454

INDUSTRIAL A N D ENGINEERING CHEMISTRY

Vol. 38, No. 4

acids occurs a t t,he outer region and increases as it approachcs the heartwood. When the heartwood is reached, a material increase in resin acid is noted, but whether the inner or outer heartwood has the larger or smaller percentage of resin acids is dcpendent upon their respective cxtractivc contents. FREE FATTY ACIDS. This constituent iiicreases in per (wit as it passes from the newly formed sapwood to the inner sapwood where it reaches a maximum; then the percentage of fatty acids decreases as it approachcs the pith. VOLATILES. This fraction usually iiicreases in per cent as it approaches the pith of the tree. ESTERS. I n heartwood the percentage of esters decrenses froni t,he outer heartwood to the pith. I n some instances the percentage continues t o increase as it approachcs the out,er sapwood; in others it tends to decrease. UXSAPONIFIABLES. I n general, the perccntage of unsaponifiable is the least a t the outer sapwood and iiicreases, in some < maximum in the outer heartwood and then decreases as it nilproaches the center of the trce. I t is interesting to note that the coniposit.ion of thc outrr niitltll(~ hear,tnood in stand I11 indicates that it is apparently in the trailsition stage from sapwood to heartwood. The relatively lo\\rwin acid content, together withihe slight increase in unsaponifiable material in this outer heartwood region, suggests that this transitional deposition of extractives was t,aking place.
APPLICATION OF RESULTS
I11 seeking means for effectively utilizing the potential c.lieriiicw1 products from ponderosa pine, it was found that this wood coiitained a sufficient quantity of extractives to warrant the possible removal and recovery of these materials from the lumber and from forest and mill wood waste. Preliminary investigation\ have shown that it is possible to extract all or a large portion 01 the extractives from lumber; the result is 8 further improveiiicnt in the lumber offered by manufacturers; in addition, a commercial volume of extractive products may become available from this wood. The amount of recoverable extractables is not uniformly distributed throughout the trunk of the tree. The average extractive content in sapwood is usually within tlie limit. 2.0 to 9.8%.of the weight of the dry wood, whilc the heartwood extractables are usually within the limits 3.5 t o 31.5% of tho weight of the dry wood. Tho greater quantities of extractivci

are obtained from the lumbci antl wood waste originating from the butt portion of the trunk and from that portion of the trcl containing massed pitch arcs?. The acetone extractives, R Iictlier from the heartwood or \ u p wood, contain, in addition to rebin acids and terpenes, free fatly acids, fats, and unsaponifiablc msteiial. Thus the extractive. differ from gum oleoresin foiIncd by wounding the tree by bhe presence of these aliphatic and un5aponifiable substances. T h e percentage of each of thesc erilitics is not uniformly distributed throughout the tree but depcntls from which part of the log thc. extractives arc obtained. I n tlic case of heartwood extractive<, the products found in approxiinaic order of quantity preicnt are resin acids, free fatty acids, unLaponifiable, esters, volatile, wntri soluble, and water and ether insoluble. In sapwood extractive. these entitios are found in thc following older: free fatty acidi, r e h acids, water soluble, estcrs, uninponifiable, mater and eth6.r iiisoluble, and volstile. Since thr conimercial value of t h e extractives is contingent in part upon the quantity and exact r i i tule of its entities, the identificdtion o f ~xc*ki of thesc produvt iindo1 inviLhtigatiori by thi- lahlr i ( o r r
ACK \ 0 \% J,LI)( ;Rf E N 1

The author is indebted to Gcorgc Schroeder and C. V. Zaayeu for collecting the wood sections antl the advice of Albert H c r r n ~ n ~ I > greatly appreciated.
LITEHA7'UL{ 1 . : c;t'rl?;l)

(1) Adariis, J. INU. ENO.C m x . , 7, 957 (1913), ( 2 ) A4nderson,Ibid., 36, 662-3 (1944).

