Experiment 5 : Wood Chemistry

ABSTRACT

Wood is a porous and fibrous structural tissue found in the stems and roots of trees and
other woody plants. It has been used for thousands of years for both fuel and as a construction
material. It is an organic material, a natural composite ofcellulose fibers (which are strong in
tension) embedded in a matrix of lignin which resists compression. Wood is sometimes defined as
only the secondary xylem in the stems of trees, or it is defined more broadly to include the same
type of tissue elsewhere such as in the roots of trees or shrubs. In a living tree it performs a support
function, enabling woody plants to grow large or to stand up by themselves. It also mediates the
transfer of water andnutrients to the leaves and other growing tissues. Wood may also refer to other
plant materials with comparable properties, and to material engineered from wood, or wood chips or
fiber. Wood is essentially composed of cellulose, hemicelluloses, lignin, and extractives. presents
major chemical compositions of some wood species. Each of these components contributes to fiber
properties, which ultimately impact product properties.

The chemical composition of wood varies from species to species, but is approximately 50%
carbon, 42% oxygen, 6% hydrogen, 1% nitrogen, and 1% other elements
(mainly calcium, potassium, sodium, magnesium, iron, and manganese) by weight. Wood also
contains sulfur, chlorine, silicon, phosphorus, and other elements in small quantity.

Aside from water, wood has three main components. Cellulose, a crystalline polymer
derived from glucose, constitutes about 41–43%. Next in abundance is hemicellulose, which is
around 20% in deciduous trees but near 30% in conifers. It is mainly five-carbon sugars that are
linked in an irregular manner, in contrast to the cellulose. Lignin is the third component at around
27% in coniferous wood vs 23% in deciduous trees. Lignin confers the hydrophobic properties
reflecting the fact that it is based onaromatic rings. These three components are interwoven, and
direct covalent linkages exist between the lignin and the hemicellulose. A major focus of the paper
industry is the separation of the lignin from the cellulose, from which paper is made.

In chemical terms, the difference between hardwood and softwood is reflected in the
composition of the constituent lignin. Hardwood lignin is primarily derived from sinapyl
alcohol and coniferyl alcohol. Softwood lignin is mainly derived from coniferyl alcohol.
INTRODUCTION

Wood is the hard, fibrous substance found beneath bark in the stems and branches of trees
and shrubs. Practically all commercial wood, however, comes from trees. It is plentiful and
replaceable. Since a new tree can be grown where one has been cut, wood has been called the
world's only renewable natural resource. The chemical composition of wood varies from species to
species, but is approximately 50% carbon, 42% oxygen, 6% hydrogen, 1% nitrogen, and 1% other
elements (mainly calcium, potassium, sodium, magnesium, iron, and manganese) by weight. Wood
also contains sulfur, chlorine, silicon, phosphorus, and other elements in small quantity.

Aside from water, wood has three main components. Cellulose, a crystalline polymer derived from
glucose, constitutes about 41–43%. Next in abundance is hemicellulose, which is around 20% in
deciduous trees but near 30% in conifers. It is mainly five-carbon sugars that are linked in an
irregular manner, in contrast to the cellulose. Lignin is the third component at around 27% in
coniferous wood vs 23% in deciduous trees. Lignin confers the hydrophobic properties reflecting
the fact that it is based onaromatic rings. These three components are interwoven, and direct
covalent linkages exist between the lignin and the hemicellulose. A major focus of the paper
industry is the separation of the lignin from the cellulose, from which paper is made.

