“MAGNETOCHEMISTRY aol be added as a correction. Pascal’ _ correction, an independent meas: In the field of coordination co ligands are realised in the form diamagnetic correction cannot and Pascal’ S constants are of invaluable aid in making such ‘urement on the groups or ions being unnecessary. mplexes, often syntheses of otherwise untractable of transition metal complexes only. In such eases, be made by actual measurements on the ligands, * constants are the only solutions to the problem. 11.7. MULTIELECTRON SYSTEMS 11.7.1. Coupling Schemes and Ground Terms : It has been noted in single elec- tron system that paramagnetism arises out of orbital and/or spin angular momenta. In multielectron system it is therefore imperative that one knows the resultant angular momenta of the system. The orbital angular quantum number, J, can take up any integral value from 0 to (2—1) where 7 is the principal quantum number. A particular value of / is associated with an orbital angular momentum yector, J, such that J = vii+ 1) 3g This vector can assume 2/ + 1 orientations in space. If a particular direction 4s specified, for instance the direction of an applied magnetic field, the projections of Jin the direction of the field may have values +! to—I. These projection values are the magnetic quantum numbers my. Similarly the spin quantum number, s, is associated with a vector s, where — The value of s is always } and single electron m, values will £ being parallel or antiparallel to the applied magnetic field. Orbital angular momentum vectors, J of individual electrons can couple a resultant vector ZL, The angular momentum vector of an electron is per- to gi Pendicular to the plane of rotation of the electron and the direction follows from a right handed screw motion (Chapter 1). Electrons have their planes of motion inclined to each other. The vectors of the individual electrons preci about a common axis while maintaining their mutual inclination and thus giving the resultant vector Z (Fig. 11.7), In order to keep electrostatic repulsions at a mini- mum electrons tend to stay on opposite sides of the nucleus and also tend to rotate about the nucleus in the same direction. This leads to a maximisation of the resultant ZL vector. Similarly the individual spin vectors, s, of electrons can also couple to give rise to a resultant spin vector, $. These orbital and spin resultant vectors L and $ can again couple (via the magnetic dipoles they induce) to give a relict vector J. This L-S coupling is also know as Rus aunders coupling ; (81,526) Whe.) = (SL) = 7 The strengths of the various couplings follow the order : % 9 > hk > SL Another coupling scheme involves the coupling of the spin and orbital vectors ofq Lectro ling of the indi ial nn vectors), being followed by a coup! ” on This aoa Jj coupling but this is of little importance for our p Each of these vectors has associated with it a quantum number. Theresultan quantum numbers can have values varying by integral steps between themaximum Fic. 11.7. Coupling of Z vectors and minimum resultants, and this will be true for both or. bital and spin quantum numbers. Thus coupling of the orbital quantum numbers ; = 1 and fy = 2 of two elec: trons can give resultant values 3, 2 and 1, these being the values of ZL permitted :to vary between th +I, = 3 and In—I, = 1. If two electrons have their spin quantum num- bers as 4 and 4 then the resultant spin quantum number can assume values 0 or 1. A multielectron system is desig- nated by certain symbols S, ?, D, F, G, H, etc. standing for the multielectron L values of 0, 1, 2,3, 4, 5, ete respec- tively. Such symbols carry a left hand superscript designa- ting the spin multiplicity 25-1 and a right hand subser- ipt giving the J value. Spin multiplicity signifies the number of ways the spins (i.e. M,) can be arranged. Thus a 2-electron system can be arranged in three ways to have M, = +1, 0, —1. Note that the spin multiplicity is also 3 = (2@-++4)+1). Thus the number of orientations of the spin vectors in a magnetic field is indicated by2S +1. The multielectron L and multielectron S can couple to’ give further resultants, again varying in integral steps between |L-+ S| and|L—S|. Thus L = 3 and S = 1 can couple to give J values 4, 3 and 2. A particular pair of L and S gives a term, that is, defines a particular energy state. The 5F, term indicates that this multielectron system has a spin multiplicity 3( 2 unpaired electrons) and a multielectron L value 