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Handbook of Wood Chemistry and Wood Composites

Roger M. Rowell

Cell Wall Chemistry

Publication details https://www.routledgehandbooks.com/doi/10.1201/b12487-5 Roger M. Rowell, Roger Pettersen, Mandla A. Tshabalala Published online on: 06 Sep 2012

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The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The publisher shall not be liable for an loss, actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material. Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Polymers Carbohydrate 3.1 CONTENTS Procedures Analytical 3.8 Juvenile Wood Reaction Wood and 3.7 Wall Cell in Distribution 3.6 Inorganics 3.5 Bark 3.4 Extractives 3.3 Lignin 3.2 of Holocellulose Preparation (Chlorite Holocellulose) 3.8.4 AshContent (ASTM D-1102-84) 3.8.3 Extraction 3.8.2 Procedures Sampling 3.8.1 pH and Inorganics 3.4.5 Lignin 3.4.4 Cellulose 3.4.3 Hemicelluloses 3.4.2 Extractives 3.4.1 Polysaccharides Minor Other 3.1.4 Hemicelluloses 3.1.3 Cellulose 3.1.2 Holocellulose 3.1.1 3 ...... Procedure 3.8.4.5 Reagents 3.8.4.4 Apparatus 3.8.4.3 Sample Preparation 3.8.4.2 Scope 3.8.4.1 Precision 3.8.3.6 Report 3.8.3.5 Procedure 3.8.3.4 Apparatus 3.8.3.3 Sample Preparation 3.8.3.2 Scope 3.8.3.1 Procedures 3.8.2.5 Reagents Materials and 3.8.2.4 Apparatus 3.8.2.3 Sample Preparation 3.8.2.2 Summary and Scope 3.8.2.1 Composition Chemical of Extractives 3.4.1.1 Softwood Hemicelluloses 3.1.3.2 Hemicelluloses Hardwood 3.1.3.1 Roger M. Rowell, Roger Pettersen, and Mandla Tshabalala A. Cell Wall Chemistry ...... 44 64 64 64 64 64 64 64 64 40 46 34 34 48 38 63 63 63 63 63 63 49 37 33 39 45 45 42 62 62 62 62 62 35 47 47 47 43 52 51 41 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 34 minor The H 3.1.1 CARBOHYDRATE POLYMERS 3.1 1984). (Pettersen America North in species available drates, lulose (26–34%), In individual woods oxygen, (18–35%). consist The network Wood References

general, A

major major complete of Preparation 3.8.5 of Chromatography Acetyl by Gas–Liquid Determination 3.8.8 of Methoxyl Groups Determination 3.8.7 Lignin of Klason Preparation 3.8.6

38–49%,

amounts lignin, (angiosperms)

mainly

and of best on

Overall, tree

olocellulose chemical and

carbohydrate the ...... cellulose,

the trace

... Procedure 3.8.5.5 Reagents 3.8.5.4 Apparatus 3.8.5.3 of Method Principle 3.8.5.2 Scope 3.8.5.1 ... Reporting 3.8.8.5 Chromatography Gas 3.8.8.4 Sample Preparation 3.8.8.3 Reagents 3.8.8.2 Scope 3.8.8.1 Report and Calculation 3.8.7.7 Procedure 3.8.7.6 Reagents 3.8.7.5 Apparatus 3.8.7.4 Sample Preparation 3.8.7.3 of Method Principle 3.8.7.2 Scope 3.8.7.1 Additional Information 3.8.6.5 Procedure 3.8.6.4 Reagent 3.8.6.3 Apparatus 3.8.6.2 Scope 3.8.6.1 Report and Calculation 3.8.5.6

defined

and

coniferous species

chemical lower

of lignin of chemical

ash other amounts dry sugar-based

component

pentosan

and hemicelluloses

as content because

23–30%, wood

sugar portion a analysis

species

softwoods composition three-dimensional

of α

...... has

of Hemicelluloses) (Determination -cellulose

of polymers ......

(7–14%) inorganics.

of . . . and polymers ......

hardwoods

. . . . an . . . the ...... accounts (softwoods)

a wood

living elemental pentosans

variation (gymnosperms) and

of content such

is lignin wood.

(carbohydrates, tree . . Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook Simple ...... for ...... composed

and .

......

biopolymer have

within as . .

. all composition ...... 19–26%). is

with

softwoods All starch water, . the

......

compared chemical a

higher

tables

each components but minor of

but and

Table

cellulose such

composite species

65–75%)

in of cellulose in on

pectin

amounts analysis

this

about the

a techniques 3.1

deciduous dry

United

and of chapter shows and (Stamm

50%

weight

wood. that composed content

can of the hemicellulose .

......

extractives,

States

a carbon,

are similarities distinguish cannot

summarize species

summary Vast basis, 1964).

. (40–45%), ......

combined

of (Pettersen amounts

6% be all

an (hardwoods) The

used

wood

and

of among hydrogen, interconnected between polymers data

higher combination

the

with

inorganics.

of to 1984).

cell

for carbohy

data species. identify

lignin lignin

wood hard walls

44% with (cel are 66 66 66 66 66 66 66 68 68 68 68 65 65 65 65 65 65 69 69 69 69 70 67 67 67 67 67 67 - - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Cell WallCell Chemistry FIGURE 3.2 FIGURE 3.1 of cellulose. structure shows apartial an age wood yield. sources (DP). 3.1).(Figure building d Cellulose 3.1.2 hydrogenresponsible (see through for bonding sorption 4). moisture Chapter other d accounts of -glucopyranose -glucose, O The approximate cellulose DP HO H sugars cellulose These Goring CH of number C using H block for 2 10,000 is ellulose OH H d Hardwoods Species Softwoods and Hardwoods for U.S. of Carbohydrate, Compositions Summary Ash Lignin, and TABLE 3.1 Source: Softwoods the -mannose, 65–70% such H molecular (40–45%) of cellobiose. structure Chemical of cellulose. structure Partial and a O for has of OH most molecular nitration would units, as glucose Adapted H cellulose Timell an Chemistry Series20,Chapter2,pp.57–126, H l HO of O abundant -rhamnose average HO d mean the H weight and which CH Holocellulose -galactose, CH units H 64.5 71.7 isolation 2 (1962) weight wood from H OH 2 H OH is H the a ± ± DP linear cellobiose organic are in determinations, 4.6 5.7 H Pettersen, and H O dry hemicelluloses a OH determined of for cellulose linked O d procedure OH at d chain H weight. -xylose, cellulose -fucose. least O chemical α R.C. 43.7 45.4 -cellulose HO H since H together length CH ± ± 9000–10,000 1984. molecule These l 2.6 3.5 H O 2 the -arabinose, These OH that H ranging done the on (15–25%) H H of The Chemistry of Solid WoodSolid of Chemistry The HO average O polymers minimized repeating approximately by OH the Pentosans 19.3 9.8 by polymers is CH H β Washington, DC: H face from ± referred ± light-scattering 2 -(1 2.2 OH O 2.2 N d and H DP HO -glucuronic H are → of are about CH unit H possibly

are the for depolymerization 4)-glucosidic H Klason Lignin 2 called made to O OH H 28.8 23.0 OH in 5 rich as earth. native 10,000 H μ cellulose O ACS. the ± ± m OH up H 2.6 3.0 as in acid, holocellulose in experiments, , degree of It H high hydroxyl Advances celluloses O wood. to is O simple and bonds. HO a H 150,000. 0.3 0.5 as is glucan CH Ash of lesser This a 15,000. ± ± and H 2 0.1 0.3 in polymerization sugars, OH groups two H from Actually and would mean H indicate maximized amounts polymer Figure 3.2 O sugar OH An that mainly, usually several H aver O unit are the the 35 of of - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 36 chain. cellulose asingle within and lose chains FIGURE the and I or native cellulose. between are Waals’ eight one symmetry diffraction The wood-derived hydrogen FIGURE 3.3 There Cellulose cellulose held accessible repeating remaining cellobiose forces. 3.4 together the are bonds. a experiments

atoms = to molecules several I. of cellulose structure crystal of the projection Axial Planar 16.34 Å cellulose unit, and The water, portion moieties. As by nonaccessible. of layers that the projection intermolecular types adjacent microorganisms, has and are packing is is, The indicate consist highly of randomly a b one lower

c cellulose = molecular of glucose 15.72 Å cellobiose density two 6 crystalline Accessible of 2 crystalline packing hydrogen 3 3 cellulose parallel 1 oriented residues in and (Figure of chains wood: Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook cellulose so unit density and and chains chains bonds. on. and 3 cellulose (Figure pack is 3.3, crystalline 2 2 nonaccessible The 6 may 6 have c 6 and

showing 2 increases, = of Gardner in There 10.38 Å surfaces contain 3 3 3.4). anhydroglucopyranose layers a is ( tendency aoi ventricosa Valonia referred are and This some and that of as crystalline (Figure also celluloses noncrystalline 3 structure crystalline much of Blackwell are 2 2 to to 6 6 intramolecular the form as held 3.4). hydrogen amorphous as refer regions intra- together is 65% cellulose The 1974). referred ) units (as to has crystalline and bond unit the are described by hydrogen The cellulose. a intermolecular and to availability are formed. between weak cell space as distance the accessible cellulose contains regions. van above) chains bonds group X-ray cellu Most der of of - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 3.3 lulose with cellulose. found microorganisms. important that nin accessible but WallCell Chemistry stress, nent 1964, abbreviation membered indicates tions letters (xylose carbohydrate, d units. structure ranosyluronic pyranose, with In H 3.1.3 chapter.this lose. cellulose hydrochloric swell explosive.potentially not Kürschner mixture isolation. of dioxide 3% (SO sulfur cellulose. literature glycerol in cellulose by at260°C. is formed III Cellulose heating IV followed

and general, ), and Cellulose Hemicelluloses Cellulose Finally, Another There the often

carbon a on The are

There l 1965,

but in and α lower that

refer and rest

the

of nature

it and c called of is from Kürschner is the by analytical It Mercerization used

d in emicelluloses reprecipitated

not but = cellulose there the ring. becomes

is, nitric also type Cross -glucopyranose, hemicelluloses is arabinose) 10.36 Å ( Whistler are tree. disulfide

to I II DP commonly moisture acid, β evaporation ring

is obtained acid, and part

compression dissolve hemicellulose wood is a refer

the because as three

anomers. cellulose insoluble of is The than standard another

Some and acid

structure. cellulose and are another designate cellulose of crystalline

and which method cellulose to

nonaccessible. in six-membered entries and to cellulose Bevan 3.4Figure the

intimately sorption, and 85% the and by

a it. hemicelluloses form used it d as is 2

important 2% (NaSO sulfite ) and sodium pure III The Richards configuration in noncrystalline -galactopyranosyluronic of

chlorination destroys configuration

also cellulose can Cellulose treatment cellulose ethyl carbon

II. phosphoric wood d Furanose most

(based for under cellulose. which

the the fraction a is for

-galactopyranose, first Cellulose form cellulose be (average soluble contains obtained ). isolating pulping,

conformation alcohol. a associated ammonia. solvents understood

where

each entry sugar five 1970,

is on type some Concepts referred ring because II. of dissolves

of treatment refers It the

xanthate of for Cellulose for acid are monomer DP cellulose

woods

some

consists of is II of cellulose

is chemical by is residue cellulose the Jones wood The of including

method

the hexoses is cellulose nonaccessible. a the usually present of

refluxing with but

Alkali to to it the shortened wood obtained by hemicelluloses. of 100–200) two

water

is a as hydroxyl of consists et al. in of derivative. meal, l degradation

first largely five-membered in cellulose cellulose -arabinofuranose, II

accessible intimately I in Kürschner the of is cellulose optical modification,

strong acid is

with ( in in has a has strong treatment glucose, Figure used

considering so extraction washed 1979). given

polysaccharide wood

hydroxyl followed a very by

space form covered of with a

chair of strong 3 and group ). for mercerization isomers higher acids Most a and cellulose and alkali. The 3.5 in meal large I collection associated and

occurs cellulose containing of making minor galactose,

and with group conformation. the This .

contribute

on alkali. the by derivative from In group the

with of such extractions, ring three the nonaccessible d amounts Alkali

cellulose analytical dried each of carbon washing liquid -galactose

method nitric the sugar d rapidly. a amounts I

conformation glyceraldehydes,

wood) -mannopyranose, (Whistler

cellulose but both and

= as also Regeneration at times of 8.01 Å, entry,

with noncrystalline and cellulose and mainly

will ammonia also carbon

polysaccharide 72% acid–ethanol name. to pyranose is one. hemicelluloses based when of with

often III It converted

mannose). the regeneration lignin procedures for and The make of the contains content cellulose

is derivatives. The

sulfuric gives et al. b cellulose

1 h the

structural other aqueous difficult The four

letter the on interactions referred = third is of

9.04 Å at

and the two with refers sugars the is referred

the second tree 1962, about

for cellulose as the sugars.

some

back designation cellulose a cellulose

d entry The isolation hemicellu mixture configura method acid, section a monomer -glucopy treatment

polymers well to solutions

pentoses of are simplest is to to 1:4 and compo It (

Timell Figure − isolate to Greek

native

-xylo hemi under in

a is entry 80°C to is (v/v) with very

41% as The cel six- lig not

the 37 an II. as of of to is is is a ------Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 38 frequency chains units backbone class Figure Hemicelluloses Hardwood 3.1.3.1 have studied. contain polysaccharides been structures to acidification celluloses A methyl-substituted galactan, to linked unit sugar higher FIGURE 3.5 gradient by the Hemicelluloses

of on the

neutralized of 3.6 lignin

hemicelluloses an

sugars

4-O-methylglucuronic glucuronoxylan,

of of

from of shows elution average

using approximately d most HO of hemicellulose. wood components monomer Sugar content H -xylopyranose α- α- α- β- β- β- β- β- β- wood. they

