Gcec631204.online. 966.

Chemical Engineering Communications
ISSN: 0098-6445 (Print) 1563-5201 (Online) Journal homepage: http://www.tandfonline.com/loi/gcec20
SOLID-STATE REACTION BETWEEN BARIUM

SULFATE AND CARBON
J. S. N. Murthy & P. Vishnu Vardhan Reddy
To cite this article: J. S. N. Murthy & P. Vishnu Vardhan Reddy (2012) SOLID-STATE REACTION
BETWEEN BARIUM SULFATE AND CARBON, Chemical Engineering Communications, 199:8,
966-990, DOI: 10.1080/00986445.2011.631204
To link to this article: http://dx.doi.org/10.1080/00986445.2011.631204
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Chem. Eng. Comm., 199:966990, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0098-6445 print=1563-5201 online
DOI: 10.1080/00986445.2011.631204
Solid-State Reaction Between Barium

Sulfate and Carbon
J. S. N. MURTHY1,2 AND
P. VISHNU VARDHAN REDDY1
1
University College of Technology, Osmania University,
Hyderabad, India
2
Vignana Bharathi Institute of Technology, Ghatkesar,
Hyderabad, India
Barium sulfate is the chief source for the manufacture of barium compounds, which
have a wide range of applications in chemical industries. In the preparation of these
compounds, the first step is the reaction between barium sulfate and carbon to pro-
duce barium sulfide. In the present work, the mechanism of reaction between barium
sulfate and carbon is investigated experimentally, covering a wide range of tempera-
tures, times of reaction, and stoichiometric ratios of reactants. The reaction is con-
ducted in air, nitrogen, and vacuum. It is also studied using the reactants in pellet
form to determine the effect of compaction pressure on rate of reaction. A model is
developed to estimate the kinetic parameters and mechanism of the reaction. An
attempt is also made to study the feasibility of conducting the reaction for continuous
production of barium sulfide in a moving bed rector using the reactants in pellet form.
Keywords Barium sulfate; Barium sulfide; Carbon; Diffusion; Reaction; Solid

state
Introduction
Solid state reactions are of considerable industrial importance in the technology of
material processing and production of commercially important chemicals, including
a number of barium compounds like barium carbonate and barium chloride. Barium
compounds are used for a number of applications like glass manufacture, paints,
drilling mud, the production of caustic soda, and others.
The main commercial process for production of purified barium chemicals is the
black-ash process in which the raw material used is barite ore, which usually contains
75% to 90% barium sulfate. It is reduced with coke at about 1100 C in a rotary kiln
to form barium sulfide, which is very soluble in water. The reaction time is about 6 h.
The solution containing barium sulfide is then used for the production of all other
commercially important barium compounds. Thus, the reaction between barium
sulfate and carbon is the essential step for the preparation of barium compounds.
However, the mechanism of such an important reaction and effect of various factors
on the reaction have not been investigated in detail.
Address correspondence to J. S. N. Murthy, Vignana Bharathi Institute of Technology,

