1000 0.04
H. A. DROLL, B. P. BLOCK AND W. C. FERNELIUS
-
Vol. 61
-
therefore that, in order to use the Svedberg equation for determining molecular weights of nonelectrolytes in such three-component systems, one must first extrapolate either the correct DA values, for which a s a l t = 0, or the Dll to zero concentration 0.02 of salt and then extrapolate the values obtained in this way to zero concentration of the non-electrolyte. Since proteins are weak electrolytes and since their net charge varies with the buffer and protein concentrations, a rigorous method for obtaining the correct value of the diffusion coefficient 0 I 2 3 4 of a protein for use in the Svedberg equation is not, c, . as yet, available. But it is hoped that the above Fig. 3.-Plot of the cross-term diffusion coefficient, Dill methods may be helpful in solving the problems versus h t c ~at Craft. = 0.76. which lie ahead. L It is felt that extreme caution should be exercised when using the Svedberg equation to calculate molecular weights of proteins and related molecules. The diffusion coefficients used in these calculations usually have to be obtained from measurements with a system of a t least three com0.435 ponents and the difficulties in obtaining the correct values are great. Thus it is not a t all surprising that the numerous values in the literature for the diffusion coefficients of various proteins do not 0.430 agree very well. Furthermore, recent ~ o r k in~ ~ 9 ~ ~ this and other laboratories, indicates that a pro0 I e 3 4 tein sample, such as BPA, may well change its Fig. 4.-Plot of one of the main diffusion coefficients, Dll, physical properties while stored in the solid state. and also (D&,o versus CICCI a t Crsff. = 0.75. Acknowledgments.-It is a pleasure to thank Professors L. J. Gosting and R. W. Baldwin and been plotted against the concentration of KC1 at also Mr. I. J. O'Donnell for helpful discussions constant raffinose concentration. As expected and suggestions during the course of this work from equation 13 these values are seen to extrap- and for their criticism of this manuscript. Finanolate, within the error of measurement, to the cial support to make this investigation possible value of the differential diffusion coefficient of was supplied by the U. S. Public Health Service raffinose a t 0.75 g./lOO mi24 At EKCl = 3.73 E-1426(C-2) and by the Rockefeller Foundation. g./100 ml. the difference between the DA for QKCI Grateful aclcnowledgment is hereby recorded. = 0 and Dll is seen to be approximately 3% so that (22) T. J. O'Donnell, t o be published. use of such DA values in the Svedberg equation (23) M . Halwer, G. C. Nutting and B. A. Brice, J . Am. Chem. Sac., would lead to considerable error. It would seem 73, 2786 (1951). -
C,=O.75
-
I
STUDIES ON COORDINATION COMPOUNDS. XV. FORMATION CONSTANTS FOR CHLORIDE AND ACETYLACETONATE COMPLEXES-OF PALLADIUM(I1)I BY HENRY A. DROLL,B. P. BLOCKAND W. CONARD FERNELIUS Contribution from the College of Chemistry and Physics, The Pennsylvania State University, University Park, Pennsylvania Received April 86, 1067
The stepwise formation constants for the chloride complexes of palladium( 11) have been determined from spectrophotometric measurements made a t 21, 29.5 and 38". The reaction between palladium(I1) chloride and acetylacetone in aqueous solution has also been investigated, but from pH measurements a t 20, 30 and 40'. The logarithm of the over-all formation constant for PdC14-P, estimated to be 15.8 at 25O, is observed to be of the same order of magnitude as that for PtCld-2 and HgC4-2. The thermodynamic stability of bis-(acetylacetonat0)-palladium(I1) is greater than would be anticipated from considerations of the electronegativity and the second ionization potential of palladium.
