predicted by 'Wades' rules' (Closo, nido or arachno) using 2n+2, 2n+4 and 2n+6 formulae.

Consider

the

Molecule:

B 3 H 7 [ F e ( C o ) 3 ] 2 , for which n=5. The three BH units Fe(Co) 3 units contribute 2 electrons each and the four contribute 1 electron each (total 14 electrons).

and extra

the H

two atoms

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23 2 Fe (Co)3 3 BH 4H = = = 2 x 2 = 4 3 x 2 = 6 4 x 1 = 4 14

Since n=5, there are 2n+4 frame work electrons and We predict a nido structure for the same. Molecule has a square pyramidal structure. This

results from the substitution of 2 BH units by 2Fe (Co)3 units in B5 H9 . C o n s i d e r R h 6 (Co) 6 : n=6. Each of the six Rh(Co)2 contributes 'I'

electron to the frame work, 4Co molecules provide 8 electrons.

6 Rh (Co)2 = 4 Co =

6 x 1 = 6 4 x 2 = 8 14

We have 14 framework electrons in 2n+2 formula (n=6; 2 x 6+2=14). Hence the complex has a close structure. There are two terminal CO group s per 'Rh' and four bridging 'CO' groups. Which span alternate triangular faces [p- (cymene) 3 - R m 3 S 2 ] 2 + has 48e- s closo structure. This can be reduced to a nido structure (50e- s).

Self

Check

Exercise 1

1.

What are closo, nido and arachno structures? and explain wade's mles with examples.

2.

Discuss in detail the different types of clusters.

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24 Self Check Exercise 2

1)

Show

how

wades

mles

can

be

applied

to

organo

metallic

clusters.

Compare with 18e rule for carbonyls.

2.3 Let us Sum Up Motal clusters of different types such as tetra nuclear and polynuclear structures are discussed in detail. The application of wades rules to metal clusters is indicated organo metallic clusters such as Rh6 (CO) 6 and the application of 2n+2 rule is also discussed.

2.4 Points for Discussion:

1. 2. 3.

Metal clusters types and structures Wade's mles Organo metallic clusters.

2.5 References:

1. 2.

Concise

Inorganic

chemistry J.D.Lee 5th edition

Inorganic chemistry Huhecy et al Pearson Education Asia.

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25 UNIT II LESSON 3 BORAZINES PHOSPHONITRILIC COMPOUNDS

CONTENTS 3.0 AIMS AND OBJECTIVES 3.1 3.2 INTRODUCTION BORAZINES 3.2.1 SYNTHESIS OF BORAZINES

3.2.2 STRUCTURE AND PROPERTIES OF BORAZINES 3.3 PHOSPHONITRIC COMPOUNDS 3.3.1 SYNTHESIS OF PHOSPHAZENES 3.3.2 STRUCTURAL STUDIES 3.3.3 PHOSPHAZENE POLYMERS 3.4 3.5 3.6 Let us Sum Up Points for Discussion

References

3.0

AIMS AND OBJECTIVES

In

this

Lesson are

the

Synthesis The

of

Borazines of

and

the and

synthesis

of

phosphazenes

discussed.

structures

borazines

phosphazenes

are also discussed. After structure systems. Understand the 'd' orbital participation in the phosphozenes structure. of going through and this lesson you should with able to and compare other the ring

Borazines

Phosphazenes

benzene

Develop interest in doing research in the fields of Phosphazenes and their applications.

3.1

INTRODUCTION The most important ring system of organic chemistry is the benzene

ring,

either

as

separate

entity

or

in

polynuclear

hydrocarbons

such

as

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26 naphthalene, analogues of anthracene benzene and B3 N 3 R6 phenanthrene. and trimeric Inorganic chemistry has two

cyclop h o s p h a z e n e c o m p o u n d s ,

P 3 N 3 X6 . Alfred Stock synthesised borazine early in this century. He was the first to study compounds such as boranes, silanes and other similar nonmetal compounds. He perfected vacuum line techniques for the handling of air and moisture sensitive compounds invaluable to the modern inorganic chemist.

3.2

BORAZINES OF BORAZINES borazine by heating the adduct of diborane with

3.2.1 SYNTHESIS Stock ammonia. 3B 2 H6 +6NH 3

synthesized

3 (BH 2 ( N H 3 ) 2 ) ( B H 4 ) D 2 B3 N 3 H6 +12H 2

- (1)

More efficient of syntheses are: NaBH4 NH 4 Cl + Bcl3 NH 4 Cl + NaBH4 Cl3 B 3 N 3 H 3 B3 N 3 H6 +H 2 + NaCl B3 N 3 H6 (2) (3)

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27 N or B substituted borazines may be made by appropriate substitution on the starting materials prior to the synthesis of the ring NaBH4 (R NH 3 ) cl + BCl3 Cl 3 B3 N 3 R3 +3LiR' Borazine Physical properties is isoelectronic of properties of Cl3 B 3 N 3 R 3 H3 B3 N 3 R3 (4) or substitution after the ring has formed R3 ' B3 N 3 R 3 + 3LiCl with benzene, and as B=N is are with C=C borazine benzene of similar. and - (5) (Fig 1.1).

The

physical

alkyl- substituted

derivatives

benzene

borazine a r e

remarkably similar. For example the ratio of the absolute boiling points of the substituted This borazines similarity to led those to a of similarly of substituted borazine properties as of benzene is

constant.

labeling the

"Inorganic borazine

Benzene". This is a misnomer because and benzene are different.

chemical

3.2.2 STRUCTURE AND PROPERTIES OF BORAZINE In both benzene and borazine the P electrons are delocalized over all

of the ring atoms. Because of the electro negativity difference between Boron and Nitrogen, more electron density is located on the nitrogen atoms. Due to this partial localization, the P b o n ding is weakened in the ring. Each

nitrogen

receives

more s - electron density from the neighboring boron than it

gives away as a P - donor.

The net effect is that the charge density on the nitrogen i n c r e a s e s . Besides nitrogen retains its basicity and boron its acidity. Borazine is more reactive undergo than benzene and undergoes addition reactions. Benzene does not

addition

reaction

with (H2 N- BH X 3 ) ; (X =Cl,OH,OR) (6)

HC'l, B 3 N 3 H6 + 3H X C6H6+Hcl

no reaction.

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28 One can compare the reactions of borazine and benzene with bromine.

It is of interest to note that borazine resembles benzene in forming arene metal complexes, thus the hexa methyl borazine complex- B 3 N 3

(CH 3 ) 6 Cr (CO)3 has been reported and closely resembles, C6 (CH 3 ) 6 C r ( C O ) 3 but is thermally less stable.

The ring metal dissociation energy of the borazine complex is about one half that of the arene complex.

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29 Self Check Exercise I

Note: Please do not proceed unless you attempt the question, and write your answer in the space below. 1. How are the following systhesised? (a) benzene. Borazine analogues of naphthalene and related hydrocarbons have been made by pyrolyzing borazine or by passing it through a silent discharge. Related four membered ceramics which rings has is R2 B2 M 2 R2 1 a n d R 4 B4 M 4 R4 1 been synthesized and from polymarised decomposed are also known Borazine and benzene (b) Bromo Derivatives of borazine and

b o r o n n i t r i de

borazine to

derivative give boron

(CH 2 = C H ) B 3 N 3 H5 , nitride

Borazine CH 2 =CH B 3 N 3 H5 125 C

o

1000o C CH2 - CH- B3 N 3 H5 n NH3 BN - (9)

Benzene may be hydrogenated to give cyclohexane. But hydrogenation of borazine results in polymeric materials of indefinite composition.

Cycloborazine B 3 N 3 H1 2 is obtained by the reduction of the chloro derivative. 6NaBH4 2 B 3 N 3 H6 +6Hcl 2cl3 B3 N 3 H9 2B3 N 3 H1 2 + 3 B 2 H6 +6Nacl - 10) Boraxine, H 3 B3 O 3 is isoelectronic with borazine. (Prepared by the explosive oxidation of B2 H6 ). Boraxine is planar and has even less P d e l o c a l i z a t i o n than borazine B3 P 3 (Ph) 3 has also been prepared 'B' and 'P' have similar

electro negativities compared to B and N and therefore polarization is less extensive in this compound than borazine and is considerably aromatic.

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30 Self a) Check Exercise 2

Compare the properties of borazine and benzene, on the basis of their structures.

(b)

How would B3 P 3 ( P h ) 3 react with Br2 ? Please do not proceed till you attempt the above questions. The space below in for your answer.

3.3

PHOSPHO

NITRILIC OF

COMPOUNDS

3.3.1 SYNTHESIS The alternating

PHOSPHAZENES are cyclic or atoms chain with compounds two that on contain each

Phosphazenes phosphorus and

nitrogen

substituents

phosphorus atom. The three main structural types are cyclic trimer (Fig 1.2), cyclic tetramer (Fig 1.3) and the oligomer or high polymer (Fig 1.4). A few cyclic pentamers and hexamers are also known. The alternating single and double bouds in the figures are written for convenience but should not be taken literally.

Fig. 1.2, 1.3, 1.4

Hexachlorocyclotriphosphazene (NPCl 2 ) 3 , is a key intermediate in the synthesis of many other phosphazenes and is manufactured commercially on

either a large or a small scale, it is readily prepared by the reaction

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31

in C2 H2 c l 4 nPcl5 + nNH4 cl (N PCl2)n + 4n Hcl (11)

This reaction produces a mixture of (NPcl2 )n species with n = 3,4,5 and low polymeric linear species. Favorable conditions give 90% yields of the n=3 or 4 species, which can be separated easily.

The compound (NP Cl2 ) 3 l i k e , O H , O R , N R 2 ,NHR, derivatives. or R,

undergoes to give

substitution fully or

reactions partially

with

groups

substituted

(NP cl 2 ) 3 + 6Na OR (NP cl 2 ) 3 + 6Na SCN (NP F2) 3 + 6Ph Li The mechanisms of these

(NP(OR)2 ) 3 + 6Nacl (NP Ph2 ) 3 + 6Li F reactions are not

- 12)

(NP(NCS)2 ) 3 + 6Nacl - 1 3 ) - 14)

fully

understood,

but

in

general they appear to involve SN2 attack on 'P' by an anion. Bromo compounds may be prepared in the same manner.

NH4 B r P Br5 Excess Br 2 The fluoride may be prepared indirectly by fluorination of the chloride. (NPCl 2 ) 3 + 6 NaF (NPF2 ) 3 + 6Nacl ( 1 6 ) (N PBr2 ) 3 (15)

Self 1. 2.

Check

Exercise 3

How are different types of phosphazenes syntherised? Why excess bromine is added in reaction (15) Please do not proceed till you attempt the above questions.

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32

Fig. 1.5 (a) & (b)

3.3.2 STRUCTURE STUDIES The angles are halide trimers consist with of SP
2

planar

six

membered of the

rings.

The

bond and

consistent

hybridization

nitrogen

approximately SP 3 hybridization of the phosphorous. Two of the SP2 o r b i t a l of third nitrogen, containing one electron each, are used for 's' bonding and the contains a lone pair of electron. This leaves one electron for the

unhybridised P Z orbital. The four SP3 hybrid orbital (containing four electrons) of phosphorous leaving a fifth electron to occupy a 'd' orbital.

are used for 's ' bonding

Resonance structures can be drawn like benzene ring indicating aromaticity (Fig 1.5a). The Planarity of the ring, the equal P- N bond distances and shortness of the P- N b o n ds, and the stability of the compounds the

suggest

delocalisation. All phosphazenes are not planar. This does not make them less stable. Phosphazenes are much more difficult to reduce. Unlike in benzene IIbonding in cyclophosphazenes involves d and p orbitals Craig and Paddock suggested the following model. The dxz orbital of the phosphorous atom

overlaps with the pz orbital of the nitrogen atom adjacent to it (Fig 1.6a). As a result of the g symmetry of the d orbitals an inevitable mismatch in the signs of the wave functions occur on the trimer, resulting in a node which

reduces the stability of the dolocalished molecular orbital. The dyz orbital

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33 which is perpendicular to the dxz, can also overlap with the p z orbital of

nitrogen, but in this case no nodal surface results (Fig 1.6b). There may be in plane P bonding between the sp2 non bonding orbital of nitrogen and the dxy and for dx2 y2 orbital of the phosphorous (fig 1.6c and 1.6d).

The structure of tetrameric phosphoazenes is more flexible than these of the trimers. The structure of (NPF2 ) 4 is planar, but others are found in a variety of conformations Inter d (tub, boat, chair, crown, saddle and structures in between). use of molecular forces play a major role in these structures. The removes the restrictions of the Huckel rule (4n+2) II

orbital

electrons

for aromaticity. Thus the model due to Craig predicts that the

tetramer is stabilized by delocalisation unlike cyclo, octatetraene)

Self Check Exercise 4

1.(a) Discuse

the

structures

of

phosphazenes

on

the

basis

of

orbital

participation of the P atom. 1.(b) is delocalisation possible in the trimer? Please do no proceed till you attempt the above questions. The space below in for your answers.

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34 3.3.3 PHOSPHAZENE POLYMERS Phosphozenes can be polymerized. Their polymers and have advantages However

o v e r c a r b o n - b a s e d p o l y m e rs

polyolefins

polyesters.

commercial application is not well developed as silicones (R2 SiO) n . Trimericchloro phosphazenes can be polymerized thermally.

D (NPcl 2 )3

cl p = N cl n --(17)

If this is done carefully, extensive

cross linking does not take place

and the polymer (n=15,000) remains stable in organic solvents, similarly:

(PNcl 2 ) n + 2n NaOR (PNcl 2 ) n + 2n R2 NH can be obtained. By varying the

[PN(OR)2 ] n + 2Nacl [PN(NR2 ) 2 ] n + 2n Hcl nature of the side chain

-----

(18) (19)

various

elastomers, Plastics, films and fibres have been obtained. They are fle x i b l e a t low temperatures and water and fire resistant. Some R groups like R=CH2 CF 3 in OR group in the above reactions are water repellant and do not interact with living and promise to be useful in fabrications of artificial blood vessels and prosthetic devices.

Self

Check

exercise 5

1. How are phosphazene polymers obtained? Indicate their uses. Space for answers

3.4 Let us Sum Up (i) The synthesis of brazine is indicated. (ii) The planarity of benzene is compared with that of borazone. (iii) The synthesis of phosphazenes and their structures are discussed. (iv) The importance of dp - pp bonding in phosphazenes is discussed. (v) polymeric phosphazenes and their uses are also indicated.

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35

3.5 Points for discussion. I (i) In the case of borazines compare its synthesis with benzene (ii)

Planarity of benzene ring to the compared with that of borazine (iii) Compare the properties especially using N. electronogativities of B and

II

(i) atom

In the case of Phosphazenes, the d orbital participation of P in forming dII- PII bonding decides its aromaticity (ii) The

synthesis of polymeric phosphozenes and their uses to be discussed.

3.6 References 1. Advanced Cotton Inorganic and Chemistry, A compre h e n s i v e T e x t - F , A l b e r t Limited New Delhi- 3 r d

G.Wilkinsonwiley

Eastern

Edition1972. 2. I n o r a g n i c C h e m i s t r y 4
th

Ed

James

E,

Huheey,

Ellen.

A.

Keiter

Richard L. Keiter pearson Education Asia 4t h Ed, Reprint, 2002.

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36 LESSON 4 SULPHUR CONTENTS 4.0Aims and objectives NITROGENRING COMPOUNDS

4.1 Introduction 4.2 Sulphur Nitrogen Compounds

4.2.1 Synthesis of S- N Compounds 4.2.2 Structural studies conductors

4.2.3 One

Dimentional

4.0 AIMS AND OBJECTIVES In this lesson the synthesis, of sulphur- nitrogen Syntheses of some derivatives of sulphur compounds and the

nitrogen compounds are discussed.

After studying this lesson you would be able to understand the bonding in S- N Compounds. Learn the application of S4 N 4 in forming (SN)x which

behaves like a super conductor. 4.1 INTRODUCTION Compounds which contain sulphur- nitrogen rings were known in t h e It is

last century, but many new ones have been prepared in the last decade. currently an area of considerable interest. 4.2 SULPHUR NITROGEN COMPOUNDS 4.2.1 Synthesis of S4 N 4 :

The ammonolysis of S2 cl 2 , either in solution or in an inert solvent or heated over solid ammonium chloride yields tetra- sulphur, tetra- nitride. NH 3 S2cl 2 S4 N 4 +S 8 + NH4 cl (1)

The product is a bright orange solid insoluble in water but soluble in some organic solvents. The crystals are reasonable stable to attack by air,

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37 they are explosively sensitive to shock or friction. Reduction of S N 4 w i t h 4 metallic potassium or sodium oxide gives S3 N 3 Reduction tetraimide of S4 N 4 with with sulphur Sn (II) chloride (Fig 2.1a). produces tetrasulphur

isoelectronic

S8 . When S4 N 4 is heated under pressure in a S4 N 2 is formed.

solution of CS2, containing

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38 4.2.2 STRUCTURAL STUDIES OF S-N COMPOUNDS It is impossible to write a simple Lewis structure for S4 N 4 . A cage structure for S4 N 4 has been suggested. This structure contains two pairs of non- bonding sulphur atoms at a distance of about only 258pm, considerably shorter than the sum of the vanderwalls radii (360pm). All of the S- N b o n d distances electrons within and this the ring are approximately considerable The molecule equal (162pm) The and has 12 P S N2 4

indicates

delocalisation.

molecule

h a s h a l f - chair

conformation.

S3 N - 3 has a planar six membered

ring. It has 10II electrons instead of six (Fig 2.1b). Still the Huckel rule is obeyed (4n+2) rule and the system is expected to be aromatic. Four of the P electrons occupy antibonding orbitals.

and this weakens the S- N b o n d .

Sulphur example the

nitrogen compounds have often unpredictable structures, for Ph SN =S=NSPh is considered to have resonan ce

compound

structures (Fig 2.2). This is based on the fact that the separation between end sulphur atoms is only 329pm (compared to vanderwals sum of 360pm).

4.2.3 ONE

DIMENSIONAL sulphur

CONDUCTOR (also called polythiazyl), (SN)x has some

Polymeric

nitride

physical properties of a metal. It is prepared from S4 N 4 .

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39 Ag S4 N 4 S2 N 2
o

(SN) x . The

S4 N 4

is pumped in a

vacuum line over silver wool at 220 C, where it polymerize slowly to a lustrous golden material. It has a conductivity near that of mercury at room temperature and it becomes a super conductor at low temperatures below (O.26K). X- rays studies indicate that the SN chains have the structure shown in Fig (2.3a). This chain can be generated from adjacent square planar S N 2 2 molecules. 165.4pm, bonds. The S- N bonds in this starting material have a bond length of between single (174pm) and double (154 pm) SN -

intermediate

For

the

(SN)x

chain

many

resonance

structures double Every

can

be

drawn.

The

single structure (Fig 2.3 b) has single bond with nine electrons on each sulphur atom.

bond

resonance

system,

S- N unit has thus one will combine

antibonding P * electron. The half filled over lapping P * orbitals

to form a half- filled conduction band in much the same way as half- f i l l e d 2 s orbitals on a mole of Lithium atoms, form a conduction band. This

conduction band lies only along the direction of the (SN)x fibres, the polymer is thus a one dimensional conductor.

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40

Self

Check

Exercise 1

1. 2.

Give the synthesis of S4 N 4 and S3 N 3 . All of the S- N bond distances within the ring are equal and what does it indicate?

3.

How does (SN)x behave like a one dimensional conductor? Check exercise 1

Model answer for Self 1. 2.

S 4 N 4 is obtained from S2 cl 2 by ammonolysis. S- N bond distances P * h a l f - filled dimension. (162pm) are equal and it has 12- II electrons, obeys Huckel rule- aromatic.

3.

orbitals

overlap

forming

conduction

band

in

one

4.3 Let Us Sum Up The synthesis of S4 N 4 is discussed. The molecule S3N3 has a planar structure dimensional and obeys Huckels the rules. (SN)x behaves like a one conductor conduction is explained.

4.4 Points for Discussion: (i) The molecule S3 N 3 has a planar six membered ring structure and has 10II electrons. The system obeys Huckels rule. (ii) The over lapping of P * orbital (half filled) in (SN)x l e a d s to one

dimensional conduction.

4.5 References 1. Advanced F.A.cotton (1972). 2. Inorganic and chemistry (4t h Ed) Re print education Asia. 2002 J.E. Huheey, E.A.Keitar Inorganic and Chemistry Wiley A comprehensive Eastern Text (3r d E d ) . New Delhi

G.Wilkinson

Limited -

R.L.Keiter

Pearson

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41 LESSON 5

CONTENTS
5.0 5.1 5.2 AIMS AND OBJECTIVES INTRODUCTION METALLIC STATE

5.2.1 FREE ELECTRON THEORY 5.2.2 BAND THEORY 5.3 5.4 5.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

5.0

AIMS AND OBJECTIVES In this lesson the conductivity of metals can be understood on the basis

of free electron theory and band theory. The behavour of semi conductors is discussed on the basis of band theory. After going through this lesson you would be able to Understand the electrical properties of metals. The electrical conductivity of semiconductors can be understood.

5.1

INTRODUCTION Metals have (2) high the following characteristics properties with (1) high

reflectivity

electrical

conductance,

decreasing

increas ing

temperature (3) high thermal conductance (4) Mechanical properties such as strength and ductility. An explanation for these properties, and for their

variations from one metal to the other, must be derived from the structural and electronic nature of metal. The electrical conductivities of

semiconductors can be understood on the basis of band theories.

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42 5.2.1 FREE ELECTRON THEORY

At the beginning of the twentieth century, a bold guess was made by Drude regarding the electronic structures of metals. The resulting free

electron theory was made by

Lorentz a few years later and is known as

Drude- Lorentz theory of metals. The basic assumption of this theory is that a metal crystal consists of positive metal ions whose velance electrons are free to move between the ions as if they constituted an electron gas. The crystal is than pictured to be held together by electrostatic forces of attraction between the positively charged ions and the negatively charged electron gas. It is further assumed that the electrons are free to move throughout the entire

crystal subject only to the laws of classical mechanics.

The mutual repulsion

between negative electrons is ignored in this theory and the potential field due to the positive ions is assumed to be completely uniform. Thus the

electrons can move from place to place in the crystal without change in their energy. The electrons collide occasionally with the atoms and have velocities determined at constant temperature according to the Maxwall- B o l t z m a n n successful in explaining

distribution laws. This model of a metal is highly

many properties of metals. For example if an external electric field is applied to metal, the negatively charged electrons are accelerated towards the

positive pole of the field. The resulting current is limited by electron atom collisions Ohms and is The proportional opaqueness to of the applied for voltage all gradient according of light to is

law.

metals

wavelengths

explained by the ability of a free electron to oscillate in the electromag netic field of the incident light beam regardless of its frequency. Similarly a free electron once excited to a higher energy by the absorption of energy, can return to its former energy by reemitting light of the same frequency in all direct ions. Because only light rays directed towards the surface can get out of the crystal, this interaction appears as a reflection of the incident light and

accounts for the so called metallic luster.

Success of the Free Electron Theory 1. It is used to verify Ohm s l a w .

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43 2. 3. It is used to explain the electrical and thermal conductivities of metals. It is used to explain the optical properties of metals.

Breakdown of classical theory 1. From the classical free electron theory the value of specific heat of

metal is given by 4.5 x R, where R is the gas constant. But experimental value is nearly equal to 3R. According to classical free electron theory, the value of electronic specific heat is equal to 3/2R. But actually it is0 . 0 1 R only.

2.

We

cannot

explain

the

electrical

conductivity

of

semi

conductors

or

insulators using this model.

3.

Ferromagnetism cannot be explained by this theory.

4.

The photo electric effect, compton effect and the black body radiation

cannot be explained by the classical free electron theory.

Self- Check Exercise 1

1.

As

the

temperature

increases

the

electrical

resistance

of

metal

increases explain.

2.

Indicate the failures of the classical free electron theory.

Please do not proceed until you attempt the above questions. The space below for your answer.

Special features of quantum free electron theory.

1.

Quantum concepts are followed. That is, the distribution of electrons in a solid is determined by Femi- Dirac distribution.

2.

The wave nature of electrons is taken into account.

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44

3.

The

physical

properties at

of

solids fermi

depend

on

the Thus

number the

of

free level

electrons

available

the

energy

level.

fermi

electrons play an important role in determining the various properties of a solid.

4.

The

correct heat,

values

of

electrical absorption,

conductivity, ferromagnetic

thermal

conductivity, are

specific

optical

susceptibility

determined by quantum free electron theory of solids.

5.

Quantum

free

electron

theory

is

not

only

applicable

for

metals

(conductors) but also for semiconductors and insulators.

6.

Thus the correct pictures of atoms and molecules and their electron distributions and bonds are identified only from the quantum free

electron theory of solids.

Electron in a Metal

Consider problem for a three dimensional metal in which the electrons move in all directions so that three quantum numbers nx ,n y , and nz a r e

needed, corresponding to the resolution of the motion into components along three perpendicular axes x, y, and z. For simplicity we will take the potential energy of the electron to be zero inside the metal and infinite outside. So that the problem is just an extension of the one dimensional problem. Therefore with a cubically shaped block of metal of sides a the levels can be written as h2 En where = 8ma2 nx ,n y , and nz can each take any number from the set 1,2,3,. etc., (n x 2 + ny 2 + nz 2 ) .. (A) permitted energy

irrespective of what numbers the others take.

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45 Similarly the wave function 8 y nx ,n y ,n z = sin a3 a nx p x sin a ny p y sin a nz p z .. (B)

The three quantum

numbers nx , n y and nz

are

required

to

specify

completely each stationary state. It should be noted that the energy E depends only on the sum of the squares of nx , n y and nz . Consequently there will be in general several different wave functions having the same energy. For example the three independent stationary states having (2,1,1,), quantum (1,2,1) numbers and (1,1,2) for nx , n y and nz have the same energy

6h 2 /8ma 2 such states and energy levels are said to be degenerate and the corresponding wave functions are Y 2 1 1 ' Y 1 2 1 Y 1 1 2 .

On the other hand if there is only one wave function corresponding to a certain energy, the state and the energy level are said to be non

degenerate. For example,

The

ground

state

with

quantum

numbers

(1,1,1)

has

the

energy

3h 2 /8ma 2 and no other state has this energy.

The degeneracy breaks down on applying a magnetic field or electric field to the system.

Electron Energies in metals and fermi energy

The expression for the energy values given in equation (A) corresponds to the permissible energy values that the valence electrons in a m t a l m a y e have, but it is essential to know what energies the electrons actually possess. For a piece of metal of macroscopic dimensions, say a centimeter cube, the

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46 energy of the ground state (nx = ny = n z = 1) is of the order of 10- 1 5 eV and hence may be taken to be zero for all practical purposes.

Also the maximum spacing between consecutive energy levels is less than 10- 6 eV. So the distribution of energy levels may be regarded as a

continuum.

If a plot is made for a large range of energy values such that the individual En values are so close together that they can be shown as a

continuum and the number of states per interval of energy, N(E) increases parabolically with increasing E as shown in figure (3.1(a)).

The dashed line shows the nature of the that occurs on heating to room temperature.

change

in

electron

energies

Fig 5.1

Figure 5.1

(a) (b)

The distribution of energy states as a function of energy E Filling of energy levels by electrons at 0 K

(a).

Fermi energy

The

valence

electrons

tend

to

occupy

the

lowest

available

energy

states. However because of the mutual interactions among all the electrons

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47 that form the electron gas, it is necessary to consider that all the electrons

are in a single system and that the Pauli Exclusion Principal applies.

According to Pauli exclusion Principle only two electrons can occupy a given state specified by the three quantum numbers (nx , n y and nz ), one with spin up and other with spin down (i.e., with opposite spins).

As a result of this principle, at0 K the electrons fill all the states upto a certain maximum energy level, Em a x called the fermi level or fermi energy E. All quantum states in the energy levels above EF are empty (figure 3.1(b). Thus the fermi level is a boundary line which separates all the filled states and empty states at 0 K in a metal.

Thus in a metal the energy of the highest filled state at 0 K is called the fermi energy EF or fermilevel. The magnitude of EF dependson how

many free electrons there are. AT 0 K all states upto EF are full and states above are EF are empty. 5.2.2 Band or Zone theory of Solids

Energy bands in solids (quantitative treatment) In an isolated atom, the electrons are tightly bound and have discrete sharp energy levels. When two identical atoms are brought together the

energy levels of each atom which are initially the same are split in to two, one higher and one lower than the corresponding levels of the separated

atoms.

The splitting only becomes appreciable when the wave functions of the electrons on different atoms begin to overlap considerably; at a given

distance it is therefore greatest for the outermost electrons and least for the inner electrons.

If more atoms are brought together more levels are formed and for a solid of 'N' atoms, each of the energy level of an atom splits into N levels of

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48 energy. The levels are close together that they form an almost continuous band.

The width of this band depends on the degree of overlap of electrons on adjacent atoms and is again largest for the outermost atomic electrons. The bands appear only when the distance between two atoms is very small. That is the bands are formed in solid only.

For example, when the distance between two sodium atoms is about 5 the splitting of energy levels is maximum and bands appear. But when the distance between sodium atoms is about 20 the splitting of energy levels is minimum formation. and there is no band formation and hence there is no solid

The electrons can take only the energy values which are in the band.

The gap between two allowed band is called forbidden energy gap (or) band gap since the electron cannot take the values of energy which are in t h e forbidden energy gap. Normally we are interested in the valence (outermost energy) band, formed by valence electrons since these are responsible for

electrical, thermal and optical properties of solids. Above the valence band there is conduction band which has no electrons at 0 K.

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49

Fig. 5.2

Figure 5.2. Energy levels of an isolated atom and the energy bands in the solid.

Figure 3.2 shows the energy levels of an isolated atom and solid which is the collection of N atoms. We can see that the allowed bands and the energy gap between the allowed bands. Thus the bands are formed in solids only and are due to overlapping of wave functions of different states and the consequent energy level splitting.

Distinguish

between

conductors,

semiconductors

and

insulators

on

the

basis of band theory of solids.

In a solid the outermost allowed band formed by valence electrons is called the valence band and is fully or partially filled. Since the valence

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50 electrons are alone determining the properties of the material, the remaining

lower allowed bands consisting of bound electrons are not considered.

The band that is above the valence band and empty at 0K is called the conduction band and is partially filled by free electrons which ar e g e n e r a l l y unbound valence electrons generated by thermal excitation or electric field.

The band gap or forbidden gap is the energy interval between the maximum conduction energy band. of In the valence band and the minimum energy of the

conductors,

there is no meaning for band gap. But in

insulators and semiconductors, the value of band gap plays an important role in determining the carrier concentration or electrical conductivity of different materials.

Solids conductors,

can

be

classified and

on

the

basis

of

their

band

structure

as

semiconductors

insulators.

Fig. 5.3 Schematic band structure of conductors

Conductors are those solids which have vacant electron energy states immediately above the highest filled level of the valence band. This can

happen in two ways. In the first case, the valence band is only partially filled as in figure 5.3 (a). The electrons here can respond to an externally applied field by acquiring extra velocity and moving into higher energy states. In the

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51 second case, a full valence band overlaps the conduction band as shown in figure 3.3(b) so that the forbidden gap is zero. Monovalent metals such as the alkali metals have one electron per atom in the outer most shell and the outer m o s t e n e rgy bands are half filled in these metals. Divalent metals such as magnesium have overlapping conduction and valence bands. Therefore they

can also conduct even if the valence band is full. The band structure of trivalent metals such as Aluminium is similar to that of monovalent metals. Thus there is no meaning for band gap in conductors.

Semiconductors are those materials which have an energy gap of about 2 to 3 eV or less. When the energy gap is 2eV or less an appreciable number of electrons can be excited across the gap at room temperature. So

semiconductors conduct much better than insulators at room temperatures but still orders of magnitude poorer than metals which have no forbidden gap. By adding impurities or by thermal excitation we can increase the electrical

conductivity in semiconductors. Figure 5.4 (a) shows the band structure of silicon. Insulators 3eV. It would has be are those materials that which millions an have of an volt/m energy of gap more than

been

estimated to

electrical to

potential jump the

necessary

accelerate

electrons

sufficiently

forbidden gap. The other possibility for a transition is that electrons cross the gap by thermal excitation. At room temperature the number of electrons that can be thermally excitedacross the gap in insulators such as Diamond turns out to be extremely small. Figure 3.4 (b) shows the band structure of

diamond.

So

the

conductors

are

the

materials

having

enormous

elect ical r

conduction; the insulators are the materials in which practically there is no electrical conduction and the semiconductors are the materials in which the electrical conduction is in between the electrical conduction of conductor and insulator.

Electron in a periodic potential (Origin of band gap and effective mass of electrons)

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52

While for electrical substances

the

Sommerfeld

theory

discussed

earlier

accounts

satisfactorily

conductivity in most metals, it failed to explain why other also contain free electrons have virtually no conductivity and

that

are considered to be excellent insulators. A solution to this problem is given by the Zone theory or Band theory of solids. The effect of the periodic lattice field on the motion of the electrons leads to the zone or band theory of solids, which is of the greatest importance for understanding the structures and properties of metals, alloys and non- metallic solids.

Figure 5.4 band structures of semiconductor and insulator

Fig.5.5

One

dimensional

periodic

potential

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53 According to zone theory, the electrons move in a periodic field

provided by the lattice. The potential of the solid varies periodically with the periodicity of space lattice and the potential energy of the electron is zero

near the nucleus of the +ve ion in the lattice and maximum when it is half way between the adjacent nuclei which are separated by the interatomic

spacing distance 'a' (Figure.3.5). This model was first postulated by Kronig and penny. So taking this model and solving the Schroedinger equation for this case, we can find the existence of energy gap between the allowed values of energy of electron.

So if we use classical theory, we can get a parabola when we plot the curve between the electron's energy and its momentum. In the figure.3.6 (a) instead of momentum 'P' h the wave vector k is used since P = hk = 2p l l 2p h . Thus the 'k'

is directly proportional to momentum 'P'. Since the curve is a parabola, we can infer that the energy varies continuously.

But

by

Kronig- Penny

model,

we

can

get

parabola

with

some

discontinuities in it as shown in figure3.6(b). Thus we have allowed bands and forbidden energy gap between the allowed bands.

Figure 5.6 Energy Vs momentum curve

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54

Self

check

exercise 2

1.

How does the band theory explain the conductivity of semi conductors?

What are intrinsic semi conductors?

Self

check

exercise - 2

Model Answer:

(i) hence

Ge and SI are intrinsic semi conductors. Their band gaps are low and even at ordinary temperatures free electrons are present in the

conduction band and has appreciable conductivity compared to insulators.

5.3 Let us Sum Up (i) The free electron theory and band theory of metals and their applications are discussed. is (ii) Quantum (iv) The free electron theory is discussed. and (iii) Fermi are

energy

explained

conductors,

semiconductors

insulators

compared using band theory (v) Kroning- Penny model is indicated.

5.4 Points for discussion:

1.

The free electron theory of metals as suggested by Drude and Lorentz successfully conductivity, explained increase of properties electrical of metals such with as electrical and

resistance

temperature

metallic luster.

2.

It failed to explain the values of specific heats of solids

3.

The modified quantum free electron theory gives the correct values of electrical conductivity, thermal conductivity, specific heats of metals.

4.

The quantum free electron theory can be applied to metals as well as semiconductors and insulators.

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55 5.5 References 1. Advanced F.A.cotton (1972). 2. Inorganic and chemistry (4t h Ed) Re print education Asia. 2002 J.E. Huheey, E.A.Keitar Inorganic and Chemistry Wiley A comprehensive Eastern Text (3r d E d ) . New Delhi

G.Wilkinson

Limited -

R.L.Keiter

Pearson

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56 LESSON - 6 CONTENTS 6.0 6.1 6.2 Aims and Objectives Introduction CRYSTAL IMPERFECTIONS 6.2.1 Point defects (Zero dimensional defects)

6.2.2 Line defects (One dimensional defects) 6.2.3 Surface defects (Two dimensional defects)

a) Volume defects (Three dimensional defects) b) Non- Stocchiometry 6.3 6.4 6.5 Let us Sum Up Points for Discussion

References

6.0

AIMS

AND

OBJECTIVES

The study of imperfections has a two fold purpose, namely (i) A better understanding of them and how they affect material

properties (ii) Exploration defects. of possibilities of minimizing or eliminating these

The

term

imperfection

or

defect

is

generally used

to

describe

any

deviation from the perfect periodic array of atoms in the crystal.

6.1

INTRODUCTION

In

an

ideal

crystal,

the

atomic

arrangement

is

perfectly

regular

and

continuous throughout. But real crystals are never perfect; lattice distortion and them. solids, various The imperfections, mechanical, irregularities and alloys or defects are generally of present in

electrical and

magnetic are

properties

crystalline by the

particularly in the

metals crystals.

profoundly

affected

imperfections

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57 6.2.1 Point Defects

1.

Point

imperfections

are

also

called

zero

dimensional

imperfections.

One or two atomic diameters is the typical size of a point imperfection.

2.

In a crystal lattice, point defect is one which is completely local in its effect, e.g., a vacant lattice site.

3.

The

introduction

of

point

defect

into

crystal

increases

its

internal

energy as compared to that of the perfect crystal. Further they produce distortions inside the crystal structure.

4.

They change the electrical resistance of a crystal.

5.

If a point defect is a vacancy, then there is no bonding. Hence the value of the mechanical strength at that point is reduced.

6.

Similarly if an impurity atom is present instead of the original atom, in the lattice, there must be some strain due to the different size of the impurity atom.

7.

Point thermal

defects

are

created mechanical

during stress

crystal or

growth

and

application they

of are

energy,

electric

field.

Further

created by irradiating the crystal by x rays, microwaves and light.

Different types of point imperfection are described below:

a. Vacancies A vacancy or vacant site implies an unoccupied atom position within the crystal lattice. In other words, vacancies are simplify empty atom sites. Vacancies may be single, two or more of them may condense into a divacancy or tri- vacancy.

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58 It may be shown by thermodynamic reasoning that lattice vacancies are a stable feature of metals at all temperatures above absolute zero. Vacancies exist in a certain proportion in a crystal in thermal equilibrium leading to an increase in the randomness of the structure.

The

every

day

industrial

processes

of

annealing,

homogenization,

precipitation, sintering, surface hardening, oxidation and creep, all involve to varying degrees, the transport of atoms through the lattice with the help of vacancies.

Vacancies

may

occur

as

result

of

imperfect

packing

during

the

original crystallization or they may arise from thermal vibrations of atoms at elevated temperatures, because as thermal energy is increased there is a

higher probability that individual atoms will jump out of their position of lowest energy.

The distorting

atoms the

surrounding planes.

vacancy tend to be closer together, thereby

lattice

Schottky defect

1.

Ion

vacanciesare

called

Schottky

defects.

2.

A pair of one cation and one anion can be missing from an ionic crystal. The valency of the missing pair of ions should be equal to maintain the electrical neutrality. So these are normally generated in

equal numbers of anion and cation vacancies in a crystal.

3.

When vacancies are created by movements of an anoin and one cation from positions inside the crystal to positions on the surface of the

srystal, a schottky defect is said to have been formed.

4.