Ghatkesar, Hyderabad, India. E-mail: jsnmurthy_ou@yahoo.com
966
Reaction Between Barium Sulfate and Carbon 967
The present work investigates the mechanism of the reaction between barium
sulfate and carbon in loose powder form through experimental studies covering a
wide range of variables: temperature, reaction time, and stoichiometric ratio of
reactants in air and nitrogen environments. The reaction is also studied using the
reaction mixture in pellet form to determine the effect of compaction pressure on
rate of reaction. In addition, the reaction is also conducted in vacuum to determine
the effect of absence of air and establish the mechanism of the reaction. The feasi-
bility of the continuous production of barium sulfide in a moving bed reactor, using
the reaction mixture in pellet form, is also tested.
Literature Review
Barium compounds have wide-ranging applications in chemical and manufacturing
industries like glass manufacturing, pigment industry, sulfuric acid industry, sugar
industry, and manufacturing of caustic soda (Shreve, 1984). The main commercial
process for production of barium sulfide from barites is the black-ash process.
Barites are reduced with coke in a rotary kiln at about 1100 C. The resulting product
called black-ash consists of crude barium sulfide. Barium sulfide is leached from the
reduction product for production of barium chemicals. Several manufacturers,
including FMC Corporation (U.S.) and Sousui Chemicals Co. Ltd. (Japan), use this
method (Bohnet et al, 2005; Kirk-Othmer Encyclopedia, 2004) for production of
barium sulfide. The method of fluidized bed reduction of barite is claimed to be more
economical for low-grade ores. However, it was not found to be commercially
feasible due to problems caused by choking of the reactor because of sintering of
the reacting ore.
Tunison (1971) has studied the reduction reaction and reported that thermal
reduction is accomplished between 900 and 1200 C. Lobunez (1973) has reported
that the reaction is completed in about 10 min at 1100 C, and 6% of the feed barium
sulfate remains unreacted after 30 min at 1050 C. Silica is generally the most com-
mon impurity in barite ore. Searls (2002) reported that if carbon is not present in
sufficient quantity, more barium silicates are formed. Muyskens et al. (2002) has
found that barium sulfate can form the orthosilicate if carbon is not present
above 1100 C. It is reported (Tunison, 1971; Muyskens et al., 2002; Brownell,
1963; Yamaguchi et al., 1972) that with increased retention times, the chance of
occurrence of side reactions increases and the amount of water-soluble barium
sulfide is decreased. The reaction between barium sulfate and carbon is reported
to take place through gaseous intermediates (Budnikov and Ginstling, 1968) as
per the following reaction scheme:
1
Initiation: Cs O2 g ! COg 1
2
Propagation: BaSO4 s 4COg ! BaSs 4CO2 g 2
Cs CO2 g ! 2COg 3
In comparison to the number of studies on gas-solid reactions, there are a limited

number of investigations on reactions between solids proceeding through gaseous
intermediates. Sohn and Szekely (1973) studied the reaction between solids through
gaseous intermediates for systems controlled by chemical kinetics with a net
968 J. S. N. Murthy and P. V. V. Reddy
generation of gaseous products. Reduction of metal oxides is a common example for

solid-solid reactions (Szekely et al., 1976) and the overall reaction is represented as
MeOs Cs ! Mes COg 4
A number of studies have been reported on the reduction of metals using either
graphite or carbon (Otsuka and Kunii, 1969; El-Guindy and Davenport, 1979;
Klinger et al., 1966; Rao, 1974; Freuhan and Martonik, 1976; Freuhan, 1977;
Wouterlood, 1979; Barin and Schuler, 1980, Maitre, 1977). Rao (1974) proposed
a physicochemical model for reduction of hematite by carbon and reported that
the reaction occurs through gaseous intermediates. The Boudouard reaction, i.e.,
the reduction of CO2 by C as shown by Equation (3), has been found to be the
rate-controlling step of the overall reaction mechanism in the above reactions.
Rao and El-Rahaiby (1985) studied and proposed a model for the reduction
of lead sulfide with carbon and lime. The reaction consisted of reduction, carbon
gasification, and lead sulfide vaporization steps. The experimental data are analyzed
by means of a physicochemical model that envisions the Boudouard reaction as the
rate-limiting step for the overall reduction process. The intrinsic rate constant values
were derived by the application of the model.
Experimental Section
The experimental work is divided into three parts: studies using the mixed reactants
in loose powder form, studies using the reactant mixture in compacted pellet form,
and experiments in a moving bed reactor.
The variables considered for the study are reaction temperature, molar ratio of
reactants, reaction time, compaction pressure (for pellets), reaction environment,
and vacuum. The experimental plan is presented in Figure 1. The scope of the
experimental data is shown in Table I.
Kinetic Studies with Reaction Mixture in Loose Powder Form

Barium sulfate and carbon were weighed in the required proportion and mixed in a
mortar and pestle. The laboratory-grade barium sulfate was supplied by Loba Che-
mie and is 99% pure. The carbon used is petro coal from Reliance Industries Limited
(India). After the reactants were mixed manually in a mortar and pestle, four sam-
ples were collected and analyzed chemically by titration for uniformity mixing (Vogel
and Basset, 1979). In addition, a gravity separation method was also used for this
purpose. The method consists of adding the reactant mixture containing carbon
and barium sulfate to carbon tetrachloride. The carbon and barium sulfate separate
into two layers. The upper layer consists of carbon only and the lower layer contains
barium sulfate. They are decanted and weighed separately to check for uniformity.
About 15 min of mixing time was found to be sufficient to achieve uniform compo-
sition. The reproducibility is within 2% with respect to the composition of the
initial mixture. The experiments were conducted under four different conditions as
mentioned below.
A compact and general purpose X-ray diffractometer equipped with a vertical
goniometer that scans with high precision was used to obtain X-ray analysis. It
was provided with an aluminum standard sample holder. The data processing
Figure 1. Plan of the experiments and scope of experimental data.
software works under the newest Windows OS so that time is saved with the
multitasking of measurement software and data processing. The diffractometer
consists of an X-ray generator with 3.0 kW power output, tube voltage of 60 KV,
and maximum tube current of 80 mA. The X-ray tube consists of a target copper
anode tube (3 KW). The detector system consists of a scintillation counter. Other
attachments included a counter monochromator, a rotational sample stage, and thin
film analysis attachment. A water chiller was supplied for smooth running of the
X-ray diffractometer.
Experiments Under Atmospheric Condition

