oe+do, P>P-+6P and D+D-+SD this gives | (eBp—pBp\do=y_ | (E.d5D—D.sdE)dv...... (44) =| (E.2P =P 2 8B)de ae (45) If in (42) we take p’=p and write D=KE, D’=K’'E, we have | o(p—9' )do= = (Fe 2B) Bde) (46) THE POISSON-KELVIN HYPOTHESIS. 95 For a differential variation K~K-+6K this gives | pdedv=—j-| 1 OF Oy EEL RE COCO (47) OF Va The identity PY o—div (oF) —o div,,.P gives —P . E=div (oP) —9 div P. Integrating over v, and applying Green’s theorem =| Pe Bao=| oP adf— | p div Pdv. V2 fe V2 Now define functions U, V by Then, by (39) ft =a, (E-+4nP) . Edy = 3] P. Bdo-+-| Edw. Ve 87 | s And ka oaido +4 | BP atp eal co div, Pai) ivi 0 wou (51) Vy fe Ve ee 2 aril: EOD Gh Wan, Secaeleampastran me irre eG ica eH yey By lok es Wee eID (52) 9. DISCUSSION OF THE LITERATURE. It is an essential part of the purpose of this paper to compare the present formulation of electrostatic theory with that given in the literature. There we find that the formulae (27) and (28) are mentioned only incidentally, their fundamental significance is unrecognized, and in many accounts they are neglected entirely. In no case are they made to play any part in the construction of the theory. Indeed most accounts give a force formula in dielectrics which is quite different from (27) and which is derived as an end result of the theory. I shall refer to this again below. On the other hand, the potential formula (30), which we regard as a mere auxiliary to the fundamental statements of mechanical effect, is usually regarded as embodying the whole content of the Poisson-Kelvin hypothesis. And then the moment distribution is replaced by the equivalent charge distributions of Poisson : 96 W. B. SMITH-WHITE. For the purpose of the following remarks it is convenient to recognize two main classes among the accounts of the theory of dielectrics which are available in the literature. On the one side there are those which attempt to keep the discussion quite general and assume no special relation between the vectors P and E; on the other side there are those which restrict all further discussion to the linear inductive case, assuming that the vectors P and E are linearly related and in particular than P=kE. It seems simplest to comment on the work of some recognized authors. Consider first de Donder (1925). He begins with the expression (3) as the ‘‘ energy ’’ of a system of point charges, and transfers it to continuous distribu- tions by the obvious procedure of replacing the sum by an integral. At the same time he regards the polarisation in v, a8 equivalent to the distributions of Poisson. In this process the exact notion of a mechanical potential energy function is obscured, but de Donder, not having emphasized this aspect, has not noticed the loss. By the transfer de Donder obtains his ‘‘ energy from the microscopic point of view ’’, viz. 3 j pedo oodf +% | epdv, 2 Ve and by (53), (54) and (51) this is the function V. By (52) this “‘ microscopic energy ” is distributed with a density By ‘“‘ neglecting the energy belonging to the moment distribution ”’, de Donder also finds an ‘‘ energy from the macroscopic point of view ”’, viz. 3 i epdv, V1 and by (48) this is the function U. By (50) this ‘“* macroscopic energy ”’ is distributed with a density i 3D ~ EL) weeset aed es ee (56) de Donder does not make clear which, if either, of his two energies is to be regarded as a mechanical potential energy function. It would seem a little incongruous to suppose an energy function to be distributed in space. de Donder remarks in his preface ‘‘ Quand on étudie l’énergie électrique localisée dans un champ électrique di 4 des volumes polarisés, il se présente une réelle difficulté ; nous la surmontons en nous placant respectivement au point de vue micros- copique et au point de vue macroscopique.’’ We can admit the difficulty, due to the misinterpretation of the Poisson-Kelvin hypothesis, that has been presented by the notion of energy in dielectrics, but it is not clear what difficulties are overcome by de Donder’s device of having two energies. The following is effectively the argument given by Stratton (1941). Suppose we have a dielectric occupying a volume v, and we accumulate gradually a charge to density pe, in the volume v,. To increase the charge density by Sp in the element dv the work done is pdedv and the total work done in increasing the charge by dp in 2, is THE POISSON-KELVIN HYPOTHESIS. 97 On the other hand the increase in charge inside v, will increase the electrical ‘potential by 5p with the consequent increase of energy of the charge pdv in dv, by an amount pdedv. So the total increment of energy is | aed, 2. NEU MONE ae ae eee (58) But the work done is equal to the increment of energy ; and so each is equal to if (pdp+pd¢)dv. Integrating we find for the energy of the system the amount U=} | epdv. V1 So, this is de Donder’s ‘“‘ macroscopic ” energy. The error in the above argument is apparent if we refer to formula (45). In general we have no grounds for asserting that the right side of (45) is zero. Stratton proceeds in his next paragraph to derive a different formula for the energy of an electrostatic system, and makes no comment on its incon- sistency with his first result. Corresponding to the increase of charge Sp in v, the work done is given by (57); and this is taken to be the increment of electro- static energy. Transforming this by (41), the increment of energy is al E . SDdv, are, 1 D al a| 1 TAPES De oat LA ka ae OE (59) on assuming that, at each point in the dielectric, D depends on E in such a way that E.65D is a perfect differential. The expression (59) is regarded as the general result and the corresponding energy density is and the total energy is 1 D a Bre OUD ay ss eos cba tiay or aislorate ou ae (60) We recognize then three different energy expressions in the literature. There are de Donder’s two expressions (55) and (56), of which the second arises also from an erroneous argument of Stratton. These two expressions are obtained without contemplating any functional relation between D and E. The third expression is (60), which is supposed to hold for a certain kind of functional relation between D and E. The text books of Jeans (1927) and of Abraham-Becker (1932), and the Lectures on Theoretical Physics by H. A. Lorentz (1931) discuss only the case when D and E are linearly related. Jeans and Lorentz do not mention the Poisson-Kelvin hypothesis in relation to dielectrics. The basis for the theory of dielectrics is effectively the assumption of Gauss’ theorem (37). Abraham- Becker derive Gauss’ theorem as above, but this is the only use they make of the Poisson-Kelvin hypothesis. With regard to the energy in dielectric systems Jeans and Abraham-Becker merely assume that results which are found by considering a simple parallel plate condenser will hold quite generally. In this way it is found that (56) represents the energy density in the medium, then by (50) that the whole energy of the system is U. It seems to be worth quoting 98 W. B. SMITH-WHITE. Abraham-Becker to see the importance they attach to the expression (56). ‘‘ The justification of the expression for the energy density of the field assumed in (4) (i.e. (56) above) will form an essential part of the following sections. Let it be remarked at once, however, that the assumption reaches far beyond electro- statics, and in particular that it remains valid even for fields which vary with the time. The main point is that it gives us a general method of calculating the forces which occur in the electrostatic field. For this application, we start from the fundamental theorem that the work done by the field in any arbitrary displacement of the charges is equal to the loss of field energy.’ In fact these authors apply their ‘‘ fundamental theorem ”’ to deformations of the dielectrics as well as displacements of the charges and in this they are not justified. Lorentz derives the same energy by an argument similar to the second one given for (3) above. He considers a system of conductors separated by dielectrics which need not be homogeneous nor isotropic. Assuming only that the vectors D and E are linearly related at each point of the dielectric, it is found that the work done to accumulate the charges on each conductor, gradually and pro- portionally,is U. So U is taken for the energy of the system. But the argument is not satisfactory, for it makes no use of a condition which is essential to the validity of the result. Using suffixes to distinguish the components of a vector, and using also the summation convention, we may write D,=Kig Hy. o ele 0 © e\e ep :0! ‘ey ehes ial selene aleb eile (61) The result is invalid unless the coefficient matrix Kij is symmetric. Quite generally U is the work done when the charge is accumulated in the manner specified, but unless the condition of symmetry is satisfied, other ways of charging the conductors would involve different amounts of work. This of course is the reason why we assert that Aj; must be symmetric for physical reasons, viz. the denial of perpetual motion. In the practically important case, when D and E are linearly related, the energy given by any of the above discussions is the same, excluding only de Donder’s microscopic energy; and this peculiarity seems to have been responsible, in part, for the failure to recognize the inadequacy of them all. It is not shown, in any account, that the energy obtained is a mechanical potential energy function for the system considered. That it is commonly assumed to be so will be evident from the discussion below. Consider next the body force acting in the dielectric or polarized medium. As has been said, the force (27) is usually neglected in the literature. It has been suggested that the body-force should be derived from Poisson’s equivalent distribution ; Chipart (1935). This would give a body-force HE div By o0 ee (62) and corresponding surface traction BP yeh i oe aca nee (63) The suggestion has the merit of consistency if Poisson’s distributions be really considered as equivalent to the distribution of electric moment. It may be noted that these formulae would give a total force and couple acting on the whole volume of the dielectric which is statically equivalent to that given by (27), (28) and (29). The usual account of the body-force in dielectrics is that due to Korteweg and Helmholtz and developed by Lorberg, Kirchoff, Hertz and others. It is expounded by Abraham-Becker, Cohn, Jeans, Stratton and also in the articles by Lorentz, Gans and Pockels in the Encyclopadie der Mathmatichen Wissens- chaften. It is included in the recent text book on theoretical physics by Weizel THE POISSON-KELVIN HYPOTHESIS. 99 (1949). This theory begins with the assumption that the energy as found above is a mechanical potential energy function for the electrical system, valid as such even when the dielectrics in the system are deformable. This assumption is of course not stated explicitly ; rather, it is said, that the work done by the body- force in a deformation of the dielectrics must, by the physical principle of conservation of energy, equal the decrease in the energy of the system. This is a mistake. These systems are semi-conservative in the sense of §6, and they are not conservative when deformations of the dielectrics in them are allowed. The argument is simplest in the case of a fluid dielectric. Let the medium in v, be subjected to an infinitesimal deformation specified by the vector u. Here u is a function of position in v,, and we suppose for simplicity that the normal component of u on the boundary of v, is zero. The charge in v, is supposed to remain fixed. We suppose also that D—=KE, where the dielectric constant K may vary from place to place in the fluid; and, for any particular element of the fluid, K may depend on the fluid density t. The energy of the system is U; and so if F™ denote the body-force in the dielectric we have | OO Oe id) ae eas sic ey) ages ae (64) From (48) and (47) 1 Seth a aa ee 2 sU=3| | ododv = E°8Kadv. To calculate 5K in terms of the displacement u, refer to rectangular coordinates OX,, OX,, OX, and suppose u has components u,, WU, uz. If AK be the incre- ment of K ‘ following the deformation ”’ we have ok Vehe = hy iG Tag and The last is effectively the hydrodynamical equation of continuity. So we find ea OK uy, AAS eS x ae Oay. Thus 1 78% 377 aes F i ae ok Cicr [Pant gal, Bae anc! Finally, owing to the special restriction on u at the boundary of f,, Green’s theorem gives so that 100 W. B. SMITH-WHITE. Hence sy A hes SU =." a) is oe “5, {ua Neng ae 7 | ee ene 65 Birt s) ee UG.) kee (65) Comparing (64) and (65), on account of the arbitrariness of u inside v,, we have Ov This is the force formula of Helmholtz which replaces (27) for fluid dielectrics. If we write K=1-+4rk, P=KE, we have Fh) _F—1V (w=95-(<)); tok ie (67) TAT 1 1 a) ee Mina AP ik: SHIA ME eel ae (2 ) JC) oie (66) which shows that F and F are in general different. Still another force-formula is common in the literature. Many authors ignore the variation of K with t and take the body force to be F, (bh) — eh, Be Oe eS ee (68) St This result is sometimes obtained independently of the above argument by connecting it with Maxwell’s stresses in the dielectric. 10. DEFORMATION OF CONTINUOUS DISTRIBUTIONS. After the digression of the preceding section we return to the development of the theory based on the force formulae of §7. The distribution of electric » moment is non-conservative in a sense already explained (§3) and it is necessary to study the deformation of such distributions. A deformation /\ of a continuous medium is determined when the displace- ment of every particle of the medium is specified. Taking a fixed rectangular system of axes, if ¥,, Ys, Y3 be the coordinates of the particle which originally occupied the position 7, %, x; then the deformation of a region is given by the three functions | (x, Lo, Ls), i=1, 2,3 defined throughout the region. If we suppose this deformation has been reached by a continuous movement from the initial to the final position then / will be regarded as a member of a family of deformations /\(t) which depend continuously on a parameter ¢: Yi=Yi (Ly, Lg, Lz, t), i=1, 2, 3. We take t=0 to correspond to zero deformation. The Jacobian O(Ys) Yor Y3) LOMA ge ORHAN A a IED 69 O(2%, Xa, X) ii V==V(t)=— is positive. An infinitesimal deformation is specified by the differentials 7] m=F At, i=1, 2, 3. eter tener eee ees (70) THE POISSON-KELVIN HYPOTHESIS. 101 We shall be concerned with infinitesimal deformations from the undeformed state; then the partial derivatives in (70) are taken for the value t=0, and Wit, and v1. Associated with the deformation there is an infinitesimal rotation. The strain is specified by the symmetric tensor du; uy peu | PL tite Am=H( Fn au) Se a a ARE (71) and the rotation by the anti-symmetric tensor , Ouj OU; Pirie (A eb Ata 2 Oi 2 ce ani) eoevreeeevr eee eee ce ee oo © (ii ) In vector notation, with the axes OX,, OX,, OX; supposed to be right-handed, we represent the rotation by CF CUI UM ee rs hewic dss leteiees os (oe) where u has components u;, © has components 0;, and 0,=0,;— —Qzp, ete. Let 9 be a function of position in the medium and suppose that » depends also on the deformation, i.e. on ¢. Denote by do the differential of 9 at a fixed point in space and by Ag the differential of ¢ ‘‘ following the displacement ”’. Then a Sp=—5n tat cei eacn Nie sn, Matte ON (74) For a vector function E let AE denote its differential ‘‘ following the displacement ”’ and referred to axes which partake of the infinitesimal rotation ©. Then applying (74) to each of the components of E and allowing for the rotation, we find is Sad ST Se OS . (7) OLy Consider now a distribution of a ‘“‘ quantity’ Q throughout a deformable medium. Let P be the density of the distribution and let p be the ‘ density ”’ reckoned per unit volume of the undeformed state. Then D—VE.. Hort —0;\v=—l. p—P, and Uy G AY Fy," ehioatcitcahe lsu et chet ste teteine. pancelce vetce ( ) So Ug, o6 From (74), oP Hence sp 7] le Sa Oe Co an, OP 7] 102 WwW. B. SMITH-WHITE. For the density P of distribution of a vector quantity, denote by Ap a differential referred to axes which partake of the rotation ©. Then, corres- ponding to (77), 0 dP= —2 (Pug) +O x P+ Ap. Lee (78) Ley For the density 9 of a conservative quantity (77) gives 7) de ene soles Gis sls ees eee (79) which is again the hydrodynamical equation of continuity. 11. THE GENERAL WORK FORMULA. Consider again an electrical system consisting of a continuous charge distribution with density o in v,, and a continuous moment distribution with density Pin v,. In the case of the non-conservative moment distribution it is useful to think of the electric moment as “‘ attached ”’ to a medium ; in fact the formulae of §10 apply to this situation. The force and couple acting in the moment distribution are supposed then to be transferred to this medium. In the application the medium will be the material substance of a dielectric body regarded as continuous. For the conservative charge distribution the notion of such a ‘‘ medium of reference ”’ is unnecessary ; or we may say that the medium is the ‘*‘ continuous electricity ”’ itself. A variation of the electrical system consists of moving the charge in v, and deforming the reference medium in v,. At the same time the electric moment associated with the parts of the medium may alter. An infinitesimal variation would be specified by defining the displacement vector u in v, and v, and by defining /Ap throughout v,. At the same time the medium in v, experiences the infinitesimal rotation ©. The work done by the forces and couples acting on the parts of the system is aw=| F.udr+{ F. udo+| G.Odo+| T. udf, where F, F, G and T are given by (25), (27), (28) and (29). This work may be transformed as follows. If 1; be the direction cosines of the outward normal to f, or f, a8 the case may be, we have, using Green’s theorem, \ Re udo= | eE. udv= = Se ants % OF v, | Oy, 7) 0 = =| pine Cuan’ al Orr. acre =— | PONGyUg df — { : pdpdv, hi 1 oH i EY. udv=|(P . udv= IE Pee an gat | Po-ge ta -|,P. u| ft ~—(P. Eu,)dv a] E. 5° -(Puy) do V2 V2 Ley, -/ oe p. ara { E. Apao— | E. 0x Pads, 2 V2 V2 Va THE POISSON-KELVIN HYPOTHESIS. 