Energy Convers. Mgmt Vol. 35, No. 12, pp.

1031-1040, 1994
Copyright © 1994 Elsevier Science Ltd
Pergamon
0196-8904(94)00032-8 Printed in Great Britain. All rights reserved
0196-8904/94 $7.00 + 0.00

PREDICTIONS OF CONCENTRATION IN THE PYROLYSIS

OF BIOMASS MATERIALS--I

V. K. SRIVASTAVA and R. K. JALAN

Chemical Engineering Department, Indian Institute of Technology, Hauz Khas, New Delhi-1 I0 016, India

(Received 9 December 1993; received for publication 26 July 1994)

Abstract--The present work involves the prediction of the concentration profiles in the case of pyrolysis
of different lignocellulosic materials in isothermal and non-isothermal conditions. The operative tempera-
ture range is from 573 to 973 K for isothermal conditions, and for non-isothermal conditions, the heating
rate ranges from 5 to 80 K / m i n (5, 20, 40, 60 and 80 K/min).
The concentration for the above mentioned conditions is predicted for various biomass components,
viz. cellulose, hemicellulose and lignin. Based on the concentration profiles of different biomass materials,
it is possible to predict the pyrolysis behavior over a wide range of temperatures under isothermal and
non-isothermal conditions for a large number of biomass materials, provided the activation energy and
the frequency factor for the various reaction steps are known. It is also possible to ascertain the degree
of combustibility of different biomass materials.
The simulation model utilizes a 4th order R u n g e - K u t t a Predictor-Corrector method to solve the
coupled ordinary differential equations. Based on thermogravimetric analysis done elsewhere, it is
considered that temperature and time have a linear relationship. The above technique enables us to predict
concentration profiles of different biomass materials for the entire range of pyrolysis. The concentration
vs time data is plotted graphically for both isothermal and non-isothermal conditions utilizing the Harvard
Graphics package on a PC-A/T personal computer.

Pyrolysis of biomass Biomass energy management Modelling

NOMENCLATURE

B = Virgin biomass
B + = Intermediate
G + V = Gases and votatiles
C = Char
CB = Concentration of B (dimensionless)
c~ = Concentration of B + (dimensionless)
c~ = Concentration of G + V (dimensionless)
Cc = Concentration of char (dimensionless)
t = Time (rain)
AI, A2, A3 = Frequency factor (min ~)
El, E2, E 3 = Activation energy (kJ/mol)
n I , n 2 , n 3 = Order of reaction (dimensionless)
R = Universal gas constant (kJ/(K) tool)
T = Temperature (K)
I"o= Initial temperature (K)
Greek letter
Heating rate (K/min)

INTRODUCTION

With increasing urbanization all over the world, in both developing and developed countries, the
quantity of municipal solid waste generated every day is increasing very rapidly, leading to more
biomass formation. The pyrolysis of biomass is an important process for the production of solid
(char), liquid (tar and other organics) and gaseous components, which can all be utilized as possible
alternative fuels. Further, it is a renewable source of energy and has many advantages from the
ecological angle.
Ecu 3s:~2-c 1031
1032 SRIVASTAVA
and JALAN: THE PYROLYSISOF BIOMASSMATERIALS--I

Pyrolysis is a process by which a biomass feedstock is thermally degraded in the absence of

oxygen/air. In order to design properly and understand the pyrolysis process, it is essential to
develop models describing the kinetics and its associated mechanisms. The study of pyrolysis is
gaining increasing importance, as it is not only an independent process, but is also a first step in
the gasification or combustion process. Consequently, several studies have been done on the
pyrolysis of biomass and other substances by Shafizadeh [1], Jegers et al. [2], Barbour et al. [3],
Koufopanos [4] and [5], etc. Further, on kinetic modelling, significant contributions have been
made by Ergun [6] and [7], Roberts [8] and [9], Bradbury el al. [10], Tran et al. [11], Brunner [12],
Thruner et al. [13], Antal et al. [14], Mulhen et aL [15], Freund [16], Matsui [17], etc. However, none
of the above studies have been able to develop a universal model that can predict the rate of
pyrolysis, final conversions and concentrations over a wide range of operating conditions. The
major shortcomings of other models are that they are useful for a particular type of biomass only,
as indicated in the work done by Mellottee et al. [18] and Ward et al. [19]. Recently, Farza et al. [20]
developed a knowledge-based software for the simulation of biochemical processes, however, no
insight is available on the pyrolysis of biomass.
In order to understand the pyrolysis process, it is essential to obtain concentration profiles and
other related information for biomass materials. Therefore, the kinetic model proposed by
Koufopanos et al. [21] is being utilized, which is useful for predicting the pyrolysis process of small
particles (below 1 mm) of several lignocellulosic materials. In order to develop a simulation model,
the description of the pyrolysis kinetics by a simple kinetic model is essential so that the overall
yield may be predicted accurately, enabling the analysis of the concentration profiles of the
products produced during pyrolysis under different operating conditions, including isothermal and
non-isothermal cases.
In a subsequent work, Koufopanos et al. [22] have attempted to model the pyrolysis of a single
biomass particle by coupling the heat transfer equations with the pyrolysis rate equation. These
effects have not been considered in the present work in order to keep the model developed in this
study as simple as possible and show how a very simple model could predict the concentration
profiles of many biomass components under diverse operating conditions so easily.
The present study involves theoretical analysis which is based on experimental data available in
the literature for different lignocellulosic materials, viz. cellulose, hemicellulose and lignin, which
are the major constituents of biomass substances. The analysis has been carried out over a wide
range of pyrolysis conditions, including isothermal and non-isothermal heating conditions from 573
to 973 K, with a heating rate from 5 to 80 K/min.