This type of point defect is dominant in alkali halides.

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59 b. 1. Interstitial Defect

An interstitial defect arises when an atom occupies a definite position in the lattice that is not normally occupied in the perfect crystal.

2.

In interstitialcies, atoms occupy vacant positions between the atoms of the ideal crystal. The interstitial atom may be lodged within the crystal structure, particularly if the density of packing (or) packing fraction is low.

3.

Interstitialcy atom tends

produces to push is

atomic the

distortion

or

strain further

because apart,

interstitial unless the

surrounding

atoms

interstitial

atom

smaller than the rest of the atoms in the crystal.

4.

By giving enormous stress (or) compressive force to a crystal, some of the parent atoms dislodge from their lattice sites and occupy the voids or interstitials present in the called self interstitial lattice. These type of imperfecti o n s a r e

imperfections.

Frenkel defect

1.

In the case of ionic crystals, an ion displayed from the lattice into an interstitial site is called a Frenkle defect.

2.

As cations are generally the smaller ions, it is possible for them to get displaced into the void space present in the lattice. Anions do not get displaced like this, as the void space is just too small for their size.

3.

A Frenkel imperfection does not change the overall electrical neutrality of the crystal. The point imperfections in silver halides and calcium

fluoride are of the Frenkel type.

4.

Frenkel and Schottky defects together are called 'Intrinsic defects'.

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60 c. Impurities

1.

Impurities give rise to compositional defects.

2.

A controlled addition of impurity to a very pure semiconductor crystal is the basis of producing of many electronic and devices like impurity diodes atoms and in

transistors.

Addition

pentavalent

tetravalent

silicon or germanium crystal increases its electrical conductivity.

3.

Foreign

atoms

generally

have

atomic

radii

and

electronic

structures

differing from those of the host atoms and therefore act as centers of distortion.

4.

Basically there are two types of impurity defects. A substitutional impurity refers to a foreign atom that substitutes or replaces a parent atom in the lattice as shown in fog. 4.1(a). for

5.

In

the

case in the

of

semiconductor are

technology

aluminium in the

and

phosphorous Further in

doped during

silicon

substitutional of Brass

impurities the

crystal. are

production

alloy,

zinc

atoms

doped

copper lattice. Here the zinc atoms are called substitutional impurities. In ionic solids, for example in sodium chloride, the substitution of Na+ by Li + produces a substitutional impurity.

Fig. 6.1 (a) Substitutional Impurity (b) Interstitial Impurity

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61

An interstitial impurity is a small sized atom occupying the void space in the parent crystal, without dislodging any of the parent atoms from their sites as shown in figure 4.1 (b). An atom can enter the interstitial or void space only when it is substantially smaller than the parent atom. For example in FCC iron, the atomic radius of iron atom is equal to 2.25. The carbon atoms with atomic radius equal to 0.777 can occupy the octahedr l v o i d a spaces in FCC lattice as interstitial impurities, But the carbon atom radius is greater than the radius of the void and so a strain is produced there. Addition of carbon atom upto 1.7% in Iron increases its mechanical strength.

d.

Electronic

defects

1.

Electronic

defects

are

the

result

of

errors

in

charge

distribution

in

solids. These defects are free to move in the crystal under the influence of an electrical field, there by accounting for some electronic

conductivity of certain solids and their increased reactivity.

2.

For

example

if

we

take

zinc

oxide,

the

zinc

ions

can

occupy

interstitials and this leads to a large number of positive charges at that place.

3.

In some places if zinc ions are missing, then in that places there is a gain of negative charges due to loss of positive charges.

4.

Thus a vacancy or an interstitial impurity may produce the excess or the deficit of positive or negative charges.

Applications of point defects

1.

Doped atoms or impurities in Si or Ge crystal increase its electrical conductivity.

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62 2. The interstitial impurity carbon atoms in iron lattice increase the

strength of iron.

3.

Addition of copper atoms in gold increase the ductility of gold so that it can be drawn into wires

4.

in copper lattice, the substitutional impurity atoms of tin increases the bearing properties of copper.

6.2.2 Line defects

1.

Line

defects

are

called

dislocation.

These

are

one dimensional -

imperfections in the geometrical sense.

2.

dislocation

may

be defined

as

disturbed

region

between

two

substantially perfects parts of a crystal. It is a line defect in a crystal structure whereby a partplane of atoms is displaced from its

symmetrically stable positions in the array.

3.

The most

dislocation metals

is

responsible for the phenomenon of slip by which plastically.

deform

4.

One may conclude that dislocation is the region of localized lattice disturbance separating the slipped and unslipped regions of a crystal.

5.

Burgers component

vector of

marks

the

magnitude

and

direction

of

the

strain

dislocation.

6.

Dislocations arise in crystals as a result of i. ii. iii. iv. v. Growth accidents Thermal stresses External stresses causing plastic flow Phase transformations Segregation of solute atoms causing mismatches, etc.

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63 7. The two basic types of dislocations are: a. b. Edge dislocation and

Screw dislocation

a. Edge dislocation

v An edge dislocation is created in the crystal by introducing an extra half plane or (any extra plane that does not extend up to the base of the crystal). v The bond lengths have been compressed to smaller than the equilibrium value. Just below the edge of the extra plane the atoms are pulled apart and are in a state of tension. v Here the bond lengths have been stretched to above the normal values. v This distorted configuration extends all along the edge into the crystal. There is an extra energy due to the distortion in the region immediately surrounding the edge of the incomplete plane. v As the region of the maximum distortion is centred around the edge of the incomplete plane, this distortion represents a line imperfection and is called an edge dislocation. v The edge dislocation is said to be negative, denoted by T, when the insertion of the extra plane is from the bottom of the crystal.

v ^ denotes + ve edge dislocation in which the insertion of extra plane from the top of it. v Let us see something about the Burgers circuit. Take a point P Starting from P, move x times the atomic distance in the positive x direction and then move 'y' times the atomic distance in the positive y direction and then move x times the atomic distance in the negatively x

direction and then move y times the y direction. After this movement

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64 we can arrive at the original starting point 'P'. The circuit is a closed one and this type of circuit is called Burgers circuit.

v We draw the burgers circuit as explained above and if the circuit could not be completed then dislocation in the circuit. v From the end point, if we want to arrive the starting point then we must move an extra distance 'b'. Therefore the vector b connecting the end point with the starting point is the burgers vector of the dislocation. Immediately one can infer that there is a

b.

Screw

dislocation

v Screw dislocation results from a displacement of the atoms in one part of a crystal relative to the rest of the crystal, forming a spiral ramp around the dislocation line. v Figure 4.2 shows what happens when one part of the crystal is displaced relative to the rest of the crystal and the displacement terminals within the crystal. The row of atoms marking the

termination of the displacement is the screw dislocation. v By means of burgers vector as shown in the figure 4.2 one can determine the magnitude and direction of the screw dislocation. v In the figure EF indicates the dislocation line. v Normally the real dislocations which occur in the crystals are the mixtures of edge and screw dislocations.

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65

Fig. 6.2 Screw Dislocation 6.2.3 Surface Defects v Surface imperfections which are two dimensional in the m a t h e m a t i c a l sense refer to regions of distortions that lie about a surface having a thickness defects. v We can classify these defects into two main types which are external surface imperfections and internal surface imperfections. of a few atomic diameters. These are also called plane

a.

External

surface

imperfections.

v The external surface of a crystal is an imperfection in itself, as the atomic visualize bonds an do not extend surface beyond the surface. a Although the we may

external

simplify

terminus of

crystal

structure, the atoms on that surface cannot be compared with the atoms within the crystal.

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66

v Because the external surface atoms have neighbours on one side only, while atoms inside the crystal have neighbors on either side of them. S i n c e t he external surface atoms are not entirely surrounded by others they possess higher energy than that of internal atoms.

b.

Internal

surface

imperfections

v Internal surface imperfections arise from a change in the stacking of atomic planes across a boundary. The change may be one of the

orientation or of the stacking sequence of the planes. v Some important internal surface imperfections are given below: i. ii. iii. iv. v. Grain Boundaries Tilt boundaries and twist boundaries Twin boundaries Stacking faults and Ferromagnetic domain walls

i. Grain boundaries v The

grain of

boundaries different

are

those

surface

imperfections,

which

separate

crystals v During crystals,

orientations in a polycrystalline aggregate. or are during recrystallization oriented with of polycrystalline respect to one

solidification new crystals

randomly

another. They grow by the addition of atoms from the adjacent regions a n d e v e n t u a lly impinge on each other. When two crystals impinge in this manner, the atoms that are caught in between the two crystals are being pulled by each of the two crystals to join its own configuration. v They can join neither crystal due to the opposing forces and therefore

take up a compromise position. The thickness of this region is only a few atomic diameters, because the opposing forces from neighboring

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67 crystals are felt by the intervening atoms only at such short distances. The boundary region is called a crystal boundary or a grain boundary.

v The crystal orientation changes sharply at the grain boundary, as shown in figure 4.3(a). v It is obvious from this that the grain boundary forms a discontinuity in the periodicity of the lattice of crystallite or grain and is therefore a

type of lattice imperfection called grain boundary.

ii. Tilt boundaries and twist boundaries v Tilt boundary is another type of surface imperfection and it may be regarded as an array of edge dislocations (^ ) v It is also a class of low angle boundaries v By rotation of an axis in the boundary it is possible to bring the axis of two bordering In this grains figure into 'h' is coincidence, the i.e. a tilt boundary, two (figure

4.3(b).

distance

between

neighbouring

dislocations and 'q' is the angle of tilt, 'b' is the Burgers Vector. v Twist boundaries are the second class of low angle boundaries result from the set of screw dislocations. In twist boundary the r o t a t i o n i s about an axis normal to the boundary.

6.3 (a)

High angle grain boundaries (b) Tilt boundary

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68 iii. Twin boundaries

v Surface

imperfections

which

separate

two

orientations

that

are

mirror

images of one another are called twin boundaries v Twin boundaries occur in pairs, such that the orientation change

introduced by one boundary is restored by the other as shown in figure (4.4).

Fig. 6.4 (a) Twin Boundaries

(b) Stacking fault

iv. Stacking faults v A

stacking

fault

is

surface

imperfections

that

results

from

the

stacking of one atomic plane out of sequence on another, while the lattice on either side of the fault is perfect. The stacking fault is a discrepancy in the packing sequence of the layers of atoms (although all the lattice sites are occupies). v For example in the case of close packed FCC structure the stacking sequence can be written as ABC ABC In that sequence it is possible in one atom layer 'A' the atoms are not positioned properly in a small region and hence deviates from the sequence, relative to the atoms of the layers above and below giving a defect, since now there is a

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69 sequence of BCBC which belongs to HCP structure instead of ABC ABC v Figure 4.4(b) shows the stacking fault in a FCC metal. So on may conclude that stacking fault may arise when the there is only small of

dissimilarity

(electrostatically)

between

stacking

sequences

close- packed planes in FCC and HCP metals. v Stacking faults are more frequently found in deformed metals than in annealed metals.

6.2

Volume defects v Volume defects such as cracks may arise when there is only small electrostatic dissimilarity between the stacking of closed p a c k e d

planes in metals. v Further when clusters of atoms are missing, a large vacancy or void result which is also a volume imperfection. v Foreign particle inclusions, large voids or non crystalline regions

which have the dimensions of at last 10 to 30 are also called volume imperfections.

Effect 1.

of

Crystal

imperfections

The addition of impurities in the case of semiconductors increases the electrical conductivity; but in the case of metals, it decreases the

electrical conductivity.

2.

The

impurity These

atoms are

in

the

lattice colour

give centers.

characteristic If we

colours pure

to

the

crystals.

called

take

copper

sulphate crystal it is colourless. but due to addition of water molecules, it turns out to be blue in colour. Similarly in the aliminium oxide

lattice the addition of chromium atoms gives the red colour to it.

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70 6.2.(b) Non- Stoichiometry

A crystal

defect

like

schottky

defect, there
-

leaves are

the equal

stoichiometry number
+2

of

the

ionic cl

unaffected.

For

example

of

+ Na and

vacancies in Nacl. These are 2cl vacancies per ca certain transition metal compounds, especially

vacancy in cacl2 . But in and sulphides, non -

oxides

stoichiometric defect occurs. This is because of the ability of the metal to exist in more than one oxidation state. A well known case is "FeO" which consists of a 'CCP' array of oxide ions with all octahedral holes filled Fe
+2

by
+3

ions. Actually some of these sites are vacant, while others contain fe sufficient about to maintain Ti O electroneutality. can be on obtained the Thus the with of stoichiometry

ions,

is

commonly

Fe0 . 9 5 O.

compositions oxygen gas

ranging while

f r o m T i 0 . 7 4 O to Ti1 . 6 7 O preparing CdO the material. oxygen loses

depending

pressure

when

heated

to

give

yellow

to

black

solids

of

compos i t i o n . C d 1 +rO similarly when Nacl is trwated with sodium vapour, it absorbs sodium to give blue solid of composition number (nr) of anion vacancies are created. Na1 + r These cl. An appropriate anion vacancies are

occupied by electrons. These cavities are 'F' Self 1. 2. Check Exercise 1

centers

(fairbe).

What are point defects? How are Frenkel and schottky defects created.

Please attempt (1) and (2) before you proceed further

Self Check 1.

Exercise 2 types of dislocations please attempt (1) before

Discuss the different you proceed further. Check Exercise - 3

Self

1.

What are non stoichiometric defects? Does schottky defect lead to nonstoichiometry.

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71 2. How are colour centers produced?

Model Answer: Exercise 3

2.

Colour

centers

are

produced

due

to

anion

vacancies

and

trapped

electrons cdo D CdO 6.3 Let us Sum Up Crystal imperfections such as i) point defects, ii) line defects, iii) Cd 1 + r O

surface defects and iv) volume defects are discussed in detail. Effect of crystal imperfections is indicated the different types of boundaries are discussed.

6.4 Points for Discussion 1. Transition metal oxides and sulphides can have non- stoichiometry,

since these metals have variable oxidation states. 2. 3. Anion vacancies can be created due to excess metal atoms. Zno, on heating loses oxygen creating oxide ion vacancies, thus zno is yellow when hot white when cold (F- centre formation).

6.5 References 1. Advanced F.A.cotton (1972). 2. Inorganic and chemistry (4t h Ed) Re print education Asia. 2002 J.E. Huheey, E.A.Keitar Inorganic and Chemistry Wiley A comprehensive Eastern Text (3r d E d ) . New Delhi

G.Wilkinson

Limited -

R.L.Keiter

Pearson

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72

UNIT III LESSON 7

CONTENTS 7.0. 7.1 7.2 Aims and Objectives I ntroduction Electrical Properties o f Solids 7.2.1 Conductivity in metals 7.2.2 Super conductors Let us Sum Up Points for Discussion References AIMS AND OBJECTIVES The aim of this lesson is to understand the electrical conductivity or electrical properties of solids in general and electrical properties of metals in particular. After going through this lesson you would be able to i) ii) understand the electrical conductivity of metals and insulators

7.3 7.4 7.5 7.0

understand the super conducting behaviour of certain materials and the applications of super conducting materials

7.1

INTRODUCTION The conductivity of metals can be explained on the basis of free

electron theory.

The quantum free electron theory successfully explains the

conducting properties of metals and the decrease in electrical conductivity of metals with the increase in temperature can be explained on the basis of collisions of electrons with metal ions. materials. Super conductors are zero resistivity The

The superconductivity is explained by means of Cooper pair.

super conductivity depends on the critical temperature.

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73 7.2. ELECTRICAL PROPERTIES and nonconductors :

7.2.1 Conductors

One of the successes of the zone theory is its ability to distinguish conductors of electricity from nonconductors. is only partly filled, as shown in Fig 1.1. Consider a Brillouin zone that In the absence of an external

0electric field, each electron moves with a velocity determined by its energy; however, no net movement occurs, since for each electron with an energy determined by k there is a symmetrically located electron at k moving in the opposite direction. When an external field is applied, the distribution can

be displaced in the direction of the electric field by moving the electrons into adjacent quantum states in the same zone, as indicated in Fig 1.1 by the dashed circle. Obviously, only the electrons occupying energy levels lying Nevertheless,

near the Fermi surface can move into the higher energy states.

a net displacement of the electrons produces a net current, and a crystal with a partially filled zone is a conductor. As this process continues, it is possible

that an electron ultimately occupies a quantum state on the Brillouin- zone boundary. At this point, it cannot mover farther in the same direction

without crossing the boundary, that is without a transition to a quantum state lying in the next zone. electron's Physically, velocity the normal Such a transition is highly improbable so that t e h to the be zone pictured boundary as being is zero in this state. by the

electron

can

totally

reflected

crystallographic planes parallel to the zone boundary at this point. of the zone model, the point of reflected on electron the "reappears" zone in in the

In terms zone at a a is

translation- equivalent successive occupation

opposite

boundary. the Brillouin

Such zone

available

quantum

states

shown schematically in Fig 1.2, where q 0 shows the initial quantum sta t e o f the electron, when an external field is applied; q R electron when reflection occurs; is the quantum state of the and q F is the final state when the external

field is removed.

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74

When the zone structure Fig a crystal is such that the energy values in of 1.1 & 1.2 two adjacent zones overlap, it is not possible to complete the filling of one zone without also occupying the lower- energy quantum states in the zone. least one partially

This means, of course, that such a crystal must have at filled zone and that it is a conductor of electricity.

An interesting situation

arises when one of the zones is very nearly filled while the next zone is only partly occupied. The relative energy of the 4s states is slightly lower t an h

that of the 3d states for the first transition series in the periodic table of elements. The partial occupation of these states by the outer electrons of

transition metals means that the corresponding Brillouin zones are also party filled. filled, For example, it can be shown that the 3d zone of nickel is 94 percent whereas the 4s zone is 70 percent empty. Furthermore, it is believed

that conductivity in these metals takes place by transitions in the 4s zone. Now, when a 4s electron undergoes a transition from a quantum state on the zone boundary to an empty state it can be either "reflected back" in to the same zone or "scattered" into the 3d zone because there are quantum states of equal energy present in both zones. Such scattering decreases the n u m b e r o f

electrons contributing to the current and is believed to be responsible for the lower conductivity observed in the transition metals. In case the Brillouin zones in a crystal are completely filled or

completely empty and separated by a forbidden- energy region, the electrons cannot undergo transitions to adjacent quantum states and the crystal is an insulator. There are special cases of insulators in which one zone is very

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75 nearly filled and the next zone almost but not quite empty. occurs in semiconductors and also leads to conductivity. metals, however, the currents in semiconductors are This situa tion

By comparison with many orders of

magnitude smaller. Conductivity in pure metals : The conductivity of most metals can be explained without recourse to the zone theory. According to the free- electron theory, electrons can undergo

transitions from one quantum state near the Fermi surface to another adjacent and unoccupied state under the influence of an external field. If this process

were allowed to continue without end, the electrons would continue to occupy ever- increasing energy states, a situation that is contrary to the observed

steady- state current, which is proportional to the applied field.

The fact that

the electrons cannot continuously increase their energy is explained by their collisions with the metal ions, which occupy most of the space in a metal. These collisions are elastic so that the electrons transfer both energy an d momentum in the process. Because of the much larger mass of the ions, an

electron loses most of its newly gained energy and momentum so that its velocity, averaged over a period of time, is altered only slightly. There is,

nevertheless, a small but finite increase in the velocity component parallel to the applied field. bouncing from Thus, even though the electron follows an erratic path, to atom in all directions, it does undergo a net

atom

displacement in a direction determined by the applied field. The increase in its velocity component parallel to the applied field direction is called its drift velocity.

The

average

distance

that

an

electron

travels

between

collisions

is

called the mean free path l.

The electron's acceleration due to the field i s The

proportional to its charge e and inversely proportional to its mass m. conductivity s or its reciprocal, the resistivity r, r = 1 mv --- = ---s nc e 2 l is thus given by . (1)

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76 where n c is the number of conduction electrons a n d v is the average velocity as determined by their average kinetic energy E v .

The temperature. ion

vibration

the ions & 1.4a crystal increases with increasing Fig 1.3 in This has the effect of increasing the probability of an electron or of decreasing the mean the mean free path. Conversely, as the

of

collision

temperature

decreases,

free path should increase.

This is actually

the case, as is shown in Fig 1.3.

Note that the mean free path tends to According to (1) this implies

infinity as the temperature approaches zero.

that the resistivity of a metal should tend toward zero as the te mperature approaches zero. This conclusion is borne out by experiment, as shown by Note

the curve of resistivity plotted as a function of temperature in Fig 1.4.

that for all temperature above a certain low temperature the resistivity is directly proportional to the temperature.

Quantitative calculations of the mean free path have been made for certain metals, using quantum mechanics. These calculations have led to

results that are in good agreement with experimental values, particularly for the simpler metals such as the alkalis. The conductivities
o

(expressed compared

in

millions of mhos per meter) of several metals at 20 C calculated values below.

are

with

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77 Fe Observed s Calculated s 10 .. Na 22 22 Al 35 .. Cu 59 161 x 10 6 m h o s / m x 10 6 m h o s / m

In

crystals

belonging

to

the

cubic

system,

the

conductivity

is

independent of direction. does depend on direction

The conductivity (or its reciprocal, the resistivity) in crystals of lower symmetry. In the case of

crystals possessing one unique axis, that is in the hexagonal and tetragonal systems, the resistivity is different for current flow parallel to the unique axis and normal to it.

Conductivity in alloys : The reasons. mean free path of an electron decreases in an alloy for two

The first is an increase in the number of scattering centers caused

by local inhomogeneities in the crystal structure produced by the difference in the sizes of the different atoms. the case of solid- solution alloys. the resistivity reaches a This effect is particularly noticeable in

In the unannealed or random solid solution, at the 50- 50 composition, since this

maximum

corresponds to the maximum

possible distortion of the structure, and drops The increase in the

rapidly at both ends as the pure metals are approached.

resistivity is due to a discontinuity in the periodic potential encountered by the electrons in the vicinity of the solute atoms. ordered alloys Cu3 A u a n d to the CuAu, the curve path At the compositions of the exhibits of the definite electrons minima, due to

corresponding

increased

mean

free

ordering, which restores a periodicity to the alloy.

In practice, it turns out

that annealing serves to decrease the resistivity also because it removes other imperfections present which may also act as scattering centers for electrons.

In a solid solution, the increased resistivity, due to the introduction of solute atoms, does not disappear at the absolute zero. remains is usually called the residual resistance. The resistance that

The residual resistance is

independent of temperature in dilute alloys but varies with changes in the composition of an alloy. According to Matthiessen's rule, the resistivity of

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78 an ideal alloy can be expressed as the sum of the residual resistance and a resistivity term which varies with temperature in the same linear manner as the resistivity of a pure metal.

Self 1.

check

exercise 1

If kentic energies and mean free paths are assumed to be equal for Na a n d A l, what would be the ratio of the free electrons nN a nA l ?

2.

Discuss alloy.

the

variation

of

resistivity

with

the

compositions

of

cu Au -

Please answer the above before you proceed further. your answer.

The space below is for

7.2.2 Zero

resistivity

materials

(Superconductors)

The without property

ability resistance are called

of is

certain called

ultra

cold

substances

to

conduct

electricity this

superconductivity.

Substances

having

superconductors.

Thus and also

superconductor as

is

conductor below

having its

almost

zero

resistivity transition

behaves

diamagnetic

superconducting

temperature.

Fig 7.5

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79

The

superconducting

transition

temperature

'Tc ' of a material is defined

as a critical temperature at which the resistivity of the material is suddenly changed to zero as shown in fig. 7.5. Thus at that temperature a material is In the figure the transition

changed from normal material to superconductor.

region is of finite width AB and depends upon the presence of impurities and internal stresses in the sample. In chemically pure crystal which is also free

from lattice defects, the width of the transition region is very very narrow. The temperature 'Tc ' of pure metals range from 0.35 K (Hafnium) to 9.22 K have higher transition temperatures. Particularly Niobium

(Niobium) and of semiconductors from 0.3K (Ge Te) to 1.25 K (NbO). Commonly alloys

compounds such as Nb3 Sn (Tc = 1.81 K) and Nb3 Ge (Tc = 22.65 K) have higher transition temperatures and so they are technically important superconductors. At observed. 1. 2. 3. 4. The electrical resistivity drops to zero The magnetic flux lines are excluded from the material There is a discontinuous change in specific heat. Further there are also small changes in thermal conductivity and the volume of the material. the transition temperature, the following physical changes are

Explanations for 1.

the occurrence of superconductivity

At the extremely low temperatures, vibrations of the nuclei of certain atoms slow down so much and they synchronise with passing waves of electrons in a flow of electric current. electric current disappears. When this happens resistance to

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80 2. BARDEEN COOPER AND SCHRIEFFER THEORY According to that, superconductivity occurs when there is a formation of cooper pair of electrons (or) bound electron pair. These two

electrons with opposite spins and momenta form a pair through electron electron interaction via the lattice deformation or phonon field. type of interaction can occur only at very low temperatures. during the transition from normal state to super conducting This Thus state

electrons of opposite spin couple with each other via the vibrations of the lattice that the material's atoms form. One electron in the

communicating pair distorts the lattice which can then take up energy from the second electron and immediately they from a bound electron pair or Cooper pair.

Fig 7.6 As shown in figure 1.6, one electron with wave vector k distorts the lattice emitting a phonon of wave vector q. The other electron with wave

vector k takes up the energy down the lattice and its wave vector changes into k + q. Thus these two electrons with wave vectors k q and k + q form

a cooper pair and superconductivity occurs.

3.

RVB Theory :

The low

conventional At

BCS higher

theory

accounts

for

superconductivity degradation

only

at the

temperatures.

temperatures

thermal

breaks

cooper pairs leading to ordinary electrical conductivity.

Thus it is unable to

explain the formation of high temperature superconductivity having high Tc ( 8 0 K )

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81 Many theories have been suggested, but none is satisfactory. the promising one is the Resonating Valence Bond (RVB) state One of theory

initiated by P.W. Anderson and the Princeton university group. that intense electron pairing needed brought about through an

According to

to explain hot superconductivity may be correlation quite similart o t h a t

attractive

responsible for bonding hydrogen atoms in a molecule.

Further it is based on

the idea that it is the short range repulsion between electrons in a narrow band which gives rise to superconductivity.

A key element of RVB theory is that electron pairs can exist in a material that is not superconducting. Superconductivity occurs when the

material is doped to create holes in it. Bose Condensation, making are

The holes then form pairs and undergo possible. p type These high

superconductivity normally called

temperature

superconductors

superconductors

since the charge carriers are holes.

Recently

'n'

type

superconductors

(Ln2 - x C e x C u O 4 - y ) where Ln = Pr, for this system

Nd and Sm have been prepared but the transition temperature are very low (20K). General properties of superconductors

1.

Electrical resistance

The electrical resistivity drops to zero at the transition temperature. One can conclude that superconductors have virtually zero electrical

resistance and they can conduct electricity without resistance.

2.

Diamagnetic property

The superconductor is a perfect diamagnet.

As the material which is

placed in an uniform magnetic field (whose value is smaller than the c r i t i c a l magnetic field Hc ), is cooled below 'Tc ' the magnetic flux inside the

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82 material is excluded from the material (fig 1.7). EFFECT. This is called MEISSNER

Thus a material can behave as a superconductor only when i) ii) the resistivity of the material should be zero and the magnetic induction in the material should be zero when it is placed in an uniform magnetic field.

Fig 7.7

Both

the

conditions state, these

are two

independent conditions

to

each

other

and

to exist

get in

superconducting the material.

should

simultaneously

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83 3. Effect of magnetic field

Below Tc destroy the

superconductivity

can

be

destroyed

by

the

application

of

strong magnetic field. superconductivity of the

At any temperature, the minimum field required to is called field critical depends field (Hc ) of the material. the temperature of Thus the

value

critical

upon

superconducting material. Hc = Ho T2 1 - ----T2 c

Where H o = critical field 0 K.

Fig 7.8 From the fig. 7.8 material increases, the The one can know that when the temperature of the value value of of the the critical will magnetic be field for decreases different

correspondingly. materials.

field

different

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84 Table 1.1 Material Al Co Hg Pb SUPERCONDUCTORS Ho ampere/metre X 103 7.9 2.4 33.0 64.0 AND THEIR CRITICAL FIELD Ho ampere/metre X 103 24.5 59.0 1.4 18.1

Material Sn Ba Bi 3 Ca Si 2 Nb 3 Sn

4.

Effect of heavy current

T h e s u per

conductive

properties

of

conductors

disappear

when

sufficiently heavy current is passed through them.

Since when current flows

through a conductor it will set up the magnetic field which destroys the superconducting wire. I c = 2p r H c Where I c is the critical current and 'r' is the radius of the wire. 5. Effect of pressure state. According to Silsbee's rule, for a superconducting

By applying very high pressure, we can bring Tc of a material nearer to room temperature i.e. if we increase the pressure on the material, T a l s o c increases. Tc is directly proportional to pressure at very high pressures. Researches are going on to get superconducting state at room temperatures by applying very high pressures.

6.

Isotope effect Maxwell found that the transition temperatures are inversely

proportional to the square roots of the atomic weights of the isotopes of a single superconductor. M
a

Thus,

Tc = a constant

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85 Where a is a constant and it is approximately equal to 0.5. For example the

atomic weights of isotopes of mercury are from 199.5 to 203.4 atomic mass units. Therefore their transition temperatures are also from 4.185 K to 4.146

K respectively.

Types

of

superconductors

Based on the value of superconducting transition temperature we have 1. 2. High 1 It High Low temperature temperature superconductors superconductors Low Temperature low superconductors transition

Temperature has high temperature

superconductors super (>

conducting 1 It 100K)

has

superconducting

transition 2

temperature (<20K) is obtained by the

Super conductivity is obtained by the 2 Superconductivity hole states. Dislocations also increase

formation of cooper pair having two electrons with equal and opposite

the value of transition temperature.

spins and momenta. 3 It does not obey B.C.S. theory. High 3 It can be explained only from BCS temperature explained superconductivity from resonance can be theory.

valence

bond (RVB) theory only. 4 It is very useful for commercial and 4 It other high applications because these have is not of so ultra useful, low due to

maintaining (20 K)

temperature

superconducting and which are can hard

transition super strong

temperatures conductors

produce

magnetic fields. 5 It is called p- type due to the from super conductor 5 It of due is called to n- t y p e s u p e r c o n d u c t o r the formation from of

formation holes.

superconductivity

superconductivity or electron pairs.

cooper pairs

Based on critical magnetic field, there are two types of superconductors i. Type I (soft) superconductors

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86 ii. Type II (hard) superconductors

Type 1.

Superconductors

Type I superconductor is the one which exhibits a complete Meissner

effect or perfect diamagnetism. i.e., above the critical field Hc , the specimen is a normal conductor. Below the critical field, the specimen excludes all the magnetic lines of force inside the specimen or it will become a diamagnetic material

2. 3. 4.

These are also called soft superconductors The values of Hc , are always too low for these materials. Example: A1, Zn, Ga.

Fig 7.9 (a) & (b)

In the Figure 1.9 Ha Hb

applied external magnetic field and Magnetic filed produced by the induced

superconducting currents when an external field is applied.

Type

II

Superconductors

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87 1. Type II Superconductors are the superconductors in which the magnetic to penetrate the specimen at a field Hc 1 electrical which is lower than

flux starts

critical field Hc . The specimen is in a mixed state between Hc 1 and Hc2 a n d i t has superconducting properties upto Hc 2 . Above Hc 2 the specimen is a normal conductor (fugure 1.9 (b).

2. large

Type II superconductors are called hard superconductors which have a amount of magnetic hysteresis induced by mechanical treatment.

Solenoids wound with wire of a hard superconductors can produce field over 100 kilo tesla.

3.

So type II superconductors can carry high super current densities in

high magnetic fields and are of great commercial importance.

4.

Incomplete Meissner effect occurs in the region between Hc 1 a n d H c 2

and this region is called vortex region. In this region the magnetic flux lines gradually penetrate the specimen as the magnetic field is increased beyond Hc 1 . 5. H e a v y c o l d - worked density and and fine recovery grains annealed are used materials for having type high II

dislocation

making

superconductors.

6.

Examples : Zr, Nb, 60% Nb 40 % Ti alloy.

High

Temperature

superconductors

Sodium tungsten bronzes and barium lead bismuth oxides are important intermetallic compounds with high superconducting transition temperatures

(20K). In Bell Laboratory, during the end of 1986, it was detected that a crystalline complex of lanthanum, strontinum and copper grown in an

atmosphere of oxygen has the highest superconducting transition temperature, 3 7 K . F o llowing the Bell Laboratory discovery , the Chinese group of

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88 scientists has found a superconducting state in an octahedral crystalline

complex of lead, lanthanum, copper and oxygen at 77K.

After that C.W. Chu and his collaborators of university of Houst n, o U.S.A. found stable superconductivity at 90K in yttrium barium- copper oxide compounds. at operating Detection of super much conductivity above 130 especially K has in yttrium performed complexes recently.

temperature

been

Now the stable and reproducing superconducting state is observed at a high transition temperature state around at room 165K. Researches are going on to get the

superconducting

temperature

conditions.

Some of the high temperature (Tc below:

> 100K) superconductors are given

T1 2 Ba 2 Ca 2 Cu 3 O y , L a 2 - x Sr x CuO 4 , Y B a 2 Cu 3 O 7 - y Here

and Bi2 (CaSr) 3 Cu 2 O y .

the value of x is less than 0.2. Further the value of y is a variable one

and depends upon the stability of the system. The rare earth oxide systems, l i k e L a - Sr=Cu=O and Y- Ba- Cu- O have so far been found to have stable

superconducting transition temperatures in the range 80- 100K range.

Recently T. Ogushi and his associates from Japan have reported in LaSr- Nb- O 255K.Some system scientists (without copper) that shows superconductivity upto

believe that this copperless Y- Sr- Nb- O or La- Sr- Nb- O real room temperature superconductors.

system may lead to the

New oxide superconductors having Tc>90K without rare earth element New oxide superconductors with above 90K transition temperatures

have been discovered in 1998. The newer compounds are still layered copper oxide materials, but they do not contain rare earth elements. In place of yttrium or other rare earths, the compounds contain metals like bismuth thallium. Thus they contain four metallic elements instead of three. or For

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89 e x a m p l e , t h a l l i u m - barium- calcium- copper oxide superconductor contains

three copper oxygen layers and it becomes superconductor at 120K.

Similarly

bismuth- strontium

calcium-

copper

oxide

has

the

superconducting transition temperature around 120K.

Preparation

and

characteristic

of

high

temperature

ceramics

superconductors

The

new

ceramic

oxide

superconductors

like

yttium

barium

copper

oxide, Lanthenam barium copper oxide, Neodymium barium copper oxide and T h a l i u m b a r i u m copper higher magnets critical having fields higher oxide and are all are types used II to superconductors manufacture which have

hence

superconducting

strengths.

Let

us

see by

the the

preparation

of

yttrium

barium

copper

oxide

superconductors four The step

'Shake the

and Bake' method. This method involves a chemicals 2. Calcination and 4. (initial The firing) 3.

process:

1.Mixing firing

intermediate

(oxygen

annealing)

final

oxygen

annealing.

1.

Mixing

the

Chemicals

The powders of yttrium oxide, barium carbonate and cupric oxide are taken such that 11.29 gram of Y2 O 3 , 39.47 gram of BaCO3 and 28.86 gram CuO so that the atomic ratios of yttrium, barium and copper are 1:2:3. A mortar with pestle is used to grind down any lumps or large particles in the

powders. Then the powder mixture is shaken vigorously in a capped jar or stoppered flask for several minutes.

2.

Calcination

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90 After the powders are thoroughly mixed, they are kept in an alumina crucible and heated in a furnace of about 950o C for about 18 hours. following chemical reaction takes place. The

0.5Y 2 O 3 +2 BaCO 3 +3 CuO

Y Ba2 C u 3 O 6 . 5 + 2CO2

This initial heat treatment is called calcinations and results in a porous dark gray or black clump and the basic crystal structure is developed. T h e material formed will be shrinked and becomes much denser than the original powder mix. 3. Intermediate Firing

The porous black clump is ground into a fine powder and placed in the furnace. After the furnace temperature reaches about 500o C, a slow flow of oxygen into the furnace is maintained. This heat treatment under oxygen flow is called oxygen for 18 annealing. hours at The oxygen The flow should be maintained of in 950o C a 950o C.

constantrate

maximum

temperature

should be reached in an hour. After this firing, the cooling rate must be no more than 100o C per hour upto 400o C and the oxygen flow is also maintained. By this manner the oxygen content of each crystal unit is increased from 6.5 atoms to 7 atoms and the chemical formula for the material becomes YBa2 , Cu 3 O 7 . At 400o C, the supply of oxygen is cutoff and the rate of cooling can be increased to 200o C per hour. Once again the material should be thoroughly re- ground in a mortar and pestle.

4. The final oxygen annealing The reground black powder is placed back in the alumina crucible. The powder should be as finely ground and as densely evenly packed. Now heat the sample between 950o C and 1000o C for about 18 hours. The cooling takes place in a very slow manner with adequate oxygen flow. The rate of cooling must be less than 100o C per hour upto 400o C. After that the rate of cooling can be increased.

Pervoskite superconductivity

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91 It is found that ceramic superconductors have the unit cell such that one atom of a rare earth metal, two barium atoms, three copper atoms and seven oxygen atoms. In the superconductors the metallic atoms are in the ratio 1:2:3. Thus these new kind of superconductors of 1- 2- 3 are called 1 2- 3 is

superconductors.

The

electrical

conductivity

superconductors

based on the presence of oxygen atoms in their unit cell. The oxygen atoms have more vacancies and so they can accommodate electrons from other

atoms. It is found that electricity flows through the material by allowing thse holes to move from atom to atom in the crystal.

The unit cell of YBa2 C u 3 O 9 is a stack of alternating cubic pervoskite structures (figures 1.11 (a) (BaCuO3 ) : (Y Cu O3 ): (Ba Cu O3 ). But is not a which is superconductor when defieicient (or defect) cubic alternating oxygen superconductor. The unit cell of YBa2 C u 3 O 7 Ta = 90K is a stack of

pervoskite structures in the idealized sequence noted, arrows. The chains of alternating Ba:Y: Ba atoms which characterize the Y Ba2 C u 3 O 7 perpendicular to Cu- O planes with alternating oxygen defects shown in figure 1.11(b). So structures. the oxygen defects induce superconductivity in the pervoskite lattice are as

(Vacancies)

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92 Applications 1. of superconductors

Electric generators

Superconducting compare with

generators

are

smaller These

in

size

and

weight consume

when very

we low

conventional

generators.

generators

energy and so we can save more energy. The superconducting d.c. generators are available which have electrical power of 2500kW having very high

current and very low voltage. These are in small size with superconducting windings. The low loss superconducting coil is rotated in an extremely strong magnetic field. Similarly there are d.c. superconducting motors which are

used in ship propulsion and large mills where very high torques are necessary even at low speeds.

2. Electric Power Transmission lines

Electric

power

companies

look

forward

to

superconducting

transmission systems that would save most of the energy now being lost from conventional power lines in the form of useless radiation and heat (I2 R Joule heat losses). The electric cables are designed with superconducting wires.

