Properties ebony-wood products § § 2

Transcription

Properties ebony-wood products § § 2
A
Study
on
the
Dark
of
Coloured Duramen
Ebony
by
K.
Griffioen
.
Table of
Contents.
page
A.
Introduction
B.
Properties
isolated
§
1.
§
2.
§
3.
781
of
the
and
ebony-wood
the
products
therefrom
782
Material.....
782
The
composition
The
isolation
of
and
the
wood
782
of
properties
the humic
acids
The
784
of
"Nitro”-compounds
§
4.
§
5.
Elementary
analysis
§
6.
The fusion
with
§
7.
Attempts
the
products
787
obtained
§ 8.
C.
Microscopy
§
1.
to
of
the
the
potassium
isolate
The "Russell
of
the
Effect”
products
hydroxide
total humic
of
789
the
....
matters.
wood
ebony-wood
Introduction
of
2.
Anatomy
§
3.
Microchemical
A
E.
Discussion
note
on
F.
Summary
G.
Literature
the
790
792
793
793
the wood
§
D.
789
nature
reactions
and the formation of humus.
794
795
801
803
806
cited
806
781
A.
Many
life.
as
They begin
to
products.
Many
coloration
of
is
supposed
to
Gtirnik
of
literature
serve
as
The
defence
a
period in their
elements
is
with
xylem
various
accompanied
formation
of
infection
against
by
a
duramen
and
to
mechanical system.
In
thoroughly
his
this
on
the
process
substances.
(15) has
duramen.
the
certain
a
the central part of the
by closing
times
the
the
strengthen
eliminate
tissue
transport
a
Introduction.
form duramen after
trees
thesis
he
and
subject
the formation
investigated
also
gives
cites
the
discussion
a
of
work of
important
Tschirch.
Tschirch
a
of the
metamorphosis
but
coloured
the
between
locally
is
the
formed.
various
of
substances
itself;
perhaps
lignin
complex.
Prael
has
while
contents,
The
filled
in
of the coloured
in
Already
the
nature
stated
the
At
a
walls
first
extracted
later
gummy-
matters
cell
walls
colouring
humic
with
humic
acids
2
and
3
the
not
cell
has
matter
oils.
action
In
always
are
of
the
on
the
If
wall
young
without
the
cells
substances.
same
tried
of
by
proceed
precipitated
and
those
composition.
to
elucidate
He
ebony-wood.
alterations
(chemical
followed
layer
yields
in the
contents
of the
(24)
and
matters
lumina
that
found
which
resins
by
resinous
the
should
Na C0
coals
or
process
elements)
from
has
ebony-wood.
Molisch
the
the
of
are
place,
enzymatic
an
duramen
gummification
of
caused
by
took
originated
duramen,
and other elements
the
1879
-of
is
duramen
mucilaginous
a
bassorins,
as
this
of
never
cells
Giirnik
the
investigated
with
colouring
the
wall.
forms
originated
(28)
of
membrane
such
alburnum the vessels
become
the
layer
the wall is coloured,
formation
membrane itself
secundary
This
the
by
contents
layers
the
in
that
states
a
of
humification.
(which
with
may
HC1)
be
and
(may be isolated with NaOH and HC1).
782
Afterwards all
According
acids
kinds of
to
Belohonbek
He
points.
a
called
of
matters
a
investigated
more
of
but he did
ebony
cannot
speak about
not
principal
the
nature
the
bound
was
is
Dafert
coals.
of
the
in
(16)
Afterwards
Compositae.
and
of
soluble
calcium.
to
that
Hanausek
by
by
of
whereby
matters
chemical way. Dafert
matters
those
of
fruits
many
were
humic
the insoluble parts
matter
plant
found
“phytomelans”
pericarp
ing
black
and
the
on
be
to
carbonization,
to
colouring
field of
%
4.63
contains
the process
humic acids
that the
Another
in
leading
should be
He stated
ebony
coals.
(2) agreed with Molisch
considered
reduction,
parts
humic
%
1.3
and
coaly substances should be formed.
Molisch
so-
the
these
Miklauz
(6)
concluded that the colour-
be classed with these substances,
the
possible engagement between
products.
According
the
to
lamella is the
above-mentioned
“melanogenous”
fact
in
connection with
B.
Properties
of
our
the
layer;
authors
which is
the
middle
important
an
problem.
and
ebony-wood
the
isolated
products.
§
1.
The material.
For
chemical
from the
the
as
name
well
tor”
and
analyses
§
2.
of
as
a.
of the
merah
Gjaja
alburnum
afterwards
I
made
Composition
I
investigation
collection
use
a
of
piece
Diospyros
=
were
sieved
of
used
ebony
laboratory, catalogized under
this
ground
by
a
in
fine
Duramen
spec.
a
“disintegra-
sieve.
For
the
“wood-flour”.
of the wood.
Moisture.
The
moisture
in
drying-oven
a
The
and
air-dry
the
content
to
is
determined
constant
weight
duramen contains
alburnum 7.10
%.
7.75
by
(t.
%
=
drying
105°).
moisture
783
b.
Ash.
The
quantity of ash is determined by incinerating
the wood in
ash
china crucible;
remains,
The ash
the
contains
alburnum
more
Cellulose
content.
obtain
0.54
in
the
Zeit.
(Chem.
based
cellulose
The ash
and
of
contains
fact
soluble
I
quantitatively
that
the
into
method
and
lignin
so-called
in alcohol,
made
and Hoffner,
This
(1931)).
changed
are
compounds
161
55,
the
on
products
wood).
%, while
phosphorus.
of the method of Kiirschner
use
the
ash.
%
greyish
compact,
more
relatively
To
Ca-carbonate
Ca-oxalate
of the duramen is 0.61
content
the latter is
the
white voluminous
a
much
containing
from
(originated
c.
a
and
is
other
„nitro”-
the
cellulose
remains.
The cellulose obtained in this
brown
content
substances
of
the
alburnum 41.0
d.
Lignin
The
to
duramen
792).
43.2
is
%
cellulose
and
of
the
content.
quantity
of
lignin is
determined
the method of Geo A. Richter
Eng.
Chem. 23
The
cellulose
is
% H 2S0 4
of
.
lignin,
also
etc.