3, Furthermore of the possible J values (4, 3 and 2), the *Fs term is the one with J = 2. A multielectron system can give rise to a large number of terms. The following rules due to Hund help in deciding the lowest energy ground state of the multielectron system 1. The ground state will always have the highest value This rule leads to minimisation of interelectroni of the spin multiplicity. ic repulsion. Electrons hate to share orbitals. N Fig. 11.7). When several terms with the same spin multiplicity with the largest L value will be the ground state. repulsive effects electrons tend to move in the orbit Vector addition of U’s therefore leads to maximis: are possible the one In order to minimise in the same direction. ‘ation of Z (examine . For a half filled or less than half filled shell, the lowest J forms the ground state, and for a more than half filled shell, the his state. This rule follows from hole equivalency shortly, ighest J forms the ground theorem to be discussedoe GNETOCHEM iis an example, say a d® ion, ined. Note first that the lower orbital and spin momenta and hence no patamagnetic moments. A p level has T= 1,so that mi can have values + 1,0 and "= 4 —I. So, of the six p electrons, two have is m = + 1, two have m = 0 and two have ms = —} m = —1. Thus we get Sm = Mz = 0 _ which means that the resultant Z is also zero. Again, three electrons have m, = + and the other three have ms = —$ So ~ that Ms = 0 which means Sis also zero. Thus a filled shell or subshell carries no paramagnetism. Allowing the highest spin multiplicity subject to Pauli principle, the three d electrons (with 7 = 2) can be arranged one each in the orbitals m; = 2, mr = 1 and mm — 0 so as to get the highest Mz, = 3, that is, the highest L value 3. Note other arrangements will give lower Mz and lower L. The ground state will have a maximum number of unpaired electrons, that is, a spin quantum number 3 which means a spin multiplicity of 4. Therefore the ground state has L = 3andS = 3.J can have values $, $, { and 3. Since d* configuration is less than half filled the lowest J = $ will be the ground state and hence the full ground state symbol is “Fs/2. Table 11.2 gives the ground state symbols of 3d” configurations. Table 11.2. Ground Terms for 3d" Configurations 3d" m =2 1 0 —l ~2 Mt Ms Ground Term Symbol aS 2eee—— WUUNRONWEN [tom awe tomer Wong 11.7.2. Derivation of Russell Saunders Terms : We examine ihe case of carbon atom which has the ground state electronic configuration: 4 tM ae + Is 2s pe 2p, Since both the 1y and 25 levels are saturated their L Oand § of carbon atom is one of a p* configuration. A p electron has | ~ of the two p electrons has m, values |- 1, 0, 0. So the case c » Uso that each ~1. Each p electron has my valueof +} or —}. We have now to consider all the possible combinations of and my's: . = Ums and Mp = Lm A symbol 1+ means we “a an electron whose mz is -+ 1 and ms is + }. Toking the m; and ms values of the first electron we can write the following six arrange- ments: 1+, 1-, 0+, 0-, —1+ and —I-, Similar six arrangements are possible for the second electron also. Of a total of 6 x 6 = 36 arrangements the six sets C4, 14), C5 1), @+, 04), © 0-), (-14, —14), (1, —1) are not Pauli per- mitted. Of the remaining 30 half become physically redundant since sets (1*, 1-) and (1-, 1+) cannot be distinguished. Finally 15 distinct arrangements of m; and ~ ms known as microstates remain (Table 11.3). Note that the microstates in the column of Ms; = 1 just change sign of their spins in the column of M, = —1. Mz = 2 means that the multielectron ZL has to be 2. Had ZL been 3, Mz would Table 11.3. Microstates for p? configuration : ie gi 1 0 =1 UM 2 iis); 1 (1+, 0+) (1*,0°), (I>, 0+) d-,0-) 0 Msi), sel als. —1s) (l-,-1>) #,0-) i (1+,0%) (-14,05, (-1-, 04) (-1-,05 3 (-14,-1-) have varied nae + 3to —3. When L = 2, Mr varies + 2 to —2. With My, =2 in this p? case M, value of the microstate is 0 so that S = 0 ie. 25 +11 Therefore 1D symbol will cover five microstates. It does not matter which five microstates we take so long as these microstates have Ms = 0 and My = +3 + 1,0, —1 and —2. Now take the case of Mz = Land Ms = 1 which orginates from L = Beas S lie. a *P term. L = 1 means My +1, 0, —1 and S = 1 means M;= + 1,0, —1. Therefore a total of nine microstates are covered. by the *P term. After segregating these 5 +9 = 14 microstates in Table 11.3 we are left with only one having M, = 0 and Ms = 0 ic. 1S term. Note that the 15 