In chemical terms, the difference between hardwood and softwood is reflected in the
composition of the constituent lignin. Hardwood lignin is primarily derived from sinapyl
alcohol and coniferyl alcohol. Softwood lignin is mainly derived from coniferyl alcohol. Aside from
the lignocellulose, wood consists of a variety of low molecular weight organic compounds,
called extractives. The wood extractives are fatty acids, resin acids, waxes andterpenes. For
example, rosin is exuded by conifers as protection from insects. The extraction of these organic
materials from wood provides tall oil, terpentine, and rosin

Cellulose makes up nearly 50 percent of woody plant mass. Trees produce cellulose to store
carbon, hydrogen, and oxygen. Cellulose also is made up the starches, proteins, and sugars trees
need to grow. It is the most abundant organic material on Earth. We can transform cellulose into
ethanol, cellophane, and cellulose ethers such as acetate, rayon, and nitrates. Due to the relatively
high manufacturing cost, many of these derivatives have only specialty applications. The primary
source of wood cellulose in the south is softwood species such as pine, but over the last twenty
years, hardwood utilization has increased.
Hemicellulose is a carbohydrate that comprises 25 to 35 percent of the dry weight of wood
residues. It is second only to cellulose in abundance. The use of hemicellulose is currently limited
due to manufacturing related costs. Lignin is a polymer that holds together the cellulose and
hemicellulose components of woody biomass. Lignin constitutes about 15 to 25 percent of the
weight of woody biomass. Lignin has not yet been used as a raw material for industrial purposes in
large quantities. This reflects the chemical complexity of lignin.
In this wood chemistry laboratory, we will do research the extractive composition,
holocellulose composition, cellulose composition and lignin composition. The material which been
given in first analysis will be used for the next determination. The standard which been used is
TAPPI T 6 m-59 standard.
First, the wood sample must been converted into powder form. This will be prepared by lab
assistant. The wood powder need to be separated so that we will get 0.1-0.4mm size of wood
powder. We will use the strainer provided. The strainer will be apply with the used of wood powder
which will gone through 0.4mm size strainer and will be discontinue with the strainer which has
0.1mm size. The wood powder must be in air dried and need to be kept in a bottle or close end
vessel. This is necessary to avoid the change of moisture content of the wood powder.
Soxlet or twisselmann apparatus with the presence of solvent materials have been used to
separate the extractives from the wood powder. Usually, we can used ordinary solvent such as
alcohol, acetone benzene or any solvent that is appropriate. This is also depend on the type of
extractives need to remove from the wood powder. Any standard provided also can be used for the
extraction. Wood powders which have been strained must be put in the timbel filtration. In this
experiment, the solvent materials used are alcohol and toluene. This kind of solvent can be used to
remove either polar or non polar type extractives. Ethanol will dissolve the polar component while
toluene will dissolve non polar component. The mixture of this two solvent will give good
extraction compare to if just one solvent been used for both extraction. The solution from the
extraction will contain extractive. The solvent also been drained out and will give the residue which
is also an extractive.
The extractive weight which been separated and calculated based on oven dried
weight of the wood powder. While the determination of holocellulose and lignin composition will
used the wood powder which been free extractive. The extract of the wood powder only can be
dried to 40°C. The solvent which contain residue will be seen together with wood powder. Ethanol
can be used to remove the residue of the solvent with hot water (40°C). Then, the powder will be
dried either air dried or oven dried at 40°C until the moisture content of the wood powder around
15%
OBJECTIVE

The objective of this experiment is to expose the student a little bit about the wood chemistry
component.

APPARATUS
i) Soxlet apparatus, (volume ≥100ml)
ii) Conical flask with round base, 250ml
iii) Filter timbles
iv) Boiling stone, from Teflon to avoid boiling delay
v) Wood powder (Meranti), air dried and been strain. Powder >0.1mm and <0.4mm
vi) Heater apparatus for soxlet. (can be replace with Twisselmann)
vii) Analytical scale