103 by (78). i G. Odv=| PXE. Odo= | E. Ox Par, Va ) Vg and | Tudf=}| P.(B.—E2)n.udf=}| P. (E,—E_)ngtigff. 2 fe Sa Also from (49) AV=4/ (059 +od¢e)du +4] PONG UyAf fi 2 -3{ (P. 3E+E. SP)dv—4 | P . E_ngtladf. Vo Hence, from (80), AW+AV+/ B. Apdv=i | (e89—gde)do—4 | ppnatladf 1 -1 (P. 3E—E. 5P)dv +4] P. E,notia lf. 2 Now the right member of this equation is zero. This follows from (45) if the deformation is such that the boundaries f, and f, remain unmoved. It follows generally from the extended form of (45) which I have given elsewhere (Smith- White, 1949). Thus This is the general work formula, the analogue, for continuous distributions, of the formula (18) for discrete systems. From (48), (49), (75), (78), Vi Au-a{ (P.d5E+E. aP)dv—a P. Engg df 0 i av+4{ ae Euz)do—4 | PE neu pele : =. (p. AE+E. Ap)dv =au-3{ (p. AE+E. Ap)dr, V2 since P=p in the initial state. So we find AW=—AU+3) (DiwNE— EVA Pp) doy ese. Ww): (82) 2 which corresponds to (20). 104 W. B. SMITH-WHITE. 12. THE THEORY OF DIELECTRICS. The considerations presented so far may be regarded as a purely analytical theory of continuous electrical distributions of charge and moment, based on the formulae for the mechanical effects given in §7. Now, by means of the physical hypothesis of Poisson and Kelvin, as we interpret it, and the physical assumption that P is determined by E, we make this analytical theory into a mathematical theory of the physical behaviour of dielectrics. The way in which E determines P at any point in the dielectric depends on the physical state of the substance at that point, including the condition of strain in the substance reckoned from some standard configuration. In the simplest circumstances we may suppose P=kE. If the substance of the dielectric is not homogeneous then k varies from place to place in it. If the substance be deformable the value of & for a particular element of the material may depend on its deformation from some standard state. A simple assumption, appropriate to the case of a liquid dielectric, is to suppose that k depends on the density t only. Then p=vP=vkE, and we find, for an infinitesimal deformation specified by the vector u, Ou p. AE—E. Ap=E?z? az) ion T) OL, Formula (82) becomes A et ce sa 20 k ao i 2 At\ rc] Oty, If, everywhere in the dielectric, te then AW=—AJU. In this case the system is mechanically conservative and U is its potential energy function. In general, however, the system is only semi-conservative ; if the dielectric is held rigid, \W=— AU, and the function U is again the potential energy function. The recognition of such non-conservative systems is a new feature in electro- statics. To make such systems acceptable from the physical point of view we must show how to fit them into a wider physical scheme in which physical energy is conserved. This offers no difficulty any more than it does in ordinary mechanics, where we are quite familiar with the fact that real mechanical systems are never completely conservative, but are erase) to a greater or less degree, dissipative. In a system which is not mechanically conservative there will exist cyclic processes in which the work done by the forces acting in the system is not zero. We assert simply that such a non-conservative cycle of operations in our dielectric system is irreversible; the cycle can be performed only in that way which dissipates mechanical energy. In the next section we consider the physical conservation of energy; and then it appears that the irreversibility asserted above is a formal consequence of the second law of thermodynamics. Consider the case in which P is uniquely determined by E and in which the dielectric body is held rigid. In this case the only variation in the system is a movement of the influencing charge. All cycles in the system are reversible. Formula (81) gives THE POISSON-KELVIN HYPOTHESIS. 105 and the denial of perpetual motion now requires that in any cycle i doifiE . 0P=0. This result may be applied to any volume element of the dielectric and so we must suppose that at each point of the dielectric E . SP is a perfect differential. From (52) AV he | SEde: At] s and combining this with (83) Nr E. Dav. AT hs Now, also, E.d5D is a perfect differential, and the system is mechanically conservative with the energy function (59). This justifies one common formula for the ‘“‘ energy’ as a mechanical potential energy function previding the dielectrics are held rigid. The system is really semi-conservative in the nomen- clature we have used. before. In particular, if the relation between D and E is linear, and represented by (61), the condition that E. dD be a perfect differential requires that K\;= Kyi, and then E.dD=}3(D.E). The energy function of the semi-conservative system is then =| D. Edv=U, Sit a by (50). Jeans (1927) reverses the above argument; he makes the proof that Ki; is Symmetric depend upon the assumption that the energy density is =D KE: 13. THE CONSERVATION OF ENERGY. Consider a piece of dielectric substance in volume v, under the electric influence of a charge distribution in volume v,, and held in equilibrium by suitable ‘* pressures ’? applied to its boundary f,. On the element df of f, acts the external force Ildf. Inside the dielectric the mechanical force and couple of electrical origin, 7.e. F and G given by formulae (27) and (28), must be balanced by the mechanical stress in the substance. The statical conditions for this internal equilibrium are written most concisely in tensor notation. Let Fi, Gi be the components of F, G in directions OX;, and if the axes OX,, OX,, OX; be right-handed, write G,=G.,= —G@35, etc. Then the couple G is represented by the anti-symmetric tensor Gi;. Let sij be the mechanical stress tensor specified, at any point A in the dielectric, thus : Draw at A a plane perpendicular to OX;, then si; is the component, in the direction OX;, of the force per unit area acting on the matter on the negative side of this plane, due to the matter on the positive side of it. The equilibrium equations are ney 84 are Tiere ie rece DEUS OT LAE Ue Mena eA TEA ROR (84) Sipe S est Gye Oey hits sacs ellen! dale, "e) 6 « (85) On the boundary f, there act the force T given by (29), the external force I mentioned above, and a force due to the mechanical stress inside v,. Tf Ti, Ti 106 W. B. SMITH-WHITE. are the components of T, II and if n; are the direction cosines of a normal to f,, outward from v,, the conditions of equilibrium of an element df of f, give — Ny So4 +7;+1i,;=0. eo: 1s (0) 6 0 0 e110) ©) #1! 6 ieiiehieniet ie (86) With regard to the charge distribution in v,, its sole purpose now is to provide the source of the electrical influence on the dielectric. We are not concerned to examine the internal equilibrium of the charge distribution in the way analogous to that for the dielectric. It is sufficient to suppose that the charge is maintained in position by some ‘“‘ external agency ’’ which provides a force, on each volume element dv of the charge, just sufficient to balance the force Fdv given by (25). For the electrical energy of the system we take the quantity ak wes 2 Veras t Edv:. bee eee ee (87) This is not now a mechanical potential energy function, but is energy in a physical sense. Only in a special case is V a mechanical potential energy function. This choice for the energy of an electrical system amounts to a definite physical assumption ; and it is justified by its consequences. There is no other obvious choice for the electrical energy of a system. It may be noted that this energy is the energy of de Donder from a microscopic point of view. We may now formulate the physical equation of energy, expressing the first law of thermodynamics, in a variation of the physical system consisting of a dielectric under the influence of electric charge. We suppose that the variation consists of a movement of the charge, a deformation of the dielectric, and an absorption or emission of heat by the dielectric substance. An infinitesimal variation is specified by the displacement vector u defined in v, and v,. If AQ be the heat absorbed by the dielectric, this is accounted for by (i) an increase /J of the ‘‘ internal energy ”’ of the dielectric, (ii) an increase AV of the electrical energy of the system, (iii) the work i F . udv done against the external agency holding the charge, (iv) the work — | Il . udf fa done against the external forces holding the dielectric boundary. So A= AT+AV+| F.udy— | We . Walls oe (88) Now set Gij== 5 (Si, Site eee aie se cee (89) a4j=4(81y — ji) Sil (4) els) 6s: 9/0. 6 6s 0) 0: lo Neleueaete (90) so that 61;, a1; are the symmetric and anti-symmetric parts of the mechanical stress tensor. Then by (71), (72), and (85) tage — (Gap +448)( A Yo8 +948) =Ge8 A YoB +408 Sef = Gap Aves —Gp 8p, THE POISSON-KELVIN HYPOTHESIS. 107 From (86), using Green’s theorem, and (84) re i 1. udf= | | Teupdf— | _, Rasoppas i | : Toupdf— : sa (Sapup)ae os i} _ Toupat— | i Ze upao a | : sap - | Tougdf + | _ Fougdo + | _ G90 — | dnp A vega =|, i a udf+| By: udo+ | G. @dv—| BB Avo RBdv. Hence, from (80) and (88), AQ=AT+AV+AW—| Sap Avago = ar—| tn Avapdo— | Bi Npdoe ew .!. (91) by (81). This result applies to any piece of dielectric substance whatever its dimensions. We infer the elementary relation A¢= At — Oo Avo —E ° APD, ey (92) where 7 is the internal energy per unit volume, and /q is the heat adsorbed per unit volume at any place in the dielectric. In a fluid @jj= —@dij, where @ is the hydrostatic pressure, and 3;;=1 or 0 as I=) or 17. Then 48 AVoR = —88a8 Ava B= —O Avon = —O Av by (71) and (76). So (92) becomes PGI INGE CEN AC = 208 AN a ea ae es Seer (93) Here /\v is the differential of a variable v determined by the state of the fluid ; whereas in (92) the Aw, are not differentials of such variables of state. Consider finally a dielectric held rigid but in which P is not uniquely deter- mined by E. For a variation of the influencing charge we now write (81) and (91) | sW= —3v—| E. 5Pdp, and 39=31— | E. 3Pdbv. Integrating over a cycle in which the influencing charge returns to its initial position and the dielectric returns to its original state, we have Q=W=—| do fiE. SP. 108 W. B. SMITH-WHITE. In this cycle heat Q is absorbed by the dielectric and an equal amount of work W is done by the mechanical forces acting on the influencing charge. The second law of thermodynamics requires that in any such physically possible cycle Q and W should both be negative. We infer that for any physically possible cycle PE. sPz0 at each place in the dielectric; and the left member is the heat generated per unit volume in such a cycle. 14. ELECTROSTATIC STRESS. The notion that all electric action between charged bodies is transmitted by, and through the dielectric, or intervening medium between them, is due to Faraday. Following him, Maxwell showed how to represent this action analytically by an appropriate system of stresses. At first the idea was that Maxwell’s stresses should be interpreted as real physical stresses in the medium, and attempts were made to assign physical properties to the medium so that these stresses might be considered to be induced by the electric ‘‘ displacement ”’ D in much the same way as ordinary elastic stresses in material bodies are induced by deformation of the substance of the bodies. This view has been abandoned, but unfortunately Maxwell’s stresses are often still described as the ‘‘ stresses in the medium ”’ or as the “‘ dielectric stresses’. These descriptions, being based on notions now rejected, are misleading. The electrostatic stress tensor merely provides an alternative and analytically equivalent way of describing the mechanical action on electrified bodies which is described otherwise by the body force (27) and the body couple (28). The analytical situation is quite analogous to the use of a scalar potential @ to describe a vector field E. In order to emphasize the purely formal aspect of the matter we develop the analytical relations, at first, independently of the application. Given a second order tensor si;, write 5,). Se MD: (104) In these formulae k and t refer to the actual deformed state of the dielectric in the existing field. For a fluid which is originally homogeneous and in which k and 7 are functions of the pressure only, the equations (103) and (104) may be integrated, giving do) and da'b) ok Dug gro? | t BD ov’ - THE POISSON-KELVIN HYPOTHESIS. 111 respectively. If, in addition, the fluid be effectively incompressible, we have : Gy — OEE Bas scans Bee i ars (105) and x Ok. Ge hee pa | sys scat seer sveine «ee ss (106) OT Thus GD) —@ =F 7? elk Ot\t If k is not proportional to t the two theories give different values for the pressure in the dielectric. Suppose we have a solid body immersed in a homogeneous fluid, the system being held in equilibrium by a suitable constraining force and couple applied to the body. The fluid develops the pressure ©. The force exerted directly by the electric field on the body has components | No Soi df HE where s;; is the tensor (98) and the integration is over the surface of the body. The reaction of the pressure in the fluid has components | cmdf= | OdQiNg Af. if uy Hence the resultant force acting on the body, which must be balanced by the constraint, has components | ; Ra tn CPT) Hae ROE mn ern (107) On the usual theory this force has components i (ME SGOS) Wadi sc. 2e! Soca ee (108) f Now from (98) and (105) or from (101) and (106) $j —05;j= UD —Godij, Mi; —@' $j; = UD —GoS4j, so that (107) and (108) reduce to the same expression i WMOmeap ke aise (109) if Thus the two theories give the same nett force acting on the solid. In a homo- geneous fluid the stress M o is self-equilibrating, 7.e. it corresponds to no body force. Then the integral (109) may be taken over any surface f in the fluid which encloses the body. From (99) the force components (109) are those of the vector K le Ce. : cam tote) an aoe oar ae (110) where n is the unit outward normal on f. This is the usual expression for the force acting on a body immersed in a fluid. 112 W. B. SMITH-WHITE. Finally, if we suppose that the coordinate axis OX, coincides with the direction of the electric force vector we see that the principal components of 2 2 2 > M) are react eee ; Minis and so this stress may be described as a tension y 87 81 8 along the lines of force of amount 2 81 pression. This is Faraday’s description of the mechanical action of an electric field ; but we see that it gives the nett force acting on the body which is the resultant of that due directly to its electrification and the reaction of the pressure induced in the surrounding fluid. In consequence this description has no fundamental physical significance. together with an equal lateral com- REFERENCES Abraham-Becker, 1932. Electricity and Magnetism. London: Blackie. Chipart, H., 1935. J. de l’Ecole Polytechnique, 2nd Ser., 33, 246. de Donder, Th., 1925. Theorie Mathematique de |’Electricite. Paris: Gauthier-Villars. Debye, P., 1925. Handbuch der Radiologie, 6, 742. Guggenheim, E. A., 1936. Proc. Roy. Soc., 135, 49, 70. Jeans, J. H., 1927. Mathematical Theory of Electricity and Magnetism. Cambridge Univ. Press. Kelvin, Lord, 1884. Reprint of Papers on Electrostatics and Magnetism. London: Macmillan and Co. Larmor, J., 1897. Phil. Trans., A, 190, 280. Livens, G. H., 1926. The Theory of Electricity. Cambridge Univ. Press. —-—-— 1948. Proc. Camb. Phil. Soc., 44, 534. Lorentz, H. A., 1931. Lectures on Theoretical Physics, ITI. London: Macmillan and Co. Smith-White, W. B., 1949. Phil. Mag., Ser. 7, 50, 466. —______———_-——— 1950. Nature, 166, 689. —-—________—_—— 195la. Nature, 167, 401. —-——_______——— 195lb. Proc. Phys. Soc., A. 64, 945. Smith-White, W. B., 1952. THis JouRNAL, 85, 15 Stoner, E., 1937. Phil. Mag., Ser. 7, 23, 833. Stratton, J. A., 1941. Electromagnetic Theory. New York: McGraw-Hill Book Co. Swann, W. F. G., 1922. Bull. Nat. Res. Council, 4, 24. Weizel, W., 1949. Lehrbuch der Theoretesche Physik. Berlin: Springer-Verlag. THE CHEMISTRY OF OSMIUM. Part VIII. THE PREPARATION OF SOME HEXAMMINE Osmium III SALTS. By F. P. DWYER, D.Sc., and J. W. HOGARTH, A.S.T.C. Manuscript received, August 2, 1951. Read, September 5, 1951. It was shown previously (F. P. Dwyer and J. W. Hogarth, 1951) that when ammonium bromosmate IV was heated at 285°C. in an autoclave under two atmospheres of ammonia, bromopentammine osmium III bromide could be extracted from the residue of the reaction. It has now been found that hexammine osmium III bromide is also formed in the reaction but, being much more soluble in water, is eliminated during the purification of the former sub- stance. By the use of a test tube to contain the ammonium bromosmate instead of small platinum boats, using a higher pressure of ammonia and allowing the autoclave to cool slowly, approximately 50% yields of the hexammine compound could be obtained. The hexammine bromide could be isolated from the reaction residue by extraction with cold water, when most of the pentammine compound remained insoluble, followed by repeated crystallization of the almost white precipitate thrown out by the alcohol from the aqueous extract. A better procedure depended on the very sparing solubility of hexammine osmium III iodide sulphate [Os(NH3),|I.SO,, which separated as white micro-cubes on the addition of sodium iodide and ammonium sulphate to the aqueous extract of the reaction residue. The iodide sulphate was transformed to the iodide [Os(NH3),|I, by treatment with barium chloride, to eliminate the sulphate ion, followed by the addition of excess sodium iodide, when yellow cubes separated. Other salts were made by double decomposition from the iodide. These were colourless or white unless the anion was coloured and much more soluble in water than the pentammine salts. The complex cation showed a very notable tendency to crystallize with mixed anions such as bromide-iodide, bromide sulphate, bromide bromosmate, etc. This behaviour recalls that of the hexammine cobalt III cation. The salts reduced silver