microstates are accounted for by the spin and orbital degeneracy: 1D means(28+1)(2L+ lie. 1X5 = 5 microstates *P means 3x3 =9 1$ means Ixl=1 Hund’s rule predicts the following energy order: *P <1p <1g 11,7.3. Russell Saunders Terms and Hole Equivalency Theorem ; Fig. 11.11 gives the Russell Saunders terms arising out of the d" electronic configurations,MAGNETOCHEMIsTRY mn An interesting result is immediateh @, d°), @, a’) and @!, d®) one c This equivalence follows from th hole formalism). A d® electron syst the introduction of two positorns in subshell can contribute only 0 to ly evident that in each of the pairs (d', d%), onfiguration has the same terms as the other. © hole equivalency theorem (also known as tem may be conceived to have resulted from na filled @"° electron subshell. Since a filled a" the Ms and My, values the Russell Saunders terms due to d" electron + d* positron will solely arise due to the d® positron configuration. Interelectronic repulsion and interpositronic repulsion being similar both d* and d? electronic configurations give the same terms. A d* configuration is the hole equivalent of d. Note that a dion is its own hole equivalent. Hole formalism concept is usefull in several areas: i 1. The Russell Saunders terms of d ions are the same as those of their hole equivalents d!°-” ions, 2. Spin-orbit coupling constants (section 11.8) of less than half-filled subshell ions is positive while those of more than half-filled shells is negative. While for \ the less than half filled shells the coupling envisages some interaction between the positively charged nucleus and the electrons, the hole equivalents envisage inter- action between the positive nucleus and an appropriate number of positrons. Hence the negative sign. «3. Because of the negative sign of the spin-orbit coupling constant (section 11.8) for more than half filled shells, the J levels of d*(n = 1—4) become reversed for the corresponding hole equivalents. Thus the energy order of the J levels of dions is °F < 8F,< *F, while that of dis *F, < °F, < Fy. 4. Under the influence of the crystal filed the Russell Saunders terms undergo splitting. Since a positron is-likely to be most stable where an electron is least so the crystal field splitting diagram of a d ion is reversed for its hole equivalent. Thus a 34° copper (II) may be regarded as a 3d" positron case so that the positron will occupy the ey set in octahedral field. The positron transition will then be €; —> fay instead of the tyy—> eg electronic transition for 3¢1 (electron) titanium (ID) case. 11.8. SPIN-ORBIT COUPLING gy is proportional to Js cos (Js) where J and s are The strength of the coupling is decided by the Proportiona- stant known as the spin-orbit coupling constant £. ¢ is relativ (~50—800 cm™) for the first transition series elements while for the | it is large (~ 1000 cm~). For the actinides spin-orbit cou the Jand s vectors of the individual el to produce resultant J(j—j coupling). The magnitude of the spin-orbit coupling constant is gi Zeit Batch s ly small lanthanides pling is so strong that irons couple to give j. The j’s then combine iven by : where Ze is the nuclear charge, e, m and r ave the charge, ma orbit of the electron, /1 the Planck’s constant and ¢ the ass and radius of the velocity of light, For aSand n represent the spin quantum number and the number o ons of the term. The ‘4-’ sign refers to half-filled or less than half: “— sign refers (0 more than half-filled shells. For a d# ion 2 is ‘+ while for d’—the hole equivalent of is ‘—”. Remember that a proton attracts an electron but repels a positron. 11.9. RUSSELL SAUNDERS COUPLING AND LANDE INTERVAL RULE The 8F ground term of a d? free ion gives three J states: 9Fs, °F and 3F, (Fig. 11.8). The 3F, state is the ground state. The difference in energy of the J states is important for evaluation of magnetic moments, and is given by the Lande Interval Rule. The energy separation between two immediate J states is given by the product of the spin-orbit coupling constant of the ion and the higher J. Just as each L has 2L +1 values of Mz and each S has 2S + 1 values of Ms, cach J has 2 +1 values of M/. Thus the*F, ground state (Fig. 11.8) has” Fic. 11.8, Splitting of 3d? ion under Russell Fic. 11.9, Splitting of the terms of d? and Z Saunders coupling and a magnetic field. The d by spin-orbit coupling, % figure shows in su configuration, spin-spin coupling, orbital- orbital coupling, spin-orbit coupling and 4 