THEORETICAL CONSIDERATIONS
It is well known that there are a large number of complex reactions involved in the process of py-
rolysis, and therefore, it is impossible to develop a precise kinetic model taking into account the vari-
ous parameters. It is generally accepted that the most important parameters in biomass pyrolysis
are temperature, concentration, time and heating conditions. The pyrolysis of various lignocellu-
losie materials is differentiated by the reaction rates and the final product distribution achieved.
We propose to develop a model which could be used to predict the concentration profiles of all
kinds of lignocellulosic materials. The pyrolysis rate of any biomass substance is considered to be
the sum of the rates of the main biomass components, viz. cellulose, hemicellulose and lignin. Each
component contributes to the formation of volatiles, gases and char, to an extent proportional to
its contribution to the composition of the virgin biomass material.
Keeping the above in view, Koufopanos et al. [21] proposed the following model for the
description of the kinetic rate of the pyrolysis of biomass which will be utilized in development
of the model.
1 2
Virgin biomass ,Intermediate , Gases and volatiles
B B+ G+V

, Char
C
 SRIVASTAVA and JALAN: THE PYROLYSISOF BIOMASSMATERIALS--I 1033

It is assumed that the three reactions follow the Arrhenius' Law for ascertaining the values of the
rate constant. This model is extremely simplistic and can predict the concentration profiles and final
char yield in different heating conditions.

MODELLING EQUATIONS
The differential equations which have been used in the model are given below, based on the
theoretical considerations mentioned above:

d~- - A, exp ~ (Cn)"'. (1)

The above reaction is considered zero-order, as at lower temperatures, the weight loss is negligible,
therefore nl = 0

d---~=A, exp ~ (CB)"'-A2exp ~ (C/~) "2

- A3 e x p ( ~ T 3 ) (C a)"3 (2)

dCG (-E2)).,
dt - A 2 e x p ~ (C + - (3)

dt =A3exp ~ (C/~)"3. (4)

The above equations are based on the following initial conditions.

At t = 0 ,

CB=I; C~=C~=C,=O. (5)

When B is near zero, while solving the above equations in the computer model, equation (1) and
the first term on the right-hand side of equation (2) are omitted, and the simulation is continued
until the intermediate material is almost exhausted. Generally speaking, in thermogravimetric
analysis, temperature and time have a linear relationship, and therefore, it is appropriate to describe
the above phenomenon as follows.

T = ~bt + To (6)

where To is the initial temperature and ~b is the heating rate in K/min.

The above equations have been solved numerically, utilizing a 4th order Runge-Kutta
Predictor-Corrector method. Values of the frequency factor, activation energy and order of the
various reactions for different materials is taken from Koufopanos et al. [21], and the concentration
profiles for a diverse range of conditions are predicted for the main biomass components, viz.
cellulose, hemicellulose and lignin.

MODELLING CONSIDERATIONS
The above equations have been solved by developing a simulation model in the FORTRAN
language, utilizing the ICL-main frame computer installed at IIT, Delhi.
A total of seven subroutines were written in order to obtain the results during the initial stage
of pyrolysis (when virgin biomass is present) and advanced stage of pyrolysis (when only the
intermediate is present and is producing gases, volatiles and char). In the initial stage, four
subroutines were written for each of the four differential equations obtained from the model. In
the advanced stage, equation (1) and the first term of equation (2) do not exist, and therefore, the
next set of three subroutines incorporate the above changes.
1034 SRIVASTAVA
and JALAN: THE PYROLYSISOF BIOMASSMATERIALS--I