nitrate to the metal on warming. One molecule of ammonia was easily lost when heated above 100° C. in the dry state or boiled with water. The pyrolysis of these substances is being investigated. The free base could not be obtained from the hexammine iodide solution and silver oxide. The silver oxide was partly reduced to the metal, whilst the dark coloured solution failed to reprecipitate the iodide after treatment with acid and potassium bromide. The hexammine could not be detected in the residue from heating ammonium hexachlorosmate IV and ammonia—the only product being the yellow substance dichloro-octammine-y-ynitrilo-diosmium trichloride described previously. EXPERIMENTAL. Hexammine Osmium III Iodide Sulphate. Ammonium bromosmate (2-0 g.) was placed in a test tube of 7 ml. capacity (4 cm. x 1-5 cm.), placed in the centre of the autoclave described previously. The air was displaced with ammonia 114 DWYER AND HOGARTH. gas and the full pressure of the cylinder (90-100 lb./sq. in.) applied for one hour. The pressure was then reduced to 40 lb./sq. in. (24 atmospheres) and the autoclave heated in an oil bath so that a temperature of 285—290° C. was attained in the centre. After one hour at this temperature, the heating was removed and the autoclave allowed to cool overnight at room temperature in the oil bath. The greyish-green mass of residue and liquid ammonia was allowed to stand in the air until the ammonia had boiled off, and was then ground up finely. The resulting almost white powder was extracted with water (25 ml.) three times and the filtered extract, which was orange coloured, treated with solid sodium iodide until a slight permanent precipitate resulted. The precipitate (probably bromopentammine osmium IIT iodide) was removed and solid ammonium sulphate (5 g.) added to the clear solution. The resulting almost white precipitate of the hexammine iodide sulphate was washed with 5% sodium iodide solution and recrystallized from hot water in the presence of a few drops of ammonia. Occasionally the substance had a rose colour due to traces of an unidentified impurity. It could also be recrystallized by shaking with a suspension of silver chloride to eliminate he iodide ion, and then addition of sodium iodide and ammonium sulphate to the clear solution. The substance crystallized in dense colourless or white cubes, which lost ammonia on heating to 110—120° with slight darkening of colour. The warm aqueous solution rapidly reduced silver nitrate solution to the metal, but only slowly decaiousZ et potassium permanganate solution or bromine water. Found: I=25:0%; N=16-5%. Calculated for [Os(NH,),]I.SO,: I=24-65%, N=16-3%. Hexammine Osmium IIT Iodide. The iodide sulphate (0:5 g.) was suspended in warm water (30 ml.) and normal barium chloride solution (5 ml.) added. The mixture was shaken for ten minutes and the barium sulphate filtered off. Addition of sodium iodide to the filtrate gave a yellow precipitate of the impure iodide, which was recrystallized twice from warm water by the addition of sodium iodide. The substance crystallized in dense bright yellow cubes. The aqueous solution was colourless. Found: Os=28:5%, I=56-2%, N=12-6%. Calculated for [Os(NH,),]I;: Os=28-25%, I=56-59%, N=12-47%. Hexammine Osmium III Chloride. The iodide was shaken with a suspension of silver chloride in warm water, and the filtrate precipitated with acetone and one drop of dilute hydrochloric acid. The substance crystallized in micro-cubes, and was deliquescent. Found: Os=47:3%; Cl=26-7%. Calculated for [Os(NH3;),]JCl,: Os=47-7%; Cl=26-5%. Hexammine Osmium III Bromide. The residue from the autoclave was extracted with the minimum volume of cold water, the extract cooled in ice and treated with alcohol. The rose-coloured crystalline precipitate was dissolved in the minimum amount of water, cooled and the slight precipitate of bromopentammine osmium bromide rejected. The pink solution was treated with solid ammonium bromide and alcohol to reprecipitate the hexammine bromide. 3 Alternatively a concentrated solution of hexammine osmium III chloride was treated with ammonium bromide and the impure bromide containing bromide-chloride dissolved in water and reprecipitated with ammonium bromide and alcohol. The substance crystallized in white cubes. The aqueous solution treated with ammonium | sulphate gave the sparingly soluble cubic bromide sulphate, which was not studied further. oe Found: Os=35:7%; Br=44:8%; N=15-7%. Calculated for [Os(NH,),JBr,: Os=35:-73%; Br=45-08%; N=15-79%. THE CHEMISTRY OF OSMIUM. 115 Hexammine Osmium III Bromide-Hexabromosmate IV Monohydrate. Hexammine osmium IIT iodide (0-2 g.) was shaken with a suspension of silver chloride in water (30 ml.), and to the filtrate was added ammonium hexabromosmate IV (0:2 g.) in water (25 ml.) containing concentrated hydrobromic acid (0-5 ml.). The dark brown solution, on scratching, deposited black stellate prisms. Found: Os=36:2%, Br=52-5%. Calculated for [Os(NH;),|Br[OsBr,].H,O0 : Os=35-9%, Br=52-81%. SUMMARY. The reaction between ammonium hexabromosmate IV and ammonia under 2-5 atmospheres at 285°C. has been found to yield hexammine osmium II bromide as well as bromopentammine osmium III bromide. The salts of the hexammine osmium III cation are usually white and much more soluble in water than the pentammine salts. ACKNOWLEDGEMENT. The authors are indebted to Mrs. E. Bielski for micro-nitrogen analyses. REFERENCE. Dwyer, F. P., and Hogarth, J. W., 1951. Tuis Journat, 84, 111. Department. of Chemistry, University of Sydney. PALLADIUM COMPLEXES. Part III. BRIDGED COMPOUNDS OF PALLADIUM CONTAINING OTHER METAL ATOMS ; COMPLEXES OF O-METHYL-MERCAPTOBENZOIC ACID WITH OTHER METALS. By 8. E. LIVINGSTONE, A.S.T.C. and R. A. PLOWMAN, B.Sc., Ph.D., A.S.T.C. Manuscript received, August 9, 1951. Read, September 5, 1951. Bridged palladium complexes have been reported by Mann and Purdie (1935, 1936), and similar compounds of cadmium and of mercury by Evans, Mann, Peiser and Purdie (1940). In all these complexes the metal atoms are the same, but Mann and Purdie (1940) prepared compounds containing both palladium and mercury, and cadmium and mercury, bridged by bromine atoms. Allison and Mann (1949) reported two bridged structures of tetravalent tin which contained mercury and palladium respectively. In our previous communication—Livingstone and Plowman (1951)—we reported bridged chloro and bromo derivatives of palladium containing o-methyl- mercaptobenzoic acid as a chelating group. Using the same chelating group and a similar method of preparation we have succeeded in preparing bridged compounds of palladium with mercury or copper as the second metal atom. They are: (i) bis(o-methyl-mercaptobenzoato)-y-dibromo-palladium (II)- mercury (II), and (ii) bis(o-methyl-mercaptobenzoato)-u-dibromo-palladium (1I)-copper (II) 2-hydrate. Pact aa LN .2H,0 S0.¢.08 on” oe: a O ch, I II The compounds are insoluble in water, very sparingly soluble in hot alcohol and chloroform, but insoluble in benzene, toluene and acetone. These compounds are interesting in view of the fact that, in the case of the bridged dipalladium and the bridged palladium-copper compounds, the configurations of both metal atoms should be planar, whereas in the case of the analogous palladium-mercury compound the palladium should be planar while the mercury atom would be expected to be tetrahedral, since divalent mercury invariably exhibits the tetrahedral configuration. Compound ii appears to be the first bridged compound of copper containing another metal that has been reported. It is theoretically capable of existing in two isomeric forms cis and trans, but since only one form was obtained, it is assumed that it has the trans configuration. PALLADIUM COMPLEXES. 117 Mann and Purdie (loc. cit.) were unable to prepare bridged compounds of mercury and palladium, using mercury (II) chloride and mercury (II) iodide ; also these workers were unsuccessful in making a mixed palladium-cadmium bridged compound. During the course of this investigation attempts were made to prepare mixed palladium-mercury bridged compounds using mercury (II) chloride and mercury (II) iodide in place of mercury (II) bromide with bis(o-methyl-mercaptobenzoato) palladium (II) but all attempts failed. Similarly no analogous palladium-cadmium compound could be prepared using cadmium (II) bromide. It has been stated by Mann and Purdie (loc. cit.) that the formation of a bridged compound containing two different metals must be dependent to a certain extent on the valency lengths and intervalency angles of each of the four-covalent metallic complexes. Livingstone and Plowman (loc. cit.) also demonstrated that the formation of bridged compounds of palladium is highly specific in its dependence on the nature of the attached ligand, since they were unable to obtain bridging using several other chelating groups attached to palladium. Similar specificity was found by Mann and Purdie (1935) in that bridged compounds of palladium were formed with trialkyl-phosphines and arsines, but not with dialkyl sulphides. Further evidence for the above state- ments is afforded by the fact that, in this investigation, bridged compounds were obtained with palladium and mercury, and also with palladium and copper, but no analogous compound was obtained containing palladium and cadmium, using similar procedures. The reaction of the chelating group o-methyl-mercapto-benzoic acid with metals other than palladium was investigated. The palladium compound has been previously described—Livingstone, Plowman and Sorensen (1951). The only metallic salts which were found to give insoluble compounds with o-methyl- mercaptobenzoic acid were those of Cu™, Hg", Cd" and Ag’. The compounds obtained were: (iii) bis(o-methyl-mercaptobenzoato) copper (II); (iv) bis- (o-methyl-mercaptobenzoato) mercury’ (II); (v) bis(o-methyl-mercapto- benzoato) cadmium (II) ; (vi) silver (I) o-methyl-mercaptobenzoate. CHs . Sees VAN -—-O > 6 CH, Where i = Cu, Hg and Cd Whether o-methyl-mercaptobenzoic acid acts as a chelating group in the case of the silver compound (vi) is open to question. The mercury compound has been previously reported by Sachs and Ott (1926), who gave the melting point as 158-9° C. We found the melting point to be 165-165 -5° C. While Pd™@, Cu™, Hg™ and Cd™ form stable insoluble compounds with o-methyl-mercaptobenzoic acid, only Cu and Hg™ were found to give bridged compounds with Pd". EXPERIMENTAL. (i) Bis(o-methyl-mercaptobenzoato)-.-dibromo-palladium (II)-mercury (1). Mercury (II) bromide (0-6 g.) dissolved in water (40 ml.) was added slowly to a boiling aqueous solution (180 ml.) of bis(o-methyl-mercaptobenzoato) palladium (II) (0-9 g.). After ten minutes heating at the boiling point crystals began to form. After a further fifteen minutes’ 118 LIVINGSTONE AND PLOWMAN. heating, the product was filtered and washed well with hot water, then acetone. The yield of 1-21 g. consisted of deep yellow tetragonal prisms of m.pt. 212° C., which were insoluble in water, acetone, benzene, toluene and only very sparingly soluble in boiling alcohol and chloroform. Found: Pd, 13:4%; Hg, 25:0%; Br, 19-97%. (C,H,O,S),PdHgBr, requires: Pd, 13-31%; Hg, 25-03%; Br, 19-94%. (1) Bis(o-methyl-mercaptobenzoato)-.-dibromo-palladium (I1)-copper (II) 2-hydrate. To a boiling aqueous solution (120 ml.) containing bis(o-methyl-mercaptobenzoato)palladium (II) (0-5 g.) and potassium bromide (5 g.) was added a solution of copper (II) bromide (1-2 zg.) and potassium bromide (8 g.) in 25 ml. water. After five minutes crystallization commenced and after a further fifteen minutes’ heating, the chocolate brown crystalline product (0-65 g.) was filtered hot, washed well with alcohol, then acetone and dried over P,O,; ; m.pt. 208° C. On heating in a closed tube, water is evolved at a temperature just below decomposition. Found: Pd, 15:3%; Cu, 9:3%; Br, (i) 22:0%, (ii) 22-0% (on a separate preparation). (C,H,0,8S),PdCuBr,.2H,O requires: Pd, 15-24%; Cu, 9:08%; Br, 22-82%. It was found that in the absence of potassium bromide, products were obtained which had low Br and slightly high Pd content. These results are consistent with the possibility that one Br bridge is replaced to a small extent by an OH bridge, this effect leing lessened by the presence of an excess of bromide ion. A similar tendency was observed in the preparation of bis(o-methy]- mercaptobenzoato)-u-dibromo-dipalladium (II) (Livingstone and Plowman, 1951). (iii) Bis(o-methyl-mercaptobenzoato) copper (II). o-Methyl-mercaptobenzoic acid (0-33 g.) dissolved in one equivalent of sodium hydroxide solution was added to a warm aqueous solution (10 ml.) of copper (II) bromide (0-33 g.). The crystalline product (iii) precipitated immediately as bright green prisms, insoluble in water and decomposing at 152° C. Found: Cu, 15-95%. Cu(C,H,0,8), requires 15-97%. (iv) Bis(o-methyl-mercaptobenzoato) mercury (II). o-Methyl-mercaptobenzoic acid (0:33 g.) dissolved in one equivalent of sodium hydroxide, was added to a hot aqueous solution of mercury (II) chloride (0-27 g.). The compound (iv) gradually precipitated, yielding 0-31 g. of thin colourless needles, often bunched together in brushes, and insoluble in water; m.pt. 165-165-5° C. Found: Hg, 37-8%. Hg(C,H,O.S), requires: Hg, 37-50%. (v) Bis(o-methyl-mercaptobenzoato) cadmium (II). To a boiling solution of o-methyl-mercaptobenzoic acid (0-75 g.) in one equivalent of aqueous sodium hydroxide (20 ml.) was added slowly an aqueous solution (10 ml.) of cadmium (IT) chloride 2-5-hydrate (0:51 g.). After two minutes well-formed colourless dendritic crystals (0-9 g.) were deposited. M.pt. 286° C. Found: Cd, 25-2%. Cd(C,H,O.8), requires: Cd, 25-16%. (vi) Silver (1) o-methyl-mercaptobenzoate. (a) Silver acetate (0-4 g.) was dissolved in 50% ethyl alcohol (40 ml.) and added slowly to a boiling alcoholic solution (30 ml.) of o-methyl-mercaptobenzoic acid (0:4 g.). Thin colourless needles of m.pt. 234° C. were deposited. Found: Ag, 39-4%. AgC,H,O,S requires: Ag, 39-22%. PALLADIUM COMPLEXES. 119 (6) A solution of o-methyl-mercaptobenzoic acid (0-4 g.) in one equivalent of aqueous sodium hydroxide (20 ml.) was added to a hot aqueous solution (20 ml.) of silver nitrate (0-4 g.). Colourless needles of compound (vi) were deposited. M.pt. 232°C. Found: Ag, 39-4%. SUMMARY. Bromo bridged compounds containing palladium and mercury, and palladium and copper, with o-methyl-mercaptobenzoic acid, C,H,O.S8, as a chelating group, have been prepared; viz. (i) (C,H,O,S),PdHgBr, and (ii) (CLH,O,S),PdCuBr,.2H,O. Compounds of o-methyl-mercaptobenzoic acid with the following metals: copper (II), mercury (II), cadmium and silver— (iti) Cu(C,H,0.8). ; (iv) Hg(Cs,H,O0.8)2; (v) Cd(CsH,0.8),; and (vi) AgC,H,O,S are also described. REFERENCES. Allison, J. A. C., and Mann, F. G., 1949. J.C.S., 2915. Evans, R. C., Mann, F. G., Peiser, H. S., and Purdie, D., 1940. J.C.S., 1209. Livingstone, S. E., Plowman, R. A., and Sorensen, J., 1951. THis JouRNAL, 84, 28. Livingstone, 8. E., and Plowman, R. A., 1951. Tuis JouRNAL, 84, 188. Mann, F. G., and Purdie, D., 1935. J. Soc. Chem. Ind., 54, 814. Mann, F. G., and Purdie, D., 1936. J.C.S., 873. Mann, F. G., and Purdie, D., 1940. J.C.S., 1230. Sachs, G., and Ott, M., 1926. Monatshefte fiir Chemie, 47, 415. Department of Inorganic Chemistry, School of Applied Chemistry, N.S.W. University of Technology. THE ESSENTIAL OIL OF A PHYSIOLOGICAL FORM OF HUCALYPTUS CITRIODORA HOOK. By A. R. PENFOLD, F.A.C.L., F. R. MORRISON, F.A.C.L., J. L. WILLIS, M.Sc., H. H. G. McCKERN, A.A.C.L, and (Mrs.) M. C. SPIES, A.A.C.1. Museum of Applied Arts and Sciences, Sydney. Manuscript received, October 12, 1951. Read, November 7, 1951. Following the announcement of the occurrence of a physiological form of Eucalyptus citriodora by two of the authors (Penfold and Morrison, 1948), the investigation described hereunder was undertaken. The results obtained have confirmed those obtained in the preliminary experiments that the chief constituent of the oil of H. citriodora (Type), namely citronellal, has been largely replaced in the new form by an equiva- lent amount of citronellol and its esters. The amount of foliage available for investigation has been insufficient for a determination of the minor con- stituents, but these will be dealt with in a subsequent communication. The principal components so far identified are citronellol and its acetic and citronellic acid esters, and citronellal. Also under investigation are oils from individual trees containing percentages of aldehyde varying from 40 to 50 per cent., percentages which indicate an intermediate position between the form described in this paper and the “‘ Type ”’ oil. It is worthy of note that the trees, whose foliage yielded essential oils containing only about 10 per cent. citronellal, were observed in their natural habitat growing in close environmental association with trees of normal oil composition (65-85 per cent. citronellal) referred to in this paper as the ‘‘ Type ”’. All the trees examined were found to be morphologically indistinguishable from one another, but for purposes of identification, the physiological form described in this paper will be referred to as Variety ‘‘ A”’. THE ESSENTIAL OIL. The essential oils obtained by steam distillation of the foliage of eight individual forest trees were almost water white in colour. All possessed a pleasant odour of citronellol modified by that of its esters. The odour differed markedly from the sharp aldehydic odour of citronellal, which is characteristic of the oil of the type species. The yields and range of physico-chemical character- istics, together with those of the ‘‘ Type” oil for comparison, are shown in Table 1. A PHYSIOLOGICAL FORM OF EUCALYPTUS CITRIODORA HOOK. 121 TABLE I. Eucalyptus citriodora Hook., Variety ‘“‘ A ’’. Eight Trees from Cordalba, Queensland. Sol- Yield, ubility Ester Ester Alde- Tree Date % on 15° n20” 20° in 70% No. No. hyde No. | Received. | Sample di D D w/w 14 hrs. after Con- Remarks. y as Re- alc Hot Acetyl- tent ceived. Vol Sap. ation % 12/ 7/48 1-4 0-8855 |} 1-4569 | +2-55° — 120-00 231 0:9 pee dry, leaf only. 2, 30/ 7/48 0:8 0:-8876 | 1-4608 |+2-1° — 149-5 228 6-1 Fresh leaves and terminal branchlets. 