magnetic field splitting, My values + 2, | 1, 0,1 and —2, On the application of the magnetic field each J state splits into 2 | levels of Mj, maintaining the pre-splitting baricentre. The following relations hold (Fig. 11.9): a2; [22 44+ 1) x3A\=[2 x 3+ 1) x [2x 24 Dx@G+Dys0 #512 x26 % BF DA +IAX3 41) x A-I@ x 4-44) x 34) =0The metal ion orbitals en ae fas ee are designated by certain e cee fe ae case symbols (eg: Ary, electron wave functions i.e, orbitals. Upp States i.e. states arising out of interaction Aug, Tyg, etc, stand for total many- Symmetry operations. *h fo the group symmetry operations in different £roup theoretical symbols. These Ag, Eq, T19, Tyu etc.) or lower case fa, ete.). The lower case symbols are used to indicate one er case symbols designate electronic of electrons in different orbitals. Thus electron interaction wave functions, Is speak of degeneracies: A (or a) is singly degenerate, E (or ¢) erate while T (or t) is triply degenerate. Left hand superscript in multiplicity. Right hand Subscript ‘g’ stands for ‘gerade’ (i.e. even) while ‘y’ le (i.e. uneven). Since an octahedron is centro- symmetric ‘g” and ‘v’ are meaning! and hence ‘g? ful. A tetrahedron has no centre of symm and ‘W subscripts a etry ite not used. 11.10.2. Crystal Fields in Relation to Russell Saunders Terms: When an ion becomes part of a complex it experiences an additional perturbation due to the crystal field. In Russell Saunders coupling the strength of the coupling varies in the order: spin-spin coupling > orbital-orbital coupling > spin-orbit coupling Depending on the strength of the crystal field, it can i coupling in several ways: intercept the Russell Saunders Case I. The crystal field is weaker than spin-orbit cou; quantum number. In such cases the ion behaves as if it were a and magnetic moments are not influenced by the crystal field, Case I. The crystal field is stronger than spin-orbit coupling but weaker than orbital-orbital coupling, Such a field is known as weak crystal field. Weak field does not allow L and S vectors to couple to give J vectors; instead the terms due to orbital-orbital coupling are split further. J is no longer a good quantum number. pling. J remains a good free ion, Spectra Case IIT. The crystal field is stronger than orbital-orbital coupling but weaker than spin-spin coupling. This is medium field, Case IV. The crystal field is stronger than ever stronger than interelectronic repulsion, Such crys are known as strong crystal field. n the spin-spin Coupling ie. it is tal fields force spin pairing and Medium and weak crystal fields produce high spin while strong fields give low spin (spin p (spin free) complexes. paired) complexes, B Weak crystal field dig-FE ae a glans ‘) eas, 274 INORGANIC CHEMISTRY i 3, to be grams have been termed as Orgel diagrams. TEE ettaa Sa ’ 4 shortly explained, give the relative energies of the ee oe crystal field terms on passing from weak to strong crystal fields. 11,10.3. Splitting of Russel Saunders terms in weak Crystal ey ga the formation of a complex the degeneracy of the cer e ee nai degeneracy of the Russell Saunders terms of a free ion is thus lifte ae ee field. The 3d® nickel (11) ion has an F ground state with seven fol ecu @L +1 = 2x 34 1), In octahedral crystal field the F state splits in ° 4 states: 4), T, and T, maintaining the total orbital multiplicity. In cee ‘ fas splittings orbital multiplicity is conserved. Further the same spin multiplicity is retained on splitting in weak field (Fig, 11.10). q An S state is like an s orbital which is singly degenerate and hence it cannot split. A P state is like p orbital and we have already seen that a p orbital cannot split in octahedral field. A P state thus merely changes notation toT;. A D State is like d-orbitals and hence splits into Tz and Estates. Aig?) ity ga Ata 18 11.10.4. Tanabe Sugano 5° Diagrams: Tanabe and Sugano have calculated the transition energies in going from weak to strong crystal field. The follow- ing points are relevant in con- nection with Tanabe-Sugano diagrams (Fig. 11.11). L. The energies of the Rus- sell Saunders terms appear on the ordinate and the crystal field strength (A. = 10 Dg) as the abscissa, 2. d, d*, d, d8 and @ systems retain the same ground state no matter how strong the crystal field is. Recall that these are the ions which cannot admit of both the high spin and low spin forms under the same octahedral geometry, It Fic, 11.10, Splitting of d# ion Russell Saunders __ IS thus predicted that 3d® nickel terms in weak octahedral erystal field. ‘The ground (UI) cannot give diamagnetic state and the first excited state are shown, octahedral complexes,d” systems ‘equilibrium under the same octahedral geometry. 