ISSN 1070-4272, Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 6, pp. 1040–1045. © Pleiades Publishing, Ltd.

, 2011.
Original Russian Text © E.I. Evstigneev, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 6, pp. 1019–1024.

MACROMOLECULAR CHEMISTRY
AND POLYMERIC MATERIALS

Factors Affecting Lignin Solubility

E. I. Evstigneev
St. Petersburg State Academy of Forestry Engineering, St. Petersburg, Russia

Received March 28, 2011

Abstract—The solubility of lignin in aqueous NaOH solutions was studied in relation to the lignin
molecular weight, temperature, liquid to solid ratio, and ionic strength. A new procedure for determining the
content of phenolic hydroxyls in lignin was developed. A formula was suggested for calculating the lignin
solubility in aqueous alkali solutions.
DOI: 10.1134/S1070427211060243

It was found previously that the solubility of lignin
in aqueous NaOH solution is a function of pH of
solution and рKа of lignin acid groups and that the
lignin dissolution in alkali is essentially the
fractionation based on differences in the acid–base
properties of phenolic hydroxyls in the dissolving
fractions [1].
In this study we examined how the lignin solubility
depends on the molecular weight, temperature, liquid
to solid ratio, and ionic strength, with the aim to reveal
the major factors affecting the lignin solubility in
aqueous alkali solution.
EXPERIMENTAL
A procedure for determining the lignin solubility in
aqueous NaOH solution was determined in [1]. In
experiments on studying the temperature dependence
of the lignin solubility, all the manipulations including
the dissolution, filtration, and washing were performed
at the same (preset) temperature. The conditions for
cooking spruce chips and recovering lignin from
liquors were similar to those described in [2]. We also
studied sulfate lignin from Solombala Pulp-and-Paper
Combine, recovered from black liquors from cooking
of coniferous wood (pine, spruce). The content of
phenolic hydroxyls in this lignin was 4.06 mmol g–1.
Lignin samples were recovered from spruce wood
by the procedures described elsewhere: Freudenberg
lignin [3], Björkman lignin [4], Pepper lignin [5], and
dioxane lignin [6].
Fractionation of dioxane lignin was performed by
fractional dissolution in the dioxane–benzene system.
A 2-g portion of lignin was poured over with 100 ml of
the mixed solvent. The mixture was stirred for 2 h with
a magnetic stirrer and left overnight. The undissolved
fraction was separated on a glass frit, and the solvent
was distilled off from the solution on heating on a
water bath to 50°С in an argon stream first in a water-
jet-pump vacuum and then in a rough vacuum. The
isolated fraction was dried to constant weight in a
vacuum oven at 50°С. The undissolved part was
poured over with a mixed solvent with a higher
dioxane content, and all the operations were repeated.
After the weight of the isolated fractions reached
approximately a half of the weight of the initial lignin
portion, the undissolved part was poured over not with
100 but with 50 ml of the mixed solvent. The mixed
solvent composition was varied by adding to benzene
increasing amounts of dioxane.
The number-average molecular weight was deter-
mined by vapor osmometry with a Hitachi Perkin–
Elmer 115 device in dimethylformamide at a lignin
concentration of 10 mg ml–1. In studies of the lignin
solubility in relation to the molecular weights, we used
the fractions with M̄ n 610, 1044, 1555, and 3645. The
spectra of dioxane lignin fractions and other lignin
samples were recorded with a Shimadzu UV-2400PC
Series spectrophotometer.
As shown previously [1], the solubility of various
lignin samples in aqueous alkali solutions can be
characterized by the quantity S at f = 0.5, i.e., by the