Ind.
by
humic
The
not
consist
of
with
only
tannins,
matters,
amount
% and in
treatment
does
lignin
in
the alburnum 38.5
the
%.
determination.
The
so-called
was
used,
hydrolysis
according
(Journ.
(1931)).
dissolved
The residue
duramen is 39.6
Pentosan
131
,
but
phlobaphenes
e.
p.
contained
The
%.
2
72
(see
still
way
furfural
which
of
transformation
pentosan
of
method
method
this
is
into
of
B.
based
Tollens
upon
pentose
compound
into
and
the
the
furfural
784
by
distillation
with
quantitatively
The
Teil
are
The
All
the
Parallel
data
d.
biol.
are
calculated
with
Abderhalden
contain
16.5
the
on
the
Abt.
1,
conversion
be followed in detail.
to
to
is
phloroglucinol.
in
where
alburnum
determinations
furfural
Arbeifsmethoden”,
mentioned too, has
the
The
with
described
as
duramen appears
and
tosan
HC1.
195—206 (1922),
5,
tables
%
precipitated
method
“Handbuch
12
12.9
%
pen-
%.
absolute
fir-wood
dry basis.
included
are
for
comparison.
TABLE
Composition
1.
of the wood
samples.
Fir-wood
Ebony
Duramen
Alburnum
percent
percent
percent
Moisture
7.7
7.1
Ash
0.57
0.51
Cellulose
Lignin
..........
Pentosan
§ 3.
Isolation
The
that
the
brown
had
these
matters
humic
part
extraction
used
47.9
35.8
25.9
11.8
15.3
12.3
properties
of the humic
acids.
or
be
in
isolated,
compared
are
in
part
really
acids)
the
duramen
humic
as
their
with
humic
alkalies
had
should
properties
well-known
be
be
products.
substances
should
be
to
These
matters.
(and
the
for
a
indicated
agents.
sodium
experiments
very
to
and
investigated
I
38.1
36.6
substances
wholly
substances
great
39.9
investigations of Molisch warranted the assumption
considered
If
and
7.3
useful).
hydroxide
concentrated
The
solution
ammonia
application
of
(from
appeared
Na-fluoride
preliminary
be
to
as
a
also
neutral
785
extraction
agent,
not
should
latter
be
able
are
change
Before
be
fats,
because
the
treating
from
wood-flour
of
parts
brown
other
and
contained
extract
was
soluble
(hymetomelanic
be
alcohol
extracted
with
from
NaOH
In
ethanol.
insoluble
the
wood,
wood
is
Therefore
quantity
not
with
lead
to
a
water
were
2—2
but
formed
coloured filtrates
The
good result;
products,
the brown acid
with
scarcely
isolated
soluble
part
a
even
carried
not
wood-flour
a
thus
in
an
y2
salt of humic acid.
extraction
the
way
acidifying
with
acid
is
solution is
acid,
2/3
and
n.
the
quantity of
quantities
which
of
yielded
dried
shaken
was
NaOH solution
contained
the
during
sodium
the Na-humate solution obtained
humic
from
precipitated
a
acid
hydrochloric
insoluble
small
extraction.
repeated
Buchnerfiltrate
From
a
because
out,
important
cleaned
hours.
The
only
not
also
after
eightfold quantity of
humic
in
partly
present
colloidal solution,
an
this
of
could
appeared from preliminary experiments that the
did
The
products
acids)
probably
equal
Humic acids
analyzed.
again
of
hours.
small
while the
contained
it
twelve
must
resins,
form.
water-soluble
in
the
afterwards
Extractions
it
not
the
begin
it
as
mixture
very
further
such
products.
a
during
only
humates
(34)).
present
a
the
from
Na-hydroxide,
solid matter, which
in
alkali
with
ethanol
because
substances
organic
extracted
was
benzene
with
substances
and
phytosterols
the
of
did
this method
alkalies,
other
Springer
wood
other
otherwise
of
use
still
solutions
(U.
soon.
very
freed
the
to
dissolve
to
by K. Simon (32)
the duramen,
on
preferred
wood and also
to
recommended
as
succesful
prove
in
to
and
water
solution.
otherwise
liberated
was
acid
It
is
acid
by
HCI
and
necessary
the humic acid
carefully
reaction.
does
The
therefore
that
not
the
preci-
pitate easily.
In order
to
prevent
all
kinds
of
difficulties
during
the
786
filtration
of
the
humic
cylinder
the
clear
is
then
for
again
fluid
is
five
and
If
of
a
to
a
is
the
does
The
65°.
is
soon
this
10
cleaning
(Preparation
For
the
solution
is
These
products
a
cannot
better method
is
way
a
marked
adsorbed
a
the
water.
fine dark brown
vacuo
above P 0
2
5
isolated
a
few weeks.
A,
I
still
dry wood-flour with
drying
hot
repeated, since the humic
takes
in
hard
with
portions with ether in
dried further in
it
is
glittering products
strongly
this
procedure
and
an
eightfold
this solution with
above-mentioned way
B).
from
of
during
extracted
by
the
brown
hot ethanol
isolated
in
with
twice
or
% ammonia, precipitating
comparison
acid
be
remainder
funnel
once
the air,
the
preparation,
briquet
was
the
off,
in small
must
yield
powder
brown coal
were
in
mass
by extracting
quantity of
humic
from
otherwise
colloidal
a
Buchner
a
washed
obtained
The entire
humic acid
HC1,
yields
siphoned
mass
operation
not
This
Besides
about
free
precipitate anymore,
not
consistence appear.
preparation
powder.
for
be
now
The
mixed,
supernatant
repeated
be treated further. Therefore it is
The
mortar.
the
acid,
slightly
water
through
residue
dry this
we
easily
is
days
off.
well
water,
is
high
a
two
siphoned
will
water, do
now
grind the half-humid
acid
at
fluid
hard, coaly
very
fluid
in
after
and
day)
process
react
acid-free
filtered
carefully
be
left
acid.
clear
water.
still
must
moreover
filter
This
and
distilled
(% —1
off.
dispersed in the
with humic
The
with
settling
quietly
settles
may
The supernatant
but
particles
and,
filled
siphoned
times.
salts,
fluid
method
following
fluid is
precipitate
supernatant
cylinder
left
the
glass,
the
acid,
recommended. The acidified
was
used
some
the
obtained
coal.