4. We can identify the spin allowed and spin aay allare Laporte forbidden. Taking the 3d2case we see that Ty (F) > "Aan *Tyy (F) + *Tyq (P) are spin allowed while #719 (F) > Toy Tu —> ‘By are spin disallowed. is reversed. 5. The splitting of a particular Russell Saunders term of a d” ion is for its hole equivalent d0-» ; d* (octahedral) = reverse of d'?-* (octahedral) Se 6, Since crystal field spitting of octahedral and tetrahedral elds are FMT of each other it follows that reversal of the octahedral crystal field a cd ular Russel! Saunders term of a d* ion will give the tetrahedral orys| of the same d” ion, 7. It follows from a combination of 5 and 6 that: octahedral d" terms = tetrahedral d1°-™ terms Oye Naa A 1 Te (P) (0/242g 1 2 3 1 2 3 ) Oq/8 (Daj Fi, 11.11, Tanabe-Sugano diagrams of d'to a! ions in octahedral crystal fields. However it should be remembered that 10 Dg: is about 4/9 of 10 Dg (oct) for the same metal ion and the same ligand. 8. Since high spin d° gives L = 0, Russell Saunders terms of d” and d5+* are the same. Hence the splitting patterns of high spin d°+" and d” will be similar. 9. The energy separation of the various Russell Saunders terms are expressed in terms of interelectronic repulsion parameters known as Racah parameters B and C. The energy gaps between terms of the same spin multiplicity are multiples of B alone while the energy gaps between terms of different spin multiplicity are expressed as sums of multiples of both B and C. Thus the energy gap between ®F and 4P of a d* configuration is 15B while the difference between 3F and 1D is 5B + 2C. In most cases C is close to 4B. In complexes the free ion B values are reduced by ~25%. 11.0.5. 10 Dy and B’ from Electronic Spectra: The tyy —> eg (ie. dey > d,_y*) transition is called 10 Dg. We briefly describe how the relative energies of the different weak field transitions (Fig. 11.10) can be had, The ground stateMAGNETOCHEMISTI of 3a is 27,, (ry x 7 wWhil ‘i Tay (P) and *4,. ge. “xcited states with the same spin multiplicity are *T zy, interaction because of singin’ t*° Lis terms Which develop some configurational Le. *P,, (F) Gros poe Symmetry properties. Integral occupation of orbitals term it can be aan 0 t29* is not quite valid. Since there is only one Tay es. When a crystal Regn the tao! e,! configuration. The 24,, term corresponds to Saunders term from Shee appears only once its energy, relative to the Russell each of the Binet a it is detived, is given by the one electron energies for "Teg term and the 34 orbitals. Thus relative to ECF) = 0 the energies of the Referring to Fig. thin terms are (—4 +6 = 2 Dg) and (+ 6-+6 = 12 Dg). etc oan, (@) and assuming that the *T yg (F) is lowered by an amount = 0 baricentre, we have (y being 2 Dg) : —3x + 3x2) Da + (1x12) Dg = Oso thatx = 6 Dg = 3A. i Thi é i ore ee ca ty take into consideration the orbital degeneracies of the ®T9, Ree onss a he energy gap between °F and *P Russell Saunders terms ee ee B is the Racah interelectronic repulsion parameter. But complex from Fig, 11.10 we have: “Tyg (F) > Tyg (P) = 3 A + 15B’ where B’ is now the interelectronic repulsion in the complex. | Not all the transitions are easily discernible from an actual spectrum of a complex. Furthermore the ratio of the different transition energies, intensities of the transitions, ete. are to be considered in order to identify an absorption band as a particular transition, Hexaaquovanadium (11),[V(H.0);J* (34°), gives three bands at 810 my (12,300 cm), 540 my (18,500 em~) and 360 me (27,900 cm). These are assigned as: 44yy — ‘Tag, 4ay—> *Tyg (F) and 449 > *Tr9 (P)- The lowest energy transition gives the 10 Dg value (12,300 cm). Tris (ethylene- diamine) nickel (II) (3d) has the following spin allowed transitions: *Aoy—> °Tag3 *Asg —>*Tig (F); *Aog > 89 (P). It shows three absorption peaks: 910 my (11,000 : om~), 540m (18,500 cm-1) and 335m (30,000 cm), 11,000 cm-! being the 10 Dg. We can have now an exact example. Crystal field diagram of tetrahedral 3d (say, nickel (I1)) will be the same as that of octahedral 3d? system. For [NiCl J? v4, v2 and vg will correspond to 8 Dge, 18 Dge, and 6 Dg: + 15B’. vy and v, are experimentally 7,550 and 14,250 cm- respectively while v, remains