658
T'ilPOH PRESSURE AKD VISCOSITY ltELhTIONSHIPS FOR A HO;1IOLOGOUS SERIES OF u,u-DINITRILES BY hLAN
L. ~T'OODMAN, WARREN J. M U R B A 4 C H AND XIARTIN H. KAUFMAX G. S. Nova1 Ordnance Test Station, China Lake, Califomia Received November SO, 1960
Iknsilies, viscosities and vapor pressures of six o,w-dinitriles, NC(CH?),,CS for n = 3 t,hrough 8, have been measured; the vapor preseure of succinonit,rile (n = 2) also has been det,ermined. Constant,s in the viscosity-temperature relation log 7 = d B / ( C T ) and in t'he vapor pressure-temperature relat,ion log p = A ' - B ' / T were calculated. Empirical equations, one relating vapor pressure, temperature and n, the other relat,ing the heat of vaporization and n were established. Ahequat'ion, derived by L. A. Girifalco, was found to give a linear relation between vapor pressure, viscosity and temperature for the a.u-dinit,riles.
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Introduction The densities, viscosities and vapor pressures of six a,w-dinitriles, NC(CH,),CN, where n equals 3 t'hrough 8, were measured; vapor pressures of succinonitrile also were measured. The densities and viscosities were measured a t 15, 25 and 35", and the mpor pressures were measured in the range of 5 to 70'. The viscosity, vapor pressure and temperature data for the a,w-dinitriles were found to fit an equation derived by Girifalco.' Experimental
chloride was removed 'inz!(ccuo and the rwidue was dist,illed to yield 364.7 g. (90.0%) of azelaoyl chloride; b.p. 96.7102.0' at 0.2 to 0.4 mm. A 4-liter beaker, fitted with an efficient stirrer, thernionirter, fritted glass delivery tube and cooled in an ethanolice bath, n-as charged with 3000 ml. (44.4 moles "3) of K",OH precooled to 0". Additional ammonia (170 g., 10.0 moles) was added from a tank. Then 364.7 g. (1.62 moles) of azelaoyl chloride was added dropmise over a onehour period at, 0 to 5' while a second 170-g. portion of ammonia was added through the gas delivery tube. Bfter 1 . 5 hours the whit,e precipitate r a s collected, nmhed with water and dried under vacuum at 60". The yield of azelaamide was 291.2 g. (96.5%); m.p. 173.4-178.1' (lit,.Bm.p. 175"). The azelaamide (1.56 moles) in 1250 ml. of pure thionyl chloride was heated to reflux over a period of four hours and then refluxed for an additional seven hours when no more gas was evolved. Excess thionyl chloride was removed in vacuo, and the residue was dissolved in 500 ml. of 1,2-dichloroethane. After washing with 10% KOH, water and saturated sodium chloride solution and t,Iien drying over anhydrous potassium carbonate, the solvent was removed. Two distillations gave 196.6 g. (83.9%) of pure azelaonitrilc, b.p. 105.0-105.2" (0.1 mm.); n 2 5 ~1.4439 (lit.? n 2 5 ~1.4426). Density.-The densit,ics were measured vith a one-milliliter SprengeMype pycnometer which had been calibrat,ed with m t e r ; the densit,ies at 15, 25 and $5" are given in Table I. The temperat,iire of the bath wa,s controlled to within =k 0.02'. Viscosity.-The viscosities, at, 15, 25 and 35", were measured with an Ubbelohde-type viscometer which had been calibrated with distilled water; the values for bhc. viscosity of water were obtained from thv data of Webers and were based on an absolute viscosity of 1.0020 centipoise at 20". Kinetic energy corrections were made where necessary. Vapor Pressure.-The vapor pressures, using between 0.3 and 1.O ml. of sample, were measured with t.he piston manometer apparatus of Pitman and Ernsberger.9 KOchange i n vapor pressure was observed over a period of about a weck indicating the absence of more volatile impurities not detectable by the infrared spectra. The temperature of t11c bath was controlled to within 10.007" and was read to the nearest 0.01' on a thermometer which had heen c wit,h a Kational Bureau of Standards platinum r thermometer.