For
at
(Preparation
first
days (large
alcohol).
C).
material
this
isolated
I
purpose
carefully
a
a
ground
treated with
quantities of bitumen
After
this
the
humic acid
787
At
last
(Prep.
is
Cassel
D).
rich
very
Cassel
The
Brown
products
acids.
this
Little
the
in
the
four
in
of
for
50
it
from
appeared
used material
of
%
products
comparison
brown coal which
that the
that the
alcohol,
methods
of
Afterwards
main
differences
variations in
material
laboratory
The table shows
agree
as
species
a
contained about
of
is soluble in
products
acid.
data of
properties
in table 2.
Brown is
in humic
unpublished
of
Brown served
Cassel
these
(A—D)
acids!
are
given
properties of the four
small
A
points.
this part is the
solubilities
part
of
the
hymetomelanic
are
the
result
of
preparation.
TABLE 2.
of
Solubility
Prep.
Almost
:etone
A
Prep.
Almost
non
soluble
:hanol........
Partly
the
humic
acids.
B
Prep.
Almost
non
soluble
soluble Little
C
Prep.
D
Non soluble
non
soluble
soluble Little
Almost
soluble
non
soluble
a-hydroxide
..
tnmonia
a-fluoride
Completely
„
Completely
„
Slowly
„
Slowly
„
„
Very
Very
....
little
Non
ater
soluble
little
Completely
Completely
„
Soluble
Very
„
little
Non
soluble
Non
Non
„
Non
soluble
Soluble
Completely
„
soluble
„
Non soluble
ydrochloric
acid
Non
The
„
is
humic acid is
in
a
easily
the
extract
results
solubility
obscure.
polymerisated
It
is
of
of
Cassel
possible
that
Brown in
here
the
less far and is therefore present
humic acid from peat,
this solvent
I could
this in agreement with
Simon).
properties
indeed
4.
complete
still
form soluble in Na-fluoride (with
The
§
for
reason
Na-fluoride
Non
„
of
the
products
from
the
wood
suggest
humic acids.
The
In the
“nitro”-compounds
preparation
of the
of the products obtained.
"nitro"-compounds the method
„
788
of Kiirschner
nitric
acid)
followed
was
well
as
the
as
mixture
(a
method of
of
ethanol
Fuchs
(5
and
nitric
n.
acid).
Preliminary
first
is
boiled
bottle
hour.
in
hot
water;
quickly.
This
mixture
for
with
again
The
with
is
on
poured
after
with
is
(4
in
1)
:
during
out
by
a
an
drops
settles
very
the alcoholic
filtration
nitric
precipitated
yields
a
through
is
powder
material
is lost
ether
and
Because
obtained.
the
an
the
during
Solubility
the
of
rather
is
a
large
quantitative
Kürschner)
Soluble
Brown
Very little
Non
acid
Na-hydroxide 2n..
soluble
Soluble
tt
ft
to
brown
Soluble
brown
the
of
deter-
from
Brown
Very
little
Brown
Soluble
ft
Very
soluble
Non
soluble
coal
(method Fuchs)
ft
soluble
Benzene
coal
(idem)
ft
Ether
treated
3.
Yellowish brown Orange
Ethanol
causing
“nitro’'-compounds.
Ebony (method
Acetone
part
nitric
omitted.
“Nitro”-humic acids
Colour
is
yellowish
to
operation,
“nitro”-product
TABLE
Glacial acetic
with
colloidal solution,
orange
a
Buchner
a
acidified
material). Afterwards the product
is
mination of
filtered
which
water
free of acid
of
absolute
Na-fluoride
the
ebony-wood
precipitate
is boiled with
and
from
mixture
and
of
superiority
water-bath
a
ochre-coloured
moment
washed
loss
nitric
filtered
precipitate
a
the
isolated
water.
(water
much
alcoholic
condenser
fluid
an
acid
“nitro”-compound
funnel,
acid
humic
the
reflux
The
hot
The
with
with
showed
experiments
method.
little
soluble
Non
soluble
Soluble
Soluble
ft
ft
ft
ft
789
For
comparison
treated
humic
used
acid
to
from
agreement
a
this
and
Elementary
from
table
there
the
of
a
coal
of
from brown
be
to
the
was
brown “nitro”-
from brown
appears
properties
those
brown
and
method of Fuchs
“nitro”-product
between
ebony-wood
acid
nitric acid
obtained. The
was
prepare
Also
§ 5.
humic
a
with alcohol and
also
was
coal.
complete
a
from
products
coal.
of the products and “nitro”-bodies
analysis
isolated.
The
Mr.
*analyses
L.
M.
v.
Meulen
en
Heslinga
Data
other
of
determined
are
d. Valk
according
(Rec.
trav.
investigators
the
request
my
the
chim.,
method
(1924)
included for
are
TABLE
Composition of
on
to
of
by
ter
551).
p.
comparison.
4.
isolated
products.
C
h
percent
perc.
N
2
2
Preparations
acid
*Humic
*
from ebony (NH 4OH
idem
Natural
idem
Humic
humic acid
4.1
59.7
4.9
59.6-60.2
3.4
60.7
3.5
58.6
4.3
NaOH
Sven
(after
Odén)
*“Nitro”-humic acid
from ebony
*
from brown
idem
"Nitro”-humic
60.4
)
„
(after Eller).
cleaned with
acids
isolation)
(NaOH
coal
acid
from
Cassel
Brown
acid
from
Cassel
Brown
(after Fuchs)
“Nitro”-humic
(after Kürschner)
§ 6.
The
This
igation
fusion
fusion
of
is
the
Hoppe-Seyler
with potassium
an
(19)
used
of
this
0.8
?
1.5
50.9
3.9
5.3
52.5
4.0
3.2
53.8
3.6
2.2
53.6
4.6
5.1
hydroxide.
important method for
composition
perc*
certain
method
a
closer
plant
already
invest-
materials.
in
1889
790
humic
on
later
by
acid
substances.
