U. S . Department of Agriculture, Forest Service a FOREST PRODUCTS LABORATOR Y In cooperation with the University of Wisconsi n MADISON, WISCONSI N ci EFFECT OF PARTIAL HYDROLYSIS ON THE ALKALI SOLUBILITY OF WOO D By L . F . Hawley, Principal Chemis t and W . G. Campbell, Commonwealth Fund Fello w Published i n Industrial & Engineering Chemistry June, 1927 4.3 /// / test was Sitka spruce ' tts composition and it s tment were first determi : tained with hydrolyze d ~e . god is given i n coy+•osition of th e er cent caustic sod a erature . Table I .--Analysis of o',iz'tnal wood (Results on basis of Weight of origina l , dry wood ) per,c4nt Water soluble . ,i Ether soluble Alkali soluble Cellulose Lignin M ethoxyl Total pentosans Pentosans not in cellulose 4i8 114 . 4. 1 .7 12 . 0 62 . 5 29 . 3 4. 8 9.9 6. 2 Table II .--Analysis of wood residue after treatmen t with 1 per cent NaOH for 1 hour a t 100° C . (Results on basis of weight of original dry wood ) Per cen t Loss on alkali treatment 13 . 7 Cellulose Lignin Methoxyl Total pentosans Pentosans not in cellulose 59 . 2 27 . 7 4. 3 7. 4 3 .9 tables t nalysi so det e se a n pentosan s ical dat th e Forme ter Experimental In studying the alkali solubility of the hydrolyze d wood, the general plan was to subject samples to differen t degrees of hydrolysis, analyze them, treat them with causti c soda, and analyze the residue . It has frequently been found , however, that on account of the difficulty of obtaining th e same , conditions throughout the mass, a chemical reactio n which takes place with small quantities of wood, such as the sample for analysis, can not be reproduced exactly whe n larger quantities are used . For this reason it was no t attempted to hydrolyze enough wood so that the residue woul d ent for an analysis, alkali treatment, and th e alysis of the resid . Instead, two samples wer e under as nearl a_sossible the same conditions , lysis and th e rmORe analyse s eight on hydrol tables show s is obtained b y ose, 1~, and .. pent : cellulermine d from tIa ~ JOiilyses of the origi rate wood (Tae, . a 1 of the n s 'e r hydrolysis,, to whin'h is also owed th wate r solu in the original wood, on the assump+% ion that this i s all 16lbved by hydrolysise It is immediately noticeabl e 'hat the calculated loss is always considerably higher than . *hat actually determined . This difference can be explained I I Co a) cdcd R O co •r1 r-) r-i N tni-tlD . q I +3 •p rl I.[1-1' r' r V N • OH I a) a) I o I . . . . . . . . . . . . . . . . . . .. .. .. . . .. . • N-\04- M q 0 00 00 00 00 0 00 00 OO 00 00 00 00 0 0 •0 Od H k 0 \-0 N-N-CV Pr\ a) q 0 00 00 00 00 00 R rl s~ O C) O 0 00 H H a) O . .. co o • O co o CO N 00 00 00 •0 00 00 00 00 00 00 00 0 . 00 00 0 o v.\ I OI •da)i I NtryN\MN-cu H#I OH 'd I) .~ R I a) •r1 Q~ R HHCV CV I 00 00 00 00 00 00 00 0 0 \-0 M N n.D 0 CV ‘•1) H H N M In Lc\ p a)•-4 I 0C ico 0 O O +' I • • • • • 4 0 cd I 0 H 150 t!1 q f1 I H q 40 I 8955 o O '.0MOCVta) O I Lc\ til O 0 N O 1 tr1111-1 4 M ri I .. .. .. .. .. .. .. .. .. .. .. .. q 'd I 00 I m. r--. N-~" I I 1o .5o■.o' 0 I NNNN N bO •ri a 00 00 OM M O only i0e 1 partl ; tip . co ~. wood whic h • . yz . 0 Tip►' , feoex-- vain uents' the ' ~ :1 03A. the Wrtlti ti _ •le ': II : cent of tio' imply lose, lignin, o pe slioul4 ada u,p .1- the partly h wood totals wte 140 TAP vrWt a yzed samples to considerably less than i . ■ per cent, th e is good reason to 'assume the presende of Some material i ' . ~ . the . laistwhich was not present in the or j,gi r ands ev does not show in any of the determination . it is la, 1ge .ly gOit;MO esubtanc,hrievdta the alkali treatment, in t,?aat. the sums of .the - htft • ! constituents de-t,erlmL'ned on 'a aa. al•i=,tr-e.stdiv~ - ~d all come very c'1oar to 100- P g-r Bent of the. aeto _iveiglt o f residue, the extreme variati me being betwe'en 04.0 ad 100 . 5 per cent . r ence s ',!,he figures 'in Table III, aside from the di between determined and calculated. losses, give little infort_ mation that has , wt been available previously . Thg., s effect of hydrolysis on th-e amount of lin and , , ~ and the continuous but not complete rye ,al of tii p1G.f>> an s a .: - s have been shown in pa ge-vious wok . This . set effurnished mainly for compar isom with $Ole IV in $4*r t o show the qus.ntit g 41we effect of the a1 1i treatmem 4 Table IV gives '*e loss in weight of- t duplicate saris le s on hydrolyai s, heir laD+ g-s in weight ''x- a:1-ali treatment , an d then the analysis of th'e residues afitOT t g Mcal i treatment . The alkali-treatment ms identical wit .4 .ttl t. , ed ii b analytical de'te- izii a,' .Nmn of the alkali-MI-kW a ~? s? ., Hof th e original wood -saea 4 ; 4.weatment with I per hydroxide at boili water temperature for 1 Sour . Despite the small differenees in the loss on .