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Journal of Scientific & Industrial Research

Vol. 66, February 2007, pp. 170-177

Physicochemical parameters, isotherms, sorption kinetics and column operations


for adsorption of copper (II) from wastewater using fly ash
Kaushik Nath*, J P Gor, P N Shah and K Modi
Department of Chemical Engineering, G H Patel College of Engineering & Technology, Vallabh Vidyanagar 388 120
Received 08 February 2006; accepted 06 September2006

The potential of activated fly ash has been investigated for the adsorption of copper (II) dissolved in wastewater.
Physico-chemical parameters such as adsorbate concentration, pH, adsorbent dose, temperature, presence of interfering ions
etc were optimized by employing batch adsorption technique. Adsorption was endothermic and followed Langmuir and
Freundlich isotherms, however, the latter fitted well. Isotherms were used to estimate thermodynamic parameters for the
adsorption process. Kinetic data were fitted to the models of intraparticle diffusion, pseudo second order and Lagergren
model which followed more closely to the pseudo second order chemisorption model. The regeneration and reusability of
the adsorbents were also assessed. Maximum removal of copper (II) was obtained at pH 4 and temperature 50°C (about 98%
for adsorbent dose of 20 g/l and 50 mg/l initial feed concentration).
Keywords: Adsorbent, Adsorption, Copper (II), Fly ash

Introduction In present study, fly ash used as adsorbent for the


Copper (II) is considered as a cumulative poison removal of copper (II) from wastewater.
capable of being assimilated or sorbed in the tissues
of aquatic organisms and causing noticeable adverse Materials and methods
physiological effect1. Effluent from metal processing Activation of Fly ash
units, picking baths and plating baths is the major Analysis of fly ash gave: bulk density, 2.18 g/cc;
sources of copper (II) contaminants. It may also be particle size, 200 µm; carbon, 1% (by wt); SiO2, 62-
present in wastewater from a variety of chemical 70%; and Al2O3, 13-14%. Fly ash, collected from a
manufacturing processes employing copper salts or local thermal power plant, was washed thoroughly
copper catalysts2. Adsorption by activated carbon is with double distilled water two times and filtered and
still by far the most widely used method. A number of again washed with deionized water. It was then dried
physico-chemical methods, available for the treatment in a hot air oven at 100±5°C for 6-7 h to impart
of wastewaters containing heavy metals include ion activation. Finally it was powdered, ground and
exchange, reverse osmosis, electrodialysis3, solvent sieved to 150-200 µm particle size.
extraction, precipitation or co-precipitation4, coagu- Batch Adsorption Study
lation and flotation5 and adsorption. Many Batch adsorption experiments were carried out
investigators have studied the absorptive removal of using an Erlenmeyer flask (250 ml) capacity.
heavy metals using low rank Turkish coal6, almond Analytical grade copper sulphate pentahydrate (SD
shell carbon7, alkali treated straw8, chitosan-cellulose Fine Chemicals) was used to prepare a stock solution
hydrogel beads9, ground nut shells and saw dust10, of copper (II) ions (2000 mg/l). Predetermined
peanut hulls11, cellulose graft co-polymer12, activated amount of adsorbent was added to the copper (II)
slag13, and so on. Activated carbon being an solution and the flask was placed in a constant
expensive material and tedious procedures for its temperature bath and stirred with the help of a stirrer
preparation and regeneration, there is a continuing until equilibrium was attained. At the end of
search for low-cost potential adsorbents. adsorption process, adsorbent particles were filtered
___________
through Whatman GF/C paper and the equilibrium
*Author for correspondence
Tel: +91-2692-231651/ext 255; Fax: +91-2692-236896 concentration of copper (II) in the supernatant was
E-mail: kaushiknath2003@yahoo.co.in then analyzed. The pH of solution was adjusted using
NATH et al.: ADSORPTION STUDY OF COPPER(II) FROM WASTEWATER USING FLYASH 171