3 2/11/48 2-0 0:°8825 | 1-4570 |+1-5° 1:25 86:5 271 11-0 Do. 4 11/ 1/49 1°8 0:8830 | 1:4544 |+0-7° 1°3 116-0 265 14-0 Fresh leaf only. 5 11/ 1/49 1-6 0:8864 | 11-4556 |+0-8° 1:3 127-0 249 12-0 Do. 6 23/ 1/50 3-0 0:-8872 | 1-4507 |+1-01° 1:4 191-4 258 6:0 Air. dry, leaf only. 7 23/ 1/50 1°5 0:8736 | 1:4541 |—0-90° 1-7 149-5° 270 11-0 Do. 8 13/ 6/50 3:4 0:8853 | 1°4521 |—0-7° 1:5 163-0 277 14-0 Do. Type 0:5 0:8640 | 1:4511 |+3° to | 1-3 to 12 to 230 to 65 to | Fresh leaves oil to to to —3° 1-5 60 to 85% and terminal] 0:75% | 0:8770 | 11-4570 292 branchlets. EXPERIMENTAL. The oil from tree No. 8 was selected for examination. The aldehyde content was determined by the hydroxylamine method of the Essential Oil Sub-Committee of the Society of Public Analysts (1932). The ester number after acetylation was equivaleent to 96-2% of acetylizable substances (calculated as C,)H,,O) in the original oil. Forty millilitres of the crude oil were fractionally distilled at 10 mm., the fractions obtained having the characteristics shown in Table II Residue — 3 TABLE II. Fraction ee 20° 20° No. B.p. Vol., ml. 15 nee Gas 1 70— 96° 6 0: 8666 1-4544 -5-6° 2 95-106° 6 0-8772 1-4536 —4-4° 3 107-—109° 24 0- 8839 1- 4504 +0-64° Determination of Ci ronellal. Fraction 1 yielded a semicarbazone, m.p. 84° from petroleum ether, and a yellow 2 : 4-dinitrophenylhydrazone, m.p. 80° from ethanol, both alone and in admixture with authentic specimens of these derivatives. Fraction 1 thus appears to consist principally of citronellal. Determination of Citronellol. A portion (20-5 ml.) of the crude oil was saponified with 0-5N alcoholic potassium hydroxide (250 ml.) at room temperature for two days. After dilution with water, 18 ml. of oil were recovered from the solution of potassium salts of the acids derived from the esters. The oil (15 ml.) after drying with anhydrous Na,SO,, was heated for two hours on the steam bath, under a reflux with phthalic anhydride (15 g.) and benzene (15 ml.). The cold reaction mixture was 122 PENFOLD, MORRISON, WILLIS, MCKERN AND SPIES. neutralized with aqueous potassium hydroxide and freed from unchanged oil by extraction with ether. After removal of ether the alcohol was recovered by steam-distillation with excess of sodium hydroxide. Ten millilitres of a colourless oil of pleasant rose-odour were obtained having , 15° 20 dis 0-8620, D. citronellol. Supporting evidence for the presence of this alcohol was obtained by the preparation of the allophanate, m.p. 106-107°, and the silver salt of the acid phthalate, m.p. 126°. (Mixed melting points showed no depression.) Hence the primary alcohol, free, and combined as ester, consists entirely of citronellol. 1-4556, a, +1:71°. These constants correspond closely with those of Determination of Acids (Citronellic and Acetic) Combined with Citronellol. The solution of potassium salts of the acids derived from the esters was evaporated to a small volume and extracted with ether to remove traces of oil. After removal of residual ether, the solution was acidified with dilute sulphuric acid. About 1-5 ml. of an oily acid separated which was converted directly to rts silver salt. 0-1003 g. silver salt yielded 0-0393 g. silver=39-18% Ag. Silver citronellate requires 38-99% Ag. 15° 15 0:9431, A further specimen of the oily acid was isolated, and had b,, 140-153°, d at 1°4591, ean +1:0°. D The benzylthiuronium ester was prepared, m.p. 146-147°, both alone and in admixture with an authentic specimen. This acid is therefore citronellic acid. The aqueous solution from the separation of the oily acid was steam distilled, the distillate being collected in three fractions. After neutralization with ammonia, each fraction was evaporated to a small volume and the silver salt of the acid prepared. Fraction 1. 0-1004 g. Ag salt gave 0-0651 g. Ag=64-84% Ag. a 2. 00-2608 g. Ag salt gave 0-1692 g. Ag=64-88% Ag. Sn 3. 0-1966 g. Ag salt gave 0:1275 g. Ag=64-85% Ag. Silver acetate requires 64-67% Ag. From a mixture of the silver salts of each of the foregoing fractions an anilide was prepared, m.p. 114°, undepressed in admixture with an authentic specimen of acetanilide. This acid is therefore acetic acid. No evidence was obtained for the presence of formic, butyric or valeric acids. REFERENCES. Essential Oil Sub-Committee of the Society of Public Analysts, 1932. Analyst, 57, 773. Penfold, A. R., and Morrison, F. R., 1948. Aust. J. Sci., 11, 29. AUSTRALASIAN MEDICAL PUBLISHING COMPANY LIMrrep | ~ Seamer and Arundel Streets, Glebe, N.S.W. = 1952 : Eee ih wy « PROCEEDINGS | oe Se Re 195%) - (INCORPORATED 1881) - gage e --. =OPART IV. (FEB 0 (05a VOL. LXXXV - Ee 2 EDITED BY ae sate IDA A. BROWNE, D.Sc. pase oe Honorary Editorial Secretary _ THE AUTHORS OF PAPERS ARE ALONE RESPONSIBLE FOR THE STATEMENTS MADE AND THE OPINIONS EXPRESSED THEREIN ee: SYDNEY : Lee ss PUBLISHED BY THE SOCIETY, SCIENCE HOUSE _—-——,s GLOUCESTER AND ESSEX STREETS = 1952 e oe Containing Papers read in December, 1951 ee 1 Plates VII and VIII, pp. 123-156 and Index, pp. XXIX-XXXI_ Part IV Arr. XIII. —The Occurrence of a Physiological Form of aioe oitieouaedt Fr. :. uel and Its Essential Oil. By A. R. Peale F. R. Momsen: J. L. Bee -McKern and a) M. C. Pee sik | Asie ta pi Pe Heat ree “Wales By Ida A. Brown and Kathleen M. Sherrard "Antimony! Tartrates, By F. P. ‘Dwyer and (Miss) i “C. Gyarfas « XVI. —Coordination Compounds of Conper AIT. ees Todo-cupra tes as f es “Acotone Solution. By C. M. Harris... oe Se as ee ee i i Ar. _XVIL—Some Complexes Derived from Silver Sli! ‘By Cc. M. Harris e ‘Arr. XVIII. —Coordination Compounds of Copper. TVs. ‘Some Cuprates (I) f Solution. BY, C. M. Harris and H. N. oS ceca eR Sage ‘Solution. By C. M. Harris and HL N. ‘Ss. Schafer : i : hee XX.—Palladium Complexes. IV. Bancieas bai Palladium Compo . Gece orem By S. E. Hiyingsions dt } THE OCCURRENCE OF A PHYSIOLOGICAL FORM OF BACKHOUSIA CITRIODORA F. MUELL. AND ITS ESSENTIAL OIL. By A. R. PENFOLD, F.A.C.L., F. R. MORRISON, F.A.C.I., J. L. WILLIS, M.Sc., H. H. G. McKERN, A.A.C.I., and (Mrs.) M. C. SPIES, A.A.C.I. Museum of Applied Arts and Sciences, Sydney. Manuscript received, November 14, 1951. Read, December 5, 1951. The species Backhousia citriodora has been described by Bentham (1866) and Bailey (1900). The tree is of medium size and occurs in restricted belts in the rain forests (‘‘ brush ’’) between Brisbane and Rockhampton, Queensland. The essential oil was first described by the firm of Schimmel & Company of Miltitz, Germany (1888). It was shown to consist almost entirely (95 per cent.) of the aliphatic aldehyde, citral. In 1923 one of the present authors (A.R.P.) examined oils from trees cultivated at Ashfield, N.S.W., and confirmed ~the above finding. Although the natural stands of this tree are not extensive, small quantities of the oil have been distilled and marketed spasmodically during the past sixty years. The oil was found to be very constant in composition, the citral content being within the range of 90-97 per cent. Mr. J. R. Archbold of Maryborough, Queensland, whilst engaged in the production of oil from trees growing near Miriamvale, about 160 miles north- west of Maryborough, as recently as June, 1950, noticed a slight difference in odour of one of the distillates, which indicated that a different kind of oil was present in some of the leaves distilled. Examination of additional single tree samples by the authors revealed the occurrence of a physiological form of Backhousia citriodora. The oil from these particular trees was found to consist largely of citronellal, in contradistinction to the Type, which contains 90-97 per cent. of citral. This observation was recorded by the authors in the Australian Journal of Science (1950). It is of interest to note that this is the first recorded occurrence of lwvo-citronellal in an Australian essential oil. The citronellal isolated from this source possesses the highest optical rotation yet recorded, viz. ap —14-21°. A survey of the area was made by two of the authors (F.R.M. and J.L.W.) in June, 1951. The trees were found scattered throughout an area of about ten acres on a steep, rocky hillside in dense rain forest: (‘‘ brush ’’). Some of the trees were very large, one in particular being 92 ft. high, with a girth at breast height of 6 ft. 8 ins.; the average tree, however, was about 12 ins. in diameter. The variant trees were located in two pockets, each containing about a dozen trees, of which six or seven were variants and the remainder normal. All the trees examined were found to be morphologically indistinguishable from one another, but for the purposes of identification the physiological form described in this paper will be referred to as Variety “‘ A”’. 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LL— Obes Mba oG L-GL— 008 -6— of8-6— 006 T498-0 GOLZ8-0 8298-0 8998-0 8648-0 FEL8-0 og 8-0 98-0 ‘aT *SOAVOT jo oTdules JUSTOAA Vo, SOHVA “TON “L vloporpa msnoyyong ‘T ATaVL se ce C6 oe 66 6e 6é ce ce a3 +“ pr® ‘eTeaureLTy £4100] 1¢/9/F 04/8/82 0¢/9/6T 0¢/9/61 0¢/9/6T 0¢/9/6T *poaleooyy eyed A PHYSIOLOGICAL FORM OF BACKHOUSIA CITRIODORA F. MUELL. 125 THE ESSENTIAL OIL. The essential oils obtained by steam distillation of the foliage of individual forest trees were of a pale lemon tint, and possessed the characteristic odour of citronellal. The oil, in fact, is almost identical with that of the Type oil of Eucalyptus citriodora, which has been marketed for many years. The yields and physico-chemical characteristics are shown in Table I. The principal constituents identified were [-citronellal and d-isopulegol. Small quantities of citronellol and esters were present. For comparative purposes, the essential oils obtained from trees of the Type species growing alongside the physiological form were also examined.. The principal constituent was citral (91-92 per cent.). The results are shown. in Table II. EXPERIMENTAL. Backhousia citriodora, Variety ‘ A”’. A total of 88 lb. of leaves and terminal branchlets was subjected to distillation in steam, six separate distillations being conducted. The respective crude oils were individually examined, and the results obtained are summarized hereunder. Determination of 1-citronellal. ‘The percentage of aldehyde present in each sample of oil was determined by the hydroxyl- amine method of the Essential Oil Sub-Committee of the Society of Public Analysts (1932). Samples 3 and 4 were used for the separation and identification of citronellal. The oil was shaken with sodium bisulphite solution, and the crystalline compound separated, washed with ether-alcohol mixture, and dried. It was subjected to steam distillation in the presence of an excess of sodium carbonate, the citronellal thus isolated possessing the following constants : bios 88°, 42° 0-8555, n2°” 1-4477, ap —14-21°. It yielded a semicarbazone, m.p. 83-5° after recrystallization from hexane, and a 2 : 4 dinitrophenylhydrazone, m.p. 81° after recrystallization from ethanol. Mixed melting point determinations with authentic specimens of these derivatives showed no depression. Determination of d-isopulegol. (a) Sample No. 6 (25 g.) was heated with an equal weight of phthalic anhydride in benzene solution on the steam bath for eight hours. The phthalic acid ester was subjected to steam distillation in the presence of an excess of sodium hydroxide. A water-white oil (3-6 ml.), possessing the characteristic odour of isopulegol, was isolated. It had the following constants : ai8” 0-9235, n2°° 1-4700, ap +8-68°. It yielded, with naphthyl-isocyanate, a well defined «-naphthyl urethane, m.p. 120°, after recrystallization from methanol. A mixed melting point determination with an authentic specimen from another source showed no depression. (6) Sample No. 5 (29 g.) cooled to 0° C. was added to a solution of hydroxylamine hydro- chloride (40 g.) and potassium carbonate (40 g.) in 200 ml. water at 0° C. After 24 hours’ agita- tion, the oximated oil was separated, dried and fractionated at 14 mm. Fraction 1 (3 ml.) had b. 94-98°/14 mm. and a}3° 0-9147, 02° 1-4726, ap +4-08°. Fraction 2 (2 ml.) had b. 98-110°/14 mm., whilst the remainder of the oil, the oxime of citronellal, distilled at 136-146°/14 mm. The physical constants of Fraction 1 agree well with those for isopulegol, and the identity of this alcohol was confirmed by its yielding with «-naphthyl-zsocyanate an «-naphthyl-urethane of m.p. 120-121° from methanol. Determination of Citronellol. The citronellal was removed from samples No. | and 2 by distillation at 9-5mm. The residue was treated with an equal weight of phthalic anhydride in benzene solution on a steam bath for 126 PENFOLD, MORRISON, WILLIS, MCKERN AND SPIES. two hours. A small quantity of phthalic acid ester was isolated, which, on steam distillation with an excess of sodium hydroxide, yielded 1 ml. of an alcohol possessing the characteristic rose odour of citronellol. On treatment with cyanic acid, the allophanate was obtained, m.p. 104: 5°, which was undepressed in admixture with an authentic specimen from another source. Backhousia citriodora, Type. Identification of the Principal Constituent, Crtral. Citral was determined as the major constituent of the oils of the Type trees growing adjacent to the trees of Backhousia citriodora, variety ‘‘ A’. The oils from the Type (see Table II) were | mixed, treated with 35 per cent. neutral sodium sulphite solution, and the citral isolated in the usual manner. The citral so obtained was water-white and had b,, 105-107°, ata 0- 8920, n20° 1-4885, a, --0°. It yielded a citryl-6-naphthocinchoninie acid, m.p. 199—200° on recrystal- D D y: yy Pp p yi lization from alcohol, unchanged in admixture with an authentic specimen from another source. SUMMARY. A physiological form of Backhousia citriodora F. Muell., has been observed in the rain forest near Miriamvale, Queensland, growing in association with the Type species, and has been designated Variety ‘‘ A’”’. The essential oil contains /-citronellal (62-80 per cent.), d-isopulegol, citronellol, and ester. The Type species from the same area contains 91-92 per cent. of citral. ACKNOWLEDGEMENTS. Thanks are due to Mr. J. R. Archbold, who drew our attention to the occurrence of this form, and for his co-operation and assistance during the visit to Miriamvale. | To the Queensland Forest Service, and particularly to Mr. W. R. Suttie, District Forest Officer at Maryborough, Queensland, and his staff, we are greatly indebted for their wholehearted co-operation in this investigation. REFERENCES. Bailey, F. M., 1900. ‘‘ The Queensland Flora ’’, Part IT, p. 644. H. J. Diddams & Co., Brisbane. Bentham, G., 1866. ‘‘ Flora Australiensis ’’, Vol. 3, p. 270. Lovell, Reeve & Co., London. Penfold, A. R., 1923. Sydney Technological Museum Bulletin, No. 5, p. 5. Penfold, A. R., eé al., 1950. Aust. J. Set., 13, 27. Schimmel & Co., 1888. Bericht., April, p. 17. Society of Public Analysts, Essential Oil Sub-Committee, 1932. Analyst, 57, 773. GRAPTOLITE ZONES IN THE SILURIAN OF THE YASS-BOWNING DISTRICT OF NEW SOUTH WALES. By Ips A. BROWN,” D.Sc., and KATHLEEN M. SHERRARD, M.Sc. With Plates VII and VIII and two text-figures. Manuscript received, November 14, 1951. Read, December 5, 1951. PART I. STRATIGRAPHY. (I.A.B. and K.M.S.) INTRODUCTION. The Yass District has been well known for its shelly faunas, especially those from Hatton’s Corner, since fossils were first recorded from Yass Plains by Strzelecki in 1845. Graptolites, however, were not recorded from the area until Mitchell (1886a) exhibited to the Linnean Society of New South Wales, from Bowning, near Yass, ‘‘. . . specimens of Graptolites, probably undescribed, and certainly the first recorded from N.S8.W., showing that the formations there which have hitherto been regarded as Devonian are in reality Silurian.” In the same year Mitchell (1886b) published an account and illustrative section of the Bowning beds, but did not refer to the graptolites. His section showed the Bowning beds folded into a syncline. In 1888(a) he exhibited further graptolites from Bowning and ‘ Belle Vale’’. He also noted (18885) ‘“‘ several graptolites from micaceous sandstones in the Lower Trilobite Bed on the eastern side of the syncline; and in shaly sandstone on the western side, in the Great Shale bed.”’ No exact locality was given, nor were the graptolites named specifically or generically. In 1902 T.S. Hall identified ‘* Monograptus allied to M. dubius ”’ in specimens collected by Mitchell from the Lower Trilobite bed at ‘ Belle Vale ’’, a large property lying between Yass and Bowning. Shearsby (1912) recorded among the fossils in the Barrandella shales at Yass, Monograptus (?) and Dendrograptus. In 1915 Mr. Shearsby (Sherrard and Keble, 1937) discovered Monograptus cf. vomerinus in a spoil-heap made near Bowning railway station during railway works. In 1937 Sherrard and Keble described several species of Monograptus from Silverdale, two miles east-north-east of Bowning and seven miles north- north-west of Yass (indicated as ‘‘ Graptolite Bed’? on Plate VII). These were the first graptolites described from the district whose exact source was known. The graptolite most abundant at this locality, as will be shown in this paper, is Monograptus salweyi from the zone of M. scanicus in the Silurian of Britain. An account of the stratigraphy of the Yass-Bowning District was published by one of us (Brown, 1941), in which all previous work was summarized and all recorded fossils from the district were assigned to their proper stratigraphical * Mrs. W. R. Browne. 128 BROWN AND SHERRARD. horizons. The field-mapping indicated that the Monograptus horizon of Sherrard and Keble, 1937, is stratigraphically above the ‘‘ Dalmanites Bed ”’ (=‘* Phacops Bed” of Jenkins, 1878; =-‘‘ Middle Trilobite Bed ”’ of Mitchell, 1886), as clearly stated in the paper (Brown, 1941, pp. 320, 324, 328, 333, 334, Plate XIV). The Dalmanites bed contains abundance of Dalmanites meridianus Eth. & Mitchell, 1895, and there is thus no justification for Gill’s assumption (1948) that the age of this trilobite is not Silurian. Portion 7 16 Ae ee petien 15 5 Ss f | is : > oo key te (oe PARISH ~ yy z U n y ; Taemas Road Fig. 1.