HOH L L L D D D D D D β a OH 4 H -arabinofuranos -arabinose -araf HO at ------

HO solution acetic

-(1 usually galp galac galac glup glucopyranose glucose wood of groups. partial varying 2

7 contain, C (Timell

CH H → is CH 6

The 3 acetyls topyranose tose H H

2 4) (1 points branch with usually acid. 2 hemicelluloses OH H OH

OH H structure H 5 glucomannan, consist

Hemicelluloses results 1 hemicelluloses

alkali units uronic H H

1982). O Further for per e

2 acid referred O O

OH OH example, 10 of linked in H

concentrations OH

of acid

They units xylose more a

H OH treatment O-acetyl-4-O-methyl-glucuronoxylan H H 1 more

to group have β OH

and Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook

linked OH -(1 usually as are than can

galactoglucomannan, units

complete

glucuronoxylans. not → so

soluble per then one with

CH 4) (Sjöström to on. → been can

10 contain HO OH

3 with the O 2), (1 type be

a The 4-O 4-O 4-O β- β- β- xylose β- β- β- be in

neutral precipitation D D D H H determined. D D D xylan H HO HO -manp -mannopyranose -mannose precipitated HO

-me -meth -meth -x -x -x used alkali acetyl of ylose ylp ylopyranose hemicelluloses →

a H 1981). -α C

CH sugar units. backbone 3), (1 and/or OOH

H ylglucopyranosyluronic acid ylglucuronic acid H H backbone for D

organic 2 This

- OH and groups H GlupA H H a arabinoglucuronoxylan,

The unit The crude

OH H H polysaccharide are Only (Sjöström from

solvent xylan O O side and consisting at

easily H OH α OH

fractionation -(1 C-2 also the → the

are chains from

is H H 6). →

hydrolyzed ratio such

or alkaline substituted contain 1981). sometimes

OH OH OH 2)

C-3 a

are

with contains hardwood. as of

one

of The ethyl quite sugars of

acetyl- solution

an the the repeating

by with arabino

detailed referred

average alcohol

short. a xylose

hemi acids. xylan these

This side and by - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 FIGURE WallCell Chemistry (1 linked arabinofuranose attached backbone averageon the of every 1.3 xylose ( units uronic sisting hexose 3-positions The galactose:glucose:mannose differing backbone slightly 1981). softwoods Table Hemicelluloses Softwood 3.1.3.2 wood species. Table oning the 3.2 shows major the hemicelluloses found hardwoods. in mannopyranose lucuronoxylan. ) (b (a) Another Another Hardwoods O

d 4-β-

-galactopyranose The 3.3 H

HO acid of units.

Glucomannan Glucuronoxylan Hemicellulose Hemicelluloses in Hardwoods Major TABLE 3.2 D branched -X

3.6

2,3 a to

H 1 ylp- shows is polymer

galactoglucomannan Ac backbone

by contains H on hemicellulose major of a carbon H

β 7

Partial the the 4-β- also -(1

their units H the D

-X chain hemicellulose average

O backbone → with 4 -β 1 ylp- OH

contain Type major 6

a of 3)-linked molecular linked

Me 4-O- backbone of galactose

H β

units branches with -(1 that → O β

of D CH hemicelluloses -X

-α Percent in - of (1

→ 2 4-β 1 ylp- d- 3) or 3 2–5%

every H polymer D O are C β -

is GlupA galactopyranose about 4) O -(1 → d- structure H is found 15–30

polymer linked

2–5 4). H polymer galactopyranose

containing xylopyranose → β the content. 2–10 H of - D

d- Wood -X

The 0.1:1:4 4)

1 ylp- principal have a mainly (1 linked arabinopyranose H

as linkages glucomannan xylose 3.8Figure (a) O glucose:mannose OH in

a from

acetyl and while single softwoods

β β Acetyl 4-O-Me- β

galactose. The H in d - - - d d d units -galactose,

units -Glup -Manp -Xylp hemicellulose residues. softwoods. O the structure

(

Figure

polymer ). the groups Units unit H low HO α heartwood and with -

d H high

composed -GlupA

side (5–10%) There H

3.7 galactose representation In a substituted H

-(1 ratio

with

d (1 galactose chain One ). -glucose, H some H

→ → are Glucose (ca. of O varies Molar Ratio

almost is O 3) 2) of

→

larches of by two an 20%)

the branches cases branches O 1 1–2 7 1 6). H 10

β α OH

fraction arabinoglucuronoxylan fraction

on H between - fractions -(1

and O d and main (b) every -glucopyranose

with is them

HO → this H

an d mannose

C H

H of OOH of -mannose 6) hemicelluloses

Linkage unit

a 1 1 1 1 O-acetyl-4-O-methyl- arabinogalactan. has

H 1:2 side an

has d linear l → → → → OH bonds. of H H -arabinofuranose -glucopyranosyl

4 4 2 4

having

and average a these

OCH

H chain ratio

a make OC or 3 O

1:1 The

200 200 DP O

CH (Sjöström polymers and ratio possibly

a of depend 3

is H

of branch 2- up

1:1:3. from

β con

O β

3–4

and the - - Its 39 d of l - - - - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 40 methyl found the also as ester. nofuranose centration treatment Degradation is polysaccharide Both 3.1.4 d FIGURE 3.8 FIGURE 3.7 -galactopyranose, found There Galactoglucomannan Hemicellulose Hemicelluloses in Softwoods Major TABLE 3.3 (Larch wood) Arabinogalactan Arabinoglucuronoxylan Galactoglucomannan softwoods O in are chemicals in t and h 4-β- the of er the 4-β- 4-O-methylglucuronoxylan. arabino of asoftwood structure Partial O-acetyl-galacto-glucomannan. of asoftwood structure Partial other M D polymer this Type d membranes -Manop and D parenchyma -galactopyranose -X inor ylop d membrane minor hardwoods such and acid, -glucopyranouronic -1 -1 P made Percent in olysacc as hemicelluloses 4-β- 4-β- fire in cell 10–15 up 5–35 7–10 5–8 D by the D -X contain retardants - of Glup h ylop walls Wood microorganisms are arides boarded repeating -1 -1 often in 4- small Me O- Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook 4-β- the β β α β α 4-O-Me- β Acetyl α β β α β β 4-β- and in ------found d d d d d d d d l l d d pits -GlupA -Arap -Galp -Xylp -Glup -Manp -Glup -Manp -Araf -Araf D β- -Galp -Galp units inner D softwoods -α amounts -X D -Manop 1 2 wood ylop -G Units 1 6 D between α lupA -G alp as d - of increases d -1 bark - -GlupA acid (Sjöströmgalactopyroanuronic 1981). a preservatives. d -1 minor -galacturonic of 4-β- where that pectins, wood 4-β- D -X Ac permeability 2 or3 part Molar Ratio ylop mainly D 1 etyl -Manop they 10 Trace cells 6 1.3 2 0.1 1 4 1 1 3 1 1–3 2–3 of -1 starch, Pectins the may acid -1 and contain 4-β- pectic α- linked act and D of -Xy in Linkage L are 1 1 1 1 1 1 1 1 1 1 1 1 1 1 -Ara 4β- 1 3 wood as → → → → → → → → → → → → → → lop the proteins. substance. D l 6 4 2 2 4 6 4 4 6 4 4 6 3 6 found f - a -1 -arabinofuranose, Glup α binder. middle -(1 to -1 Average DP → in water-based Pectin 4). 200 100 100 100 high l Pectin lamella. -Arabi Pectin con is is a - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 made (Figure 3.9) Lignins LIGNIN 3.2 α units nose found WallCell Chemistry 3 FIGURE hydrolyzing volume cell syringylpropane is shown in to of “guaiacyl combinations between content ent syringyl, elements consists of acomplex of phenolic substituted units. arrangement content (Adler ofsors lignin 1977). hardwood Structure (Figure 3.9, hol -configuration = 1:2 coniferyl sinapyl alcohol.

Starch Lignin Lignins Lignins Lignins Softwood types (Figure wall

units at

(Sarkanen up in

of of of α

3.9

25%

are the of (Sjöström and of

with -(1 2 lignin.”

hardwoods can is 21%. middle

linked can from

found is C–O–C 3.10Figure

woods. and

Structure

the that wood the 3.9, →

p amorphous, lignin the Chemical linked and be

-hydroxyphenyl the be

Lignin

sinapyl 6) polysaccharides and in softwoods units principal are

predominate isolated

Structure α lamella 35%. classified Hardwood in

cell (amylopectin). highest

CH the 1981). -(1 There

and has together Ludwig OH CH CH

considered woods 2 is 3). (Sarkanen OH

polymer. → (Adler 1977). does

structures wall. The usually alcohols. C–C a

Structure

All from

to is 4) highly reserve concentration

methoxyl

are

in phenylpropane 1),

a not contain secondary

(amylose)

Starch 1971). lignins both wood

linkages. wide

several precursor moieties,

wood mainly in coniferyl

have Amylopectin to of and with The

the Amylose

complex, by

polysaccharide 1 variation be lignins

A lignin normally are

significant

Ludwig a is in ether range content CH ratio ways proposed 72%

an a single or cell

a OH CH CH The several although 2 mainly of polymerization 2 OH

minor precursors. in encrusting α alcohol

consist of

and softwood

can but sulfuric -(1 of wall, occurs

precursors the mainly of

these repeating 1971).

occurs of 18–25%, is

they → carbon be structures structure OCH ways. “syringyl–guaiacyl

precursor amounts middle highly

15–16% about other

4) mainly

substituted

(Figure two in

as 3 are acid. Lignin

with lignin, aromatic, substance.

The a plants. =

aromatic

where

70% varies of

usually unit helix branched. p granules product lamella.

for -coumaryl

carbon

It of of within branches lignin while so-called of CH 3.9, is is

like and three a of constituents

both

structure Small at O distributed the in highly hardwood

the divided

polymers Structure

the type The

Structures cellulose different of linkages biosynthesis

hardwood

different

and lignin Because basic CH softwood lignin

coniferyl alcohol,

about lignin” α OH CH CH Klason 2 amount

three-dimensional 3 units

condensed OH , is

according

building content , composed lignin

throughout or

other lignins (Sakakibara

of every wood the also of 2), of 2 2 as

located OCH lignin γ lignin

and the = alcohol

and of

positions are the phenylpropane solid they coniferyl and

exist (

of 3 than

Fagus sylvatica starch species. 25 hemicelluloses blocks and hardwood

from 3 p to difference softwoods

is -coumaryl

are has of are sinapyl glucopyranosyl state in

in their obtained does the and guaiacyl-

d the

1991).

a a many both

can into -glucopyra of a alcohol,

polymer

copolymer ratio The secondary due are structural

methoxyl cell guaiacyl, not

lignins, also alcohol various precur

differ called in varies lignin to of alco wall. units truly after

and

but the the 4:1 L.) be 41 is - - - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 42 understood. Hundreds used can As EXTRACTIVES 3.3 cellulose. with is associated evidence lignin that complexes weight amolecular has of approximately 11,000. highly closer anative to isolate alignin lignin. 30–50% flour “Milled enzymes represent FIGURE 3.10 CH Lignins The the be 3 O to and name condensed, extracted molecular wood extract of HC HC to O the CH then of that CH are the In give implies, O[ 3 extractives HOCH lignin O lignin” CH lignin. of asoftwood structure Partial other HC native extracted O associated are CH CH them, 2 OH using OH] an HC HC 2 weight 2 OH has O resistant cases, in “enzyme extractives or CH H lignin for HC molecular several 2 O its CH COH 3 Björkman O have CH of with example, it CH with native 3 OCH O lignin is to is 3 OH O CH HC CH not solvents. lignin” suitable been isolated HOCH hydrolysis 3 (also the OH HC 2 HC OH O O C C C weights state clear OH lignin depends 2 water-soluble hemicelluloses identified referred OCH CH that in using why organic In 3 O 3 can Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook from even the some is on they HC H be HC this CH CH to OH much 2 wood. C=O OH[O COH the and under 260 2 isolated solvents as OH cases, O are procedure. or OCH -C natural method CH forming, in to ] closer present HC toluene–ethanol The 3 3 pulping O CH CH O 50 million HOH some OH the by 2 OH (Björkman HC OH HC products) 2 polysaccharides OCH O extractives C using of to HO (Rowe This cases, in 3 extraction. a conditions CH OCH native some a 3 (Goring O vibratory is 3 1989). CH HOH are their 1956, a 3 or O are cases, tedious O HC lignin CH CH 2 chemicals C ether-soluble OH Klason (Obst 2 HC Extractives, HC role classified OH 1962). C O CH can 1957). OH ball

C 2 = OH O lignin–carbohydrate than O procedure in H 1982). be mill lignin, Björkman H HC HC the in 2 Approximately, O removed C Klason by the on such tree There extractives. O O OH the OCH wood fine since but CH CH CH solvent is as 3 lignin. OCH lignin wood 2 using is does pine well that it 3 no is Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Cell WallCell Chemistry age (cork and bark. Bark BARK 3.4 1968). Côté and of extractives (Kollmann for (Figure densed hemlock. mon and structures. are alcohols omy (taxonomy constituents). on chemical based The woods higher pounds. alcohols, adefense some as act and mechanism. Some binder. pitch 3 FIGURE = 4 pinosylvin, The Resins The

the mainly of is found qualitative in is and skin). The of made the extractives durability are They most softwoods extractives a tannins