Fig. 1Effect of adsorbate concentration on the adsorptive Fig. 2Effect of adsorbent dose on the adsorptive removal of
removal of copper (II) copper (II)

dilute NaOH and H2SO4. The adsorption amount was estimates between two different sets of experimental
calculated as follows: data points were carried out using data analysis and
v(c1 − c2 ) technical graphics software Microcal Origin 5.0 and
q= variation was within ±5%.
w
where q =adsorption amount, mg/g; w =weight of Results and Discussion
activated fly ash, g; v=volume of solution; and c1 and Batch Adsorption
c2 are the concentrations (mg/l) of each ion before and Effect of Initial Concentration and Contact Time
after adsorption respectively. Effect of initial concentration of copper (II) on
adsorption by activated fly ash was studied at
Column Adsorption Study different initial concentration (25-250 mg/l) at a fixed
A Pyrex glass column (length, 30 cm; internal dose of adsorbent (10 g/l). Maximum contact time of
diam, 4.5 cm) was used as the fixed bed adsorber. adsorption was 140 min. During the experiment, pH
Adsorbent bed was supported by glass wool and glass (4.0) and temperature (30°C) were also kept constant.
beads to ensure uniform liquid distribution. For The percentage removal (Fig. 1) of copper (II) was
packing the column the supporting medium, glass found to increase with the decrease in initial
wool was packed by hydraulic filling. The bed was concentration of copper (II). Major adsorption (>98%)
thoroughly rinsed with deionized water and kept for of copper was observed within 1 h up to an initial
24 h to ensure a closely packed arrangement of concentration of 50 mg/l. For an initial concentration
adsorbent particles without voids, channels and of 100 mg/l, 95 per cent removal was recorded.
cracks. Copper (II) containing solution was fed to the However, with higher initial concentration, the
bed by a pump in the down flow mode. Samples were percentage removal dropped significantly. This might
collected periodically and analyzed for copper (II) be due to the lack of available active sites at high
concentration. The column runs were carried out up to concentration resulting in increased competition for
a point of 90% of breakthrough capacity. The the adsorption sites and the adsorption process will
regeneration of the column was also accomplished. increasingly slow down. Similar observation is
reported by the adsorption of eosin dye on activated
Methods of Analysis carbon and adsorption of nickel on fly ash14.
Copper (II) concentration in the solution before and
after adsorption was estimated by inductively coupled Effect of Adsorbent Dose
Plasma via Optical Emission Spectroscopy (ICP- Effect of adsorbent dose on removal of copper (II)
OES) (Perkin Elmer) technique at a wavelength of was studied by varying the dose of adsorbent
327 nm. A pH electrode (Systronics) measured pH of (5-40 g/l) at fixed pH, temperature and initial concen-
feed solution. All results are the average of a tration (Fig. 2). Percentage removal of copper (II)
minimum of duplicate experiments. Variation increased with increase in the dose of adsorbent and
172 J SCI IND RES VOL 66 FEBRUARY 2007

the feed concentration and adsorbent dose (20 g/l)


constant (Fig. 4). With an increase in temperature,
adsorption capacity increased, thereby indicating the
adsorption as an endothermic process. With increase
in temperature, the number of active sites available
for adsorption must have increased resulting in
enhancement of percentage adsorption of copper (II)
on to activated fly ash. Maximum adsorption was
recorded at 50°C. Another possibility of decreasing
the thickness of the boundary layer surrounding the
adsorbent with rise in temperature cannot also be
ruled out since this tends to reduce the mass transfer
resistance of adsorbate in the boundary layer18.
Fig. 3Effect of solution pH on adsorption of copper (II) on to Moreover, as diffusion is an endothermic process, the
fly ash increase in uptake of copper (II) may also be due to an
enhanced rate of intraparticle diffusion of sorbate. An
increase in pore diffusivity of adsorbate with
temperature leads to increased removal of copper (II)
by its adsorption. The thermodynamic parameters of
the adsorption were determined as

∆Go =∆H o −T ∆S o … (1)