Portable superconducting transformers with low loss are available for step up or step down a.c. voltages.

3.

Magnetic

Levitation

In

Japan,

superconducting

magnets

have

been

used

to

levitate

an

experimental train above its rails and drive it at great speed with minimal expenditure of energy. A similar magnetic propelsion system may be used t o launch satellites in to orbit directly from the earth without the use of rockets.

Principal

of

Magnetic

levitation

The diamagnetic property of a superconductor is the basis of magnetic levitation. A sheet of superconductors in the superconducting state is kept

below the horizontal bar magnet suspended from a flexible chain and then

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93 lowered over the the loop superconductor. supporting below the chain magnet As becomes the limp magnet and approaches eventually the

superconductor, down in a

dropped the

which floats

horizontally

above

superconductor. The magnetic field due to the approaching magnet induces current in the surface is zero, of the the superconductor. persists in Since the the resistance of and the a

superconductor

current

superconductor

magnetic field due to this induced current repels that the bar magnet. When a superconductor levitates a magnet, a magnetic mirror image is formed in the superconductor superconductor such directly that there the is always a north pole induced in the

below

north pole of the levitating magnet and a

south pole is induced in the superconductor directly below the south pole of the levitating magnet. The mirror image moves with the magnet as the magnet moves so that the disk magnet can be given a rapid spin without affecting its levitation. In fact the magnet may continue to spin for quite a long time because its spinning When the encounters no friction air other is than the friction the of air

resistance. magnet

surrounding

pressure

reduced,

levitating

rises

higher.

Instead superconducting supporting

of

permanent

magnet, a

the

supporting The

field

is

provided between

by the

solenoid field

earring and

current.

repulsion surface

magnetic

superconducting

having

persistant

current is the basis for magnetic levitation of trains and other machines.

4. Ore Separation High efficiency ore- separating machines may be built using

superconducting magnets which are also used to separate tumour cells from healthy ells by high Gradient Magnetic separation method.

Self Check Exercise 2 1. 2. 3. 4. Explain the BSC theory and RVB Theory What are type I and type II superconductors Explain the term meissner effect Give a few applications of superconductors

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94 Source : 1) Introduction to solids A z a r a f f New Delhi 1 9 6 0 .

TMH EdN Model Answers Self 2. check Exercise 2

Type I super conductors exhibits a complete meissner effect or perfect diamagnetism Hc (Critical field is too low) (eg) Al, Zn, Ga

Type II Can carry high super current densities in high magnetic fields. (eg.Zr, Nb etc.) 7.3 Let us Sum Up Conductivity in metals and alloys is discussed on the basis of zone theory. Different types of super conductors, their synthesis and theories of super conductors such as BCS theory and RVB are discussed in detail

Magnetic levitation is explained. 7.4 Points i) for Discussions

The variation of electrical conductivity with 'T' in the case of metals and semiconductors are different 1 concentration

ii)

Resistivity of a metal at a given temperature is a Carrier

iii)

Cooper

Pair

concept

explains

the

low

temperature

super

conductivity

7.5 References 1. Advanced F.A.cotton (1972). 2. Inorganic and chemistry (4t h Ed) Re print education Asia. 2002 J.E. Huheey, E.A.Keitar Inorganic and Chemistry Wiley A comprehensive Eastern Text (3r d E d ) . New Delhi

G.Wilkinson

Limited -

R.L.Keiter

Pearson

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95 LESSON 8

CONTENTS
8.0 8.1 8.2 AIMS AND OBJECTIVES INTRODUCTION MAGNETIC PROPERTIES 8.2.1 DIAMAGNETISM, PARAMAGNETISM & FERROMAGNETISM

8.2.2 DOMAIN STRUCTURE 8.3 8.4 8.5 8.0. LET US SUM UP POINTS FOR DISCUSSED REFERENCES AIMS AND OBJECTIVES The aim of the lesson is to study in detail, the magnetic pro p e r t i e s o f materials. fundamental magnetic materials After going of is through this lesson The you would of understand the types theories of the of

theories

magnetism. important for

knowledge different

properties for various

selecting

magnetic

applications.

8.1

INTRODUCTION

When a substance is placed in an inhomogeneous magnetic field, it is either attracted toward the strong part of the field or repelled toward the weaker part. If it is attracted by the field, it is said to be paramagnetic, if repelled it is said to be diamagnetic. A Ferromagnetic solid is one that can have a permanent magnetization, after the magnetic field is removed.

8.2.1 MAGNETIC PROPERTIES

Diamagnetism:

when

substance

is

placed

in

an

inhomogeneous

magnetic field, it is either attracted toward the strong part of the field or repelled toward the weaker part. If it is attracted by the field, it is said to be paramagnetic, if repelled, it is said to be diamagnetic. The force F with

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96 which a diamagnetic substance is repelled when placed in a H and gradient dH/dx is determined by dH F = x VH dx Where x is called the magnetic susceptibility and V is the volume of field of strength

the substance. The magnetic susceptibility is a measure of the change in the magnetic moment of the atoms caused by an applied field. It is usual to speak of the atomic susceptibility x A which is determined according to Langevin's N 0 e2 xA =
2

equation. r2 .(2)

6mc = - 2 . 8 3 x 1 0 1 0 r2

where N0

is Avogadro's number; e, m, c have their usual meaning for an r is the average radius of the orbits of the electrons. Note that

electron; and

the right side of (2) is negative, which indicates that the force in (1) is negative. This is in agreement with Lenz's law that t h e m a g n e t i c flux

produced by an induced current opposes the change in the magnetic field which produces it.

In quantum mechanics, The Langevin equation is valid provided that the electron distribution is spherically symmetrical. Thus it is quite usefu l when dealing with inert gases, ions, and neutral atoms. The value of r is determined by the wave function, and since the susceptibility is proportional t o r 2 , it follows that the outer electrons make the largest contribution. The v a l u e o f x A , calculated using quantum mechanics, is in good agreement with the values found experimentally. For most elements, including Cu, Zn, Ga, Ge, As, Se, Br, Ag, Cd, Te, and the inert gases, the magnitude of the atomic susceptibility lies in the range 10- 6 to 10- 5 , w h e r e as for Sb , Au, Hg, TI, Pb, and Bi it is greater than 10- 5 . Bismuth is exceptional in this regard; xA = 1.35 x 10- 4 in MKS units.

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97 Paramagnetism: It is possible for an atom to have a net magnetic moment moments resulting and the from spin a particular combination of of its the orbit a l m a g n e t i c The unit for

magnetic

moments

electron.

measuring the spin magnetic moment of an electron is the Bohr magneton. eh = 4p mc = 9.27 x 10- 2 1 erg/gauss. ..(3)

If an external magnetic field is applied, the spin moments can line up either parallel to the field or antiparallel to the field.

The

magnetic

properties

of

many

materials

were

first

studied

systematically by P.Curie before the end of the nineteenth century. He found that the paramagnetic susceptibility xp was inversely proportional to the

absolute temperature. C xP = T Where C is the Curie constant and Langevin later applied classical mechanics is to characteristics paramagnetism of in the material and .(4)

gases

found that the Curie constant could be expressed theoretically N 0 m2 C = 3k where N0 is Avogadro's number k is Boltzmann's constant m is a average magnetic moment per molecule .(5)

It also follows from classical mechanics that, for free electrons in a metal, the Curie constant can be written n C = k
2

.(6)

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98 where n is the number of free electrons per unit volume. By substituting (6) in (4) it is possible to calculate the paramagnetic susceptibility of any metal. The value obtained in this way is approximately 100 times larger than the values obtained experimentally. This is one theory of the properties explain of metals,

therefore, that the classical free- electron

cannot

correctly.

The

total

magnetization M is defined as the magnetic moment per unit

volume and is given by M = XP H n M = kT Now, according to the Curie law (4), the susceptibility and, hence, the
2

H.

magnetization should vary with the temperature. Again, this is not the

Fig 8.1 case for many metals. The observedx weak and temperature- independent can be explained by applying Fermi- Dirac statistics to this

paramagnetism problem.

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99 The distribution of electrons in a metal at the absolute zero of

termperature is shown in Fig.2.1 by plotting the parabola- s h a p e d f u n c t i o n representing the density of states as a function of energy. In the absence of an external magnetic field, the electrons occupy all the available states

having energies less than the Fermi energy E 0 . They are shown divided into two groups, in Fig.2.1A, accordingly as their spins are plus are minus. When an external field is applied, the magnetic moments due to the spins line up either parallel or antiparallel to the field. Assuming that a plus de notes

electrons which have antiparallel moments, these electrons undergo a shift in e n e r g y + H, equilibrium, transitions to as shown of lower in the Fig. 2.1. This in situation the is not stable, states to the and at

some the

electrons parallel

antiparallel This leads

undergo situation

energy

states.

shown in Fig.2.1C. The magnitude of the energy shift, even due to a fairly strong field, H = 105 gauses, is very small, H ~ 1 0 - 3 e V , so that, at room ~0.03 eV, is sufficiently greater to keep

temperature, the thermal energy, kT

the numer of electrons having parallel ands antiparallel moments very nearly equal. Not only but does also in this explain the the very small is value virtually of the observed of

susceptibility reasonable

why

susceptibility

independent

changes

temperatures.

8.2.1 Ferromagnetism. It has been assumed, in the above discussion, that the magnetic moment of the atoms was due entirely to the electron spin. This i s a fairly accurate picture for such metals as Li, Na, Mg, AI, and K. In these metals, the valence electrons are quite free to migrate through the crystals so that filled they and contribute contribute primarily spin moments, whereas the inner shells are

only weak diamagnetism. On the other hand, if an atom

has incomplete inner shells, then it is possible that not only the spin moments but also the orbital moments can contribute to the magnetic moment of the atom. This normally leads to large paramagnetic susceptibility in accord with the Curie law. Such relatively large susceptibilities are found among the rare earths and the platinum and palladium- group metals. An anomalous behaviour is encountered in the case of Fe, Co, and Ni, which are paramagnetic at elevated temperature temperatures but become ferromagnetic below a transition

called the Curie point. A ferromagnetic solid is one that can

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100 have a permanent magnetization after the external magnetic field is removed. This permanent magnetization was first explained by P.J. Weiss in 1907 as

being due to a parallel orientation of the permanent magnetic moments of the constituent atoms. The paramagnetic likened, therefore, to the disorder temperature, moments favours thermal agitation oriented, is ferromagnetic transition can be order transition. Above the Cur e i responsible below which for the more keeping Curie point the the magnetic energy are

randomly an

whereas in

ordered

arrangement

magnetic

moments

aligned in one direction than in another. In order to explain why an excess of magnetic moments along one direction is more stable than a uniform,

distribution, Weiss proposed that a molecular field exists in the crystal and favors such an alignment.

Heisenberg was the first to propose an explanation of this molecular field based on the principals of quantum mechanics. He treated the problem similarly to the Heitler- Londom treatment of the hydrogen molecule. In this treatment, an exchange interaction between electrons in different quantum

states is shown to lead to a lower energy for a molecule than that obtained by a mere superposition of the wave functions of each atom. Experiments have proven that the magnetic moment, due to the electron spins rather than the orbital moments, contributes to the permanent magnetic moment of the irongroup explain atoms. why, The in exchange certain forces, the therefore, atoms are have necessary electrons in with order to

metals,

parallel

magnetic moments. It is reasonable to expect that such exchange forces are negligible unless the atoms are brought closely together. It can be shown that, as two in atoms each the approach assume each other, the electron As spins they by of are unpaired brought

electrons closer

atom spin

parallel are

orientations. maintained

together,

moments

parallel

increasing

forces. As the interatomic distance is decreased still further, however, these exchange forces decrease until finally they pass through zero and an

antiparallel spin orientation is favored. It has been shown by

Bethe that, fo r

the iron group, the conditions favoring parallel orientations occur when the ratio between one- half the interatomic distance in a crystal and the average

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101 radius of the 3d shell is greater than 1.5. Some typical values of this for these metals are Mn Ratio 1.47 Fe 1.63 Co 1.82 Ni 1.98 ratio

As can be seen, the ratio for manganese is lightly less than 1.5, which explains why magnese crystals are not ferromagnetic whereas compounds

containing manganese atoms spaced farther apart are. Notable examples are the Heusler alloys Cu2 MnSn and Cu2 MnAl. alloys contain neither Fe, Co, or Ni) (Note that these ferromagnetic

According to the zone theory, two factors determine the energy of a crystal. The first is the Fermi energy, which makes a positive contribution to the total energy, and the second comes from the exchange integral and makes a negative contribution. A crystal then is ferromagnetic when the negative energy due to the exchange integral is greater than the positive- e n e r g y t e r m due to the kinetic (Fermi) energy of the electrons, which tends to randomize the spin directions. The exchange integral used in this calculation is

somewhat different from the one proposed by Heisenberg in that it is based on the electrostatic interaction between one electron and the electrons in an identical fictitious crystal having a hole in place of this electron. It turns out that this exchange integral is independent of interatomic distance and does

not vary too much from atom to atom in the metal. In order to explain ferromagnetism, therefore, it is necessary to compare the Fermi energies of different metals. Although only nickel has been examined in detail, the

r e s u l t s c a n be extended to show that the Fermi energy is smaller than the exchange energy in Fe, Co, and Ni. As expected, it is somewhat greater in the case of Mn. It should be noted that a small Fermi energy denotes a narrow energy zone, that is , a larger number of electrons having very closely spaced

energies. Thus this calculation supports the earlier partially filled d zones, which do not overlap in

conclusions that narrow, neighboring atoms to any

appreciable extent, are necessary and sufficient for ferromagnetism to occur.

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102 More occurrence recently, of Zener has The proposed exchange a different integral, explanation as calculated for in the the

ferromagnetism.

Heitler- London model for the bonding of two atoms, is negative. Heisenberg, therefore, obly when was forced to postulate that the exchange integral was negative

the atoms were brought very closely together and became positive

when the unfilled d shells did not overlap appreciably. It has never been proven, however, that such a reversal in the sign of the actually occurs. Zener has suggested that the exchange exchange integral integral always

remains negative and that ferromagnetism is due to an interaction between electrons occupying quantum states in the partially filled d and s zones. The proposed interaction, which accounts for the exess of parallel spin moments of one kind, similar to the interaction (Hund's rule) that causes unpaired

electrons in different orbitals to have parallel spins. According to this model, a n o v e r - all decrease in the energy is obtained when the electrons occupying states in the d zones have parallel spin moments and the s- z o n e e l e c t r o n s contribute a small moment in the same direction. Because of the approximate nature of the calculations used to support the above stated competi g n

theories, it is not possible to decide, at present which one describes most correctly the interactions responsible for ferromagnetism.

On an atomic scale, the reason for the permanent magnetic moment of Fe, Co, and Ni atoms is best understood by considering their electronic

structures. Each atom has two 4s electrons and an incomplete 3d shell. 3d 6 4 s 2 3d 7 4 s 2 3d 8 4 s 2

Fe Co Ni

The atomic moments of these metals should be, respectively, four, three and two Bohr magnetons. The actual values turn out to b e Fe Atomic moment 2.22 Co 1.70 Ni 0.61 Bohr magnetons

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103 The no integral number of electron spins per atom determined from saturization magnetization measurements given above is explained by making use of the zone theory as follows: The 3d 4s zones of these metals overlap,

as shown for the case of nickel in Fig.2.2. Since the relative occupation of these two zones is determined by the Fermi energy E0 , it is assumed that 0.6 electron occupies states in the 4s zone and 9.4 electrons in the 3d z n e . O f o these, five must have one kind of spin and 4.4 the other, leaving 0.6 spin of the same kind per atom. The accuracy of this model can be readily checked by alloying nickel with copper or zinc. The substitution of a copper atom for a nickel atom introduces one additional electron in the crystal, whereas zinc introduces. Two additional electrons. It is reasonable to expect that these electrons will prefer the lower- lying 3d states of nickel and therefore, as more copper (or zinc) is added, the magnetic susceptibility should decrease. It has been

shown from saturization magnetization measurements that this is indeed the case; the magnetization becomes virtually zero when 60 per cent Cu or 30 per ent Zn is added, that is, when enough electrons are added to the 3d zone of nickel. fill completely

8.2.2 D o m a i n S t r u c t u r e . cobalt, and nickel are

The

above

discussion but it has

has not

explained accounted

why for

iron, such

ferromagnetic,

physical properties of magnets as, for example, the well- k n o w n h y s t e r e s i s loop, field. relating Even the before amount the of magnetization mechanism to of the strength of the was applied clearly

atomic

ferromagnetism

understood, Weiss assumed that a single crystal of iron consists of small regions or domains, within each of which the electrons have all their spins parallel, but that the spins of neighboring domains are not parallel.

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104

Fig. 8.2

Fig. 8.2 Schematic representation of overlapping 3d and 4s states of nickel. On an average, 9.4 of the 10 available 3d states and 0.6 of the 2 available 4s states are occupied (After Slater).

When an external field is applied, the domains that have net moments parallel to the directions of the field have their energy reduced, whereas

those domains that do not have their energy increased. The crystal's energy, obviously, can be lowered if all the domains align themselves parallel to the field. This can be accomplished in either of two ways. Either the direction of magnetization of an entire domain changes at once, or a domain that is

favorably oriented grows in size at the expense of a less favorably oriented domain. When the external field is reversed in direction, all the domains must be reoriented, and , owing to several causes discussed below, this requires an additional field to overcome the factors opposing such reorientation so that a hysteresis loop results.

In turns out that magnetization is an anisotropic for example, it is easier to magnetize iron (body- centered

property cubic)

in

crystals. (100)

along

than along any other directions, and most difficult along (111). It is common

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105 practise to refer to these as easy and hard directions sensitive of magnetizati n, o the easy

respectively. To show that this is a structure

property,

directions in nickel are (111) (normal to the closest packed layers) and the hard closest The directions packing are of (100). Similarly, the easy direction in the hexagonal

cobalt is normal to the hexagonal closest- p a c k e d l a y e r s . of single in crystals their along certain directions For is invariably iron right

magnetization by

accompanied crystals

changes along the

physical of

dimensions.

example, at

expand

direction

magnetization

and contract

angles to it so that the total volume tends to remain the same. In a nickel crystal, the dimensional direction and changes expands are in reversed; directions it contracts to it. along Thus the the

magnetization

normal

magnetization of ferromagnetic crystals depends on the way that the structure is strained, a phenomenon called magnetostriction. As might be expected,

magnetostriction is related to the elastic properties of the crystal and can be used to explain the formation of magnetic domains in crystals. With six (100) directions equally easy, it is natural that a single crystal of iron has domains containing magnetic moments aligned parallel to each of these six directions. Obviously, the domains must be separated by boundaries in whic t h e h

magnetic moments undergo a gradual transformation from one orientation to the other. The exchange energy favoring parallel alignment of all moments prefers favors thick a boundaries. It is opposed the by easy the magnetic of anisotropy, which A

minimum

deviation

from

directions

magnetization.

compromise between these opposing forces is reached, and it turns out that the boundaries have thicknesses of the order of hundreds of atoms in actual crystals. The domains themselves can have various sizes, dete rmined

primarily by the free energy of the boundaries, whose contribution to the crystal's energy decreases with increasing domain size, since the ratio of

boundary area to domain volume decreases. Lest it be deduced from this that a single crystal consisting of a single domain has the lowest possible energy, it should be realized that such a crystal is a permanent magnet whose

magnetic field contains magnetic energy. Thus the domain structure proposed by Weiss serves to lower the over- all energy, thereby ne u t r a l i z i n g t h e

individual

permanent

magnets.

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106 When a weak magnetic field is applied parallel to an easy direction of a crystal, the domains having lower energies, because of their more

favorable orientation, grow in size owing to the reorientation of the m o m e n t s in the boundaries . The resulting movement of boundaries can actually be observed by sprinkling a fine powder of Fe2 O 3 on a polished crystal surface. The powder particles align themselves along the domain boundaries and a socalled bitter pattern is obtained. Several domains can be seen in the Bitter

pattern of a single crystal of iron shown in Fig.2.3. It has been observed that the movement of domain boundaries is impeded by imperfections and

proceeds in jumps. These jumps can be made audible by su r r o u n d i n g t h e crystal with an effect induction is even by coil connected to an if amplifier. the This so called their more

Barkhausen magnetization

more

noticeable The

domains effect

change

directions

rotation.

latter

becomes

prominent when the strength of the field is increased. Fig 8.3

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107 In a polyerystalline material, magnetization is impeded by the random orientation of the grains. Consequently only some of the grains have their easy directions parallel in to the direction of the applied strains in field. their More over

magnetostriction

these

crystallites

produces

neighbors

which, In turn, affect the ease of magnetization in a more complicated way. Thus, if a material that is easily magnetized is it is necessary to Such find a it one material simply having does reaches desired say, for transfor mers, little not magnetic necessarily more anisotropy have rapidly. higher On is the an or

magnetostriction. saturation

magnetization,

saturation strong

hand, if a permanent magnet is desired, the

magnetostriction

asset. This is so because, once such a material is magnetized along a given direction, it is more difficult to change its magnetization direction.

Self 1.

Check Using

Exercise - 1 Langevin's equation, calculate the value of the constant in the

equation. 2. 3. Calculate from =eh/4p mc If xp = 1.732, calculate, curie constant at 300 K.

Self Check Exercise 2 1. 2. Discuss the ferromagnetism of Fe, Co, Ni Write a note on domain theory

Model Answer Exercise I 2. b= exh = 4p x m x c = 3. xp = C T C = xp x T = 1.732 x 300 = 5.19 x 102 = 5.19 x 102 4.8 x 10- 1 0 x 6.627 x 10- 2 7 4 x 3.14 x 9.1 x 10- 2 8 x 3 x 101 0 9.27 c 10- 2 1 erg/gauss

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108

8.3 Let us Sum Up Langevin equation is discussed paramagnetism and Caries law explained. Theories of ferromagnetism (for e.g., Zeners theory discussed in detail). 8.4 Point for Discussion 1. 2. 3. The curie The constant is characteristics of the material. susceptibility explain that is a 1 / T the is exchange due to an integral

are are

Paramagnetic theory negative to

Zener's always

ferromagnetism ferromagnetism

is

and

interaction

between electrons occupying quantum states in and 's' zones. 8.5 Reference:

the partially filled 'd'

1. Introduction to Solids Azaroff TMH Edn- New Delhi - 1960

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109 LESSON 9 CONTENTS 9.0 9.1 9.2 AIMS AND OBJECTIVES INTRODUCTION THERMOELECTRIC PROPERTIES AND THEORETICAL CXONSIDERATION MATERIALS

9.2. 1 GENERAL 9.2.2 MATERIAL

PRINCIPLES

PREPARATION

AND

THERMOELECTRIC

9.2.3 APPLICATIONS 9.3 9.4 9.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

9.0

AIMS AND OBJECTIVES

The aim of this lesson is to study the phenomenon of thermoelectricity and to learn the several applications and thermo of thermoelectric materials, After such as

thermoelectric

generations

electric

refrigeration.

studying

this lesson you would be able to

i) ii)

Understand

the

Phenomena

of

Thermoelectricity

Know about the synthesis and applications of thermoelectric materials like lead telluride, bismuth telluride.

9.1

INTRODUCTION In Several space crafts the source of electric power, is the

thermoelectric material like RTG (Radio Isotope thermoelectric geberator).

The

thermoelectric

material

uses

the

Seebeck

effect

and

the

reverse

phenomenon, the Peltier effect. The Seebeck effect converts the heat from a radioactive and the heat Peltier and source effect directly are the into electrical energy. The of Seebeck effect

principal with

elements

thermoelectrics t h e generation and

science

technology

associated

thermoelectric

refrigeration.

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110 9.2.1 GENERAL PRINCIPLES AND THEORETICAL CONSIDERATION

An electric

potential

(Voltage)

is

generated

with

any

isolated

conducting material that is subject a temperature gradient, this is the absolute Seebeck effect, (ASE). The absolute Seebeck coefficient (ASC) is defined as the instantaneous rate of changes of the ASE with respect to temperature at a

given temperature. ASC = d(ASE dT T

The simple example of the way in which this phenomenon is used is to form a thermocouple by composed of two dissimilar conductors, or

thermoelements,

electrically joining one set of their ends. The application

of a temperature difference or gradient, between the ends of the device will produce a voltage across its unpaired terminals that is a function of the temperature distribution. The resulting voltage is the relative seebeck emf,

'RSE"/ It results only from the difference between the internal potentials or ASE, within the individual conductors of which it is composed. Relative

seebeck coefficient is the variation of relative seebwck emf with temperature, i.e.

RSC

[d(RSE)/dT)]T . The seebeck effect is not affected by Thomson thermoelectric circuit. But seebeck effect exists as long as

or Peltier effects. Thomson and Peltier effects are present only when current flows in a

temperature gradient is maintained, regardless of whether current flows in the circuit or not . The greatest application of the seebeck effect is in thermal electric thermometry. This results from the fact that thermoelectric emf circuits obtained

convert thermal energy into electrical energy. The open circuit

this means is the RSE, which can be used to measure temperature. Thermo couples composed of standardized metallic conductors are widely used for the accurate sensitive, and reliable instrument and /or control of temperature.

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111 Peltier showed that heat is liberated or absorbed when a current crosses an interface between two different conductors. The peltier coefficient, p AB i s the change in the reversible heat content at the junction of conductors A and B w h e n unit current flows across it in unit time.

p AB = p A + p B. p A a n d p B are the absolute Peltier coefficients of the conductors. The direction in which current flows across a junction and the values p A a n d p B determine whether heat is liberated or absorbed. The

peltier effect is a result of the change in the entropy of the electrical charge carriers as they cross the junction. It is not an emf inspite of the fact that p AB can be expressed in energy units involving volts.

For a constant current the peltier effect is proportional to RSC, and at any fixed junction temperature, it is proportional to the current. These

reversible effects are independent of the shape or dimensions of the junction. This is different from joule heating which is a function of dimensions, does not require a junction and is irreversible.

The Thomson effect is the reversible change of heat content within any single homogeneous conductor in a temperature gradient when an electrical

current passes through it.

T h i s m a y occur in any non- isothermal

segment

of

conductor.

The

Thomson coefficient is the reversible change of heat content within a single conductor per unit temperature gradient per unit current flow. Thomson

termed it the "Specific heat of Electricity".

The Thomson effect is not a voltage. But it can be expressed in energy unit involving volts. Let be the relative Seebeck emf generated by the

temperature circuit.

difference

EA B . For a unit current flow in a thermoelectric EA B = d EA B T dT (1)

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112

The other energy factors in a closed thermoelectric circuit are Peltier effects and Thomson effects.

Peltier effect at the junctions. Heat absorbed at the hotter junction = Heat liberated at the colder junction = p AB (T + T) - p AB (T)

Thomson effect within the conductors; Heat absorbed in conductor B Heat liberated in conductor p a n d are peltier and Thomson show that for a unit current flow: dE A B dT dp AB + ( B A ) dT --(2) A = A (T) coefficient, respectively. It is possible to = B (T)

This thermoelectric

is

the circuits. It

fundamental shows the

thermodynamics relation

theorem

fo c l o s e d r seebeck

between

electrical

effect and the thermal Peltier and Thomson effects.

By a rigorous analysis it is possible to show that p

AB

~ dEA B dT

(3)

This devices.

equation shows

is why

helpful

in

understanding of

the

operation with

of large

peltier peltier

This

combination

thermoelements

effects must be used for power generation or refrigeration.

9.2.2 MATERIAL MATERIALS

PREPARATION

AND

THERMOELECTRIC

Compounds and alloys have

like, been

Bimuth

Telluride, and

antimony studied

telluride, for their

lead

Telluride

synthesized

thermoelectric

properties. The deviation in stoichiometry of the compound bismuth Telluride

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113 accounts for its usefulness as a thermoelectric device. Bismuth telluride has a hexagonal cell, which is formed by the stacking of layers as; Te
(1)

Bi -

Te ( 2 ) B i T e

(1)

The Te Bi Te ( 2 )

(1)

Te ( 1 ) bonds are of vanderwaals type while Te ( 1 ) Bi and ionic covalent type. The energy gap for Bi2 T e 3 Sb2 T3 have been obtained by travelling

bonds are of

was found to be 0.16eV at 300k and 0.18eV at Ok. For example binary compounds of Bi2 T e 3 and ingot) in a quartz

heatermethod. In this method a molten zone passes through a polycrystalline ingot (source ampoule sealed under high vacuum. The

source ingot is prepared by the synthesis

of high purity components with the

stoichiometric composition of the compound to be prepared (Bi2 T e 3 , S b 2 T e 3 ) . This method allows single crystals to be prepared at a temperature lower than the melting temperature and consequently of high quality. The transfer of the zone through the source ingot improves the purity of the material by a zone melting process. Single crystals of n and p type were grown by the traveling heater method, at different temperatures. In this preparation, the carrier concentrations on the p- type (~10 2 0 / cm3 ) are greater than the n- type. It is found that the change in type occurs at about 583o C. The concentration

of charge carriers is directly related to the concentration of inherent defects. These defects are responsible for deviation from stoichiometry. Sb T e 3 2 figure of

prepared by the above method shows p- type useful than S b 2 T 3 as a thermoelectric

conduction.

Bi2 T e 3 is a more

material.

Thermoelectric

merit is given by the relation. Z= a 2 / ( lp), where 'a ' is the seeback coefficient l = thermal conductivity and P = electrical resistivity.

Z is a common measure of the effectiveness of a material to function in a thermoelectric couple for heating or cooling applications various types of 'Z' meters have been developed for the measurement of figure of merit of thermoelectric materials. By measuring a , l and P, one can calculate 'Z' for any material. For example Bi2 T e 3 ( P - type) has a 'Z' value of Z. 10- 3 = 2.2 at

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114 582 o C . ' Z' has been found to be anisotropic. Along the 'C' axis Sb2 T e 3 has a Z value of 1.6 x 10- 3 K - 1 .

At present solid solutions of the compounds Bi2 , T e 3 , S b 2 T e 3 and Bi2 , Se 3 have the highest thermoelectric figures of merit in the tenperature range around room temperature. Lead telluride and alloys of Pb- Sn- Te have also been studied for thermoelectric characteristics.

9.2.3 APPLICATIONS 1. THERMOELECTRIC POWER GENERATION

Thermoelectric power from

power

generations generated

have in

been

employed

for

generating arrays

milli- microwatts a

miniature chip)

thermocouple to the

integrated nuclear As

into

semiconductor

microelectronic

multikilowatt

reactor

powered and sensors

generators. miniature thermocouple arrays (thermopiles) have in the

detectors

found wide applications as pyrometers and as sensor elements used measurement of magnetic, radiation, chemical and mechanical signals.

Thermoelectric generator consists of a large number of thermocouples connected electrically inseries to form a module the module is the basic

building block of the generator.

Heat from a variety of sources is applied to one surface of the module (referred to as the hold side) and rejected at a lower temperature from the opposite surface across (Cold the side/Heat module, power sink). electrical from Provided power a a temperature be difference to is an

maintained external

would

delivered is

load.

The

output

thermocouple

approximately

proportional to area and inversely proportional to the length.

The

best

known

medical

application

of

miniature

thermoelectric

batteries is in the cardiac pacemaker thin film thermo elements, deposited on glass slides (Bi2 T e 3 + Bi2 S e 3 and Bi2 T e 3 + S b 2 T e 3 ) have been employed for power generation.

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115

All of the currently available generators that operate on gaseous fuels (Propane or natural gas) are intended for stationary out door application. The output of these generators is fixed. The generators produce a constant amount of power. The thermoelectric converters used in commercial ther m o e l e c t r i c generators use either lead telluride or bismuth telluride.

The important data

heat

sinks

are of

usually

series

of

aluminium are

fins.

The

most

applications and

thermoelectric

generators

cathodic usually higher.

protection, used for

gathering

telecommunication. have out puts of

The generators 60W are

cathodic

protection

Thermoelectric

refrigerators (Peltier Cooling) are silent and have neither moving parts nor, gases to leak away. Thermoelectric refrigerator. of maximum refrigerators If the do not pollute generator coefficient the is of

atmosphere as operated under is

conventional conditions high.

thermoelectric power, the

cooling

performance

Self Check Exercise

-1

1. 2.

Explain

Seeback

effect

How are peltier and Thomson effects are different from seeback effect?

Self Check Exercise 1. Give the

-2 fundamental thermodynamic theorem for closed

thermoelectric circuits? 2. Explain the term 'Z'? How can it increase?

9.3 Let us Sum Up See back, Peltier and Thomson effects are explained. Thermoelectric material defined. synthesis is indicated. of Thermoelectric materials figure are of merit Z is

Applications

thermoelectric

indicated.

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116 Model Answers: Self Check Exercise -1

2)

The seeback effect is not affected by Thomson or peltier effects. T h e latter are present only when current flows in a thermoelectric circuit. But seeback effect exists as long as temperature gradient is maintained, regardless of whether current flows in the circuit or not.

9.4 Points for Discussion i) Absolute seeback resistivity materials. ii) The utility of thermoelectric materials in power generation and would coefficient, decide the thermal figure of conductivity merit of a and electrical

thermoelectric

applications have to be discussed.

9.5 References 1. Introduction to solids Azaroft Delhi 2 7

TMH Edition- Publisher Tata Mc Grahi H i l l New - New Delhi 2 7 2. CRC Hand Book of Thermoelectrics Edited by

D.M.Rowe

Ph.D,

D.Sc- CRC Press N.Y, London, Tokyo 1 9 9 5 .

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117

UNIT I V LESSON 1 0
CONTENTS 10.0 10.1 10.2 AIMS AND OBJECTIVES INTRODUCTION N- P- RATIOS DIFFERENT TYPES OF NUCLEAR FORCES 10.2.1 10.2.2 10.3 10.4 10.5 NEUTRON PROTON RATIO

NUCLEAR FORCES

LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

10.0

AIMS AND OBJECTIVES

To learn,

how

neutron/proton

ratio

helps

in

the

understanding

of

nuclear stability and to understand the basic nature of the forces that bind nucleons together

10.1

INTRODUCTION:

The

packing

fraction

is

an

important

concept

in

understanding

the

stabilities of nuclei. A negative packing fraction implies exceptional stability of the nucleus and a positive packing fraction suggests that the nucleus is somewhat less stable. This chapter describes the other important concepts

like n/p ratio and binding energy, in understanding nuclear stability.

10.2.1

NEUTRON

PROTON

RATIO

A review of the nuclear compositions and masses of various nuclides has revealed a number of general rules concerning the stability or instability

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118 of atomic nuclei. Consider the variation with increase in mass number, the ratio of neutrons to protons in the stable nuclides. The results are plotted with the number of protons (z) on the x- axis and the number of neutron s ( A Z) on the Y- axis. A line is drawn at an angle of 45o , so that points lying on this line represent nuclei containing equal numbers of protons and neutrons. For elements of low mass numbers the neutron t o proton ratio is equal to unity for stable nuclei of the 18 nuclides with mass numbers through 20, there are equal numbers of neutrons and protons in eight and a difference of only one in nine others. This exact equality is to be expected from the similarity of (P- P ) . ( n - n) and (n- p) forces. To maintain stability the number

of neutrons must exceed the number of protons. For the heaviest stable 206 nuclides, such as 82 Pb and 83 209 Bi, the ratio of neutron to proton is slightly

greater than 1.5. Each proton repels and is repelled by, all others present in the nucleus. As a result the electrostatic repulsive force grows rapidly with increase in atomic number. The total repulsive energy in a nucleus is roughly proportional to Z2 /R, Z is the number of protons and R is the radius of the nucleus. R varies as A1 / 3 (A=mass number). Hence electro static repulsion is determined by (Z2 /A 1 / 3 ). For e.g., the repulsion energy of protons in 209 Bi, is about ten times as great as that of 40 Ca (N/P = 1). 83 To attain stability, the heavier elements should contain larger proportion of neutrons. The additional (n- n) and (n- p) attractive forces then compensate for the growing p- p repulsion.

Nuclei containing even numbers of both protons and neutrons are much m o r e c o m m o n than any others. Nuclei containing odd number of protons and even number of neutrons and vice versa are equally common. But those

containing odd numbers of both protons and neutrons are rare. Stable nuclei contain even numbers of both neutrons and protons. Those odd numbers are very unstable. Thus six nuclides
48 16

containing Mg,
28

both
40

O,

24

Mg,

28

Si,

Ca,

Ti,

56

Fe, constitute about 80% of the earths crust. Thus a pair of neutrons neutrons may be regarded as constituting a sub- shell, leading to

and

of

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119 greater stability than would be the case for incomplete sub- hell i.e., with odd numbers of nucleons.

4 He is highly stable (2P and 2n). But 5 He and 5 Li which contain one 2 neutron and one proton more than 4 He expel the extra nucleon 9 Be,
13 13

respectively,

almost

instantaneously

C and

17

O, with one excess neutron are stable

nuclides. But 9 B,

N and

17

F with one excess proton are not. There are only

four nuclides of the odd- odd type = 10 14 B and N. The stability of 2 D, has been attributed to the 1 3 5 7 attraction of neutron and proton, having the same spacial co- o r d i n a t e s a n d D Li parallel spins. In the other three stable odd- odd nuclides, the numbers of 2 6

neutrons and protons are equal, so that the extra, unpaired neutron and proton probably have the same spatial coordinates. In 27 Na Al, the one extra neutron, causes stability in these nuclides 9 11 13 Sn(Z=50) is the only element with stable isotopes (115, 117 and 119). F 19 23

If the atomic number is odd, the element has few stable isotopes, never more than two. In general regardless of its atomic number no element (with exception of Sn), has more than two stable isotopes of odd mass number.

Isobars and b -decay

If

there

are

two

isobars

of

adjacent

elements,
3

with

atomic

masses

which differ by a small amount, the one with the larger atomic mass will tend to disintegrate by b - d e c a y c o n s i d e r 3 T a n d He. The atomic masses are

3.016049 and 3.016029 amu, respectively; the mass difference is thus only 0.00002 amu, equivalent to 0.018MeV. But tritium is radioactive, since it has the higher atomic mass, decaying to form 3 He, with the emission of

b - particle, having a maximum energy of 0.018MeV. Consider for e.g., Cd- 113

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120 a n d I n 113 and Sb- 123 and Te- 123. These pairs differ by 1 unit of atomic number. These pairs appear to be quite stable. The reason given for the stability is probably that the beta transitions are highly for bidden because of the large differences of nuclear spins. For e.g., the nuclear spin of Cd- 1 1 3 i n the ground state is , Whereas that of 1 1 3 In is 9/2 and the energy difference is small. It may be noted, however (isomeric state) the negative b - decay of a 'metastable' of 1 1 3 Cd with an estimated nuclear spin of 7 / 2 , has been

observed to the ground state of In- 113. It would appear therefore that Cd- 113 is beta active. In the pair Sb- 123 and Te- 123 also a similar situation exists. Te- 123 decays by orbital electron capture with a half- life of 1.2 x 101 3 years.

10.2.2 i)

NUCLEAR FORCES Packing Fraction: It is defined as : Packing fraction = Atomic mass mass number x 104 Mass number The following observation can be made when packing fraction is

plotted

against mass number. The packing fraction is high for elements of

low mass number, apart from (He- 4 ) , C - 12 and 0- 16), but it decreases rapidly w i t h m ass number. Then after passing through a flat minimum, the packing fraction begins to increase slowly but steadily. Negative packing fraction

implies exceptional nuclear stability. On the other hand a positive packing fraction suggests that the nucleus is somewhat less stable. Nuclides He- 4 , C 12 and 0- 16are very stable. Elements of high mass numbers having positive packing fractions are unstable and radioactive.