1040
 FACTORS AFFECTING LIGNIN SOLUBILITY
solubility of the sample in which phenolic hydroxyls
have been titrated by half. In this connection, it is
necessary to develop a procedure allowing determina-
tion of these groups with sufficiently high accuracy in
relatively short time.
Two methods are mainly used today for determine-
ing phenolic hydroxyls. The first of them is the
Mansson’s method [7] based on aminolysis of
acetylated lignin under the action of pyrrolidine:
O H
N practically does not overlap with the adjacent bands.
H3C C O Lignin +
O
H3C C N + OH Lignin.
The content of phenolic hydroxyls is determined
from the kinetic curves in the following coordinates:
amount of acetylpyrrolidine formed–reaction time. The
method is highly selective but time-consuming and
requires preliminary derivatization of lignin.
The second method is based on the bathochromic
shift of bands of phenolic compounds upon ionization
of phenolic hydroxyls [8]. The method consists in
taking a differential, or so-called Δε, spectrum by
directly measuring the extinction of the alkaline
solution (pH 12) of lignin and model compounds using
as reference solution neutral (pH 6) solutions of equal
concentration. The differential spectrum of lignin (Fig. 1)
has three characteristic maxima: at 250, 300, and 350–
360 nm. The content of phenolic hydroxyls is
calculated from the extinction coefficients of model
ΔI, rel. units
λ, nm
Fig. 1. Differential spectrum of sulfate lignin from
Solombala Pulp-and-Paper Combine. Lignin concentration
0.036 mg ml–1. (ΔI) Intensity and (λ) wavelength.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 6 2011
1041
compounds. The method is fairly rapid but insuf-
ficiently accurate because of the overlap of bands used
for the analysis (at 300 and 350–360 nm). Further-
more, it requires availability of model compounds of
various structures.
The method I suggested combines the advantages
of each method and involves differential spectroscopy
of a lignin sample with a known content of phenolic
hydroxyls. Their content was determined by amino-
lysis. The band at 250 nm (Fig. 1) is symmetrical and
Therefore, it is well suited for construction of a
calibration curve.
Initially we plotted the calibration curve in the
coordinates optical density–lignin concentration (Fig. 2).
Then, knowing the content of phenolic hydroxyls in the
sample, we plotted the curve in the coordinates optical
density–concentration of phenolic hydroxyls. Having
recorded the differential spectrum of a test lignin
sample and knowing its concentration, we calculated
the content of phenolic hydroxyls in the test sample.
To evaluate the accuracy of the suggested method,
we examined a wide range of alkali lignins in which
the content of phenolic hydroxyls was determined by
aminolysis [9]. The standard deviation of the method,
based on the results of eight replicate determinations,
starting from weighing the sample, was ±0.13 mmol g–1.
The results are given in Table 1. As can be seen, for
the majority of samples the absolute determination
error was within the standard deviation. The same
concerns the samples recovered by mild treatment
(Table 2).
ΔI, rel. units
c, mg ml–1
Fig. 2. Optical density of the absorption band at 250 nm ΔI
as a function of concentration c in differential spectra of
sulfate lignin from Solombala Pulp-and-Paper Combine.
1042 EVSTIGNEEV