CHEMICAL AND SUBSTANCES USED

Solvent: ethanol and toluene.
Need 100ml toluene and 200ml ethanol for each determination.
METHOD AND DETERMINATION
Extraction
Moisture content of the particular wood powder is determinate first. From it we can
conclude that the moisture content would be the same. We can make a calculation oven dried weight
of the wood powder of desire. 10g of desire wood powder is prepared which is base on oven dried.
The wood powder is put into a timble and be stuck off with cotton wool to prevent it to spill out of
the timble during extraction. The timble fill with wood powder is put in soxhlet apparatus.
Before that, round flask need to be dried first in the oven, let it cool for a while in
desiccators and weight. 200ml of solvent (mix of toluene and ethanol with ratio 1:2 of it volume) is
put in the round flask. A couple of boiling stone (3-4) is put in the round flask. This is because to
make sure the boiling is in the moderate state. Then, the heater is switched on and controlled so that
the solution boiled. The extraction is run in 6 hours. The extraction from either soxlet or
Twisselmann until there are no coloured produce. If the extraction still produce coloured, then the
process still not finish. Continues until there is no coloured produce.
Wait until it cool for a while, remove the boiling stone from the round flask. The solvent mix
with the extractive is distilled with rotary evaporator with vacuum. Caution must be taking part not
to throw the solution. After the solvent and water been distilled, round flask is dried in the oven at
105°C until the weight of the round flask is same. The gain of the round flask’s weight is the
amount of extractive composition of certain wood. If the boiling stone did not first removed then it
need to be deducted from the round flask’s weight.
This extractive material cannot be used again for the next determination/research because it
been oven dried in the oven and the arrangement of it chemistry structure is changed.

Determination of holocellulose composition

The wood powder which is free from extractive is oxidizing with ClO 2. This oxidizes form
from this chemical reaction:
NaClO2 + CH3COOH → NaOOCCH3 + HClO2
4HClO2 → 2ClO2 + HClO3 + HCl + H2O
Lignin been oxidize and dissolve. Hollocellulose is collected from it residue. This because,
ClO2 produced is less and the oxidization occurs slowly, adding sodium chlorite is on stages which
are once per hour. Reciprocal with sodium chlorite is usually known as reciprocal as quote of
WISE. Usually oxidizing with sodium chlorite is carried out at 75°C for about 3 hours for hard
wood and 4 hour for soft wood. If one wants to know the holocellulose composition, the lignin
composition must be determination first.
Method of determination
Wood powder which been extract (mix with toluene/ethanol, remove from timble) is mixed
with ethanol been filtered with vacuum attach on it. After that, the wood powder is washed with hot
water (temp 40°C) and filtered. These processes are repeated 3 times. Then, the wood powder is
spread out onto a piece of paper and dried. For the quirkiest drying, the process could be done under
vacuum dryer until the powder is air dried.
The wood powder which is air dried is put in bottle with close lid. The moisture content of
that powder is determined. 5g of wood powder (base on oven dried) is put in an Erlenmayer 200ml
volume with wide neck. 1.5g NaClO2 is dissolved in 160ml distilled water and 10 drop of acetic
acid. This solution then been mixing with wood powder. The Erlenmayer is close with another small
size of Erlenmayer which been upside down. Oxidizing is carried out at 75°C. Once a while the
erlenmayer been shaken up. After one hour, 1.5g NaClO 2 and another 10 drop of acetic acid is
added more. The total amount of sodium chlorite is 3 x 1.5g.
After 3 hour, the product of oxidation is cooled with place the erlenmayer glass into ice
water or ice cube. After cooled, it been filtrated with filter crucibles with 2G2 strain which been
first known it constant weight. The residue first is washed with ice water until the filter water is
neutral and next is washed with acetone. The 2G2 filter crucibles with holocellulose id dried in
oven dried at 40°C until the constant weight.
Usually, holocellulose which been separated still have a little amount of lignin. If ones want
to know the holocellulose composition, the amount of lignin must be determined first. This
composition is less than the composition which been getting from above process.
Apparatus
1. Analytical scales
2. Erlenmayer flask, 200 ml with wide neck
3. Erlenmayer flask, 50 ml with narrow neck
4. Water bath
5. Drop tube
6. Filtering flask
7. Vacuum pump
8. Filter crucibles 2G2
9. Vacuum oven
10. Weighting bottles
11. Glass rod 12. Measurement Cylinder 250ml
Chemical
1. Acid acetic
2. Sodium Chlorite
3. Acetone
4. Distilled water

Determination of cellulose by Cross-Beven

This kind of determination is been standard by TAPPI – T9m-54
Holocellulose which been separated still have contain hemicelluloses. For determination for only
cellulose decomposition, holocellulose is dehydrolysis with encer asid. Other than hemicelluloses,
cellulose part which is amorphous also been dehyrdolysis. The residue of the process I known as
Cross-Bevan cellulose.