Determination

of

Binding

Energies

Binding energy is a more important concept in understanding n u c l e a r stabilities. True mass defect is obtained as follows: True Mass defect = (ZmH + (A- Z)m n )- M

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121 Zm H is the mass of the protons and (A- Z)m n gives the mass of neutrons. M is the experimentally determined atomic mass. The mass defect may be regarded as the loss of mass or more correctly the mass which would be converted into energy, if a particular atom were to be assembled from a given numbers of electrons, protons and neutrons. The same amount of energ y would be

required to break up the energy equivalent of true energy'.

atom into its constituent particles. Therefore the mass defect is taken as a measure of 'binding

Hence binding energy in MeV, is given by= Binding energy = 931.4[ZmH + (A- Z)m n - M]- MeV. The masses of the proton and of the neutron are respectively 1.007825 and 1.008665, amu. the atomic mass of 20 Ne, is 19.992440amu. A is 20 and Z=10. Therefore the binding 10 = 931.4[(10 x 1.007825) + (10 x 1.008665) 19.992440] = 160.6 MeV . 160.6/20 =- 8.0 (B.E per nucleon)

energy is

Self Check Exercise

-1 Bi,using the same values of

Calculate the binding energy for 209 83 masses for protons and neutrons. The atomic mass of this isotope is 208.9804 and also the B.E per nucleon.

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122 The binding energies of some of the lighter nuclides such as 2 D a n d

3

He are very low, but over a very considerable range of mass numbers, the

binding energy per nucleon is close to 8MeV. As mass number increases, the binding energy decreases to 7.6MeVper nucleon (say for Uranium). It is this diminution in binding energy which is the fundamental cause of the release of energy in the fission of nuclei of high mass number. Calculation of mean binding energy per nucleon indicate that - decay is common among elements with mass numbers exceeding 210.

Nucleon Nucleon Forces:

We have to understand the nature of forces which bind together the protons and neutrons in the nucleus. These forces are fundamentally different from the more familiar gravitational and electrostatic forces of attraction as well as from weak interactions involved in beta decay. The nucleon forces are known as short range forces, operating over very short distances only, of the order o f 1 0 - 1 3 cm. number of The binding This is energy attributed is to approximately the proportional character to of the the

nucleons.

saturation

forces between nucleons that is to say each nucleon attracts those in its immediate neighbourhood, but is relatively indifferent to the others. Thus the

nucleus may be compared to a liquid drop.

Each molecule in the drop attracts those with which it is in contact but has no influence on the more distant molecules. As a result, the total energy and volume of a liquid drop are proportional to the number of molecules it contains. The same is true of atomic nuclei; the binding energy and volume are related to the mass number, i.e., the number of nucleons in the nucleus. The existence of (p- n ) , ( p - p) and (n- n) forces of attraction can be proved by consideration of a few simple nuclei. The relative stability of the deuteron made up of one proton and one neutron shows that the (p n) force has

appreciable magnitude. Tritium contains an extra neutron. Its binding energy increases partly due to (n- n) forces. He- 3 contains 2 D+ 1 H 3 He

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123 1 1 2 contains an extra proton and its binding energy increases due to (p- p) forces. The binding energy of 3 T is greater that that of 3 He. It would appear that

(n- n) forces are larger than (p- p) forces. The interaction between two protons always involves a force of electrostatics repulsion. It looks as though that the attractive nuclear forces between two neutrons and two protons is essentially, identical. This result is referred to as the charge symmetry of the inter nucleon forces. The scattering of protons and neutrons by protons is studied with targets of hydrogenous materials. Such scattering studies indicate that

(n- p), (p- p) and (n- n) forces are equal.

This principle is known as the 'charge independence' of the nucleon force. Comparison of binding energies of certain isobaric nuclides e.g., Be- 1 0 , B - 10 and C- 10 confirms that nuclear forces are charge independent.

I n B - 10 however, the number of (n- p) forces is different from that in other two nuclides. Theoretical considerations indicate that if the nucleon forces

are charge independent, there should be an excited state of B- 10 with the same binding energy, apart from electrostatic effects, as the other nuclei in their ground states. There is evidence that such an excited state of 1 0 B exists. The remarkable constancy of charge independent principle. nuclear densities is also in agreement with

Characteristics

of

Nucleon

Forces:

There

is

undoubtedly

an

attractive

central

force

between

nucleons.

There is a force of attraction acting along the line joining the nucleons, that depends on their distance apart. This force is independent of charge, on the nucleons and is the same for all three types of nucleon pairs, namely (n- n) (n- p) and (p- p). It is a short range force that decreases sharply at distances greater than 10- 1 3 cm. Its magnitude depends on the directions of the spins of nucleons. Deuteron having a nuclear spin of 'One' (I=1) i.e., the proton and neutron have parallel spins, is stable.

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124 But diproton and dineutron, in which, the nucleons would have anti- parallel spins do not exist.

The magnetic properties of the deuteron can be accounted for only by postulating the existence of a 'tensor force' between the proton and neutron.

The magnitude of this force depends on the directions of spin axes of the nucleons with respects to the line joining the particles; but unlike the central force, it does not necessarily act along this line.

Another type of inter- nucleon force to be considered results from the interaction of the spin and orbital angular moments. Evidence for the spin orbit force comes from the scattering of protons by protons. The possibility o f s p i n - orbit interaction is also indicated by the success achieved in

arranging the nucleons in various groups or shells, in a nuclei. Nucleon Nucleon repulsive force also has to be taken into account. If the forces

between the nucleons were only attractive, with no repulsive forces , n e i t h e r the binding energy nor the nuclear volume would be proportional to the

number of nucleons. If the nucleus were to be stable, then there should be a repulsive force operating over a shorter range than the attractive force.

The Meson Field Theory of Nucleon Forces:

H.Yukawa proposed a theory of nucleon forces, based on an analogy with electromagnetic forces. The photon is referred to as the field particle of the electromagnetic field. Yukawa proposed that the (Strong) by interaction postulating

between nucleons might be accounted for in a similar

manner

an appropriate 'field particle'. He showed that the field particle could have a mass roughly 200 times the mass of an electron. Such a particle was

discovered in cosmic rays and is known as muon. But another particle heavier than muon was discovered in cosmic rays. This particle is known as pion and it is now called pi- meson.

The pion occurs in positive, negative and neutral forms and has a mass about 270 times the electron. It has properties like spin and parity which

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125 qualify to be the field particle. The theory of nucleon forces based on Pi meson may be stated as follows. Every nucleon is surrounded by a meson field through which it interacts with other nucleons, just as a charged body interacts with other charged bodies through an electro magnetic field. The

pion then serves the same function in the meson field as the photon does in the electro magnetic field.

Interaction between the two nucleons occurs by the transfer of a pion from one particle to the other. In order to account for the existence of the meson emitting field, and it is postulated positive, that neutrons and and protons are continuously mesons

absorbing,

negative

neutral

pions.

These

remain free for such an extremely short time that they are undetectable and these mesons are called 'Virtual Mesons'. The meson has a mass of about 270Me. The uncertainly in energy corresponding to this is about 2.22 x 10 - 1 4 erg. Hence the time interval in which a virtual meson can exist without being detected is about 5 x 10 - 2 4 sec.

E x t = h/2 ;

t =

h 2 x E

= 6.63 x 10- 2 7 2 x 3.14 x 2.22 x 10- 4 5 x 10- 2 4 s e c

The distance a meson can travel and get remain undetected is 5 x 10- 2 4 x 3 x 101 0 cm/s = 1.5 x 10- 1 3 cm (3 x 101 0 cm is the maximum speed of meson) This distance is close to the range of nucleon forces; hence the concept of virtual emission of mesons appears justified.

The force between a proton and a neutron could result alternatively from the transfer of a positive pion from the proton to the neutron and the transfer of a negative pion from neutron to proton.

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126

P ++ n o Initial state P ++ n o Initial state

Po

+ Pion Transfer

no

no + P+ Final State

P+

no

no + P + Final State

i.e., the positive proton is converted into a

(neutral) neutron and vice versa,

leaving the combination unchanged. In such a change from one nucleon to the other, the spin angular momentum is conserved. Experimentally it is known that the spin of Pi- meson is zero. (Neutron and proton each have a spin of ). The interaction of a Pi- meson field is called strong interaction. Coupling

constant calculations shows that for the pion- nucleon field, the value of the coupling coupling constant is about 15. It is about 2000 times greater than the

constant of an electromagnetic field.

Repulsion has been accounted for by the transfer of two or three pions between nucleons.

Self Check Exercise 2

i)

Discuss the concepts of 1) 2) N/P ratio and Binding energy

ii)

Discuss in detail the different types of nuclear-

nucleon forces.

10.3 Let us Sum Up Packing fraction and finding energy calculations are explained. N/p

ratio and like different types of nucleon forces are discussed. Meson theory is also discussed.

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127 10.4 Points for Discussion

i) ii) iii)

Packing fraction and binding energy curves. N/P ratio and the stabilities of nuclei Nucleon Nucleon forces- strong interaction pions and heavier mesons.

10.5 References

1) 2)

Atomic physics J.B.Rajan. S.Chand & Co, New Delhi. Source book on atomic energy Glass tone East- West press, New Delhi.

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128

LESSON 1 1
CONTENTS

11.0 11.1 11.2

AIMS AND OBJECTIVES INTRODUCTION NUCLEAR STRUCTURE 11.2.1 11.2.2 11.2.3 LIQUID DROP MODEL SHELL MODEL COLLECTIVE AND UNIFIED MODEL

11.3 11.4 11.5

LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

11.0

AIMS AND OBJECTIVES

To study and understand the behaviour of nucleus on the basis of different types of models proposed for the nucleus.

11.1

INTRODUCTION

The forces between the nucleons could not be explained quantitatively and hence several models have been proposed for the nuclear structure. The liquid drop is discussed point first of and view, then can the be shell model, The representing collective a and

diametrically

opposed

discussed.

unified models. Combine certain features of the other two models.

11.2.1 LIQUID DROP MODEL

Since proportional character)

the to

binding the nucleus

energies of been

and

volumes

of

nuclei

are

approximately saturation N.Bohr

number has

constituent compared

nucleons, to a drop

(indicating of liquid.

the

proposed the liquid drop model of the nucleus to explain nuclear reactions on the basis of compound nucleus theory. According to this model, each nucleon

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129 in a nucleus interacts with adjacent nucleons, in the same manner as

molecules in a liquid. Hence any excess energy of a given nucleon would be very rapidly shared among the other nucleons. The energy levels of the

nucleons are thus regarded as quantum states of the nucleus (or liquid drop) as a whole, rather than of a single nucleon. The application of the liquid dro p model in nuclear fission has already been considered. Other achievements of the model related to nuclear binding energies and the properties of isobars will now be considered.

calculation

of

Nuclear

Binding

Energies.

Since nuclear forces are of a short range character each nucleon will be held strongly by those in the immediate vicinity. But each will be unaffected by the others. As a result, to a first approximation, there will be an attractive (or volume) energy, proportional to the number of nucleons in the nucleus; in other words the energy term will vary approximately as the mass number, A. This energy can be represented as a1 A, where a1 , is a constant. This value of energy of attraction is correct when the number of protons is equal to the number of neutrons. But most nuclei contain an excess neutron. These extra neutrons are inevitably in higher quantum states, than the other nucleons and they contribute a smaller amount (Per nucleon) to the total bin d i n g e n e r g y . Statistical calculations indicate, the energy corresponding to this 'asymmetry effect' or composition effect, can be represented as : - a 2 ( A - 2Z) 2 / A , where (A2Z) is the neutron excess and 'a2 ' proportional to = - a 3 ( Z 2 /A
1/3

is

constant.

Long

range

electrostatic

forces due to repulsion of protons, decrease the binding energy by a quantity ), where 'a3 ' is a proportionality constant.

The nucleon at the surface of the nucleus will be less tightly bound than those in the interior. The binding energy is reduced by an amount,

proportional to the surface area of the nucleus. This 'surface effect' is given by the term = - a 4 A 2 / 3 ( A 2 / 3 is the area). The influence of even or odd- odd nuclei can be represented a term = a 5 / A + sign corresponds to even e v e n nuclei and sign to odd- odd type.

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130

by adding all the above mentioned terms, the binding energy B.E can be written as: B.E. = a1 A a2 ( A - 2Z) 2 a 3 Z2 a 4 A2 / 3 a5 / A A A1 / 3

- - - - (1)

the five constants must be known for calculating B.E. a3 can be obtained from electrostatic obtained theory. The other four constants are empirical respect and to can Z be and

from

experimental

data.

Differentiating

with

equating to zero, 'a 2 ' can be calculated. a5 is zero for an odd- even or an evenodd nuclei, the two remaining constants, and a4 can be calculated from the known binding energies of any two nuclides of this type. The spin effect constant nuclei. a5 is obtained empirically from binding energies of even- even

Inserting these constant in equation (1) we have: B.E.(MeV) =15.75A 23.7 (A- 2Z) 2 0.710 A Z2 A1 / 3 - 17.8A 2 / 3 130 A ..(2)

The relative effects of the various factors on binding energy can be seen by performing calculations for nuclides of low, medium and high mass numbers. 40 Ca, B.E. per nucleon is about 8.52MeV. 20 The estimated binding energies for 40 Ca 20 50 120 Sn a n d 238 U are 92

342, 1019and 1805MeV, compared with values 342, 1026 and 1800 MeV, respectively derived from atomic masses.

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131 Self Check Exercise 1

Calculate

the

binding

energy/nucleon 120 sn and

for 238 U using the

above

50 92 equation and tabulate the values corresponding to the different effects.

The

Values

agree

well

with

the

observed

binding

energies

upto

three

significant figures.

For

elements is

of

high due

atomic to the

number, marked

the increase

decrease in the

in

binding

energy/nucleon

mainly

electrostatic by

repulsion of the protons. This is responsible for the a - particle elements of high atomic numbers and also for the

emission, of

liberation

energy

accompanying

nuclear

fission.

By plotting the binding energy against atomic number, of nuclides of odd mass numbers, a parabolic curve can be obtained. All isobaric nuclides whose binding energies are less than that of the stable nuclides, will lie on

the two arms of the parabolic curve. They will be unstable and decay in an appropriate manner. The nuclides of lower atomic numbers (on the left arm of parabola) For e.g., 73 Zn 30 31 b73 Ga b73 Ge (Stable) 32 would exhibit negative b - decay.

Isobars on the right arm of the parabolic curve have more protons and decay either by the emission of positron or by electron capture. 73 Se 34 33 b+ 73 As 32 Ec 73 Ge (Stable)

For isobars of even mass number, the results are different due to the inclusion of the odd- even (spin effect). For all nuclides with even numbers of protons and neutrons, the bindings energy is increased, and for those with

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132 odd numbers of protons and neutrons, it is decreased. This indicates that no s t a b l e o d d- odd nuclide should exist. For isobars of odd mass numbers, the instability is greater and hence the half life should be shorter. In a chain of b - disintegration, the half- life increases regularly as

stability is approached. For e.g., in the chain (b - decay) 133 Sb 51 133 Cs 55

(stable) the half life increases from 2.3min to 5.3days as Cs is approached. For even mass numbers also a similar effect in noticed = 140 xe 54 16s 140 Cs 55 1.1min 140 Ba 56

11.2.2

NUCLEAR SHELL MODEL

This model is sometimes referred to as 'independent particle model'. It is based on the fact that there are specific numbers of protons and neutrons, generally known as magic numbers or shell numbers, for which the nuclei exhibit exceptional stability. This is like atoms containing certain numbers of closed shells of electrons. T.H.Bartlett indicated the possibility that nucleons

might occupy quantum groups or shells just as electrons in an atom.

It was pointed out that the concept of nuclear shells could explain the magnetic moments of nuclei. Magic numbers of nucleons are 2,8,20,50,82 and 126. These apparently represent closed shells in the nucleus. Elements having the largest numbers of stable isotopes are those containing 20 and 50 protons or 20, 50 and 82 neutrons. Sn- 50 has ten isotopes and also three isotopes of odd mass numbers (115,117 and 119). The more abundant nuclides in the universe are those with magic numbers of neutrons or protons 16 O 8 40 20 Ca etc,

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133 Nuclides containing magic numbers of neutrons, have small cross sections for neutron 126, capture cross (they are stable). When the neutron numbers are 50,82 or for neutron capture are much lower for 1MeV

the

sections

neutrons.

Similarly for thermal neutrons, extremely low cross sections for (n, ) reaction are observed, when the nuclei contain 20, 50, 82,or 126 neutrons. Excited nuclides 17 87 137 O kr xe lose neutrons 8 36 54 readily to get the magic number of neutrons. The alpha particle energy is exceptionally the magic large, number when the decay during product the (daughter nuclide), of belongs the to

category,

radioactive

decay

heaviest

nuclides.

The end products of the four 206 Pb 82 207 Pb 82 208 Pb 82 and

radioactive 209 Bi, 83

series, contain magic numbers.

The following also can be correlated with the special stability of magic numbers. 1) 2) High binding energy of the last neutron in such nuclides. The departure of the total binding energy determined from the atomic mass from that calculated using equation (2) 3) a particle emission among isotope of certain elements of medium

mass number. 4) The non existence of stable isotopes of elements 43 and elements 61. 5) The variation of quadruple moments with the numbers of neutrons and protons.

Hence the behaviour of atomic nuclei, can be correlated with excess or deficiency of nucleons, with respect to closed shells of magic numbers just as

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134 the chemical and spectral properties of atoms are dependent deficiency of electrons. on excess or

In the shell model each nucleon is essentially independent of the other. The other nucleons provide the potential energy field which determines the quantum states and hence the numbers in closed shells. In the shell model the c o u p l i n g ( l - s) nucleons (magic concept is employed in different to account for the total number of

numbers)

shells. Each 'l' levels is split into two

sublevels characterized by the j term.

j=l+

and

j=l-

(except

l=0).

Each

of

these

sublevels

can

accommodate (2j+1) neutrons and (2j+1) protons. For eg., when l =1, j= 3 / 2 and (2j+1) = (2 x 3 / 2 +1) = 4 nucleons with j = (3 / 2 ) and (2j+1) = (2 x +1) = (2 x + 1) = 2 nucleon with j = , written as (3 / 2 ) 4 and () 2 ; arranged in this manner each shell can have a magic number of nucleons such as 2,20,50,82, and 126 l=0 will have '2' nucleons l=1 will have 8 nucleons etc

The spin of a nucleus with odd mass number, in the ground state should 123 depend only on the odd nucleon. The nuclide Sb has one proton beyond 51 the closed shell of 50 and its spin is 7/2, as expected l=4 and j=l- = 4- = 7/2. The shell model gives a qualitative interpretation of the observed

nuclear magnetic moments, by relating this property to the j value of the odd proton, certain groups of two or three isotopes of odd atomic number and odd mass number have identical spins and closely similar magnetic moments e.g.
107 109

Ag and

Ag; In 113 and In 1 1 5 ;

The quadrupole moment is a measure of the deviation of the charge distribution, in a nucleus from the spherical form. of nucleons should have a sphericlaly symmetric Nuclei with closed shells charge distribution, and

therefore zero quadrupole moment. Experiments indicate that this is true.

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135

For nuclei beyond closed shells, the quadrupole moment is negative. The quadrupole moment of an odd proton is not very different fro t h a t m caused by an odd neutron. The shell model predicts that a proton would

produce a greater distortion in the spherical charge distribution and give a larger quadrupole moment. This is a failure of the shell model.

11.2.3 This

Collective and unified model model differs in a fundamental respect from the independent As a the

particle model by postulating, a mutual interaction between nucleons. result of the collective or co- operative action among the particles,

nucleus behaves like a drop of liquid and may suffer permanent deformation. The deformation is not stationary. This travels around the nucleus producing motions which are equivalent to oscillations and rotations of the nucleus as a whole. the collective model requires a distortion of the nuclear core, and an When the shells, the

associated quadrupole moment, when the odd particle is a neutron. numbers of nucleons are in between the values for closed

collective model predicts larger quadrupole moments than expected from the independent particle model.

On the basis of collective models, the nuclear- rotational have been postulated. number. 220).

energy

levels

The levels have integral values of rotational quantum

Consider the nuclei with mass number from 150 to 190 (and over They lie between closed nucleon shells, such nuclei, with large

deformation, have their nuclear rotational energy levels very close.

For nuclei with numbers of nucleons, near to closed shells, the spacing of rotational energy levels are large. levels should also be considered. superimposed, like ordinary In such nuclei, the vibrat i o n a l e n e r g y

Vibrational and rotational energy levels are

molecules.

Rotational energy values for Pu- 238 have been determined and are very close to the theoretical ratios of the energies.

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136 The unified model of the nucleus is an attempt to combine the desirable features of both the concepts. According to this model the individual

nucleons move in a potential field that can be deformed, especially in the regions between closed shells. Because of this distortion, the order of filling

of the nucleon quantum states is often different from that required by the independent particle model. Other states have also been introduced to

explain the various energy levels.

These are known as "Nilsson Sta e s " . t

Thus this model has been able to explain the behaviour of nuclei, such as magic numbers, spins, quadrupole moments, low energy excited states etc.

Self 1.

check exercise 2 Discuss the liquid drop model and indicate how binding energies can be calculated on the basis of this model.

2.

a) b)

Write an account of the magic numbers. Discuss the shell model on the basis of closed shells of magic numbers.

3.

Write a note on collective model.

11.3 Let us Sum Up T h e d i f f e r e nt types of nuclear models are discussed in details. Their successor and failures in explaining the behaviour of nucleus are also

indicated. Calculation of finding energy and the various effects involved is illustrated. 11.4 Points for discussion 1) Different types of nuclear models and their successes and failures in explaining the behaviour of nucleus 2) Calculations of binding energies and the various effects involved.

11.5 References 1) Delhi. Source book on atomic energy. G l a s s t o n e East West press N e w

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137 LESSON-12 CONTENTS 12.0 12.1 12.2 AIMS AND OBJECTIVES INTRODUCTION NUCLEAR PARTICLES 12.2.1 NEUTRON 12.2.2 12.3 12.4 12.5 ELEMENTARY PARTICLES

LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

12.0

AIMS AND OBJECTIVES

The aims and objectives of this lesson are is to learn, the discovery of neutron and understand a few other elementary particles.

3.1

INTRODUCTION

This lesson describes the discovery and properties of neutron. A few elementary particles such as mesons etc are also described. The primary

radiation arising from the bombardment of 'Be' by -

particles was thought

t o b e - rays. But Chadwick proved that the particle obtained in the above reaction was uncharged, with a mass approximately that of the proton. 9 Be + 4 2 4 He 6 12 C+ 1 n+Q 0

3.2.1 NEUTRONS

Chadwick obtained the mass of the neutron using the reaction: 11 4 B + He 5 2 14 N + 7 0 1 n

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138 Since the atomic masses of the nuclides B- 1 1 , H e - 4 and N- 1 4 , a r e known the mass of the neutron can be calculated using the Q va lue of the r e a c t i o n . T h e a - p a r t i c l e ( H e- 4) obtained from polonium had on energy of 5.25MeV. The mass equivalent of this will be 0.00565amu 'Q' of the reaction in mass unit = - 0.00154. For B- 11, He- 4 and N- 14, Chadwick used the v a l u e s

of 11.00825 amu, 4.00106 and 14.0042 amu respectively. From the Q value and the other atomic masses, Chadwick obtained a value of 1.0067amu. For the neutron mass. 2 D + 1 1 From the reaction. 1 H + 0 1 n;

more accurate value of the mass of the neutron was obtained as 1.00867am. In the C- 12 scale the values is 1.008665amu.

Radioactivity of the Neutron:

I n t h e b - decay, a neutron is converted into a proton and an electron together with an antineutrino. If the mass of the antineutrino is zero then, 1 n 0 1 1 H + -1 o e

would involve an energy release of 0.782MeV. 1.008665 amu (for 1 n) and 1.007825 amu for proton ie., (1.0086650 1.007825)= 0.000840amu.

This

corresponds

to

the

energy

of

0.782MeV.

Since

the

energy

is

released in this reaction, it would occur spontaneously. The half- life for this b - decay can be shown to has been found to be be about 20min. Experimental values of half life 700sec. This is in agreement with the calculated

value(~20min). Hence it can be proposed that the free neutron is radioactive and disintegrates with the emission of an electron, leaving proton as a

residual particle.

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139

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140 Diffraction Neutrons

Neutrons diffraction. In

like other

other words

particles neutron

(proton, a - particle should have

etc) wave

should properties

exhibit like

electrons, in accordance with Debroglie's

relation l = h/mv.

Experimentally

neutrons

were

found

to

be

diffracted

by

crystals

like

sodium chloride, like X- rays. The energy 'E' of the neutron is kine t i c e n e r g y equal to MV2 ; l = h 2mE 6.627 x 10- 2 7 2 x 1.67 x 10- 2 4 x 1.6 x 10- 1 2 E 1.67 x 10- 2 4 =m (mass of neutron) l = 2.87 x 10- 9 E diffracted l would have to be 2 x 10- 8 cm cm, where 'E' is in electron volts

l =

For

neutrons

to

be

and

hence

neutrons having 0.02ev would exhibit diffraction phenomenon with crystals.

Self

Check

Exercise 1 wavelength of neutron having an energy of 0.06ev.

Calculate the

Compare this with that of an electron, having the same energy.

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141 X- ray diffraction depends only on the number of orbital electrons of the

atom. Hence it is not feasible to detect positions of hydrogen and other light atoms, by X- rays. In the diffraction of neutrons, however , it is in the scattering by the nucleus, which determines the extent of diffraction. In this respects, the effect of hydrogen, is quite considerable. Hence neutron

diffraction makes possible the location in crystals of hydrogen and other light atoms. Alloys of cu and Ni are studied easily by neutron diffraction. A fair yield of neutron can be obtained by (a ,n) reaction with

Beryllium.
2

D ( ,n) 1 H

and 9 B e ( ,n) 8 Be

have

been

largely

used

to

produce

neutrons. These are photo neutron reactions. Slow neutrons can be detected by their reactions with B- 10; 10 B + 5 1 n 0 7 Li + 3 2 4 He + 2.5MeV

This energy is carried off by Lithium and alpha particle. These produce considerable ionization in their tracks. By using a chamber of suitable and using enriched B- 10, every neutron entering the chamber can be counted by a counter.

3.2.2 ELEMENTARY PARTICLES i) Antineutron The antineutron, like the positron and antiproton, however would not be a constituent of ordinary matter. After the availability of a fair source of antiprotons, antineutron was discovered. When a proton and and antiproton, meet to mutually other, for annihilation although takes place. If the two particles come fairly close not close to be enough for annihilation from of this positive both to occur, to it is the

each

possible negative become

electric

charge or vice

transferred Because

proton

antiproton electrically +

versa.

part c l e s w o u l d i

neutral. neutron + antineutron

Proton

antiproton

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142 Antiprotons produced by means of Bevartron, were allowed to enter a vessel of liquid with hydrogen. hydrogen to About form three out of every thousand antiprotons the

interacted

antineutron.

The

neutron

annihilated

antineutron produced, and energy was released. A flash of light in a detector accompanied the release of energy. Although neutron is electrically neutral, it has the properties of a small magnet, associated with charge. It is possible that the neutron has some a spinning in negative an

structure

which,

electrically charged centre is surrounded by a region of opposite charge. It can be assumed then, while spinning in the same direction, the neutron and antineutron will produce oppositely directed, magnetic fields. It has been

established that an antineutron can exist so that there is an attractive force between antiproton and antineutron.

ii)

Muons and Mesons:

The heavier

existence

of

both and

positive lighter

and than

negative protons,

particles in

having

masses was

than

electrons

cosmic

rays

established. These particles were produced in the laboratory and were found to have a mass about 206.8times that of an electron.

These particles are now known as "muons ' C m -

particles) Both positive

and negative muons are singly charged particles. They carry a charge positive and negative equal in magnitude to that of an electron.

negative

muon

interacts

with

proton

in

an

atom

produc n g a i negative

neutron plus energy. If this does not occur within 2 x 10- 6 muon

seconds,

breaks down spontaneously into an electron, together with a neutrino

and antineutrino, and energy. Mean life time of a negative muon is about 2.3 x 1 0 - 6 seconds. Positive muon does not generally interact with matter. It has the same mean life time as negative muon. It decays to positron and energy. m+ ( o r m - ) e + (or e- ) + neutrino + antineutroni + energy

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143 Pi-Mesons (or pions)

Pions having masses intermediate between the electron and proton were found in cosmic rays. These particlescalled pi(or ) Mesons have also been produced in the laboratory. They occur in three forms + , - and the third is electrically neutral, o . + is and lighter mesons (264.3times have that masses of 273.2times electron) (- )

h e a v i e r t h a n e l e c t r o n . o

interacts with proton more readily than m - to form a neutron. - + p n+ or n+ o

They decay giving muons thus: + -

m+ neutrino + energy m - antineutrino + energy

+ and - mesons have a mean life time of 2.6 x 10- 8 sec (less than 100 times that of a muon) o mesons have a very short life and hence are not observed in cosmic rays. In the laboratory o was produced by bombarding Beryllium, carbon or other element with protons of high energy. Neutral pion has a lifetime of 10- 1 6 seconds. o decays very rapidly; all its mass is converted

into energy. In o , the particle and antiparticle are indentical.

K-Mesons or KAONS

Another

particle

having

mass

between

electron

and

prton. It is the

Kmeson or kaon. K- meson exists as positive and negative and in two neutral forms. The charged K- mesons have the same mass, namely 966.6electron masses. They have the same life time: 1.2 x 10- 8 sec. Each type of charged kaon can decay in six different sometimes with e or e
+

ways,

the

products

being

pions,

muons,

and a neutrino (or antineutrino) negative kaons can

inter act readily with protons in atoms.

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144 12.3 Let us Sum Up i) Neutron; its discovery and different types of neutron reactions are d iscussed Neutron diffraction method is explained. ii) Elementary particles like a) antineutron; b) muons and mesons; c) pions; d) kaons are discussed. 12.4 Points for Discussion 1) a) b) Write notes on: Neutron its discovery, reactions and diffraction methods. Different types of elementary particles.

12.5 References 1) Source book on atomic energy. Glass tone East West press New Delhi.

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145

UNIT V LESSON 1 3 CONTENTS 13.0 13.1 13.2 AIMS AND OBJECTIVES INTRODUCTION ALPHA, BETA, GAMMADECAY, NUCLEAR ISOMERISM

13.2.1 ALPHA, BETA- AND GAMMA DECAY THEORIES 13.2.2 13.3 13.4 13.5 NUCLEAR ISOMERISM

LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

13.0

AIMS AND OBJECTIVES The aims of this lesson are to study and understand the theories

concerned with the decay of , b a n d particles. After going through this lesson you would be able to learn the existence of nuclear isomers.

13.1

INTRODUCTION

Radio elements either in the pure state or as compounds emit radiations quite spontaneously and without any preliminary treatment. In this lesson, the p r o p e r t i e s o f , b a n d rays would be reviewed and theories of concerned with the decay of these particles would be studied. In the magnetic field rays are not affected at all, the b particles are considerably deflected and

the direction of, deflection indicates that they are negatively

charged. The

- rays are also deflected in a magnetic field and the direction of deflecti n o indicates they are positively charged. Certain radio elements emit - particles which nothing are identified with Helium nuclei. Since outside the nucleus except

electrons

exist,

the - particles must be supposed to proceed out of

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146 the nucleus it self. b - particles identified with electrons should also arise

from the nucleus. The emission of b - particles is irreversible and the b - decay gives rise to a new atom, which is different from the parent atom. Henceb particle cannot be extra nuclear electron - rays have been identified with

electromagnetic radiation ' '- rays emitted are of extremely short wave length. Any radiation of shorter wavelength, as at least some of the - rays are, must therefore come from nucleus.

Another type of radioactive decay i.e., by isomeric transition, has been brought to light by a study of artificial radionuclides, although it is actually an aspect of of of the familiar gamma ray emission. different known as F.Soddy radioactive nuclear predicted the

existence, Substances

isobaric this type

isotopes have

having become

prop erties. isomers. The

phenomenon is known as nuclear isomerism.

THEORY OF ALPHA DECAY

In experiments on the scattering of - particles, it was found that even the fastest of such particles from radioactive sources, having an energy of 10MeV, are generally repelled by atomic nucleus. It is an undoubted fact that radioactive nuclei emit alpha particles, hence such particles must be able to exist, at least for a short time within such nuclei. The interaction between a radioactive nucleus and an alpha particle (inside or outside the nucleus) can be understood by a potential energy diagram i.e., a plot of potential energy v s distance from centre of nucleus. The diagram shows increasing electrostatic repulsion of an alpha particle as it approaches the nucleus. The sharp fall in potential energy indicates the region within the nucleus. This implies

attraction of the alpha particle by the nucleons in the nucleus. The potential barrier represents a repulsive force. It can be shown that the force of

repulsion between a proton and a nucleus is less than for an alpha particle, whereas there is essentially no repulsion between a nucleus and a neutron calculations indicate than an alpha particle must have an energy of 25MeV to

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147 get into the nucleus from outside. Therefore an alpha particle must have the same out of energy to escape from the nucleus.

In other wards a potential barrier prevents the escape of the - particle from the nucleus. But - particle are produced from radioactive sources with

energy as low as 4 MeV, and for no natural element does the - particle energy exceed 10.6MeVwave mechanics shows that there should be a

definite, if small, probability that such a particle from the interior will be found outside the nucleus. In other words, there is a definite probability that the alpha particle will escape from the nucleus even when its energy is less than that of the top of the hypothetical barrier.

It follows, therefore, that greater the energy of the alpha particle in a radioactive atom, the more likely is it to be found outside the nucleus. This is the fundamental basis of the fact that radio elements which disintegrate

rapidly emit alpha particles, of high energy and long range, whereas the long lived elements produce particles of relatively low energy and short range. An approximate value of the frequency with which alpha particles reach the

exterior surface of the nucleus can be obtained by dividing the radius of the nucleus expressed escape, by as the the the result estimated number would speed per give of the is alpha particle. by If the this frequency of

second the

multiplied with

probability alpha

frequency

which

particles

actually escape. The value of l (decay constant) will in general be larger the greater the energy of the - particle. mechanical treatment leads to a Using simplifying between assumptions, the decay the wave

relationship

constant,l

and the energy of the alpha particle. This equation is similar to the Geiger Nuttall rule.
3

Log l =

/ 2 A log Eo+B1 . 'A' is the slope when log l is plotted against

E o . B 1 is a constant for each radioactive series. The wave mechanical theory of - decay shows that for naturally occurring radio elements, the energy of the alpha particle must be at least 3.8MeV, if the decay constant is to be

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148 greater than 10- 2 0 s e c - 1 . Thorium with a half life of 1.39 x 101 0 alpha particles with the lowest energy, 4 MeV. Assuming the radius of the nucleus is about 10- 1 2 cm and the speed of the alpha particle moving in the nucleus as 108 cm/sec, then an alpha particle would find itself at the exterior of the nucleus. 108 /10 - 1 2 = 102 0 time/sec. If the decay constant say for Th- C' is 107 s e c - 1 , then the alpha particle escape probability would be: 10 2 0 x escape probability = l 10 2 0 x escape probability = 107 then escape probability = 107 /10 2 0 = 10- 1 3 years emits

This means even with a very s h o r t - lived radio element Th- C', an alpha particle with an energy of 9 MeV, makes on the average, 101 3 escape from the nucleus. For Th the escape probability is 1/103 8 THEORY OF b -DECAY When b - particles the emitted energy a of b - particles is plotted against the number of is observed (Emax). From the energy attempts to

maximum

distribution it can be shown that the average energy of the b - particles from a given source is during emitted considerably the as b of less than the maximum indicated energy. the Energy electrons

considerations which are

emission

of b - particles

that

rays by radioactive nuclei must result from the a neutron into a proton by the and electron. of Pauli another

spontaneous suggested

conversion that this

process

was

accompanied

emission

particle, called a neutrino, this was assumed to be electrically neutral and to have very small rest mass, compared to that of the electron. 1 n 0 1 1 Proton + -1 0 electron + 0 0 neutrino

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149 I n t h e b - decay electron and neutrino of process are the proton In remains to in the nucleus, for the that but t h e continuous the total

ejected.

order

account

distribution

energy

among b - particles

Pauli

suggested

available energy, equal to Emax, was divided between the electron (b particle) and the neutrino. Thus the difference between Emax and the actual value for any b - particle would be carried off by neutrino. If a spin quantum number of is assigned to neutrino, spin can be conserved neutron into a proton and electron (b - particles ). b - decay is an example of the phenomenon known as weak interaction in contrast interaction and to the stronger electromagnetic For are interaction and the no even barrier stronger exists of the in the conversion of a

between long

nucleons. half lives

emission accounted

of b - particles for by the

relatively

weakness

interaction between the neutron and proton with the electron neutrino field. POSITIVE b -DECAY: Nuclei having too many protons, for stability emit positive b - particles, called positrons. 1 P 1 0 1 n + +1 0 e + 0 particles have a continuous distribution of 0 neutrino

The energies of positive b -

energy. The emitted neutrino shares energy with positron and also conserves spin.

GAMMA RAY EMISSION

Gamma

rays

are

electromagnetic

in nature

like

other

radiations,

one

might say these rays emitted by radioactive nuclei are merely the excess of energy radiated away in the form of quanta by the excited nucleus returning to a more stable state- Experiments indicate that this is actually the c a s e . T h e - ray emission is usually Owing accompanied to the by o r b of o r b disintegration, particle of a the

radioactive

nucleus.

emission

from

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150 nucleus, from the nucleus becomes to excited another and of hence transition with can the take place

this

excited

state

lower

energy

consequent

emission of the excess of energy as a '- ray. If there are several lower states transitions may take place to these states giving rise to ' ray ' spectra.

''- ray spectrum has been experimentally observed. Certain atoms are known to disintegrate without emitting '- ray e.g, RaE emits b - particles without resulting product nucleus

- ray emission. After the b - particle is ejected the

is left in an excited state, which therefore returns to the normal state by the e m i s s i o n o f - rays. As regards the - rays associated with d i s i n t e g r a t i o n ,

there are reason to believe that the - rays may be emitted either before or after the departure of - particles.

INTERNAL CONVERSION OF GAMMA RAYS. Information concerning gamma ray energies has been obtained from the

phenomenon now known as 'internal conversion'. In emerging from a nucleus the - ray (photon) may produce a kind of photo electric effect with one of the orbital (or extra nuclear) electrons of the same atom. As a result, the

energy of the photon is transferred to the electron. The - ray is then said to be 'internally converted'. The electron which interacts with the - r a y p h o t o n is ejected from the atom with kinetic energy 'E- P' where 'E' is the - ray energy and 'P' is the binding energy of the electron in the atom of the element e m i t t i n g t h e - radiation. This is presumed to be the daughter element in the given disintegration. If the ejected electron came from the K- level of the atom then, 'P' can be replaced by Ek. Ek is the energy of the K- line of the characteristic X- rays of the daughter element. Hence kinetic energy o f t h e then kinetic

ejected electron is E- Ek. If the electron comes from the L- Level, energy of the ejected electron is E- EL.