Table 1. Content of phenolic hydroxyls in soda and sulfate Table 2. Content of phenolic hydroxyls in spruce lignin
lignins samples recovered by mild treatment
OHphen content, mmol g–1 OHphen content, mmol g–1
Cooking time, absolute
min Sample absolute
aminolysis spectroscopy determination
aminolysis spectroscopy determination
error
error
Soda cooking
Björkman lignin 1.80 1.78 –0.02
60 2.67 2.82 +0.15
Pepper lignin 2.66 2.58 –0.08
90 2.95 3.05 +0.10
Dioxane lignin 2.83 2.93 +0.10
120 3.06 3.15 +0.09
150 3.13 3.25 +0.12
180 3.22 3.42 +0.20 is the amount of groups accessible to solvation, rather
than the macromolecule size [10].
Soda–anthraquinone cooking
Using the method developed, we determined the
60 3.09 3.23 +0.14 content of phenolic hydroxyls in dioxane lignin
90 3.34 3.30 –0.04 fractions. It decreased in the following order with an
increase in the molecular weight of the fraction: 3.40,
120 3.42 3.65 +0.23 3.15, 2.95, 2.05 mmol g–1. This trend becomes more
150 3.51 3.62 +0.11 descriptive if we express the content of phenolic
hydroxyls as the number of groups per 100 phenyl-
180 3.78 3.90 +0.12 propane units (n/100 PPU). Then this series will be 62,
Sulfate cooking 58, 54, 38/100 PPU. In other words, the lignin
solubility is determined by the ratio of the number of
60 3.14 3.11 –0.03
hydrophilic groups to the number of phenylpropane
90 3.49 3.38 –0.11 units in the macromolecule. The higher this ratio, the
higher the solubility.
120 3.41 3.47 +0.06
By plotting the dependence in the coordinates
150 3.70 3.89 +0.19
solubility–content of phenolic hydroxyls, it is possible
180 3.81 3.75 –0.06 to determine the minimal ratio n/100 PPU required for
Sulfate–anthraquinone cooking
lignin to pass from the solid phase into the solution.
Extrapolation of the linear portion of the curve to the
60 3.22 3.30 +0.08 abscissa showed that this ratio was about 1.7 mmol g–1,
90 3.59 3.50 –0.09 or 31/100 PPU.

120 3.74 3.80 +0.06 The adequacy of the results obtained was checked
independently, by analyzing changes in the content of
150 3.90 3.92 +0.02 phenolic hydroxyls in the dissolved and residual
180 4.05 3.90 –0.15 lignins in the course of sulfate cooking of coniferous
wood and Freudenberg lignin according to [2, 11–14].
The results obtained show (Fig. 4) that, throughout the
cooking process, the content of ОНphen in the residual
The dependence of the lignin solubility on the lignin (solid phase) does not exceed 1.64 mmol g–1, or
molecular weight is shown in Fig. 3. A decrease in the 30/100 PPU. In the dissolved lignins, the minimal
solubility with an increase in the molecular weight is content of ОНphen is 40/100 PPU. Thus, the value
typical of all polymers, but lignin has certain specific obtained (31/100 PPU) is well consistent with the
features. For example, thermodynamic studies showed independently obtained data. Note that it is
that the decisive factor in formation of lignin solutions characteristic both of native lignin (lignin in wood) and

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 6 2011

 FACTORS AFFECTING LIGNIN SOLUBILITY
Sf =0.5, wt fraction
log M
Fig. 3. Solubility of spruce dioxane lignin fractions Sf =0.5 as
a function of the logarithm of the molecular weight М.
Sf =0.5, wt fraction
T, °C
Fig. 5. Temperature dependence of the solubility Sf =0.5 of
sulfate lignin from Solombala Pulp-and-Paper Combine.
of the recovered samples (dioxane lignin and Freuden-
berg lignin).
The temperature dependence of the lignin solubility
is shown in Fig. 5. With an increase in temperature, the
lignin solubility linearly increases with a relatively low
temperature coefficient, i.e., the ratio Sf=0.5/1°C =
0.004, and at 100°C the lignin fully dissolves. High
solubility of lignin at room temperature should be
noted.
The dependence of the lignin solubility on the
liquid to solid ratio is shown in Fig. 6. The dependence
is stepped. It shows that the lignin solubility decreases
with an increase in the liquid to solid ratio. The
maximal solubility is attained at Н = 5 l kg–1. This
trend can be accounted for by the following facts. In
all the experiments, the lignin solubility was
determined at f = 0.5, i.e., at a constant ratio of the
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 6 2011
1043
OHphen, n/100 PPU
OHphen, mmol g–1
L, %
Fig. 4. Content of phenolic hydroxyls ОНphen as a function
of the degree of delignification L in (1, 2) dissolved and
(3, 4) residual lignins in the course of sulfate cookings of
(1, 3) coniferous wood and (2, 4) spruce Freudenberg lignin.
Sf =0.5, wt fraction
Н, l kg–1
Fig. 6. Solubility Sf =0.5 of sulfate lignin from Solombala
Pulp-and-Paper Combine as a function of liquid to solid
ratio Н.
amount of hydroxide anions in solution to the amount
of phenolic hydroxyls. With an increase in the liquid to
solid ratio, the water volume in the system increases,
which leads to a decrease in the NaOH concentration.
At the Н values of 5, 10, 20, 30, 40, 50, and 60 l kg–1,
the alkali concentration was 0.4, 0.2, 0.1, 0.07, 0.05,
0.04, and 0.03 M, respectively. Thus, the lignin
solubility depends not only on the relative con-
centration of the base in solution but also on its ab-
solute concentration. All the other experiments
described in this paper were performed at H = 40 l kg–1.
Our results confirm the conclusion made in [1] that
the lignin dissolution in alkali is actually fractionation
based on differences in the acid–base properties of the
dissolving fractions.
The dependence of the lignin solubility on the ionic
strength was studied in the NaCl concentration range
1044 EVSTIGNEEV