,
Introduction first transition series of the periodic table, a few The bulk of the studies of formation constants to non-transition-series elements, and silver(1). The date has been concerned with the cations of the Primary reason for the choice of cation appears be the desire t o have a simple species, the aquated (1) li'rolll a Portion of a thesis presented by Henry A. Drollin partial ion, as the reference cation. Because mostof the fulfillmcnt of the requirements for the degree of Doctor of Philosophy, secondelements do not JanllsrJr, ISM. Preceding paper R. M. Ieatt, w. C. ~ ~and ~ ~ and third-transition-series ~ l i ~ ~ B. P. Block, THISJOURNAL, 69, 235 (1955). readily form.Tsimple aquated cations, studies of
July, 1957
FORMATION CONSTANTS OF CHLORIDE COMPLEXES OF PALLADIUM (11)
their solutions have not been pursued extensively. I n view of the general relationship that exists between log KlK2 and second ionization potential or electronegativity2 for aquated bivalent cations, it is desirable t o investigate those elements which are not present as simple aquated cations under the usual conditions for formation constant determination. The palladium(I1)-acetylacetonate system was chosen for this study. Although an aquated Pd++ species may exist in highly acid solutions, the dissociation of acetylacetone is suppressed by acid and, consequently, the formation of acetylacetonate-palladium(I1) species is hindered in such conditions. I n order to suppress the hydrolysis of aquated Pd++ to hydroxy-containing species in the more basic solutions needed for this study, chloride was introduced. The various palladium(11) chloride species in aqueous solution have been characterized by Sundaram and Sandel13 and AyresP4but the only formation-constant data are the over-all constants reported by Templeton, Watt and Garners and Latimer.6 It was therefore necessary t o investigate the palladium(I1) chloride system quantitatively before the acetylacetonate system could be investigated. Experimental Materials.-An acid solution of Pd( C104)zwas prepared from C.P.grade PdCls (Fisher Scientific Go.) as follows. Palladous. oxide was precipitated by the addition of a 20% NaOH solution to a dilute hydrochloric acid solution of PdC12. The precipitate was washed with distilled water until the washings were neutral to litmus and gave a negative test for chloride. For about 12 hours the freshly precipitated oxide was refluxed with approximately 120 ml. of a 4 M HC104 solution. After the refluxing period, the mixture of undissolved PdO and supernatant liquid was allowed to cool. The superiiatant was decanted from the remaining undissolved oxide and subsequently filtered. To reduce the acidity of the filtered solution, about 68 ml. of 10% (CH&NOH was added, and the ( CHs)4NC10dwhich y c i p i t a t e d was separated from the solution by filtration. he filtrate was brought to a volume of one liter with distilled water. The alladium concentration of the final solution was found to e! 1.573 X M from an analysis of two 25-ml. aliquots by the precipitation of bis-(dimethylg1yoximato)-palladium( 11).7 The formality of HClO4 was 0.416 as determined by titration with 0.1264 M NaOH to the phenolphthalein end- oint of two 1.00-ml. samples, to each of which was adde8lOO ml. of distilled water. The hydrolysis of palladium was considered to be negligible in view of the small concentration of Pd(C104)2relative to the large concentration of HC104. The procedure of Cope and Barab8 was employed in the determination of total perchlorate in the palladium solution. The total perchlorate concentration was found to be 0.438 M . By difference, the concentration of (CHa)4NC104was calculated to be 0.019 M , The palladium solution, in addition, a slightly positive test for chloride. The amount of c loride was estimated to be 1.4 X 10” M , by titration of a 5.00-ml. sample of solution with 0.0020 d4 AgC104. (2) (a) M. Calvin and N. C. Melohior, J . A m . Chem. Soc., TO, 3270 (1948); (b) R. M. Izatt, W. C. Fernelius, C. G . Haas, Jr., and B. P. Block, THIS JOURNAL, 69, 170 (1955). (3) A. K. Sundaram and E. B. Sandell, J . Am. Chem. SOC.,77, 865
(1955). (4) G. H. Ayres. Anal. Chem., !25, 1622 (1953). (5) D. 13. Templeton. G. W. Watt and C. 8. Garner, J . A m . Chem. Soe., 6 6 , 1608 (1943). (6) W. M. Latimer, ”Oxidation Potentials,” 2nd Ed. Prentioe-Hall, Inc., New York, N. Y., 1952, p . 203. (7) F. P. Treadwell and W. T . Hall, “Analytical Chemistry,” VoI. 11, 8th Ed., John Wiley and Sons, New York, N. Y., 1942. (8) W. C. Cope and J. Barab, J . Am. Chem. Soc., 39, 506, 511
(1917).