( 3 ) Assoc. of Official Agr. Chein., Methods of Analysis, pp. 469-71 (1940). 141 Benson and Jones. .J. ISD. $hi;. CHEM.. , 9. , 1096 (191'7i Dore, I t ~ i d . , 11, 556-63 (1919). (6) Hihbert and Phillips, Can. J . licssnrch, 4 , 1-34 (1931) (7) Koch and Kricg, Chem.-ZtN., 15, 1 4 0 - 1 (1938). (8) Kiajriiiovic, Ibid., 55, 894 (1931). (9) Kurth, IXD. ENG. CHEM., 23, 1156 (1931). (10) Schorger, U. S. Forest Service, Bull. 119 (1913). (11) Trendelertburg and Schailc, Papier-Fnhr., 35, 221-30 (1937). (12) Tiertelak and Garbaczowiia, lsn. RSG. CHBM., ANAL. ED., a , 110-11 (1935). (13) JTise, "Wood Chemistry", pp. X i 3 - 4 , A.C.S. Monograph 87 New York, Reinhold Pub. Gorp., 1944. (14) \TOM and Scholae, Chern,-Zlg., 38, 3G!)-70 (1914).

issociation Pressure of Ammonium Car

k.
P. EG-kN, JR., J. E. POTI'S, JR., AND GEQRGETTE 1). POn'S
Tennessee Valley A u t h o r i t y , Wilson D u m , Ala.
The present paper cover5 .t study of the dissociation preism c of solid ammonium carbamate over the temperature range 35' $ 0 83' C. and in the absence of 'til excess of either gaseous reactvnf From the vapor pressure data tlie lree energy of dissociatioii and the heat of dissociation h a w bwn derived.
PREPARATION O F SOLID A3tMOh'IUR.I CARBAMATE

EMPERATURE-pressure relations for the dissociation of solid ammonium carbamate into gaseous ammonia and carbon dioxide have been measured by several investigators. (1-5). The reported values are divcrgeiit; at a total pressure of 40 atmospheres the divergence is as much as 17 atmospheres. Briggs and Migrdichian (1)-measured the dissociation pressure of ammonium carbamate over temperature range 10" to 49" C. and obtained very consistent data. They also studied the effect of excess ammonia or carbon dioxide and found excellent agreement mith the mass Ian accoiding to the equation:

KII&OZ1\"2

(solid)

BTH,(gas)

+ COz (gas)

(1)

Solid ammonium carbam i t e ~ v n sprepared directly in a 50-c sample bulb (Figure 1) which later was connected to the pre?siirci measuring system. Stoichiometric proportioning of the r('ii< tants, as was employed by Briggs and Migrdichian ( f ) , proved ta br unnecessary. Thc carbamatc n a s deposited in the bulb fron,

April, 1946

INDUSTRIAL AND ENGINEERING CHEMISTRY

455

system was evacuated t o 10-4 mm. of mercury. After three such cycles of degasification, the sample was assumed t o be free of foreign gases. On completion of the purification step, all the tubes joining the sample bulb were sealed off, except a short control manometer. The purified sample vas riot weighed but was estimated t o be 0.2 to 0.4 gram. Each preparation was checked for quality by comparison of its dissociation pressure at an arbitrarily selected temperature of 34.5 O C. with the value interpolated from the d a t a of Briggs and Migrdichian (1). About one third of the preparations were discarded because their dissociation pressures exceeded the adopted tolerance of 1 mm. of mercury deviation from the interpolated value of 170 mm. of mercury. None of the preparations yielded a pressure of less than 170 mm. a t 34.5" C.
Figure 1. Apparatus for Preparing Ammonium Carbamate 1 IP Dissociation Pressure
it

r i d hleasuring

MEASUREMENT OF DISSOCIATION PRESSURE

roughly equimolar mixture of ammonia and carbon dioxide which was charged a t a rate of 1 liter per minute. Deposition of carbamate in the inlet and outtet tubes was prevented by maintaining the temperature of the tubes a t 100" C. The gases, which were of commercial grade, were dried thoroughly t o prevent the formation of ammonium carbonate and bicarbonate. The carbon dioxide first was washed with acid permanganate and then was dried successively with sulfuric acid and Dehydrite. The ammonia was dried with freshly pulverized fused potassium hydroxide. I n preliminary trials in which the sample bulb waa cooled with dry ice, expansion of the product on warming t o room temperature shattered the bulb. This indicated either a high coefficient of expansion or a phase change in solid ammonium carbamate between -78" C. and room temperature. In subsequent work, therefore, the bulb was cooled in an ice-salt bath. The ammonium carbamate was purified by alternate partial vaporization and evacuation through a vacuum line that contained a trap cooled with dry ice. The sample was first warmed until the dissociation pressure reached 700 t o 800 mm. of mercury, then wm cooled w<th a mixture of dry ice and acetone, and the
ti