The experiments were conducted as per the following procedure. A refractory boat
was initially weighed and then filled with the required quantity of the reaction
mixture. The boat was placed in a tubular furnace and subjected to the desired tem-
perature for a given time. The reaction was conducted at 900 , 950 , 1000 , 1050 ,
and 1100 C. The reaction time ranged from 120 to 1800s. The boat was taken out
of the furnace and weighed, and the mixture was analyzed chemically by titrating
it with 0.1 N HCl. Reproducibility of the results was checked by analyzing two
Table I. Scope of experimental data
Parameter Value
Temperature ( C) 900, 950, 1000, 1050, 1100
Reaction time (s) 120, 180, 420, 600, 900, 1200, 1800
Molar ratio (BaSO4:C) 1:2; 1:4, 1:6, 1:8
Compaction pressure for pellets (kg=cm2) 10, 20, 30, 40
Environment Air, nitrogen, vacuum
samples for each run. The results were in agreement within 2% with respect to the
conversion obtained. The procedure was repeated for all experiments. The X-ray
diffractograms of pure barium sulfide and one of the samples reacted in air are
shown in Figures 2 and 3 respectively. The high intensity peaks for pure barium sul-
fide are present at 24, 28, and 40 . These peaks are seen clearly in the diffractogram
of the reacted sample, indicating the presence of barium sulfide.
Experiments in Nitrogen Environment

The experiments were conducted in nitrogen atmosphere in order to study the effect
of inert atmosphere. The refractory tube in the furnace was closed on one side with a
cork fitted with a tube to pass nitrogen. First, nitrogen from a gas cylinder was
allowed to reach reaction temperature. After that, the experiments were conducted
following a procedure similar to that adopted for studies under atmospheric con-
ditions. The X-ray diffractogram of one of the samples reacted in nitrogen is shown
in Figure 4. The peaks present in the sample agree with those for pure barium sulfide
shown in Figure 3.
Experiments Under Vacuum

Experimental studies were made to determine the effect of the virtual absence of any
reaction environment. It is also possible to establish whether the reaction is a true
solid-solid reaction or takes place through gaseous intermediates. A reaction mixture
prepared in stoichiometric ratio was placed in a quartz tube, and the tube was sealed
under a vacuum of 2 104 mm Hg. The tube was placed in a furnace at the required
temperature and then cooled. The tube was broken and the sample from the reacted
mixture was taken for analysis to estimate the percentage of conversion. The X-ray
diffractogram of one of the samples reacted in vacuum is shown in Figure 5. There
are no peaks of barium sulfide present in the diffractogram, comparing those of pure
barium sulfide shown in Figure 2, indicating that there is no formation of barium
sulfide.
Figure 2. X-ray diffractogram of pure barium sulfide.

Figure 3. X-ray diffractogram of reacted sample.
Kinetic Studies with Reaction Mixture in Compacted Pellet Form

The reaction mixture was placed in a mold plunger system and was compacted under
the desired pressure using an electrically driven press. The pellets prepared were
1.65 cm in diameter and 0.6 to 0.75 cm in length, depending on the compaction press-
ure. The pellets were made under compaction pressures of 10, 20, 30, and 40 kg=cm2.
Experiments in Atmospheric Condition

The pellet of the reaction mixture was placed in a refractory boat and subjected to
the desired temperature for different times in a tubular furnace. The boat was then
taken out of the furnace, cooled, and weighed. The pellet was ground and then
analyzed.
Experiments in Nitrogen Environment

Nitrogen gas was passed through the furnace and allowed to reach the required
temperature. The experiment was then carried out as per the procedure adopted
for reaction studies under atmospheric conditions.
Experiments in Moving Bed Reactor

The pellets made under a compaction pressure of 30 kg=cm2 were used for the
continuous reactor studies. The total length of the reactor is 65 cm, which includes
25 cm of preheating zone, 15 cm of reaction zone, and 25 cm of cooling zone.
First the pellets made of pure barium sulfate were charged and above them
thepellets of the reaction mixture were charged. The movement of the pellets was
controlled by means of a conveyer pulley arranged at the bottom of the reactor.
Figure 4. X-ray diffractogram of reacted sample in nitrogen.