However
formed.
found
Also
The
latter
own
For
are
the
work
been
not
ebony
fused with 3
250°
continually.
during
and
water
The filtrate
a
was
of
used.
half
as
with
high C-content.
by
out
of
the
Van Scher-
shaken
melt
an
in
taken up
oil-
stirred
HC1
of humins settled.
precipitate
The further
with ether.
Van
humic
gramme
in
being
mass
was
and
tube
very
report.
a
0.5
sample
the
hour,
ebony
silver
a
been
warrant
of
each
KOH in
the
have
point
fir-wood,
dark brown
place according
a
masses
fusion
treatment
obtained
From
an
cooling
to
the
this
on
gramme
After
and
the
KOH
products.
results
lignin
were
brown
Eller
worked
carefully
investigations
but
this
at
protocatechuic
the fusion with
yielded
to
fusion
for other
(30)
superficial,
acid of
found
(35), who isolated
yielded humins with
the
of
products
penberg
My
those
have
products
with
fusion
According
products.
method
isolated
took
the
That
KOH of humic acids
and
as
pyrocatechol and phloroglucinol
as
(8) has occupied
acids.
accessory
bath
such
acid.
Eller
humic
was
with
agree
by Tropsch and Schellenberg
isophtalic
of
such
phenoles
results
Organic acids
investigators.
and
are
His
Scherpenberg.
operation
The results
given in table 5.
are
TABLE
Products present
in
the
extract
5.
from the
fusion
with
KOH,
Protocatechuic
Phloroglucinol
Pyrocatechol
Present
Present
acid
From
fir-wood...
From
ebony
From
humic
§
7.
In
of
acid.
Attempts
the
the
Present
ft
ft
ft
ft
—
to
isolate
preceding
humic
ft
acids
the
total
paragraphs
was
humic
the
matters.
alkali-soluble
investigated;
the
reddish
fraction
brown
791
of
product
the
wood
and
parenchyma
of
the
medullary
cells.
ray
In order
cellulose
isolate also the dark brown and black
to
and
lignin
be
must
removed
in
products
some
lignin and cellulose from humus containing
Karrer
and
prolonged
of
Bodding-Wiger
acetyl bromide (addition
the
a
of
method
and
lignins
on
sixfold
applied
humic
also
bodies
to
a
quantity
acetic acid promotes
in
this
case,
acetyl bromide
desirable,
seems
the absolute usefulness
the method.
To 1 gramme of the duramen-flour of
acetyl bromide
a
a
the action of
conclusion may be drawn
matter
recommended
22)
with
glacial
was
preliminary study
a
different
on
before
of
This
reaction).
although
(21,
of the material
treatment
To
way.
dissolve
flask
with
during
By
a
days.
few
It
with
only
This
to
of
was
residue
with
afterwards
of about
phenol
3
and
a
the
%
It
long
fractions
seems
of the
to
reaction
exposure
5
a
HC1
of
me
is
to
the
the
drying
A
longer
certainly yield still
% of
the
original
brownish
black
isolate
to
phenol
more.
crystals
quantity
and
by
matters
HC1 with
cellulose.
which
it, for
acids
case,
phenol
phenol
seems
to
also
believe
the
a
and
dissolve
(23)).
control
I
to
to
method
investigated
(Kreulen
for
Finally
However this
insufficiently
of
powder.
humic
from
obtained.
importance
time in this
to
and
wood.
in
40—45°
quantity of phenol
residue
humic
of
at
product soluble in ethanol and
was
difficulties adhere
many
centain
water-bath
the
gramme
warmed
was
much dissolved that the residue
wood with
lignin is converted in
liberate
so
considered
the
a
of
%
tenfold
a
about
residue
still
was
treatment
15—16
drops of HC1
amounted
wood.
on
ebony 12.5
whole
filtering, washing
After
to
the
with the solvent should
treatment
a
condenser
amounted
treatment
and
reflux
five
residue
added and
was
the
influence
that
cellulose
by
very
may
be
50
792
attacked.
point
in
As
is
Macrothis
formerly
which
be
cannot
acid it
amounted
these
The
in
have
of
after
acid,
Roughly
estimated
in alkali.
The
%
graphic plate.
wood with
It
of
difficult,
the
on
there
boiling
%
the
wood.
All
the
for
humic
after
a
acids
3
week
still brown. Moreover,
are
Effect”
effect
its
with
3
The alkali
weeks,
HC1,
appeared
about
5.5
%
wood basis.
should
and
be
in
present
3—5
humic
%
the
bodies
of the wood.
is the action of the wood
smooth
to
continually.
after
dry
acid
The method
dark and
employed
surface
keep it about
on
a
was
a
on
photo-
a
place
to
a
photographic
week in
an
piece
plate
incubator
at
37).
found
was
action,
of
weight
assembled
humic
“Russell
The Russell
(29,
repeated
the cellulose in 72
much.
very
very
the
brown
brown part remains and
lignin proceeds
calculated
insoluble
40°.
the
precipitation
5—6
in the
of
us
also
wood,
duramen
of
that this
%
after
dissolve
determination
is
of the
the
contain,
§ 8.
we
in
contains
keep in mind that, under the influence of alkali,
to
extracts
to
seem
isolated
ebony
with NaOH the filtrates
autoxidation
humic
not
alkali
treatment
to
3
tell
quantitative
soluble
we
do
cellulose
of
removed
If
appeared
about
to
data
the
stated,
in alcoholic nitric acid.
sulfuric
reactions
microchemical
determinations
quantitative
pieces,
and
direction.
while
Therefore
that
the
duramen
the alburnum
the
duramen should
had
rather
a
without influence
was
be
the
seat
marked
(fig.
1).
of oxidations.
In this connection I may refer to the
study of Haslam (18),
who has
coal
a
found that substances like
photographic
of this process
plays
an
plate.
must
According
be ascribed
important part.
to
to
have
him
the
an
action
main
on
cause
oxidation, while moisture
793
It
is
not
however,
possible,
experiment,
the
as
basis
of
to
the
conclude much from
Russell
effect
still
this
seems
obscure.
Fig.
1.
"Russell
week
at
40°.
A
Effect”
=
of Diospyros
alburnum,
duramen, positive
C.
§
of
Microscopy
1.