T h e pressure of dissociation of solid ammonium carbamate into gaseous ammonia and carbon dioxide was measured over the temperature range 35' to 83' C. The results, when plotted as log P against 1/T, fall o n the same straight line as the data of Briggs and Migrdichian for the range 10' to 45' C. The combined data of the two studies are represented by, the equation: log P (mm. Hg) = -2741.9/T

4-11.1448 (283' to 355" K.)

The slope of the curve defined by this equation indicates that the heat of dissociation of ammonium carbamate, if assumed to be constant over the experimental range of temperature, is 37.6 kg.-cal. per mole. This value agrees with calorimetrically determined values reported previously. The equation is applied also in the derivation of the free energy of dissociation.

In the technique used for the pressure measurements. the autogeiious dissociation pressure was allowed to come to equilibrium at a given temperature with the gases exposed only t o the sample bulb and the short control manometer. The control manometer was a null-point instrument with sealed-in electrical contacts in a circuit that automatically balanced the dissociation pressure with nitrogen pressure. The measuring manometer was in the nitrogen system, as Figure 1 shows. The control-manometer used for pressures above 1000 mm was a glass Bourdon gage t h a t established electrical contact at the tip of the free end of the elastic element. This gage had the advantage that it presented only glass surface t o the products of dissociation, but its sensitivity t o temperature introduced a significant correction factor a t pressures below 1000 mm. At these lower pressures, therefore, a mercurial control manometer was used. A correction factor representing the pressure required t o establish electrical contact was determined for each type of gage and was added algebraically t o the observed dissociation pressures. The balancing pressure was obtained from a nitrogen cylinder through a reducing valve. The dissociation pressure was balanced by continuously bleeding a small amount of nitrogen from the system t o a vacuum and intermittently introducing nitrogen under pressure through a solenoid valve t h a t would pass a slow stream of gas under a differential pressure of about 10 cm. The valve consisted of an 8-mm. tube t h a t terminated with a fritted glass disk slightly above a pool of mercury in a n integral jacket t o which the nitrogen source was connected. A cylindrical iron plunger surrounded the 8-mm. tube and floated on the mercury. A solenoid 'surrounding the jacket pulled down the plunger and thereby raised the mercury surface sufficiently t o seal the fritted disk and prevent the passage of nitrogen. The solenoid w a a actuated through a vacuum tube relay and the contacts in the null-point manometer. At equilibrium the intermittent action of the solenoid caused fluctuations of less than 0.2 mm. in the level of mercury in the measuring manometer. Pressures up t o 1000 mm. were measured on a mercurial manometer with B 12-mm. bore. One leg of the manom6ter waa evacuated t o < 10-4 mm., which made the manometer absolute within the accuracy of the readings. T o eliminate parallax, a glass mirror scale and a sliding hairline index were employed for

456

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 38, No. 4

approaching equilibrium from both the high- and the lorn-pressure sides. Thr pressure was read at half-hour interval5 until three surressive readings agreed within 0.5 mm.
DISCUSSION O F R E S U L T S

Table I gives the measured dissociation pressures. Of the d a t a previouslj reported, only those of Rriggs and Rligrdichian ( 1 ) fall on the same straight line with the present measurements when plotted as the logarithm of the pressure in millimeters of mercury against the reciprocal of the absolute temperat,urr Application of the method of least squarca to the combined data of Briggs and RIigrdichiaii and of the present work yields the following equation or thc dissociation pressure of solid ammoniiirri carbamate:
log P
Figure 2.
=

Dissociation Pressure of Solid

Amrnotiiiiiri

(:arbamate

-2741.9/T $11.1448 (283" to 355" K.)