q  ∆S o −∆H o
log  e  = + … (2)
 Ce  2.303 R 2.303 RT

where qe = maximum copper (II) adsorbed per unit


mass of fly ash, mg/g; Ce = equilibrium concentration,
mg/l; R = gas constant, 8.314 J mol/K; and T =
Fig. 4Effect of temperature on adsorption of copper (II) on to
activated fly ash temperature, K.
Experimental data considered for calculation of
maximum adsorption was at adsorbent dose of 20 g/l thermodynamic parameters (∆G°, ∆S° and ∆H°) are
beyond which no further increase was noticed. This in the linear range of equilibrium adsorption isotherm.
could be due to the increased availability of active Hence, Eq. (2) can be used with the experimental data
adsorption sites and surface area resulting from the to evaluate entropy of adsorption ∆S° and enthalpy of
conglomeration of the adsorbents especially at higher adsorption ∆H° from a plot of log (qe/Ce) versus 1/T.
adsorbent dose15. Gibbs free energy is then calculated from Eq. (1). The
Effect of pH
values of thermodynamic parameters, for three initial
Copper (II) removal by fly ash was studied at feed concentrations (25, 50 and 100 mg/l) are given in
various pH (2-8) with constant optimum conditions Table 1. Negative value of ∆S° suggests that there is
(Fig. 3). Highest removal efficiency was observed at little reduction of randomness as a result of probable
pH 4.0. However, at higher pH, copper removal change in internal structure of fly ash during
decreased significantly attributed to the hydrolysis of adsorption of copper (II)19.
copper. A similar behavior is reported for the
Effect of Interfering Ions
adsorption of Hg (II)16 and copper and zinc from
To study the effect of interfering ions, feed solution
wastewater by fly ash17.
containing copper (II) was supplemented with 10 mg/l
Effect of Temperature and Thermodynamic Parameters of these ions. Absorbent dose (10 g/l) and the initial
Adsorption studies were carried out at three concentration of copper (100 mg/l)) were kept
different temperatures (30, 40 and 50°C) and keeping constant. A marginal decrease in the scavenging
NATH et al.: ADSORPTION STUDY OF COPPER(II) FROM WASTEWATER USING FLYASH 173

Table 1Thermodynamic parameters for the adsorption of copper (II) on fly ash

Concentration ∆Ho −∆So ∆Go


of copper (II) kJ/mol kJ/mol/K kJ/mol
mg/l 303 K 313 K 323 K

25 30.58 0.005 15.04 11.56 9.95

50 30.17 0.005 16.12 11.78 8.56

100 29.58 0.042 15.56 10.69 8.41


Table 2Langmuir and Freundlich adsorption isotherm constants for adsorption of copper on fly ash

Temperature Langmuir constant Freundlich constants


°C Q b, l/mg R2 k n R2

50 5.56 4.35 ×10-3 0.97 73.23 5.34 0.98

40 5.67 4.21×10-3 0.965 70.45 4.67 0.99

30 5.71 3.97×10-3 0.97 67.52 4.32 0.97

efficiency of the adsorbent was observed in presence and b are Langmuir constants. The values of Q and b
of these ions (data not shown) as compared to the are calculated from the intercept and slope of the plot
control experiment (without interference). The effect of Ce/qe versus Ce.
of ionic interaction can be explained using the rate of
adsorption capacity of the ion in a single component Freundlich Isotherm
system (qo) to that in a multicomponent (qm) system. The relation between the copper uptake capacity
The presence of interfering ions would reduce the qe (mg/g) of adsorbent and the residual copper
uptake (qm/qo < 1) of copper. The presence of other concentration Ce (mg/l) at equilibrium is given by
ions in the solution affects the adsorption of a
particular ion of interest compete for each other for 1
ln qe = ln k + ln Ce … (4)
available adsorbent sites. Those having the greater n
ionic potential (ratio of charge to ionic radius) or the
most electronegative one would be removed first and where intercept ln k is a measure of adsorbent
if the sites were still undersaturated, then those having capacity and the slope 1/n is the sorption intensity; k
lower ionic potential or lower electronegativity would and n are calculated from the intercept and slope of
be removed in the sequence15. However, in the present the plot of ln qe versus ln Ce respectively.
study as the decrease in maximum percentage The coefficients of Langmuir and Freundlich
reduction of uptake of copper (II) is very small in isotherm models (Table 2) provide information on the
presence of other ions, it may be concluded that maximum amount of activated fly ash required to
adsorption is effective even in the presence of adsorb a particular mass of copper (II) under specified
interfering ions. system conditions. Correlation coefficients are also
calculated (Table 2) by fitting the experimental
Adsorption Isotherms
Langmuir Isotherm
adsorption equilibrium data for the copper-activated
Langmuir model is expressed as: fly ash system, using both the isotherms. It was found
that the adsorption isotherm for the copper-activated
QbCe fly ash system could be represented well by the
qe = … (3) Freundlich isotherm.
1+ bCe
where qe = amount of adsorbate adsorbed per unit Adsorption Kinetics
weight of adsorbent, mg/g; and Ce = equilibrium The kinetics of adsorption controls the process
concentration of the adsorbate, mg/l. The constants Q efficiency19. Adsorption has been treated as a first
174 J SCI IND RES VOL 66 FEBRUARY 2007