Method of determination
2g of holocellulose(oven dried) is weighted and is put in a 500ml beaker. 200ml of sulfuric encer
acid (1.3%) is added. Hydrolysis is conducted in water bath that contain boiling water. Water that
gone through vaporizes is frequently replaced by distilled water, until the volume of sulfuric acid is
same. After 2 hour, the cellulose or the residue is filtered in crucible filter 2G2 which first known it
weight. The cellulose then is wash with distilled water until the filtration become neutral (use litmus
paper). Then, it been wash with ethanol and the residue is dried in the oven at 105°C until the
constant weight. The cellulose composition by Cross-Bevan is calculated with respect to wood
powder without extractive and oven dried.
Apparatus
1. Holocellulose from previous determination
2. 500ml beaker
3. Water bath
4. Filter crucible 2G2
5. Weight bottles for weighting the crucible
6. Wash bottle
7. Oven
Chemical used
1. Sulfuric acid (1.3%) 4. Litmus paper
2. Ethanol
3. Distilled water
Determination of lignin (Lignin Klason)
Determination of lignin with using of sulfuric acid with hydrolysis polysaccharide until it dissolved
and only lignin as it residue. TAPPI Standard T 13 m-54 used two type of sulfuric acid. First, high
concentration sulfuric acid (72%) and second is encer sulfuric acid (3%). The reaction of wood
powder with high concentration of sulfuric acid will make condensate the lignin until it not
dissolves in high concentration of sulfuric. Hydrolysis with encer sulfuric acid then will hydrolyze
the polysaccharide until it dissolved in water. Because others organic material such phenol-phenol
and protein in wood can condensate, all of it will need to be extract fist before we can determine the
lignin composition. In the accurate determination of lignin ash, the amount is been less from the
product of determination of lignin.

Method of determination
1g wood sample (oven dried weight) which been extract and dried is put in small beaker (25 or
50ml). 25ml of cool high concentration sulfuric acid (72%) from refrigerator is given part by part to
the wood powder and been stir with glass rod. Given times is 1 minutes. Then, it been put in water
bath for 2 hour at 20°C. once a while the solution is stir with glass rod. After 2 hour, the solution is
then transfer into erlenmayer flask with the use of all 560ml distilled water. Then the erlenmayer is
heated with reflux until it completely boil the polysaccharide to hydrolysis occur. After finish, let it
cool and let it precipitate for a while and filter with crucible filter 2G3 which first known it weight
with vacuum and filtration flask. Usually the residue is hard to be filter. Washing is conducted with
all 500 ml hot water until the filter is neutral. Then the crucible is dried in oven until constant
weight.
Apparatus
1. Wood powder without extractive (from previous determination)
2. 25 or 50ml beaker
3. Erlenmayer flask, condenser reflux volume 1:1
4. Crucible filter 2G3
5. Wash bottle
6. Filtration flask
7. Oven
Chemical
1. High concentration sulfuric acid (72%) 3. Litmus paper
2. Distilled water and ice
 DISCUSSION