3.11-5) such These the 3.11

very phenols, resins, Tannins and

outer bark. in found CH One located The HO up extractives

common have 3 pine as

O fats complex of Chemical

and chemicals difference = glycerol of H (Hemingway bark, The

thickness have 5 pinoresinol, in 3 H of three C

also heartwood. 3 content terpenes, in (Gottlieb the are

C CH in are 1 heartwood are cedar OH wood inner 3 4

the been which most made terpene found a layers:

tissue in CH usually and C OCH structures group heartwood 2 wood. wood than in exist of O bark, can O used

important steroids, mainly and up is application extractive the 1989, that

Lignans the (Kai = in

be sometimes hardwoods of 6 and acid, gallic of associated as are Yoshida for which α softwoods periderm

phellem classified is resin -, cell

of monomers, occur 1991). precursors Porter centuries β composed resin and some -, polyphenols are

wall content is acid and in CH

1989). HO

in some Abietic referred (cork acids, referred HO a and HO 1989). with medicine, varies

of sapwood.

into γ 2 is chemicals combination and CH -Thujaplicin to the α to most dimers, of from are Conidendrin cells),

-pinene sugars waterproof three =

fatty rosin, 5 acid other

greatly Gallotannins two α extractives to OH is OH to responsible -, CO of

species

as Resin pinosylvin

cosmetics, β 2 as (Figure acids, classes: phellogen principal H -, and waxes, mainly chemicals, the (Haslam and the (Figure rhytidome of between (Figure

extractives acids

phloem wooden polymers. two respectively. γ to (Figure

in -thujaplicin. 3.11-1) gallotannins, and consisting for species are wood. zones:

and (Figure 3.11-2) (cork phenylpropane have 1989). H 3.11-6) 3 some and many C C the is polymeric

or boats, is as

3.11-4) a O also

cambium), CH in 1 a

bast the color, within In a free O is Tropolones and

= common are 2 3 3.11-3) preservative Fatty other both H γ 6 are abietic the general, of β α inner known used

carboxylic is ellagitannins, OH in other is 3 fats, examples smell, basis CH

complex species softwoods response acids esters minor found which units in bark CH

acid, and type CH CH similar fatty as torches softwoods of are

3 3 and are CH CH the of in the organic (Hillis and and

chemotaxon and acid of is 2 3 3 of in

responsible acids, spruce to = gallic esters

durability. very resin periderm, phellogen and

this chemical structure are the α and

wounds, with function and -pinene, 1989). hard

outer com com

toxic class acid. fatty have con with acid as and the 43 a - - - - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 44 NaOHaqueous (Holloway is used 1973, Deas and 1984). Kolattukudy phenolic step followed extraction sequential elucidation can bark and the pounds 27.5% reported and (NaOH) extractives. loblolly bark of can The 3.4.1 between baphenes, complexes polysaccharides different also wood or xylem the layer from iscambium divided bark by vascular the (Sandved 1992). et al. panion and extraction. Owing The The

presence

also therefore be is

extractives between uses polysaccharides. using, composed

very cells, chemical analysis in

pine complicate E softwood species by acids,

xtractives

bark hot to and (suberin), extraction step of

petroleum an different of

the

parenchyma the may For Polysaccharides Component Bark Hardwood and Average of Softwood Composition Chemical TABLE 3.4 b a Ash Extractives Suberin Lignin andpolyphenols bark

water, the

flavonoids). suberin ethyl that

that

from Data composition of Data content methods (cellulose, hemicelluloses, indicates

interference composition inner of example,

and lead chemical

with are

analysis obtained Quercus suber and several yields obtained alcohol solvents

and even

Suberin,

hardwood

and in to ether, not of

extractives

hexane,

developed that bark a

cells, yields

bark

hemicellulose,

Table outer for waxes, found holocellulose McGinnis from

from types composition Pinus pinaster of step

of the of benzene,

of tends

the bark polyflavonoids, is

the Nunes, L.

ideoblasts, bark

increasing and bark Pereira, species,

chemical that condensed 3.4 in benzene, quite of same Wood Sci. Technol. fatty

(fats, extractives

for to wood lignin,

cells

illustrates suberin is yields (Toman

E., and limit

wood high ethanol, equally H.

bark. acids,

species.

oils, Quilhó,

that Pinus pinaster and of

which constituents Parikh including 1988.

Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook

resulting and polarity. ethyl access condensed bark compared

tannins, IAWA Journal phytosterols, is cannot

pectic monomers et

fats, T., and complex, not lactifers. the Chemical

Pinus pinaster

and al. interfere These polysaccharide ether, begin (1975) and 22:211–218.

11.4 43.7 41.7 of

pure 1.2 1.5

1976). variability other

resin

materials),

in sieve A be Percent Oven-Dry delignification cold Pereira,

and of

± ± ± ± ± common false to

tannins,

0.6 0.2 2.2 2.4 0.9

used apparent and with ethanol,

enough composition

17(2):141–149. reported bark

and Not

from wood,

high acids, with and tubes, resin Proximate water-soluble

H. Quercus suber high

for

an varies all can

1996.

hot of these molecular

the lignin acids,

flavonoids, to protocol but extraction phytosterols, bark cell

fiber

and differences water, values be 19.9% the

permit water. and

residue

Anatomy reagents

between

values classified

analysis

types

chemical Weight lignin directly. waxes, and chemical Quercus suber cells, variability

of and extractives

14.2 39.4 23.0 19.9

begins carbohydrates. Labosky weight 1.2 fractionation polyphenols,

, lignin

occur reported and protocol from and respectively. analysis,

albuminose

and tannins, ± ± ± ± ± 1% depend methods.

into 0.2 1.1 1.7 0.5 2.6

and There

chemical analysis the composition phenolics. of

with

within condensed the sodium in content

four cork lignin terpenes. b (1979) for every

in that

are on procedures terpenes, third a

major

For the hydroxy of loblolly diethyl

species,

the

many cells, in consists in

hydroxide individual bark bark.

The extracted literature

example,

step, the

bark.

method tannins of groups: This release

phlo com bark, com ether third from

bark pine

acid The and 1% for of is - - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 of Extractives Composition Chemical 3.4.1.1 (Chang Mitchell 1955, yieldsand fraction lignin Hemingway 1981, 1991). Laks suberin sugars extraction give neutral ether separate WallCell Chemistry a (Mian xylan xylans, methyl-glucuronoxylan 4-O-methy-glucuronoxylans, are arabino-4-O-methyl-glucuronoxylan sylvatica The H 3.4.2 xylose, rhamnose. and mannose, up sugars. tose, reaching For mainly by extraction procedure. the altered be can structure alkali unit. sugars. are 1960, They weight 1971). Vedantham and (Seshadri dry total the the a 1981). (Hemingway coatings fruit in and fertilizers, and papers hardwood A The

ratio linear lot The Free The Hydrolysable Flavonoids Terpenes

in esters monoterpenes similar

example, waxes hemicellulose

Low the

xylose, of fraction are the 1962).

backbone

solutions of and

and condensed Over composed The the extract components, sugars research or monomers,

about each

alcohols (Dietrichs a of often hemicelluloses. DP

waxes

Timell emicelluloses followed cyclic maximum in xylose to condensed

carboxylic most

Their are 20

mannose,

the bark tannins against are ones

into

are 1:1

fractions found

different α (Hemingway and a

has were

free-sugar structure. a -(1

abundant

1960).

to function of are condensation and units tannins also

content are

group easy-to-analyze found et al.

condensed

phenolic by 1.4:1 glucose

→ been tannins, aqueous as are α in

produced esters

tannins. acids salts extracted

- (Painter

and are hot 2).

glycosides. 1978). the Glucomannans

hydrolysable

and from

of soluble in (Timell

Other

are done of

seems

The

They

one connected

compounds water of content

sucrose. wood. and fall

of and different β et al. a acids, glucomannans, terpenes, sodium -pinenes

the

tannins The fatty

high group Sodium ratio on being

of sugars commercially sugars and (Laks from

fructose in can to 1961b).

extraction above-mentioned two softwood

Other

main 1983). mixtures

polar be Many

is in molecular acids, and of Purves

Hydrolysis

also

tannins of arabinose. bark. barks

bicarbonate

β low

are 1991).

that deciduous or

released xylose based found -(1 from hydroxide and polymers

The hemicellulose an hemicelluloses. hemicelluloses solvents

and

more contain also It tree

→ are dicarboxylic,

Hot

varies antioxidant, is waxes 1960,

flavonoids.

mannans early deciduous of of Other on

have

in this

for major easily barks difficult O-acetyl-galactoglucomannan, weight 5-carbon water

compounds. during firs the a of and These GluU

barks.

polishes, whereas based

15-carbon,

amount various separates from been extraction spring Jiang but the minor

and

insoluble

steps extractives are hydrolyzed the extraction

long-chain

from is in very

sugars hot to hydrolysis

barks isolated

9.3%

on pigment, The pines. In

that rich

glucuronic 10 and hydroxy-fatty, conifer isoprene Sulfuric and functional varies isolate are

free the a general, lubricants,

water the little to

the

hydroxylated

have hydroxylated neutral For

in of for Timell contain

increases then high ether are 1 Birch

sugars barks

from

fatty mono- from

the

yields to with barks

depending Quercusrobur and on example,

monohydroxy pure extract been

tied (2-methy-1,3-butadiene) are give acid

DP subjected bark acid insoluble

hardwood

fraction

bark.

bark

fraction groups. acids 1972, of growth oaks a mannose

additives glucose,

found is fractions about

tannins and

benzoic DP isolated aspen treatment during

and

a groups xylans

as can

tricyclic C-15 galactoglucomannan The

(Nonaka

and of partitioning polyflavonoids Dietrichs on

bark ferulic glycosides, 5% in regulator

The

yields

to is and residue between contain

hydrolysable the

waxes. resin and and are

fructose,

the bark

acid flavonoid

to alcohol from and to of are then free further

most willow,

yields

concrete, unit growing of

23.1%

soluble tannins growing

glucose

et al. derivatives attached soluble acids. glucomannans acids O-acetyl-4-O-

include

sugar barks saponified the 1975).

gives

(Laks At 171 (Laks common fatty the workup or

more galactose,

1985). to monomer for one galactose

insoluble

from (Hergert in

and

fraction Ethanol units are and units season. tannins include

25% soluble carbon diethyl

season simple

1991). galac In Fagus 1991). acids. dilute to time,

free tied

234 and and the the the the

45 of of in to to in - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 46 is less. of crystallinity (cellulose wood degree butlattice the normal as I) grandidentata Populus 125 The lulose 1978). unextracted The 3.4.3 composition. the in some variations 1960). Purves and (Painter arabinogalactan of galactose 1960, Timell and 1961b). Timell of arabinose galacturonic (Timell The DP units 7:3:1. 33 Timell Table 3.5 hydrolysis shows present after sugars bark. the in polysaccharides of the In A Arabinans

outer ( cellulose

backbone Betula papyrifera Betula were

β pectic almost

so 30–50 The -(1

Small 1961b). C the

and bark

of (1961a,b)

ellulose → found high

bark, Picea abies Abies amabilis Species in Hydrolysates Present Tree ofSugars Some Barks TABLE 3.5 Source: Quercus robur Fagus sylvatica Inner bark Betula papyrifera Outer bark Inner bark Pinus taeda Pinus sylvestris Outer bark Inner bark Pinus contoria Picea engelmannii

cellulose 9:1 substance (Timell acid 4)-linked

all have content arabinose

amounts usually is

extractive and

A was cases,

as the α backbone Adapted been

group -(1 side and Reactions and

another 1961b). cellulose

found

content of

contains → ) ) the galactose

has

of Mian chains. reported units to barks to 5)

of content, glucose, from 6900 hemicelluloses in 700 α been

arabinofuranose one is galacturonic

-(1

content the (Toman and

ranges .

usually less Fengel, The W. de.Gruyter, Berlin. ( consisting → ( Pinus contorta Pinus in units bark Pinus contorta Pinus

isolated Timell especially

xylose, 4) cellulose

the ratio

was from 32.3 29.7 28.0 15.8 21.3 30.2 26.8 40.9 35.7 36.6 37.4 Glu D.

et al. low with of with barks and

of spruce (1960), between Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook

acid

and from and found

16% of arabinose manose:glucose:galactose

Wegener, 1976). side

Man than of 0.5 0.2 0.2 2.6 2.5 5.4 2.5 2.5 2.9 6.5 8.0 of units galacturonic

the

rhamnose suberin, polymers

aspen, ) to ). bark barks, chains

found in the

and cellulose

20.2% Bark The 41% Gal and 1.0 2.5 3.1 2.4 4.2 4.3 2.4 1.3 1.6 1.3 3.1 G. bark

inner with side a 1984. spruce,

pure a which in at depending requires cellulose weight

for were are 21.0 16.4 20.1 number Xyl has

3.8 2.1 5.8 3.4 3.7 3.8 4.8 3.2 C6 bark chains the

a acid, is Wood:UltrastructureChemistry,

pine ratio galactan

similar degraded of been and also case contains

(Harun 10.6

average Ara arabinose,

harsh the 2.7 1.8 5.6 2.1 5.5 3.3 1.8 3.2 2.0 3.1 and has average of in

pine on found isolated of a galactose backbone.