Table 3. Solubility of lignin samples recovered from spruce Sf = 0.5

wood. 20°С, liquid to solid ratio 40 l kg–1 S= × 100,
H
Content of where Н is the liquid to solid ratio (l g–1).
Solubility phenolilc
Lignin samplea For example, the solubility of sulfate lignin at a
Sf=0.5 hydroxyls,
OHphen/100 PPU liquid to solid ratio of 40 l kg–1 is 22.5 g l–1.
Theoretically it is possible to determine the maximum
Freudenberg – 21.5 possible solubility of lignin in aqueous alkaline
Björkman 0.46 33.0 solutions, taking Sf =0.5 = 1, Н = 5. It will be 200 g l–1.
Pepper 0.53 48.7 In the general case, the solubility S (g l–1) of lignin
in aqueous alkaline solutions is determined by the
Dioxane 0.55 51.8
relationship
Soda 0.88 59.0 Sf
Soda–anthraquinone 0.90 69.1 S= × 1000,
Hf
Sulfate 0.90 69.8
where Sf is the lignin solubility at given f and Hf is the
Sulfate–anthraquinone 0.90 74.1 liquid to solid ratio at given f (l g–1).
a
Cooking time in preparation of alkali lignins 180 min.
CONCLUSIONS
0.01–0.4 M. The dependence is weakly pronounced,
(1) The solubility of lignin in aqueous alkali
and up to the NaCl concentration of 0.1 M the lignin
solutions is determined by the ratio of the number of
solubility does not change (Sf=0.5 = 0.7), whereas at
phenolic hydroxyls to the number of phenylpropane
higher concentrations it linearly decreases, reaching
units in the macromolecule. The higher this ratio, the
Sf=0.5 = 0.6.
higher the solubility.
The solubility data for the lignin samples tested are
(2) The minimal content of phenolic hydroxyls
given in Table 3. As can be seen, the solubility of
required for lignin to pass from the solid phase to
various lignin samples recovered by both mild and
solution is no less than 31 ОНphen/100 PPU.
alkali treatment increases with an increase in the
content of phenolic hydroxyls. In view of the (3) The results obtained in this study allow
differences in the preparation and recovery conditions, calculation of the lignin solubility in aqueous alkali
it becomes obvious that the increase in the content of solutions.
phenolic hydroxyls is accompanied by a decrease in
the lignin molecular weight. For Björkman, soda, ACKNOWLEDGMENTS
soda–anthraquinone, sulfate, and sulfate–anthrax-
quinone lignins, the number-average molecular weight The author is sincerely grateful to S.M. Krutov and
determined by vapor osmometry was 2088, 1593, I.V. Sumerskii (St. Petersburg Academy of Forestry
1556, 1587, and 1560, respectively [15]. As already Engineering) for the submission of a Björkman spruce
noted when discussing Fig. 3, this means that the lignin sample.
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