—Sketch-map to show relationship of graptolite-bearing beds in Portion 15, Par. Hume, near junction of Good Hope and Taemas roads. In 1947 Messrs. G. Packham and J. Veevers, under the guidance of Mr. A. J. Shearsby, discovered Monograptus bohemicus in shale immediately below the Dalmanites bed, west of Hatton’s Corner, two miles west of Yass. Subse- quent collecting by Mr. Shearsby and the two present writers has confirmed this discovery and shown that the bohemicus bed persistently underlies the Dalmanites bed, wherever the latter is shown on the accompanying map (Plate VIT). Miss G. L. Elles of the Sedgwick Museum, Cambridge, has kindly examined specimens from this bed and states they are of the type of M. bohemicus which is characteristic of the top of the M. nilssoni zone of the Silurian. GRAPTOLITE ZONES IN THE SILURIAN OF THE YASS-BOWNING DISTRICT. 129 Furthermore, the sandstone described by Sherrard and Keble (1937) with graptolites from the zone of Monograptus scanicus has since been located at several places about two miles south of Hatton’s Corner, not far from the eastern edge of Portion 15, Parish of Hume, near the junction of Taemas and Good Hope roads (Text-fig. 1; Plate VIII, figs. a, b). On the side of a grassy hill near this point Monograptids, though rare, have been found on at least three horizons, up to 200 feet stratigraphically above the Dalmanites bed, which outcrops below the sandstone with M. scanicus zone graptolites. Beneath the Dalmanites bed is found shale with M. bohemicus. Finally, Monograptus vomerinus has been found about the middle of the Black Bog shales in the western branch of Reedy Creek near its crossing by the Good Hope road (Plate VII). SEQUENCE AND CORRELATION. The Silurian sequence in the Yass-Bowning district has been described by one of us (Brown, 1941). The sedimentary rocks have been divided into the Bango, Yass and Hume Series in ascending stratigraphical order, separated from each other by rocks of igneous origin. Graptolites have been found in the Hume Series alone, which is therefore the only one considered in this paper. This series consists of limestones, shales, sandstones and conglomerates arranged in the following descending order : | | Approximate | ‘Thickness Accompanying Graptolites. (in Feet). Tuffaceous conglomerate... ae 150 Shale and sandstone oe: nal 50 (?) Upper Trilobite bed .. ois sie 20 Shale and conglomerate ae es 100 Sandstone ile ys - sot 12-20 .| Monograptus salweyi, M. cf. twmescens, Dictyonema. Sandstone ie re hs 5 eae 200 M. salweyt. Middle Trilobite bed (Dalmanites | bed) .. oN ef Se: eae 4 bohemicus bed ie Bes Me 6 M. bohemicus, M. nilssoni, M. crinitus, | M. roemeri, Dictyonema. Black Bog Shales... ae Se | 200 M. vomerinus. Hume Limestone (=Lower Trilobite | | bed) .. ay ee AC Set 0-20 Monograptus allied to M. dubius. Barrandella Shales... se a 5-150 Monograptus (?). Bowspring Limestone it a 0-100 Although it has been generally recognized, and particularly by Etheridge (1891) and Dr. Dorothy Hill (1940), that the shelly fossils of the Hume and Bowspring Limestones and the associated beds are approximately of the same age aS those of the Wenlock (Etheridge) or Wenlock-Ludlow boundary (Hill) of Britain, few, if any, of the species are identical. On the other hand the graptolitic fauna, which has now been found in close association with the shelly fauna, includes on one horizon (the bohemicus bed) four species of Monograptus which are all restricted to the zone of M. nilssoni of the Lower Ludlow of Britain. The same assemblage is found in the Henryhouse Shale of Oklahoma, U.S.A. (Decker, 1935). Moreover, the dominant graptolite of the overlying salweyi beds at Yass-Bowning is highly characteristic of the M. scanicus zone of Britain. 130 BROWN AND SHERRARD. The graptolites thus permit a more exact correlation of the Yass-Bowning and British sequences as indicated below : Zones in Britain. Equivalents in Hume Series. Monograptus scanicus. M. salweyi (in sandstone). LOWER Dalmanites (Middle Trilobite) bed. LuDLow. Monograptus nilssoni. | WM. bohemicus (in shale). Cyrtograptus lundgrent M. vomerinus (in Black Bog Shales). WENLOCK. to Monograptus allied to M. dubius (in Lower Trilobite Bed). Cyrtograptus murchisoni. Monograptus (?) (in Barrandella Shales). It will be seen, however, that there appears to be no marked break in the sedimentation at Yass between the equivalents of the Wenlock and Ludlow, since about half-way up the thick Black Bog Shales occurs Monograptus vomerinus, which is found throughout the Wenlock succession in Britain, while immediately above the Black Bog Shales is the six-feet bohemicus bed with its assemblage of graptolites restricted to the M. nilssoni zone of the Lower Ludlow in that country. PART II. SYSTEMATIC DESCRIPTIONS. (K.M.S.) Order GRAPTOLOIDEA Family Monograptidze Lapworth, 1873. Genus Monograptus Geinitz restricted, 1852. Monograptus bohemicus (Barrande, 1850). Plate VIII, Fig. d; Text-fig. 2, d. Monograptus bohemicus (Barrande), Elles and Wood, 1911, 367, pl. xxxvi, figs. 4a-d. Rhabdosomes up to 7 cm., but more usually about 2 cm. long and 1-3-2 mm. wide. Strong ventral curvature of the rhabdosome continuous throughout length in the short examples, but with straight distal section in the few long ones. Thece 10 to 14 in 10 mm., up to 2 mm. long and 0-5-0-7 mm. wide. Proximal thece sometimes seem longest and are impressed into a sigmoidal bulge by the overlying thecze where the rhabdosome is most curved. Distal thece are straight. Apertures of thecze in proximal region appear convex, but become concave distally. Overlap one-third to one-half. Inclination 35 to 40 degrees. Sicula 1 mm. long and 1 mm. wide at its base, with virgella 0-7 mm. long. Gregarious habit. Associates : M. nilssoni, M. roemeri, M. crinitus, Dictyonema, cf. Orbiculoidea, Pterinea retroflexa, Cardiola fibrosa, Hurypterid. Localities: Beneath Dalmanites bed, 200 yards south of Yass River, west of Hatton’s Corner, Portion 7, Par. Hume; Portion 15, Par. Hume, near junction Good Hope and Taemas roads ; Portion 5, Par. Yass, on Black Range road, beneath the Dalmanites bed outcropping near this road between the Hume Highway and 14 miles south-south-west of it. GRAPTOLITE ZONES IN THE SILURIAN OF THE YASS-BOWNING DISTRICT. 131 Monograptus nilssoni (Barrande). (Plate VIII, figs. ¢, f; text-figs. 2e, g. h.) Monograptus nilssoni (Barrande), Elles and Wood, 1911, 369, pl. xxxvii, figs. la-e. ere a (Barr.) Frech, 1897. Lethea paleozoica, i, 662, Taf. A, ewe. Rhabdosome 5 em. long with slight concave curvature. Width 1 mm., thece 8 in 10 mm., just under 2 mm. long and 0-4 mm. wide. Overlap a quarter. Thecee have convex ventral walls and an aperture at right angles. Inclination 20 degrees. uD Big: 2: (c) M. salweyi (Hopkinson), Portion 15, Par. Hume. d) M. bohemicus (Barrande), Portion 7, Par. Hume. e) M. nilssoni (Barrande), Portion 7, Par. Hume. M. roemeri (Barrande), Portion 7, Par. Hume. (h) M. nilssoni (Barrande) ‘“‘ Linograptus ’’, Portion 7, Par. Hume. (A.M., F44613.) (a) Monograptus crinitus Wood, Portion 7, Par. Hume. (A.M., F44615.) ) Monograptus nilssoni also occurs in groups of rhabdosomes branching off from near sicula forming what has been called ‘‘ Linograptus’’ (Frech, 1897 ; Boucek, 1932). Four, six or more branches radiate from a small central plate with webs joining each stipe near the point of bifurcation. Very slight curvature, thece developed (8 in 10 mm.) on inner side of curve, overlap negligible. Branches 0-3 to 0-5 mm. wide and up to 7 mm. long. Thecal apertures slightly concave. Associates and locality: As for M. bohemicus. 132 BROWN AND SHERRARD. Monograptus salweyi (Hopkinson). (Plate VIII, figs. a, b; text-figs. 2b, c.) Monograptus chimera var. salweyt (Hopkinson), ENies and Wood, 1911, 400, pl. xxxix, figs. 5a-d. Monograptus salweyi (Hopkinson), Elles, 1944. Geol. Mag. Ixxxi, 275. Monograptus flemingu (Salter), Sherrard and Keble, 1937, 313. Rhabdosome up to 2:0 cm. long, sometimes showing slight dorsal curvature proximally, which is probably due to the graptolites being observed from a dorsal aspect. Width, proximally 0-8 mm., distally 1-6 mm. Sicula, including virgella, 1 mm. long, reaching to opposite aperture of first theca. Thece 13-11 in 10 mm., up to 2-5 mm. long, with a spine which is usually curved and is up to 1 mm. long.. Proximally spines occupy one-half to one-third width of rhabdo- some, distally one-quarter to one-fifth. Overlap one-half to two-thirds. Thece 0-4 to 0-6 mm. wide. Thecal apertures sometimes concave, sometimes convex. When convex and the aperture has a curved spine, the appearance of a hook is suggested. Proximally, the walls of thece are first convexly curved then bent over in a concave curve. Virgula prolonged 3 mm. beyond rhabdosome, as is characteristic of M. salweyt. M. salweyi from Silverdale (Portion 34, Par. Derringullen) is slightly wider and longer and has fewer thece in 10 mm. than those from the Parish of Hume. Those from the former locality show a more pronounced S-shaped curvature of their thecal walls, which when continued into a spine almost amounts to a hook. Associates : Monograptus cf. tumescens, Dictyonema, Craniops, (2) Zygospira, ef. Lissatrypa, cf. Parmorthis, Howellella, Plectodontid, Serpulites. Localities : Portion 15, Par. Hume; Black Range road, Portion 125, Par. Yass; Portion 34, Par. Derringullen. Discussion.—At Silverdale the sandstone, in which this graptolite was first found, is not underlain by the Dalmanites bed nor by shale with M. bohemicus, so that its age relative to the bohemicus band is not obvious. When first found, this graptolite was identified as M. flemingw (Sherrard and Keble, 1937). How- ever, in 1950, when Miss Elles generously made available for comparison type specimens of M. chimera var. salweyi (Hopk. m.s.), it was evident that the graptolite from Silverdale, previously named M. flemingii, is actually M. salweyt (Elles, 1944), occurring here in the rigid form which is characteristic of the zone of M. scanicus. At Silverdale, these graptolites are imbedded in the sandstone in such a way that a certain amount of torsion has occurred, giving a hooked appearance to the thece in some views. The discovery, near the junction of Good Hope and Taemas roads, of M. bohemicus (characteristic of the zone of M. nilssoni) in a bed conformably underlying sandstone containing the graptolite under discussion, is confirmation that the latter must belong to the zone of M. nilssoni or higher, and therefore cannot be M. flemingu, which does not range higher than the zone of M. vulgaris. Monograptus crinitus Wood. (Text-fig. 2a.) Monograptus crinitus Wood, Elles and Wood, 1913, 435, pl. xliv, 3a-e. Rhabdosomes 2 cm. long, 0-5 mm. wide. Usually occurs as bundles of fragments. Slight ventral curvature. Thece 9-10 in 10 mm., 1-5 mm. long, 0-3 mm. wide. Overlap less than half. Angle of inclination 25 degrees. Apertures horizontal, sometimes pressed out to denticles. Associates and locality: As for M. bohemicus. GRAPTOLITE ZONES IN THE SILURIAN OF THE YASS-BOWNING DISTRICT. 133 Monograptus vomerinus (Nicholson). Monograptus vomerinus (Nicholson), Elles and Wood, 1911, 409, pl. xli, la-e. Rhabdosome straight, 1-5 cm. long, 1 mm. wide. Distal fragments only preserved, with virgula. Thece 13 in 10 mm., nearly 2 mm. long, 0:5 mm. wide. Thece have convex ventral margin with well-marked thecal edge, overlap one-half to one-third. Inclination 30 degrees. Aperture concave, almost pouch-like with denticle or spine occasionally suggested. 3 Locality : Reedy Creek crossing of Good Hope Road, in Black Bog Shale. Monograptus roemeri (Barrande). © (Plate VIII, fig. g; text-fig. 2f.) Monograptus roemeri (Barrande), Elles and Wood, 1911, 397, pl. xxxix, 2a-d. Rhabdosome under 2 mm. wide with ventral curvature. Thece 18 in 10 mm., each 2 mm. long, 0-3 mm. wide, overlap three-quarters. Associate: M. bohemicus. Locality: As for M. bohemicus. Order DENDROIDEA. Dictyonema sp. (Plate VIII, fig. e.) One poorly preserved fragment, 2-5 cm. long, 1 cm. wide, apparently flabelliform, but incompletely preserved. Branches 8 in 10 mm., each branch about 0-3 mm. wide and 0:25 mm. apart. Dissepiments up to 20 in 10 mm., mesh 0-5 mm. long and 0:3 mm. wide. Monograpius bohemicus is superimposed on specimen ; from bed below Dalmanites bed. Dictyonema sp. also occurs at Silverdale with M. salweyt. ACKNOWLEDGEMENTS. Facilities for carrying out this work have been kindly made available to the writers by Professor C. E. Marshall, D.Sc., Ph.D., of the University of Sydney. Professor W. B. R. King, F.R.S., of the University of Cambridge, England, was good enough to allow one of us (K.M.S.) to examine graptolites in the collections of the Sedgwick Museum. She also wishes to thank Miss G. L. Elles of the Sedgwick Museum for the generous help and advice she gave her. The other writer wishes to acknowledge financial assistance for field expenses from the Commonwealth Research Grant (University of Sydney). REFERENCES. Boucek, B., 1932. Vestnik Stat. Geol. ustav. Ceskoslav. Rep., 8, 145. Brown, I. A., 1941. Tuis Journnat, 74, 312. Decker, C. E., 1935. Journ. Pal., 9, 434. . Elles, G. L., and Wood, E. M. R., 1911, 1913. Mon. Pal. Soc., 64, 66, 359, 415. Etheridge, R., Junr, 1891. Rec. Aust. Mus., 1, 201. Etheridge, R., Junr., and Mitchell, J., 1895. Proc. Linn. Soc. N.S.W., 10, 485. Gill, E. D., 1948. Tuis JourNAL, 82, 16. Hall, T. 8., 1902. Proc. Linn. Soc. N.S.W., 27, 654. Hill, D., 1940. Jbid., 65, 388. Jenkins, C., 1878. Jbid., 3, 21. Mitchell, J., 1886a, 6. Jbid., 1, 577, 1193. —-———— 1888a. Jbid., 3, 150. — 1888). Rept. Aust. Ass. Adv. Sci., 1, 291. Shearsby, A. J., 1912. Jbid., 13, 106. Sherrard, K., and Keble, R. A., 1937. Proc. Linn. Soc. N.S.W., 62, 303. Strzelecki, P., 1845. Physical Descriptions of New South Wales and Van Diemen’s Land. 134 BROWN AND SHERRARD. EXPLANATION OF PLATES. Pruate VII. Geological sketch-map of the Yass District. (Reprinted from These Proceedings, Vol. LX XIV, 1941, Plate XIV.) PLATE VIII. All photographs taken by I. A. Brown. | The numbers refer to specimens registered in the collections of the Australian Museum, Sydney. (a) Monograptus salweyi (Hopkinson), Portion 15, Par. Hume. No. F44607. Mag. x2.3. (6) M. salweyi (Hopkinson), Portion 15, Par. Hume, No. F44608. Mag. x2.3. (Note extension of virgula). (c) M. nilssoni (Barrande), Portion 7, Par. Hume. F44609. Coll. Messrs. G. Packham and J. Veevers. Mag. X2.3. (d) M. bohemicus (Barrande), Portion 7, Par. Hume. F44610. Coll. A.J. Shearsby. Mag. x 2.3. (e) Dictyonema sp. and M. bohemicus, Portion 7, Par. Hume. F44611. Coll. Messrs. G. Packham and J. Veevers. Mag. x2:-3. (f) M. nilssons (Barrande) ‘‘ Linograptus”’, Portion 7, Par. Hume. F44612. Coll. Mr. C. V. G. Phipps. Mag. x2.3. (g) M. roemeri (Barrande), Portion 7, Par. Hume. No. F44614. Mag. x2.3. (h) Dalmanites bed and underlying bohemicus bed, showing true dip. Half mile south of Yass River and half mile west of Hatton’s Corner, Portion 7, Parish of Hume. ne ee ee a Boambolo a Journal Royal Society of N.S.W., Vol. LNXXV, 1951, Plate VIT 2 4 i——|] F Sook Ee SEN ‘ac! 9 Sat 5 fides : S tas 3; 3 a , 2 fs S Za | i ; =) = is zy : 3 qo é > ) BE ey i Ge Se 2 Re, S wD i: : : i HB of x LORS = 2 § rs z 3 se, BE So) dp} 5 z 2 KN 8 a ae ee S| > z ss Oo OEM eL . ‘sung, * ) ¢ AY gPirapee g Ans hs fachells Creek 2 & HUI Journal Royal Society of N.S.W., Vol. EXXXYV, 1951, Plate VIII Se ROOTS ie ae RS SSS SS SOR eS we teitp D fy * ' 5 a ; 1 ti as THE RESOLUTION OF TRIS-2: 2’-DIPYRIDYL METAL COMPLEXES THROUGH THE IODIDE ANTIMONYL TARTRATES. By F. P. DWYER, D.Sc., and (Miss) E. C. GYARFAS, M.Sc., Ph.D. Manuscript recewed, November 13, 1951. Read, December 5, 1951. In a previous paper (Dwyer and Gyarfas, 1950) it was shown that when a solution of d,l-tris-2 : 2’-dipyridyl ruthenium II antimony! tartrate was frac- tionally precipitated with potassium iodide solution, l,tris-2 : 2’-dipyridyl ruthenium II iodide antimonyl tartrate [Ru(dipy).]5.1,.(SbO.Tart),.18 H,O separated as the least soluble fraction. Subsequently, d-tris-2 : 2’-dipyridyl ruthenium II iodide separated. This is the most convenient method of resolution of the ruthenium compound. It has now been found that the crystallization of the iodide antimony] tartrates is the most efficient method of resolution of the analogous dipyridyl complexes of iron II, osmium IT and nickel. The three complex ion groups in the lattice compound always have the same configuration— laevo in the Na-D line, except the iron compound, which is dextro owing to rotatory dispersion. The iron II and nickel I1 compounds have been resolved previously, like the ruthenium II compound, through the tartrates (Werner, 1912; Morgan and Burstall, 1931). The tartrates, however, have a high water solubility, and as a result Werner isolated only the laevo form of tris-2 : 2’-dipyridyl iron IT iodide ; whilst Morgan and Burstall were forced to use both d and / ammonium tartrates in order to obtain both forms of the nickel compound. A further complication with both of the above compounds is the rapid racemization of the enantio- morphous forms. In the resolution of the osmium compound (Burstall, Dwyer and Gyarfas, 1950) through the antimonyl tartrates, both diastereoisomerides were very soluble in water and difficulty was encountered in preparing the pure optical forms. The sparingly soluble iodide antimony] tartrates can be obtained by several procedures. The racemic iodide can be transformed to the antimonyl tartrate with silver antimony! tartrate, and the resulting solution treated fractionally with potassium iodide. Alternatively a solution of the racemic chloride can be treated with excess of potassium antimony] tartrate, and with potassium iodide. The addition of alkali after approximately half of the complex salt has precipitated destroys the antimony] tartrate radicle, and ensures a high degree of purity for the other antipode. Since the rate of racemization of the nickel and iron compounds is raised considerably by hydroxyl ions (Davies and Dwyer, 1952) after making alkaline, all operations must be conducted quickly. The lattice compound can be decomposed by either dilute acid, or alkali or sodium acetate solution. The rate of solution in sodium acetate is not high and usually requires warming. If acid is used it should be dilute sulphuric or nitric acid, since the halogen acids tend to form precipitates of the form [M(dipy)s|[(SbX,).]