1001
A solution of palladium(I1) chloride in dilute aqueous HC1 prepared by Datt9 in this laboratory was analyzed for palladium and total chloride concentration. Palladium was determined as the bisdirnethylgly~ximate,~ and the total chloride was determined gravimetrically on four 5-ml. portions of the PdC12solution.10 Prior to the chloride determination, palladium was separated as the bisdimethylglyoximate, and the excess of dimethylglyoxime in the filtrate from the palldium separation was removed by precipitation with nickel perchlorate. The filtrate after the separation of excess dimethylglyoxime was then analyzed for total chloride. The composition of the solution established by analysis was C I in chloride, and 1.49 X 10-1 M in Pd(II), 5.71 X 10-2 1 2.74 X lo-* M in HCI (by difference). The perchloric acid, sodium chloride and potassium chloride used in this work were reagent grade, and their solutions were analyzed by conventional methods. Sodium perchlorate (reagent grade) solutions were analyzed for perchlorate according to the method of Cope and Barab.8 Eastman white label (CH8)dNOH (10% aqueous solution) was standarized potentiometrically with a standard HC1 solution. A solution 0.0819 44 in the base was prepared by diluting the 10% solution with the requisite amount of distilled water that had been boiled previously to remove dissolved COZ. Eastman white label acetylacetone was used and without further purification. Solutions 4.38 X 7.46 X 10-2 M in acetylacetone were prepared by dissolving weighed amounts of the pure material in distilled w@er and diluting the resultant solutions with distilled water in volumetric flasks. The concentration of &diketone in each solution was computed from the weight and the density of pure material taken. Beckman No. 14044 p H 4 and Beckman No. 14049 pH. 9 powdered buffers were dissolved in previously boiled dlstilled water. The final volume of each buffer solution was adjusted to 500 ml. A Beckman model G pH meter was used to measure p H . A Beckman type E 1190-80 glass electrode and type 1170 saturated calomel electrode served as indicator and reference electrodes, respectively. To avoid access of KC1 in the calomel electrode to the palladium solutions, a saturated KNOa bridge was employed. The salt-bridge receptacle was fashioned from the outer glass jacket of a Beckman calomel electrode in a manner such that the greater part of another Beckman calomel electrode conld be inserted snugly in the receptacle. A layer of solid KNOa 5 to 8 mm. thick was present a t the bottom of the receptacIe under the saturated KNO, solution. Water-bath temperatures in the range 20-40’ a t 10”intervals were maintained constant by mercury thermostats purchased from the H. B. Instrument Co., Philadelphia, Pa. A Beckman model DU quartz spectro hotometer was used with 1-em. Corex cells for all spectray measurements. Temperatures were controlled to within 0.2” by circulating water through the tilter compartment from a reservoir maintained at constant temperature wit8h a thermostat. Constant temperatures of 21, 29.5 and 38” were attained in t$ cell compartment by water maintained at 20, 30 and 40 , respectively, in the reservoir. Determination of the Chlorocomplexity Constants of Pd(11).-Although no change in the absorption spectrum (visible region) was observed for palladium perchlorete solutions at varying C104/Pd ratios, the spectrum was significantly altered when the hydrogen ion concentration of the colored solutions was varied. The change in the spectrum was attributed to the hydrolysis of palladium according to theequationPd(H20),++ f H20aPd(OH)(HzO)+,-l f- H@+. Measurements of the average extinction coefficient of the solutions as a function of the hvdrogen ion concentration were made at 21, 29.5 and 38”. The average extinction coefficient a, is defined by the ratio D/(Z ZPd), in which D is the optical density, I is the length of the solution in centimeters, and XPd is the total palladium concentration. In Fig. 1 it is seen that the value of the maximum a t 400 mp becomes greater with decreasing hydrogen ion concentration. The effect of the ratio Cl/Pd on the average extinction coefficient of sohtions containing a constant con(7.86 X 10-4M) and of HClOd (0.208 centration of Pd(C104)~ (9) R. M. Isatt, Ph.D. thesis, The Pennsylvania State University, 1954. (10) I. M. Kolthoff and E. B. Sandell, “Textbook of Quantitative Inorganic Analysis,” The Mscmillan Go., New York, N. Y., 1947, p. all.
H. A. DROLL,B. I?. BLOCK .4ND W. C. FERNELIUS
1002
Vol. Gl
held constant a t 0.440 with NaC104. The spectra of the Pd(C10& solutions differed from those of Sundaram and Sandell3 only with respect to the wave length of maximum absorption. They reported the maximum to be at 380 mp whereas the maximum was observed at 400 mp in this study. The successive chlorocomplexity quotients were calculated from spectral data for solutions in which the ratio CI/Pd was varied from 0.6 to 4.8. I n eq. 1, derived using Beer's 150 EPdClm [PdClma-m]
(1) law, E signifies the molar extinction coefficient for the species indicated by the subscript written without charge; ;is defined above. The concentration terms [PdOH+)and [PdClm2-m] are given by eq. 2 and 3 in which the Q terms are the chloro-
tu
50
0 400 500 600 Wave length, cm.-'. Fig. 1.-Absorption spectra of Pd( C104)z solutions at 29.50" with p = 0.43 and ClOa/Pd = 278. Curves A, B and C represent solutions 0.416, 0.208, and 0.139 A l in HCIO,, respectively, and 1.573 X 10-8, 7.865 X and 5.234 X 10-4 Jf in Pd(C10&, respectively.