Introduction
For
the
the
Also
of
these
species
D
a
=
effect.
ebony-wood.
investigation
was
observations
Diospyros ferrea,
effect.
.
microscopic
Gjaja merah. This wood
igation.
ferrea after
negative
D.
was
celebica
kindly
also
made
were
and D.
sent
was
used for
to
on
discolor.
me
chiefly
chemical
used
invest-
sections
of
The material
by the "Forestry
794
Station”
Experiment
were
cut
had
2.
Buitenzorg,
at
wood
a
undergone
during
§
with
microtome
other
no
sections
which
blockletts,
than
operation
The
Java.
from
boiling
in
water
hours.
some
Anatomy.
The anatomic characterisation of the wood may be brief
as
this
on
subject
(24),
Ebenaceae
wood
1°
parenchyma
broad,
Vessels
ted,
only
dullary
one
row,
three
other,
tangential
and
there,
parenchyma
these
tra-
me-
and
in
to
two
each
structures.
very
dark
samples, especially
where
ferrea,
black.
nearly
The
it
is
points
Fig.
the
2.
Transverse
duramen
Diospyros
chyma;
M
of difference and agreement
the
anatomy
species
6.
of
are
the
a
stated
in
T
T with
P
=
a
merah
wood
are
mass,
dark
F
rays;
=
The
filled with
those
brown
substance.
=
paren-
wood vessel.
and M
reddish brown
and
section through
Gjaja
medullary
=
lumina of P
va-
of
spec.
wood fibres;
table
cells.
Ca-oxalate.
duramen is
D,
rious
cell
one
species investigated
in these
in
rows,
and
2).
showed
in
vessels,
containing
of
The
The
the
isola-
here
next
rows
around
generally
occur
many
crystals
(fig.
here
The
but
there also cells
of the
position
very spar-
are
rays
Janssonius (20).
characteristic
narrow,
in radial rows;
are
row
scattered
some
distributed.
sely
one
in
either
occur
or
cheids
or
in
interrupted
sometimes
a
and
namely:
metatracheal:
3°
by
given by Molisch
are
(27), Wright (38)
marked
are
paratracheal:
2°
in
good descriptions
Parmentier
to
of
F
black
795
TABLE
Colour
of
the
cell
Gjaja
Medullary
ray
cells
6.
of the
contents
merah
Reddish
three Ebony
D.
brown
Empty,
ferrea
a
times
s
3
Ö
Ui
X>
<
few
D.
celebica
sometimes
Empty,
some-
yellowish
yellow
brown
Wood
Reddish brown
parenchyma
Empty
Empty
cells
Wood fibres
Without
coloured
Without
contents
Wood vessels
Some
Medullary
ray
coloured
with
yellow Some
with
contents,
empty
empty
D.
Reddish brown
coloured
contents
contents, further
cells
Without
contents
Gjaja merah
ö
species.
yellow Some
further
with
yellow
contents, further
empty
ferrea
Yellowish
D.
celebica
Dark
brown.
brown
to
brown
to
<y
sometimes
a
rö
Ui
Q
Wood
Reddish brown
parenchyma
black
black
Brown
Dark
cells
black
Wood
fibres
Dark
brown
Black
to
Light coloured.
black
Wood vessels
The
walls
the
of
the wood of D.
The
structure
showed
very
rather
§
3.
a
limit
a
Microchemical
me
If
places
The
we
results
are
of
at
of black
between
this
lamella
of
Black
coloured,
a
D. celebica
in
except
yellowish
the
consequence of
duramen
and
transition
in
tinge.
and D. ferrea
products present
narrow
very
in the cell
alburnum
zone
is
is present.
reactions.
microchemical
in
the
table,
between alburnum and
primary
not
“coaly” aspect
the
collected
look
are
of the duramen of
sharp, only
The
by
at
elements
ferrea, where they have
large quantities
lumina.
brownish?
Black
Black
the
following
we
can
reactions
performed
table.
percieve great differences
duramen. The middle lamella
two
parts
are
strongly
plus
lignified.
796
TABLE 7.
PROPERTIES^
MICROCHEMICAL
DURAMEN
Secundary layers
Reagents
lamella
Middle
+
lamella
prim,
parenchyfl
Wood
Vessels
Libriform
medullary
Phloroglucinol
and
Dark
Yellow
sulphate
Fuchsin +
Mäule
here
and
rays^
there
all
1103
uncoloured inner lamella
HC1
Aniline
with
Red,
Red
red
13
HCl
Red
to
Yellow
little
a
more
feeble
Yellowish red
brown
Brownish
react.
Ruthenium
red
red
Yellowish red
Red
Almost
uncoloured
%
Oxamin
4
blue
Rx
Violet
to
Yellowish brown,
here
and
there
lighter
light-brown
Methyl
red
Diethyl
Iodine
Yellow
red
in
Yellow
orange,
sometimes
Yellow, here and there
pink
more
more
pink
ZnCl
in
„
to
Yellow,
on
the
damaged spots
blue
KI+ H 2S0 4
Does
acid
Sulphuric
not
and
72%
dis-
solve, swells
up
becomes
brown.
Dissolved
for
a
great part;
Dissolved
party brown
(humification)
Phenol +
HC1
after prolonged
Walls
dissolved ;
dissolved
contents
become
treatment
Trichlor
acid
Walls
dissolved.
Contents
dissolv
e
acetic
after
longed
not
lighter
pro-
treat-
Walls
dissolved ;
dissolved
contents
become
not
lighter
Walls
contents
dissolved
not
e
d
diss
ment
Sodium
hydro-
Unchanged
xide
Alcoholic
nitric
acid
Acetyl
Contents
become
bromide
almost
not
dissolved,
Contents
dissolv®^.
Contents
dissolv
light yellow
Contents
not
dissolved
ed
797
Actions
of
ebony-wood.