Fig. 5Kinetics of copper (II) removal according to the Fig. 6Kinetics of copper (II) removal according to pseudo-
Lagergren model at initial copper concentration of 25, 50 and 100 second order model at three different initial concentration of
mg/l copper

order20,21, pseudo first order23,24 and pseudo second (t/qt) versus t (Fig. 6) gives the value of qe and from
order25 processes. In the present study, adsorption of the intercept k2 can be calculated.
copper (II) on activated fly ash has been described by Diffusion Model
first and pseudo second order models and also by a The intraparticle diffusion model is based on the
diffusion model. theory proposed by Weber & Morris26 as

Lagergren Model q = kd t … (7)


Lagergren proposed a pseudo-first order kinetic
model as where kd = rate constant of intraparticle diffusion, mg
g-1min-1/2.
Kad Applicability of this model can be examined by the
log(qe − q ) = log qe − t … (5)
2.303 linear plot of q versus t1/2. The pore diffusion
coefficient for the intraparticle transport of copper (II)
where q = amount of copper (II) sorbed (mg/g) at time was calculated assuming spherical geometry of the
t (min), qe = amount of copper adsorbed at sorbent using following equation
equilibrium (mg/g) and Kad = equilibrium rate
constant of pseudo-first order adsorption (min-1). 0.03ro2
The plot of log (qe–qt) versus t gives a straight line t1/2 = … (8)
D
for the first order adsorption kinetics (Fig. 5) First-
order rate constant Kad is obtained from the slope of
the straight line. where ro = radius of the sorbent, D = pore diffusion
coefficient, 8.67×1010 cm2 s-1; and t1/2 = time for half
sorption. Applicability of the above three models was
Pseudo Second-order Model
Pseudo-second order rate equation is given by examined by each linear plot of log (qe–qt) versus t
(Fig. 5), (t/qt) versus t (Fig. 6), and q versus t1/2
(Fig. 7). Correlation coefficient R2 showed that the
1 1 t
= + … (6) pseudo second order model, an indication of
qt k2 qe2 qe chemisorption mechanism, fits better the experimental
data (R2 > 0.997) than the pseudo first order
where k2 = rate constant for the pseudo second-order Lagergren Model (R2 is in the range of 0.956-0.973).
adsorption kinetics, g/mg min. The slope of the plot The interparticle diffusion had also some role in the
adsorption of copper (II) by fly ash (Fig. 7). The
NATH et al.: ADSORPTION STUDY OF COPPER(II) FROM WASTEWATER USING FLYASH 175

Fig. 9Variation of breakthrough curve with bed depth for


adsorption of copper (II) on to activated fly ash
Fig. 7Kinetics of copper (II) adsorption according to the
intraparticle diffusion model at initial copper concentration of 25, adsorption system. The applicability of the following
50 and 100 mg/l
Bangham equation29 to present the adsorption of
copper (II) on to fly ash was tested.
 Co   ko m 
loglog   = log   +α log t … (9)
 Co − qm   2.303V 

where Co = initial concentration of adsorbate in


solution, mmol/l; V = volume of solution, ml; m =
weight of adsorbent used per liter of solution, g/l; q =
amount of adsorbate retained at time t, mmol/g; and
α (<1) and ko are constants. The log log (Co/Co – q m)
was plotted against log t (Fig. 8). The linearity of the
plot confirms the applicability of Bangham equation.
This further indicates that the diffusion has predo-
minantly controlled the adsorption process23,28.