Other important points considered while developing the model include:

(l) Different time steps in the initial and advanced stages of the pyrolysis.
(2) Maximum time of simulation was assumed as 20 min, as beyond this time, pyrolysis is
considered to be slow and not of practical importance.
(3) At higher temperatures, viz. 873 and 973 K, the equations are unstable and concentration
profiles cannot be obtained for cellulose and hemicellulose. However, concentration profiles for
lignin were obtained by reducing the time step to 0.0001 in the initial stage and 0.02 in the advanced
stage of pyrolysis.
(4) However, at higher heating rates, viz. 80 K/min, it was not essential to reduce the time step
set earlier at 0.1 and 0.2 for the initial and advance stages, respectively. However, in all cases, the
pyrolysis was completed in less than 3.5 min only.
(5) The data generated on the mainframe computer were plotted for various rates, viz. 5, 20,
40, 60 and 80 K/min, and a number of isothermal conditions, viz. 573, 623,673, 773,873 and 973 K,
to the extent possible in order to obtain the concentration profiles in each case. This was done
utilizing a Harvard graphics package on a PC-A/T system as the ICL-main-frame system does not
support any graphic packages at the present time.

RESULTS AND DISCUSSION

Keeping in view the large volume of data generated and graphical plots obtained, it is proposed
to analyze and present the typical characteristics and salient features of the concentration profiles
of the pyrolysis process. Consequently, Figs 1-3 indicate the concentration profiles for cellulose,
hemicellulose and lignin at a heating rate of 5 K/min. Each result indicates the trend in
concentration of each component, viz. virgin biomass, intermediate, gases, volatiles and char as
a function of time.
The results obtained for cellulose and lignin have a similar nature as both graphs were terminated
at 20 min (the maximum allowable time). However, the yield of gases and volatiles is higher in the
case of cellulose when compared to lignin. In the case of hemicellulose, the pyrolysis was completed
in only 14.6 min and also indicated substantial production of gases, volatiles and char when
compared to the results for cellulose and lignin. This is natural as the pyrolysis process was
completed in the case of the hemicellulose.
Now, it will be appropriate to analyze the results obtained with a maximum heating rate of
80 K/min for each of the three components mentioned above. The nature of the three results,
shown in Figs 4-6, is similar for all three components, viz. cellulose, hemicellulose and lignin.
However, the pyrolysis process is completed the earliest in the case of hemicellulose (1.6 min),
followed by cellulose (2.0 min) and lignin (3.3 min). It is interesting to observe in Fig. 5 when

Legend
• Virgin biomass
I.Oq + Intermediate
~N• + Gases and volatiles
"7 0.8
-- \ • f [] Char

0.6 _ \+
~ +~'+

0 0.4
/+ \
0.2
/+
I
5 l0 15 20 25
Time (min)
(Cellulose heating rate - 5 K/min)
Fig. 1. Concentration vs time.
 SRIVASTAVA and JALAN: THE PYROLYSIS OF BIOMASS MATERIALS--I 1035

1.0 ~ Legend
II • Virgin biomass
IO + + ~
0.8 h / ~ + Intermediate
"7 [ . Gases and volatiles
t- 0.6 I y ~ ~ DC h a 2 + / ,
o

0~

I
0 2 4 6 8 10 12 14 16
Time (min)
(Hemicellulose heating rate - 5 K/min)
Fig. 2. Concentration vs time.

1.0q
t, o
"7 ~o
0.8 - .+ - - +~ . + .......~.+
m
o

0.6 Legend
f-
• Virgin biomass
o
0.4 + Intermediate
÷ Gases and volatiles
0.2 D Char

•- ",I ~, ~ I
5 IO 15 20 25
Time (min)
(Lignin heating rate - 5 K/min)

Fig. 3. Concentration vs time.

Legend
• Virgin biomass

"T
1.0
- °-.....o.....O~O\o\, +
*
Intermediate
Gases and volatiles
0.8
o Char
~+
0.6
t-,

0.4 /
. j r
0.2
f+
I
0.5 1.0 1.5 2.0 2.5
Time (min)
(Cellulose heating rate - 80 K/min)

Fig. 4. Concentration vs time.

 1036 SRIVASTAVA and JALAN: THE PYROLYSIS OF BIOMASS MATERIALS---I

1.0 m

Legend
_ • - ~- + • Virgin biomass
0.8
~ + + Intermediate
"7 " ~ / / ~ + Gases and volatiles
N N ~ + ~ D Char
0.6

0.4
O

0.2

= = _z.-~ ~ - - - ' ~ - - - _ J o I . I
0.5 1.0 1.5 2.0
Time (min)
( H e m i c e l l u l o s e heating rate - 80 K/min)

Fig. 5. Concentration vs time.