»
—
ALBURNUM
Secundary
Middle
'
layers
NOTES
lamella
prim,
Wood
lamella)
Vessels
Libriform
chyma
lary
Dark
Red,
red
no
colourless
Yellow
Red
Red
Red
medul-
;
rays
Colour alburnum
with
something
than
duramen
orange
stains
Consequently
Colourless
Red
dar-
zones
ker
öeep yellow
Red
paren-
red
lignified
strongly
lamella
‘Wish
Colourless,
violet
here
and
there
on
the
damaged
blue
spots
pH
Red
about
duramen,
5.8—6,0?
here
Yellow;
the
and
there
fibres
with
a
Walls
lighter
wall
zone
in
little
dissolved
of
the
dissolved
A
“town
lignin
Dissolved
but
brown
dissolved
dissolved,
not
in
the
contents
un-
visible
not
sections
humification)
vessels
brown
more
Cellulose
Not
4.4
pH alburnum about
Red
;
changed
After
Walls
Walls
dissolved;
no
contents
dissolved
is
dissolved
Contents
Walls
dissolved;
no
contents
for
boiling
time
short
a
only lignin
contents
dissolved,
(mace-
ration mixture)
not
dissolved
After
short
the
tissues
broken,
not
treatment
are
only
dissolved,
(maceration agent)
Contents
Unchanged
dissolved
Contents
|
After prolonged
treat-
ment
Lignin is
cellulose
dissolved
reaction
dissolved
positive
Contents
1
not
partly
dissolved
Lignin
and
dissolved
cellulose
798
(It is
the
certain
not
red of
the
cellulose
takes
pectin).
It
iodine
in
(with
a
yellow
colouring
3.
of
Transverse section
through
the
Diospyros
spec,
with
ment
duramen
stance
P
and
as
M
in
it
has
we
except
4.
xide,
the sub-
2.
and
From P
the
in
lamella
that
brown.
(A
very rich
in
swells,
but
humification,
lignin).
does
not
perhaps
Sulfuric
acid
after
spec,
and
as
M
fig.
sub-
in
pits
black
spots
figure.)
and
because
this
does
attack
not
in
the
disappeared
the
(the
the
dissolve
of
treat-
sodium hydro-
from
walls
section
duramen
has
stance
not
walls
primary
Radial
Lettering
except
not.
the
the
with
ment
and
are
the walls swell
Diospyros
fig. 2.
that
chloride
acid)
undamaged
see
Fig.
treat-
has disappeared
from F
zinc
the
ruthenium
remarkable
through
of
sodium hydro-
Lettering
From
after
is
sulfuric
dissolve,
they
with
colouring
potassium iodide plus
Afterwards
clearly.
xide.
red
to
place. With 72 % sulfuric acid
very
Fig.
only
the
points
reactions
with iodine in
positive,
that
lamella
becomes
lamella
the
is
cell
contents.
These
contents,
different
namely
according
reagents, may
the
reddish
be
brown
to
their
divided in
mass
behaviour
at
from
least
the
two
towards
groups,
parenchymatic
799
tissues
and
the
vessels
and
the
solution
dark
brown
the reddish
causes
dissolved, while the black
The
wall
black
is
brown
acid
masses
in
of
dissolves
matter
in
(4
but
1),
:
is
The black
insoluble
nitric
in
sodium
As in
The
the
be
reagents
very
that
changed
lumina. G.
finds
position
vessels
that
boxilation
This
and
Czaja
be
to
alcoholic
phenol
plus
fibres
humic
of
(13)
the
of
such
a
matter,
leads
interesting
dyes;
the
into
deposited
humic
cell
contents.
moreover
in alkalies,
the
to
undergone
a
sup-
decar
-
humins.
in
my
strong
preliminary
cell
results
(5).
blue
4
in
the
dyes.
On
support
metachromatical
regarding
oxamin
could
acid
insoluble
have
rather
with
dyes
us
Jr. believes that perhaps
formed
acids
finds
sections
published
acids,
mentioned
already
duramen make
“duramification”
Ca-containing
the
some
in the fact that Ca-humate
under the formation of
opinion,
two
the
black
the behaviour of these
with
the
by
the
these
communication
coloration
not dissolve.
lightbrown,
to
the
into humic
that
accumulated in the
the
colour
denied.
of
explanation
so
of
changed
Iterson
van
an
insoluble,
The presence
in
the
appear
and
acid
acetic
bromide,
acid
reactions
lignin
been
this process
fibres
acetyl
acetic
cannot be
supposition
has
the cell
hydroxide,
the colour
cases
these
weaker
justify
lignin
hydrochloric
alcoholic nitric
an
reagents
and
reddish
acid.
some
action of
vessels
a
towards
The
and
trichlor
in
these
4).
filled with
are
matters.
phenol
totally
3 and
(fig.
behaviour
and in
the
hydroxide
be
to
light-yellow, but does
trichlor
mixture,
hydrochloric
is
in
With
of
contents
The
insoluble
of the substance becomes
cells
humic
also
bromide.
acetyl
contents
ray
alkali.
characteristic
sodium
remain intact
medullary
from
products
with
brown
(after prolonged treatment)
mixture
and
the
insoluble
mass
alkalies
of
pits
black
to
Treatment
fibres.
walls
After
Rx
in
general
colouring
and
brillant
800
the
the alburnum
blue,
Congo
duramen
substance
dense
that
the finest
particles
The
blue
the
damaged
with
the
the
parts
the
the
not
particles
of
be
to
in
preparation
cellulose
which
that
particles
is
the
be
to
fact
that
quoted for
fully
be
cannot
that the
accepting
has
the walls
of
the
this
Method
igation
of
cutin and
between
analogy
and
therefore
I
used
recommended
from
pH
4.4—6.0
The walls of
and there
a
the
a
the
method
be
may
acids
fatty
data
obtained
indicators
and
Range
applied
used
an
to
duramen
are
lignin
red
trusted
diethyl
red
yellow,
derived that
the
less
be
range
yellow.
to
here
with
those of the alburnum
be
now
is
They have their
coloured
too
invest-
and
cannot
methyl
by Armstrong.
may
is
(33)
(resp. 6.5) and change from
facts it
explained
higher fatty acids (1). Just
on
higher
as
Small
react
has acid char-
walls, according
lignin
feebly pink tinge,
From these
the walls
by
without
the duramen. The
from
(R.I.M.)