Figure 5. X-ray diffractogram of reacted sample in vacuum.
The experiments were conducted at temperatures of 950 , 1000 , 1050 , and 1100 C.
The reaction was studied for 5, 7, and 15 min. After the reaction, the pellets were
ground and analyzed. Comparison of conversion data for the moving bed reactor
and batch experiments at a compaction pressure of 30 kg=cm2 is presented in
Table II.
Estimation of Conversion by Chemical Analysis

The progress of the reaction was studied by determining the quantity of barium sul-
fide formed due to the reaction. Barium sulfide is readily soluble in water, while the
other two constituents present in the mixture, barium sulfate and carbon, are inso-
luble. The weighed sample was dissolved in hot distilled water at 70 80 C. The
liquid was decanted into a conical flask and titrated with 0.1 N HCl using methyl
Table II. Comparison of conversion data for moving bed reactor and batch
experiments
% Conversion from % Conversation from

S. No. Temperature Time batch experiments moving bed reactor
1 950 5 50.0 52.1
7 62.4 61.5
15 53.7 56.3
2 1000 5 67.8 68.2
7 74.5 75.1
15 56.3 55.8
3 1050 5 83.5 84.1
7 87.3 88.2
15 70.6 69.5
4 11000 5 95.5 94.6
7 82.2 83.5
15 58.4 59.2
Compaction pressure 30 kg=cm2.
orange as indicator. The end point was noted when the colorless solution changed to
a light pink color.
Development of Mathematical Model

In this section an attempt is made to propose the mechanism of reaction, determine
the rate-controlling step, and formulate equations to estimate the kinetic parameters.
The reaction between barium sulfate and carbon is reported to take place
through gaseous intermediates (Budnikov and Ginstling, 1968). In order to test this
statement, the reaction was carried out under a vacuum of 2 104 mm Hg in a
quartz tube as mentioned earlier. It was determined by X-ray diffraction and also
by chemical analysis that there was no formation of barium sulfide, thereby confirm-
ing that the reaction is not a true solid-solid reaction. Hence, it is concluded that the
reaction proceeds through gaseous intermediates. The reaction may thus be repre-
sented in two steps, as shown by Equations (1)(3).
The entrapped air in the reaction mixture reacts with carbon to form carbon
monoxide, which may be considered as the initiation reaction. Carbon monoxide
gas thus produced reacts with barium sulfate, producing barium sulfide and carbon
dioxide. Thus, in this reaction for each mole of carbon monoxide diffusing and react-
ing with barium sulfide one mole of CO2 is produced, which diffuses out. The
initiation reaction is important at the beginning only. Hence, the main reactions
to be considered are those represented by Equations (2) and (3).
Kinetics of reaction (3), called the Boudouard reaction, which produces carbon
monoxide, becomes the first step for the progress of the reaction. The reaction
between CO2 and carbon particles regenerates CO and thereby tends to restore
the reducing potential of the gas phase contained within the pores of the sample.
Kinetics of Boudouard Reaction

The reaction kinetics of the Boudouard reaction has been well studied by Wu (1949).
The rate equation is of the Langmuir-Hinshelwood form and is given by
K1 Pco2
Rc RCO2 0:5 Rco g mol=g of C s 5
1 K2 Pco K3 Pco2
The value of K2 and K3 are those proposed by Wu (1949) and are accepted for
all sources of carbon. They are given by the equations below:

253000
K2 3:26 1011 exp 6
RT

27700
K3 1:74 103 exp 7
RT
The value of the rate constant K1 is dependent on the source of carbon and is
found from experimental data using the carbon conservation equation.
The reduction of barium sulfate by carbon monoxide is a gas-solid reaction.
The fundamentals of these reactions are extensively discussed in the literature
(Szekely et al., 1976; Levenspiel, 1999). The reaction mechanism based on the
unreacted core model is found to be suitable for the reduction of barium sulfate by
carbon monoxide.
Mechanism of Reduction Reaction of Barium Sulfate