As a result of internal conversion a number of groups of electrons having discrete energies are emitted. Because of their definite energies, the

internal conversion electrons are said to give a line spectrum, which is super imposed upon the continuous spectrum of beta particles. As a general rule

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151 only a small proportion of the - ray converted. The fraction of the photons so have their e n e r g i e s i n t e r n a l l y called the internal

energy

converted,

conversion coefficient depends on the energy of the gamma rays.

The energies of the internal conversion electrons have been determined by the magnetic spectrograph. If to these are added the energy values for the appropriate daughter K,L etc., the lines sum of the characteristics give the X- rays of spectrum the - ray Ra- C, of prior the the to

element, For

should

energies Ra- B

conversion.

example in

the conversion of

energy of the electron emitted is added to the characteristic X- r a y e n e r g i e s (say K.L etc) of the daughter element (Ra C), the - ray the energies are

obtained. These values are in excellent

agreement

with

accepted

values

for the energies of gamma rays. For eg: Energy of ejected electron = 0.0368 MeV; 'L' line of Ra- C has the energy = 0.0161 MeV. The total 0.0368 + 0.0161 = 0.0529 MeV is the - r a y e nergy.

The measured

binding kinetic

energies energies

of from

the the

electrons, known

obtained gamma ray

by

subtracting energies, and

their the

observed frequencies of the characteristics X- rays are definitely those of the daughter and not of the parent. These facts provide clear proof that the

- rays are emitted from the excited daughter nucleus, which remains after the parent has ejected either an alpha or b - particles.

ORBITAL ELECTRON CAPTURE

In expected. nuclides.

some Another Instead

instances, type of a of

where decay

N/P has

ratio been

is

low, to a

position occur

activity

is

found

with

artificial with the

proton

being

converted

into

neutron

emission of a position, the nucleus capture one of the extra nuclear (orbital) electrons, which immediately combines with a proton to form a neutron, thus with a neutrino being formed at the same time. 1 P+ 1 -1 0 e 0 1 n+ 0 0 neutrino.

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152

This process increases N/P ratio. This gives rise to a product with the same mass number and the atomic number decreases by one unit. 55 Fe 26 This process + -1 is known 0 e 25 as decay by orbital electron capture. The 55 Mn

electron is usually captured from the K- level, for such an electron is more likely to be found near the nucleus. This process is also known as K- electron capture or K- capture. Examples of L- level capture are known but they are not common. Due to K- capture, emitted. For eg., 49 V + 23 K- series of X- rays K- electron capture. -1 belonging If as a 0 e 22 to 'Ti'. This shows that vanadium decays by result of orbital electron capture, the product 49 Ti, this process gives rise to characteristic X- rays of the product nucleus are

nucleus is left in the ground state, the change will not be accompanied by - rays. The decay of 49V, by K- capture is not accompanied by gamma- rays. Such a K- capture is known as pure K- capture. In most instances, however the product nucleus is found in a high- energy excited state and the excess energy is given off in the form of gamma radiation. This - radiation is internally

converted; the energy of the gamma ray photon is transferred to an orbital, which product is consequently are ejected. produced. Thus It is characteristics possible to X- rays show that lines for of the

nucleus

positron

emission a minimum of 1.02MeV energy is required. If the energy is less than this value, then K- capture is In would occur. Positron several When emission cases of the is energy is less among have than the been

1 . 0 2 M e V K - capture heaviest recorded. elements.

favoured. these cases

unknown K- capture

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153 13.2.2 NUCLEAR ISOMERISM

Study of radioactive decay of artificial nuclides, indicates a transition known as Isomeric transition. Nuclides having the same mass number and same atomic number, but having different radioactive properties are known as nuclear isomers. This phenomenon has been called nuclear isomerism.

O.Hahn found U- Z to be isotopic with and also to have the same mass number a s U - X2 . But both differ in the rates of decay. Later several isomers had been reported; for e.g., Br2 . When a target containing bromine was bombarded with slow neutrons, the product was found to exhibit three different half life periods of radioactive decay, Viz, 17.6 min, 4.5hr and 35.3hr. The reaction is o f ( n , ) type. The explanation for this behavior is as follow:
80

Br exhibits nuclear isomerism; each isomer has a different half- life.

The difference between the nuclear isomers of 8 0 Br, and in fact of all other cases of nuclear isomerism is attributed to difference in the nuclear energy states. One isomer represents the nucleus in the ground state, whereas the other is the same nucleus in an excited state of higher energy. Frequently the transition from a higher to a lower energy state (associated with - rays) requires a very short time, less than about 10- 1 3 sec. The excited state then has an extremely short life. If the transition is "forbidden", the high energy state (excited state), referred to as 'meta stable state', will have an

appreciable half- life. This half- life varies from small fraction of a second to several days. Such a metastable state represents one isomeric form of the particular nuclear species, whereas the ground state, ie., the state of the the meta by lowest energy, represents the other. For eg, in the case of 8 0 Br, stable form is represented as 8 0 Br m . Nuclear isomers can be

obtained

various ways.
82 83

(Kr(d,P)

K r m and

80

Se ( , n ) 8 3 K r m

Three

types

of

nuclear

isomers

may

be

distinguished.

Isomers

of

independent decay each; isomer decays independently of the other with its

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154 own particular half- life. In such cases transition from metastable to ground
52 71

state is highly forbidden e xamples: Mn (b + , 5.7days, b + , 21 min) Zn (b - , 4.1hr, b - 2.4 min) Cd(b - , 43 days, b - , 2.3 days)

115

The second class of isomers are called genetically related isomers. The parent meta stable state decays to the ground state with a definite half- l i f e , a - ray photon is expelled. This decay process is known as isomeric transition

(IT). In most cases the gamma rays are internally converted characteristic X- rays are emitted. The ground state decays to form the product with another half- life. Examples are:
44 80

Sc (IT, 2.44 days, b + 3.91hr) Br (IT, 4.5 hr; b 17.61min).

Half life of IT is longer than that of the b decay (+ or - ).

The third category of nuclear isomerism is that in which, the active species are isomers of stable nuclei. The decay process now involves an

isomeric transition from the meta stable excited state to the ground state of the than stable 30 nuclide, stable accompanied are by the emission of - ray emission. More Examples, 8 3 K r , S r - 8 7 , A g - 1 0 7 , S n - 117,

species

known.

Ba- 137, are known to form metastable states of appreciable half- life. Isomers of short life are also known.

Self Check Exercise 1

1) 2)

Discuss the theories of a n d b - decay The speed of the - particle moving in a nucleus is 105 cm/sec. if the 104 s e c - 1 , calculate the

radius is assumed to be 10- 1 2 cm and decay constant escape probability of the -particle. Self 1) 2) Check Exercise 2

Discuss the theory of - ray decay. Discuss the different types of nuclear isomers

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155 3) Discuss the orbital electron capture. How are characteristics - rays

produced in an orbital capture?

13.3 Let us Sum Up a a n d b decay and the theories of a , b a n d g- decay detail Different types of nuclear isomers and are discussed production in are

their

explained.

Internal

conversion

of g- ray is explained.

13.4 Points for Discussion i) ii) iii) The production of different types of nuclear isomers Internal conversion of - ray

The a n d b decay theories.

13.5 References i) ii) Atomic Physics by J.B.Rajan S.Chand & CO, New Delhi 1972

Source book on atomic energy Glasstone E a s t West press- D e l h i .

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156

LESSON 1 4
CONTENTS 14.0 14.1 14.2 AIMS AND OBJECTIVES INTRODUCTION Q- VALUE NUCLEAR 14.2.1 IN CROSS NUCLEAR SECTIONS REACTIONS Q VALUES REACTIONS, COULOMBICBARRIER,

NUCLEAR

14.2.2 COULOMBIC BARRIER AND NUCLEAR CROSS SECTIONS 14.3 14.4 14.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

14.0

AIMS AND OBJECTIVES

The aims and objectives of this lesson are to understand the calculation of 'Q' values of different types of nuclear reactions and also to understand the concepts of coulombic barrier and cross sections.

14.1

INTRODUCTION:

The

bombardment

of

nitrogen

by - particle

was

the

first

artificial

transmutation reaction studied. The 14 4

nuclear reaction may be represented as

17 1 N + He O + H. The reaction energy corresponding to 7 2 8 1 such reaction is termed as the 'Q' value. The best value of reaction energy obtained for the above reaction was about 1.26MeV. From the masses and kinetic energies of the reactant nuclei and product nuclei, one can calculate the reaction energies. High energies are required to surmount the coulombic barrier. To reach the nucleus of an atom an particle should have energies

of the order of 20 to 30MeV, according to classical electrostatic theory.

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157

Nuclear cross sections represent the effective area of cross section of a single nucleus of a given species for a particular reaction.

14.2.1

NUCLEAR REACTIONS Q VALUE.

nuclear

reaction

equation,

satisfying

the

universal

principal

of

conservation of energy can be written in a general way:

Mo + (M1 + E1 ) = (M2 + E2 ) + (M3 + E3 )

M 0 , is the rest mass of the nucleus bombarded, M1 and E1 , the mass and kinetic similar energy, quantities respectively of the of two the projectile, of M2 and E2 and M3 and E3 viz, the outgoing products transmutations,

particle and the product nucleus. It is to be noted that the two sides of the above equation can be expressed in terms of either energy or mass.

In the nuclear reaction equation, the reaction energy is known as Q value.

Q = (M0 +M 1 ) ( M 2 + M3 ) = E3 + E2 E 1 Hence 'Q' can be calculated using the masses of the particles involved or by means of the kinetic energies of the particles. Q may be positive or negative, depending on the nature of the process. Thus, if Q is positive, that is if the process is accompanied by liberation of energy, there must be a decrease of mass the total mass of the products will then be less than that of the interacting nuclei by an amount equivalent to this energy. A negative value of 'Q' means that the en r g y i s e absorbed and there is a gain of mass on the nuclear reaction.
7

When

Li is reacted with 'H, the energy liberated 'Q' value was found

to be 17.2 MeV; hence the mass equivalent of this energy is 17.2 = m(amu) x 931 m=0.0185 amu ; since Q is positive, it can be calculated that sum of the masses of the products will be less than the interacting nuclei by 0.0185 amu
7

Li + 1 H

H e + 4 He

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158 Masses of interacting particles =

7

Li = 7.0160 H = 1.0078 8.0238 amu

2 4 He loss of mass

= 2 x 4.0026 = 8.0052 = 8.0052 8.0238 = 0.0186 amu and this is close to the equivalent of energy

released.

0.0186 x 931 = 17.3 MeV

This

also

establishes

Einstein's

mass

energy

relationship. T h e a t o m i c

masses of certain nuclides, either too unstable or too rare to be measured by mass spectrometer
17

methods,

have

been

determined

from

nuclear

reaction

energies.

O is obtained as result of the interaction of the - p a r t i c l e w i t h

nitrogen nucleus.
14

N + 4 He

H +

17

O + Q. From the known energy of the

- particle and the measured range of proton, the nuclear reaction energy Q is found to be 1.16MeV. The mass equivalent of this energy = - 1.16/931 =

- 0.00124 amu. Since 'Q' is negative in this reaction, the total mass of the products will be greater than those of the interacting particles. The atomic masses of
14

N and 4 He are: 14.00307 and 4.00260, respectively. Total mass of

reactants = 18.00567. Total mass of products 1 H = 1.00782, Q= - 0.00124. Hence mass of 1 7 O would be = 18.00567 1.00658 = 16.9991 amu

COULOMBIC BARRIER:

Nuclear reactions of various nuclei with charged particles involve th e electrostatic or coulombic barrier. It can be shown that at any distance 'd', the energy of the electrostatic (or coulomb) repulsion of an - p a r t i c l e ,

having two unit positive charges, by an atomic nucleus with 'Z' such charges (Z=atomic number) is 2Ze2 / , where 'e' is the unit electronic charge. It is

clear that the energy with which an alpha particle is repelled from a nucleus

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159 increases with the atomic number. Hence nucleus having high atomic n u m b e r

would repel strongly an energetic alpha particle. Therefore alpha particles of energies in the range 20 to 30 MeV, would only be able to surmount the potential barrier required to react with nuclei of high atomic numbers. The application of wave mechanics, to the problem of nuclear penetration showed that particles could both leave and enter the atomic nucleus even though their energies G.Gamow are considerably that less than the the top of the hypothetical lower, barrier. but the

showed

not

only

was

energy

barrier

probability of penetrating it and reaching an atomic nucleus also increased, as the charge and mass of the incident particle decreased. Thus for a given value of the particle energy, a proton with unit charge and unit mass, is much more likely to enter the nucleus than an alpha particle, carrying two charges and having a mass of four units.

NUCLEAR

REACTION

CROSS

SECTIONS

The efficiency of a nuclear reaction can be defined in terms of the number of particles emitted (or of nuclei undergoing a quantity transmutation). The

interaction probability is expressed in terms of

known as 'nuclear

cross section'. when the probability of the process if high, the nuclear cross section will be large; on the other hand when the probability is low, the c r o s s section will be small.

If 'I' is the number of incident particles striking in a given time a certain area of target material, containing 'No' target nuclei per sq cm and 'A' is the number of these nuclei that undergo interaction in the specified t me, i then the nuclear cross section 's' expressed as sq cm per nucleus, is defined by: A s= No x I sNa is the fraction of the surface, which is capable of taking part in the nuclear reaction (Na = atoms/sq cm) cm 2 /nucleus

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160

This also represents the fraction of the incident particles 'I' falling on the target surface. The number actually reacting is = sNa I and this is equal to 'A', the number of target nuclei undergoing transmutation. A= s x Na x I i.e., A ----- = s NaI

Hence given nuclear

's' gives the effective cross section of a single nucleus for a reaction. The larger the fraction of the incident particles

reacting, the greater is the probability that the process will occur under the given conditions. The value (s ) of the nuclear cross section depends on i) the nature of the target element, ii) on the particular reaction under consideration and iii) the energy of the incident particle. The total cross sections for all processes in which the incident particles are removed, can be determined by a simple procedure. Let Io be the number of incident particles, in a narrow (or collimated beam), falling in a given time on the target material, which is on the form of a sheet of thickness 'x'cm, and 'I' is the corresponding number of these particles, emerging from the other side of the sheet in the narrow beam, the difference Io- I has been removed in various nuclear reactions then I = e -N x Io section.
s

- 'N' is the number of target nuclei/cc and 's' is the total cross it is possible to determine 's ' from measurements of the

Hence

intensity of the beam of incident particles before and after passage thr ough the target material.

Experimental

values

for

nuclear

cross

sections

are

usually

in

the

neighbourhood of 10- 2 5 to 10- 2 3 sq cm per nucleus. 's' may be as high as 10- 1 8 cm 2 /nucleus. The average diameter of the nucleus may be taken as 10- 1 2 cm and the actual in the area unit of of cross barn section equal to is approximately 10- 2 4 cm 2 /nucleus.
10 2 4 cm 2 . ' s ' i s

expressed

Nuclear

cross

sections are frequently in the range of 0.1 to 10 barns.

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161 A c u r ve showing the variation of 's' with the energy of the incident particle is called the excitation function, of that reaction. In the case of Cu 63 with protons in the energy range upto 35MeV, the excitation function curves show, that at the lowest energies (p,n) reaction predominates; at about 15MeV the (p,pn) and (p,2n) reactions start to replace the (p,n) process. The

cross section for a given nuclear process increases with the energy of the incident charged particle, provided there is no competitive reaction.

Competing reactions cause the cross section to decrease at high energies.

Self 1. 2.

Check

Exercise 1

Discuss the principle of Q- value 2 In the (d,n) reaction: 1 D 2 + D 1 3 He 2 + 1 n + Q 0

Q has been to and to be 3.16MeV. Using this value indicate how you would obtain the mass of the neutron.

Self 1. 2.

Check

Exercise 2

Write a note on coulombic barrier Discuss nuclear cross section.

14.3 Let us Sum Up Q- values is defined calculation of Q- value is illustrated. Nuclear

cross section and Coulombic barrier are discussed in detail. The use of Q value in calculating the mass of 1 7 O is illustrated.

14.4 Points for Discussion i) ii) iii) Q- Value and its uses Evaluation of nuclear cross section Coulombic barrier

14.5 References 1) 2) Atomic physics J.B.Rajan S.Chand & Co New Delhi (1972) Source book on a atomic energy Glasstone East- West press.

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162

LESSON 1 5
15.0. AIMS AND OBJECTIVES 15.1. INTRODUCTION 15.2 NUCLEAR REACTIONS

15.2.1. Different types of nuclear reactions 15.2.2 Spallation 15.3 15.4 15.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

15.0. AIMS AND OBJECTIVES

The aims and objectives of this lesson are to learn, the different types of nuclear reactions and to know how they are brought about.

15.1. INTRODUCTION

The

first

successful

nuclear

transformation

using

artificially

accelerated protons was achieved by Rutherford. achieved can be written as, 7 1 Li + H 3 1 4

The nuclear reactions thus

4 1 He + He, Where H is the incident 2 2 1 The process

proton and the two helium nuclei are the alpha particles formed.

occurred to a detectable extent with protons of 125,000 eV ie., 0- 125 MeV, a value considerably less than the height of the potential barrier between a lithium nucleus and a proton, namely about, 0.45 MeV. Artificial nuclear

reactions have been classified in six general categories.

The various types of

processes are (i) transmutation (ii) stripping and pick up (iii) fission (iv) spallation (v) fragmentation and (vi) scattering.

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163

N u c l e a r r e a c t ion

is

represented

by

simple

method

for

e.g.1 4 N

(a ,p) 1 7 O, is the reaction in which 1 4 N, is the target nucleus; the

'a ' p a r t i c l e

is called the incident particle or projectile; a proton is ejected (P) and an 17O, nucleus known as the recoil nucleus, remains. The general group of

nuclear reactions studied by Rutherford can be referred to as (a ,p) type.

i)

Transmutation

reactions

These reactions involve particles of energy 50 MeV. In the first step the target nucleus completely absorbs the projectile to form what is called, a 'compound nucleus'. Before forming the compound nucleus, the projectile

must overcome the barrier due to electrostatic repulsion forces. found that the deuteron is capable of initiating

It has been nuclear

several

transformations, through the formation of the compound nucleus, at relatively low energies. takes place In the compound nuclear redistribution of additional energy rapidly.

The average life of a compound nucleus, i.e. the average time elapsing between the capture of the projectile and the emission of a particle is estimated to be 10- 1 4 sec or less.

The nature of the particles expelled from

the compound nucleus, depends on i) its excess or excitation energy ii) the heights of the various coulomb barriers, iii) stability of the coil) nucleus. remaining (re -

Since no barrier exists for neutrons, these particles will in

general be able to escape from the compound nucleus, much more readil y than either, protons, deuterons or alpha particles. This is especially true

when the target nucleus has high atomic number. small atomic number, neutrons are more strongly

For target elements of bound in the compound

nucleus than protons.

The energy barrier is not also too high and the ejection The compound nucleus can given rise

of a proton or a - particle may occur.

to different reactions, depending on the available energy. 63 2 cu + H 29 1 65 Zn (Compound nucleus) 30

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164 65 Zn 30 30 64 Zn + 30 64 cu + 29 a) Transmutation by protons : 1 0 1 H etc. 1 n 65 Zn +

In these reactions the projectile has less than about 50 MeV energy. For a number of lighter elements (P, ) process is observed for eg 27 Al (P, )
20

28 Si, other examples are 7 L i ( P , ) 8 Be, c r ( P , )

51

14

N ( P , )

15

O,

19

F ( P , )

Ne,

50

Mn.

If

the

incident

proton

has

an

energy
63

in

excess

of
63

20

MeV,
62

the

compound nucleus has sufficient excitation energy to permit the expulsion of two or more nucleons.
88

Examples are :

Cu (p, pn) 6 2 Cu,

Cu(P, 2n)

Zn,

Sr (P, 3n)86 Y.

If proton energies are more than50 MeV, more than three nucleons may be emitted. (P, a ) reaction is expected only with targets of low atomic

number, for eg. 14 N+ 7 9 with 4 Be 1 1 + H 1 1 H 6 8 Be + 4 1 11 C 4 + 2 2 H; (p, d) are more common with heavier Hc; rare case of a (P, d) reaction

elements and protons of fairly high energy, but they appear to be pick- up reactions not involving compound nucleus formation.

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165 b) Transmutation by deuterons:

The deuteron is a particularly effective projectile for causing nuclear transmutations, because a relatively small amount of energy, about 2 Mev, is sufficient to cause its rupture into a neutron and proton. This small binding In the (d, p)

energy of the nucleons of a deuteron facilitates nuclear changes.

reaction, the efficiency of the process increases with increasing energy of the incident particle. Oppenheimer Philips mechanism, explains the ease of the

(d, p) reaction. According to this the deuteron behaves as a relatively loose combination of a neutron and a proton, since the binding energy is relatively small. When the deuteron approaches a nucleus, the electrostatic forces of

the positive charges tends to force the proton away, but the neutroni s n o t affected. If the energy of the incident deuteron exceeds about 2 MeV, the

proton portion breaks off and be repelled, but the neutron will enter the target nucleus. Then the If enough energy is available neutron may also be expelled. (d, pn) occurs. (d, p) reactions are observed with all

reaction

elements.

Examples : 8 Li + 3 2 Cd + D 1 2 D 1 48 210 Bi + 83 1 H 1 1 Cd + 1 1 H 1 H

7 2 Li + D 3 1 114 48 209 Bi + 83

115

2 D + 1

2 D 1

3 T + 1

1 H (3 T is tritium); deuterons of moderate 1

energies give neutrons i.e., (d,n) type. 2 D+ 1 1 3 T 2 3 He + 0 1 n

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166 2 D+ 1 1 3 T 2 4 He + 0 1 n This reaction is a convenient

method for producing neutrons with 14MeV energy. Other examples are: 6 Li + 3 209 1 2 D 7 Be + 4 210 54 1 n 0

2 Bi + D 53 1

1 Po + 0

n. At high energies over 50 MeV, the

(d,n) reaction like the (d,p) reaction, becomes a stripping process, that does not involve compound nucleus formation to any extent (d,a ) only with deuterons atomic weight. are observed

of moderately high energy and elements of fairly low

40 Ca
20

2 D
26

20 1 N e ( ( d , a ) 18 F,

38 4 K + He; others are 6 Li (d, a ) 4 H e , 19 2 M g ( ( d , a ) 2 4 , Na, ((d,2n), (d,3n), (d,2p) and ((d,pa ) a r e

also known when high energy deuterons (about 20 MeV or more) are used. Transmutation by 3 T:

c)

When tritons obtained by the action of 10MeV deutrons on Be, are used as projectiles, (t,p) reactions occur.

29 e.g., 27 Co +

3 T 1

61 Co 27 +

1 H; 1 (t,p) reaction probably occurs by

oppenheimer Philips mechanism. The proton present in the triton is repelled by the target nucleus, leaving the two neutrons to combine with the target nucleus to form a compound nucleus. In 6 Li (t,d) 7 Li and 6 3 c u ( t , d ) 6 4 c u a l s o the oppenheimer Philips mechanism operates.

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167 d. Transmutation by alpha particles:

(a , p) process was the first artificial transmutation studied. This occurs in common with elements of low atomic number. With highly accelerated a particles this reaction occurs even with elements of higher atomic numbers (above potassium) (a ,n) reaction: 9 e.g., 4 Be + He 4 2 12 6 1 C + 0

n. By using energetic alpha particles,( a , n)

reactions have been observed with the heaviest elements, including uranium and artificial elements of higher atomic numbers with increase in energy of the a - particles, (a ,np), (a ,3n), (a , 4 n ) , (a ,3np) have been detected.

e.

Transmutation

by

radiation:

By

using

gamma

radiation,

deuterium

nucleus

could

be

disintegrated

into a neutron and a proton:

2 D + 1

1 H+ 1 0 2

n. Gamma ray from Th- C, has sufficient

energy to breakup the 1 9 Be + 4 4 8

D nucleus.

1 Be + 0

n. Reaction of this type brought about by high

e n e r g y r a d i a t i on, have been described as photo disintegrations or as photo nuclear reactions. of When lithium nuclear the by 17- MeV, protons of were the radiations employed, (,n) type. produced number A neutron by of the nuclei can be

bombardment exhibited

photo

reactions

removed from any nucleus by - rays of about 10MeV, energy. If the - ray energy is not sufficient, to remove a neutron, the nucleus may enter into one

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168 of its excited states; the excess energy is then emitted as radiation. Such a process is described as (- 1 ), where the energy of 1 is equal to or less than that of the incident photon. f) Nuclear reaction with heavy ions:

Accelerated carbon ions and 'Al' target is an example of a nuclear reaction particle with energy heavy is ions. 2 7 A l ( 1 2 C, a n)3 4 cl and 1 9 7 Au( 1 2 C , 4 n ) 2 0 5 At. The relatively high (about 10 MeV) per nucleon, certain

reactions in which heavy ions take part are called transfer reactions'. 14 N+ 7 7 14 N 7 13 15 N + 7

N (Neutron is transferred)

14 N+ 7

10 B 5

13 7

11 N + 5

B (Neutron is transferred)

14 N+ 7

14 N 7

13 6

15 C + 8

O (Proton is transferred)

15.2.2

Fission,

Spallation

and

Fragmentation

Reactions

Fission (compare with

can

also

be

initiated with

by

charged

particles

of

high can

energy occur

neutron).

Fission

energetic

charged

particles

with many nuclides of lower mass number. Alpha particles of about400MeV, energy can cause fission of Bi, Pb, Tl, Pt and Ta and 200MeV deuterons are effective for Bi, Pb and Tl. The lightest element that is known to undergo f i s s i o n b y a - p a r t i c l e s is Ta (Z- 73). In the fission of Ta- 181 by high energy protons, the masses of the product nuclei vary from about 60 1 2 0 . T h e -

distribution of the products depends to some extent on the energy of the projectile particles. Another type of reaction, different from fission, but also leading to many different product nuclei, was discovered in 1947 by

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169 G.T.Seaborg. When bombarded by high energy charged particles e.g.,

400MeV protons or 200- MeV deuterons, many target nuclei do not break up into two parts of similar mass, as in fission. Instead such nuclei emit various numbers of nucleons commonly 10 to 20 and to a lesser extent up to 30 or more, singly or in clusters , leaving a series of products, with mass numbers lower than that of the target nucleus.

The

name

"Spallation"

is

used

to

describe

this

type

of

reaction.

Spallation is known to occur with many different nuclei from the lightest e.g, Mg to the heaviest using charged particles with energies of several million electron volts. With heavier elements, fission and spallation often occur at

the same, time as indicated by the masses of the product nuclei. In spallation most of the products have masses that differ from that of the product by up to 10 to 20 units, smaller amounts of lighter products. The mass with

distribution of the products is the only way of distinguishing between fission and spallation. 75 For example when arsenic ( As) is bombared by high energy a 4 33 38 particles ( He), one of the mirror products is cl, the net decrease in 2 17 the number of protons is 18 and that in the number of nucleons is 41; this particular mode of spallation is expressed as 75 As (a , 18Z41a) 33 38 cl. Some 17

writers use the equivalent representation

75 38 As (a , 9 a 23n) cl, 33 17

but this is misleading as it implies the emission of 9a particle, which may or may not occur. by The mechanism is suggested accepted for . high The energy high fiss ion and

spallation,

R.Serber

generally

energy

projectile

enters the target nucleus and strikes a single nucleon; the latter known as the knock- on particle, may be ejected or it may strike another nucleon, which may in turn be ejected or it may share its energy with other particles in the nucleus. The incident particle may still have enough energy to strike or

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170 possibly eject another nucleon, or again the energy may be shared and so on. This stage of the process is cascade in which several knock- on nucleons may
be expelled from the target nucleus. When the cascade is over within 10 2 2

sec or so, the remaining nucleus is left in a highly excited state. It is similar to a compound nucleus, but with a much larger amount of excess energy A . distribution of energy then occurs, over a period of about
10 1 4 s e c , a n d

several individual nucleons (or small groups of nucleons) are emitted. The result would then be a spallation reaction. Alternatively and simultaneously, after expelling a few nucleons the excited nucleus may split into two parts in various ways, thus undergoing fission.

In

reactions

of

some

nuclei,

particularly

of
24

medium
28

or

high
32

mass

number, with high energy particles, the products include finite quantities of nuclei with mass numbers from 18 to 32, e.g., 1 8 F, Na, Mg and P. These

are apparently too light to be fission either or spallation products. Reactions leading to the formation of such species are called nuclear fragmentation.

After the cascade stage mentioned above but before there has been time for the energy to be distributed in the excited residual nucleus, a relatively large amount of energy may be concentrated in a limited region of the nucleus. As a result, there is a rapid break up of the nucleus, leading to the formation of nuclei consisting of 20 or 30 nucleons.

Self Check Exercise

-1

1. 2.

Discuss the different types of nuclear reactions Explain the oppenheimer Philips mechanism

Self

Check

Exercise 2

1. 2.

Compare the fission and spallation reactions Write a note on fragmentation

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171 15.3 Let us Sum Up Nuclear explained open reactions brought about by different is types of particles are

Himer- Philips

mechanism

discussed.

Spallation

reaction

and its mechanism are explained.

15.4 Points for discussion

1) 2) 3)

Compound nucleus formation in nuclear reactions Philips- oppenheimer mechanism Mechanism of spallation reaction.

15.5 References 1) 2) Atomic Physics J.B.Rajan S.Chand & Co Source book on atomic energy By Glasstone East West press.

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172

UNIT VI LESSON 1 6
CONTENTS 16.0 16.1 16.2 AIMS AND OBJECTIVES INTRODUCTION NUCLEAR FISSION AND FUSION 16.2.1 FISSION THEORIES 16.2.2 FISSILE AND FERTILE NUCLIDES 16.2.3 FUSION STELLAR ENERGY 16.3 16.4 16.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

16.0

AIMS AND OBJECTIVES

The aims and objectives of this lesson are i) To learn and calculate the energy released in nuclear fission and fusion reactions.

ii)

To study the theories of fission

16.1

INTRODUCTION

In particle, nucleons. neutrons.

the breaks The The

fission up

process into two

nucleus, of in fission

after roughly the is

interacting similar

with mass

a plus

projectile a few

nuclei

nucleons most

obtained of

fission that

process by

are

invariably But

important

caused

neutrons.

fission can also be initiated by charged particles of high energy. The neutron fission is restricted to a few heavy nuclei, whereas fission with energetic charged particles can occur with many nuclides of lower mass number. Thus alpha particles of about 400MeV can cause fission of bismuth, lead, thallium and platinum.

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173

The fission process is accompanies by the liberation of large amounts of energy. The important point to remember is that fission, which is initiated by neutrons, is also accompanied by the emission of neutrons. These emitted neutrons cause a chain reaction to occur and more energies and neutrons and produced. Uranium can be split by neutrons of all energies, i.e, by slow, intermediate and fast neutrons. Fission of more abundant U- 238 neutrons with energy exceeding 1MeV, 233 U 92 94 239 Pu are fissionable by neutrons of all requires fast

energies. Fission cross sections are generally high for slow neutrons. Fission of Th requires fast neutrons of energies of about 1 MeV. Protactinium also requires fast neutrons. The combination of two or more of the lightest nuclei by a process of fusion, like fission, result in the liberation of energy.

Many reaction between nuclei of low mass number can be brought about by accelerating one or other of the nuclei in a suitable manner. These are fusion reactions, accompanied by the release of energy. The energy of the sun is due to the fusion reaction.

The

power

production corresponding to the fission of 1 g of Uranium

or Plutonium per day would be 1 mage Watt. To obtain the same amount of power by combustion would require more than 3 tons of coal per day or 600 gallons of fuel oil per day.

16.2 NUCLEAR FISSION AND FUSION 16.2.1 FISSION THEORIES

Before studying the theories of nuclear fission one should know the amounts of energy liberated in a nuclear fission reaction. In the fission

reaction we have to calculate the mass loss, in a nuclear fission reaction. But we know the energy corresponding to the mass loss of l a m u = 931 MeV.

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174

lamu=

1 6.0225 x 10- 2 4

= 1.6604 x 10- 2 4 E = m x c2 = 1.6604 x (2.998 x 10 1 0 ) 2 x 1 0 - 2 4 E = 1.6604 x 10- 2 4 x (2.998 x 10 1 0 ) 2 g cm /sec2 x cm = 1.6604 x 10- 2 4 x (2.998 x 10 1 0 ) 2 e r g s (note g cm2 / sec2 = ergs) = 1.4924 ergs = 1.602 x 10- 1 2 ergs = 1ev hence E = 1.4924 x 10- 3 e v 1.602 x 10- 1 2 E = 931.4 MeV / amn

A l t h o u g h U- 235 splits in many different ways, the nuclei obtained in the greatest yield in fission by slow neutrons have mass numbers of about 95 and 139. The initial products are radioactive and undergo several stages of negative b - decay ultimately, after the emission of a total of seven beta

particles (electrons), the stable nuclides Mo- 95 and La 139 are formed.

The fission process in this particular case can be represented as:

235 U+ 92

1 n O

95 Mo 42

139 + La + 57 - 1

O 1 7b + 2 0

Some neutrons are always liberated in the fission process. The atomic mass of U 235 is 235 0439amn and the mass of neutron is 1.0087amu.

The total mass on the left hand side of the equation is 236.0526amu. The masses of Mo- 95 and La- 139 are 94.9058 and 138.9061 amu, respectively

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175 and the mass of the electron is 0.00055amu; the total mass on t he right side is 235.8332 amu. The mass loss is equal to 236.0526 235.8332 = 0.219amu

Energy equivalent of this mass is = 0.219 x 931.4MeV

~ 204 MeV

The actual process of fission is probably accounted for by the large value of repulsive force in heavy nuclei, and so it is responsible both for fission and for the release of energy accompanying the nuclear reaction.

The energy released in the fission process appears in several different forms. The major part occurs as kinetic energy of fission fragments and a substantial amount as radioactive decay energy of the fission products. In

addition, neutron and gamma rays liberated at the instant of fission carry appreciable amount of energy. Thermal neutron fission of U- 235 is far from symmetrical. If the compound nucleus splits into two equal of fragments, the mass of each is 117or 118, only 0.01% of the nuclei under going fission by thermal neutrons break up in this manner. There are 90 possib e m a s s l

numbers in the range of from 72 to 161, it is understandable that this may represent the total number of different nuclides formed as direct fission

fragments. The amount of symmetrical fission by thermal neutrons is about 0.02% for U- 233 and 0.04% for Pu- 239.

Experimental undergoing fission

studies between

indicated three and

that four

for

each

atom were

of

uranium on the

neutrons

emitted

average. The average number of neutrons released per fission increases with the energy of the neutrons inducing fission. Thus in the fission of U- 2 3 5 b y

14MeV neutrons, an average of 4.5 neutrons are produced per fission. The average number of neutrons increases in general with the number and the atomic number of the fissioning nucleus. The great majority (over 9 9 % ) o f the neutrons produced in fission are released within about 10- 1 4 sec. These are referred to as prompt neutrons. A small proportion of fission neutrons are

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176 delayed neutrons, which are emitted sometime after the fission process has taken place. In the fission of U- 235 by neutrons upto atleast 1MeV energy, 0.65% of the neutrons emitted is delayed. The emission of delayed neutrons is an important factor in the control of nuclear fission reactors. For thermal neutron fission of plutonium 239, about 0.21% of the neutrons are delayed,

and for U- 233, about 0.26% are delayed.

THEORY OF NUCLEAR FISSION A useful approach to understanding the mechanism of fission is by means of the liquid drop model of the nucleus. It is postulated that, just as the

surface tension forces tend to maintain a liquid drop in a stable from which resists distortion, so the nuclear forces serve to keep the nucleus in s stable state. Only if considerable distortion occurs due to the addition of energy a drop of liquid can be broken into two smaller drops. Similarly for a nucleus to undergo only fission, if there must be is considerable available. distortion, This is which basis will of be the

possible

additional

energy

the

interpretation of fission indicated by Meitner and Frisch.

The

general

idea

of

the

proposed

mechanism

for

fission

may

be

understood by considering a drop of liquid which is made to break up into two smaller droplets, by the application of a suitable force. The system

passes through a series of stages. The drop is at first spherical, it is then elongated into an ellipsoid. If insufficient energy is available to overcome the surface tension, the drop will return to its original spherical shape. But, if the deforming force is sufficiently large, the liquid acquires a s h a p e s i m i l a r to a dumbbell. Once it has reached this stage, it is unlikely to return to the spherical form, but it will rather split into two droplets.

The

situation for

in a

nuclear liquid

fission

is

regarded

as

analogous

to

that

just

considered

drop. A large nucleus combines with a neutron to

form a compound nucleus; the energy gained by the nucleus is equal to the binding energy of the additional neutron plus any kinetic energy the neutron may have possessed. The excitation energy may then be emitted a s g a m m a

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177 radiation or the compound nucleus could, if sufficient energy were available split in to one or more nucleons.

If the nucleus has obtained enough energy to permit it to form the dumbbell shape, (like the liquid drop), the restoration to the initial becomes very improbable. The reason is that the shape (spherical) repulsion

electrostatic

between the positive charges on the two ends of the dumbbell, can now over come the relatively small portion of the nuclear binding force, operative in t h e c o n s t r icted region of the dumbbell. Consequently the dumbbell shaped

nucleus, undergoes fission to two separate nuclei. The series of changes just described can occur only if it is accompanied by a net decrease of mass, that is, by an emission of energy. The state, consisting of two separate nuclei is then more stable.

CRITICAL ENERGY FOR FISSION

The critical energy (or activation energy) required for fission to occur is the energy that must be supplied to the original nucleus in order to deform the nucleus to the dumbbell state. The repulsive energy is proportional to Z2 /A / 3 ,

whereas

the

surface

energy

depends on A2 / 3 . Therefore the ratio of these two energies namely, Z2 /A, for a given nucleus is a measure of the ease with which, it will undergo fission. The large the value of Z2 /A, the smaller the amount of energy that must be supplied from outside sources to cause fission to occur.

It was shown that if the electrostatic repulsion energy was more than twice the surface energy, a nucleus should undergo instantaneous fission. The

condition for instantaneous fission was shown to be.

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178 0.710 Z2 >2 x 17.8 x A2 / 3 A1 / 3 Z2 or A The closer Z2 /A for a particular nucleus is to 50, then shorter should be the half life for spontaneous fission. IfZ2 /A is approximately less thann 40 fission cannot occur at a significant rate unless energy is supplied to the nucleus; this is the 'Critical energy' of fission. For plutonium 239, Z2 / A s 37.0, for Uranium 233 it is 36.4 and for Uranium 235 it is 36.0, these are fairly high, but they are sufficiently less than the limiting values to require appreciable energies for fission. The critical energy for U235 after > 50

absorbing a neutron has been estimated to about 5.5 MeV. Similar values have been estimated for the other two fissile species. For lighter elements such as bismuth, lead and tantalum Z2 /A is about 30 or less and critical energy for fission is large. It can be understood, why fission does not occur with these substances.