32.6% to

was is the

the ratio Rha

conditions

0.1 0.3 0.3 0.3 0.5 1.2 pine, during — — — — and (Painter those water-soluble either of

same in 1.3:1:0.5 method DP

and

4000 Labosky of for these from the UrA 2.2 2.1 4.6 7.7 9.9 8.0 5.6

— — — — the for found galacturonic to

oak galactose A galactose type and average

arabinose

to isolation bark ( highly

polymers of Abies amabilis, amabilis, Abies birch.

with (Dietrichs

0.8 0.2 0.5 0.8 Ac — — — — — — — isolate

Purves 1985). in of extraction. and cellulose

wood crystalline an branched DP One in alone

process. consists average the of acid a (Mian 1960).

is et al. ratio with

10:1 is cel

95 In or of to a - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Hemingway 1981). as bark inner the in is less lignin There lignins from extracted 46.0% give high depending As 3.4.4 WallCell Chemistry 3.13 content of inorganic of some list the woods. for a partial varies concentration of tree. growth. Pb, Shiraishi lates, 1966). amount silica, ture measure The INORGANICS 3.5 tree. content to southern bark sapwood. in than bark in more Ca and bark in sapwoodP in than bark sapwood sapwood; example, (Young as Bark 3.4.5 wood. corresponding the and havedifference found lignins most been between bark (Andersson more phenolic

4.6 a In There 13% with Rb,

of tree inorganic false are Young

compared contents is 38%

carbonates, general, p for however, depending Ca, when 575 -hydroxyphenyl of generally are Sr, and, of 1971, Inorganic Na, L I

other of OH

0.9%; pines (roots, 1991). norganics the is sapwood. with ignin Ca sweetgum high to on Mg, inorganic Ti, ± similar the et and a K, 25°C. 58% groups in including outer in

the lower of of al. Choong

the Au, analyses content alkali

ranging mineral and, values Ca, and to in the Other general, Guinn bark, condensed higher each 1973). and on method (Labosky

ions most normal pH Ga,

bark to Mg, The The outer K ash, to ratio

the outer material and sulfates

(McGinnis the of wood, elements of make element OCH

are al. et In, of (1966) both from salts

cases, units in While Mn, involving inorganic outer of

environmental outer the bark lignin bark

of lignin of a wood. p inorganics La, absorbed 10.4%, willow H 1979). 3 wood and extraction

Zn, and up lignin OCH inner about (Clermont 1976, and

in bark 12.3%, the determined contains is Li, (Volz there varied present content. 80% the

from hydrolysable

and coniferous other lower For and leaves) inorganic Sn, 3 content The bark inner is

contains

bark 3.1 has and Hattula wood groups into are

P 1971). usually of than example, inner Parikh V,

the widely

to (Choong inorganic elemental (Kurth a than a are conditions components, 1970). the condensed some

contains For 12.8%,

and lower the 3.8 and wide or wood can normal the Na, 12.1%, in The ash

11.5% and content bark bound

normal example, tree with Zr referred 1975). concluded within tannins distribution differences aspen and be There

variety pH Martin Si, in et al. (Ellis pH sapwood of Johanson matter composition through quite

more as wood. an

sapwood wood. Smith in ash, than B, to the tannins

is of Other

wood are bark compared average 1976). literature which and carboxyl Mn, to and less 1965).

the bark of and high same

the inorganics the in more The that its 1954, These the elements between in 0.5%; of Klason

than Fe, outer bark. the to compared than sulfuric the

1978, researchers

due inner Gray inner but 0.9%. decreases There the in ash the

12 inorganic species Some of roots both and guaiacyl Mo, fiber

groups woods Higuchi values

to in 0.5% only tree to inorganic 3.4 elements ratio

content red

Harder bark (1971)

bark The functional lignin the is the the the Cu, species. as and

acid (Ellis of after to lives. more oak 20.4% (Sarkanen (Browning

containing compared in

higher 3.5 these 13.1% slightly wood for major presumably total wood units (ash) Zn, have transported

et al. insoluble reported components, pectic which from combustion and outer

probably 1965, compared elements lignin See Na, Ag, The are inorganic when content in found

group and inorganic compared inorganic 1967). of Einspahr K, Pinus taeda Pinus Tables with deciduous materials 8.9%, Al, is essential Young and inorganic the 1967).

to content large Mg, a the suberin an the

lignin due existed content Ba, higher throughout in the the

can Bark Hergert

to same at pH no 3.11 approximate inner Mn, various bark content

elements amounts a

Co, and to a This age 1980). outer to content be

structural pH (Hon values for can tempera

bark

contains contents a that through 0.9%

Zn, ratio content species as

as of bark Cr, higher of is 11.1%, Guinn

of wood small 1971, vary bark bark high oxa part first the

and and and and can For Ni, 4.4 the

47 of of of of in in is - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 The DISTRIBUTION IN CELL WALL 3.6 approximately 4.7. wood. late to wood compared early content as in wasinorganic higher different black 48 cellulose. any, and if little, very and lignin between contact (0.1–0.3%)shrink direction. longitudinal the in layer mechanical is S the in S lamella galactoglucomannan content hemicelluloses. and (13.3%) lamella summerwood. than more lignin contains encrustation sapwood contains (Saka springwood. taken. 2

known because The Saka Figure The Figure 18.3% content is spruce 1991). Softwoods angle 2 pH and and 14–19°. of and layer layer. the is evenly throughout distributed and more elements is 3.12 3.13 as xylan it hemicelluloses. transformed of primary primary properties of even is Goring of ( Table the of Latewood Picea mariana Picea

wood

glucuronoarabinoxylans. shows cell a shows Source: Glucuronoarabinoxylan Arabinan Glucomannan Galactan Cellulose Cell Cell Wall Latewood and in Pine Polysaccharides in Earlywood TABLE 3.6 It the pit The much is fibril less is including are wall Wall Component lowest 3.6 membranes cellulose varies wall (1983) because wall S is the Adapted more cellulose 3 thicker different of

angle. pp. 59–88,New shows higher layer components into contains distribution is wood. contain in The from mainly studied detail heartwood, Na,

microfibrils this the Mill) has layer It the from in (0.7%). S with Mg, from is For 4.2 S 2 the more angle little the

of 2 cell layer composed Saka, one

using as the layer York, NY: Marcel Dekker, Inc. depends ( normal of the Al, S the highest Pinus sylvestris Pinus compared 2 hardwoods, wall The or distribution

components of Heartwood glucomannans is than aspiration S. is S, cell energy-dispersive in formation and Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook no so 1991. the composed K, S the polysaccharides wood, 1 the on low wall. concentration lignin, of

higher layer Ca, most Wood and Cellulosic Chemistry Cellulosic Woodand various Earlywood lignin the to S in 1 of Fe, the

18.6 20.3 56.7 It heartwood of or contains the tree 1.0 3.4 is across of the important 13% the ) shows in of Ni, inorganics S middle composed (84%) to as tyloses microfibril 3 cell the thick species

15.1% bordered layers. 5.3 Cu, cellulose, compared the of x-ray S wall possible more with 1 in ( % lamella S

Zn, Fagus sylvatica Fagus lignin and cell from occurs lignin, 2 structural

and earlywood On layer layers, of from analysis lesser pits and extractives wall angle S 51.7% a where and 3 but sapwood lignin–carbohydrate

to and percentage layers. takes Pb. that 54.3% in the of amounts in earlywood there 87% , of Latewood hardwoods. primary parameters (EDXA). They Chapter scotch lignin, relation pith in wood compared 14.1 24.8 56.2 place the 1.8 3.1 The the cellulose, than ) is hemicelluloses. and to with also cellulose more of tree does 2, basis, pine. in 30.0% the concentration wall. sapwood to latewood hemicelluloses but They softwoods found an the the outer determining lignin Springwood to not The the and earlywood average The cellulose, fiber sample latewood found in bonding swell that middle middle ring and 30.6% the lignin in from axis The and the the 15 S as or of of of is 2

Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Cell WallCell Chemistry or mature. cell more rapidly the as decreases content more Juvenile bril described Juvenile JUVENILE WOOD AND REACTION WOOD 3.7 (Chapterwall 11). Chapter FIGURE 3.13 FIGURE 3.12 gravitational Normal A angle further hemicelluloses, as 15. wood wood in (up wood the Strength the discussion to wall. cell wood of the Schematic pine. of scots wall cell of composition the Chemical has is cells forces, chapter. 55°) the growth a S Hemicellulose Cellulose Lignin lower mature wood 1 properties and and S Hemicellulose Cellulose Lignin abnormal 3 of is Juvenile lignin have density that erect the and develops a distribution of and compared 10.5 woody a high 3.7 6.1 wood and wood gradual 5.2 0.8 - vertical. strength content cells tissue in are the to decrease of related are When mature of early is the than shorter, formed compression hemicelluloses a mature to stages wood. in tree the Hemicellulose Cellulose Lignin hemicellulose in have is distribution of different wood. forced There tree S Hemicellulose Cellulose Lignin smaller wood 2 ML P growth. in Juvenile is out Lignin parts Hemicellulose Cellulose Lignin a as 28.7 40.3 28.0 the cell gradual of of content. compared this cell hemicelluloses of Glucomannan It diameter, 18.4 32.7 wood Glucomannan 9.1 Cellulose physical the pattern wall Lignin Xyn la increase Cellulose The tree has to can larger to lignin either mature properties less 1.4 0.7 8.4 compensate be in in cellulose, cellulose found microfi by the content wood. wind cell are 49 in - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 over cent wood pared 1980, tension as to wood. referred are and or branch referred conditions. woods for 50 wood is normal rounded microfibril mannans

probably Table Table the

of the

Timell and to has

are the abnormal wood

to remaining normal tracheids 3.7

Source: Other polysaccharides Glucuronoarabinoxylan Galactan 1,3-Glucan Galactoglucomannan Cellulose Lignin Cell Wood in Softwoods of Compression Composition Chemical TABLE 3.7 3.8 in

lower the

as lignin angle out responsible

In normal shows

shows Wall Component 1982).

compression and lignin Source: Galactosans Acetyl Pentosans Cellulose Lignin Cell of Tension Composition Chemical Wood in Hardwoods TABLE 3.8 softwoods, Adapted of

wood. lignin

Hill, New

is growing Wall Component that lower

vertical

the

part the Compression the in

wood AdaptedfromSchwerin,G.1958. is

chemical are the

The largely content for modified chemical

from of elastic York.

10–40% and outer the the are

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is Laboratory. critical as may of the much the exact vary to USDA, report information depending analytical Forest these Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Softwoods and Hardwoods American of North Composition Chemical TABLE 3.11 Liriodendron tulipifera Liquidambar styraciflua Laguncularia racemosa Gleditsia triacanthos Fraxinus pennsylvanica Fraxinus americana Fagus grandifolia Eucalyptus gigantea Celtis laevigata Carya tomentosa Carya pallida Carya ovata Carya glabra Carya cordiformis Betula papyrifera Betula nigra Betula alleghaniensis Arbutus menziesii Alnus rubra Acer saccharum Acer saccharinum Acer rubrum Acer negundo Acer macrophyllum Botanical Name

Common Name Yellow-poplar Sweetgum White mangrove Honey locust Green ash White ash American beech Sugarberry Mockernut hickory Sand hickory Shagbark hickory Pignut hickory Bitternut hickory Paper birch River birch Yellow birch Pacific madrone Red alder Sugar maple Silver maple Red maple Boxelder Bigleaf maple — Holo cellulose 77.0 72.0 71.0 69.0 71.0 71.0 78.0 73.0 74.0 77.0 — — — — — — — — — — — — — — α -cellulose 44.0 44.0 45.0 42.0 47.0 45.0 46.0 45.0 46.0 40.0 52.0 40.0 41.0 49.0 49.0 40.0 48.0 50.0 48.0 49.0 44.0 45.0 41.0 47.0 Hardwoods Pento sans 23.0 20.0 17.0 19.0 18.0 20.0 22.0 19.0 20.0 19.0 22.0 18.0 15.0 20.0 14.0 22.0 18.0 17.0 18.0 17.0 19.0 23.0 23.0 23.0 Klason Lignin 21.0 24.0 22.0 21.0 21.0 30.0 25.0 20.0 21.0 23.0 21.0 26.0 26.0 22.0 22.0 21.0 21.0 23.0 21.0 24.0 25.0 18.0 21.0 21.0 1% NaOH 23.0 16.0 15.0 21.0 16.0 10.0 18.0 17.0 15.0 29.0 19.0 19.0 16.0 14.0 16.0 23.0 17.0 18.0 18.0 17.0 16.0 17.0 21.0 16.0 Hot 15.0 Water 5.0 3.0 3.0 4.0 3.0 2.0 2.0 3.0 7.0 7.0 2.0 7.0 6.0 5.0 7.0 5.0 5.0 5.0 2.0 4.0 2.0 — — Solubility EtOH/Benzene 1.0 2.0 6.0 5.0 5.0 2.0 4.0 3.0 4.0 4.0 3.0 4.0 4.0 3.0 2.0 2.0 7.0 2.0 3.0 3.0 2.0 3.0 — — Ether 0.2 0.7 2.1 0.4 0.4 0.5 0.8 0.3 0.3 0.4 0.4 0.4 0.4 0.5 1.4 0.5 1.2 0.4 0.5 0.5 0.6 0.7 0.4 0.7 continued

Ash 1.0 0.3 0.4 0.2 0.6 1.0 0.6 0.8 0.3 0.7 0.7 0.3 0.2 0.4 0.5 — — — — — — — — —