unresolved. B’ then works out to be 780 cm-. Free ion 15B’ value is 16000 cm-? whence B becomes 1066 cm-*. Thus on complexation a substantial reduction in interelectronic repulsion occurs. This is explained as a nephelauxetic effect (cf. p. 241). r 11.11. SOME QUANTITATIVE RELATIONS FOR PARAMAGNETIC SUBSTANCES 11.11.1.Curie Equation : Magnetic susceptibility of a substance is connected to its moment via Curie equation. In order to determine the magnetic suscepti- bility ofa substance it has to be subjected to an applied magnetic field, The magne- tic field endeavours to bring about an alignment of the paramagnetic dipoles218 i INORGANIC CHEMISTRY temperature endeavours to etic dipoles will increase etween susceptibility and with the direction of the field. On the other hand, a disrupt this alignment. Thus the alignment of the a at low temperature and high field. An inverse relation temperature thus exists. 7 i Jf Coat N (Avogadro number) paramagnetic centres sc Se netic moment #, These paramagnetic entities will have a ran OO ee i. On the application of magnetic field these will assume differen ¢ te these will be at different angles with the field directions 4,925 055 ete, uc) e would mean that although each molecule has a real moment p it is not sI he 2 during measurement due to imperfect alignment with the field. A molecu fe areal moment uz) at an angle @ makes a contribution }- cos along H. Since di ferent molecules make different contributions we assume that an average moment p is contributed by each molecule under the conditions of susceptibility measurements. Then the following relations hold: xe = 2s ae = xo XM = xM=pxV Buiz—= oer magnetic moment _ Nit molar volume V hw =F XY = pA x y= Our problem is to derive a value for jz. Le = contribution towards by the fraction of molecules at an angle @ with the direction of H. = 4 cos 8 x fraction of molecules at an angle 8. The fraction of molecules at an angle @ is determined by the difference in energy between two levels in relation to the prevailing thermal energy. Thus if and n¢ are the number of molecules at the Oth and ith level and if AE is the energy diffe- rence between the two levels, then Boltzmann law states: m= ngexp(—AE/KT) 2. = exp(— = AEIKt) If m is large compared to nr then m/n9 represents the fraction of molecules. Again on the application of a magnetic field there is a lowering in the energy of the magnetic dipoles: AE eH

P). So spin pairing occurs and all five electrons are forced to stay in the three fyy orbitals, one remaining unpaired. Problem: Predict the spin magnetic moment of Ks [Mn (CN)«)] Noie that cyanide is a monodentate ligand and that the oxidation state of manganese is -+ 3. Trivalent magnanese has 25—3 = 22 electrons ie. it is a 1225! 2p! 3s? 3p° 3d! or simply a 3d* system. So we have to examine the spin moment (orbital magnetic moment is neglected) of a 3d ion in octahedral geometry. The question now is whether the complex will be high-spin or low-spin. Since cyanide is the strongest ligand it will generate an inner orbital octahedral complex i.e. the hybridisation will be d® sp®. Hence 4 electrons will stay in the three non-bonding d orbitals, So according to Hund’s rule we will have two unpaired electrons: in crystal field terminology the complex will be low-spin octahedral ie. tag e%g, once again there will be two unpaired electrons. The spin magnetic moment will be around 2.83 B.M Problem: Predict the spin magnetic moment of Li [Ti@ipy);] Note dipyridyl is a neutral bidentate ligand. Stereochemistry around titanium (—1) is octahedral. Uninegative titanium has a total of 23 clectrons. It is a Ls® 292 2p! 3s? 3p® 3d° ie. a 3d° system, Taking dipyridyl as a strong ligand we assumeMAGNETOCHEMISTRY 287 that the co} RG : eeicn, ae isan inner Orbital octahedral complex. Hence the five non-bonding cipating in the eee in the three of the five d-orbitals which are not parti- ment 1.73 BM, yon tSAtion process. Then one unpaired electron with spin mo- spin complex i.e. oe how up. According to crystal fild theory it will be a low- moment 1.73 Be o es an there will be one unpaired electron with spin Yah Si) oe _ Problem: Bis (dimethyletyoximat diamagnetic, How do we interpret on Note dimethyiglyoximate ion (se the Coordination number of nickel a chemistries namely tetrahedral and Seometty is possible only with wea geometry, In VB model a square planar bipositive nickel is a 38 the four non-bonding de Paired up. Hence the diamagnetism, In crystal