Fission process has also been explained by potential energy diagram. In this diagram, the energy of the fragments is plotted as a function of their distance apart. The exact shape of the curve depends on the target nucleus. At the extreme left of the diagram, the fission fragments are supposed to be brought together (i.e,) the point at the left of diagram represents the energy of the target nucleus and an incident neutron. At the extreme right the fission fragments are at a considerably distance apart and their interaction is zero. This diagram is similar to the activation energy diagram. The top of the barrier corresponds to the state of critical deformation of the nucleus. If

fission is to occur then the target nucleus plus neutron (i.e,) the compound nucleus, must acquire sufficient energy to reach the top of the barrier. By

using neutrons of 1 MeV energy, the energy of the system is increased so that it now lies above the barrier and fission takes place. The critical energy depends on the quantity Z2 /A for the given nuclide. T h e l a rge the value of Z2 /A, more closely will the energy of the compound

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179 nucleus, indicate approach the U- 235 that of the be critical fissioned deformation by slow energy. Calculations Whereas fast

could

neutrons.

neutrons are required for fission reaction when U - 238 is used U- 233 and Pu239 would also undergo fission by means of thermal neutrons. Their critical deformation energies are about 5.1MeV and 4.8MeV for U- 233 and Pu- 239 respectively. In the case of Th- 2 3 2 , P a - 231 and Np- 237, critical deformation

energies are about 6.0 to 6.6 MeV. In these three cases neutrons of about 1.1 MeV fission. energy Thus must be absorbed to produce critical deformation even leading numbers Np.237, to of with

U- 2 3 5 , U - 233 and Pu- 239,

which

contain

protons and odd number of neutrons, are called

fissile

nuclides.

an odd number of protons and an even number of neutrons, and Th- 2 3 2 a n d U- 238 which are of the even- even type are fissionable species requiring fast neutrons to induce fission.

NUCLEAR

POWER

PRODUCTION

A large amount of energy is released in a fission reaction which is a chain reaction induced by neutron. Hence power can be nuclear reactor. produced by means of a (235grams) energy. by It

It can be shown that 1gm atom of U- 235

means of a fission reaction, would produce 1.93 x 101 3 w a t t - sec

follows that the complete fission of 1 gram releases 8.2 x 101 7 ergs. It is equivalent to 8.2 x 1010 watt- sec or 8.2 x 107 kilo watt- sec. This is equivalent to 2.3 x 104 (Kw- h) or 2.3 x 104 / 2 4 = 0.96 x 103 kilo watt days. T h e ( h e a t ) power production corresponding to the fission of 1gm of uanium or plutonium/day would thus be 0.96 x 103 kilo watts, roughly 1000 kilo

watts or 1 mega watt. The same amount of power can be obtained only by the combustion of about 3 tons of coal or about 600 gallons of fuel oil per day.

The total number of nuclei 'A' undergoing fission per second in the reactor is given by the expression. A=nvNs V

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180 Where 'n' is the average neutron density, ie the number per cc, U is the average speed, so that, 'nv' is the average neutron flux; 'N' is the number of fissile nuclei (U- 235) per cc, s square cm is the cross section for fission , a n d 'V' cc is the volume of the reactor. 3.1 x 101 0 fission per cc produce 1 watt of power, hence the power 'P' of a nuclear reactor in watts is obtained upon dividing the fission rate 'A', by 3.1 x 101 0 (ie)

nuNs V P= . (1) 3.1 x 101 0 The product 'NV' is equal to the total number of fissile nuclei in the reactor and this is related to the mass 'm' grams by 235 x N x V m= the atomic 6.02 x 102 3 where 235 is Watts

weight of U- 235. The fission cross section s of U- 235, for thermal neutrons is 577 barns (ie) 577 x 10- 2 4 c m 2 and upon inserting these values in equation (1), we have, P= 4.8 x 10- 1 1 m n

This

equation

shows

that

the

power

output

of

given

reactor,

containing a definite amount of fissile material, is proportional to the neutron flux- nv. Therefore reactor power is generally determined by measuring the appropriate neutron flux, by means of a suitably calibrated instrument. In the to

reactor the chain reaction has to be controlled. Controls are necessary prevent the chain reaction from becoming too violent. Once the

desired

energy level is reached, control rods of Cd, boron steel or other material with a l a r g e capture cross section for slow neutrons are used. These rods are inserted in the reactor to such a depth as will permit them to absorb all excess neutrons. In other level, words, the when rods the serve reactor to has reached the a

predetermined

power

control

keep

effective

multiplication factor to unity. If it is required to increase the power, the

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181 controls are partially removed, the multiplication factor then exceeds unity

and then neutron flux increases. When this attains the desired value the controls are inserted to the

extent necessary to keep the flux (or power level) constant.

When the shutting down the reactor, the control rods are inserted to a considerable depth, the rods then capture so many neutrons than the effective multiplication factor becomes less than unity. Then neutron flus thus

decreases and the nuclear chain reaction then is no longer maintained. A reactor consists of an active core in which the fission chain is maintained and in which most of the energy of fission is released, as heat. The core contains the fissile material in a suitable form i.e the reactor fuel, and also a

moderator if it is required to slow down the neutrons. The relative amounts of and nature of the fuel and moderator determine the energy of the neutrons

causing most of the fission. The core is surrounded by a reflector of a material which is largely dependent on this neutron energy. The combination of core and reflector, to gether with other components present, e.g, coolant and structure must be capable of maintaining a fission chain.

The

operation

of

the

reactor

at

appreciable

power

levels

depends

on

the

ability to remove the heat produced by fission as fast as it is liberated. This involves the use of a coolant, which must circulate through the reactor core in such a manner as to maintain a temperature distribution that is as uniform as possible. If the energy generated in the reactor is to be converted into electrical power, then the heat must be transferred to a working fluid to produce steam or hot gas. The resulting vapour or gas can be used to generate power in a conventional manner, for example by means of a turbine.

Reactors are classified as "thermal", "Fast" or intermediate "according to the neutron energy region in which the majority of the nuclear fissions occur. In thermal reactors most fissions are due to the absorption of slow neutrons. In order to slow down the fast neutrons released in fission a sufficient amount of moderator must be included, in the core of the reactor.

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182 Thermal reactors have the great advantage of flexibility in size. The size can be attained by size. Varying For the a nature reactor and properties natural of the fuel as and fuel the and

moderator

example

with

uranium

graphite as moderator, is roughly 20 feet across at least with a fuel material highly enriched in U- 235 and ordinary water as moderator, a thermal reactor may have linear dimensions of not more than one or two feet. An important draw back to thermal reactors is the loss of neutrons due to parasitic capture by constructional and other materials as well as by fission products.

In a fast reactor, the majority of fissions occur by interaction of fissile material with neutrons of high energy. The use of a moderator or of any material of low mass number, which might slow down the neutrons, must

consequently be avoided as for as possible. Parasitic capture of neutrons is a relatively minor problem in a fast reactor. On the other hand there is some limitation in the choice of fuel materials. A fast reactor requires an enriched

fuel containing about 20 to 25% of fissile material, e.g, U- 235, U- 233 or PU239. A disadvantage of a fast reactor is the larger mass of fissile material necessary to attain criticality. Because there is no moderator, the critica l s i z e may be quite small e.g, a foot or less across, and then the heat removal is difficult when the operating power is high. The outstanding as pect of certain fast reactors is their ability for to his breed reason fissile that material, such Plutonium 239, in are alternating

p a r t i c u l a r . I t is interest.

mainly

reactors

An intermediate reactor is one in which fissions are caused mainly by neutrons slowed down into a broad energy range between fast and thermal energies. Some moderation is necessary, but not as much as in a thermal

reactor. In a sense an intermediate reactor is compromise between thermal and fast reactors. Parasitic capture of neutrons can be less than in a thermal reactor. 239. An intermediate reactor also offers the possibility of breedingP-

U- 233 is fissionable by slow neutrons and it is obtained from Th- 232 by means of neutrons available in a reactor.

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183 232 233 Th+n U 90 90 233 Th 23.5m 91 27.4d 92 b 233 Pa

16.2.2 FISSILE AND FERTILE NUCLIDES

U- 235 will undergo fission by neutrons of any energy, from almost zero upward, but U- 238, requires neutrons of al least 1 MeV to induce

fission. U- 233 and P 239 are like U- 235 in the respect that neutrons of any energy can induce fission, such species are known as fissile nuclides. On the other hand, U- 2 3 8 , T h - 232 and certain other species, which have a fission threshhold at about 1 MeV are said to be fissionable nuclides. In general

fissile nuclides have either an even number of protons and an odd number of neutrons or odd numbers of both. Of the fissionable nuclides, only the even even species U- 238 and Th- 232 are of practical interest, because they can be

converted into fissile nuclides by reaction with neutrons. Both U- 238 and Th232 will undergo fission by fast neutrons with energy greater than 1 MeV, but it is not possible to sustain a chain reaction in these isotopes. Since both U- 238 and Th- 232 can be converted into fissile species, however, they are referred to as 'fertile materails'.

One of the remarkable aspects of nuclear reactors is that they can be designed so as to produce their own fuel, by conversion of fertile to fissile material. Such reactors are called regenerative reactors or convertors.

Plutonium production reactors fall in this category. In these reactors U 235 serves to maintain the fission chain, but some of the neutrons are captured by the fertile U- 238 reactor new with can fissile the ultimate useful to formation energy that of while plutonium- 2 3 9 . A converting fertile a

regenerative material reactor into with

produce material,

replace

consumed.

Consider

U- 233 as the fissile material. For every one of these nuclei fission, more than on would be produced by the capture of

undergoing

neutrons in Th.232. Such reactors are called breeders and the regeneration process is known as breeding. By the use of breeding, the stock pile of fissile

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184 material material could be be steadily into increased. fissile Thus not but only the would amount al l of the the fertile latter

converted

material,

available, and hence the rate of power production could be steadily increased.

This would not go on indefinitely, because a time would be reached in the ultimate future when all the fertile material was consumed.

16.2.3 FUSION STELLER ENERGY

The energy obtained by the fusion of light nuclei would be more practical than the energy that would be obtained by the fission of heavy nuclei. The to the binding energy per

liberation of energy in fission is due- essentially

nucleon being less in the heavy elements, than it is in those of intermediate mass number formed in fission. In the case of fusion, the combination of two more of the lightest nuclei should result in the liberation of energy.

Many reactions between nuclei of low mass number can be brought about by accelerating one or other of the nuclei, in a suitable manner. These are o ften fusion processes accompanied by release of energy. To have practical value, fusion reactions must occur in such a manner as to make them self sustaining, that is more energy must be released than is consumed in initiating the reaction.

S o m e i n d i c a t i on considering the

of

how of

this the

might

be

achieved amounts

can of

be

obtained

by

source

enormous

energy

produced

continuously in the stars. A.S. Eddington suggested that the energy of the sun resulted Eddington helium from the mutual that annihilation energy of was positive liberated and in negat v e c h a r g e s . i the formation of

proposed

stellar

from

hydrogen.

Energy might be liberated in th stars as a result of nuclear fusion reactions occurring at the very high stellar temperatures, from 15 to 30 milli ns, o

degrees Kelvin. Such processes are called thermonuclear reactions and these

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185 reactions can occur at rates sufficient to account for the release of large amounts of stellar energy.

In order for two nuclei to interacts, they must have enough kinetic ene r g y t o over come the electrostatic repulsion barrier which tends to keep them apart. Simple calculations indicate that for the nuclei of the lowest atomic number e.g., the isotopes of hydrogen the energy required to make the nuclear

reactions occur at a detectable rate is about 0.1 MeV. But the temperature would have to be as high as 1000 million degrees Kelvin, if the average energy of the particles is to be 0.1MeV. Such temperatures are considerably higher than those existing in stars. At any given temperature, Maxwellian distribution of energies among the molecules of there a is a At

gas.

temperatures of millions of degrees a gas does not consists of molecules, but rather of a completely ionized system called a 'Plasma'. A plasma contains equal quantities of positively charged nuclei (ions) and negative electrons.

The concept of distribution of energies should be applied. Therefore there will always be a certain proportion of nuclei, which have energies greatly exceeding the average. Thus at a temperature of 20million degrees, for

example, where the average kinetic energy is only 0.002 MeV, there are an appreciable number of nuclei with energies of 0.1MeV or more. These have sufficient energy to permit them to take part in thermonuclear fusion

reactions, resulting in the release of energy.

Most of the thermonuclear reactions are due to nuclei with energies in excess of the average H.H. Bethe suggested the following to explain nuclear

reactions at high temperatures. Two sets of nuclear reactions have been found to account for the energies of what are called "Main Sequence" stars. The first is known as the 'Carbon Cycle', in which the carbon acts as a sort of catalyst in facilitating the combinations of four protons to form a Helium nucleus. The second is known as the proton proton chain, since the first step involves by the the combination release of of two protons. Other occur nuclear in older reactions (holter)

accompanied stars.

energy

undoubtedly

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186 In the carbon cycle (Bethe's) a proton interacts with a C - 12 nucleus, with a release of fusion energy. 12 1 13 C + H N is radioactive and has a 1 7 13 energy. N 7

half life of 10.1min; hence it decays as: 13 N 7 The Stable

13

13 C 6 +

O e +1 1 H, releasing more energy. 1 (Positron)

C nucleus reacts with another

13 + 6

1 H 1

14 N + 7 1 energy.

14

N combines with another 1

H to yield energy

14 N 7 15 +

1 H 1

15 O + 8 energy.

O is a position emitter with a half life of 2.05min 8 15 O 8 7 15 N + +1 O e and finally the 1 5 N interacts

with the fourth proton

15 N 7 +

1 H 1

12 C + 6 He. When we add all the

4 2

above equations, we have 1 4 1 H 2 4 He + 2 +1 O e + energy

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187

The net result in thus the conversion of four hydrogen atoms into a helium atom, plus energy amounting to a total of about 26.7MeV.

In the Proton Proton chain, two protons fuse to produce a deuterium nucleus and a positron:

1 H 1 +

1 H 1

2 D + 1 e + energy

O +1

2 D 1 +

1 H 1

3 He + energy 2

3 He + 2

3 He 2

4 He + 2 2 H + energy

1 1

The energy released is the same as in carbon- cycle, namely 26.7 MeV for each helium nucleus. at low temperatures (Stellar), the proton proton -

chain predominates, but as the temperature is raised, the carbon cycl e r a p i d l y becomes of increasing significance. Thus in hotter stars (larger), all the

energy comes from the carbon cycle but in the smaller (cooler) stars, the proton- proton chain is the main source of energy.

Self Check Exercise-1

1. 2.a)

Discuss the theory of nuclear fission Show that 1 amu = 931 MeV

b) Calculate the energy released in the fission reaction. 235 U+ b + 92 o 1 1 n 2 n 0 95 Mo 42 + 57 139 La 0 + 7 -1

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188

Self Check Exercise 2 1. 2. Discuss the different types of nuclear reactors Write a note on fissile and fertile nuclides 3.a) Discuss the fusion reaction by using Bethe's carbon cycle and proton proton chain. b) Explain how power production is feasible using fusion reactions?

16.3 Let us Sum Up Fission theory is discussed carbon The in detail. is Fusion reactions in stars are

explained. production fusion

Bethes is

cycle

illustrated. of power

Nuclear production

power using

discussed. is

feasibility

reaction

indicated.

16.4 Points for Discussions

i) ii) iii)

Theories of fission Fusion reactions in stars The feasibility of power production from fusion reactions.

16.5 References

1)

Source book on atomic energy Glass tone East, West, New Delhi. 2) Theory and problems of physical chemistryMcGraw Hill New Delhi. Schaum's Outline Series

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189

LESSON 1 7
CONTENTS 17.0 17.1 17.2 17.3 17.4 17.5 17.0 AIMS AND OBJECTIVES INTRODUCTION SYNTHETIC ELEMENTS 17.2.1 THE TRANSURANIUM LET US SUM UP POINTS FOR DISCUSSION REFERENCES AIMS AND OBJECTIVES The aim of this lesson is to study the synthesis of elements by artificial means. After going, through this lesson you would be able to learn the ELEMENTS

methods by which several transuranium elements have been obtained.

17.1

INTRODUCTION

In view of the existence of the speculation concerning the

lanthanide of the

series,

there

has of

been an

much

possibility

occurrence

analogous

'actinide series', beginning with the element actinium, atomic number 89. The four elements of this possible series, whose properties were gener a l l y k n o w n at the time, namely actinium, thorium, protactinium and uranium are placed in groups IIIA, IVA, VA and VIA. Prior to 1945, most chemists would have doubted the existence of an actinide elements, series. A study Pu(94), of the chemical Cm(96),

properties of the new "artificial"

Np(93),

Am(95),

Bk(97), Cf(98), Es(99), Fm(100), and Md (101), has shown clearly that these elements similar to have the properties, lanthanide which series. would The make nearly them studies members of the of a series

tr nsuranium a

elements led to the development of the remarkable techniques of quantitative ultramicro chemistry, this made possible experiments with fractions of a

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190 cubic centimeter of solutions containing a few millionths of a grain of

dissolved substance.

17.2 SYNTHETIC ELEMENTS Neptunium (93)

A thin layer of uranium oxide was exposed to slow neutrons. A non recoiling beta emitting product (t = 23min) was obtained. This was shown to be U- 239. This U- 239 days) 238 U 92 + 0 1 n 92 239 U + decayed emitting b r a y s to give, Np (93) (t =2.3

239 U 92

239 Np 93 +

O e (b - decay) -1

This new synthetic element does not precipitate with H2 S in acid solution; it is not reduced to the metallic state by Zn. In a reducing SO2 solution, Np would be precipited with Ce (III) as fluoride ie, NpF3 or NpF4. The neptunium activity could be separated with sodium uranyl (VI) acetate. Np resembles U; both exist in III, IV, V and VI oxidation states. NpO2 and NpF4 are more stable.

Another Seaborg: 238 2 U+ D is b active. 1

isotope

of

Np,

Np- 238

(t

=2.1

days)

was

obtained

by

238 Np 93

1 +2 0 n; Np 2 3 8

92

Eight Np isotopes with mass numbers ranging from 231 through 241 have been obtained by the bombardment of either one or other of the isotopes of Uranium by deutrons or alpha particles. Tracer techniques are used to

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191 identity the synthetic elements like the transuranium, elements. In this

technique an inactive carrier is used to follow the behaviour of a radio active element present in tracer amounts. Provided the material has a reasonably strong activity, it is possible to, trace quantitites as small as 10- 1 0 gm or less. For example if an appreciable quantity of 'Th' is added as carrier to a solution containing acid, a it tracer will amount of Np, in the reduced state in aqueous be found that the Thorium fluoride (ThF4)

hydrofluoric

precipitated contains essentially those of the neptunium activity. From this it followed that Np forms an insoluble fluoride namely NpF4. Using ultramicro chemical synthetic techniques elements are extremely analysed. small amounts (from Np has 1m g to 0.02m g)of states III,

Quantitatively

oxidation

IV and VI in solutions.

Pu : Plutonium 238 named after Pluto is an alpha emitter and is formed from Np238:

238 Np 93

238 Pu 94 +

O e -1

Tracer

techniques

showed

that

plutonium

like neptunium

is

precipitated

as

fluoride or iodate with a rare earth element or thorium as a carrier.

Pu- 239 is an important fissile material. It is formed from Np- 239.

239 Np 93

239 Pu 94 +

O e ; Pu- 239 is an alpha emitter -1 with a half

lifeof 24, 360years. Several isotopes of Pu have been obtained by nuclear reactions.

232 Pu : 235 U (, 7n) 234 Pu : 233 U (, 3n) 237 Pu : 235 U (, 2n) 241 Pu : 238 U (, n)

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192

Pu has four oxidation states, III, IV,V and VI. Like Np Pu resembles Uranium in many of its chemical properties. The IV state of Pu is more stable than VI state. The stable oxide of Pu in PuO2 .

PuO 2

1500o C thorium.

PuO 3 . P u F 4 , Pu(IO 3 ) 4 and Pu(0H)4 are insoluble like those of

Plutonium metal (used as a reactor fuel) is made by heating the PuF4 in a closed vessel:

with calcium

Pu F 4 + 2 Ca F2 .

Pu + 2Ca

Am:

Americium:

Third

transuranic

element

obtained

as

follows:

U2 3 8 i s -

bombarded with 40- M e V ' ' particle to get Pu- 241.

238 U+ 92

4 He 2

241 Pu 94 +

1 n 0

241 Pu 94

241 Am + 95

O e ; -1 241 Am is also obtained by

(,2n) reaction with Pu- 239. Am has the stable III state. Am is separated from the rare earth carriers by Ion- exchange methods. Am x 3 (x=Cl, Br,I) are known. Ba(Vapour) Am- silvery o 1000 C

AmF3

white

metal m . p t

134o'c cm: curium obtained by bombarding Pu- 239 using cyclotron with - particle.

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193 239 Pu + t 94 4 He = 162.5days 2 242 Cm 96 + n; 0 1 cm 96 242 has

It was also obtained from metastable Am- 242 242 Am 95 96 242 Cm + -1 0 e+ . From this reaction cm was obtained

as cm 2 O 3 . 13 isotopes of Cm (from 238 to 250) are known. Bk and Cf: Berkelium (is analogus to terbium) 241 4 Am + He Bkwas seperated 2 243 Bk 97 +2 0 1 n

95

from Am by ion exchange methods. Bk exists predominantly in the (III) state. eight isotopes (mass numbers 243 through 250) are known t of Bk is 4.5hrs.

Californium (Cf) is obtained by the action of 35MeV alpha particle on cm- 2 4 2 . T h e reaction is (,n) 242 4 245 Cf 98 +2 0 1 n; Cf- 245

Cm + He has t 44 min 96 2

Cf exists only in the (III) oxidation state. Es(Einsteinium) and fermium (Fm): Es247 is obtained by the reaction:238U (14N, 5n) 247 Es. It has 11 isotopes from 245 to 256. Es- 254 (t =270days) is obtained in weighable amounts. Fm- 248 is obtained using.

240 Pu (12C,4n) reaction 240 Pu + 94 238 U+ 92 6 12 C 6 16 O 100 248 Fm 100 249 Fm +5 0 +4 0 1 n 1 n

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194

238 U+ 92

16 O 8 Mendelevium

250 Fm 100 (Md): +4

1 n 0 atomic no 101. A very small amount of Es253 is

bombared with 48MeV alpha particles.

The product nuclei were collected by

recoil on a gold foil, so that they were free from Es. The gold foil was dissolved and the new element isolated by the ion- exchange method. Md- 256has a t of 1.5hrs 253 Es + 99 2 4 He 101 255 Md +2 n 0 1

No: Nobelium (102): produced by the bombardment of cm- 246 with C- 12 ions using the 246 Cm + 96 heavy 12 C 6 ionaccelerator 254 No 102 +4 0 1 n

Obtained also by:

238

U ( 2 2 Nc,6n)

254

No ; 2 4 3 Am ( 1 5 N, 4n) 102

254

No 102

No- 252 produced from Cm has t of 2.5sec. LW: Lawrencium (103): The method used to obtain the new element was to

bombard a mixture of californium, with mass numbers 249, 250, 251 and 252, with a beam of B- 10 and B- 11 ions from the heavy ion accelarator . Lw was found to be an alpha particle emitter. By counting the alpha particles, its t was found to be about 8 sec. Element 242 104 22 (Kurchatovium): 260 + 4 n 0 1 b y

Pu + Ne 104 bombarding Pu- 242 94 10 104

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195 u s i n g N e - 22 ions, t was given as 0.3sec. The chloride of the new element was reported elements. Self 1) Check Exercise I to be more volatile than the chlorides of other transuranium

Discuss the synthesis of transuranium elements 2) Compare earths. the properties of transuranium elements with those of rare

17.3 Let us Sum Up The synthesis of transuranium elements is explained in detail. Several nulear reactions are illustrated. The synthesis of Pu- 239 fissile material) is indicated. The exidation states of (an important

tr ansuranium

elements are also explained.

17.4 Points for Discussion:

i) ii)

Discussion of several nuclear reactions Discoveries of transuranium elements and their seperation.

17.5 References 1) Source book on atomic energy Glass tone East, West, New Delhi. 2) Theory and problems of physical chemistryMcGraw Hill New Delhi. Schaum's Outline Series

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196

LESSON 1 8
CONTENTS 18.0 18.1 18.2 AIMS AND OBJECTIVES INTRODUCTI0ON HOT ATOM CHEMISTRY AND RADIO ISOTOPES 18.2.1 HOT ATOM CHEMISTRY 18.2.2 APPLICATIONS OF RADIO ISOTOPES 18.3 18.4 18.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

18.0

AIMS AND OBJECTIVES

After going through this lesson you would be able to understand the simple principle of hot atom chemistry and you would be able to learn about and use in future, the radio isotopes.

18.1

INTRODUCTION

Several

isotopes

both

radioactive

and

inactive The

have

been method

employed represents

to a

investigate

various

chemical

processes.

isotopic

powerful tool for the solution of numerous problems in biology, physiology, chemistry, physics and other sciences. Some of these problems, particularly those having an important bearing on life processes, could not have been solved without the use of isotopes.

It is only in recent years that isotopes have become available in such variety and in such quantity as to make their use as wide spread as it is at present time.

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197 The more important applications of isotopes depend on the fact that the

chemical properties of isotopes of a given element are essentially identical. A radioisotope can be detected by its radioactivity, and an inactive isaotope of spectrometer. Therefore,

particular mass can be identified by means of the

the characteristics property of the isotope namely, its activity or mass can act as a 'tag' or 'label'. The element which has been tagged or labeled is

consequently called a tracer element.

In

general

an For

element example

can

be

labeled 'C'

by

changing 1.1% of

its

natural

isotopic

composition.

ordinary

contains

C- 13, but if the

proportion of this isotope in a particular compound is increased, the carbon has become labeled.

Suppose that acetic acid, in which only the CH3 carbon is labeled, is supplied to an organism then among the metabolic products, appears CO2 gas. Upon testing the gas it is found to be inactive, This shows that the carbon in the 'CO 2 ' originated from the COOH group and not from the CH3 - group. This example is a simple illustration of the type a problem for which an unequivalent solution could not possibly obtained without the use of an

isotopic tracer.

18.2.1

HOT ATOM CHEMISTRY

The name "hot atom chemistry" is given to the study of chemical reactions resulting from the transfer to valence bonds of energy produced in nuclear processes of various kinds.

Isomeric transition is sometimes accompanied by the breaking of a chemical bond.

This many make possible a separation of the isomeric nuclei. An interesting example is provided by the isomers of tellurium, for (eg) Te- 131. If to a Tellurate solutions (Te (VI), containing this species, is added some ordinary

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198 inactive tellurite (Te(IV), then upon separating the latter chemically, it is This is explained as follows: the

found to contain the 25- minutes

isomer.

gamma ray emitted by the upper (1.2days) isomeric state undergoes internal conversion, resulting in the ejection of an electron from a K or L level o t h e f product atom, that is from the lower (25min) isomeric state. As a result of what is known as the "Auger effect', the high energy of this inner (KorL) electron electrons), is transferred which are to one or more of the outer electrons (Valence

consequently removed from the atom. This detachment

of valence electrons from the 25- min isomer results in the breaking of some of the bonds between is the tellurium by and a oxygen change atoms, from the consequently VI to the

isomeric

transition

accompanied

the I V

oxidation state i.e., from tellurate to tellurite.

L.Szilard separate emission residual chemical molecule.

and the of

T.Chalmers product of

employed, an (n,)

this reaction

type

of

hot the

atom targot

chemistru, material.

to The

from

a - ray photon following the capture of a neutron causes the to recoil; the recoil particular energy atom is to sufficient the to break of the the

nucleus bond The

attaching product

this

remainder

atom,

although isotopic with the target atom, will thus

be in a different chemical form, and a seperation from the oroginal material becomes possible. for example, if an aqueous solution of NaclO3 is subjected to the action of slow neutrons, the reaction 3 7 cl(n,) 3 8 cl takes place, but

many of the cl- 38 atoms formed are detached from the chlorate and pass into solution as cl(- ) ions. By adding a small amount of in active chloride to the solution and precipitating with silver nitrate, the resulting Agcl is found to carry the whole of the cl- 38 activity.

18.2.2

APPLICATIONS OF RADIO ISOTOPES

In much of the work in which an isotope is used as a tracer it is necessary to introduce the tracer element into a certain compound to be studied. In

biochemical investigations the object of the study is to determine the fate of the different portions of a given compound. The preparation of labeled

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199 compounds has become an important aspect of tracer studies. For example consider labeled) the synthesis of C- 1 4 l a b e l e d acetic acid (CH3 group is to be

BaCO3

containing

C- 14 is employed. The sequence of reactions can

be represented as:

H BaC * O 3 C * H3 CN (H+) H2 O
*

P C* H3 OH C* H3 I I2

NaCN C* O 2 Catalyst
*

CH 3 CN

CH 3 COOH

To Label COOH, carbon, consider the reaction: CH 3 Mg Br + * CO 2 CH 3 * COOH

TRACER APPLICATIONS: The use of isotopic tracers in biological studies is to obtain information that w i l l m a k e possible a better understanding of many complex processes which take place in living organisms.

Linseed Oil, which contains fats derived from doubly and triply unsaturated acids, was partially "hydrogenated" by means of deuterium as as to give a mixture of both saturated and unsaturated fats, in which two or four of the hydrogen resulting atoms deutero attached fats to the fed carbon to were replaced by deuterium. showed that The the

were

animals.

The

analysis

major part of the deuterium was found to have been deposited in the fatty portion of the body. Further studies indicated that the saturated fats are

desaturated by the removal of deuterium and at the same time the unsaturated fats are saturated by the addition of hydrogen (or deuterium) from water.

Deuterium studies indicate tat only singly unsaturated fats could take part in the equilibrium. Such deuterium studies in animals indicate that the highly unsaturated fats are indispensible in the sense that they must be supplied in the diet, the body being unable to synthesis them. By lebeling various dietary

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200 amino acids with both isotopic nitrogen and deuterium it has been shown

that the formation of creatine in the body requires contributions from three amino acids, namely glycine, arginine and methionine. The creatine is

produced in this manner and is converted into creatine Creatine is the an hydride of the amino acid

at a fairly steady rate, creatine, an important

constituent of animal tissue. An approximately constant amount of creatine is excreted daily in the urine. Tracer studies using radio active iron as tracer indicate that iron is stored in the body in the form of an iron protein combination known as ferritin. When the store of ferritin has attained its normal value it does not increase further, no matter how much iron may be supplied orally. If the iron reserves decrease, then the amount of ferrition decreases, the body is able to absorb iron.

Radio iron studies that indicate iron remains in the hemoglobin as long as the red blood- corpuscles are intact. But when the corpuscles are destroyed, the iron is not lost, it is almost wholly retained in the body and is rapidly incorporated into the hemoglobin of new red corpuscles. It is this

phenomenon which accounts for the small absorption of iron from the food under normal conditions.

Radioactive isotopes have become a valuable tool in the diagnosis and understanding of many diseases. A simple instance is provided by the use of radio sodium to study cases of restricted circulation of blood. A small

quantity of sodium chloride solution, in which the sodium has been labeled w i t h N a - 24, is injected into a vein of the patient's fore arm, a gamma ray counter is then placed in contact with one of the feet. If the blood circulation is normal, the presence of radioactivity is very soon detected in the foot, it increases rapidly and reaches a maximum value within less than an hour. If there is a circulatory impairment of some kind, however, the radioactivity

will increase slowly, showing that blood has difficulty in reaching the foot. By moving the counter to different parts of the body the position of the restriction can be located, and the necessary treatment applied.

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201 It has been found by introducing iron- 59 into the blood of a normal human being that the iron is deposited in and then removed from the marrow, th e spleen and the liver in a manner that is specific for the particular organ. In cases of anemia (deficiency of red blood cells) and polycythemia (excess red cells), the normal behaviour is changed in a manner typical for each disease. In the case of anemia the activity of iron- 59 increases with time. But in the case of a normal human being the activity increases and then decreases with time. In refractory anemia associated with hypoplastic (under developed

marrow), for example, the iron is found preferably in the liver rather than in the marrow where the re d blood cells are formed.

The

tracer

experiments

have

also

demonstrated

that

red

cell

formation

is

controlled by a hormone called erythropoietin, which circulates in the blood stream. At normal conditions are associated with an excess or deficiency of

this hormone.

V i t a m i n B - 12

(comples

organic

compound

containing

cobalt)

has

been

prepared with the cobalt as a radioactive isotope, either co- 57, - 5 8 o r 6 0 a n d its rate of absorption and loss from the body has been studied with the whole body counter. From the results it is possible to distinguish three types of behavior, normal, second, inability to absorb B- 12 from the intestine and

third pernicious anemia, in which there is a deficiency of the vitamin i n blood. Whole- body radiation measurements with labeled B- 12 are being used in the study of pernicious anemia. The position of tumours have been

identified using radio isotopes. I- 131 has been used to study the functioning of thyroid gland. Brain tumor is detected using tracers like the positron

emitter Ga- 58 and the isomer of technetium- 99 in the form of pertechnetate ion. After injection of the radioactive tracer the location of the brain tumor can be found by means of a suitable scintillation camera or a multiple

detector scanner. Co- 60 obtained from the reaction 59Co(n') 6 0 Co, is usedin cancer therapy.

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202 Brain tumors are destroyed using an internal source of alpha particles (and lithium ions). reaction. particles are obtained from B- 10 by means of (n, )

Radio

active

isotopes

have

been

extensively

employed

in

agricultural

research. The use of P- 32, is indicated below. Phosphoric acid containing a k n o w n p roportion of P- 32, is converted into a phosphate such as calcium

superphosphate, tricalcium phosphate or hydroxyapatite suitable for use as a fertilizer. A definite quantity of the labeled phosphorous is then applied to the soil, in which plants are grown. At certain intervals a number of these plants are harvested and the total phosphorous derived from both soil and fertilizer, is determined by chemical analysis of their ash. The radioactivity of the plant ash, combined with the measured specific activity of the

fertilizer, gives the amount of phosphorous which the plant takes up from the fertilizer.

It has been shown by such studies that (in poor soil conditions) corn requires most of its phosphorous fertilizer at the beginning and less toward the end of the growth with potatoes on a similar soil, from 50 to 60% of the

phosphorous uptake came from the fertilizer during the whole period of the growth.

Radioactive Wetting, examples

tracers

have and

been

employed

in

several

industrial

processes.

detergency of surface

floation of minerals, adsorption and lubrication are upon which work has been done with

phenomena

radioactive tracers. Age hardening, annealing, quenching and cold rolling of alloys have been subjected to radio tracer studies to understand the effects of such treatments.

Activation Analysis is a powerful tool in many aspects of science and industry. The basic principle of activation analysis is that one (or more) of the stable isotopes of a given element is activated "i.e, converted into a radioactive nuclide, by a suitable nuclear treatment e.g, bombardment with

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203 neutrons, with accelerated particles or by high energy X- rays. The product

can then be identified by its radiation, i.e, beta particles, or gamma rays and by its half life. By using a comparison sample containing a known amount of the particular element and treating it in exactly the same way as the unknown specimen, the analysis can be made quantitatively. The most common

application of the techniques is probably in testing highly purified substances for traces of impurities. Construction materials and moderators for nuclear

reactors, for example, must be exceptionally free from elements that capture neutrons to a significant extent. Activation analysis provides a sensitive

means for detecting such impurities. Small amount of oxygen present in the steel is detected
16

by

measuring

gamma

ray

from

N- 16

produced

by

the

reaction

O(n,p) 1 6 N

Tracer Analysis

Tracer material

analysis (a

involves

the

addition

of

known

amount

of

an

isotopic

known amount refers to a known rate of particle emission as

determined by a suitable counter) suppose it is required to analyse a solution for the element 'A', present in very small amount. Let the element B be one which forms an insoluble compound AB; a solution of 'B' is prepared with one of its radio isotopes in known proportion i.e, known specific activity. The solution 'B' is then added to 'A', to precipitate all of the 'A' as the insoluble observed 'AB'. count The rate precipitated the total AB is separated of 'B' in and the counted. From can the be

quantity

precipitate

calculated, this is equivalent to the amount of 'A' in the precipitate.

Solubilities of a sparingly soluble salts can be determined by tracer method. A sample of Pb (NO3 ) 2 is prepared containing a known ratio of the alpha emitting isotope Ra- D. The nitrate is dissolved in water and a solution of sulphate is added. The solid PbSO4 containing Ra- D as tracer is then used to prepare a saturated solution in water. This solution is evaporated a n d i t s activity measured. The total amount of lead in the solution and hence the

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204 solubility of lead sulphate can be calculated from the known proportion of Ra- D.

The dilution principle has been applied to determine the volume of water in the body. For this purpose either the stable isotope D2 or tritium can be used as a tracer. A definite volume of water containing one of these isotopes is injected into the body and after allowing about an hour for uniform mixing to take place, a sample serum is withdraw and its isotope content is measured.

From the change in concentration, the volume of water in the body can be calculated. If the isotope concentration is found to be decreased by a factor of 1000, for example the volume of water in the body is 1000 times that originally injected.

Age of uranium can be estimated as follows: Nt = NO e - lt ; N O = U - 238 originally present in the mineral and Nt is the amount left

after the lapse of time 't'. This represents the age of the m ineral. Since essentially all the U- 238 has been converted into Pt- 206, the quantity of Pl206 present is equal to: (N O - Nt) Therefore = (2 3 8 U = 2 3 8 U + 2 0 6 Pl) e lt knowing the

amount of U- 238

and Pl- 206 present and knowing l of U- 238, 't' the age of the mineral can be estimated.

By means of radio carbon dating the age of a dead wood or animal can be estimated.

Several generation

radio in

nuclides satellites.

have

been

employed

as

heat

sources

for

power thermo

Pu- 238 is the heat source in the 25- walt

electro generator used in some satellites.

Self

Check

Exercise 1

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205 1) 2) Explain the term 'hot atom chemistry' and discuss its applications. Discuss the uses of radio isotopes in the fields of i) Biology ii) Medicine iii) Agriculture. 3) Discuss tracer analysis

Self Check Exercise 2

1)

A sample of 14 CO2 was to be mixed with ordinary CO2

for a biological

tracer experiment. In order that 10 cm3 of the diluted gas at STP should have 10 4 dpm, how many/mci of radioactive C- 14 are needed to prepare 60L of the diluted gas? (Ans: ~27 m ci).

2)

In order to determine the volume of the blood in an animal, a 1.00ML of an aqeous solution containing tritium is injected into the animal's blood serum. The sample injected has an activity of 1.8 x 106 sufficient time, of the sample of blood is found to be 1.2 x 10 4 animal's blood (Ans: ~ 300ML). CPS (Counts/sec). After

2.00ML of blood are withdrawn from animal and the activity CPS. Calculate volume of

3)

A sample of uraninite, was found to contain 0.214g Pl- 206, for every gram of uranium. If all the lead came from the disintegration of U- 238, age of the mineral (T50 U- 238 = 4.5 x 10 yrs)
9

estimate

the

18.3 Let us Sum Up Hot atom chemistry is defined. The uses of radio isotopes in the fields of biology, medicine and agriculture are discussed in detail. illustrated. Tracer studies are

18.4 Points for Discussion: 1) Hot atom chemistry definition and other examples.

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206 2) Several uses of radio isotopes

18.5 References 1) Source book on atomic energy Glass tone East, West, New Delhi. 2) T h e o r y a nd problems of physical chemistryMcGraw Hill New Delhi. Schaum's Outline Series

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207 UNIT V I I

LESSON 1 9 CONTENTS

19.0 19.1 19.2

AIMS AND OBJECTIVES INTRODUCTION EXPERIMENTAL METHODS FOR DETECTION OF NUCLEAR RADIATIONS 19.2.1 19.2.2 CLOUD BUBBLE CHAMBER CHAMBER

19.3 19.4 19.5

LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

19.0

AIMS AND OBJECTIVES

The lesson describes the various experimental techniques such as cloud chamber, bubble chamber for the detection of nuclear radiations, After go ing through this lesson you would learn how such instruments like Wilson's cloud chamber made possible the discovery of particles like positron, muon,

various mesons and other particles.