300
0.9
0.8 0.7
a 0.0
t: i
I C 0.5
99
0.4
[PdClma-m] = [PdCl!;-"t] [Cl-]&,CI, m = 1, 2, 3, 4 (3) complexity and hydrolysis quotients. It was assumed that the hydrogen ion concentration is equal to the stoichiometric HClO4 concentration inasmuch as the HC104 concentration is about 250 times the total palladium concentration, so that any contribution to the over-all acidity of the solutions by the hydrolysis of palladium is negligible. The equilibrium chloride-ion concentration was evaluated by the method of successive approximations and by assuming that only the species Pd++, PdOH' and PdCl+ are present when C1/ Pd = 0.6-0.8, that only PdC1+ and PdCla are present when Cl/Pd = 2.2-2.4, and that only PdC12,PdC13- and PdCI,-are present when Cl/Pd = 4.0-4.8. Good fits of the experimental points on the theoretical Beer's law plot of B against [Cl-] in each case supported the assumptions made. The distribution of the various chloride complexes calculated from the valueslfor is presented in Fig. 2. For the conversion to thermodynamic formation constants, the molarity quotients were corrected through the use of activity coefficients calculated from the Debye-Huckel equation." Determination of the Formation Constants of Pd( CHAc2) + and Pd( CHAcz)z.-Preliminary experiments indicated that the reaction between acetylacetone and palladium( 11) chloride is too slow for practical investigation by the PH titration technique. Consequently, solutions containing palladium chloride and KCl were prepared by mixing measured volumes of the 0.0149 M palladium chloride solution with 0.0819 M (CH&NOH and 1.401 M KCl in the proportions indicated in Table I. The final volume of each m x ture was adjusted to one liter with distilled water. The pH of 100-ml. portions of each mixture, to which had beeii M or 7.46 added a measured volume of either 4.38 X X M acetylacetone, was measured about 24 hr. following the mixing of metal and ligand solutions. A second pH reading about 4 hr. later usually agreed with the first reading to within experimental error; where agreement was lacking, readings were taken until a constant pH reading was obtained. A nitrogen atmosphere was provided
D
TABLE I
0.3 Soh.
0.2
0.1 0.0 2 4 ZCI/ZPd. Fig. 2.-Distribution of the palladium(I1) chloride complexes a t 21" with ZPd = 7.86 X 10-4 M , [HC104] = 0.208 M , and p = 0.440. Curve A represents P d + + Pd(OH)+':-"; B, PdClf; C, PdCIz; D, PdCla-; E, PdClr--. M ) but varying concentrations of NaCl was studied also a t 21, 29.5 and 38'. The ionic strength of these solutions was 0
+
0.0149 M Pd(I1) soh., ml.
1.401 M KCI, ml.
0.0819 M (CHahNOH, F i n d concn. ml. KCl, moles/l.a
1 .oo 0.305 75.00 1 3.00 1.00 .0491 2 3.00 35.00 1.00 ,0281 20.00 3 3.00 1.oo ,0141 10.00 4 3.00 a Final concentration of components other than KCI in solutions: 4.47 x 10-6 M Pd(II), 8.19 X 10-6 M (CH3)4NCl, 3 X 10-7 d.I HC1.
during the actual measurements, and the pH of each solution (contained in 6-ounze polyethylene bottles) was observed at 20, 30 and 40 . The value of %, the average number of enolate ions (Ch-) bound per palladium, was (11) H. 8. Harned and B. B. Owen, "The Physical Chemistry of Electrolytic Solutions," 2nd Ed., Reinhold Publ. Corp., New York, N. Y., 1950, pp. 39, 119.