{hydro l ysis between the second -column_ of T :'tLe IV aid the secon d column of Table III, some eonclua,i:ons may say be vn from a comparison of the analytical d6ke rni,m,a .ons a t. stand . It will be noti'ced -that in every c ape 'td o weight due to the alkali treatment is r a OP gf in each of the constituen - -,= mined, axed .:toms is als* e the orig . ., A. -wmo d I ev : "W I. ' r Ij ~ 1 -. -C• I =P " t err if• j if . 'y J• i _ - - 1 ' . . yy r' ~-" ` !~ ~ :~~ 1, ;L .' , ij.~ each constituent is less in Table IV than in the corresponding part of Table XII . There is always a decrease in th e constituents shown in Table IV as the severity of the hydrolysis increases, with the exception that the lignin during th e first three hydrolyses remains practically constant . The largest variations between the two tables,however, are in the cellulose . Comparing the sixth column o f Table IV with the fourth of Table III, it is seen that th e alkali solubility of the cellulose becomes very high afte r the last four hydrolyses, although there is no orderly in crease in the alkali solubility with increasing severity o f hydrolysis . The lignin, on the other hand, is rendered onl y slightly solid Z by the hydrolysis, and even after the mos t drastic'treatment, with 15 per cent hydrochloric acid, onl y 3 per cent out of the 26 per cent present after hydrolysi s is removed by the subsequent alkali treatment . The methoxyl is removed by the alkali treatment i n increasing amounts as the hydrolysis progresses . Although after the first three hydrolyses the amount of methoxyl de creases while the lignin determination remains stationary , this fact should not be considered an indication that the methoxyl was not a part of the original lignin, since th e chemical method by which the lignin was isolated has bee n shown to Fesult in the loss of a considerable portion of th e methox 1 - _an d_ it is in this relatively unstable portion tha t ~y e p hoxyl . loss on alkali treatment may be suppose d : • - O ' . }i . ". 1 ' „'I f occu -a .1 f whit out great inse, lignin , le -effect on th e 5 per cent pentosans in the h _ ., _ ecre a e nt by the alkali treatment, although in the origin . ood pentosans to the amount of 7 .4 per cent were insolubleal i (Table II) . This high alkali solubility of the p s in the partly hydrolyzed wood was progressive as hy d became ire severe . *I'' x' • r- e gr = -= AL, in; is no abl ' ver lubilit onst i A, 'b¢ OttOMAIW94 tom'= alk 'Itolubility, Table I I to ttrQ c pn . 0 ' Z. otter one' eofis'tx t with eel nex soluble) . In partly hydrolyzed wood the most soluble constituent at all stages of hydrolysis is the cellulose, th e loss in cellulose reaching 12 .8 per cent in two cases . Th e li t in, on the contrary, is very little affected by th e olysis, the lignin of the original wood being almost a s e in alkali as the lignin in the hydrolyzed residues . r-~x - r- : . V - ;7 = ~I ''" }r Remark s . V_I II :' r ~ rp 44: F rY ~ , ~I i y or qv st f v . -Ir • r .7; r~, C . er ex`: hat di►t Irs los e as e avail !•l e ood e partly decaye d I thQ s of te, :I Iff ~~ ay . p l I __ fr Pillrl~ •• }' . I acto condi t • c_ ' At pape r p, pro en . ac = d, shows an : ;mina , •; although it is quit e can no manufacture lign i d pulp .- Another instanc e ht be made from comparativ e nd in the pulping of woo d r i cellulose Hawley and Wise, op . cit ., p . 259 . %Ming and Statdl, '4r • Jl. .• , -8♦1 ' 4 snc e , w . s -ete"rmined a s e analytical re- ' ial might not have ' ic .. } ata on th.' 1 w. od A ed . d ct o is o ans, . tires .+I n w Qf . ' ids " rmi S ±forde d on . . '•-' ' •'t, o Sum ma Mary , . , Although- f ft in-nt. Wf,emt 4** on wood, so far . as removal of cm,st4tuents is apparentl y the same as a hydei*ysi6, yet these two ptoeeb6 .a differ i n their effecIt on the alkali solubility of the resi0e . 2. The total alkali solubility of paVtIV decaye d wood is much greater than that of wood whioh has been hydrolyzed to thel same extent (as shown by equal lmssA41 weight) . 3. The solubility of the lrn :n: alkali is ver y slightly increased by partial hydVolyas-, wa$sZeaq; decay ma y render the lignin 50 per cent soluble . 4. The solubility of the .reRid4al cellw1o6e i, =considerably increased by partial hydrOlyeia l but prObably root to the same extent as it is by decay . 5. There is .in partially hydrolyzed wood ,s ), terialvprobably a degraaation product of the cellulose, whiff not determined as cellaose, -Iignin, or pentosans . Thi s is soluble in 1 per cent sodium hydroxide . t .