Cell Wall Chemistry Wall Cell 53 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Ulmus crassifolia Ulmus americana Tilia heterophylla Salix nigra Quercus velutina Quercus stellata Quercus rubra Quercus prinus Quercus marilandica Quercus lyrata Quercus lobata Quercus kelloggii Quercus falcata Quercus douglasii Quercus coccinea Quercus alba Prunus serotina Populus trichocarpa Populus tremuloides Populus deltoides Populus alba Nyssa sylvatica Nyssa aquatica Melaleuca quinquenervia Lithocarpus densiflorus Botanical Name Softwoods and Hardwoods American of North Composition Chemical ( TABLE 3.11

continued

Cedar elm American elm Basswood Black willow Black oak Post oak Northern redoak Chestnut oak Blackjack oak Overcup oak Valley oak California blackoak Southern redoak Blue oak Scarlet oak White oak Black cherry Black cottonwood Quaking aspen Eastern cottonwood White poplar Black tupelo Water tupelo Cajeput Tanoak Common Name ) Holo cellulose 73.0 77.0 71.0 69.0 76.0 70.0 60.0 69.0 59.0 63.0 67.0 85.0 78.0 72.0 71.0 — — — — — — — — — — α -cellulose 49.0 47.0 52.0 45.0 45.0 43.0 46.0 50.0 50.0 48.0 46.0 48.0 41.0 46.0 47.0 44.0 40.0 43.0 37.0 42.0 40.0 46.0 47.0 45.0 49.0 Pento sans 19.0 18.0 23.0 17.0 16.0 19.0 20.0 19.0 17.0 17.0 19.0 20.0 18.0 22.0 19.0 20.0 18.0 19.0 23.0 20.0 22.0 18.0 20.0 20.0 19.0 Klason Lignin 19.0 23.0 16.0 27.0 24.0 27.0 19.0 27.0 22.0 20.0 21.0 24.0 24.0 24.0 24.0 26.0 28.0 19.0 26.0 25.0 27.0 28.0 27.0 21.0 21.0 1% NaOH 18.0 15.0 20.0 15.0 16.0 21.0 20.0 14.0 16.0 20.0 19.0 18.0 21.0 22.0 21.0 15.0 24.0 23.0 26.0 17.0 23.0 20.0 19.0 18.0 18.0 Hot 10.0 11.0 Water 3.0 2.0 4.0 3.0 4.0 4.0 5.0 3.0 2.0 4.0 6.0 8.0 6.0 7.0 5.0 9.0 5.0 6.0 6.0 6.0 4.0 3.0 — Solubility EtOH/Benzene 2.0 4.0 2.0 5.0 4.0 5.0 5.0 4.0 5.0 7.0 5.0 4.0 5.0 3.0 3.0 5.0 3.0 3.0 2.0 5.0 2.0 3.0 2.0 3.0 — Ether 0.3 0.5 2.1 0.6 0.2 0.5 1.2 0.6 0.6 1.2 1.0 1.5 0.3 1.4 0.4 0.5 0.9 0.7 1.2 0.8 0.9 0.4 0.6 0.5 0.4

Ash 0.4 0.7 0.2 1.2 0.4 0.4 0.3 0.9 0.4 0.4 1.4 0.4 0.1 0.5 0.4 0.4 0.5 0.6 0.7 — — — — — —

Handbook of Wood Chemistry and Wood Composites Wood and Chemistry Wood of Handbook 54 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Pseudotsuga menziesii Pinus taeda Pinus sylvestris. Pinus strobes Pinus sabiniana Pinus resinosa Pinus ponderosa Pinus palustris Pinus monticola Pinus elliottii Pinus echinata Pinus contorta Pinus clausa Pinus banksiana Pinus attenuata Picea sitchensis Picea mariana Picea glauca Picea engelmannii Libocedrus decurrens Larix occidentalis Larix laricina Juniperus deppeana Chamaecyparis thyoides Abies procera Abies lasiocarpa Abies concolor Abies balsamea Abies amabilis

Douglas fir Loblolly pine Scotch orscotspine Eastern whitepine Digger pine Red pine Ponderosa pine Longleaf pine Western whitepine Slash pine Shortleaf pine Lodgepole pine Sand pine Jack pine Knobcone pine Sitka spruce Black spruce White spruce Engelmann spruce Incense cedar Western larch Tamarack Alligator juniper Atlantic whitecedar Noble fir Subalpine fir White fir Balsam fir Pacific silver fir 66.0 66.0 68.0 68.0 71.0 68.0 69.0 64.0 69.0 68.0 66.0 69.0 56.0 65.0 64.0 57.0 61.0 67.0 — — — — — — — — — — — 43.0 45.0 37.0 48.0 44.0 40.0 41.0 43.0 46.0 49.0 42.0 44.0 45.0 45.0 47.0 45.0 46.0 47.0 41.0 44.0 43.0 46.0 45.0 45.0 44.0 43.0 47.0 45.0 43.0 Softwoods 13.0 10.0 12.0 11.0 10.0 12.0 11.0 11.0 10.0 12.0 11.0 12.0 10.0 11.0 13.0 14.0 12.0 9.0 6.0 9.0 8.0 5.0 9.0 9.0 8.0 8.0 9.0 9.0 7.0 29.0 28.0 34.0 27.0 26.0 34.0 33.0 29.0 29.0 28.0 29.0 29.0 27.0 27.0 28.0 27.0 27.0 26.0 26.0 30.0 25.0 27.0 28.0 26.0 27.0 27.0 27.0 27.0 27.0 12.0 11.0 16.0 14.0 16.0 16.0 10.0 12.0 13.0 11.0 11.0 13.0 11.0 15.0 12.0 13.0 16.0 12.0 13.0 13.0 12.0 13.0 12.0 13.0 11.0 12.0 11.0 — 9.0 3.0 2.0 3.0 6.0 7.0 3.0 3.0 2.0 3.0 5.0 4.0 3.0 4.0 2.0 1.0 4.0 3.0 4.0 4.0 3.0 4.0 3.0 2.0 4.0 2.0 3.0 3.0 4.0 3.0 4.0 3.0 6.0 1.0 4.0 5.0 4.0 4.0 4.0 4.0 3.0 3.0 5.0 1.0 4.0 2.0 2.0 2.0 3.0 2.0 3.0 7.0 6.0 3.0 3.0 2.0 3.0 3.0 — 1.3 2.0 1.6 3.2 2.5 5.5 1.4 2.3 3.3 2.9 1.6 1.0 3.0 0.7 1.0 1.1 1.1 0.8 0.8 0.9 2.4 2.4 0.6 0.6 0.3 1.0 0.7 — — continued

0.2 0.2 0.2 0.2 0.5 0.2 0.2 0.4 0.3 0.4 0.3 0.2 0.3 0.3 0.2 0.3 0.4 0.3 0.3 0.4 0.5 0.4 0.4 0.4 — — — — —

Cell Wall Chemistry Wall Cell 55 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Source: Tsuga mertensiana Tsuga heterophylla Tsuga canadensis Thuja plicata Thuja occidentalis Taxodium distichum Sequoia sempervirens Botanical Name Softwoods and Hardwoods American of North Composition Chemical ( TABLE 3.11 AdaptedfromPettersen,R.C.1984. continued Mountain hemlock Western hemlock Eastern hemlock Western redcedar Northern whitecedar Bald cypress Redwood secondgrowth Redwood oldgrowth Common Name ) The ChemistryofSolid Wood Holo cellulose 60.0 67.0 59.0 61.0 55.0 — — — α -cellulose , Advances inChemistrySeries20,Chapter2, pp.57–126, 43.0 42.0 41.0 38.0 44.0 41.0 46.0 43.0 Pento sans 14.0 12.0 7.0 9.0 9.0 9.0 7.0 7.0 Klason Lignin 27.0 29.0 33.0 32.0 30.0 33.0 33.0 33.0 1% NaOH 12.0 14.0 13.0 21.0 13.0 13.0 14.0 19.0 Washington, DC: Hot 11.0 Water 5.0 4.0 4.0 5.0 4.0 5.0 9.0 Solubility ACS. EtOH/Benzene

< 14.0 10.0 5.0 4.0 3.0 6.0 5.0 1.0 Ether 0.9 0.5 0.5 2.5 1.4 1.5 0.1 0.8

Ash 0.5 0.4 0.5 0.3 0.5 0.1 0.1 —

Handbook of Wood Chemistry and Wood Composites Wood and Chemistry Wood of Handbook 56 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Pinus radiata Pinus banksiana Picea rubens Picea mariana Picea glauca Picea abies Larix laricina Larix decidua Juniperus communis Gingo biloba Abies balsamea Ulmus Americana Quercus falcata Populus tremuloides Populus deltoides Platanus occidentalis Liquidambar styraciflua Fagus grandifolia Betula papyrifera Betula alleghaniensis Acer saccharum Acer rubrum Scientific Name WoodsPolysaccharide American ContentNorth of Some TABLE 3.12 Radiata pine Jack pine Red spruce Black spruce White spruce Norway spruce Tamarack Larch Juniper Ginko Balsam fir White elm Southern redoak Quaking aspen Eastern cottonwood Sycamore Sweetgum Beech White birch Yellow birch Sugar maple Red maple Common Name Glu 47 43 39 46 43 47 52 46 42 46 44 44 45 43 46 46 41 40 46 52 41 49 15 15 18 19 26 20 15 19 12 19 17 Xyl 6.5 7.1 6.2 6.0 9.1 7.4 4.3 6.3 6.9 4.9 6.4 Hardwoods Softwoods < Gal 1.4 2.2 0.8 1.2 0.6 0.9 0.1 0.6 2.8 1.4 2.2 2.0 1.2 2.3 2.3 2.0 3.0 3.5 1.0 0.9 1.2 2.0 Arab 0.6 0.6 0.3 0.5 0.5 0.6 0.8 0.5 2.7 1.4 1.4 1.5 1.5 1.4 1.0 2.5 1.0 1.6 0.5 0.6 0.4 0.5 2.9 2.0 3.1 2.1 1.8 3.6 2.3 2.4 12 10 12 9.4 11 9.5 13 11 9.1 10 12 2.4 2.0 2.1 Mann Uronic 4.8 5.1 4.8 4.6 4.2 4.4 3.5 2.5 3.9 4.7 5.1 3.6 5.3 2.9 4.8 5.4 4.6 3.4 3.6 4.5 4.3 — Acetyl 1.9 1.2 1.4 1.3 1.3 1.2 1.5 1.4 2.2 1.3 1.5 3.9 3.3 3.7 3.1 5.5 3.9 4.4 3.3 2.9 3.8 — Lignin 27 29 28 30 27 29 29 26 31 33 29 24 24 21 24 23 24 22 19 21 23 24 continued

Ash 0.2 0.2 0.3 0.3 0.3 0.5 0.2 0.2 0.3 1.1 0.2 0.3 0.8 0.4 0.8 0.7 0.2 0.4 0.2 0.3 0.3 0.2

Cell Wall Chemistry Wall Cell 57 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Source: Tsuga canadensis Thuja occidentalis Pseudotsuga menziesii Pinus taeda Pinus sylvestris Pinus strobus Pinus rigida Pinus resinosa Scientific Name WoodsPolysaccharide American ContentNorth of Some ( TABLE 3.12 Adapted from continued Pettersen, Eastern hemlock Northern whitecedar Douglas-fir Loblolly pine Scots pine Eastern whitepine Pitch pine Red pine Common Name ) R.C. 1984. The Chemistry of Solid Wood Glu 44 43 44 45 44 45 47 42 10.0 Xyl 5.3 2.8 6.8 7.6 6.0 6.6 9.3 , Advances Gal 1.2 1.4 4.7 2.3 3.1 1.4 1.4 1.8 in Chemistry Arab 0.6 1.2 2.7 1.7 1.6 2.0 1.3 2.4 Series 11 8.0 11 11 10 11 9.8 7.4 Mann 20, Chapter Uronic 3.3 4.2 2.8 3.8 5.6 4.0 4.0 6.0 2, pp. 57–126, Acetyl 1.7 1.1 0.8 1.1 1.3 1.2 1.2 1.2 Washington, Lignin 33 31 32 28 27 29 28 29 DC:

ACS.

Ash 0.2 0.2 0.4 0.3 0.4 0.2 0.4 0.4

Handbook of Wood Chemistry and Wood Composites Wood and Chemistry Wood of Handbook 58 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Quercus prinus Quercus nigra Quercus marilandica Quercus ilicifolia Quercus falcata Quercus coccinea Quercus alba Populus deltoids Platunus occidentalis Persea borbonia Oxydendrum arboreum Nyssa sylvatica Nyssa aquatica Magnolia virginiana Liriodendron tulipifera Liquidambar styraciflua Gordonia lasianthus Fraxinus Americana Fagus grandifolia Cornus florida Carya tomentosa Carya illinoensis Carya glabra Aesculus octandra Acer rubrum Scientific Name United States (Percent Wood) Southeastern of Oven-Dry the from Hardwoods of Selected Composition Chemical TABLE 3.13 Chestnut oak Water oak Blackjack oak Scrub oak Southern redoak Scarlet oak White oak Eastern cottonwood Sycamore Redbay Sourwood Black tupelo Water tupelo Sweetbay Yellow poplar Sweetgum Loblolly-bay White ash American beech Flowering dogwood Mockernut Pecan Pignut hickory Yellow buckeye Red maple Common Name 40.8 41.6 33.8 37.6 40.5 43.2 41.7 46.5 43.0 45.6 40.7 42.6 45.9 44.2 39.1 40.8 43.8 39.5 36.0 36.8 43.5 38.7 46.2 40.6 40.7 Cell Carbohydrates Total Hemi 29.1 29.1 29.4 35.4 27.7 30.2 26.7 25.8 30.4 29.9 34.8 28.2 27.5 24.2 29.2 28.4 26.6 27.2 25.6 34.6 27.3 24.0 37.7 28.0 30.7 Gluco 4.1 3.8 2.7 3.4 1.5 1.6 1.1 3.6 3.5 2.9 3.0 2.0 1.0 1.7 2.3 3.1 4.4 2.3 1.0 1.3 3.6 3.5 4.3 4.9 3.2 mann Components ofHemicelluloses AcGlu UrXyl 22.1 22.1 23.5 27.2 21.5 24.7 22.1 18.6 23.5 23.8 28.9 21.0 22.3 18.6 23.3 21.0 16.8 22.3 23.2 31.9 18.0 18.6 20.2 20.1 21.4 Arab Gal 1.1 1.4 1.3 1.0 1.3 1.6 1.2 1.0 1.6 1.8 2.2 2.3 1.8 1.7 1.4 1.6 1.6 1.4 0.9 1.0 1.0 0.8 1.6 0.7 1.3 Pectin 1.8 1.9 1.8 5.0 3.5 2.3 2.3 2.6 1.9 1.4 0.7 2.9 2.4 2.2 2.2 2.7 1.8 1.2 0.5 0.4 4.8 1.1 1.6 2.4 4.9 Lignin 22.3 19.1 30.1 26.4 23.6 20.9 24.6 25.9 25.3 23.6 20.8 26.6 25.1 24.1 30.3 22.4 21.5 24.8 30.9 21.8 23.6 23.2 23.2 30.0 23.3 Total Ext 6.6 4.3 6.6 8.0 9.6 6.6 5.3 2.4 4.4 5.0 3.6 2.9 4.7 3.9 2.4 5.9 5.2 6.3 3.4 4.6 5.0 3.4 3.4 3.1 5.3 continued