1003
FORMATION CONSTANTS OF CHLORIDE COMPLEXES OF PALLADIUM(II)
,July, 1957
calculated from each pH datum in the usual manner.12 Since chloride ions may also be bound to palladium, the expression relating % to [I'd++] must be derived from eq. 4
TABLE I1 oc. 20
log
81'or Ki
Cl, moles/l.
t,
1% Qa' or Kz
Ppt. 0.102 10.2 I'pb. ,0484 18.6 n = (4) Ppt, ,0278 18.1 n m Ppt. .0000 16.7 [Pd++l [Pd(Ch),C1,2-m-nl 8.0 30 0.102 18.3 Expressing all concentration terms in eq. 4 in terms of for8.2 ,0484 17.8 mation molarity quotients and dividing both numerator and 8.8 ,0278 17.5 denominator by [Pd++],eq. 4 is converted to 10.9 .0000 16.2 7.9 40 0.102 17.5 8.1 ,0484 16.8 8.7 .0278 16.4 10.5 0000 15.4 +ICh-I2{QIQz [Cl-lP~,z [C1-lzPz,~1 [C1-lmQ,,C1 1 negligible effect on the calculations of & I and Qz. TWO palladium chloride species were found by spectrophotometric measurements to be present in solutions in which the ratio Cl/Pd exceeded 1540. An equilibrium constant of in which was calculated for the reaction PdClmZ-" C1- Frr? n
m
2n[Pd(Ch),C1,2-m-m]
+
+
+
+2
.
+
4
PdClkL? ( m 2 4). The term
[Cl-]mQmc'ineq. 5 differs 1
6
[C1-ImQmC1 (assuming m = 5 and QP=
from the term 1
to the extent of about 1.5 parts per thousand. This difference has no effect on the calculated values of QI and Qz.
TABLEI11 Reaction
+ Ch-
Pd++
Pd(Ch)+ Pd++
F'C Pd(Ch)+
+ Ch-
$ Pd(Ch)z
+ C1- F? PdC1+
PdCl+
+ C1- ~t PdClz
PdClz
+ C1- F? PdC13-
PdCl3-
+ C1-
PdCla--
AFO
t, oc.
log K
(kcal. mole-2)
20 30 40 30 40 21 29.5 38 21 29.5 38 21 29.5 38 21 29.5 38
16.7 f 0 . 2 16.2 15.4 10.9 f 0 . 2 10.5 6.2 f 0 . 1 6.0 5.9 4.7 f 0.1 4.5 4.1 2.5 f0.1 2.4 2.2 2.6 f 0.1 2.6 2.5
-22.5 f 0 . 2 -22.5 -22.2 -15.1 =k 0 . 2 -15.0 - 8.3 f 0.1 - 8.3 - 8.4 6 . 3 f 0.1 6.2 - 5.8 - 3 . 4 f 0.1 - 3.3 - 3.1 - 3 . 5 f 0.1 - 3.6 - 3.5
and PI,I, pz.1, PI,? and PZ,Zare the molarity quotients for the formation of the respective species Pd(Ch)Cl, Pd( Ch)Cl2-, Pd(Ch)zCl- and Pd(Ch)zC12-- from the simple ions. It is readily seen that the terms [C1-]mp,,m are zero when [CI-] equals zero. Therefore, an extrapolation procedure was employed to evaluate K 1 and K z , the formation constants. Values of &I' and QI'Q~', calculated at three different total chloride concentrations in the ZC1 range from 0.102 to 0.0278 W 3through the use of eq. 5 were plotted as their logarithms against X I . The true log K values were obtained by extrapolation of the log Q' values to zero chloride concentration. In view of the large excess of chloride, 1'21-1 was assumed to equal ZC1 in all reaction mixtures. The values determined, which are uncertain to f 0 . 2 , are listed in Table 11. The presence of PdC1,2-m species ( m < 4) in the palladium chloride-acetylacetone system was considered to exert a (12) R. M. Ieatt, C. G. Haas, Jr., B. P. Block and W. C. Fernelius, THIEJOURNAL, 68, 1133 (1954). (13) Formation of a precipitate in the solutions which were 0.0140 M in total chloride precluded the use of p H data from these solutions in the caloulation of molarity quotients.