Reagents.--hll of the dinitriles except, suberonitrile and azelaonii rile were obtained from commercial sources. Succinonitrile as obtained from the Matheson Co. and needed no purification since sublimation and recrystallization failed to change the vapor pressure or the freezing point (57.4"; lit.2 56.9"). The infrared spectra of glutaronitrile, adiponitrile, pimelonitrile m d sebaconitrile indicated the presence of small of caarbonyl containing impurities. These imere removed by t>reatingthe dinitriles with either 10% aqueous KOH or methanolic KOH solution. In most instances one distillation sufficed to give spectroscopically pure material. Using the above procedure the following materials irere obtained: glutaronitrile, b.p. 94.9" (1.1 mm.), n251) 1.4332 (lit,.3 ~ Z O D 1.42947); adiponitrile, b.p. 101.5-101.7° (0.7 mni.), n25~1.4366 (lit.4 n25~ 1.4369); pimelonitrile, b.p. 116.0-116.1" (0.9 mm.), 7 2 2 5 ~ 1.4398 (lit.6 n2Oti 1.4472); and sebaconitrile, b.p. 127.0' (0.2 mm.) 7 1 2 5 ~1.4462 (lit,.5n% 1.4474). Suberonitrik-A solution of 205.6 g. (3.0 moles) of 95% IiCN in 250 nil. of water and 875 ml. of 95% ethanol was heated to reflux. The heating mantle was removed, and then 408.6 g. (1.21 moles) of 1,6-diiodohexane was added over a pwiod of 35 minutes. When the exothermic reaction had subpided, the mixture was refluxed for two hours. Approximaiely 900 ml. of ethanol-water then was removed by distillation under reduced pressure. The suberonitrile layer was separated, and the aqueous phase extracted with benzene. The extracts were combined with the crude dinitrile and washed, respectively, wit,h water, 10% sodium thiosu1f:itcX :ind saturatrd sodium chloride solution, and then tiricd over anhydrous magnesium sulfat,e. Distillation of the rrude dinitrile gave a material which contained halogcn Results hnt no carbonyl impurities. To remove the halogen-containing impurities the dinitrile n-as treated with methanolic The plot of the logarithm of the viscosity agniiist ICOH. One distillation gave 113.6 g. (68.970) of pur(% the reciprocal of the absolute temperahre gave 11011subcronit,rile, h.p. 120.1-120.3" (0.8 mm.), n Z 6 1.4419 ~ (lit .5 n2*n 1.4448). linear curves ; however, a suitable equation, g i x w Aze1aonitrile.--h mixture of 338.8 g. (1.8 moles) of azelaic by Gutmann and Simmons,1o as found t o be acid and 1000 ml. of thionyl chloride was he:ttcd to reflux over a plirioci of 1 . 5 hours and then refluscd for four hours ( G ) I. Heilbron and H. M. Bunbury, cds., "Dictionary ot Orrranii, \\-hen ovolution of SO, and IlCl had ceased. E:xcess tliionyl C'oinl>ounds," Oxford University Press, New York, N . Y., 1953, Val. I . 1). 224.
( 1 ) I,. .4. Girifalco, .I. Chem. Phgs., 23, 244B (1955). (2) h. ban de Vlocd, Bull. soc. chim. Belg., 48, 229 (1939). . Vopel, J . Chem. Soc., 674 (194P). (3) G. 11. Jcffery and .iI. (4) h.E;. Rulikova, E. N. Zil'berman, T. K.Roginskaya a n d R1. A I . Smirnnvn, ZL7tr. i7riklnd. Khim.,32, 227 [19:9); C . .4., 53, 11217i (1 959). ( 5 ) It. I h i i l o n i l 5 . l'i,iit.litclii,tf Bicll. s o r . r i i i 7 n . F m ! i r e . 170 (l94!1).
(7) D. T. Afowry and E. L. Ringwald, J . . I m < ' / < m Sot., , 7 8 , 4430 (1950). ( 8 ) W. Weber. %. a n g e w . Phys., 7 , 96 (1955). (9) H. TI'. Pitman and I.. hl. Ernsberger, Reu. Scz. Inslr.. 26, 58-4 (19.55). (10) 17. Giihiriaiin ancl I,. 11. Simmons, J . .dppl*.d f h y s . , 23, 977 (1952J.
659 T.\BLE
1)mwriEs OF Compound
d'5a
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Gliitaronitrile
THE
I DINITRILES
dl54
Lit. values
a334
0.9892 0.9811 0.9733
hciponitrile
,9664
,9579
Piinelonitrile
,097
,9414
TABLE
111
\.r24IJVR I'REHSURES O F T H E I ) I N I T R I L D r
1.002!13, d154 0.09112, dad 0 .9Xl30" d354
ti4
0.0T661b;d204 0.9879" ,9515 dlg19 0.O5ldd,o 0 .0610e ,9344 tlr 0 .96181, d154 0.05070: daa 0.93961"; dZO4 0 . 948'
Temp.,
Compound
Succinonitrile
P
(P)
"C.
(obsd.)
6.24
1. 156 1 7$2 2,370
10.16 13.06 16.15 17.74 19.63 25.14
3.238 3.798 4.589 7.774
1.154 1,751 2,3G 3.238 3.707 .1.576 7.784
Glutaronitrile
1.115 1. !N1 2.9fjti
4.51 10.16 11.16 18.14
25 54 30.65
4.35; 8,590 13.45
1 , LI!) 1 . 0x3
2 , !I58 1.331
8 ..5e-r 13 . 50
'
Bdiponitrilc
B +c + 2'
in which 7 is the viscosity in centipoise and 2' is the absolute temperature. The constants A , B and C, determined by a least squares analysis, are given in Table I1 for each of the dinitriles. The standard percentage error (s.p.e.) of fit, defined by in which hr is the number of experimental points, is given in the last column of Table I1 for each compound.