Legend
• Virgin biomass
+ Intermediate
1.0 ~e ~ Gases and volatiles
~e [] Char

I
"7
0.8
¢-
+~+_ ~ +
\. / ~ +
0.6

" 0.4

0.2

/ I
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Time (min)
(Lignin heating rate - 80 K/rain)

Fig. 6. Concentration vs time.

compared to Fig. 4 that the concentration of gases and volatiles and char is higher in the case of
lignin when compared to cellulose. However, the yield of gases and volatiles is highest in the case
of hemicellulose, and the yield of char for hemicellulose is comparable to lignin.
The behavior of the concentration profiles at 20, 40 and 60 K/min for the main biomass
components mentioned above is indicated for both non-isothermal conditions in the following
table. For comparison purposes, the total pyrolysis time and the concentration of gases, volatiles
and char is presented at the end of pyrolysis.
Table I indicates that, in the non-isothermal case, the total pyrolysis time is lowest for
hemicellulose, followed by cellulose, and as usual, the pyrolysis time is highest for lignin. However,

Table I. Final pyrolysis time vs concentration

Concentration at end of pyrolysis
Total pyrolysis time (min) 20 K/min 40 K/min 60 K/min

Component 20 K/min 40 K/min 60 K/min G+ V C G+ V C G+ V C

C 8.2 4.5 3.2 0.61 0.16 0.56 0.14 0.52 0.13
HC 5.1 3.0 2.1 0.56 0.25 0.55 0.25 0.50 0.22
L 12.4 6.8 4.9 0.46 0.30 0.40 0.24 0.41 0.25
C---cellulose; HC--hemicellulose; L--lignin.
 SRIVASTAVA and JALAN: THE PYROLYSIS OF BIOMASS MATERIALS--I 1037
Legend
• Virgin biomass
+ Intermediate
"7 1.0 i , k ~ m~- CharGasesand volatiles
¢. 0.8 -- •
o

\o ~
e- 0.6- ~O +/
e"

r) 04 - /X.,,,

I
0 5 10 15 20 25
Time (rain)
(Cellulose isothermal - 573 K)
Fig. 7. Concentration vs time.

1.0 ~- Legend
• Virgin biomass
~1 + Intermediate
0.8 ~ * Gases and volatiles
I~.~ [] Char
'7
0.6 [-~1 + ~
i. Io.I ~ +
e-

0.4 ~ •
k.)

0.2 I / , ~ ~ * ~ *

0 5 10 15 20 25
Time (min)
(Hemicellulose isothermal - 573 K)
Fig. 8. Concentration vs time.

Legend
Virgin biomass
1.0 ,~- + Intermediate

0.8
_'-.,,, •
[]
Gases and volatiles
Char
~. + +

0.6 -- + ~ ~ ~

0.4

t_. .t ]- I
0 5 10 15 20 25
Time (min)
(Lignin isothermal - 573 K)
Fig. 9. Concentration vs time.
1038 SRIVASTAVA and JALAN: THE PYROLYSIS OF BIOMASS M A T E R I A L S - - I

1.0 --

Legend
• Virgin biomass
0.8 E_ + Intermediate

e-
O
0
0.6
\ ÷ Gases and volatiles
[] Char

t-

t- 0.4
O

0 . 2 ~ D..o

0 0.05 0.10 0.15 0.20

Time (min)
(Cellulose isothermal - 773 K)

Fig. 10. Concentration vs time.

1.0 m
•~ Legen___.!d
: •~ • Virginbiomass
0.8 •~ + Intermediate
'7 •~ + Gases and volatiles
[] Char
~ 0.6

¢-
0,4
O
r,.) +~+~ / ~ ~+~.
0,2 - /+I" , ~ ~ []

I
0.005 0.010 0.015 0.020 0.025 0.030 0.035

Time (rain)
(Hemicellulose isothermal - 773 K)

Fig. 11. Concentration vs time.