Ash 0.4 0.3 1.3 0.5 0.5 0.1 0.2 0.6 0.1 0.2 0.3 0.6 0.4 0.2 0.3 0.2 0.3 0.4 0.3 0.4 0.6 0.6 0.5 0.3 —

Cell Wall Chemistry Wall Cell 59 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Note: Source: Ulmus Americana Sassafras albidum Quercus virginiana Quercus velutina Quercus stellata Quercus rubra Scientific Name United States (Percent Wood) Southeastern of Oven-Dry the from Hardwoods of Selected Composition Chemical ( TABLE 3.13 Cell =Cellulose. AdaptedfromPettersen,R.C.1984. continued American elm Sassafras Live oak Black oak Post oak Northern redoak ) Common Name The ChemistryofSolid Wood 42.6 45.0 38.1 39.6 37.7 42.2 Cell Carbohydrates Total Hemi 26.9 35.1 22.9 28.4 29.9 33.1 , Advances inChemistrySeries20,Chapter2, pp.57–126, Gluco 4.6 4.0 1.0 1.9 2.6 3.3 mann Components ofHemicelluloses AcGlu UrXyl 19.9 30.4 18.3 23.2 23.0 26.6 Arab Gal 0.8 0.9 1.7 1.1 2.0 1.6 Washington, DC: Pectin

< 1.6 0.1 1.9 1.9 2.3 1.6 Lignin 27.8 17.4 25.3 25.3 26.1 20.2 ACS. Total Ext 13.2 1.9 2.4 6.3 5.8 4.4

Ash 0.8 0.2 0.6 0.5 0.5 0.2

Handbook of Wood Chemistry and Wood Composites Wood and Chemistry Wood of Handbook 60 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Source: Tsuga Canadensis Tilia Americana Quercus falcate Quercus alba Populus tremuloides Populus deltoids Pinus strobes Picea rubens Liquidambar styraciflua Fraxinus Americana Betula papyrifera Acer rubrum Abies balsamea Scientific Name Woods of Some Composition Elemental TABLE 3.14 AdaptedfromPettersen,R.C.1984. Eastern henlock Basswood Southern redoak White oak Quaking aspen Eastern cottonwood Eastern whitepine Red spruce Sweetgum White ash White birch Red maple Balsam fir Common Name The ChemistryofSolid Wood Ca ppt 0.3 0.7 0.8 0.8 1.0 0.1 0.3 0.5 1.1 0.9 0.2 0.8 0.55 K ppt 2.6 0.3 0.7 0.8 0.4 2.8 0.6 1.2 1.2 2.3 0.3 0.2 0.3 , Advances inChemistrySeries20,Chapter2,pp.57–126, Mg ppt 0.18 0.12 0.27 0.11 0.35 0.03 0.31 0.27 0.29 0.07 0.07 0.34 1.8 P ppt 0.01 0.15 0.03 0.12 0.02 0.10 0.05 0.15 — — — — — Mn ppt < 0.03 0.07 0.13 0.15 0.01 0.01 0.03 0.2 0.03 0.14 0.08 — — Fe ppm 100 — — — — 10 11 13 30 12 10 14 6 Cu ppm — — — — — 17 73 4 5 5 7 5 4 Washington, DC: Zn ppm — — — 38 17 30 11 19 28 29 11 2 8 ACS. Na ppm 940 63 44 21 81 31 18 6 5 9 8 9 5 Cl ppm

0.3 — 38 — 15 — — 19 — — 10 18 —

Cell Wall Chemistry Wall Cell 61 Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 parts anatomical Different a. sample was Date taken 2. Sampling: c. sampled tree of the Part b. location Geographic a. wood: of the 1. Source laboratories. different workers conditions 62 Materials and Reagents 3.8.2.4 Apparatus 3.8.2.3 mesh (0.40 40 pass to ground mm) using aWileyare Mill. milled parts. to It Preparation Sample 3.8.2.2 so could extractives analysis.lulose, hemicellulose, cellulose, lignin and Wood materials Summary and Scope 3.8.2.1 3.8.2 analyses. chemical technique reporting and 4. Calculations applied method Drying used procedure 3. Analytical d. Sample size c. of biological any Degree if deterioration, b. is

avoid on. following analysis:The should chemical each accompany information one volume one volume mix and of ethanol ofToluene–ethanol toluene mixture, Toluene, reagent grade (ethylEthanol alcohol), proof 200 Vacuum oven hood fume Chemical action boiling for taming granules or any inert boilers, beads, chips,glass Boiling or equivalent device, mantle Heating heating Soxhlet extraction tube mL, 500 extraction flask, apparatus, Extraction thimbles Extraction Buchner funnel Neutral This All highly

Dry be the while method in

E fungal applied xtraction

samples above-mentioned solvents, different and recommended in frozen

wood. procedures attack. describes =

according Extractives are

water, laboratories. However, order oven Peel to a

toluene

used. to procedure dried have to off criteria

the other prevent holocellulose the Without

This a

for nature or fresh

bark could

solvents ethanol, h 24 for way, oxidation

sample. of from Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook this extraction (usually contribute

extractives it

+ ranging or information, may lignin the

combinations or If stem at not, other be of

105°C) in + from

possible wood (ash). inorganics and keep and one undesirable

it diethyl sample the separate way prior is for

of not to

sample further solvents or

reproduce ether possible type, another milling. chemical the

frozen analysis,

to that

are sample

1% to

toward employed is, the Wet compare

reactions. or NaOH,

bark, such results into in samples a variations

refrigerator

leaves, component as

and to data by Samples holocel

remove

can so other from

and on, be in - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Generally, not vent, tion liquid bumping. toluene:ethanol tor vacuum Weigh Procedures 3.8.2.5 WallCell Chemistry the temperature. cover indicated of at as portion covered tends is directly balance. weigh cover crucible and ture, the analytical on the at Carefully Procedure 3.8.3.4 of 575 atemperature adjusted maintain to silica Crucible: Apparatus 3.8.3.3 weight avacuum in oven at105 the 5 mg Obtain Preparation Sample 3.8.3.2 quantitatively them. to equal necessarily longer The Scope 3.8.3.1 3.8.3 the for 95% polarity matrix

575 well

the Place

moisture 1 for toluene/ethanol fiber.

exceeding

with ash

alcohol, and

or least

may boiling

and ±

residue 1 of can 2–3

a carbonized, 25°C.

added

less, oven

of content over during flare A necessary

all, h representative

wash A the clean the

Carry by

allow

and solvents the 3 h be also g platinum

a toluene:ethanol

Reweigh the a sample not however, up of so

After

and

used. burns

the the extraction

specimen 45°C

low ontent weigh. as the

this

mixture

of be

that

out samples or exceeding absence the

much

sample samples

add

longer to

fiber

empty done. mixture.

flame

may lose

step. ignition, taking

the Analytical siphoning crucible for and with burn crucible

the Then ( more two sample

is as ash be ASTM D extraction

in 24 of

the

If Pettersen is crucible into is

if of

defined off

ash a

practicable,

with

necessary.

successive

care a about the unknown,

h. 45°C

complete

during

flame. a needed, as place

cool mixture, nature black or

500 all

Bunsen and to covered

When

of from the

± crucible ethanol. dish

balance

3°C. not the

cool for

slightly the 5 g

and mL -1102-84) as

the

calculate

flame in particles, (1984)

Place charring, of

carbon.

with the

to 24 the

to fiber,

dry,

a cover, take determine Browning

burner thimbles extractives.

somewhat. round extractions,

of preweighed

blow

well-ventilated h, burn extractor Place moisture-free is this

residue having

subsides.

± lid and

the the

extracted

or remove too 25°C. the preferably

It the

and or

stage; to

bottom remove portions the weighed place

crucible off (or

them is small thimbles cover

a in

percentage remaining a ignite a it

(1967)

crucible preferably

constant is all

measure

Then by Second

Soxhlet sensitivity

Continue them 4

however, in extraction no

pine

to h

is the drying flask

ground the a

the

wood specimen

in them of

with less

recommended. hold

chemical desiccator.

suggests

from

place

to sample carbon.

the the crucible vacuum

should

weight. and

of with extraction than

after

based a ethanol

to on a

the for

heating

the to furnace mineral ash the

of corresponding desiccator

constant the thimbles. in

the

pass ashing,

four entire

several ignition 4

0.1 mg. with

extractability fume extractors, be

When from

oven on Cool third When h

from

hearth

the desiccator

followed

of covered, times

with a

the

salts units. at

acetone/water, If

40-mesh specimen,

successive crucible.

hood over weight

the

the preferably extractions

boiling the

platinum 575 ignition Place at cooled for moisture-free Electric

the

of in per

575 thimbles

crucible.

night Place

furnace, specimen drain

an ±

for the

the with burner or

in hour. and 25°C depends

the ±

screen.

to hour

Burn at chips

fiber, 2 25°C a

furnace)

gently at

muffle extraction

200

in room muffle the h,

distilled

least

thimbles with

cool

not

temperatures

complete, After

for only

duplicate. followed keeping If

replace and

the

but excess to

to mL

for a

Weigh, weight available,

a upon tempera

partially different burn a

constant to desicca

furnace furnace

prevent sample it sample as extrac until

weigh. period 3 h,

of water room is

with long

sol

the not the the the the

63 by as

or of

to If it a - - - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 can for reported the The Precision 3.8.3.6 0.1%. is less ash than the if figure significant Report Report 3.8.3.5 64 disc is funnel end without completely lost be (Rowell also remove but hemicellulose will will 1980). more lignin the acid and reaction in To Procedure 3.8.4.5 Reagents 3.8.4.4 Apparatus 3.8.4.3 of holocellulose. 9.2 The Preparation Sample 3.8.4.2 of holocellulose purity is checked following analysis. standard lignin The method. (1) chlorination to Browning Holocellulose Scope 3.8.4.1 P 3.8.4

removed. a

Addition NaClO chlorite, Sodium Acetic reagent acid, grade hood fume Chemical Filter paper Water bath Erlenmeyer mL 25 flasks Erlenmeyer250 mL flasks Buchner funnel

g 2.5 the is

ignition polysaccharides

of 1 g results 250 mL sample glass and skipped

24 determination significant until the

of further

of flask. as 1 g

h thimble, p re

sodium

ash

sample, of being

separated

of temperature If should of the sodium Erlenmeyer

aration (1967) for duplicate

is reaction,

the The 0.5 as

addition yellow method, defined some

losses a

weight

chlorite mL wash mixture

add be percentage accordance and there chlorite

from of

reason, extractive

acetic

determinations color

mL 80

cool ash.

in affects the with of H as

flask. (2) of

are sodium,

2 are acetic lignin.

olocellulose a 80% grade, , technical is

application Special the

the are modified

(the acetone, acid water-insoluble the heated three of added.

of An

the with

holocellulose sample added and

hot weight color

the acid

and

It optional calcium, weight

precautions ways

this moisture distilled usually in moisture-free

After vacuum-oven should chlorination and 1

with

of of

and

a of g method.