. After solution and filtration of the antimony oxide, the active compounds can be precipitated as the iodide or perchlorate Werner (loc. cit.) found 136 DWYER AND GYARFAS. [x ]2?0— —440°, and —520° for J, Fe(dipy)3I,.6H,O and the bromide hexahydrate. By the new procedure both enantiomorphous forms of the iron compound have been obtained with almost ten times these rotations—Fe(dipy);(ClO,),.2H,O, [x ]29— +4,800 and —4,100°. EXPERIMENTAL. 1-Tris-2: 2’-Dipyridyl Nickel Iodide Antiumonyl Tartrate Octadecahydrate. Nickel sulphate heptahydrate (1-35 g.) in water (50 cc.) was treated with dipyridyl (2-35 g.), and the mixture heated to dissolve the dipyridyl. The resulting red solution of the complex sulphate was cooled in ice and solid potassium iodide (0-2 g.) added. The slight precipitate of the racemic iodide was filtered and the clear solution treated with potassium antimony] tartrate (4 g. in 25 cc. of water at 10° C.). On scratching the sides of the vessel, pink micaceous plates of the lattice compound separated. The precipitate was collected and washed with ice water and ether. Addition of potassium iodide fractionally to the filtrate gave a little more of the lattice compound, followed by the dextro iodide, and finally a little racemic iodide. A 0:04% solution of the lattice compound in N/20 sodium hydroxide gave «;,,,=—0-12° (2 dm. tube), whence [x ]5 96, =—150°. Found): Ni»: 34965) 50—14-09% 5 U—a-io,- Calculated for Ni;(C,)>H gN.2).(C,H,O,SbO),I,.18H,0 : Ni=5-34%; Sb=14-72%; I=7-80%. 1-Tris-2 : 2’-Dipyridyl Nickel II Perchlorate Trihydrate. This was obtained by dissolution of the lattice compound in 0:05N. sodium hydroxide at 10° C., and after removal of the antimony oxide, adding sodium perchlorate. The pink flakes were washed with ice water and ether. A 0:-1% solution in water gave a54.,=—0-96° (2 dm. tube), whence [«]}%.,=—480°. Found: Ni=7:6%. Calculated for Ni(C,,H,N,)3(ClO4)..3H,O : Ni=7-53%. d-Tris-2 : 2’-Dipyridyl Nickel II Perchlorate Trihydrate. The d iodide obtained from the mother liquid of the lattice compound was ground up with an excess of silver chloride and a little ice water until double decomposition was complete. After filtration from silver halide, sodium perchlorate (20%) was added. A 0:1% solution in water ZAaVe M516; = +0:°95°, whence ee = +475°. Found: Ni=—7-6%. Calculated for Ni(C,,H,N,)3(ClO,4)..3H,O0 : Ni=7-53%. 1-Tris-2 : 2’-Dipyridyl Osmium II Iodide Antimonyl Tartrate Octadecahydrate. The racemic iodide (0:8 g.) was transformed to the antimony] tartrate by shaking with silver antimony] tartrate (0-8 g.) in water (80 cc.). After filtration, a further amount of the racemic iodide (0:8 g.) was dissolved in this solution by warming. On cooling, the crystalline lattice compound separated in dark green micaceous plates. Alternatively the compound was prepared by transforming the whole of the racemic iodide to the antimony] tartrate, and then fractionally precipitating with potassium iodide. Laevo tris-2 : 2’-dipyridyl osmium IT iodide and the dextro compound, obtained respectively from the lattice compound and the filtrate, had the same rotation, as previously found (Burstall, Dwyer and Gyarfas, loc. cit.). A 0:005% solution of the lattice compound gave «=—0-07° (1 dm. tube), whence [x ]e% 6; =—1400°. Found): Os— lor 7194; Sb— le 6c lie ae: Calculated for Os3(C,>H gNe)9(C,H,O,SbO),1,.18H,O : Os=15-8% ; Sh=13-5% ; I=7-16%. THE RESOLUTION OF TRIS-2 : 2’-DIPYRIDYL METAL COMPLEXES. 137 d-Tris-2: 2’-Dipyridyl Iron II Iodide Antimonyl Tartrate Octadecahydrate. The racemic iodide (2-6 g.) was shaken with silver chloride excess and water (25 cc.). After filtration and washing of the silver halide, the total volume was made up to 50 cc. and the solution cooled in ice. A solution of sodium iodide (0:9 g.) in water (20 cc.) was also cooled in ice. Potassium antimony] tartrate (2 g.) was dissolved in the iron solution by stirring, and then 2 ec. of the iodide solution added with scratching the sides of the vessel. After two minutes the lattice compound was filtered, and washed with ice water. The remainder of the sodium iodide added in equal portions to the filtrate, filtering between each addition, and carrying out the operations as quickly as possible gave strongly laevo rotatory products for the first two fractions, and weakly laevo rotatory for the last. All fractions were washed with ice water, then ether. A 0:01% solution of the deep red micaceous plates of the lattice compound gave ap = +0: 21° (1 dm. tube), whence [a}/®= +2100°. Hounds) He—5-12%; Sb—14-6% ; I=7:7%. Calculated for Fe;(C,,>H,N.),(C,H,O,SbO),I,.18H,0: Fe=5-08%; Sb=14-76% ;s LST SL ye. d-Tris-2 : 2’-Dipyridyl Iron II Perchlorate Dihydrate. The iodide antimony] tartrate (1 g.) was dissolved in 0-:05N sodium hydroxide (20 cc.) at 4°C. After filtration of the antimony oxide, and addition of sodium perchlorate, the deztro perchlorate was obtained as red micaceous plates. The active perchlorate was less soluble than the racemate. The substance was washed with ice water and ether. A 0:01% solution in water gave ap=—+0-48° (1 dm. tube), whence [a ]t°= +.4,800°. Found: Fe=6-8%. Calculated for Fe(C,,>H,N.)3(ClO,4)..2H,O : Fe=6-72%. 1-Tris-2 : 2’-Dipyridyl Iron II Perchlorate Dihydrate. The laevo iodide fractions from the iodide antimony] tartrate separation (vide supra) were ground up in a mortar with silver chloride and a little ice water. The silver halide precipitate was removed quickly, and the deep red solution of the active chloride precipitated with sodium perchlorate. Approximately 25% of the substance was left in the solution in order to avoid separation of any racemate. A 0:01% solution in water gave ap =—0-41° (1 dm. tube), whence [a }t> = —4,100°. Found: Fe=6-62%. Calculated for Fe(C,,H,N,)3(ClO,4)..2H,O : Fe=6-72%. SUMMARY. The complex ions M(dipy),++, (M=Fe, Os, Ru, Ni) yield sparingly soluble isomorphous iodide antimonyl tartrates, /-[M(dipy).],.I,.(SbO.Tart.),.18 H,O and d-[Fe(dipy).],.I,.(SbO.Tart.),.18 H,O. These curious lattice compounds have been found to be the most suitable substances for the resolution of the dipyridyl complexes. In this way both optical forms of the iron compound have been isolated, and their rotations are almost ten times that described by Werner for the laecvo antipode. REFERENCES. Burstall, F. H., Dwyer, F. P., and Gyarfas, E. C., 1950. J. Chem. Soc., 953. Dwyer, F. P., and Gyarfas, E. C., 1950. THis JouRNAL, 83, 174. Dwyer, F. P., and Davies, N. R., 1951. Trans. Faraday Soc., 1952. In press. Morgan, G. T., and Burstall, F. H., 1931. J. Chem. Soc., 2213. Werner, A., 1912. Ber., 45, 433. Department of Chemistry, Sydney University. COORDINATION COMPOUNDS OF COPPER. PART III. CompLtEex I[ODO-CUPRATES (I) FROM ACETONE SOLUTION. By C. M. HARRIS. Manuscript received, November 12, 1951. Read, December 5, 1951. Marsh and Rhymes (1913) found that silver iodide dissolved in acetone solutions of the iodides of ammonium and the alkali metals. They obtained from these solutions a series of compounds of the general type M[Ag,I,].nC,H,O containing acetone of crystallization (where M=Cs and n=0; M=K and Rb and n=2; and M=Na and NH, and n=3) and from aqueous acetone, the compound Rb[AgI,].0-5 H,O. Copper (I) iodide dissolved in a similar manner but they failed to isolate any compounds. This communication reports the preparation of some complex iodo-cuprates (I) from acetone solution. Saturation of an acetone-sodium iodide solution with copper (I) iodide and evaporation under a variety of conditions always led to precipitation of copper (I) iodide. A compound approximating to Na[Cu,I,] (1) was isolated by pouring the above solution into anhydrous ether and drying the crystals that were deposited, at 100°C. This compound was extremely unstable to water and difficult to obtain pure. An attempt was made to isolate more stable compounds using pyridinium and N-methyl-pyridinium iodides. Yellow prisms of pyridinium diiodo-cuprate (I), [C;H;NH][Cul,] (11), and N-methyl-pyridinium diiodo-cuprate (I), [C;H,NCH,|[Cul,] (II1), were obtained on cooling a boiling acetone solution saturated with respect to both components. These compounds were obtained in an exactly similar manner from methyl ethyl ketone. Compound III was also obtained by treating an acetone solution of copper (I) iodide and sodium iodide with N-methyl-pyridinium iodide. Red prisms of N-methyl-quinolinium diiodo-cuprate (I), [C,H,NCH,][Cul,], were similarly obtained. This compound has previously been isolated from aqueous solution by Kohn (1912). The reaction of either compound III or copper (I) iodide and sodium iodide, dissolved in acetone, with an aqueous acetone solution of bis(ethylenediamine)- copper (IT) iodide, yielded mauve plates of bis(ethylenediamine)copper (IT) triiodo- , cuprate (I) 1-5 hydrate, [Cu™(C,H,(NH.,).).|[Cutl,].1-5 H,O (IV). An analogous propylenediamine compound [Cu™(CH,CH(NH,)CH,NH,),|[Cutl,].1-5 H,O was also prepared. Both these compounds readily lose their water of hydration at 100° C. It is interesting to note that compound IV is not obtained on reacting a hot aqueous solution of potassium iodide and copper (I) iodide with bis(ethylene- diamine)copper (II) iodide. From aqueous solution, only brown prisms of | bis(ethylenediamine)copper (II) diiodo-cuprate (1), [Cu™(C,H,(NH,).).|[Cutl,]., have been obtained (Harris, 1948). Compounds IV and V are decomposed by boiling water, [Cu™(A), |[Cutl,] — [Cu™(A),]?++2I-+Cul, COORDINATION COMPOUNDS OF COPPER. 139 depositing copper (I) iodide. By carrying out the decomposition with dilute acetic acid in the presence of potassium iodide the divalent copper liberates iodine 2[Cu™(A), ][Cutl,]+8H* — I,+4[AH,]?*++4Cul, which can be titrated with thiosulphate in the usual way. Compounds I-V reduce aqueous silver nitrate to metallic silver, instantly in the cold, due to the univalent copper they contain. All copper (I) structures yet investigated have been shown to possess copper involved in either two linear or four tetrahedral bonds (Wells, 1945). Thus compounds II and III apparently contain the diiodo-cuprate (I) ion of which numerous derivatives have been obtained from aqueous solution (Abegg, 1908, and Mellor, 1923) and for which the linear configuration [I-Cu-I]- would be expected (Pauling, 1940). Compounds IV and V could possess one of a number of structures. They could contain [Cul,]?- ions, bridged [Cu,I,|*~ ions, or [CulI,]- ions in the form of a mixed anionic compound [Cu(A),][Cul,]I. The last two would appear the most likely since three covalent copper (I) complexes have not been verified by structure determinations. HXPERIMENTAL. (i) The Reaction of an Acetone Solution of Sodium Iodide with Copper (I) Iodide. Excess of finely powdered copper (I) iodide was refluxed with a boiling acetone solution (10-0 ml.) of sodium iodide (0-60 g.). The solution, on saturation, was filtered into anhydrous ether (100 ml.) and the crystalline mass formed was broken up beneath the ethereal solution, filtered rapidly, and washed with anhydrous ether followed by anhydrous benzene. The benzene vapour was removed under vacuum over phosphorus pentoxide. Yield 1-5 g. On heating at 100° C. the compound lost 4-2 per cent. of its weight. The following analyses are calculated on a dry weight basis. Found: Cu, 23:4; I, 71-1%. | Na[Cu,I,] requires Cu, 23-9; I, 71-7%. The compound is deliquescent and decomposed readily by moisture from the air. It is not completely soluble in acetone being partially decomposed to copper (I) iodide and thus requires some excess of sodium iodide for its preparation. (ii) Pyridinium Duiodo-cuprate (IL). Acetone (200 ml.) was refluxed in the presence of excess pyridinium and copper (1) iodides. The resulting saturated solution was filtered hot and cooled to 15°C. The yellow prisms that were deposited were washed with anhydrous ether and dried under vacuum over phosphorus pentoxide. Yield 1-5 g. Methyl ethyl ketone (100 ml.) similarly gave 0-6 g. Found: Cu, 16-1; I, 63-:3%. [(C,H,NH][Cul,] requires Cu, 16-0; I, 63-8%. The compound is decomposed by water. It can be recrystallized from acetone or methyl ethyl ketone. During the course of this work it was noted that copper (I) iodide was soluble in molten pyridinium iodide and on cooling and washing out excess pyridinium iodide yellow prisms remain. This compound is probably the same as the above. (iii) N-methyl-pyridinium Dviiodo-cuprate (I). Prepared similarly to the previous compound, it also crystallized in the form of yellow prisms. Acetone (300 ml.) gave 1-8 g. and methyl ethyl ketone (650 ml.) 3-0 g. Found: Cu, 15:4; I, 61:8%. (C,H,NCH, ][CuI,] requires Cu, 15-45; I, 61-7%. M 140 Cc. M. HARRIS. This compound was also readily obtained by adding a hot solution of N-methyl-pyridinium iodide (2-5 g. 0-011 g. mole) in acetone (10 ml.) and water (2-0 ml.) mixture to a boiling acetone (15 ml.) solution of sodium iodide (3-1 g. 0-021 g. mole) and copper (I) iodide (1-9 g. 0-010 g. mole). The yellow prisms that were deposited were washed with a small amount of acetone and dried under vacuum. Yield 3-0 g. (73%). Found: Cu, 15-6; I, 61:8%. The solubility of this compound in acetone and methyl] ethyl ketone permits of its recrystal- lization from these solvents. It is decomposed by water, particularly on heating. Copper (1) iodide is also soluble in molten N-methyl-pyridinium iodide, presumably forming the above compound, and yellow prisms can be isolated by washing out the excess of pyridinium salt with methyl] alcohol. A solution of compound III in acetone was titrated conductimetrically with an acetone- sodium iodide solution but no evidence of ion formation, such as [Cul,}-+I- & [Cul,]?- was obtained. N-methyl-quinolinium Diiodo-cuprate (1). Prepared similarly to compound III from an acetone solution of sodium iodide and copper (I) iodide by treatment with an aqueous acetone solution of N-methyl-quinolinium iodide. The compound which crystallized in bright red prisms was obtained in almost theoretical yield. Found: Cu, 13-8; I, 54:-6%. Calculated: Cu, 13-77; I, 54-98%. (iv) Bis(ethylenediamine)copper (II) Triiodo-cuprate (I) 1- a Hydrate. To a boiling solution of bis(ethylenediamine)copper (II) iodide dihydrate (1-5 g. 0-0032 g. mole : Morgan and Burstall, 1926) in water (25 ml.) and acetone (100 ml.) mixture was added a boiling solution of sodium iodide (4-0 g. 0-027 g. mole) and copper (I) iodide (0-61 g. 0-0032 g. mole) in acetone (75 ml.). The mauve hexagonal plates that were deposited on cooling were washed with cold acetone and air dried. Yield 1-4 g. (68%). Found: Cu(total), 19-4; Cu, 9-8; I, 57-5; H,O at 100°C., 4-0%. [Cu™(C,H,(NH,),), ][Cu'l,].1-5 H,O requires Cu(total), 19-4; Cu%+, 9-7; I, 58-1; H,O, 4-1%. If too much sodium iodide is used in this preparation the compound fails to appear on cooling. This compound was also readily obtained by treating a boiling solution of bis(ethylenediamine) copper (II) iodide dihydrate (0-90 g. 0-0019 g. mole) in water (20 ml.) acetone (75 ml.) mixture with a boiling acetone (200 ml.) solution of compound ITI (0-80 g. 0-0019 g. mole). The immediate precipitate of hexagonal plates was isolated and washed as before. Found: Cu(total), 19-5; H,O at 100°C., 3-6%. The compound is slowly decomposed by water in the cold but inateatiy on boiling forming a purple solution of bis(ethylenediamine)copper (II) iodide and a white precipitate of copper (1) iodide. ‘The compound is decomposed by acid as described previously. It reduces silver nitrate solution instantly to metallic silver due to the univalent copper it contains and on dehydration at 100° C. its colour deepens. (v) Bis(propylenediamine)copper (II) Triodo-cuprate (I) 1-5 Hydrate. Bis(propylenediamine)copper (II) iodide dihydrate (0-88 g. 0-0018 g. mole) was dissolved in water (5:0 ml.) and acetone (35 ml.). After the addition of sodium iodide (1-0 g. 0-0067 g. mole) the solution was heated to boiling and treated with a boiling solution of copper (I) iodide (0:50 g. 0:0026 g. mole) and sodium iodide (2-0 g. 0-013 g. mole) in acetone (35 ml.). The solution was cooled to room temperature and the purplish crystals that were deposited were filtered, washed with acetone and air dried. Yield 0-5 g. (42%.) Found : Cu(total), 18-6; Cu+, 9-1; I, 55-3; H,O at 100°C., 3-64, 3-94%. [Cu(CH,CH(NH,)CH,NH.,), |[Cul, ].1-5 H,O requires Cu(total), 18-61; Cu*+, 9-3; I, 55-75; H,O, 3:96%. The properties of this compound are similar to its ethylenediamine analogue. COORDINATION COMPOUNDS OF COPPER. 