field model we can no to go for the tetragonally elongated ©) nickel (LI) is experimentally known to be VB and CF models ? ction 10.16.1) is a bidentate ligand, Hence I) is four. When C.N. is four two stereo- square planar are possible. Since tetrahedral K coordinating ligands, we safely exclude this Seometry means a dsp* hybridisation. Again System. Hence these eight electrons will be arranged in orbitals and according to Hund’s rule all eight will be longer take the octahedral splitting. We have or square planar splitting: Problem: Predict the number of unpaired electrons in [CoCl,}2-. Since chloride ion is a monodentate ligand and since there are four of them in the coordination zone the geometry may be tetrahedral or square planar. But chloride ion is a very weak ligand and hence square planar stereochemistry is tuled out. For tetrahedral stereochemistry VB theory predicts. sp° hybridisation. So cobalt (L1) being a 34 ion its seven electrons will be housed in the five 3dorbitals. According to Hund’s rule only three electrons will remain unpaired, In crystal field model the complex has to be high spin and the electron distribution wit! be et, so that three electrons will remain unpaired, 11.15. DETERMINATION OF MAGNETIC SUSCEPTIBILITY A number of methods are known for the purpose. Gouy method is the most commonly used technique. The sample, in the form of a cylinder, is suspended between the poles of a magnet, preferably an electromagnet. The bottom of the Substance coincides with the centre ofthe magnetic field, and the substance eaters to a length of about 10 cm such that the magnetic field is Zero at the upper point. The sample is packed uniformly into a glass tube of suitable size and ie Vertically288 INORGANIC CHEMISTRY suspended from the beam of a bala The mass of the sample is determine Similar determination is also carried out for a diamagnetic correction of the glass tube. ce (Fig. 11.15). in a drought free enclosure (I ed with and without the magnetic field a with the same sample tube so as to allow Fig. 11.15. Apparatus for the Gouy method A magnetic sample is composed of innumerable micromagnets with random orientation. On the application of a magnetic field there is an alignment of the micromagnets with the field, If the sample were in the form of a very small sphere at the centre of a uniform magnetic field there would be no net force acting on it. Instead if it is suspended in the form described above its lowest part would be in the strongest field while the topmost part will be in a weak or zero magnetic field. Hence there will be a net magnetic force acting on the cylindrical sample. ‘As a result of this a paramagnetic sample will be drawn into, while a diamagnetic sample will be drawn out of the strongest part of the magnetic field. Also note that the derivation of the xg by the Gouy method involves two limits of the mag- netic field between which the force is integrated. The small force dF experienced by a sample of volume susceptibility « and small volume dy in a magnetic field H is given by: ie = gE ak dh pa Where pe is the field gradient. dH : = H. «. A, dx. el where A is the cross-sectional area and dx is the small height of the sample. <. dF = A. «. HdH 4 4 Intergrating, F = J dF = J A. &. HdH = A. x. § (HBA) Ho Ho H and Hy are the lower and upper limits of the magnetic field.MAGNetocHEMistRY Ee A: xe ph (HH) (recalling that x0 = *) OT = Xo F 4 (HH) where m and 1 stand for the Mass and length of the sampl tae ple. (» = 37) Simplifying further that Hy can be neglected we have: Ux F : Hm Force Fis determined by the change in the weight of the sonple ie. by the product of w (the change in mass of the sample in the magnetic ind) and g, the acceleration due to gravity. The change in the mass of the sampleis the sum of the apparent change of mass of the sample in the magnetic field ead the change of mass of the empty glass tube, Then: Xo ae we _ 2 (in em) x w (a gm) X 981 H*xm H® (in gauss’ gm) Some people prefer to express w in milligrans and min gm so that 21 (in om) x w (in milligram) x 10-? x 981 (in gausy x m(ngm) _ _ 21 nem) x w in milligram) FG gauss) x7 Gn em) x 1.019 Since His of the order of 10? our final x, will come out in the order of 1 xm = xq X A where M is the molecular weight Xo O-®cgs units. The quantity me is called the ‘ube calibration constant, The tube constant is first determined by taking a measurement on a standard substance, such as, copper (Ii) sulphate pentahydrate (xp = 5.92 10~* cgs units), [Hg Co(SCN),] (yg = 16.44 X 10-* cgs units), for which xg is accurately known. The same tube is then cleaned and used to determine the xy of the substance under investiga- tion, For paramagnetic substances the above yar is corrected for the diamagnetism of the ligands using Past I’s constants. The corrected yy is then used to calculate the magnetic moment with the help of the Curie equation) Table 11.5 gives some spin only magnetic moments for various numbers of unpaired electrons alongwith the corresponding susceptibilities. ‘Table 11.6. Spin only Susceptibiliies and Moments for 1-5 Unpaired Electrons 1 jespin only xa« (corrected) ( Me 1,250 x 10-8 3.87 6250 fe 10,000 5.92 14,600290 INORGANIC CHEMISTRY STUDY QUESTIONS 5.92 B.M. whereas Ko{Fe(CN)s] has @ value of 1. (NHyrEeF,] has a magnetic moment of ‘a crystal field model. 1.73 B.M. Explin both on the valence bond model and thi 2. Guess the nagnetic moments of [Ti(dipy)s] and LilTi@ipy)sI- 3. Molybdenun (V) is a 4d? system. (NHa[MoOCk] is paramagnetic (u~1.7 BM, but [Mo0.Q.py] is diaménotic (QH = quinaldinic acid), Chemical studies show that 17 [Mo0,Q.p¥1 wwe still have a pentarvient molybdenum. How would you explain this anomalous magnetic behaviour? . | 4, Transition metal conpounds are often paramagnetic whereas non-ti pounds are diamagnetic, Conment., 5. Strong ligands are mct likely to enforce spin pairing. Comment. Show on the crystal fiold mode! that it may be possite to synthesize complexes with some ligands where magneto~ chemical equilibrium between hig: spin and low spin forms of the same complex may exist. 6. What is meant by the symbo.29f? Show that it represents a total degeneracy (orbital plus spin) of 21. 7, In general elements of the secont and third transition series form morespin pairedcom- plexes than elements of the first transitin series of the same group. Attempt an explanation based on the relative sizes of the orbitals. 8. Account for the following magnetic nixments observed in various complexes: V*H1,7 to 1.8; V+ 2.6 to 28; Gd 7.94 BM. ransition metal com- 9. The brown ring compound has the following structure in aqueous sulphuric acid medium, [FeCNO\E,O)SO,. The magnetic moment is 3.90 8.M. What will be your guess about the valence of iron in this compound on spin-only consideretions? 10. Comment on the following magnetic susceptibilities: (a) Ks[CoF.] has « = 4.2 B.M. but K,[CuF,] has 2.8 B.M. and K,[NiFy] is diamagnetic. (@ monovalent silver (coordination number = 2) is diamagnetic, bivalent silver (C.N. 4.and 6) is paramagnetic (~ 1.7 B.M.) and trivalent silver (C.N. 4) is again diamagnetic. 41. Calculate the magnetic moment of an ion with *F, ground state following the #1s,445 and pes equations, What will be the ground state of its hole equivalent? Calculate the moments of the hole equivalent. 12, Explain why the 2s equation is not applicable to Sma** (4f%) and Eu®* (4f*) although it is quite good both for Pr? (4f*) and Tb** (4f%). 13. How is the orbital moment quenched in most of the first transition series complexes? Why the quenching is not perfect in nickel (£1 in octahedral fold and cobalt (C1) in tetrahedral field? 14, What do you understand by spin-orbit coupling constant? What factors govern its magni- tude? How does it influence the magnetic moments of lanthanides and the first transition series? 15. (a) What informations can be had from the following relation (W) Discuss the usefulness of Pascal’s constants, 16, Ad?iou has the energy sequence *F, < °F < *Fs. Whatis the energy sequence ofa dion? 17, What informations do the following symbols provide? @ ‘Ty Ar ~@*P6H,0, 5.1 BM. 20, Isit possible to synthesize a complex of a dion with #. = 2.83 BM. with catalan tetrahedral geometry? 21. Give valence bond and crystal field explanation of the spin magnetic moment of K,[Mn(CN);] being 2.8 B.M. BIBLIOGRAPHY EaRwstaw, Introduction to Magnetachemistry, Academic Press, 1968 Ficcts aNp Lewis, in Modern Coordination Chemistry, Interscience, 1960 SeLwoop, Magnetochemistry, Interscience, 1956 HeERzBERG, Atomic spectra and Atomic structure, Dover, 1944 Lever, Inorganic Electronic Spectroscopy, Elsevier, 1968. BAREFIELD, BUSCH AND NELSON, Iron, Cobalt, Nickel Complexes having anomalous magnetic moments, Quarterly Reviews, 1968 Dura, Orbital contribution to spin magnetic moments in transition metal Complexes, Indian J. Chem. Educ, 1979, 6(3), 9 DUTTA AND SYAMAL, Elements of magnetochemistty, S. Chand & Co., 1982 renin