= =

(2)

whwe P T

pressure, mm. of I l g absolute temperature

reading the manometer. The pressurc reading5 u t'w c7orrertPd to 0 " C. for the expansion of glass and mercury. Pressures above 1000 mm. Kere read on a three-stage compound mercurial manometer in which the interstage spaces were filled with freshly boiled distilled water. Ss with t h e qimple manometer, the final leg of the compound manometer was evacuated The manometer was mounted on a heavy paper scale that differed from the glass scale by less than 1 part in 1000. The pressure differentials in the three stages of the manometer, corrected for the head of water in each stage, were added t o give the total pressure. The total pressure as corrected t o 0" C. for the expansion of mercury. The sample was heated in a thermoregulated oil bath. The temperature of the bath was estimated to the nearest 0.01 O C. with a calibrated thermometer; the over-all accurary probably was +=0.1"C. The attainment of equilibrium x-as ensured by

The average deviation of the present measuremrnts from Equation 2 is *0.47, and the maximum deviation is 1.4Cr0; the corresponding values for the data of Briggs and htigrdichian are ~ 0 . and 3 1.3%, which are of the same magnitude as for an equation representing Briggs and hIigrdichian's data alone Figure 2 compares calculatrd and rnpnwred dissociation presqui-es. If it is assumed that d i d ammonium carbamate dissociateq according to Equation 1 and that the vapor is a perfect gas w e tem,

TABLE I.
Temp.,
OC.

DISSOCIATION PPESSrRY: O F d l l M o N I U M

4RB 4\lATE
P, \Im. H g

T-dues of the dissociation constant, K p , as calculated frum smoothed dissociation pressures derived from Equation 2, are presented in Table I1 together v i t h values for the free encrgy of dissociation as calculated from the relation:
AFo = - R T l n K ,

P,
h i m . Hg 170.1 171.2 170.9 294.2 295.1 366.8 388.9 479.2 517.2 603.2 610.2 641.6

Typ.,

C.

P,
Mm. Hg

'Temp., C. 68.91 70.43 71.74 73.18 74.40 76.47 77.30 78.82 80.27 81.81 83.33 83.38
OF

34.49 34.55 34.59 42.99 43.18 46.48 47,53 50,92 52.19 54.73 55 00 55.78

56 98 58 26 59.31 59 8 3 61 24 62 09 62 09 62.13 65 20 66 19 67 20 67 56

688 7 743.7 790.1 812.5 881.9 924 2 925 7 927.2 1096 1158 1223 1248

1327 1450 1551 1673 180.5 1998 2093 2264 2456 2659 2856 2864

TABLE 11. FREE EXERGYOF DIssocraTrox A\rvon-~r-arCARBAMATE

I.

SOLID

I errip.,
0" 20 40 60 80 1OOb 120b 140b

P , Aim.

Xp,

Atm."

Ak' ', Cal./hIole

7700 5500
3310

The heat of dissociation corresporiding to Equation 1, as c-ulculated from the slope of the vapor pressure line in Figure 2 on the assumption of constancy of the heat of dissociation, is 37.6 kg.-cal. per mole of solid ammonium carbamate. This value agrees with calorimetrically determined values (3) but is lower than the heat of dissociation calculated by Krase ( 3 ) from the dissociation pressure data of Briner (9). I n this paper no correction of measured pressure to fugacity has been made. A trial calculation, assuming the absence of mixture effect, indicates that, a t the melting point, the fugacity of the mixed gases mould be about lOyolower than the pressiire. n-hich is within t.he error int,roduced by extrapolation.
LlTERATUHE CITED

0 0167 0,0811 0.3212 1,078 3.153 8,223 19.45 42.33

10-7 7 . 9 0 X 10-6 4 91 x 10-3 1 . 8 6 X 10-1 4.64 8 . 2 3 X 10 10.90 x 1 0 2 1 1 . 2 3 X lo3

6.90

1110

- 1080

-3270 - 5460 - 7660

K p = A P s , where P is dissociation pressure in atmospheres. 27 Extrapolated.

R., and Migrdirhian, V., J . Phus. Chem.. 28, 1121-35 (1924). 121 Briner. E.. J. chim.nhws.. 4. 267-84 (1906'1. {3j Curtis,' H.'A., "Fixed Nitrogen", Chap. XIII, New York, Chernical Catalog Co., 1932. (4) Xlatignon, C., and Frejacques, M., Bull. S O C . chim., 31, 307-16 (1922). ( 5 ) Tokuoka, M., J . Agr. f'hmri. .SOC. Japan, 10, 1333-44 (1034).
( I ) Bnggs, T.