141 Bis(propylenediamine)copper (II) Iodide Dihydrate. Prepared from pyopylenediamine and copper (I) iodide in a somewhat analogous manner to bis(ethylenediamine)copper (II) iodide dihydrate (Morgan and Burstall, loc. cit.). A mixture of copper (I) iodide (19 g. 0-10 g. mole), propylenediamine (10-0 ml. 0:12 g. mole) and water (40 ml.) was refluxed for 3 hours. The purple solution was filtered and concentrated till crystal- lization occurred. The purple crystals were filtered and washed with two small lots of acetone and air dried. Found: Cu, 12:7; I, 50-0; H,O at 100°C., 7-0%. [Cu(CH,CH(NH,)CH,NH,), |I,.2H,O requires Cu, 12-7; I, 50:6; H,O, 7:2%. This compound is very soluble in water and reasonably soluble in aqueous acetone and alcohol. ANALYSES. Copper was estimated volumetrically by the thiosulphate method. On the addition of potassium iodide to a solution containing divalent copper and pyridinium or quinolinium salts, there is precipitated a complex pyridinium or quinolinium tetraiodo-cuprate (II) (Datta, 1913; Datta and Ghosh, 1914), which removes portion of the divalent copper from solution. It was thus found necessary to first remove the pyridine or quinoline by boiling with a shght excess of sodium hydroxide solution for 30 minutes. Copper was determined on the remaining solution in the usual way, iodine being first removed by fuming with concentrated sulphuric acid containing small amounts of nitric acid. The estimation of divalent copper in the presence of copper (I) in compounds IV and V was carried out as follows: The compounds were decomposed by a small amount of hot water (20 ml.) to yield a solution of the bis(amine)copper (II) iodide and a precipitate of copper (I) iodide. A small amount of potassium iodide (2-0 g.) was added to the cooled solution followed by acetic acid (1-3 ml. 17N). A large excess of potassium iodide (10 g.) was added to completely dissolve the copper (I) iodide and the liberated iodine then titrated with thio- sulphate to a starch end-point in the usual way. SUMMARY. The preparation of three types of complex iodo-cuprates (1) from acetone or aqueous acetone solution has been described. These are (a) Na[Cu,I,} ; (b) [C;H;NX][Cul,] (where X=—H and CH,); and (ec) [Cu™(A),][CuI,].1-5 H,O (where A=C,H,(NH,), and CH,CH(NH,)CH,NH,). They are all, except (a), well defined, coloured, crystalline compounds. During the course of this work bis(propylenediamine)copper (II) iodide dihydrate [Cu(CH,CH(NH,)CH,NH,),|I,.2H,O, was prepared by the action of propylenediamine upon copper (I) iodide. : REFERENCES. Abegg, R., 1908. Handbuch der anorganischen Chemie, 2, Pt. 1, p. 550. Hirzel, Leipzig. Datta, R. L., 1913. J. Chem. Soc., 103, 426-432. Datta, R. L., and Gosh, T., 1914. J. Am. Chem. Soc. 36, 1020. Harris, C. M., 1948. THis JouRNAL, 82, 218-224. Kohn, M., 1912. Montash, 33, 919-922. Marsh, J. E., and Rhymes, W. C., 1913. J. Chem. Soc., 103, 781-786. Mellor, J. W., 1923. ‘‘ A Comprehensive Treatise on Inorganic and Theoretical Chemistry”’, Vol. 3. Longmans, London. wis Morgan, G. T., and Burstall, F. H., 1926. J. Chem. Soc., 1503. Pauling, L., 1940. ‘‘ The Nature of the Chemical Bond ”’, p. 89. Cornell University Press. Wells, A. F., 1945. ‘‘ Structural Inorganic Chemistry’, pp. 502-508. Oxford University Press. i School of Applied Chemistry, N.S.W. University of Technology, Sydney. SOME COMPLEXES DERIVED FROM SILVER HALIDES. By C. M. HARRIS. Manuscript received, November 12, 1951. Read, December 5, 1951. It has been reported in a previous communication that copper (I) iodide dissolves in concentrated ammonium or alkali bromide solution (Harris, 1950). From these solutions tetramminecopper (II) and bis(ethylenediamine) copper (II) derivatives, [Cu%(A),][CuIBr], (where A=NH, and 2A—C,H,(NH,),), were isolated. Reaction of these solutions with ammonia and ethylenediamine afforded indirect evidence that they were not mixtures of the [CuI,]- and (CuBr,|~ ions (loc. cit.). This communication reports the result of a similar investigation using silver iodide in place of copper (I) iodide. Silver iodide dissolves appreciably in boiling concentrated solutions of ammonium or alkali bromide presumably forming the bromo-iodo-argentate (I) ion, AgIi+Br- = [AgIBr]-, similar to copper (I) iodide. Dilution decomposes the complex ion precipitating silver iodide. Purple crystals of bis(ethylenediamine) copper (II) bromo-iodo- argentate (I), [Cu(C,H,(NH,).).][AgIBr],, and orange crystals of the analogous nickel (II) complex, [Ni(C, H,(NH,).,).|[ Agi Br],, were obtained by metathesis from these solutions. The nickel complex was obtained by reaction of the argentate (I) solution with tris(ethylenediamine)nickel (II) bromide. The isolation of the bis(ethylene- diamine) nickel (II) complex instead of the tris-compound is apparently due to the fact that in solutions of tris(ethylenediamine)nickel (II) salts there exists the equilibrium [Ni(C,H,(NHe)2)3]** = [Ni(C,H,(NH)2)2]** +C.H4(N Ho), and, in this case, the bis-derivative is the least soluble. The failure of Bucknall and. Wardlaw (1928) to resolve the octahedral tris(ethylenediamine)nickel (IT) ion could be attributed to this equilibrium. Failure to resolve the tris(ethylene- diamine)copper (II) ion is probably due to the same type of equilibrium. The existence of this equilibrium in the case of copper (II) is supported by the work of Amiel (1934), who found that copper (II) complexes such as (Cu(C,H,(NH4)2)3](ClO,)2.H,O lose one diamine group to pass over anthe the more stable bis(ethylenediamine)copper (II) complex. Both the above argentate (1) complexes are decomposed by water, particu- larly on heating, forming a solution of the complex copper (II) and nickel (II) bromide and a precipitate of silver iodide. Whilst the corresponding bromo-iodo-cuprate (I) solution reacts immediately with ammonium hydroxide to yield a precipitate of (Cul),.NH, (loc. cit.) the bromo-iodo-argentate (I) solution failed to yield a similar compound. LEthylene- diamine also gave no visible reaction. A series of silver complexes, (AgX),.C,H,(NH,.). (where X =Cl, Br and I), similar to the copper (I) complex (Cul),.C,H,(NH,), (loc. cit.), were obtained SOME COMPLEXES DERIVED FROM SILVER HALIDES, 143 during the course of this work by dissolving the appropriate silver halide m ethylenediamine and precipitating with alcohol. These compounds are unstable to water and acids and are light-sensitive. The corresponding propylenediamine compound with silver iodide was prepared but proved to be unstable, losing propylenediamine. EXPERIMENTAL. Bis(ethylenediamine)copper (II) Bromo-iodo-argentate (1). A boiling solution of ammonium bromide (180 g.) and silver iodide (4:7 g. 0-020 g. mole) in water (185 ml.) was added with stirring to a boiling solution of bis(ethylenediamine)copper (II) bromide monohydrate (3-6 g. 0-010 mole: Johnson and Bryant, 1934) and ammonium bromide (10 g.) in water (25 ml.). An immediate purple precipitate appeared. The solution was cooled to 65° with stirring and the purple prisms were filtered, washed well with methanol to remove ammonium bromide followed by acetone and air dried. Yield, 3-9 g. (48%). Hound; ‘Cu, 7:7; Agl, 57-2; Br, 19-7%. [Cu(C,H,(NH,)2). [Agi Br], requires Cu, 7-82; AglI, 57-76; Br, 19-66%. Bis(ethylenediamine)nickel (II) Bromo-todo-argentate (1). Prepared similarly to the previous compound save that tris(ethylenediamine)nickel (II) bromide dihydrate (4-3 g. 0-010 g. mole) was used in place of the copper (II) complex and 200 ml. of water instead of 185 ml. The solution was cooled to 60° C. when the orange crystals that deposited were filtered and washed, and dried as before. Yield 2-6 g. (32%). Found: Ni, 7:2; AglI, 58-6; Br, 19-6%. [Ni(C,H,(NH,),). [Agi Br], requires Cu, 7-26; AglI, 58-1; Br, 19-78%. The tris(ethylenediamine)nickel (II) bromide dihydrate used in the above preparation was prepared by treating a solution of nickel bromide with an excess of ethylenediamine and pre- cipitating with alcohol. The compound was washed with acetone and air dried. Found: Br, 37:0; H,O, 7-:9%. Calculated for [Ni(C,H,(NH,),),]Br2-2H,O ; Br, 36:8; H,O, 8-3%. The Reaction of Silver Halides with Ethylenediamine. The powdered silver halide was dissolved in anhydrous ethylenediamine by gentle warming and the solution filtered into 95% ethanol. The colourless crystals were washed with acetone and dried under vacuum. Silver Halide. Silver Halide. Compound. (Found.) _ (Calculated.) (AgCl),.C,H,(NH,). aes fd os 82 s 5 82 S 6 (AgBr),.C,H,(NH,), he ate Ag 86 ., 7 86 : 2 (AgI),.C,H,(NH,). site he oh 88 * l 88 y 6 These compounds are light-sensitive and decomposed by water. The silver halide was estimated by boiling the compound with dilute nitric acid and weighing the residue. The Reaction of Silver Iodide with Propylenediamine. Powdered silver iodide dissolved in propylenediamine at room temperature. Pale yellow micro-crystals were obtained by pouring into methanol. The product was washed with acetone 144 C. M. HARRIS. and air dried to remove acetone. The compound smelt strongly of propylenediamine and it had evidently lost a considerable amount as was indicated by the analysis for silver iodide. Found: AglI, 91:4%. (AgI),.CH,CH(NH,)CH,NH, requires AgI, 86:4%. SUMMARY. Silver iodide dissolves in the presence of a large excess of bromide ions to form colourless solutions containing the bromo-iodo-argentate (I) ion. Complex derivatives of this ion with bis(ethylenediamine)copper (II) and bis(ethylene- diamine)nickel (II) ions have been prepared from such solutions by metathesis. A series of compounds of general formula (AgX),.C,.H,(NH.). was prepared from ethylenediamine and the silver halides. Propylenediamine forms an unstable silver iodide complex. REFERENCES. Amiel, J., 1934. C.R., 199, 201. Bucknall, W. R., and Wardlaw, W., 1928. J.C.S., 2739. Harris, C. M., 1950. Tuts Journat, 84, 111-116. School of Applied Chemistry, N.S.W. University of Technology, Sydney. COORDINATION COMPOUNDS OF COPPER. Part IV. Some CupPpRATES (I) FROM ACETONE SOLUTION. By C. M. HARRIS and H. N. 8. SCHAFER. Manuscript received, November 12, 1951. Read, December 5, 1951, In a previous communication, one of us (Harris, 1952) reported the prepara- tion of various iodo-cuprates (1) from either acetone or aqueous acetone solution. This communication describes the following additional compounds : I. [Cu™(C,H,(NH,)»)o][CuCl,].1°5 HO. II. [Cu™(C,H,(NH,).)9][Cu'Br,].2°5 H,0. Ill. [C,H;NH][CulBr]. IV. [C,H;NCH,][Cul(CNS)]. V. [C;H,NCH,][Cu(CNS),]. Compounds I and II were prepared by reacting the appropriate copper (1) halide, dissolved in an aqueous solution of the corresponding ammonium halide, with the required bis(ethylenediamine)copper (IT) halide. These two compounds are analogous to the complex iodo-cuprates (1), [Cu™(A),][CutI,].1-5 H,O (A=C,H,(NH,), and CH,CH(NH,)CH,NH,) previously described (Harris, loc. cit.). Copper (1) iodide dissolves in boiling acetone or methyl ethyl ketone solutions of pyridinium bromide. On cooling, yellow prisms of compound III, pyridinium bromo-iodo-cuprate (I), are deposited. This type of compound has recently been obtained from aqueous solution (Harris, 1951) in the form of the complex copper (IT) cuprates (I), [Cu™(A),][CutIBr], (where A=NH, and 2A =0,H,(NH,)2). Yellow prisms of compound IV, N-methyl-pyridinium iodo-thiocyanato- cuprate (1), were crystallized from an acetone solution of N-methyl-pyridinium iodide which had been saturated with copper (I) thiocyanate. The yellow dithiocyanato-cuprate )I) compound (V) was also prepared by treating an acetone solution of ammonium thiocyanate and copper (I) thiocyanate with N-methyl- pyridinium iodide. These compounds are all decomposed by water, acids and alkali, particularly on heating. They are insoluble in organic solvents, such as benzene, chloroform and ether, and reduce aqueous silver nitrate solution to silver due to the univalent copper they contain. EXPERIMENTAL. (i) Bis(ethylenediamine)copper (II) Trichloro-cuprate (I) 1-5 Hydrate. To a solution of bis(ethylenediamine)copper (II) chloride monohydrate (2-5 g.: Johnson and Bryant, 1934) and ammonium chloride (2:5 g.) in water (35 ml.) was added acetone (90 ml.). The solution was refluxed over a mixture of excess copper (I) chloride and copper powder for 10 minutes and on filtering was cooled rapidly to room temperature in an atmosphere of coal gas. 146 HARRIS AND SCHAFER. The purple needles that were deposited were filtered and washed with methyl] alcohol followed by ether. The ether was removed under vacuum. Yield 0:6 g. Found: Cu (total), 33-2; Cl, 27-7; H,O at 100°C., 7-1%. [Cu"(C,H,(NH,))2 [Cu'Cl,].1-5H,O requires Cu(total), 33-4; Cl, 27-9; H,O, 7-4%. This compound is instantly decomposed by water to white copper (I) chloride and a purple solution of bis(ethylenediamine)copper (II) chloride. The compound is oxidized in moist air assuming a blue-green colour. It reduces silver nitrate solution to metallic silver. (ii) Bis(ethylenediamine)copper (I1) Tribromo-cuprate (1) 2:5 Hydrate. To a solution of bis(ethylenediamine)copper (II) bromide monohydrate (3-6 g. 0-010 g. mole) in water (50 ml.) was added ammonium bromide (2:0 g.) followed by acetone (200 ml.) and the solution heated to boiling. To this solution was added a boiling solution of copper (1) bromide (1:6 g. 0-011 g. mole) in acetone (250 ml.) and water (50 ml.) containing ammonium bromide (4-0 g.) and one drop of 7N hydrobromic acid. The solution was cooled to 20° C. with stirring and the compound that was deposited was filtered and washed with 90% alcohol followed by ether. The ether was removed under vacuum. Yield 2-0 g. (40% “«ipurple prisms. Found: Cu(total), 24-2; Br, 44-9; H,O at 100°C., 8-6%. [Cu™(C,H,(NH,),),][Cu'Br3].2-5H,O requires Cu(total), 23-9; Br, 45-1; H,O, 8-5%. This compound is decomposed by water depositing a white precipitate of copper (I) bromide and forming a purple solution of bis(ethylenediamine)copper (II) bromide. The compound is oxidized in moist air assuming a blue-green colour and it reduces silver nitrate solution instantly to metallic silver. (iui) Pyridintum Bromo-iodo-cuprate (I). Pyridinium bromide (3-0 g.) was refluxed with excess of powdered copper (I) iodide and methyl ethyl ketone (500 ml.). The yellow solution was filtered hot and cooled to 0°C. The yellow needles were filtered, washed with dry ether and dried under vacuum over phosphorus pentoxide. Yield 2-4g. The compound can also be prepared in a similar manner from acetone. Found: Cu, 18-1, 18:2%; 0-3518 g. complex gave 0-4246 g. AgIl+AgBr. [C,H,NH][CulBr] requires Cu, 18-:1% ; 0-3518 g. complex to give 0-4241 g. Agl4+AgBr. The compound is readily decomposed by water to copper (I) iodide and reduces silver nitrate solution to metallic silver. It is hygroscopic. (iv) N-methyl-pyridinium Iodo-thiocyanato-cuprate (I). Excess of copper (I) thiocyanate and N-methyl-pyridinium iodide were refluxed with acetone (500 ml.) to form a yellow solution. The filtered solution was cooled to 20° C. and the yellow crystals that were deposited were washed with a small amount of cold acetone and dried under vacuum over phosphorus pentoxide. Found: Cu, 18-3%; 0-243 g. complex gave 0-283 g. AgI+AgCNS. [C;H,NCH,][Cul(CNS)] requires Cu, 18-56%; 0-243 g. complex to give 0-284 g. AgI+AgCNS. The compound is readily decomposed by water and reduces silver nitrate solution to metallic silver. (v) N-methyl-pyridinium Dithiocyanato-cuprate (I). Copper (I) thiocyanate (1-2 g. 0-010 g. mole) was dissolved in a boiling solution of ammonium thiocyanate (7-0 g.) in acetone (50 ml.). To this was added a hot solution of N-methyl-pyridinium iodide (3-3 g. 0-015 g. mole) dissolved in a mixture of acetone (20 ml.) and water (3-0 ml.). The clear yellow solution on standing overnight deposited golden yellow crystals which were filtered off, washed with acetone and dried under vacuum. Yield 1-3 g. (47%). Found: Cu, 23-1; CNS, 43:-4%. [C,H;NCH, |[Cu(CNS),] requires Cu, 23-3; CNS, 42-4%. COORDINATION COMPOUNDS OF COPPER. 147 The compound was contaminated slightly with iodide, giving a high value for thiocyanate which was determined as its silver salt. The compound is decomposed by water slowly in the cold and readily on heating and reduces silver nitrate solution to metallic silver. REFERENCES. Harris, C. M., 1951. THis Journat, 84, 111-116. —-—_—____——— 1952. Tunis JouRNAL, 85, 138. Johnson, C., and Bryant, S., 1934. J. Chem. Soc., 1783. School of Applied Chemistry, N.S.W. University of Technology, Sydney. SOME HALOGENOARGENTATES (I) AND HALOGENOPLUMBATES (II) FROM ACETONE SOLUTION. | . By C. M. HARRIS and H. N. 8S. SCHAFER. Manuscript received, November 14, 1951. Read, December 5, 1951. In previous communications (Harris, 1952; Harris and Schafer, 1952) the preparation from acetone or aqueous acetone solution of various types of cuprates (I) has. been described. This communication records the preparation of the following halogenoargentates and halogenoplumbates (II) , I. [Cu(C,H,4(NH-2)o)2][AgBre]p. Il. [C;H,;NCH, [Ag], ]. Ill. [C;H;NCH,][Ag,]I,]. IV. [C;H;NCH,][PbI,]. V. [Cu(O,H4(NH3)2)2][PbBr,]. VI. [Cu(C,H,(NH,)>).][PbIy]. VII. [Cu(C,H,(NH,).).