Based on the experiment, wood analysis comprises the determination of wood composition as
well as the isolation, purification and characteristics of the wood constituents. As wood is a natural
material, modified procedures and methods for wood and wood-related substances are applied
besides the classical methods of analytical chemistry.
The method of wood analysis are more or less standardized. A distinction can be made
between methods which are mainly used in scientific research and those applied in the industrial
production and control of wood-derived products such as pulp, and others. They can differ with
regard to the required precision and the special objective of analysis.
In the intermediate steps of determination of wood chemistry, lignin portions remain with
the isolated polysaccharides and even cellulose and polyoses can hardly be separated quantitatively
without degradation and changes in molecular properties.
Determination of wood composition can be carried out very differently, by determining only
the main cell wall components, namely the holocellulose, cellulose and lignin in addition to the
extractives and ash.
From the determination of extractive composition
Extractives are substances that tend to be deposited in association with the transition from
sapwood to heartwood. They also tend to be present in greater concentrations in barks. Large
extractive concentrations are present in woods only in exceptional cases, most of these being
tropical species. Generally, however, extractives constitute less than 5-10% of the biomass. Water-
soluble carbohydrate compositions of woody biomass tend to be particularly low, 0.6% (Garstang et
al., 2002), with higher concentrations likely if bark and foliage elements are included in the
harvested biomass.
From this experiment, a mixture of solution which comprise of polar and non-polar solvent
have been used for extraction of both extraction material which are hydrophilic and lipophilic. The
solvent which have been used are toluene and ethanol in the ratio of 1:2. A mixture of ethanol and
toluence was found to remove the same materials from wood as ethanol-benzene. However, the
mixture of ethanol and toluence does not boil and reflux at constant temperature and rate. Ethanol
will dissolved the component which is polar while toluene will dissolved non-polar component.
After 6 hour, the colour of the solution will change to brighter and this indicates that the
reaction is completed. The solvent mix with extractive is distilled in the rotary evaporater to get rid
of the solvent and remain the extractive with help of vacuum. After complete distillation of rotary
evaporater, the remain component left in the round flask is extractive. Thus, we can weight the
weight of the extractive by deducting the round flask plus extractive with empty round flask. The
result of percentage of extraction is 1.549%. This in the rage of composition of extraction all wood
which is 1-5%.
It is dangerous to use benzene compared to the toluence in solvent mixture to extract wood,
due to its carcinogernic properties for which it has been long banned. Any contact with the skin or
inhalation of benzene vapour must be avoided. Extreme safety precautions must be taken in
carrying on the above procedure. Thus, toluence was used in this experiment.