Armstrong
implicitly.
red,
from
determination. This
pH
for suberin,
plain
stain
duramen
lignin complex which
partly disappeared
Indicator
the
the
supposition,
our
accepted
less acid than those of the alburnum. This could be
to
are
has
size).
opinion
my
criticism,
acter
so
able
are
only by different staining
explained
different
A second argument that is
by
is
cannot
less dense and
yellow,
the
largest
dye
lignin has partly
has become
of
wall
(That the strongly lignified primary lamella is stained
violet is
but
of
and
the
alburnum
which stain
dyes;
adsorbs
the
duramen the
dye,
colourless
Consequently
particles
structure
of the
interstices
largest
in
be
to
in
lignin)
smallest
the wall
penetrate.
blue.
the
even
disappeared,
coloured
to
and
Apparently
penetrate.
to
yellow
(cellulose
appeared
brown.
are
lignin
red.
from
(and chiefly from the secundary layers) undergoes
humification.
According
(17)
now
to
the
the
latest
presence
publication
of
lignin
in
of
Harlow
these
in
layers
1933
seems
801
be
to
demonstrated,
fact,
a
formerly
disputed
by
some
investigators.
In
with
agree
wood of
While
the
the
general
the
had
layers
nization process.
The
still
The
be
to
seen
humification
In
walls.
small
globules
A
D.
these
note
on
of
the
wood
reactions
lying
the
Ohara
the
was
for
the
unchanged,
carbo-
great
a
part,
pressed together
rays
reddish brown
a
in
humic
lost
medullary
in
kept
were
humification and
a
structure
and
began
layers
of
microchemical
(26), who has investigated
undergone
but remains of vessels
were
the
than 1800 years old, found in Korea.
more
inner parts
outer
of
those of Ohara
coffin,
a
results
ground
secundary
could show
mass.
of
layers
the
the presence
of
formation
of
matter.
and
concept
the
“Humus”.
While
exhaustive discussion of this
an
the scope of this paper,
that
pertinent
are
We
to
indebted
are
a
few
our
investigations
Oden
study about humic acids with
to
1919,
in
this
in
In
this
study
humus
way:
and the
alkalies)
he
coals
Waksman,
prominent
highly
have
that
for
the
us
the
complex
been
they
used
are
which
great
for
water
into
and
other
soil
entities”,
of
the
is
(36).
investigator,
caused
humus.
giving
the
by the
“Words
impression
The “humic
formula
empirical
acid",
Especially
acids”
QHj. 75O0 •95
they have colloidal properties, adsorb
matters
very
humins under evolution
Eller
American
which
insoluble
“humic
are
up
products
part
acid”.
confusion
an
humic
(the
which
preparations,
gives
should be tetravalent;
the
“fulvic
nomenclature
chemical
Oden
and
extensive
an
literature index
humins
or
for
(25)
large
soluble parts,
acid"
shown
a
classified
“hymetomelanic
has
will be mentioned
problem.
Sven
to
lies outside
matter
(7) has also worked
strongly
of C0
on
2
and
may
change
.
humic acids.
He
compared
802
the
natural
hydrates
the
acids
and
natural
with artificiel
phenoles.
humic
acids
artificiel acids from
from
concluded
that
lignin and humic acid
related
formula
molecule
for
should
oder
mehrfach
vermindert
um
lieferenden
should lead
The
to
with
Marcusson,
of
formed
are
believes
doppelt
und
and
he
adds
molecules,
(12).
has
because
from
others
occupied
many
that the
for
plead
Grosskopf
theory which
Schrader
of the presence
the
of
is
(31)
etc.
are
benzene
a
able
to
supporters
nucleus
prove
in
from
of
a
the
the
his
KOH.
in
According
nature
Fischer
study,
gave
the
acids
formation
in
the
this
investigator
Schrader
their
important theory
of
time
afterwards
of
coal;
the
this
the
of
presence
and
course
and
to
(10),
on
lignin is
is
lignin
presence
process
alkaline
on
also
substances!
Schrader’s
the formation of coal.
transformed
procedure
cellulose
and
experiments
this
building
for-
furan
molecule.
lignin yields humic acid by autoxidation in the
occurs
In
accepts
Do
Chardet,
lignin?
ring in the molecule. On the contrary Eller, Fischer
Schrader,
that
finally
by dying plant material.
and
(4)
Benzolcar-
Lignins,
graphite
or
a
that
und Protocatechusaure
nature
cellulose
Burian
gives
(19) already stated
Seyler
from
even
he
verkniipft
such
to
be built
must
“den
des
Lignins"
humus in
of
Hoppe
originate
from
up
rise
give
mation from cellulose,
of
the
treatment
He
Ringschliessung
the formation
humic substances
and
hydroxylreichen
which
formation
investigators.
they
built
Bauelemente des
processes
acid
Grundkomplex
durch
die
molecules.
humic
be
bonsauren lieferenden
that
of
properties
closely
more
agree
from carbo
phenolic bodies than with those derived
closely
very
structural
the
the
and of natural humic acids with nitric acid Fuchs
from
the
obtained
that
investigation of the products yielded by
an
lignin
(11)
up
acids
thinks
carbohydrates.
From
of
He
goes
on
to
humic
until
decomposed
by
the
the
803
activities
at
first
to
the
of
would
lignin
The
in
to
successive
consisted
parts
the
fir-wood;
and
stated
believes
lignin
the
All
complexes
the
the
part,
convinced
shows
products
it
complexes
of
“humic
acids",
because
of the
of
states
the
still
that
way
but
with
an
he
other
cellulose
humic acids
and
from
E.
Discussion.
lignin
course
of
He
markedly
follows:
as
as
acids
to
status
of
as
of
the
as
do
so
presence
the
entire
coal
give
further
are
latter
matters.
the
term,
terminalogy.