Fig. 8Bangham’s plot for the adsorption of copper (II) on to Column Adsorption
activated fly ash To design and scale-up of the fixed bed adsorber
system, it is required to use the results of the batch
linear portion of the plot for a wide range of contact experiments in adsorbent columns. Maximum uptake
time between adsorbent and adsorbate does not pass of copper (II) was achieved at a flow rate of
through the origin. Such deviation from the origin or 0.50 ml/min (data not shown). Maximum (90%)
near saturation can be attributed to the difference in copper (II) can be removed at the lower flow rate
rate of mass transfer in the initial and final stages of (< 1 ml/min) while removal decreases with increasing
adsorption. Further, this deviation also indicates that flow rate. This is probably associated with the avail-
the pore diffusion is the only rate controlling step. ability of adsorption sites able to capture copper (II)
There are two distinct regions – the initial pore ions around or inside the cells. With the gradual
diffusion due to external mass transfer effects occupancy of these sites the uptake becomes less
followed by the interparticle diffusion (Fig. 7). The effective15.
observations agree well with those obtained The total quantity sorbed in the column for a given
Allen et al27 during the adsorption of basic dye on to feed concentration is equal to the area under the
sphagnum peat27. breakthrough curve obtained from the plot of
Kinetic data was further used to interpret the slow adsorbed concentration versus effluent volume. The
step that might have taken place in the present breakthrough study is required to design of a fixed
176 J SCI IND RES VOL 66 FEBRUARY 2007

bed adsorber and prediction of the length of the 1 Moore J W & Ramamoorthy S, Heavy Metals in Natural
adsorption cycle between regeneration. Breakthrough Waters. Applied Monitoring and Impact Assessment
(Springer, New York) 1984, 69-75.
time (the duration for zero column outlet 2 Marshal S, Metal and Inorganic Waste Reclaiming
concentration) increases (Fig. 9) from 4 to 8 h, when Encyclopedia (Wayers Beta Corp. Park-Ridge, New Jersey)
the bed depth is increased from 4.0 ×10-2 m to 1980, 115-123.
7.0 ×10-2 m, for the same flow rate (0.50 ml/min). The 3 Canet L, Ilpide M & Seta P, Efficient facilitated transport of
lead, cadmium, zinc and silver across a flat sheet-supported
shape and gradient of the breakthrough curves for the liquid membrane mediated by lasalocid A, Sep Sci Technol,
two bed depths are almost identical. It suggests that 37 (2002) 1851-1860.
the fixed bed of certain dimensions has a definite 4 Esalah O J, Weber M E & Vera J H, Removal of lead,
capacity to adsorb the solute entering the bed. It cadmium and zinc from aqueous solutions by precipitation
further indicates that adsorbent packed in the bed with sodium di-(n octyl) phosphinate, Can J Chem Eng, 78
(2000) 948-954.
would remove pollutant not only until the attainment
5 Zouboulis A I, Matis K A, Lanara B G & Neskovic C L
of equilibrium but also upon the transfer mechanism Removal of cadmium from dilute solutions by
and the rate of adsorption. hydroxyapatite. II. Floatation studies, Sep Sci Technol, 32
(1997) 1755-1767.
6 Karabulut S, Karabakan A, Denizli A & Yurum Y, Batch
Desorption Studies
removal of copper (II) and Zinc (II) from aqueous solutions
Regeneartion and recovery of the column, under with low rank Turkish coals. Sep Purif Technol, 18 (2000)
suitable conditions, without destroying adsorbent 177-184.
materials are very important aspects of wastewater 7 Toles C A & Marshall W E, Copper ion removal by almond
treatment. For the present study, desorption of the shell carbons and commercial carbons: batch and column
column was carried out using three different eluents studies, Sep Sci Technol, 37 (2002) 2369-2383.
8 Kumar A, Rao N N & Kaul S N, Alkali treated straw and
(dilute NaOH, dilute HCl and dilute HNO3). insoluble straw xanthate as low cost adsorbents for heavy
Complete desorption of copper could be metal removal—preparation, characterization and
accomplished with 1N HNO3, which was passed application, Biores Technol, 71 (2000) 133-142.
through the column at a very slow rate (2 ml/min) for 9 Li N & Bai R, Copper adsorption on chitosan-cellulose
3 h and then washed by deioninzed water for next 3 h. hydrogel beads: Behaviors and mechanisms, Sep Sci
Technol, 42 (2005) 237-247.
The column lost its capacity (2-3 %) after the first run
10 Shukla S R & Pai R S, Adsorption of Cu (II), Ni(II) and Zn
and about 5 per cent after more than 5 runs. (II) on dye loaded ground nut shells and saw dust, Sep Sci
Technol, 43 (2005) 1-8
Conclusions 11 Periasamy K & Namasivayam C, Removal of copper (II) by
adsorption onto peanut hull from water and copper plating
Maximum removal of copper (II) on activated fly
industry wastewater, Chemosphere, 32 (1996), 769-774.
ash in batch mode was obtained at pH 4 and 12 Okieimen F E, Sogbaike C E & Ebhoaye J E, Removal of
temperature 50°C (about 98% for adsorbent dose of cadmium and copper ions from aqueous solution with
20 g/l and 50 mg/l initial feed concentration). The cellulose graft copolymers, Sep Sci Technol, 44 (2005) 85-
effect of changing the bed depth was studied in 89.
column adsorption, where the maximum uptake of 13 Gupta V K, Equilibrium uptake, sorption dynamics, process
development, and column operations for the removal of
copper (II) was achieved at a flow rate of copper and nickel from aqueous solution and waste water
0.50 ml/min. The breakthrough time increased from using activated slag, a low-cost adsorbent, Ind Eng Chem
4 h to 8 h, when the bed depth was increased from Res, 37 (1998) 192-202.
4.0 ×10-2 m to 7.0 ×10-2 m, for the same flow rate of 14 Purkait M K, Dasgupta S & De S, Adsorption of eosin dye
0.50 ml/min. Equilibrium and kinetics of the process on activated carbon and its surfactant based desorption, J Env
Management, 76 (2005) 135-142.
were investigated as well. Freundlich model fits the
15 Ucer A, Uyanik A & Aygun S F, Adsorption of Cu(II),
isotherm data well. Adsorption was endothermic. The Cd(II), Mn(II), and Fe(II) ions by tannic acid immobilized
data thus obtained may be helpful for designing and activated carbon, Sep Pur Technol, 47 (2006) 113-118.
establishing a continuous treatment plant for water 16 Sen A K & De A K, Adsorption of mercury (II) by coal fly
and wastewaters containing copper (II) metals. ash, Water Res, 21 (1987) 885-888.
17 Gupta V K & Ali D I, Utilisation of bagasse fly ash (a sugar
industry waste) for the removal of copper and zinc from
References waste water, Sep Sci Technol, 18 (2000) 131-140.
18 Coskun R, Soykan C & Sacak M, Adsorption of copper (II),
nickel (II) and cobalt (II) ions from aqueous solution by
NATH et al.: ADSORPTION STUDY OF COPPER(II) FROM WASTEWATER USING FLYASH 177