From determination of holocellulose

The wood powder which is free from extractive is oxidizing with ClO 2. This oxidizes form
from this chemical reaction:
NaClO2 + CH3COOH → NaOOCCH3 + HClO2
4HClO2 → 2ClO2 + HClO3 + HCl + H2O
Wood powder (extractive-free) has gone oxidation with NaClO 2 will remove lignin and the
remainder is holocellulose. Holocelleulose comprise of cellulose and hemicelluloses which is the
main component in wood. From the experiment, the percentage holocellulose content (%) is 1.838%
(without extraction). The removable of extractive is determined when the brown colour of the wood
powder is gone in the determination of holocellulose process. The remainder (holocellulose) was
washed with cold water until neutral, then washed with acetone for futher dissolving any lignin that
still left. At this stage, the wood powder will turn light in colour (whited-cream like). In the mean
times, the colour of the filtration also change from colourless to light yellow. Generally,
delignification also can determine the holocelullose. It was then found that along with the extended
number of chlorination, the residue became yellowish, and then whitish. Accordingly, the
holocellulose yield was reduced. Thus, in order not to lose any part of the holocellulose, the number
of chlorination was found to be minimized so as for the residue to remain yellowish.
From determination of cellulose – cross-Bevan
Cross and Bevan cellulose consists largely of pure cellulose, but also contains some
hemicelluloses. It is obtained by chlorination of wood meal, followed by washing with 3% SO 2 and
2% sodium sulfite (Na2SO3) water solutions. Cellulose usually is not dissolved in most of the
solvent and also strong alkaline. We find it hard to separate it from the wood in pure composition
because it has strong lingkage with lignin and hemicelluloses. Cellulose cross-bevan is comprised
of most pure cellulose but also comprise hemicelluloses. The absence of a characteristic red
(angiosperm) or brown (gymnosperm) color developed in the presence of chlorinated lignin signals
complete lignin removal. From the experiment, the powder from previous method (holocellulose
with extraction-free) is added it sulfuric encer acid, been hydrolyze in water bath and the
hemicelluloses is dissolved and give the remainder (cellulose). The cellulose is wash with distilled
water until neutral and after that with ethanol (to dissolved any other hemicelluloses left) and been
filter and dried in the oven. The cellulose composition by Cross-Bevan is calculated with respect to
wood powder without extractive and oven dried. From the experiment we found that the percentage
of cellulose is 40.26 %. From the percentage of cellulose we also know the percentage of
hemicelluloses by deducting the percentage of holocelluloce with the percentage of the cellulose
and the percentage of hemicelluloses is 16.82%.
From determination of lignin
Based on theory, the lignin fraction is usually between 20 and 35%, depending on tree
species. It is generally considerably less in temperate hardwoods (~22%) than in softwoods, where
it is usually 27-29% (Hakkila, 1989). Species variations between softwood lignins are relatively
negligible (Slater and Beevers, 1958), in contrast with hardwoods (Pridham and Hassid, 1966). The
lignin contents of woods presented in the tables of this chapter are Klason lignin, the residue
remaining after solubilizing the carbohydrate with strong mineral acid. The usual procedure, as in
Tappi Standard T 222 or ASTM Standard D 1106, is to treat finely ground wood with 72% H 2SO4
for 2 h at 20 °C, followed by dilution to 3% H 2SO4 and boiling or refluxing for 4 h. An equivalent
but shorter method treats the sample with 72% H2SO4 at 30 °C for 1 h, followed by 1 h at 120 °C in
3% H2SO4. In both cases the determination is gravimetric. Softwood lignins are insoluble in 72%
H2SO4 and Klason lignin provides an accurate measure of total lignin content. Hardwood lignins are
somewhat soluble in 72% H2SO4, and the acid-soluble portion may amount to 10-20% of the total
lignin content.
The acidsoluble lignin can be determined spectrophotometrically at 205 nm. (Table XIV
contains lignin values that add the acid-soluble component measured at 205 nm to the Klason
lignin. Lignin contents of hardwoods in all the other tables are low). Preconscious step also need to
be take care, such when added sulfuric acid, must be conducted in fume board. Next, in the
determination of holocellulose process, erlenmayer flask needs to submerge in cold water or ice to
stop oxidation process. Next, the use of small erlenmayer flask for the lid is compulsory to avoid
the solution from being fade away. Based on the experiment, the value of lignin content is 28.29%
 CONCLUSION.
As a conclusion, in the wood, cellulose, a crystalline polymer derived from glucose,
constitutes about 41–43%. Next in abundance is hemicellulose, which is around 20% in deciduous
trees but near 30% in conifers. It is mainly five-carbon sugar that are linked in an irregular manner,
in contrast to the cellulose. Lignin is the third component at around 27% in coniferous wood vs 23%
in deciduous trees. Lignin confers the hydrophobic properties reflecting the fact that it is based
on aromatic rings from the experiment conducted, we found that the Angsana wood have extractive
composition about 16.86%, while the cellulose composition is 40.26%, 16.82% of hemicelluloses
composition and the lignin composition is 28.29%. Almost all of the chemical composition in the
Angsana sample is in the range of the basic chemical composition of all wood. we can say that the
theoretical of the wood component is prove through the lab experiment conducted due the each
component such as lignin, hemicelluloses, cellulose and extractive are locate in the range of
standard wood chemical composition.
 KNOWLEDGEMENT

First of all, thanks to Allah SWT who help and give me strength to complete this experiment
without causing any injury happen to me. Not to forget, Prof Datuk Dr Abdul Khalil Bin
Shawkataly and Dr Muhamad Haafiz Bin Muhamad Kassim that kindly and always guide me in
conducting experiment until successful. Next, also to laboratory’s assistance Mr. Azhar and Mrs.
Hasni which help us preparing apparatus and materials. Also two master students miss Norha and
miss Nora that guide us when our lecturer are not around. Thanks a lot to my group members that
also help me in my experiment and this report will not finish without all of above help. Thank you
very much.
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3. Pettersson, R. C. (1984). The chemical composition of wood. The chemistry of solid wood.
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4. Pridham, J. B. and W. Z. Hassid (1966). Biochem. J. 100: 21.

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