Legend
1.0 * Virginbiomass
i",
I-4-
+ Intermediate
S 0 8 I-'\ Gases and volatiles
" ]1-
I ~ N. O Char

°61-
o

~ i _ I l _ I ] _ I .
0 i 2 3 4 5 6
Time (rain)
(Lignin isothermal - 773 K)
Fig. 12. Concentration vs time.
 SRIVASTAVA and JALAN: T H E PYROLYSIS O F BIOMASS M A T E R I A L S - - I 1039

the concentration of gases and volatiles produced is the maximum for cellulose and the minimum
for lignin at the end of the pyrolysis process. As far as concentration of char is con-
cerned, the proportion is reversed, as it is highest for lignin and lowest for cellulose. This is to be
expected as a high concentration of gases and volatiles would lead to a lower concentration of char
in order to maintain the material balance of the system.
Now, it will be appropriate to analyze the isothermal conditions for the three materials
mentioned above. It is shown in Figs 7-9 that, at 573 K, the pyrolysis in each case is incomplete,
and insignificant concentrations of gases and volatiles and char are observed for cellulose and
lignin. However, there is a significant concentration of gases and volatiles and char in the case of
hemicellulose. This is to be expected as pyrolysis for hemicellulose is faster than for the other two
components. The pyrolysis process is incomplete, even after 20 min, as the temperature is relatively
low. However, at 773 K, the concentration profiles for each of the three biomass components shown
in Figs 10-12 clearly indicate that the pyrolysis process is completed in each case, and significant
concentrations of gases and volatiles are observed for all the materials at the end of the pyrolysis.
The behavior of the results is similar to the non-isothermal conditions, heating rate of 80 K/min,
however, the rate of pyrolysis is much faster in the isothermal condition for cellulose and
hemicellulose. In the case of lignin, the pyrolysis at the isothermal condition takes more time, as
higher temperatures are required in order to complete the pyrolysis process.
For the intermediate temperatures of 623 and 673 K, no other significant conclusions
or observations can be made, as the behavior of the results is similar to the cases discussed
above.

Legend
• Virgin biomass
0.8 + Intermediate
÷ Gases and volatiles
,7 Char
0.6

0.4
. + ..[~ 'O
+ --,,,.._.
0.2
"1--- +

A .I
0.1 0.2 0.3 0.4 0.5 0.6
T i m e (rain)
( L i g n i n i s o t h e r m a l - 873 K)

Fig. 13. Concentration vs time.

0.8 ~ - Legend
• Virgin biomass
dL_ + Intermediate
S 0.6 | / , - - - - , ~ * Gases and volatiles
y x,,
~ [] Char

0.4"~ + ~ ~ - ~ * ~ ~

I
0 0.02 0.04 0.06 0.08 0.10 0.12

T i m e (min)
( L i g n i n i s o t h e r m a l - 973 K)

Fig. 14. Concentration vs time.

1040 SRIVASTAVA
and JALAN: THE PYROLYSIS OF BIOMASS MATERIALS--I

At isothermal temperatures beyond 773 K, the modelling equations are unstable, and data could
only be generated for lignin at 873 and 973 K as shown in Figs 13 and 14, respectively. The above
data were obtained by reducing the time step in the initial stage of the pyrolysis significantly to
0.0001, and the pyrolysis process is completed almost instantaneously in less than 0.6 min in both
cases, as shown in the figures mentioned above. However, the concentration of gases, volatiles and
char is significantly higher at 873 K as compared to 973 K for lignin, as at 973 K, other
processes/reactions are important, which have not been considered in the development of the
present modelling equations.

CONCLUSION

The analysis mentioned above is based on a simple kinetic model and enables us to analyze the
concentration profiles under varying conditions for both isothermal and non-isothermal operations
of major biomass components, viz. cellulose, hemicellulose and lignin. The concentration profiles
for the virgin material, intermediate, gases, volatiles and char provide an insight into the pyrolysis
process at different conditions and residence times. This is very critical while designing the
incineration systems used for the disposal of municipal solid waste. The detailed design of
incinerators is discussed in Perry and Green [23].
The equations developed are of an extremely general nature where activation energy and
frequency factor values for any material can be fed to the model along with the operating
conditions, enabling one to obtain the concentration profiles easily right up to the completion of
the pyrolysis process. The purpose of this model is to demonstrate its simplicity and strength to
predict the concentration profiles, which compare well with the ones obtained experimentally for
various cases according to data available in the literature for a wide range of operating conditions,
including isothermal and non-isothermal cases. The model developed in the study utilized the
kinetic model developed by Koufopanos et al. [21], based on its excellent correlation between the
experimental and predicted data.
However, further work has been done in this area by Koufopanos et al. [22] by incorporating
thermal and heat transfer effects. These have not been considered in the present study in order to
maintain the simplicity of the model. The model can also incorporate mass transfer effects, particle
size distribution characteristics of the biomass and char, two-dimensional analysis, convective and
radiative heat transfer, etc. However, these have not been considered in the present study in order
to keep the model simplistic, as mentioned earlier. Based on the completion time of the pyrolysis
process, it is also possible to predict the degree of combustibility of the major biomass components,
viz. cellulose, hemicellulose and lignin for a wide range of operating conditions.

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