-
a50
(cal. deg. -1 mole-')
15 i 13 14 14 -11 A 13 - 10 1 f 10 1 1
-10 f 10
- 10 -11
+
-14 10 - 14 14 -15 A 10 14 - 14
-
-
AH0
(kcal. mole-')
-18 i 4
-18 f 4
-
8 1 2
-
9 f 2
-8
f 2
-8
f 2
Results The results of this investigation are presented in Table 111. The values of AHo were obtained from the slope of a plot of log K against 1/T. AFO and AS0 were evaluated from the usual thermodynamic relationships. Discussion Values of log K for the over-all reaction between palladium(I1) and chloride in the formation of PdC14-- a t 25' have been reported in the literature as 12.36and 13.3.5 The results of the present work, however, indicate a value of 15.8 a t 25" which is of the same order of magnitude as the over-all log K for the formation of PtC14-- ( l 6 ) I 4 and HgC14-( 15.0). (14) W.M. Latimer, ref. 8, p. 206. (15) B. Lindgren, A. Jonmn and L e l l e n , Acto Cham. 8eand., 1,479' (1947).
1004
NOTES
The extraordinary stability of Pd(Ch) + is reflected in the large positive AX and negative AH (Table 111). Izatt, et ~ 1 observed . ~ ~a linear relationship to exist between '/z log Kl& for the formation of the bisacetylacetonates of the first transit,ion series metals at 30" in water and the second ionization potential of the gaseous metal atoms. A linear relationship between '/z log K1Kz and the electronegativity of the metals in the first transition series was also found to exist. The position of palladium(I1) in each of these plots is interesting
Vol. 61
because it lies far above the straight line. The deviation of palladium from the linear trend exhibited by the first transition series metals suggests the possibility of a similar straight line relationship for the metals in the Second transition series. The straight line for this series would be above that for the first series, Le., in the direction of greater stability. Acknowledgment.-The authors are indebted to the United States Atomic Energy Commission for the financial support furnished this work under Contract AT(30-1)-907.
NOTES RADIATION STABILITY OF COPPER PHTHALOCYANINE BY MARKT. ROBINSON AND GILBERT E. KLEIN' Solid State Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee' Received November .%3* 1966
The great thermal stability of copper phthalocyanine, C32H1ahTsCu,has long been known. * We report here some brief experiments on the stability of this substance t o nuclear reactor radiations. Four 0.7-g. samples of Solfast Sky Blue,' sealed in quartz capsules, were irradiated in the ORNL Graphite Reactor to integrated doses ranging from about 2 X 1018 to about 1 X 3Olg thermal neutrons/cm.*. Two similar capsules were irradiated in cadmium envelopes for about 7 X lo'* thermal neutrons/cm.*. The 7-radiation intensity was increased about nine times in these ca sules over that prevailing in the absence of cadmium. 'fhe temperature of the irradiations was 25 to 40". After irradiation and subsequent delay to allow decay of induced radioactivity, the six capsules were opened. No measurable evolution of gas had occurred (limit of detection -0.5 ml.). X-Ray diffraction patterns were recorded for the original material and for two irradiated samples, using Ni filtered Cu K a radiation, with a 114.59 111111. diameter powder camera. I n another series of experiments, unweighed samples of tetragonal (CY)"' and of monoclinic (8)' copper phthalocyanine. were irradiated in a beam-hole of the Low Intensity Test Reactor (LITR) at a temperature of about 30". These samples were contained in small capsules constructed of Dow magnesium alloy 58135. The tetragonal form was prepared as previously described .6 The monoclinic material was prepared by mulling the tetragonal material in cyclohexanol. X-Ray diffraction patterns were recorded on a Norelco diffractometer for samples exposed to about 5 X 10'8 and about 2 X lolo thermal neutrons/cm.*. The samples irradiated in the Graphite Reactor were initially nearly amorphous tetragonal material. A sample exposed to 2 X 3018 neutrons/cm.2 partially crystallized during or shortly after exposure. After six months at room temperature, this sample was found to be highly crystalline. (1) Deceased. (2) Operated for the
U. 8. Atomia Energy Commiasion by Union Carbide Nuclear Co., Division of Union Carbide and Carbon Corporation. (3) P. A. Barrett, C. E. Dent and R. P. Linstead, J . Chem. SOC., 1719 (1936). (4) Sherwin-Williams Company trademark for their brand of copper phthalooysnine. (5) A. A. Ebert and € B. I. Gottlieb, J . A m . Chem. ~ o c . , 74, 2806 (1952). (6) M.T. Robinson aad G. E. Klein, dbid., 74, 6294 (1952). (7) J. M. Robertson, J . Chem. SOC.,815 (1936); R. P. Linstead and J. M. Robertson, {bid., 1738 (1938).
A sample exposed to about 7 X 1018 neutrons/cm.2 was found to be nearly amorphous. The samples irradiated in the LITR retained their crystallinity, with small unit cell expansions (