Bergius
formation.
rise
of
compo-
to
connection that
lignin
formed
products
this
the
complexes
avoid
of
not
are
chemical
to
this
is
publications,
accept
These
greater
bacteria.
imply. Waksman
variable
different for both
such
—�
During
the
humification
conception
be
may
by
latest
seem to
wishes
well
for
rendered resistant
are
confusing
should be
the
of
microorganisms.
lose
In
his
others
It should be mentioned in
has
coal.
humic
—�
attacked
reasonable
very
complexes
(3)
be
to
process
disappeared
is
questions
ligno-protein
attack
brown
which should contain aromatic
one
sition.
rapid
the
cellulose
in
the
is
These
youngest
remains
decreases
content
substance
(36),
that
that
of
substances
Grosskopf and
as
the
and
great
which
composition of these materials
of
course
this
Waksman
simple
needles
consisted
lignin
humification the
because
of
are
hardly attacked by microorganisms.
are
(9)
should lead
proportional increase of humic products.
a
these
(14)
humification;
green
parts
intermediary
—>■
humins.
of
the chemical
that
this
He used natural materials,
almost
eldest
concomittant with
He
Grosskopf
stages
of
compared
now
of
subject.
our
Fischer
to
acids.
humic
investigations
According
acetic acid and
yield
formation of
importance
were
microorganisms.
to
coal,
From
He
but
cellu-
intermediary products
not
investigation
originate.
it
appears
that
the
804
from
lignin
disappeared
been
acids
walls
in
From
transition
instance
phenes
humic
has
of other
the
of
lignin
an
with
the
humic
in what
It
ebony-wood.
is
in this formation.
the duramen
phloba-
is still
the
Moreover,
uncertain
relatively
ebony-wood
of
lignin
than
composition
the
lignin
oxidation process. The
formation
ideas
current
oxidation
and
of
disappearance
duramen
the
on
reduction
be
may
of
presence
in
systems
the
cells.
living
the wood
elements
to
parenchyma and medullary
remain
substances
be
alive
which
regarded
as
lumina,
precipitate,
because
humification,
initial
—
the
stage of
While
oxidation
we
which
goes
paper,
cell
In
see
Ca-compounds
as
calcium
contents
the wood
already
therefore
this
on
coloured substances
in
oxidation
matters
products.
products
in the
is
cell
present
non-“duramified”
the
may
meet
we
These
appearance
be
regarded
—
of
this
as
the
“duramification”.
during
less-soluble
time,
alkali.
of the first
perhaps
in
longest
in
cells, which
ray
of the walls and the oxidised
(crystals of Ca-oxalate).
alburnum
soluble
some
out
the
during
still
are
lignin oxidises
probably
this
humic
to
conceive of the formation of humic
the
during
have
perhaps be transformed
that the
other
must
as
the
that in
general
possible
of
lignin
remains obscure
in
place
of
partly
products
(Hoppe-Seyler).
in
somewhat
lignin
complicated
the
it
has
properties
products participate
lignin
plants. We
explained
The
but
appeared
substances
a
acids from
are
has
is very well
again
In
takes
duramen
lumina
present and these could
are
constitution
and it
it
the
cell
transition
a
possible,
that still other
possible
into
literature
be
of
the
characteristic
with
the
to
seems
this
For
of
cell
that
deposited
acids.
way
the
and
“duramification”
with
are
alkalies;
the
full
products
cells
strength
and
which
become
found,
but
the
in
from
the
case
wood
die,
more
the
brown
increasingly
investigated
parenchyma
in
and
805
medullary
part
so
What
In
is
these
that
insoluble
in
consequently
not
be
does
with
nearly
in
these
Still
a
zation
take
It
is
not
It
stages
be
(to
the
appears
wood
far
that
C-content,
fibres
are
been
left
passed
the darker the
and
case
very
positae
to
which
Fuchs
humic
are
and
products become.
and
carboni-
incomplete
final
matters
to
which
also
in
the
black
of
products
seem
to
products
are
the
formed
This idea has
that
acids
the
be
to
this
peculiar
the author that the above-ment-
rise
related
closely
the cell wall.
of
give
more
Ebenaceae.
acceptable
they
the
quickly,
very
plainly
very
not
with
The
place.
is
mass
that
possible
taken
why
moreover,
brown
ferrea).
the
products
may
parenchyma
ioned processes of "duramification” would be able
so
They
and
has
seen
this
have
been
these
be,
may
that
possible
to
further
walls
have
intermediary
duramen of
oxidised
clear,
very
be
might
the
brown
vessels
the
soluble reddish
Diospyros
Whatever,
it
vessels?
with
explanation which
of
decarboxilation
place
humification
the
It
proceeds,
further
the
dark
is
and
rays
while
different process
duramen of
to
mass
the
first
“duramification”
Probably
that the
so
the lumina
dark
anywhere.
the
and
already
How is
medullary
elements
oxidation
that
the
largest
in the lumina of these elements?
uncoloured!
present
or
for
the
exclusively
which
product
a
decarboxilated.
apply.
not
nearly
for
in alkalies.
wood fibres
NaOH,
contain calcium,
accepted
filled
the
meet
we
substance is present
do
of
transformed
non-soluble
are
condition
probably
and
been
not
they
elements
substance
black,
have
rays
far
finally
related
with
identical
with
phytomelans
in
perhaps
graphite
the
a
of
primary
to
proceed
very
high
in any
or
the Comlamella
support in the
should
compounds.
a
of
opinion
originate
from
806
F.
Summary.
The
1.
of
of the duramen and of the alburnum
composition
have
ebony-wood
been
with
compared
that
of
firwood.
2.
In
the
which
The
3.
duramen substances
are
soluble
partly
substance
soluble
and
in
The
5.
contents
alkali
appeared
of
have
to
humic
a
the
acid.
acid.
From
strated
examination
microscopic
a
that
another
the
duramen
than
way
duramen has
6.
cell
agreed in qualities with “nitro”-
“nitro”-products
humic
the
partly insoluble in alkali.
properties and the composition
4.
in
occur
the
partly
behaved
could be
demon-
microchemically
The
alburnum.
lignin
of
in
the
disappeared.
The
humic substances
their
in
origin
it
the
in the
lignin
cell
that
contents
might find
disappeared
from
the
walls.
7.
Due
of
the
to
The author
Dr.
in
Ir.
G.
these
Dr.
Ir.
part of
May,
lack
total humic
wishes
van
Iter
problems
A.
C.
this
of
good
did
matter
to
Jr
for
for
his
for
the
determination
succeed.
not
express
son
and
Sleep
methods
his
thanks
his
unwavering
to
Professor
interest
helpful criticism and
her kind
help
with
to
miss
the chemical
study.
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for
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