19.1

INTRODUCTION

Instruments like cloud chamber are useful for the transmutation. compelling A single cloud chamber photograph are can

study

of

artificial with single

demonstrate in a

evidence

how

many

fragments

formed

transmutation, process and the directions in which they fly away and how far they are able to travel through the gas in the chamber.

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208 19.2.1 CLOUD CHAMBER

In 1911, Wilson showed that the path of could be made visible. The apparatus is

single as

ionizing

particle Air

known

cloud

chamber.

contained in an enclosed space can be saturated with the vapour of water or any other liquid the amount of the vapour necessary to produce saturation decreasing as the temperature is lowered. Imagine a vessel containing air saturated with water vapour enclosed by a piston. The piston is maintained in position by the pressure of air below it. If the pressure under the piston is

suddenly released, so that it falls, it will result in the immediate expansion of the air or gas in the vessel. The sudden adiabatic expansion causes the air to be cooled and it now contains more vapour at this lower temperature. particles of dust are present in air, they will act as condensation nuclei, If and

the excess of water vapour will separate out as fine droplets of liquid in the form of a cloud or mist.

The

air is saturated with water vaopur and the piston is allowed to

drop to such an extent as will expand the volume of the air by a factor of 1.25 to 1.37 this being the range in which cloud formation can occur. If an ionizing particle after enters the the chamber, the either ions immediately left in the before, path during act or as

immediately

expansion,

will

condensation nuclei, a close array of fine droplets, ie. a kind of linear cloud, called a cloud track will thus be formed. By using strong illumination from the side, the track appears as a white line on the dark back ground. This can be photographed by means of two cameras at right angles, so that a record can be attained from which the path of the single ionizing particle in three dimensions can be studied. Cloud chamber photographs have shown that

alpha particles travel in straight lines.

In the earlier cloud chambers a layer of water or oil was used on the floor of the chamber as a seal for the piston and this meant that the piston could be used only in the horizontal position. Wilson constructed a cloud chamber in which the piston was replaced by a thin rubber diaphragm fixed at its edge. The diaphragm was maintained in a state of tension by means of

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209 compressed air in the back or lower part of the chamber, and when this was released the gas in the chamber underwent sudden expansion. A cloud

chamber of this type can be used in any desired position. To saturate air in the Wilson's chamber water was initially used. But ethyl alcohol or propyl alcohol or a mixture of alcohol and water can be employed to saturate the air in the chamber. The use of alcohol gives better condensation on positive ions, than does water alone and in addition, the extent of expansion necessary for droplet formation is diminished from 1.25 to 1.10 at ordinary pressure. Cloud chambers containing argon are also employed. The pressures range from

b e l o w a tmospheric to about 200 atm. The higher pressures are desirable for the study of high energy (or long range) particles which might otherwise pass right through the chamber without taking part in an event of interest.

For the study of radioactive radiations and for many similar purposes, relatively simple cloud chambers, with air at ordinary pressure, are quite

adequate. Because of the low penetrating power of alpha particles, the source of the radiation, must be inside the chamber. But a substance emitti g ' b ' n particles can be placed outside and the rays cloud allowed tracks to enter through a

'window'. Gamma rays and x- rays,

yield

because

they

liberate

electrons which produce ionization in their paths. These tracks are howeve r very faint. By making visible the track of an ionizing particle, the range of the particle and its energy can be calculated. Eo = 2.12- R 2 / 3 - - - - - - - (1)

Eo = initial energy of the alpha particle in MeV and R is its range in cms of air .

By counting the drops in the cloud track the specific ionization can be determined and the nature of the particle identified, it is thus possible to distinguish between an alpha particle, a proton, a meson and an electron. The particle has the highest specific ionization and gives a short dense track,

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210 while an electron, unless it is moving with very high speed, leaves a track which is diffuse. By determining the radius of curvature of the cloud track in a magnetic field of known strength, the momentum of the particle can be estimated. The direction of curvature indicates the sign of the electric charge

of the ionizing particle. The discovery of the position was made in this manner.

The basic disadvantage of the condensation cloud chamber is that, be cause of the low density of the gas, the significant phenomenans are not very frequent.

19.2.2

Bubble

Chamber

In 1952 D.A.Glaser at the University of Michigan conceived the idea of using super heated liquid to display the track of ionizing particles, just as a cloud chamber uses a super heated vapour. The instrument based on this concept is called a bubble chamber, be cause the tracks consist of a series of closely spaced bubbles, analogues to the small droplets of liquid in the cloud chamber.

Glaser found that when such a super heated liquid was exposed to nuclear radiation, the resulting ions acted as nuclei for the production of small bubbles. The bubbles are spaced at something like a hundredth of an inch apart depending on the specific ionization of the imitating particle, so

that they appear as a fairly continuous track which indicates the path of the particle. As in the cloud chamber, the tracks can be photographed against a dark background.

The medium in the first bubble chambers was diethyl either, but liquid hydrogen, D 2 , He, propane and other liquids have been used successfully. For studying the interaction of particles with protons, the liquid in the chamber is hydrogen. Along with liquid H2 , C 3 H 8 is also used, in the chamber.

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211 For neutron interactions liquid deuterium is employed in the chamber. For studying 'g' rays, liquid containing heavy atoms is favoured. Freon type compounds such as trifluoro bromomethane and liquid xenon have been

employed in the chamber.

The operation of a bubble chamber is similar in many respects to that of an expansion cloud chamber. The liquid is compressed and the temperature is raised to well above the normal boiling point at atmosphere pressure. For (eg) propane has a normal boiling point of - 42 o C. It is compressed to about 21 atmospheres and heated to a temperature of 58o C . T h e pressure is then

decreased suddenly and the liquid becomes super heated. In this condition it is sensitive to the passage of ionizing particle. Even if no such particles enter the chamber, boiling with bubble formation would invariably occur within a short time. Regardless of whether a particle track is formed or not, the liquid must be recompressed before it is again ready for operation.

The earliest bubble chambers had linear dimensions of only one inch or two and were made with smooth glass or lined internally with glass. Larger

bubble chambers (upto 14 feet in length) have been designed for tracking particles of higher and higher energies. Bubble chambers are almost

invariably placed in a magnetic field, of known strength. The momentum of t h e c h a r g e d particles can then be determined from the radius of curvature of the bubble track. For particles of high momentum, the curvature is small, and difficult to measure unless a strong magnetic field is used.

In many studies with high energy particles, it is necessary to analyze a large number of bubble chamber events and then to plot the data in a suitable manner to obtain the probability distribution of various events. This

statistical analysis can also be performed by a computer. The results are then displayed in some convenient graphic manner for use of interpretation.

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212 Nuclear Emulsion In 1909 Miigge (Germany) and S.Kinoshita (Japan) observed that the blackened regions of a developed photographic plate, resulting from exposure to alpha particles, appeared to be made up of individual grains. It was later

realized that the positions of the grains were related to the path of the alpha particles. It was found that ionizing particles, in general record their tracks in a photographic emulsion, as a series of closely silver. spaced black specks of

Because photographic

of

the

relatively the

high

density

(and by

stopping

power)

of

the very

emulsion,

tracks

produced

charged

particles

are

short compared with those found in a cloud chamber. These tracks do not differ greatly from bubble track emulsions They this were tracks. Due to the development of special nuclear is used largely in employed ray in tracking and led charged to the

method widely

particles.

cosmic

studies

discovery of Pi- a n d K - mesons.

T h e c o m p o sition of emulsion had been changed so as to make itmore suitable for the study of various ionizing particles, such as alpha partiles, protons, mesons and even electrons. By adding Boron or lithium contain to the

emulsion neutrons can also be detected. The modern emulsion

silver

bromide to the extent of 80% or more of the dry weight, this being about ten times the quantity present in plates or films used for normal photographic purposes. The silver halide grains are extremely small. The smaller the grain, the more sensitive is the emulsion to ionizing radiations originally the

emulsions were deposited (roughly one eighth of a centimeter thick) on glass plates. Now, stripped emulsions are available without backing.

The tracks produced in a photographic emulsions are very short, (eg) a few thousandth's of an inch for alpha particles from radioactive sources, but they can be magnified and photographed.

The photograph emulsion resembles the Wilson cloud chamber in the respect that it can record individual events involving atomic nuclei and other

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213 charged obtained particles. from Information on concerning the the particles tracks. involved Tracks can caused be by

measurements

photographic

heavy, strongly ionizing particles have numerous thin wavy tracks project ng i from their sides. These are called delta rays and are produced by electrons ejected from the nuclei in the path of the particle. From the number of delta rays per unit track length, the magnitude of the charge in the particle can be estimated.

B y t h e use of very strong magnetic fields, the deflection of long

(but

not short) tracks in photographic emulsions has been observed. This gives the sign of the charge, but the large amount of scattering makes the deflected tracks useless for calculation of momentum. This is a disadvantage of nuclear emulsion.

Self 1) 2)

Check

Exercise 1

How is a cloud formed in the cloud chamber? What are the other compounds that can be used in the cloud chamber? Indicate the advantage.

Self

Check

Exercise 2

1)

How

does

bubble

chamber

work?

Discuss

the

advantages

when

compared to the cloud chamber. 2) Write a note on nuclear emulsion method, in tracking nuclear particles.

19.3 Let us Sum Up The designs of cloud chamber and applications are explained in detail. The advantages of bubble chamber and nuclear emulsion techniques are

indicated.

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214 19.4 Points for Discussion

i) ii)

The designs of the cloud chamber and applications The advantages of the bubble chamber and nuclear emulsion

techniques.

19.5 References 1) Source book on Atomic Energy by Glass tone East West press India.

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215 LESSON 2 0 CONTENTS

20.0 20.1 20.2

AIMS AND OBJECTIVES INTRODUCTION THE DIFFERENT TYPES OF COUNTERS 20.2.1 20.2.2 Proportional Scintillation Counters counters

20.3 20.4 20.5

LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

20.0. AIMS AND OBJECTIVES

After going through this lesson, i)

you would be able to understand

some of the most useful procedures for the detection and

measurement of radiations like Alpha & Beta particles.

ii)

the way in which the measurements of radiations are carried out.

20.1. INTRODUCTION

Becquerel are ionised, as

found the

that result

gases of

become exposure

electrical to

conductors that is they from radioactive

radiations

substances.

The amount of radioactivity could be measured, by measuring

the extent of ionisation by a radioactive source.

A rapidly moving charged particle like alpha or beta particle has the ability to eject orbital electrons from the atoms or molecules of a gas The ejected form negative

through which it passes, thus converting them into positive ions. electrons ions. attach themselves to other atoms or molecules, to

Thus the passage of a charged particle, through a gas results in the

formation of Ion- pairs consisting mainly of positive ions and free electrons. A term 'Specific ionisation' is used to express the intensity of ionisation

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216 produced by a charged particle in its path. formed per cm of path. It is the number of ion- pairs

For particles of same mass and energy, the specific

ionisation increases with the magnitude of the charge, and for particles of the same energy and charge it increases with the mass.

The

total

number

of

ion- pairs

produced

by

charged

particle

is

determined largely by the energy.

20.2.1

PROPORTIONAL

COUNTERS

One has to understand the behaviour of ion- pairs in electric fields. Quantitative measurements of radiations are based on counting of individual

particles, as well as on the determination of total radiation received in a given interval of time. For these purposes instruments have been developed

in which the positive and negative ions formed by the ionising radiations are driven towards the collecting electrodes, by means of an applied potential

under various conditions.

Consider for example an apparatus consisting of a vessel, containing gas or air, in which two electrodes, connected to a battery are fixed. circuit also contains a current measuring instrument. The

Normally the air in the If any

vessel does not conduct electricity and hence no current is observed. ionising radiation such as alpha or beta particle enters the vessel small electric

and when a

potential is applied to the electrodes, the ion- p a i r s p r o d u c e d

and the applied potential would produce a pulse of current. The magnitude of the charge collected and therefore the size of the current pulse will depend on two factors viz.

i)

the number of ion- pairs produced between the electrodes and

ii)

the

applied

voltage.

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217 When number of logarithm regions of pulse be size is plotted A few against these applied regions voltage have a

could

obtained.

been

employed to measure the radiations.

The

proportional

counter is based on the fact that, for a given applied

voltage across the electrodes, the size of the current pulse is proportional to the number of Ion- pairs produced between the electrodes. best obtained by using a cylindrical chamber, which acts This condition is as the negative

electrode, with a central wire, is the positive electrode.

When the voltage is high enough, the electric field near the central wire becomes so large that the electrons, produced by the primary ionization of the gas, by an alpha or beta particle, would move toward it with very high speed. When the speed becomes very high the electrons would cause the

ionization of the other atoms or molecules in the gas, this produces more electrons which cause further ionization. This multiplication effect is often

known as 'Townsend avalanche or Townsend Cascade.

The

total

number o f i o n - pairs produced by a single primary ion- p a i r i s

called the gas amplification factor. The size of the current produced by a single particle is thus increased to a very great extent, so that considerably less external amplification is required. Pulse counting is employed in a

proportional counter.

In the proportional counter the magnitude of the potential ranges from 500 to 800 volts. Various gases have been employed for filling proportional counter tubes. A mixture is used consisting of a simple gas such as hydrogen

or Argon, which favours high amplification and a gas like carbon dioxide, methane or pentane, to provide stability of operation For (eg) a typical gas mixture consists of methane and 10 to 20% by volume of argon.

The proportional

total

pressure of

is the

always

less

than an

1 alpha

atm.

Because will

of give

the a

character

amplification,

particle

larger pulse than a Beta particle or a gamma ray photom. Hence proportional

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218 counting instruments are particularly useful for counting alpha part c l e s i n i

the presence of beta particles and gamma rays.

Geiger Muller Counter

This counter is widely used in radioactive counting. It is known as GM counter. Because the detecting portion is commonly in the form of a tube, the names Geiger - Muller tube or G- M tube are commonly used.

The essential difference between the proportional and the GM counter is that, in the proportional counter an electron from an ion- pair, produces an

avalanche at one point only, whereas in the G.M. Counter, the avalanche spreads along the whole length of the central wire. In the Geiger counter, the amplification is so great that the size of the pulse is almost independent of the number of Ion- pairs. When the applied potential in the instrument reaches a value known as 'Geiger threshold potential', the number of pulses per

minutes ( due to the production of ion- pairs by the entering alpha or beta particles), becomes essentially constant. The range of potential plateau, over which

this occurs is known as 'Geiger

plateau'. Beyond this

continuous

discharge occurs and counting is not possible. Most G.M counters are filled with gas at pressure below atmospheric pressure, when the plateau may

extend over a range of two or three hundred volts in the region from about 800 to 1500 volts. The trouble with GM counter is that, the separate pulses produced by different particles entering the Geiger tube are not resolved. To improve the resolving power of the G.M counter a mixture of gases like argon and methane is used for filling the Geiger tube. This quenches the discharge (self quenching) and resolution is improved.

When properly quenched (internally or externally) a G.M counter will have a resolving time of about 200 micro second, in other words, particles arriving at intervals of not less than 2 x 10- 4 seconds will give separate

pulses. If the particles were produced at a uniform rate, a maximum of 5000 pulses could be counted per second. less- than this maximum. Actually the practical counting rate is

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219

The GM tube is almost invariably used to determine the rate at which radiation is being received at a particular point. For this purpose the output

of the GM tube, generally without amplification is applied to a counting rate meter.

Because of their versatility GM tubes have been made in great variety of sizes and shapes from 1 cm to 1 m in length and from 0.3 cm to 10 cm in diameter. The walls can be of metal, e.g., copper, or a metal cylinder may be In another form of GM tube the interior

supported inside a glass tube.

surface of the glass tube is coated with a thin layer of an electrical conductor like silver or graphite. The central wire of the GM tube (which acts like 0.05 mm the

anode) is usually made of tungsten, with a thickness of 0.02 to pressure in the GM tube is usually less than atmospheric pressure.

G- M

counters

are

mainly

used

for

counting

beta

and

gamma

rays,

partly became it is difficult to make tubes with windows thin enough to be penetrable by alpha particles. When the penetrating power of the beta

radiation is small, the tube may have a very thin glass or mica window through which the particles can pass.

In health protection operation, it is required to know that radioactive material is present and to know a rough indication of the quantity of

radiation. convenient.

For this purpose the GM counter with a rate meter is very GM tubes are rarely designed to detect alpha particles, because

of their short range in air and small penetrating power.

For

the

detection

and

rough

measurement

of

the

intensity

of a l p h a

particles, some form of proportional counter is generally used.

20.2.2.

SCINTILLATION

COUNTER

: It is based on when of certain these

This is one of the oldest methods of counting particles. small flashes are of light (or to scintillations), nuclear which are The produced

materials

exposed

radiations.

production

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220 scintillations, involves the initial formation of high energy (or excited)

electronic state of the molecules (or atoms).

The excess energy which has

been obtained from the nuclear radiation, is then emitted within a very short time as a flash of light. Each particle produces a flash of light.

The scintillations

first they

attempt generated

to in

count a

alpha

particles was made

by by

observing

the

diamond

E Regen e r i n -

Germany in 1908.

Ruther Ford and Geiger, at the same time compared the

number of pulses, produced by Ra- c source, in an ionization counter and the number of scintillations produced by the same source, on a ZnS screen and they found that the numbers were the same. Thus if each alpha particle gives

one pulse in the counter, it also gives one flash in the scintillation counter.

In this manner, Ruther the scintillation method of

Ford and Geiger established the reliability of counting, produce alpha particles. when Certain exposed large organic to and

inorganic

phosphors

which

scintillations

nuclear quantities

radiations, are transparent

to the light they emit.

Therefore

of the scintillator can be used in the counter.

This ensures high probabilit y Thus using a

of interaction with the radiation and high detection efficiency.

photo multiplier tube in a scintillation counter along with the phosphor, helps in the counting of particles from a radio active source. o f n a p h t h a l e n e as scintillation counter. phosphor was employed with a A large clear crystal phototube in the

The crystal of the phosphor,

surrounded by thin aluminium foil, is The purpose of the A particle of nuclear

attached to the top, close to the cathode of the phototube. foil is to reflect the light flashes on to the cathode.

radiation (or gamma ray photon) entering the phosphor causes a flash of light, which falls on the photo cathode. As a result electrons are emitted and electric pulse

these are subsequently multiplied to produce a relatively large

at the output of the tube. Of the solid organic scintillators, anthracene and transstilbene appear to be the best. Liquid scintillators (solution containing

xylene as the solvent and a few percent of diphenyl oxazole as the solute have also been employed in scintillation counters. One of the best inorganic

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221 scintillators 0.1%. expecially as for gamma rays, Zns, is crystalline by sodium Ag is iodide an with

Thallium

activator.

activated

excellent

scientillator and is made in thin layers. of alpha particles. Inert

Its chief application lies in the study

gases have also been used as scintillators.

When

rapid

response

is

required

NaI

scintillator

cannot

be

satisfactorily used.

(the light pulse produced has long decay time)

Scintillation reasons : i) iii) iv) vi) vii)

counters

have

found

many

uses

due

to

the

following

they are simple

ii)

Flexible

and

versatile

high sensitivity to all forms of nuclear radiations. rapid response v) very short resolving time

can be used to measure photon energies superior to GM counters for gamma ray detection.

Self Check

Exercise 1

1. 2. 3.

How are ion- pairs produced in an ionization chamber? Discuss the design and uses of proportional counters. Write a note on G.M. counter and also indicate its advantages

Self Check

Exercise 2

1. 2.

Discuss the design and uses of scintillation counters How many types of phosphors are used in the scintillation counters?

20.3 Let us Sum Up The designs and advantages of different types of counters are explained in a detailed manner. The G.M. Counter is explained and its advantage is indicated. Examples of different types of phosphors used in Slintillation

counter are given.

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222 20.4 Points for discussion

i) ii)

The designs and advantages of different

types of counters

A comparative study of different types of phosphors employed in scintillation counters.

20.5 References i) ii) Inorganic chemistry J.D. Lee Source book on atomic energy g l a s s t o n East west press - India

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223 LESSON 2 1 CONTENTS 21.0 21.1 21.2 AIMS AND OBJECTIVES INTRODUCTION PARTICLE ACCELERATORS 21.2.1 CYCLOTRONS 21.2.2 BETATRON- BEVATRON 21.3 21.4 21.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

21.0

AIMS AND OBJECTIVES

The aim of this lesson is to make an in depth study of different types of particle accelerators.

After going through this lesson one would be able to understand

i)

The design and the uses of accelerators for accelerating the variou s types of particles

ii)

The

energies

attained

by

different

particles,

when

particles

are

accelerated by various types of accelerators.

21.1

INTRODUCTION

A particle accelerator is a device for increasing the kinetic energy of electrically charged particles. Upto about one tenth of the velocity of light, the kinetic energy can be calculated by means of Mo V2 , where mo is the rest mass of the particle and V its velocity.

Since 'm' is constant, increase of kinetic energy implies increase of v e l o c i t y . I t is kinetic energy, the for is this called reason an of that the machine As mass the also employed velocity for of increasing particle these

'accelerator'. light, its

the Under

approaches

velocity

increases.

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224 circumstances, an accelerator can increase the kinetic energy with very little increase in velocity.

M a n y n u c l ear

reactions

have

been

studied

by

high

energy

particles.

Accelerators have been used in the creation of new particles. The muon and mesons have been discovered using high energy particles. Several additional

particles not previously known have been found using high energy particles. Calculations indicate that protons with energy of 5.6billion electron volts

would be required to create antiprotons and antineutrons. The anti protons and antineutron and of are not known to occur in nature. For was the discovery at of the

antiprotons University

antineutrons.

Beaverton

accelerator

designed

California.

Accelerators have also been designed to study the nuclear structure, the nuclear forces and strong and weak inter actions.

Protons of 400 to 1000 MeV energy are used to produce intense beam of pions. Natural decay of pions may inturn yield muons and neutrons of high energy.

The

growth

of

high

energy

particle

physics

is

due

to

the

particle

accelerators.

21.2.1 CYCLOTRONS

Lawrence

modified

the

'Wideroe'

Cylindrical

(linear

accelerators)

accelerator by using a magnetic field to make the charged particles follow a spiral path, of increasing radius. The length of the path would then increase

automatically with the speed of the particles. The 'cyclotron' was designed on the basis of this principle.

The first accelerator to yield protons of energy in excess of 1 MeV was the cyclotron constructed by Lawrence and Livingston in 1932. It had a magnet with pole faces 11 inches in diameter. The energy to which a particle

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225 can be accelerated in a cyclotron increases with the radius of the magnet and with the strngth of the magnetic field.

The cyclotron consists of two flat semicircular boxes known as 'dees' because of their shape. These does are surrounded by a close v e s s e l , d

containing a gas at low pressure, placed between the poles of a magnet. A radio- frequency alternating potential, of about 10 to 20 mega cycles per

second, is applied between the dees, which act as electrodes. An electrically heated filament in the vessel, produces a stream of electrons, which cause ionization of the gas such as deuterium or helium contained in the vessel. The filament deuterons thus or can alpha be regarded as the source at of any positive particular ions (protons), the

particles.

Suppose

that

instant

alternating potential is in the direction which makes the first 'dee' positive and the second 'dee' negative. A positive ion from the source would be attracted to the second D which is negative), but as a uniform magnetic field a c t s i n a direction at right angles, the particle will move in a circular path. The radius 'r' of the particle is given by r = mv/Be (1) where

'm' is the mass of the ion, 'e' is its charge 'v' its velocity and 'B' is the strength of the magnetic field.

While it is in the interior of the dee, the speed of the ion remains constant. But after describing semicircular path through the second dee, the particle reaches the gap between the dees, where it becomes subject to the action of the applied of potential the difference. When the the first dee, ion becomes will be

negative,

(because

alternating

potential)

positive

accelerated toward the first dee. Since its energy is consequently greater than it was originally the ion will move faster, i.e, 'v' will increase. Therefore the

circular path in the first dee will have larger radius, under the influence of the magnetic field, as per equation (1). The significant property of the

cyclotron is that the time taken by the particle to traverse the semicircular path is independent of the velocity of the particle or of the radius of the path. In other words, the increase in length of the path, due to the larger radius, is exactly compensated by the increase in velocity of the ion. The time taken to

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226 traverse the path 'T' is given by T= p r/V ----------- (2); r = radius of the path. from (1) T = p m/Be ----------- (3).

Thus 'T' is independent of both V and r. This means that if the frequency of oscillation is adjusted to the nature of the ion and to the

strength of the magnetic field, the charged particle will always keep in phase with the changes of electric potential between the dees. Thus each time the particle crosses the gap from first dee (D1 ) to second dee, ( D 2 ) it will receive an additional impulse toward D2 ; on the other hand when it crosses from D2 t o D 1 it will be accelerated toward D1 , for the direction of potential will then be reversed. The result of these repeated impulses is that the energy of the ion is steadily increased, and at the same time it describes a flat spiral of increasing radius. Eventually the ion reaches the periphery of the dee and it can be brought out of the dee chamber by means of a deflecting plate, which is charged to a high negative potential. The attractive force acting on the

positive ion draws the latter out of its spiral path, and it can be used to bombard any desired material. Although the above description refers single particle, the source supplies ions to a

continuously, thus a stream of high

energy particles will emerge from the cyclotron.

The maximum velocity at the periphery is given by : BeR/m (R is the radius of the dee).

Therefore the kinetic energy 'E' of the ion, coming out of the cyclotron is: E= M (BeR/m)2 E = B2 R 2 /2 x e2 /m. It can be seen from this equation
2 that the maximum energy acquired by a particle is determined by B R2 .

Therefore in order to obtain ions of high energy, it is necessary to increase the strength and size of the magnet. By using a 60 inch particles of 40MeV were obtained. cyclotron alpha

SYNCHROCYCLOTRON At higher energies, the rest mass of the particle increases (due to

increase in velocity). For example a deutron having an energy of 20 MeV

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227 (obtained from 60 inch cyclotron) has a velocity about 0.145 times the

velocity of light. Its effective mass is 1.01 times the rest mass, as given by. m = mo/ 1- V2 /C 2 ; V is the velocity of the particle, mo is its rest mass and 'C' the velocity of highest.

At higher energies, the mass of the particle increases to such an extent that its effect becomes appreciable. As the mass of the ion increases, the time of transit 'T' also increases (T & m at constant B). Because of this the particle will no longer be in phase with the alternating potential, and

consequently it will gain no additional energy.

For the 'T' to be unaffected by the increase in mass, the magnetic field is left unchanged but the frequency of the oscillating potential is decreased so that fm = constant, f = frequency m mass of the particle. MCmillan

(1945) pointed that if the oscillation frequency is adjusted continuously to coincide revolution with of the the decreasing charged frequency is of revolution of the particl,the with the

particle

automatically

synchronized

changing frequency of the alternating of potential. The action is similar to that in a synchronous motor and hence the name 'Synchrotron' was proposed by Mc Millan.

The cyclotron was modified to permit variation of oscillation frequency to compensate for the increase in mass of the machine is referred to as a 'Synchrocyclotron' accelerated or a ions. Hence the

frequency

modulated

cyclotron. It uses a single dee instead of two dees, the oscillating potential being applied between it and a ground connection. Every time a charged particle enters or leaves the dee, it acquires additional energy, so that it follows a spiral path (just as if two does were employed) R.F frequency is

decreased to compensate for the gain in mass of the particle as its speed increases. energy By using produced. improved frequency modulators, protons of 720MeV

were

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228 ELECTRON CYCLOTRON:

The conventional cyclotron is not used to accelerate electrons because of the large relativistic increase in mass even at fairly low energy. This is because deuteron. mo for electron is very small compared with that of a proton or

For

specified

particle

energy,

lower

magnetic

field

strength

is

required in a cyclotron of a given size for the acceleration of electrons than for protons because of smaller mass. Electron cyclotrons have been designed

without iron- core magnets, the necessary magnetic fields being provided by the passage of electric currents through suitably shaped coils.

21.2.2

BETATRON:

For the acceleration of electrons to high energies, above approximately 1MeV, the cyclotron principle is not applicable. Electrostatic accelerators of the type 'van de Graff' generator are useful upto 10 to 20 MeV. For energies

of the order of 100 MeV, other devices have to be employed. For this purposes, D.W.Kerst developed 'Betatron', since it was designed to accelerate

electrons (which are identical with beta particles). The first useful induction accelerator, the betatron, accelerated an electron to an energy of 2.3 MeV.

The

action

of

the

betatron

is

based

on

the

familiar

principle

of

transformer. In the transformer an alternating current applied to a primary coil induces a similar current, usually with a higher or lower voltage, in the secondary windings.

In the betatron the secondary is an annular

(ring shaped) evac uated

glass (or ceramics) tube. It is often called a 'dough nut'. This is placed between the poles of a specially shaped electromagnet, energized by pulsed current passing through the coils. The purpose of this magnet is to produce a strong field in the central space or "hole" of the dough nut, and therefore it is constructed with a good amount of iron in the core. Heated filaments produce

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229 electrons and these are given initial acceleration by application of an electric field having a potential difference of 20,000 to 70,000 volts. Even with low energies, thus obtained, the electrons travel at very high speeds, from nearly 1/5th to the velocity of light.

As the field strength starts are injected due into to the an field. doughnut. induced

to increase, the partly accelerated electrons The energy within of the the moving electrons by is the

increased growing

EMF,

doughnut,

caused

magnetic

Since the electrons are moving

in a magnetic field, the electrons are

forced into a curved path. The increasing magbetic field keeps them moving in a circle of constant radius. The equation r = mv/Be shows that as the field strength moves in proportion to the momentum of the electrons, 'r', remains constant. Thus, the electrons are kept moving around the doughnut in a fairly stable, circular path. in each trun the electron acquires energy. When the magnetic field reaches the maximum point of the since wave cycle, a pulse current is sent through an auxiliary coil, which suddenly changes the

magnetic field. The high energy electrons are displaced from their stable path and can be used to produce x- rays or can be used for other purposes.

Betatron operation electrons, energies of due might

can the to he

produce betatron increase is in

electrons

with by

very the

high

energies. in

Since of

the the high

unaffected energy, by it

increase appear

mass

would of

that But

extremely the

possible

means

betatron.

accelerated

electrons lose energy by radiation and hence there is a limit to the energy that can be acquired by electrons in the betatron. Energy losses have been

minimized by means of large doughnut radius (120cms)

PROTON SYNCHROTRON Attempts were made to produce particles of very high energies in the range of thousands of MeV ie billion electron volt (109 ). Radiation losses, i n

the case of electrons prevented from acquiring electrons of BeV range. But

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230 with protons loss due to radiation is small. Hence protons can be accelerated to very high energies using cyclic accelerator.

By means of 'Proton Synchrotron' 2 to 3 BeV protons

were

produced.

The proton synchrotron consists of four quadrants joined by straight pieces. In the Berkeley beavatron, the radius of each quadrant is about 55' and the connecting pieces are ~20' long. Alternating current is used for energing

purposes. The magnet consists of a large number of plates surrounding only the quadrants of the doughnut. Protons accelerated to about 6 to 10 MeV, initially by vande Graff generator, is injected into the synchrotron. After

having their energy increased, as a result of many revolutions, the protons are removed by a deflector. Injection and removal take place outside the magnetic field.

To keep the protons in the synchrotron moving in a circular path of constant radius, the strength of the magnetic field is increased in proportion

to the momentum. Similarly for proper synchrotron action, the frequency of the radio frequency alternations is increased in such a manner that the

condition of phase stability is maintained.

In proton synchrotron deviations from circular path, of particles occur, as a result of fluctuations. The deviations are observed both in horizontal and vertical direction. are The magnet is designed in such a way that both the

deviations

decreased.

Zero gradient synchrotron is designed to accelerate energies by using a stronger magnetic field than in

particles to higher the conventional

synchrotron.

Self 1.

Check

Exercise 4

Calculate the mass of an electron, when its velocity becomes equal to 1/5th the velocity of light.

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231 2. Discuss the cyclotron in detail.

Self 1.

Check Discuss

Ecercise 2 the principle of synchrocyclotron

2.

Write briefly on i) ii) Betatron Bevatron

21.3 Let us Sum UP i) Cyclotron and its design are discussed in detail. Synchroogclotron is explained. synchrotron Betatron is and Bevatron are discussed in detail. Zero gradient

explained.

21.4 Points for Discussion i) Cyclotron and its design

ii)

How does the mass increase affect the operation of cyclotron and the modifications introduced in Synchrocylotron?

iii)

The different types of proton synchrotrons to be discussed.

21.5 References 1) Source book on atomic energy by Glass tone East West press India.

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232

UNIT VIII THERMAL ANALYSIS LESSON 2 2

CONTENTS 22.0 22.1 22.2 AIMS AND OBJECTIVES INTRODUCTION THERMAL ANALYSIS 22.2.1 TG D T A 22.2.2 APPLICATIONS 22.3 22.4 22.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

22.0

AIMS AND OBJECTIVES

The

aims of

and

objectives

of

this

lesson

are

to

understand such as

the

methodologies gravimetric

different and

thermal

analyses thermal

techniques .

thermo through

analysis

differential

analysis

After

going

this lesson you would be able to use these methods to Obtain information concerning the detailed structure and composition

of different phases of a given sample. Understand how heats of reactions are obtained and used to determine the purity of materials.

22.1 22.2.1

INTRIDUCTION TG D T A RELATED TECHNIQUES

Thermal

analysis

includes

group

of

techniques

in

which

specific

physical properties of a material are measured as a (Table 1.1). The production of new high

function of temperature

technology materials and the

resulting requirement for a more precise characterization of these substances have increased the demand for thermal analysis techniques. Current areas of

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233 application product Thermal properties coals. measure dimensional An include environmental stability, has been chemical used to measurements, reactions determine boards, and the composition dynamic and analysis, properties. chemical and can

reliability, analysis of

physical

polymers,

electronic

circuit

geological

materials, 1.1)

integrated, transition changes,

modern

thermal

analysis

instrument energies

(Figure of

temperatures, and

weigh

losses,

transitions,

viscoelastic

properties.

Thermal analyses.

analysis may their and

is be

useful

in

both and

quantitative characterized Information phases

and by

qualitative qualitative the

Samples of

identified

investigations detailed

thermal

behaviour. of different

concerning

structure

composition

of a given sample is

obtained from the analysis of thermal data. Quantitative results are obtained from changes in weight and enthalpy as the sample is heated. The

temperatures of phase changes and reactions as well as heats of reaction are used to determine the purity of materials.

Table 1.1 SUMMARY OF THERMAL ANALYSIS THECHNIQUES Techniques Differential scanning calorimetric (DSC) Quantity Measured Heats of and Temperatures and Typical application Reaction analysis kinetic, polymer purity cures

transitions

reactions Differential thermal analysis (DTA) Thermo gravimetric analysis (TGA) Thermo mechanical analysis (TMA) Dynamic mechanical analysis (DMA) Evolved (EGA) gas analysis Dimension changes Modulus, damping and and Temperatures of transitions and reactions Phase diagrams, thermal

stability Thermal stability compositional analysis

Weight change

viscosity Softening temperatures, expansion coefficients Impact resistance, mechanical stability Analysis organic of volatile of

viscoelastic behavior Amount of gaseous products of thermally

components

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234 induced reaction shale

FIG 22.1

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235

The

use

of

microprocessors

has

both

enhanced

and

simplified

the

techniques of thermal analysis. The sample is heated at a programmed rate in the controlled environment of the furnace. Changes in selected properties of a sample are monitored by specific transducers; which generate voltage signals.

The signal is then amplified, digitized and stored on a magnetic disk along with the corresponding direct temperature responses from the sample. The

data may also be displayed or plotted in real time. The microcomputer is used to process the data with a library of applications software of designed for

thermal systems

analysis allow a

techniques. single

The

multitasking to

capabilities several

some thermal

computer analyzers

microcomputer

operate

simultaneously

and

independently.

major

advantage

of

microcomputer

systems

in

thermal

analysis

is

that the operator seldom, if ever, needs to repeat an analysis because of an improper choice of ordinate scale sensitivity. The software does this

rescaling after all the data have been collected. In some systems both axes are automatically rescaled after the last data point has been received. When the amount is of time necessary For to obtain a thermal data is considered, the

advantage 10 o C/min

obvious. room

example, to

differential

scanning c a l o r i m e t r i c r u n

from

temperature

1100 o C takes 100 min, and thus the

rerun of the sample would take longer than 2hr including the time required for cooling and sample reloading.

DIFFERTIAL ANALYSIS

SCANNING

CALORIMETRY

AND

DIFFERENTIAL

Differential thermal analysis

scanning techniques.

calorimetry In this

(DSC)

has

become sample

the

most

used

technique,

the

and

reference

materials are subjected to a precisely programmed temperature change. When a thermal transition (a chemical or physical change that results in the

emission or absorption of heat) occurs in the sample, thermal energy is added to either the sample, or the reference containers in order to maintain both the sample and reference at the same temperature (Figure 1.2(a)). Becaus t h e e

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236 energy transferred is exactly equivalent in magnitude to the energy absorbed or evolved in the transition, the balancing energy yields a direct calorimetric measurement of the transition energy. Since DSC can measure directly both the temperature and the enthalpy of a transition or the heat of a reaction, it is

often substituted for differential thermal analysis as a means of determining these quantities except in certain high- temperature applications.

In

differential

thermal

analysis

(DTA),

the

difference

in

temperature

between the sample and a thermally inert reference material is measured as a function of temperature (usually the sample temperature) (Figure 1.2(b). Any transition that the sample undergoes results in liberation or absorption of

energy by the sample with a corresponding deviation of its temperature from that of the reference. A plot of the differential temperature, T, versus the programmed whether the temperature, transition analyses T, is indicates the transition or the temperature (s) and and as a

exothermic of

endothermic. change in

DTA weight

thermogravimetric

(measurement

function of temperature) are often run simultaneously on a single sample.

FIG 2 2 . 2 ( a ) & (b)

In DTA, the furnace contains a block with identical and symmetrically located chambers. The sample is placed in one chamber and a reference

material such as a - Al 2 O 3 , is placed in the other chamber. A thermocouple is

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237 inserted into the centre of the material in each chamber. The furnace and sample blocks are than heated by a microprocessor controlled heating

element. The difference in temperature between sample and re f e r e n c e ( S , R ) thermocouples, After connected (about in 1000 series times) opposition, by a is continuously again, measured.

amplification for

high

low noise dc

amplifier

microvolt level signals, the difference signal is recorded as

t h e y - axis. The temperature of the furnace is measured by an independent thermocouple and recorded as the x- axis. Because the thermocouple is placed in direct contact with the sample, DTA provides the highest thermometric accuracy of all thermal methods. DTA can be used in the from - 190 temperature range to 1600o C. Sample sizes are similar to those used in DSC.