12.66 17.05 20.13 25.84 30.15 36.26 41.35
0 . 753 1,189 1.612
2.81.5 4.222 7.341 11.40
0.756 1.186 1,614 2.810 4.213 7.332 11.44
Pimelonitrile
33.98 34.48
40.06 44.21 45.29
2,275 2.105 4. 065 5 . S7!I (i.421 1i.50
2.2!)3 2,400 4 039 5 . s72 (i.411
li.6-1
TABLE I1
(Autaronitrile ldiponitrile P melonitnle Hiiberonitrilc .izelaonitrile Sehaconitrile
-0 -0 -0 -1 -0
9025 8016 (3017 0664 9849 -1 0172
B
233 201 22-1 267 250 264
-0 $-0 G 0 +0 -0
2 5 2 O
0 3 1
-0.1 -0.1 $0.3 +0.5 $ - 0 .1 -0.4 __ =to.3
-0.4 ;0.3 --0.1
M . 2 '0.2
t o .1 -0.3
-0
s
T O 2 $0 t i +o 1 -0 2
-0 3 10,4
vISCOSITIES O F DIXITRILES, CONST.4NTS I N THE EQUATION
.i
+o
10 2
5i.08
Compound
iJt?V.
f0.2
SuheronitriIc , $1347 ,9269 ,9186 t P 1 o . o ~ o ' :izeIaonitrik ,9255 , 9178 ,9115 d l 0~. w!)'~ Se1)aconitrile .9179 .Y 107 ,9033 d204 0,013' H. Serwy, BdZ. SOC. chinz. Belg., 42, 483 (1033). R. Lcgrand, ihid., 53, 166 (1944). Reference 3. I. Heilbron and H. M. Bunbury, eds., ref. 6, Vol. I, p. 31. e Reference 4. Reference 5 . logo = A
r
P
(calcd.)
C
83 92 59
-159 12
03 16 18
-159 75
Suberonitrilc
s p.c 0 01
-171 52 -168 31
01 00 01 00 01
-166 63 -166 58
Azelaonitrile
f h e vapor pressure data are given in Tahlc 111. The vapor pressure of sebacoiiitrile has 1)ccn rrported previously.11 The data are bt.lieved to hc nviburate to nithiii ICc.'' Table ITr lists the coiistants in thc. equation log p (micron\) = ,2' - B'/2'
35. ti; 40 00 42.06 45.00 -18 27 .is. 60 67.70
0 . !)66 1.262 1.872 2,503 2.93ri
6 ,304 21.66
0 . 787 1.213 1 . -Hi9 I . !J70 2 Ci(i i 4 .30-t 14.90
0 . !Hi!) 1, ?(i4
1.863
2.407 2.025 ti 311'
21.31;
Chrm P h y s
24,
-0.3 -0 2 $0.5 +0.2 $0. 4 -0.0 $0.4
0,7R3 I .'LC(i 1 . 476 I !)ti 1 '3 ti71 i : Ni(I1) > hIn(II1) > Fe(II1) > Co(I1) > Co(II1) > Th(1V): some other chelates were inert under these conditions: Al(III), Zr( IV), Be(II), Cr( 111), In(II1). Comments and int’erpret,atiorisare givcn.
Introduction pounds on the reaction reccntly have been sumIn the last several decades a large number of marized also.5 T o our knowledge the only systematic studies studies have been directed toward an understanding of the attack of molecular oxygen on organic that have yet been made of the autoxidation of molecules. A description of this work and the con- chelates are those which apply t o LLoxygcn-c:irryIn contrast, we have bren coiiclusions derived from it are available in several ex- ing” cellent review^.^.^ The effects of metallic com- rerned with what might propcrly he called “destructive autoxidation” of chelates in nhich the at(1) Department of Chemistry, University of Pittsburgh, Pittsburgh 13,Pennsylvania. Inquiiies should be sent to this author. (2) Dep trtment of Chemistry, University of Arizona, Tucson, Arizona. ( 3 ) C. Walling, “Free Radicals in Solution,” John Wiley and Sons, lnc., i’iew York. N. Y.,1957. Chapter 9.
(4) G. Russell, J . Chem E d , 36, 111 (1959). ( 5 ) F. Basolo and R. Pearson, “Mechanisms ot Inorgan~cReac1958, Chaptei 8. tions,” John Wiley and Sons, Inc., N e w I‘ork, N. Y., (6) A. E. hfartrll and .If. Calrin. “Chemistry of the Chelate Conipounds,” Prentiee-Hall N c n I-oili, N. T., 1952, Chapter 8