methacrylic acid/acrylamide monomer mixture grafted poly 23 Tutem E, Apek R & Unal C F, Adsorptive removal of
(ethylene terephthalate) fiber, Sep Pur Technol, 49 (2006) chlorophenols from water by bituminous shale, Water Res,
107-114. 32 (1998) 2315-2324.
19 Manju G N, Raji C & Aniruddhan T S, Evaluation of 24 Ho Y S & McKay G, The sorption of lead (II) ions on peat,
coconut husk carbon for the removal of arsenic from water, Water Res, 33 (1999) 578-584.
Water Res 32 (1998) 3062-3070. 25 Ho Y S, Ng J C Y & McKay G, Removal of Lead (II) from
20 Jain A K, Gupta V K, Bhatnagar A & Suhas, A comparative effluents by sorption on peat using second order kinetics, Sep
study of adsorbents prepared from industrial wastes for Sci Technol, 36 (2001) 241-261.
removal of dyes, Sep Sci Technol, 38 (2003) 463-481. 26 Weber W J & Morris J C, Kinetic of adsorption on carbon
21 Haribabu E H, Upadhya Y D & Upadhyay S N, Removal of from solutions, J Sant Eng Div. ASCE, 89 (1963) 31-36.
phenols from effluents by fly ash, Int J Environ Studies, 43 27 Allen S J, Mckay G & Khader K Y H, Intraparticle Diffusion
(1993) 169-176. of Basic Dye During Adsorption on to Sphagnum Peat,
Environ Pollut, 56 (1989) 39-43
22 Pandey K K, Prasad G & Singh V N, Copper (II) removal 28 Aharoni C & Ungarish M, Kinetics of activated
from aqueous solution by fly ash, Water Res, 19 (1985) 869- chemisorption, part 2- Theoretical models. Faraday Trans,
873. 1(73) (1977) 456-464.