(

Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook of water holocellulose

excess of of sodium the C

mL 25 shaking. each irons, filter

preparing

h the takes sodium

be carbohydrate water, is lorite extractives free

are

bath desired, suspected

ash,

Porcelain succeeding chloriting the

and

chlorite and 6–8 Erlenmeyer required method, wood

dry 0.5 mL

The at holocellulose chlorite only

copper

holocellulose prepared

olocellulose 70°C. h

at filter

should delignification

values if white)

105°C crucibles fraction in should

acetic in two and they chloriting

hour,

at the After

the the

flask

repeated temperatures

significant after

(3)

obtained differ and

for water

holocellulose use

acid, fresh be on accounted of

min, 60

can chlorine 24 is

and )

the avoided. Procedure filter of

wood

and

by inverted

bath

and h,

also process

portions

platinum until odor

their

more at place

the paper figures, 1 g

0.5 mL 575 for materials. be

over dioxide

for

the

of Continued modified

sample

than of used on in in

over degrades

± 9.2. in

chlorine of

using

crucibles.

wood sodium 600°C.

a 25°C the a the

0.5 mL

desiccator of 0.5

tarred in night. If and

to neck

calculation

can acetic most According

Procedure a

mg. should sample methods:

only Buchner

reaction some chlorite chlorite dioxide

fritted At

of There acetic

Since cases acid

one

left the the

for be

of is Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Extractive-free, Principle of Method 3.8.5.2 or cold 5% NaOH. alkalies, hot dilute lose The Scope 3.8.5.1 P 3.8.5 holocellulose an WallCell Chemistry adesiccator in for weighing bottle and 1 hbefore weighing. bottom an free tilled draw cellulose cellulose applying steptwice. suction. again this and Repeat water, crucible particles residue with glass for at20°C allow 1 hbefore stand to and filtering. for 45 NaOH time min. treatment total the making 30 min Continue vals, tion. lightly beaker, provided Weigh Procedure 3.8.5.5 Reagents 3.8.5.4 times. positionupright atall of A Apparatus 3.8.5.3 residue as defined thermostat

20 additional Pour Filter Add Acetic 10% acid, solution hydroxideSodium solution, NaOH, 17.5 8.3% and porosity. of medium thimbles glass or fritted crucibles of Alundum Filtering hour, preparation of is 100 mL After add off crucible ± water carefully defined with 0.1°C acid out cover and 33 mL in 15 mL

is have the the by to and with 5 mL this p re the the facilitated about at as the a sides suction acetic cellulose

of aration or 250 mL with glass in should weigh. 20°C been crucible, of a indicated procedure addition as of of acid 8.3% other breaking lignin-free more glass a of medium distilled the with 2 g container 10% α a rod α acid. transferred but, and soluble-cellulose. hemicellulose content. The the represents fraction watch treatment

-cellulose be NaOH cell The constant-temperature

of of by cover. of of with a with acetic of

continue while allow determined distilled by cloth vacuum-oven-dried Without

the releasing

up wall until α porosity. the water holocellulose glass, litmus - holocellulose the a large solution cellulose Add the NaOH flat acid first the to and for components is from the aid at cellulose and drain the water a end 10 mL enough cellulose releasing 3 min paper. portion at place 20°C the continuous Transfer NaOH of

and solution, at the maintain washing room so ( suction completely. suction, through 20°C.

from that 250 mL to subtracted it of should Give is to mat etermination of overnight is temperature the is device that the 17.5% treated hold all entire 17.5% holocellulose still After consumed. the at and at with the into procedure mixture. suction, filling the

the are not 20°C 20°C beaker a time covered cellulose NaOH will thoroughly Repeat specimen cellulose row

the the a with holocellulose readily

NaOH from contain in glass the in with the be NaOH tarred, of an fill into Thoroughly

to NaOH a

of Allow solution the from required with crucible the at suction water solution rod oven the hydrolyzed the H and a distilled

the in

least any becomes weight final washing wash emicelluloses stir alkali-resistant so crucible. acid, Procedure the crucible and place crucible, to bath. the

residue as lignin to three is washing the crucible. that to dry to solution

then release to mix released; water, of the mixture within Manipulate the into soaked mixture

until separate will by at the

250 mL almost Washing holocellulose and the with to drawing specimen, 105°C. 9.4. hot

prepared a by making maintain the Dry the has the

) contents 6 mm 250 mL the to then dilute with The acetic Alundum drawing, suction. to with cellulose crucible, any passed beakers the

stand Cool lignin the the the the term apply the of certain crucible

lumps at mineral holocellulose. the acid, a sample holocellulose of top glass acid in the temperature NaOH the 5 min at through

Subject by hemicellu the content or kept glass suction a and residue 20°C with top with crucible 250 mL present, suction, into that fritted- beaker beaker on acids, in inter wash in solu with rod. dis the the the the the the

for all 65 an of to is - - - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 .. P 3.8.6 where Calculate Report Calculation and 3.8.5.6 66 possibledone indicate to content. protein when Condensation AdditionalInformation 3.8.6.5 content weights. from lignin weigh. and Klason hour Calculate an the rinsed Remove sugars secondary a sample. To weigh Prepare Procedure 3.8.6.4 Reagent 3.8.6.3 Apparatus 3.8.6.2 acid lignin. sulfuric called cedure (milled-wood study Klason Scope 3.8.6.1 water Fucose, 24.125 4% %in H H acid, Sulfuric Glass 2.1 micro-filter, cm No. Cat 1827-021,Filter paper, Whatman 934-AH Glass fiber Water bath Glass rods Desiccator 8240 Pyrex tube, centrifuge 100 mL Buchner funnel Autoclave W W the residue 1 2

tissues of = = out are into is sample holocellulose oven-dry weight sample. original of the weight oven-dry of the bath lignin samples Stir the lignin a the p re to approximately hydrolysis. thoroughly modified crucibles, samples and at be containing aration percentage lignin) reactions gives 30°C in structures analyzed by disperse a 2 Procedure SO 100 mL a for from version should

dried, of quantitative Add with 4 , 72 4% and by volume involving min. 60 significant of K by mg 200 the and the α lason 1 mL hot be HPLC and -cellulose centrifuge of mixture 2 9.2 SO autoclave some prepared water α ASTM Add tarred) α residue,-cellulose and and 4 L fucose of [w/w] protein (%)-cellulose measure as protein ignin other ground-vacuum-dried dry and 56 mL thoroughly a on D-1106-84. part tube, and in (Sjöström the internal dry the Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook lignins can crucibles contents of of filter sample of basis at add cause the the distilled 105°C = with standard such off 1 mL analysis). ( of acid-insoluble 1981) The W are at using artificially the the 2 45°C a / overnight. as W analyzed. lignin water. glass of oven-dry for lignin, I cellulolytic ) suction, sample, (this × 72% in Autoclave the 100 rod a isolated This vacuum study high with procedure (w/w) Move lignin A twice, holocellulose keeping into results nitrogen glass Klason enzyme of at using H to oven a and lignin then 121°C, 2 SO 100 mL a fiber in is desiccator, the is this overnight. 4 determination lignin incubate a required

lignin, for structure. not 4% solution sample, 15 psi, filters procedure each centrifuge suitable solution measurements or (filters the and only for Accurately as 100 mg hot. Björkman This tubes follows: min. 60 let for for can is if Wash tube. were pro it also five the the be sit of in - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 by solution In Principle of Method 3.8.7.2 D-1166-84. using ASTM, determined phenylpropanes Methoxyl Scope 3.8.7.1 3.8.7 WallCell Chemistry ... Reagents 3.8.7.5 Apparatus 3.8.7.4 analysis. to prior accordingly extracted and ground, sample is dried, The Preparation Sample 3.8.7.3 factor is obtained. reaction: methoxyl bromine. acid solution containing of acetate potassium tion nitrate modification the Hydroiodic acid. 90%. acid, Formic dioxide gas. Carbon Sodium Potassium iodide solution—Dissolve 1 L. to dilute water and 100in g of KI Potassium Phenol. solution—Dissolve sulfate Cadmium 67.2 g of CdSO liquid. Bromine, vesselsAbsorption Scrubber Vertical condenser air-cooled Heat source Reaction flask One The filtration, (ferric L. to 1 acid. acetic 1 L of glacial original solution methoxyl excess was D content groups etermination alum acetate diluted washed, is acetate bromine method, and based and indicator (–OCH group is solution—Dissolve titration with determined in solution and on the is is methyl

3 water, of ) equivalent absorption destroyed are weighed solution). polysaccharides M of in present et the IBr acidified iodide acetic by h oxyl unused CH + titration HIO in to by 2Br In of in acid. was 3 the six 415 g G I this addition 3 the the with

+ 2 +

rou Br atoms + silver manner 5HI absorbed Anhydrous 3H mainly procedure, lignin with methyl 2 nitric of

p → 2 s → 0 sodium nitrate of of CH sodium → 3I and usual acid, iodine acid, as iodide HIO in 2 3

Br + methoxy lignin potassium 4 the an with 3H

and acetate ⋅ and + for 4H 3 thiosulfate and,

IBr alcoholic + in methyl 2 5HBr O boiled. standard 2 halide derivatives the 1 LofO in water. a consequently, known uronic trihydrate iodate acetate iodide The determinations. solution of potassium acids. the volume equivalent silver as (100 g) is side in iodine collected a of Methoxyl water iodide favorable chains silver of thiocyanate is liberated standard dissolved of A and was in the nitrate. of volumetric analytical content an aromatic dilute removed original acetic in silver in solu The the 67 is - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 60 the of in Weigh Procedure 3.8.7.6 68 by chromatography. gas analyzed are Acetic methyl acid and acetate. acetate (3) groups three The Scope 3.8.8.1 3.8.8 where Report Calculation and 3.8.7.7 blue solution H mic acid. sodium required. Usually, are 50 min not more than Continue of CO stream passing auniform while temperature flask reaction to of contents of joint molten a drop the the with ground-glass Bring phenol the rod. aglass from seal of rod. aglass water drop from asmall with receiver solution, reagents. the present in usually which are for vapors 2 the equal SO one volume of acid—Mix H Sulfuric solution indicator Starch (10 g/L). Sodium Table 3.9 G N V Wash Adjust Remove Let bubbles min, 30–45 trans-esterificaion; inlet

acid acetyl

color. = = = Rotate ways: 4 1 L. to dilute reaction of Na milliliters of Na normality , sample free of moisture grams the of the are

and acetate and

volumes just D tube

about the the and the the distilling sample, etermination split per and thiosulfate the

shows methoxyl the softwoods. content ofand hardwoods some common (1)

5 mL titrate the before boiling contents rate

of heating allow Methoxyl, % flask minute distilling or acid

0.6 mL from formyl

solution. the flask of of longer to

about

the

flask heating CdSO 15 mL hydrolysis; scrubber the the the HI polysaccharides

until for of solution through sample

2 2 groups of

liberated

S S rise end second, if solution

flask

cool 2 2 100 mg of both Dilute a O bromine, 4 O necessary,

of the solution time

so 3 3 A = about point for titration solution the required solution is ( below HI, and

that

is cetyl that receivers VN the color (0.1 N)-Dissolve sample covered

and

with treated sufficient iodine of to

7 g introduce

100 mm is the scrubber. × are

and and

31.030 100°C. wood

stand attach by reached, of to

of with water vapors

G in is remove the 2

phenol, mix. to with SO with into hydrolyzed

as the Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook or hot for

a 2 into to the bromine

In S 4 × the – to Heat depth (sp 1.84) gr volumes nine with of water.

2 of 50 mg

100)/( Add

methanol L a polysaccharide O complete Na continuing alkaline the 1–2

receiver

iquid approximately methoxyl-containing the the 3 250 test and g 25 . 2 The the meantime, S

approximately min. of condenser. boiling 2

G specimen.

mL O of a is C of

to flask about 3 boiling volume ×

lignin solution discharged, to h

1000 solution, in

the Na form Add Erlenmeyer romatogra

the the acid HI and 2 4 mm. S reaction

add

2 apparatus. 10 and portion acetic × titration tube. rise

O of Heat Immediately 125 adjust 6) or and 3

mL solution · to adding 15 mL about H place alkaline

Adjust mL Place 2 the then mL 20 acidified ( apparatus. the through

acid,

2 or and of ph O flask VN the can

flask

other and y in 100 mL

KI in Seal

/ add

of should 1 G rate sweep in the (2)

be the mL 200

the

of that solution ) mL

solution the reconnect the add

under ×

interfering to 12 the determined saponification; disappearance the of 0.517 flow reaction

form mixture of contains scrubber

more into be heating out 6 ground-glass potassium

drops starch these of of adjusted to

the the and acetic

CO water drops the form flask. substances condenser.

conditions apparatus. so

of a 15 2 10 in indicator flask

to mixture the

that acid,

acetate methyl formic

and so mL mL one of acetyl of about Place joint

first

that for and the the

or of of of - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 ... Reagents 3.8.8.2 WallCell Chemistry acetyl: percent acid or as acetic percent as Report Reporting 3.8.8.5 1 liliter area solution then into curve. calibration the from pionic I.D.; 120°C; oven 150°C; injection port temperature F.I.D. 175°C; nitrogen mL/min. 20 Column: Chromatography Gas 3.8.8.4 Milligrams ofaceticacidaredeterminedfromthecalibrationcurve. glass acid flask Quantitatively ture flask chips. sample 50 mg; The Preparation Sample 3.8.8.3

week. by chromatography. gas determined acetyl and is saponification here presented procedure The % Acetyl % Acetic acid Preparation The NaOH solution lN: Weigh hydroxide, 4 gsodium dissolvewater. deionized 100 in mL Acetic Internal Internal H of deionized mL acid 900 to of formic 90% 2% 2 mL acid. Dilute formic

10 amount and of and to and add wool

volume to water. make flask, deionized with metric volumeto water. deionized with volume to make flask, 2% with acid. formic of Pipette acid

the ratio AC the mL in a

three make Supelco acetic

water-cooled the pipette acid 0.2 a

average, to

standard standard propionic (internal 10%, volumetric long of = of solid

remove mL

acid % acetic 2 mL transfer times

to standard

the of acid. sample handled 25 mg; = volume

60/80

a 1 mL 85% acid found acetic mg/mL residue area

sample weight mg in calibration standard l solution: stock

standard).

by Standard acid N solid reflux

the

flasks.

is Carbopack is phosphoric solution: NaOH GLC. AC of with weighing

determined solution: based (internal with liquid CH particles. propionic × 15%, condenser deviation, Pipette

0.7172

distilled Pipette 3

Calculate The COOR curve: and solution several CH on from Weigh 20 mg; C/0.3%

Weigh

average tube

sample standard). 3 the acid. COONa Analyze 10 mL

by 1 Pipette the + water. acid portions

and and approximate NaOH mL to and

100 mg dividing the

25.18 g AC reaction Make carbowax

wash of solutions

reflux stock precision of

(internal transfer × ratios +

This the 1,

10 %100 mL the 20%,

H Plot propionic →

of 2,

down 99.7% + sample to solution of the ratios CH for

solution

distilled 4, → flask the

by 15 mg; 99+% volume

it 20 acetyl 6, CH area can of 1 h.

3 standard)

dividing to COONa the average

glacial and is M/0.1% each to

acid 3 an be into Cool used of COOH propionic neck the may water.