Although reaction sample's and the

the area of a DTA peak is proportional to the heat of mass of the sample, is it a is inversely function of proportional grain to the and

thermal

diffusivity,

which

size

compactness. This inverse relationship prevents. DTA peak areas from being used to provide direct calorimetric measurements. It is necessary to calibrate a DTA instrument for each type of sample and to carefully control

experimental parameters to obtain useful thermodynamic data.

THERMOGRAVIMETRY Thermogravimetry (TG) or thermogravimetric analysis (TGA) provides

a quantitative measurement of any weight changes associated with thermally induced transitions. For example, TG can record directly the loss in weight as a function of that temperature involve or time (when or under isothermal conditions) for

transitions

dehydration

decomposition.

Thermogravimetric

curves are characteristics of a given compound or material due to the unique sequence definite of physical transitions The and rates chemical of these reactions thermally that occur over

temperature

ranges.

induced

processes

are often a function of the molecular structure. Changes in weight result f r o m physical and chemical bonds forming and breaking at elevated temperatures. These processes may evolve votatile products or from reaction products that result in a change in weight of the sample. TG data are useful in

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238 characterizing materials as well as in investigating the thermodynamics and

kinetics of the reactions and transitions that result from the application of heat to these materials. The useful temperature ranges for TG is from ambient to 1200o C in either inert or reactive atmospheres.

In TG

the

weight

of

the

sample

is

continuously

recorded

as

the

temperature is increased. Samples are placed in a crucible or shallow dish that is positioned in a furnace on a quartz beam attached to an automatic recording balance. Figure 1.3 shows a TG instrument that contains a tautband suspension electromechanical transducer. The horizontal quartz beam is

maintained in the null position by the current flowing through the transducer coil of an electromagnetic balance. A pair of photosensitive diodes acts as a position sensor to determine the movement of the beam. Any change in the weight of the sample causes a deflection of the beam, which is sensed by one of the photodiodes. The beam is then restored to the original null position by a feedback current sent from the photodiodes to the coil of the balance. The current is proportional to the change in weight of the sample.

FIG 22.3
Linear heating rates from 5 to 10o C/min are typical. Sample sizes range from 1 to 300mg. Computer software allows the computation of w/ t,

which is important in kinetic interpretations of reactions and processes. TG has been used in the kinetic analysis of polymer stability, Compositional

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239 analyses of multi component materials, atmosphere analyses and corrosion

studies, moisture and volatiles determinations, and accelerated tests of aging.

EVOLVED GAS DETECTION AND ANALYSIS The analysis, is useful analysis differential in of the purge gas exit stream from differential thermal

scanning

calorimetry, mechanism evolved

and and

thermogravimetric analyzers stoichiometric relationship the of

establishing In

thermal

decompositions.

gas

analysis

(EGA)

absolute

identities of the gaseous components are determined, whereas in evolved gas detection (EGD) the presence of only a single. preselected component of the evolved gas is sensed. An appropriate analyzer may be coupled to a

thermogravimetric system for performing either EGA of EGD. The resulting hyphenated methods are powerful analytical tools. Two analyzers that have

been successfully coupled to TG systems are mass spectrometers (MS) and flame ionization detectors (FID). The TG- MS or TG- MS- MS used for evolved gas analysis, whereas the TG- FID evolved gas combination is

combination

provides

detection. These hyphenated methods are used in studies of the

votatile organic pyrolysis products of oil shales.

The is shown

simultaneous in figure.

TG- DTA- MS analysis of copper sulfate- pentahydrate 1.4. The quadrupole changes of mass water during spectrometer during the
o

detects

the to

temperature- d ependent 300 o C. The evolution

intensity of

dehydration

sulpur

dioxide

two s t e p s u l f a t e -

decomposition to copper (II) oxide between 600 and 900 C is also clearly seen. Electron impact ionization in the MS is responsible for the production of sulfur monoxide (SO) radical ions.

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240

FIG 22.5
22.2.2 APPLICATIONS METHODOLOGY DIFFERENTIAL AND OF THERMOGRAVIMETRY, CALORIMETRY ANALYSIS

SCANNING

DIFFERENTIAL

THERMAL

Thermogravimetry (TG)

The weight- change TG curve for calcium oxalate monohydrate is shown in Fig- 1.5. Water is evolved beginning slightly above 100o C. At about 250o C the curve breaks at the stoichiometry corresponding to that of the anhydrous s a l t . F u r t h er heating gives definite weight plateaus for the carbonate (from 500 to 600o C) and finally the oxide (hotter than about 870o C ) . E x a c t

locations of the weight plateaus are dependent on the heating rate (a slower heating rate shifts values to lower temperatures) and the ambient atmosphere around the sample particles. The curve is quantitative in that calculations can be made to determine the stoichiometry of the compound at any given

temperature.

Thermal Deviations

analysis by

is

affected

by

the include

experiments\a l c o n d i t i o n s. furnace atmosphere, size

caused

instrumental

factors

and shape of the furnace and sample holder, sample holder material and its

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241 resistance to corrosive attack, wire and bead size of the thermocouple

junction, heating rate, speed and

response of the recording equipment, and

location of the thermocouples in the sample and reference chambers. Another set of factors that influence layer the results depends size, on the sample

characteristics;'

these

include

thickness,

particle

packing density,

amount of sample, thermal conductivity of the sample material, heat capacity, the ease with the which gaseous effluents can escape, and the atmosphere

surroundings

sample.

Thermogravimetry, a valuable tool in its own right, is perhaps most useful when it complements differential thermal analysis studies. Virtually

all weight- change processes absorb or release energy and are thus measurable by DTA or DSC, but not all energy- c hange changes in weight. to be This made difference between in the processes two and are accompanied enables a by clear the

techniques chemical

distinction

physical

changes

when

samples are subjected to both DSC (or DTA) and TG tests.

EXAMPLE - 1 Thermogravimetry can also be

FIG 22.5
used to determine the composition of

complex materials such as carbon black- filled rubber. Figure 1.6 shows the

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242 result of rapidly heating a rubber sample in an inert atmosphere of nitrogen

from room temperature to 950o C and then quickly changing the atmosphere to air. Heating the sample in an inert environment results in the

FIG 22.6
pyrolitic decomposition of the rubber and gives the first major weight loss observed in the scan. The addition of air at 950o C causes the carbon black to undergo combustion to produce the second loss in weight, leaving in the balance pan only inert filler. All the major components of the rubber sample were determined quantitatively from a single TG scan.

DIFFERENTIAL

SCANNING

CALORIMETRY

(DSC)

AND DIFFERENTIAL THERMAL (DTA)

In general, each substance gives a DSC or DTA curve in which the number, features shape serves and as a position means of of the various endothermic of and the exothermic substance.

qualitative

identification

When an endothermic change occurs, the sample temperature lags behind the reference temperature because of the heat in the sample. The initiation point

for a phase change or chemical reaction is the point at which the curve first

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243 deviates from the baseline. When the transition is complete, thermal diffusion brings the sample indicates back the to equilibrium at quickly. which The the peak reaction (or is minimum) completed.

temperature

temperature

When the break is not sharp, a reproducible point is obtained by drawing one line tangent to the baseline and another tangent to the initial slope of the curve.

Various The blank

behaviors

deduced for a DTA curves are shown in Figure 1.7.

heat capacity at any point is proportional to its displacement from the

FIG 22.7
baseline. A broad endotherm indicates a slow change in heat capacity. A "Second order or glass" transition observed as a baseline shift (T1 ), denotes a decrease in order within the system. This is the temperature at which a polymer material. changes The from lower a the brittle, glass glasslike transition material to a tough, the resilient the

temperature,

lower

temperature at which the polymer is useful in applications, such as adhesives o r i m p a c t - resistant structures. In a thermoset, a high glass transi ion t

temperature indicates incomplete cure of the resin; In a thermoplastic, a high galss transition temperature in the indicates the of use the of the wrong itself. plasticizer or

incomplete generally

reaction represent

formation

polymer

Endotherms

physical rather than chemical changes. Sharp endotherms transitions for

(T 3 ) are indicative of crystalline rearrangements, or solid- state relatively pure materials. Broader endotherms (T2 ) cover

behaviour

ranging

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244 from of with dehydration polymers. the and temperature dependent (without a phase phase behaviors decomposition) or chemical of a to is the melting associated Narrow system,

Exothermic in

behaviour of

decrease usually

enthalpy

system.

exotherms

indicate

crystallization

(ordering)

metastable

whether it be supercooled or annealing of stored

organic, inorganic, amorphous polymer, or liquid, energy resulting from mechanical or stress. curing Broad of

exotherms thermosetting

denote resins.

chemical Exotherms

reactions, with

polymerization,

decompositions

can be either narrow or

broad depending on the kinetics of the behavior. Explosives and propellants are sharpest, and the "Unzipping" of polyvinyl chloride is rapid, whereas

oxidative combustion and decomposition are generally broad.

On cooling one would

expect the reverse of features observed on the

heating cycle (Figure 1.7). Since T4 does not recur on cooling, the reaction is obviously taking the nonreversible system up (perhaps to T4 , a the pyrolytic cooling decomposition). be started Instead before of that cycle

temperature. As it cools, the substance is seen to lose its transition peak at T3. Judging from the area under the T2 peak, the transition energy of T3 h a s been added to T2 . retained energy This indicates in a one metastable large condition at a at T 3 , lower with the being released step temperature.

Further along the cooling curve, the glass transition at T1 falls properly into place to complete the cycle.

Determining

the

significance

of

thermoanalysis

curves

is not always a

straightforward task. A reference library of curves of specific interest to a particular storage products laboratory and or quick thermal is vital. Computerized of data. points systems offer the capability on of

retrieval transition

Thermoanalysis for pure

data

commercial in the

substances

reported

literature are of little value for the comparison with a dynamically scanned thermal thermally profile. evolved Complementary gaseous techniques with are valuable. The correlation calorimetry of or

products

differential

scanning

differential thermal analysis transitions using evolved gas analysis or evolved gas detection often assists in elucidating the decomposition mechanism.

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245 Running thermal decompositions in inert, oxidative, or special atmosphere s

can often provide valuable clues from changes in the curves.

Example 2 The TG and DTA curves of manganese phosphinate monohydrate shown in Fugure.1.8. The are

weight loss data (TG curve) from a 200- mg

sample run under vacuum and with the analysis of effluent gases showed the loss of 1 mole of water at 150o C, 1 mole of phosphine at

FIG 2 2 . 8 ( a ) & (b)

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246

o 360 o C, and the slow loss of another mole of water starting around 800 C.

After comparison with the DTA curve, two major peaks remain unidentified: the large exotherm at 590o C and the endotherm at 118o C, plus several smaller thermal under features. vacuum and Thermogravimetric in a nitrogen data obtained failed from to runs show performed any loss

atmosphere

associated with these peaks. Each sample was measured for its real density. The resulting data are shown on the DTA curve, Undoubtedly the sharp DTA exotherm at 590o C represents a phase change. The relatively small endotherm starting above 900o C must represent a recrystallization exotherm following

the elimination of water. Which is superimposed on the latter endotherm. The peak at 1180o C is due and to melting. With this information the thermal

decompositions

reaction

phase changes are:

Mn(PH 2 O 2 ) 2 H2 O(s ) Mn(PH2 O 2 ) 2 (s ) - M n H P O 4 (s ) 2 MnHPO4 ( s ) Mn 2 P 2 O 7 (s)

Mn(PH 2 O 2 ) 2 (s) + H2 O(g) Mn HPO 4 (s) + PH3 ( g ) b - MnHPO 4 (s) Mn 2 P 2 O 7 (s) + H2 O(g) Mn 2 P 2 O 7 (l) (and recrystallization)

Thermal studies with polymers can predict a product's performance in use that is, its stiffness, and toughness, or stability. are Melting point, Phase Once

transition,

Pyrolysis,

curing

temperatures

accurately

measured.

a polymer has been broadly classified by other, methods, curves are often used to establish, by comparison with known reference materials, the degree of polymerization, the thermal history of the sample, crystal perfection and orientation, of the effect of different the coreactants extent of and catalysts, branching. branched the For chain percentage example, polymer

crystalline for a

polymer,

and

chain

curves

low- molecular- weight,

nonlinear,

show a continuous series of rather broad and low- melting- point endotherms, whereas single a high- molecular- weight, and cured, stereo regular, endotherm. may linear If a an polymer polymer reveals has a

narrow

higher- melting- point the heating cycle

been at a

incompletely

reveal

exotherm

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247 temperature exotherm which just close to the the one melting is used for the polymerization "cold being reaction. An

below if a

temperature quenched and

indicates after

crystallization," melted. On

results

sample form

quickly

reheating,

crystallites

rapidly

exothermically just prior to remelting

of the polymer. Annealing temperatures are similarly revealed as exotherms.

If the molecular weight or density of a polymer has been established by appropriate (often lengthly) methods, subsequent determination of its melt

temperature (a 15- min process) can be related to molecular weight or density. Product polymer appropriate quality is maintained to obtain subsequently molecular by simply or examining densities curves from of an

materials

weights

calibrated graph.

Instead of using the traditional method of preparing a derivative from the organic sample and a reagent, the sample is heated with a specific reagent at a programmed heating rate in a selected atmosphere. The DTA or DSC curve shows the derivative forming reaction, the physical transitions of the

sample or reagent (whichever is in excess), and the physical transitions of the intermediates and final products. When one reactant is volatile and in excess, a rerun usually shows only the derivative characteristics.

The area of exotherms or endotherms is used to calculate the heat of the reaction or the heat of a phase transition. Suitable calibration is necessary with DTA equipment, but the values are given directly with DSC instruments.

Example 3 Polyethylene is a semi crystalline thermoplastic that when heated

undergoes a process of melting. This melting destroys the crystal structure of the polymer and is an endothermic process. Although plastics usually melt over a temperature range, the melting point is defined as the temperature at which the melting is complete. The melting point of a plastic is an important property because it is minimum temperature for processing the plastic and the maximum temperature for applications where structural integrity is required.

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248 A second important is the its property percent useful for the characterization Many are of semi crystalline that

thermoplasticsc gives the

crystallinity. attributes

physical on

properties the

plastic

dependent

percent

crystallinity.

Both the melting point and the percent crystallinity are obtained from a single differential scanning calorimetry scan (Figure 1.9). The melting is taken as 133o C, d i f f e r e n t i a l scanning where the melting is is approximately quantitative, the complete. peak point Since area is

calorimetric

directly

equal to the heat fusion. Hf , in units of calories per gram. The percent crystallinity is determined by assuming that the heat of fusion is proportional to the percent of crystallinity of the sample. Thus if the heat of fusion of 100% Polyethylene has been determined to be 68.4 cal/g and the measured

heat for the sample is 54.5 cal/g the percent crystallinity is 79.7%, as shown in figure 1.9.

FIG 22.9

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249 Self 1. Check What Exercise - 1 are the different

thermal

analysis

techniques?

give

their

applications in a few words. 2. 3. 4. Self 1. 2. 3. What is the importance of microcomputer system in thermal analysis. Explain the process of DTA. Give any one disadvantage of DTA . Check Exercise 2

Describe thermogravimetry. Discuss the thermogravimetric method with an example. 20 Mg sample of crystalline calcium oxalate of molar mass 146, in a thermal sample. study loses about 2.46mg H2 O above 150o C. Formulate the

Activity: Run a TGA and DTA for a known sample from the instrument available in the Chemistry Department of Bharathiyar University.

Model Answer Self 4. Check Exercise 1 to the heat of a

Although the area of a DTA peak is proportional

reaction and the mass of the sample, it is inversely proportional to the sample thermal diffusivity which is a function of inverse relation prevents, DTA peak areas grain size and compactness. The from being used for direct

calorimetric measurements. It is necessary to calibrate a DTA instrument for each obtain type of sample and to carefully control experimental parameters to

useful

thermodynamic

data.

22.3 Let us Sum Up i) Theories of TGA and DTA are discussed in detail ii) Experimental methods are illustrated iii) The applications of TGA and DTA techniques are illustrated using typical TG and DTA curves for a few compounds.

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250 22.4 Points for Discussions: i) ii) The different thermal methods and their application may be discussed. Obtain interpret TGA the and DTA curves from a standard source and try to

results.

22.5 References 1) 2) ATKINS PHYSICAL CHEMISTRY 7th Edn. OUP INDIAN - 2 0 0 2

Instrumental methods of analysis Willard, Merrtts Dean 7th Edn CBs New Delhi.

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251

LESSON 2 3
CONTENTS 23.0 23.1 23.2 AIMS AND OBJECTIVES INTRODUCTION AUGER 23.2.1. ELECTRON Principle and SPECTROSCOPY experimental (AES)

method

23.2.2. Applications 23.3 23.4 23.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

23.0

AIMS AND OBJECTIVES

The aim of the lesson is to study and understand the auger emission phenomenon and to understand the importance of Auger emission

spectroscopy in studying surfaces of solids. would be able to learn :

After studying this lesson you

The principle of Auger effect Auger effect effectively takes the fingerprint of the material.

23.1

INTRODUCTION

When an atom is excited by the removal of an electron from an inner energy level, it may return to its normal state by transferring an electron from some outerlevel to the vacant inner level. The energy of this transition

either appears as X rays or is used to eject a second electron from the outer shell Fig. 2.1. This latter method is called the Auger emission process;

observation of the energy of such an ejected electron leads to a method of

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252 analysis emitted, known their as Auger emission are spectroscopy of (AES). that If element X rays and are their

wavelengths

characteristic

intensities are proportional to the number of excited atoms. emission methods can be used for both qualitative and

Thus, X ray quantitative

measurements.

Atoms are excited in several ways : by direct bombardment of the material with electrons and other Auger particles (direct emission (particle emission analysis, electron bombardment PIXE), or probe with by

microanalysis, protons or

spectroscopy), by x- ray

induced

emission,

irradiation of the material with X rays of shorter wavelength.

In the latter

case, the exciting X radiation causes an inner electron to be ejected with subsequent emission of the characteristic X rays of the sample (fluorescence analysis). It is also possible to measure the energy of the electrons ejected

from the sample, and this leads to a method of analysis known as electron spectroscopy for chemical analysis (ESCA)

Another method of X- ray analysis uses the differing absorption of X rays by different materials (absorption analysis). Major discontinuities in the

absorption of X rays by an element occur when the energy of the X rays becomes sufficient to knock an electron out of an inner level of an atom.

Still

another

method

of

using

rays

in

analytical

work

is

the This

diffraction of X rays from the planes of a crystal (diffraction analysis).

method depends on the wave character of the X rays and the regu l a r s p a c i n g of planes in a crystal. analysis, they are Although diffraction methods are used for quantitative most widely used for qualitative identification of

crystalline phases.

Since electrons quickly lose their energy by colliding with molecules, methods that involve electron bombardment or detection of emitted electrons must be carried deeply out into in solid a vacuum. materials or Furthermore, escape from since any the electrons significant surface cannot depth of

penetrate

when generated in a solid, such methods

characterize

layers

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253 solids (AES) and and are useful for analyzing for surfaces. chemical Auger analysis electron (ESCA), spectroscopy are carried

electron

spectroscopy

out in a vacuum and usually characterize not more than the outer 2 nm of the surface under investigation.

In

1913

Moseley

first

showed

the

extremely

simple

relationship for

between atomic number, Z, and the reciprocal of the wavelength, 1/ l

each spectral line that belongs to a particular series of emission lines for each element in the periodic table. c --l = a(Z - s ) 2 . (1) This relationship is expressed as

FIG 23.1

23.2 23.2.1

AUGER

EMISSION measures

SPECTROSCOPY electrons emitted

(AES) from a surface, induced by

AES

electron bombardment (Fig. 2.1b). atomic level by a primary electron.

The first step is ionization of an inner Once the atom is ionized, it must relax

b y e mitting either a photon (an X ray) or an electron (the nonradiative Auger process). In most instances nature chooses the Auger process. electron For example, the initial

a KLL Auger transition means that the K- level

undergoes

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254 ionization, An L- level electron moves in to fill the K- level vacancy and, at

the same time, gives up the energy of that transition (L to K) to another L- level electron, which then becomes the ejected Auger electron. Other

Auger electrons originate from LMM and MNN transitions. atom is doubly ionized.

At this point the

The energy of the ejected electron is a function only

of the atomic energy levels involved in the Auger transition and is thus characteristic of the atom from which it came. A threshold energy, related to

t h e t ransition energy, exists and a primary energy five to six times greater than the Auger energy maximizes the sensitivity to that particular transition. All elements except hydrogen and helium produce Auger peaks. Most

elements have more than one intense Auger peak so that a recording of the spectrum of energies of Auger electrons released from any surface, compared with the known spectra of pure elements, enables a chemical analysis to be made.

Since an excited atom can lose energy by the X- ray emission process or by Auger electron emission, the relative sensitivities of these two techniques are complementary when considering the relative abundance of X rays and Auger electrons after ionization of a particular level. (Z < 30), the Auger sensitive. For process dominates, the which electron makes In the light elements AES relatively becomes more more

heavier

elements,

microprobe

sensitive for transitions following ionization of inner shells. of AES is maintained, however, by utilizing Auger transition

The sensitivity between outer

shells for example, MNN where the Auger process dominates.

Although the penetration of the primary electron beam may be as deep as 1 m m for highaverage, of much energy electrons, the Auger electrons emitted are, on the lower energies. Electrons of such low energy must

originate very close to the surface if they are to escape without being lost by inelastic scattering before reaching the surface. Typically, Auger electrons

come from the first few atomic layers; the sampling depth is about 2 nm.

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255 The sensitivity of the Auger technique is determined by the probability of the Auger transitions involved, the incident beam current and energy, and the collection efficiency of the energy analyzer. With a high s e n s i t i v i t y

cylindrical mirror analyzer (CMA), the detection limit for the elements varies between 0.1 and 1 atomic percent (or 10- 3 of a monolayer). Because the

electron beam can be focused to a small diameter (50 mm), it is possible to do spatial resolution or surface mapping of a sample. manner, AES is run resulting elemental usually with in referred to as the Auger guns When operated in this microprobe. and this on AES is

traditionally analyzers, primarily

high- intensity fast analysis. with

electron

low- resolution limits chemical one to

Unfortunately, little information

information

bonding,

such as one clearly obtains in the chmical shifts of electron scattering for chemical analysis (ESCA), or in the molecular fragments found in secondary ion mass spectrometry (SIMS). For example, hydrocarbon compounds appear

in AES only as a C peak, since H is not observed.

Fig. 2.2 shows the Auger spectra of Ag, Cd, In and Sb, the (MNN transitions). The spectra are very similar; the only major difference is the

shifts in energy from one element to the next.

These shifts are of the order

of 25eV and, since the peak positions can be measured to an accuracy of + 1 eV, there is no ambiguity in the identification of adjacent elements in the p e r i o d i c c hart. eV. The KLL Auger spectra of all the elements lie between 50 and 1000 transitions correspond quite nicely with tabulated X ray -

energies.

There are, however, some minor differences due to the energy The Auger lines are the exact origins and

Auger electrons must lose in escaping from the sample. relatively broad due to the double uncertainty of

destinations within a sublevel of both the electrons that fall into inner levels and those being expelled from outer level. Lines due to LMM transitions

tend to correlate with X- ray energies, but some lines begin to appear that the selection rules for photon emission forbid. As the atomic number increases,

the Auger spectra become more complex and may overlap.

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256

FIG 23.2
The strength of AES is its ability to give both a qualitative and

quantitative nondestructive analysis of the elements in the immediate surface atomic layers from a very small area of a solid. c o n t r o l l e d r e m oval of surface layers by ion When combined with a AES provides the

sputtering,

means to solve some very important problems, such as corrosion on metallic surfaces. To provide ion sputtering for surface cleaning and / or depth

profiling, the sample chamber is backfilled with argon and an electron impact source is used. AES Instrumentation The Auger spectrometer consists of an ultra- high vacuum chamber

console, a sample carrousel and manipulator unit, and a combination electron

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257 gun / energy analyzer unit. incidence electron gun and a Auxiliary equipment often includes a grazing sputter ion gun for cleaning surfaces and

profiling studies.

Auger spectrometer are available as large- b e a m ( ~25- m m)

depth- profiling instruments or as Auger microprobes with beam diameters of 5m m. also If an instrument is to be used as a high- sensitivity depth as a high lateral resolution microprobe, two electron profiler may and be

guns

required to realize the optimum use of each operating mode.

The

energy

distribution

of

electrons

emitted

from

the

target,

NE

is

evaluated by scanning the negative voltage applied to the outer cylinder of the cylindrical mirror analyzer (CMA) (Fig. 2.3) Thus as the voltage applied to the outer cylinder is scanned, the secondary electron distribution is

measured by the current output of the analyzer. superimposed electrons, function. it on has a rather large popular continuous to

Because the Auger pea k s a r e background of secondary the N E

become

differentiate

electronically

FIG 23.3

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258 23.2.2 Quantitative Analysis with AES APPLICATIONS Quantitative of peaks depend analysis on the is possible in principle. The relative intensities cross

following

variables:

inner- level

ionization

sections, Auger transition rates, and inelastic scattering of the emitted Auger electrons. With careful calibration, quantitative analysis of a homogeneous

sample should be achieved with an accuracy of about 10%. Thus, although quantitative value in Auger spectroscopy analysis. is- not very exact, it is still of significant

surface

The difficulties in the quantification of Auger data are illustrated in depth- profiling analysis. In this operation the change in peak shape of the differentiated concentration. oxidation where changes state spectra Changes of the distorts in the conventional shape atom. in occur This the is peak- height because of estimates changes severe in in of the cases

peak

emitting are

particularly

bonding also

orbitals may be

involved by

Auger effects, may

transitions. since be the

Peak 'shape energy in the loss

induced effect on

matrix shape

mechanisms matrices.

and To

their provide

peak

different within

different normal

accurate

quantitative

information

quantitative limits of AES, it is necessary to use the total Auger current. This i s e x p r e ssed by the area under the curve for the peak of interest, with background subtracted. By using undifferentiated data and integrating over

the total number of Auger electrons in the peak, one still has a choice of the limits of integration. Now chemical shifts may be observed and a depth

profile can be realized with no artifacts.

Scanning

Auger

Microprobe

(SAM)

The scanning Auger microprobe has a finely focused, scanning electron beam as the probe for AES analysis of a surface. For a surface area, the SAM provides an electron micrograph, an Auger image of selected elements on a cathode ray tube display for observation or photographing, and a depth -

composition profile. First, the cathode ray tube image is used to determine specific points or an area of interest on the sample surface. From the

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259 micrograph chosen for obtained, points of interest or an area up to 200m m can be

compositional

analysis.

The image mode is useful because the positions of various elements in the sample are delineated in a few minutes. An xy recording of a line scan across a selected region of the image for a given element gives a relative quantitative measure of its concentration.

The thin- film analyzer mode of the SAM simultaneously sputter- etches a relatively large surface area (several millimeters in diameter) and

multiplexes the Auger signals from a smaller area about 15 m m in diameter. U p t o - six selected Auger peaks can be recorded as the surface is etched.

Depth resolution is about 10% of the total etched thickness. Elements are detected when present in quantities down to 0.1%of a monolayer.

At best, the spatial resolving power of SAM'is 500 nm with tungsten thermionic emitters as the electron source. The use of LaB6 , the resolying power to 100- 200 brightness. Field emitters, nm because provide of their high which even higher emitters electron extends optical are

brightness,

expected to allow one to analyze smaller areas in less time when they come into use.

Many

surface

composition

problems

involve

compositional

in-

homogeneity, both in depth and across a material surface. Scanning Auger microscopy offers high images, resolution combined with in the form of scanning electron For

microscope- type

elemental

mapping

capabilities.

example, graphite present in spherical nodules indicates that a specimen of cast iron is ductile cast iron. Examination of the carbon Auger images shows carbon to be present not only in the graphite concentration, circular in regions around between nodules. nodules. The iron nodules is image but not also, at lower in to the be

Carbo'n Auger

evident iron

regions

shows

present everywhere in the specimen surface except in the graphite regions.

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260 Self Check exercise 1 1) Explain how Auger emission occurs? 2) 3) Compare the Auger emissions with other X- ray methods Explain the terms KLL and MNN transitions.

Model answers Self 3) check exercise 1

KLL Auger transition means that the K level electron undergoes initial

ionisation, an L- level electron moves into fill the K- level vacancy and at the same time gives up the energy of that transition (L to K) to another L level electron, which then becomes the ejected Auger electron. the atom is doubly ionised. In MNN transitions

Self 1) 2)

Check

exercise 2

Indicate the limitation in AES method. Discuss the applications of the AES techniques.

23.3 Let us Sum Up i) Auger emission is explained; ii) Auger emission is compared with o t h e r X - ray methods. Applications of AES are illustrated. The limitation of

AES method is also indicated.

23.4 Points for discussion i) Comparison of various X- ray techniques ii) The importance of AES in the analysis of surfaces by SAM

23.5 References 1) 2) ATKINS PHYSICAL methods CHEMISTRY 7th Edn. OUP INDIAN - 2 0 0 2 of analysis Willard, Merrtts Dean 7th Edn

Instrumental

CBs New Delhi.

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261 LESSON - 2 4 CONTENTS 24.0 24.1 24.2 AIMS AND OBJECTIVES INTRODUCTION PHOTO ELECTRON SPECTROSCOPY 24.2.1THE TECHNIQUE 24.2.2 ULTRAVIOLET PHOTO ELECTRON SPECTROCOPY AND X- RAY PHOTO ELECTRON SPECTROSCOPY 24.3 24.4 24.5 LET US SUM UP POINTS FOR DISCUSSION

REFERENCES

24.0

AIMS AND OBJECTIVES

To

understand

the

spectral

methods photo

such

as

ultraviolet

photoelectron

spectroscopy and X- ray

electron

spectroscopy.

The objective is to

i)

Learn

the

importance of solids.

of

these

techniques

in

studying

the

surface

characteristics ii)

How UPS can be used to study the details of valence shell electrons.

24.1 INTRODUCTION PHOTO ELECTRON SPECTOSCOPY

The technique of Photoelectron spectroscopy (PES) measures the ionization different energies. energies orbitals, The of molecules the used when electrons to are infer and ejected the the from orbital important

and uses is

information to study

technique

solids

information that it gives about species at or on surfaces.

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262 24.2.1 THE TECHNIQUE

Because energy is conserved when a photon ionizes a sample, the energy of the incident of photon hv must be equal to the sum of the the sample and the kinetic energy of the

i o n i z a t i o n e n e r g y , I, photoelectron, the

ejected

electron

(Fig.3.1)

FIG 2 4 . 1

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263 1 hn = 2 This equation (which is like the one used for the photoelectric effect, can be refined in two ways. First, Photoelectrons may originate from one of a number of different orbitals, and each one has a different ionization energy. Hence a series of different kinetic energies of the photoelectrons will be obtained, each one satisfying 1 hn = 2 w h e r e 1 i is the ionization energy for ejection of an electron from an orbital i . Therefore, and by measuring the kinetic ionization interpreted Which energy energies energies in terms states of of can of that the the be an the me v2 + 1i . (2) me v2 + 1 . (1)

photoelectrons, determined.

knowing n spectra

these are

Photoelectron called 1i

approximation ionization electron

Koopmans is equal to

theorem. the

energy (formally

orbital

ejected

1i = - Ei). That is, we can identify the ionization

energy with the energy of the orbital from which it is ejected. Th e theorem is only an approximation because it ignores the fact that the remaining electrons adjust their distributions when ionization occurs.

The ejection of an electron may leave an ion in a vibrationally excited state. Then not all the excess energy of the photon appears as kinetic energy of the photo electron, and we should write. 1 hn = 2 w h e r e E + v i b is the energy used to exite the ion into vibration. Each vibratioal quantum that is excited leads to a different kinetic energy of the photoelectron, electron and gives rise to the vibrational structure in the me v2 + 1i + E+ vib

photo

spectrum.

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264 The ionization energies of molecules are several electrovolts

even for valence electrons, so it is essential to work in at least the ultraviolet region of the spectrum and with wavelengths of less than about 200nm. Much work has been done with radiation generated by a discharge through helium: the He(I) line (1s1 2p 1 1s2 ) lies at 58.43nm,

corresponding to a photon energy of 21.22 eV. Its use gives rise to the technique electrons of ultraviolet photoelectron spectroscopy (UPS). When core

are being studied, photons of even higher energy are needed

to expel them: X- rays are used, and the technique is denoted XPS. A modern version of PES makes use of synchrotron radiation, which may be continuously turned between UV and X- ray information that stems from the variation energies. of the The additional

photoejection

probability with wavelength is a valuable guide to the identity of t e h molecule and the orbital from which photo ionization occurs.

Example 1

Photoelectrons energies of 5.632eV

ejected (1eV

from =

N2 with He (I) radiation had kinetic 8065.5cm 1 ). Helium (I) radiation of and therefore

wavelength 58.43nm

has wavenumber 1.711 x 105 c m 1 of 21.22eV. So

correspondents to an energy

Then from eqn 21.2 eV = 5.63 eV+Ii

Ii = 15.59 eV. This ionization

energy is the energy needed to remove an electron from the HOMO of the N 2 molecule, the 3s g bonding orbital.

Self

Check

Exercise 1 same circumstances, photoelectrons are also detected

Under the at

4.53eV. To what ionization energy does that correspond? Suggest on origin.

The kinetic energies of the photoelectrons are measured using an electrostatic deflector that produces different deflections in the

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265 paths of the As photoelectrons the field as they is pass increased, between charged of plates different

(Fig.3.2).

strength

electrons

speeds, and therefore kinetic energies, reach the detector. The electron flux can be recorded and plotted against kinetic energy to obtain the photoelectron spectrum.

FIG 2 4 . 2
24.2.2 Ultraviolet Photoelectron Spectroscopy

A typical photoelectron spectrum (of HBr) is shown in (ig.3.3). If we disregard the fine structure, we see that the HBr lines fall into

two main groups. The least tightly bound electrons (with the lowest ionization energies and hence highest kinetic energies when ejected)

are those in the nonbonding lone pairs of Br (with I = 11.8 eV). the

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266 next ionization energy lies at 15.2 eV, and corresponds to the removal of an electron from the H- Br s b o n d .

FIG 2 4 . 3

The accompanied principle

HBr by

spectrum a long account an (HBr)+

shows

that

ejection

of The if

as

electron

is

vibrational for this

progression. progression of ion

Franck- condon ejection bond in a were length bond-

would by

accompanied between HBr

appreciable

change the

equilibrium is formed

and

because

compressed state, which is consistent with the important bonding effect o f t h e s electrons. The lack of much vibrational structure in the two

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267 bands labeled 2 P is consistent with the nonbonding role of the Br4pp

lone pair of electrons, for the equilibrium bond length is little changed when one is removed.

Example

The highest kinetic energy electron in the spectrum of H2 O u s i n g 21.22 eV. He radiation are at about 9 eV and show a large vibrational spacing of 0.41 eV (or 3310 cm 1 ), which is similar to the vibrational wavenumber molecule of the symmetric stretching mode of the neutral HO 2 cm 1 ). Therefore, we can suspect that the electron is

(3652

ejected from an orbital that has little influence on the bonding in the molecule. That is, photoejection is from a largely nonbonding orbital).

X-Ray

Photoelectron

Spectroscopy

In electrons

XPS, are

the

energy from

of

the inner

incident cores are

photon of

is

so As to

great a

that first

ejected core

atoms.

approximation,

ionization

energies

insensitive

the

bonds

between atoms because they are too tightly bound to be greatly affected by the changes are that accompany of bond formation, so core rather ionization than the

energies overall

characteristics

the

individual

atom

molecule.

Consequently, XPS gives lines characteristics of the

elements present in a compound or alloy. For instance, the K shell ionization energies (eV) of the second- row elements are

Li 50

Be 110 690

B 190

C 280

400 530

Detection of one of these values (and values from other inner shells) indicates is the

corresponding of the the

to

ejection

presence for

corresponding name

element.

This

appliation

responsible

alternative

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268 electron spectroscopy for chamical analysis (ESCA). The technique is

mainly limited to the study of surface layers because, even though Xrays may penetrate into the bulk sample, the ejected electrons cannot escape except from within a few nanometers of the surface. Despite (or because of) this limitation, the technique is very useful) for stud ying the surface state of

heterogeneous c a t a l y s t s , t h e

differences between surface and bulk

structures and the

FIG 2 4 . 4
processes that can cause damage to high and semiconductors wafers. temperature superconductors

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269 Whereas it is largely true that core ionization energies are

unaffected by bond formation, it is not entirely true, and small but detectable shifts can be detected and interpreted in terms o the f

environments of the atoms. For example, the azide ion, N3 , gives the spectrum shown in Fig.3.4. Although the spectrum lies in the region of 400 it has a doublet + structure with splitting 6 eV. This splitting can be understood b y n o t i n g that the structure of the ion is N = N= N, with more negative charges (eV (and hence is typical of N1s electrons),

on the outer two 'N' atoms than on the inner, the formal charges are 1 , + 1 , - 1).

The presence of the negative charges on the terminal atoms whereas the positive charge on the

lower the core ionisation energies, central atom rises it.

This inequivalence of the atoms results in two

lines in the spectrum with intensities in the ratio 2: 1 observations like this can be used to obtain valuable information about the presence of chemically inequivalent atoms, of the same element. The other applications are give below : The XPS (X- r a y p h o t o electron spectroscopy) is able to finger print the materials presen . t

The UPS which examines electron ejected from valence shells, is more suited to establishing the bonding characteristics and the details of

valence shell electronic structures of the substances on the surfaces. Its usefulness is its ability to reveal which orbitals of the adsorbate are involved in the bond to the substrate. spectroscopy studies indicate the For example the photo emission in p electron energies of This

differences

benzene in the free state and in the adsorbed state, on palladium.

difference is due to the fact that benzene molecules tie parallel to the surface and are attached to it by their p - orbital.

Self 1. 2.

Check

exercise 2 How is it useful?

State Koopman's theorem.

Discuss the applications of PES & UPS spectroscopies

Model answer self check exercise-1 hn = KE + Ii hn = 21.22 ev and KE = 4.53ev

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270 Hence I = 21.22 4.53 16.7ev this corresponds to the origin of the electron from 1p u .

24.3 Let us Sum Up i) Kopopmans theorem is explained. ii) Applications of PES and UPS spectroscopies are discussed. iii) PES spectrum of HBr is illustrated.

24.4 Points for discussion 1) Analysis of Ionisation energies from photo electron spectroscopy

provides evidence for the molecular orbital structures of molecules. 2) One can specify which is the Homo of the molecule from the ionisation energy value. 3) Analysis of the photo electron spectrum of a molecule like HBr shows, that the lowest energy bands correspond to Bromine lone pair and the highest energy band corresponds to removal of 's' bond electron.

24.5 References 1) 2) ATKINS PHYSICAL methods CHEMISTRY 7th Edn. OUP INDIAN - 2 0 0 2 of analysis Willard, Merrtts Dean 7th Edn

Instrumental

CBs New Delhi.

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271