|[PbI,Br],. Compounds I, II, IV, V, VI and VII were obtained by treating an aqueous acetone solution of the silver or lead halide and sodium or ammonium halide with the appropriate N-methyl-pyridinium or bis(ethylenediamine)copper (II) halide. Compound III was obtained from an aqueous acetone solution of ammonium and silver thiocyanate by treatment with N-methyl-pyridinium iodide. If bis(ethylenediamine)copper (II) bromide or iodide was added in place of N-methyl-pyridinium iodide, compound I or its iodine analogue, bis(ethylene- diamine)copper (II) diiodo-argentate (I), was obtained. This last compound has previously been prepared by Spacu and Spacu (1931) as well as the propylene- diamine analogue (Spacu and Spacu, 1932). Compounds of the general type M[Ag,I,] have been prepared before from acetone solution by Marsh and Rhymes (1913) and the compound Rb[AgI,].0-5 H,O obtained by them from aqueous acetone. It is interesting to note that with copper (I) halides three types of complexes, M[Cu,X,], M[CuX,], and M,{[CuX,] have been obtained (loc. cit.) from either acetone or aqueous acetone. All the above compounds are unstable to water, on boiling, and insoluble in common organic solvents such as benzene and chloroform. HXPERIMENTAL. (i) Bis(ethylenediamine)copper (II) Dibromo-argentate (1). To a boiling solution of bis(ethylenediamine)copper (II) bromide monohydrate (1:0 g. : Johnson and Bryant, 1934) and ammonium bromide (2-0 g.) in a mixture of water (15 ml.) and acetone (100 ml.) was added a boiling solution of ammonium bromide (10 g.) in acetone (200 ml.) and water (30 ml.) saturated with silver bromide. The immediate precipitate of mauve micro- crystals was filtered and washed with methyl! alcohol followed by ether. Dried under vacuum. Yield 1-5 g. Found: Cu, 8-75; Ag, 29:8; Br, 44:2%. [Cu(C,H,(NH,).). [AgBr,], requires Cu, 8-84; Ag, 30:0; Br, 44-4%. SOME HALOGENOARGENTATES (I) AND HALOGENOPLUMBATES (IT) 149 The compound is insoluble in cold water but decomposed readily on heating to a purple solution of bis(ethylenediamine)copper (II) bromide and a precipitate of silver bromide. (1) N-methyl-pyridinium Dvriodo-argentate (1). To a warm solution of silver iodide (1-0 g. 0-0043 g. mole) and sodium iodide (10 g.) in acetone (100 ml.) was added a warm solution of N-methyl-pyridinium iodide (1-5 g. 0-0068 g. mole) dissolved in a mixture of acetone (10 ml.) and water (1-0 ml.). On standing cream micro- crystals were deposited, which were filtered and washed with a small amount of cold acetone and dried under vacuum. Yield 1-4 g. Found: Ag, 23:5; I, 55-5%. [C,H,;NCH, |[AgI,] requires Ag, 23-7; I, 55-7%. Water decomposes the compound into its constituents. il) The Reaction of N-methyl-pyridinium Iodide with an Acetone Solution of Ammonium and Silver Thiocyanates. A hot solution of silver thiocyanante (1-7 g. 0-010 g. mole) and ammonium thiocyanante (10 g.) in acetone (100 ml.) was treated with a solution of N-methyl-pyridinium iodide (2-5 g. 0-011 g. mole) dissolved in a mixture of acetone (10 ml.) and water (2-0 ml.). The immediate precipitate of white prisms was filtered from the cooled solution, washed with acetone and dried under vacuum. Yield 2:2 g. (82%). Found: Ag, 31:2; I, 54-5%. [C;H,NCH, |[Ag.I,] requires Ag, 31:3; I, 55-1%. The compound is decomposed by water, particularly on heating. The Reaction of Bis(ethylenediamine)copper (If) Halides with an Acetone Solution of Ammonium and Silver Thiocyanates. (a) With Bis(ethylenediamine)copper (II) Bromide. A boiling solution of silver thiocyanate (3-3 g. 0-020 g. mole) and ammonium thiocyanate (4-0 g.) in acetone (60 ml.) was mixed all at once with a boiling solution of bis(ethylenediamine) - copper (II) bromide monohydrate (1-8 g. 0-0050 g. mole) in a mixture of acetone (50 ml.) and water (10 ml.). The precipitate of mauve microcrystals was washed with acetone and dried - under vacuum. Yield 1:4 g. (80%) of compound I. Found: Ag, 29-7; Br, 44:1%. (6) Weth Bis(ethylenediamine)copper (II) Iodide. To a boiling solution of bis(ethylenediamine)copper (II) iodide monohydrate (2-3 g. 0-0050 g. mole) and ammonium thiocyanate (2-0 g.) in acetone (150 ml.) and water (20 ml.) was added all at once a boiling solution of silver thiocyanate (1:7 g. 0-010 g. mole) and ammonium thio- cyanate (10 g.) in acetone (100 ml.). The immediate precipitate of mauve microcrystals was washed with acetone and dried under vacuum. Yield 1-8 g. (78%) of bis(ethylenediamine)copper (II) diiodo-argentate (I). Found: Cu,'7:08; Ag, 23-8; I, 55-33%. Calculated: Cu, 7-01; Ag, 23-8; I, 56-0%. This compound was also obtained by reacting a sodium iodide-silver iodide solution in acetone with bis(ethylenediamine)copper (II) iodide. Found: Cu, 6°95; Ag, 23:6; I, 55:7T%. (iv) N-methyl-pyridinium Triiodo-plumbate (II). Lead iodide (2-0 g. 0:00043 g. mole) and sodium iodide (5-0 g.) dissolved in boiling acetone (40 ml.) was treated with N-methyl-pyridinium iodide (2-0 g. 0:0091 g. mole) dissolved in a boiling mixture of acetone (10 ml.) and water (2:0 ml.). The immediate precipitate of pale 150 HARRIS AND SCHAFER. yellow prisms was filtered from the cooled solution and washed with acetone followed by ether. Dried under vacuum. Yield 2-4 g. (80%). Found: Pb, 30-4; I, 55-5%. [C;H,NCH,][PbI,] requires Pb, 30-4; I, 55-9%. The compound is immediately decomposed by water depositing yellow lead iodide. (v) Bis(ethylenediamine)copper (II) Tetrabromo-plumbaie (IZ). To a boiling solution of bis(ethylenediamine)copper (II) bromide monohydrate (2-0 g. 0-0055 g. mole) and ammonium bromide (40 g.) in acetone (200 ml.) and water (35 ml.) was added a boiling solution of lead bromide (2-0 g. 0-0054 g. mole) and ammonium bromide (40 g.) in acetone (410 ml.) and water (80 ml.). The immediate flocculent precipitate of mauve micro- crystals was filtered from the hot solution and washed with acetone followed by ether. Dried under vacuum. Yield 2-9 g. (75%). Found: Cu, 9-1; Pb, 29-0, 29-1; Br, 45-1%. [Cu(C,H,(NH,).).][PbBr,] requires Cu, 9-0; Pb, 29-2; Br, 45-0%. The compound is decomposed by water, readily on heating, depositing a precipitate of lead (II) bromide and forming a purple solution of bis(ethylenediamine)copper (II) bromide. (vi) Bis(ethylenediamine)copper (II) Tetraiodo-plumbate (II). Lead iodide (2-0 g. 0:0043 g. mole) and sodium iodide (10 g.) in boiling acetone (150 ml.) was added to a boiling solution of bis(ethylenediamine)copper (II) iodide monohydrate (0°90 g. 0-0020 g. mole) and sodium iodide (2-0 g.) in a boiling mixture of acetone (75 ml.) and water (10 ml.). The immediate precipitate of greenish-grey microcrystals was washed with acetone followed by ether and dried under vacuum. Yield 1-8 g. (95%). Found: Cu, 7:06; .Pb, 22-9; I, 56-3%. [Cu(C,H,(NH,).). |[PbI,] requires Cu, 7:08; Pb, 23:1; I, 56-5%. The compound is decomposed by water similarly to the previous compound. (vil) Bis(ethylenediamine)copper (II) Diiodo-bromo-plumbate (IT). Lead iodide (2-0 g. 0-0043 g. mole) was dissolved in a boiling mixture of acetone (200 mal.) and water (20 ml.) that had previously been saturated with ammonium bromide. This solution was added to a boiling solution of bis(ethylenediamine)copper (II) bromide monohydrate (1-6 g. 0-0044 g. mole) in acetone (100 ml.) and water (15 ml.). The immediate precipitate of mauve microcrystals was filtered and washed with acetone followed by ether. Dried under vacuum. Yield 2-6 g. (95%). Found: Cu, 5-1; Pb, 32-3%. 0-289 g. compound gave 0-303 g. AgBr+AglI. [Cu(C,H,(NH,).), ][PbI,Br], requires Cu, 5:0; Pb, 32-7%. 0-289 g. compound to give 0-300 g. AgBr+Agl. SUMMARY. The halogeno-argentates (I), [Cu(C,H,(NH,).).|[AgBr.]., [C; H;NCH,][Agls], and [C,;H,NCH,|[Ag,I,], have been prepared from aqueous acetone solution. Halogenoplumbates (II), [C;,H;NCH,][PbI,], [Cu(C,H,(NH,).).|[PbBr,], [Cu(C,H,(NH,).).|[PbI,], and [Cu(C,H,(NH,).,).][PbI,Br],, were also obtained using this solvent. REFERENCES. Harris, C. M., 1952. THis Journat, 85, 138. Harris, C. M., and Schafer, H. N. §., 1952. Turis Journat, 85, 145. Johnson, C. H., and Bryant, S. A., 1934. J.C S., 1783. Marsh, J. E., and Rhymes, W. C., 1913. J. Chem. Soc., 103, 781-786. Spacu, G., and Spacu, P., 1931. Bull. soc. Stinte Cluj, 5, 387-421, 473-487. —_—_——______—_____————. 1932. Z. anal. Chem., 90, 182-189. School of Applied Chemistry, N.S.W. University of Technology, Sydney. PALLADIUM COMPLEXES. PARTIV. REACTIONS OF PALLADIUM COMPOUNDS WITH 1: 10 PHENANTHROLINE. By 8S. E. LIVINGSTONE. Manuscript recewed, November 14, 1951. Read, December 5, 1951. Coordination compounds of 1 : 10 phenanthroline with several of the metals, e.g. iron, nickel, osmium, etc., are known but it appears that only two complexes of palladium with this ligand have been reported (Ryan, 1949). 2: 2’-Dipyridyl is very similar to 1 : 10 phenanthroline in the type of coordination compounds it forms with the metals; dichloro-2 : 2’-dipyridyl palladium was prepared by Morgan and Burstall (1933). A series of compounds was prepared of the type Pd phen X, where phen=1: 10 phenanthroline and X=Cl, Br, I, CNS, NO, and 2X =C,0,. These compounds are all insoluble in water and organic solvents and probably have the structure since divalent palladium almost invariably exhibits the four covalent square planar configuration, involving dsp? orbitals. These compounds are prepared by treating a solution of K,PdX, (where X=Cl, Br, I, CNS, NO,; 2X=C,0,) in hot water with a hot aqueous solution of 1:10 phenanthroline monohydrate (I). The compound [Pd phen X,] is immediately precipitated. It is interesting to note that no precipitate or change in colour occurs in the case of K,Pd(CN),. Also these compounds dissolve in aqueous KCN to give colourless solutions, precipitating 1:10 phenanthroline. This tends to confirm the fact that the bond between Pd and CN is very strong, stronger even than that between Pd and I. When chlorine is passed through a suspension of [Pd phen Cl,] (II) in chloroform bright red prisms of tetrachloro-1: 10 phenanthroline palladium (IV) are formed. [Pd phen Cl,]+Cl, CHCl, an {Pd phen Cl,] _ ee Wy heat 150°C. = VII 152 S. E. LIVINGSTONE. This compound VIII rapidly loses chlorine in moist air, and on heating to 150° C. is converted back to the dichlorodiammine II. The tetrachlorodiammine VIII is analogous to Pdpy,Cl, and PdenCl, (where py=pyridine and en=ethylenediamine) (Rosenheim and Maass, 1898) and Pd(NH;),Cl, (Drew et alia, 1932). The reactions of II with various amines were investigated. (a) 1: 10 Phenanthroline. Compound II dissolves on warming in excess aqueous 1:10 phenanthroline to give a clear yellow solution. Concentration and precipitation with acetone yields the original compound II. However, Pa phen Cl, Le phen eee yellow Solution II evaporation + acetone (PR. d phen,| (C1O,), (Pa phen,|(C joke OHSQ),. 2H,O Pd phen CL IX X I pole yellow prisms deep yellow prisms addition of a solution of ammonium perchlorate to the clear solution yields bis(1: 10 phenanthroline) palladium (I1) perchlorate, which can be recrystallized from water. Similarly, addition of a solution of sodium 2-naphthol-6-sulphonate to the yellow solution yields bis(1: 10 phenanthroline) palladium (II) 2-naphthol- 6-sulphonate dihydrate. If a large excess of sodium chloride is added to the yellow solution, pale cream needles of II are precipitated. It seems certain that the yellow solution contains the tetrammine chloride [Pd phen, ]Cl, in solution and that there exists an equilibrium [Pd phen Cl,]+phen = [Pd phen,|+*+ +2Cl- The tetrammine ion [Pd phen, |** is apparently only stabilized by the presence of a large anion such as perchlorate or naphthol sulphonate. Fy phen e nee Fer ——— pole yellow solution Concentretion or treatment with c\O4 acetone yee [Ps phen Pye| (C10,) Pa phen CL XI II (b) Pyridine. When II is warmed with water containing a little pyridine, it dissolves to a pale yellow solution which, on treatment with NH,CI1O,, yields dipyridine-1: 10 phenanthroline palladium (II) perchlorate which can be recrystal- lized from water. PALLADIUM COMPLEXES. 153 If, however, the pale yellow solution is concentrated, or if acetone is added, the original dichlorodiammine II is precipitated, in analogy with the solution of [Pd phen,|Cl, mentioned above. It is interesting to note that Morgan and Burstall (1934) found that [Pt dipy Cl,] dissolves in excess aqueous dipyridyl and also in aqueous pyridine to give yellow solutions, but evaporation led only to viscid gums which decomposed into the original [Pt dipy Cl,]. (c) Ammonia. II dissolves to a very pale yellow solution when treated with dilute aqueous ammonia at 40°C. Addition of NH,CIlO, precipitates diammino- 1: 10 phenanthroline palladium (If) perchlorate. This compound XII is obtained as colourless crystals by recrystallization from water. (d) Ethylenediamine. A solution of the tetrammine ion [Pd phen en|+* is obtained when II is warmed with a slight excess of aqueous ethylenediamine. Precipitation with NH,ClO, and subsequent recrystallization yields colourless needles of ethylenediamine-1: 10 phenanthroline palladium (II) perchlorate-X1I1. (e) Quinoline. II dissolves to a yellow solution when boiled with water and a considerable excess of quinoline. Addition of NH,CIO, results in precipitation of a brownish resin from which no definite compounds were obtained. 2 EXPERIMENTAL. (II) Dichloro-1: 10 Phenanthroline Palladium (II). To a hot aqueous solution (70 ml.) of K,PdCl, (2 g.) was added a solution of 1 : 10 phenanth- roline-[ (Halcrow and Kermac, 1946) (1-2 g.) in boiling water (50 ml.). Pd, 20:52%. (d) Ethylenediamine (XIII) Hthylenediamine-1: 10 Phenanthroline Palladium (II). IT (0-4 g.), water (20 ml.) and 3% aqueous ethylenediamine (4 ml.) were warmed to 40° C. for three-quarters of an hour when solution was complete. Hxcess of NH,ClO, was added to the almost colourless solution and the subsequent white precipitate was recrystallized twice from water. 0-12 g. of colourless needles were obtained from the second recrystallization. Found: Pd, 19-4%. PdC,,H,N.C,H,N,H, (C104), requires ° ied: 19: 55%. (e) Quinoline. II (0:4 g.) was suspended in boiling water (25 ml.) ; addition of a consider- able excess of quinoline produced a clear yellow solution ; when this was treated with NH,CI1O, a brownish resin was thrown down. Attempts to free this resin from quinoline were unsuccessful and no definite compound was isolated. SUMMARY. Some reactions of palladium compounds with 1:10 phenanthroline (compound I) have been investigated. I reacts with K,PdX, to form a Series of compounds of the type [Pd phen X,] (where phen=1:10 phenanthroline and X=Cl, Br, I, CNS, NO, and 2X=C,0,): the oxalato compound was obtained as the monohydrate. [Pd phen Cl,|—compound II—is oxidized to [Pd phen Cl,|— (compound VIII) by passing chlorine through a suspension of II in chloroform. II dissolves in excess of aqueous solution of I to form a solution of the tetrammine chloride [Pd phen, |Cl,, which could not be isolated from solution ; but treatment of this solution with ammonium perchlorate and sodium 2-naphthol-6-sulphonate yields compounds IX—[Pd phen,|(ClO,), and X— [Pd phen, |(C,,H ,OHSO;),.2H,O respectively. IT also dissolves in aqueous pyridine (py), ammonia and ethylenediamine (en) to yield solutions of mixed tetrammines from which the following compounds were obtained on treatment with NH,ClO,: XI [Pd phen py,|(ClO,),; XII [Pd phen (NH3),|(ClO,),; XIII [Pd phen en](ClO,),. ACKNOWLEDGEMENT. The author is indebted to Dr. E. Challen for the carbon, hydrogen and nitrogen analyses. N 156 S. E. LIVINGSTONE. REFERENCES. Drew, H. D. K., Pinkard, F. W., Preston, G. H., and Wardlaw, W., 1932. J.C.S., 1895. Halcrow, B. E., and Kermac, W. O., 1946. J.C.S., 155. Landersen, G., 1926. Z. anorg. Chem., 154, 429. Morgan, G. T., and Burstall, F. H., 1933. J. Indian Chem. Soc., P. C. Ray Commemoration Vol, 1-16. Morgan, G. T., and Burstall, F. H., 1934. J.C.S., 965. Rosenheim, A., and Maass, T. A., 1898. Z. anorg. Chem. 18, 331. Ryan, D. E., 1949. Can. J. Research, 27B, 938. Department of Inorganic Chemistry, School of Applied Chemistry, N.S.W. University of Technology. INDEX A Page An Elementary Non-Conservative Electrical System os ie 221d Annual Dinner of the Society .. cop Xt Annual Report of the Council eee Authors, Guide to a ae eae hig Awards of the Society .. ce oa VI B Backhousia citriodora F. Muell. and Its Essential Oil, The Occurrence of a Physiological Form of ee see L23 Balance Sheet... 28 Se XXill Bequest, Form of : iv Berndt, R. M., and Bode ©. ate — Joint Award of ae David Medal for 1950 Age XXi Brown, Ida A., and Sherrard, Icathiecn M.—Graptolite Zones in the Silurian of the Yass-Bowning District of New South Wales... eel Warf Burfitt Prize, Awards of ae Walter thio. € b.< Burke-Gaffney, T. N.—Seismicity of Australha 5 es Ae pa TAY: C Challinor, R. W.—Obituary Notice XXVI Chemistry of Osmium. Part VIII (1X) 113 Clarke Memorial Lecture for 1951, by Dr. A. B. Edwards.—The Ore Minerals and their Textures... ‘ 26 Clarke Memorial Medal for 1951, Award of Zz A OS6:4 Commemoration of CRG: Scientists Pee xX Contour Trench Formations in Upland Plains of New South Wales .. ee | fas} Conversazione Be rey KER: Cook Medal, Awards of the James XViil Coordination Compounds of Copper— Part III. Complex Iodo-Cuprates (I) from Acetone Solution ae .. 138 Part IV. Some Cuprates () from Acetone Solution... .. 145 Copper, Coordination Compounds of— Part IIT. Me ae ae .. 138 Part IV. i : oh .. 145 Enamedoniaphora sinuosa Pesvormardl se nov. ae aa A ae ae ite) O D Page David Medal, Awards of the Edgeworth xviii Distinguished Visitors .. Xxl Dwyer, F. P., and Gyarfas, E. ‘C.—The Resolution of Tris-2 : 2’-Dipyridyl Metal Complexes through the Iodide Antimony]! Tartrates .. 135 Dwyer, F. P., and Hogarth, J. W.—The Chemistry of Osmium. Part VIII (IX), The Preparation of Some Hex- ammine Osmium III Salts .. oo Ll EK Edgeworth David Medal for 1950, Award of the... a Sif bg BED 9 'o:G., and (Mrs.) Spies, M. C.— The Essential Oil of a Physiological Form of Hucalyptus citriodora Hook. 120 The Occurrence of a Physiological Form of JBackhousia citriodora F. Muell. and Its Essential Oil .. 123 Plowman, R. A.—See Livingstone, S. E., and Plowman, R. A. Poisson-Kelvin Hypothesis and _ the Theory of Dielectrics .. 82 Popular Science Lectures pod Presidential Address—By F. R. Morrison General 1 The Science Museum—Its Duties and Its Dues 3 R Report of the Council .. xx Resolution of Tris-2 : 2’-Dipyridyl Metal Complexes through the Iodide Anti- monyl Tartrates a5 i .. 185 Robertson, W. H. — Occultations Observed at Sydney Observatory during 1950 be i a si ea Ss Schafer, H. N. S.—See Harris, C. M., and Schafer, H. N. S. Science House Management Committee, Society’s Representatives nen o.< Section of Geology, Report XXV1 Seismicity of Australia .. ew Wi Sherrard, Kathleen—The Geology of the Nanima-Bedulluck District, near Yass, New South Wales a 63 Sherrard, Kathleen—See Brown, ‘Ida Ase and Sherrard, Kathleen. Silurian of the Yass-Bowning District of New South Wales, Graptolite Zones im) Ghee 2 127 Silver Halides, Some Complexes Des .. 142 rived from INDEX Xxxi Page Smith-White, W. B.— An Elementary Non-Conservative Electrical System .. 15 The Poisson-Kelvin igmoeneas an the Theory of Dielectrics .. 82 Society’s Medal for 1950, Award of ie Btin.o-4 Some Complexes Derived from Silver Halides .. a a Ke .. 142 Some MHalogenoargentates (I) and eee ombates ay from Acetone Solution : . 148 Spies, M. C.—See Penfold, A. R., e¢ al. Stillwell, F. L. — Clarke Memorial Medallist for 1950 Es re Beale. &:<| Vv Page Vonwiller, O. eee Medal for 1951 ay: : a Spe, <:< WwW Waterhouse, G. A.—Obituary Notice xxvii Wiesener, F. A.—Obituary Notice XXVii Willis, J. L.—See Penfold, A. R., e¢ al. Y Yass-Bowning District of New South Wales, Graptolite Zones in the Silurian of the .. 127 Yass, New South ‘Wales, The “Geology of the Nanima-Bedulluck District, near a oe OS t ; ‘ ary LA RA, ¥ ’ ry ty . . ; © « ’ t i " | Oy int 1 . . , { Ant lagen Pah Ae eke eat ¥y bt F age 1 ahs AUSTRALASIAN MEDICAL PUBLISHING COMPANY LIMITED Seamer and Arundel Streets, Glebe, N.S.W. _ fore te 1952 ie ies pee 1 i Ff f « | 7 y \ & ‘ « ¢ i \ y = i F —— ; mat +m i ; Fj . ‘ eer, rs Til = Ff : | i Ve aire ‘ ae , a és ¢ P F i i i \ , : 5 ) i ‘ ns ; 1 a :) f ; | f at oF i ( Boris Boe al aE PUAN Meee +a a boon Vy git SM IAN INSTITU “AEA niin 3 9088 01308