AC content:

8 GLC

acetyl stored the with

sample.

mL internal a volumetric

acetic

the to ratios + 25%, mL 200 the be of H acetic into ROH

and determine Add 3 of distilled PO reaction filtered the digestion

in area

acid Acetyl standard

10 mg. The against acid

determine 4 a

the standard –3 ft flask. 0.2 mL acid

volumetric 10 mL of in

flask. results refrigerator through into

flask mL 500 by the 1/4 content water. mg/mL flask Connect Weigh

milligrams 2

acetic O. the of

in. acetic Wash into volumetric the to 100 mL may 85% and

area O.D. a room Analyze flask, an

volumetric

(AC) average of small each acid

the the

be acid add phosphoric for oven-dried acetic of and

tempera

reported make per solution volu reaction reaction

the sample, 0–10%, at plug

boiling by 4 mm

flask. ratio.

least each mil pro acid

- the 69 of - - - Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Browning, G.L.1967. Björkman, Björkman, ASTM, 1984.Standardmethodforashcontentinwood andwood-based materials,D-1102-84. ASTM, 1984.Standardmethodforlignininwood, D-1106-84. ASTM, 1984.Standardmethodformethoxylcontentinpulpandwood, D-1166-84. Andersson, Adler, E.1977.Ligninchemistry:Past, presentandfuture. REFERENCES 70 Kai, Jones, Jiang, Hon, D.N.-S.andShiraishi,N.1991. Holloway, Hillis, Higuchi, Hergert, Hergert, Hemingway, Hemingway, Hemingway, Hattula, Haslam, Harun, J.andLabosky, P. 1985.Chemicalconstituentsoffive northeasternbarks. Harder, M.L.andEinspahr, D.W. 1980.Levels ofsomeessentialmetalsinbark. Gottlieb, Goring, D.A.Iand Goring, D.A.I.1962. Gardner, Fengel, D.and Ellis, Dietrichs, Dietrichs, H.H.1975.Polysaccharidesinbark. Clermont, L.P. 1970.Studyofligninfromstonecellsaspenpoplarinnerbark. Choong, Chang, Y. E.L. tion Chapter 6,pp.215–255, New pith fromstalksofselectedwoods, tion ofagalactoglucomann 12: 1721. Plants Technol The ChemistryofFlavonoidCompounds Products Journal bond locatedinloblollypinebarkprocyanidins. Plants Organic ChemicalsandBiomass. analysis andhighresolutionspectroscopy. Woody Plants Chapter 7.3,pp.439–511,New 232–237. Press, pp.181–189. Holzforschung Tappi solvents fromsoftwoods andhardwoods. Papperstid K.S. W.E. R.W., 1991. Y.-P.

T. H.T. E.T, H.T. E. T., K.H. O.R.

H.H., products. 1965. P.J.

A. and A. and A., 38(5):315. 1989. Ito, 1989. . I.Chapter1.1,pp.1–12,New . I.Chapter7.6,pp.571–650,New

R.W. Chemistry and Abdullah, Krull, R.W., R.W. 1962. . 1:585–595. 1960. 1956. 1957.

and and Erickson, Wegener, G.1984. Timell, Johanson, and Y., Graves, . 59:477–485. Cellular Ultrastructureof Cellular Woody Plants Mitchell, Gallic Historical Timell, 1989. Blackwell, Shimada, Deas,

1981. . I.Chapter7.2,pp.399–438,New Karchesy, Yoshida, J.H., Economic XI. Chemical Studies 32(2):60–67. Studies The physical chemistryoflignin. Methods in Wood Chemistry T.E.

10:610–617. G., Structure of K.,

M., Biflavonoids acid Blessin, A.H.B. M. Bark: T.E. 1962.Molecularweightofnative celluloses.

extractives. and 1972. R.L. Behrenwsdorf,

on uses M., on Fridh, M. 1978. derivatives J.J., J.

composition importance Kowalczuk, finely finely Its

1974. 1955. and . CelluloseChem. Technol 1989. of 1973. Polysaccharides of C.W., Wood: Chemistry, Ultrastructure andReactions

McGraw,

H., Determination York, NY: MarcelDekker, Inc. chemistry the extractives Kawamura, Wood andCellulosicChemistry York, NY: Springer-Verlag. divided and

In: divided

The and Chemical Chapter10,pp.189–248,BocaRaton,FL:CRCPress. bark Lignins. Epoxyoctadeconic and Cereal Chem and Hon, proanthocyanidins. of

D., J. Miksche, hydrogen York, NY: Springer-Verlag. of

lignins

Inglett, G.W., flavonoid 1976. hydrolysable wood. tannins , Chapter17,New and and Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook Holz alsRoh-und Werkstoff wood. D.N.-S. York, NY: Springer-Verlag. Svensk Papperstid and Radiochem. Radioanal.Letters In: I. composition in , of Sinner,

1967. prospects Louisiana and of Vol. 2, New exudates.

the G. Rowe, Part G.E. some bonding

Part hardwoods Phytochem . 56(5):441. and York, NY: Springer-Verlag. Pure Appl. Chem compounds: and Wielesek, E. bark Chemical .

1: 1973. M. W.A. Wood Sci. Technology 2: 1979. polyphenolics acids . 6:503–505. of Shiraishi, tannins. J.W. Extraction

of for The State 1978. In: In: the in of

aspen York, NY: Gas Côté in

naïve York, NY: MacMillan. Neutral chemical Rowe, Rowe, (ed), . 22:275. and . 60:158–169. trace common properties R.A.

University, properties plant Wood Studies

In: chromatographic . New

N. softwoods. Jr. ( Populus tremuloides cellulose. aua Pout o od Plants Woody of Products Natural elements of Rowe, 1983. . 5:233–254. J.W. J.W. (ed), (ed), cutins sugars from lignin and Wiley Interscience. . 33:13–20. utilization. York, NY: MarcelDekker, Inc. North on Tappi of (ed), (ed), Wood and Cellulosic Chemistry

of New Wood Heterogeneity bark. the J.W. conifer 32(1–2):35. lignins and Tappi

bark 11:169–218. of with in Holzforschung Tappi Biochim. Biophys. Acta Biochim. Wood andFiber 45(6):454–460. . American carbohydrates NaturalProducts of Woody Natural Products of Woody W. de.Gruyter, Berlin. York: bark hemicellulose

(ed), In: suberins. Utilization

lignins. neutral 63(2):110. analysis 53(1):52–57. In: wood extracted Geissmann, by Natural Products of Products Natural Syracuse Goldstein, ), neutron pulpwood III. of Cellulose Chem. and solvents.

Phytochemistry of

Notes, 27: interflavaniod

The in lignin 17(2):274. with bark. fractions

University tree 189–193. activation T.A. constitu I.S.

No. neutral

Svensk oxida Forest barks. parks,

(ed), 343:

Ed. 29. . of I. - - ,

Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Moore, Mian, McGinnis, Martin, R.E.andGray, G.R.1971.pHofsouthernpinebarks. Laks, Labosky, P. 1979.Chemicalconstituentsoffoursouthernpineparks. Kurth, Kollmann, Kolattukudy, P.E. 1984.Biochemistryandfunctionofcutinsuberin. WallCell Chemistry Timell, Timell, Timell, Timell, Timell, Stamm, Sjöström, Seshadri, Sandved, Schwerin, Sarkanen, Sarkanen, Sakakibara, Saka, Saka, Rowell, Rowe, J.W. (ed),1989. Porter, Pettersen, Pereira, Panshin, Painter, Obst, Nunes, Nonaka, J.R. S. Canada Springer-Verlag. Technology 685–688. pp. 51–67,New cies of Around the World Pinus radiate. Holzforschung York, NY: (eds), Chemistry by Cellulosic Chemistry Sci. pp. 651–688,New Advances inChemistrySeries20,Chapter2,pp.57–126, 211–218. 143–153. Journal I. tures Forest Service,Forest ProductsLaboratory. ( Chapter 7,pp.257–330,New P.E. A.J. S.

Betula papyrifera E.F. L.J. T.E.

E., T.E. 1965. T.E. 1964. W. T.E. 163. T.J. andPurves, C.B.1960.Polysaccharidesintheinnerbarkofwhitespruce. A.J. 1964. T.E.

H. R.M. and G., A.J. anddeZeeuw, D.1980. TEM-EDXA. 1991. 13(2):102–110. T.R. K.B., R.C. 1982.

K.V. K.V. and 1991. E.

G. Quilhó, G.D. 1988.

of and F.P.

1989. 1961b. and Lignins, Occurrence, Formation, Structure andReactions Nishimura, A. Goring. 1961a. American origin. 1982.

17(2):141–149. . 55:125. stenophyllanins 1980. 1981. 1958. and Timell, 1984. and Chemical Johnson, Prance, and

1991. , Chapter4,pp.113–175,New Guaiacyl and and Smith, Wiley-Interscience. Chemistry 16:83–122. Chemical Condensed

Wood hemicelluloses.Part 2. Wood hemicelluloses.Part 1. Vedantham, Wood andCelluloseScience T., Isolation Ludwig, Recent

Hergert, Distribution The Parikh, Characterization od oyacaie, od hmsr, udmnas n Applications and Fundamentals Chemistry, Wood Polysaccharides, Wood D.A.I. Côté, The and York, NY: T.E. Chemistry

Mokuzai Gakkaishi Natural Products of Woody Plants . Portland,OR: G.T., H., J.E. ). York, NY: Springer-Verlag. D. chemistry chemical and composition Pereira, Can. Journal Chemistry

1960. , Chapter2,pp.59–88,New

and composition W.A. progress 1983. of of S. 1967. 1954. C.H. H.L.

and A, tannins.

syringyl

polysaccharides Phytochemistry 1975. bark. T.N.C.

Nishioka,

B, of Academic Press. Isolation Prance, (eds), The of Jr. 1971. H. Procedures for the chemical analysis of wood and wood products wood and wood of analysis chemical the Proceduresfor

The 12:43–48. composition reacted and York, NY: MarcelDekker, Inc. of

In: The lignin. in 1996. 1968. Textbook of Wood Technology of 1971. In: distribution lignin reaction

Timber Press. and C, chemical Hon, 1971. the Classification

and celluloses

chemical A.E. I.

Rowe, and novel 29:648. chemicals

Anatomy distribution. 1985. chemistry rnils f od cec ad Technology and Science Wood of Principles Chemical In: variability composition D.N.-S.

10:897. Lignins: Occurrence, Formation, Structure and Reactions characterization from 1992. , New York, NY: MarcelDekker, Inc. wood.

of Advances inCarbohydrate Chemistry Advances inCarbohydrate Chemistry tannins Hon, J.W.

nature Tannins

38:1191–1198. of wood. constituents

from the Bark: The Formation,Bark: The Bark of Uses and Characteristics, inorganic York, NY: and in and (ed), II. D.N.-S.

examination and bark and York, NY: MarcelDekker, Inc.

of from southern In: of , IandII.New In: the

The chemical in and Shiraishi, cork distribution,

Natural Products of Woodyof ProductsPlants Natural the topochemistry of Hon, hardwood Rowell,

Quercus stenophylla. J. Chem. Soc. Perkin Trans bark

Forest Products Journal

polysaccharides related

gymnosperms. of of constituents and from Washington, DC: lignin The RonaldPressCo.

a pine loblolly D.N.-S. of cellulose , McGraw-Hill, New composition of Shiraishi, N. R. Wood Science QuercusL. suber WoodSci. Technol.

, New compounds: gymnosperms. modified the of cell (ed), M. In: York, NY: Springer-Verlag. Canadian J. Botany Douglas-fir

pine. barks and components. (ed), of Sarkanen, York, NY: in from

Wood and Cellulosic Chemistry WoodCellulosic and Svensk Papperstid black compression N.

Shiraishi, of Wood Science with and The Chemistry of Solid Wood of ACS. the

Eucalyptus goniocalyx Eucalyptus (ed), Part 12(2):80–85. Pinus Pinaster spruce heartwood methyl inner Svensk Papperestid Svensk bark. . 20:409–483. . 19:247–302. 21(3):49–52. Tappi K.V.

Wiley-Interscience. 26. od n Cellulosic and Wood Holzforschung York. N.

Isolation bark , and wood Pulp Paper.Mag. Pulp 43:729–736. wood. 62(12):2918. isocyanate. (eds), New

7(4): . . of

I Ludwig, of 64: , Chapter as

Betula bark. white Chapter

York,

od Sci. Wood 295–297. Wood and Wood and 651–661. determed , USDA,

36(3): . Wood IAWA struc birch

. C.H. New

spe NY:

7.7, and 22: 64: 71 3, - - . , , Downloaded By: 10.3.98.104 At: 17:48 23 Sep 2021; For: 9781439853818, chapter3, 10.1201/b12487-5 Young, Young, Whistler, Whistler, Volz, K.R. 1971.Influenceofinorganic contentonthepHofbark. Toman, 72 Second edition Cellulose Chem. Technol ( Tappi chemical elementsincompletetreesofeightspeciesMain. Vols. 1–6, New ai alba Salic H.E. H.E. R., R.L. R.L., 49(5):190–197. Karacsonyi, 1971. and and Wolfrom, ), Guinn, Richards, Preliminary structure Vol. 2A, pp.447–469,New York, NY: S., V.P. M.L., and E.L. of 1966. . 10:561. estimates the Academic Press. Kubackova, and 1970. acidic Chemical BeMiller, Hemicelluloses. of and bark M. elements Handbook of Wood Chemistry and Wood Composites Wood and Chemistry of Wood Handbook J.N. neutral 1976. York, NY: percentages (eds). Studies In: oligosaccharides in W. 1962–1980. complete Academic Press. Pigman and on chemical Holz-Zentralbl pectin Forest Products Journal mature and Methods in Carbohydrate Chemistry Carbohydrate in Methods obtained D. present elements Horton trees . 97:1783. in of by (eds), the seven of partial bark bark The Carbohydrates species 21(5):56–59. acid of percentages white hydrolysis. in Maine. willow and . ,