The overall reduction reaction of barium sulfate is given by
BaSO4 s 4COg ! BaSs 4CO2 g 2
The barium sulfate particles are surrounded by the carbon monoxide and carbon
dioxide. CO diffuses through the product layer and reacts with BaSO4 particles to
produce an equal number of moles of CO2 and barium sulfide. The process is repre-
sented in Figure 6 for a single particle of BaSO4.
The model is developed based on the following assumptions:
1. The reaction takes place at pseudo steady-state condition. The reaction interface
is considered to be stationary at any time due to high density of solid compared to
that of a gas.
2. The particles are assumed to be spherical.
3. The concentration of gases is assumed to be constant at the surface of the particle.
4. Temperature of the system is constant.
5. The reaction takes place at atmospheric pressure. Hence, the sum of the partial
pressures of CO and CO2 equals atmospheric pressure.
6. The ratio of partial pressures of CO and CO2 is assumed to be constant as they
are dependent on the stoichiometry as per the reaction Equations (2) and (3).
7. The diffusion fluxes of CO and CO2 are equal and opposite in direction with
respect to barium sulfate as per Equation (3). The diffusion of gases is in the
radial direction.
8. Only a fraction of the gases produced is utilized for reactions.
The model equations are developed based on the unreacted core model
(Levenspiel, 1999). External mass transport through the gas boundary layer usually
provides a negligible resistance to the progress of the reaction and hence has only a
small effect on the overall rate. Hence, the other two steps, namely diffusion of the
Figure 6. Reduction of single BaSO4 particle.

gases through the product layer of barium sulfide and the surface reaction between
carbon and barium sulfate, are to be tested for rate-controlling steps in order to find
the rate-controlling step.
To test the rate-controlling step, a plot of [1-(1-Xb)1=3] versus time is plotted as
shown in Figure 7, where Xb is the conversion of barium sulfate to barium sulfide
(Levenspiel, 1999). If the surface reaction is rate controlling, the plot would be a
straight line. As the plot in Figure 7 is not a straight line, it is inferred that the dif-
fusion of CO though the product layer of BaS is the rate-controlling step with refer-
ence to the reaction given by Equation (2). Accordingly, the corresponding model
equations are developed and the equation for the diffusion coefficient of CO through
barium sulfide is derived.
Development of Model
The porous reaction mixture consisting of barium sulfate and carbon powder is con-
tained in a refractory boat, as shown in Figure 8. Only the upper surface is exposed
to the atmosphere. To aid the formulation of mass conservation relationships for the
species CO and CO2, a reference volume element of thickness Dz located at z is con-
sidered, as shown in Figure 8.
A part of CO gas generated by the Boudouard reaction is utilized in
oxide-reduction, while the rest is transferred into the volume element. Similarly, a
portion of CO2 gas produced is consumed by the Boudouard reaction, the remaining
being accounted for by mass transfer.
From stoichiometry, it is evident from the reaction given by Equation (3) that
one-gram atom of carbon gives two-gram moles of carbon monoxide. However, not
all of the CO gas thus generated is available for reduction of barium sulfate particles.
Let b denote the fraction of CO gas utilized for the reaction given by Equation (2).
The net rate of production of CO is then given by
21 bK1 Pco2
Rco g mol=g of C s 8
1 K2 Pco K3 Pco2
Figure 7. Plot for testing the experimental data for rate-controlling step.
Figure 8. Reaction system finite element in the reaction mixture.
From the reaction given by Equation (2), it is known that each mole of CO pro-
duces one mole of CO2. The quantity of CO produced by the reaction as given by
Equation (3) is 2 moles. As b is the fraction of CO utilized, the quantity of CO gas
utilized is 2 b moles. Hence, the quantity of CO2 produced is 2 b moles. But of the
total quantity produced, one mole of CO2 is used in the Boudouard reaction.
Hence, the net rate of production of CO2 is
2b 1K1 Pco2
RCO2 g mol=g of C s 9
1 K2 Pco K3 Pco2
The mass transfer of the species CO and CO2 through the porous sample is influ-
enced by it structure. The flux of CO and CO2 through the powder structure may be
expressed by the equations proposed by Rao (1974):
1 dPco
JCO DCO 10
RT dz
and
1 dPco2
JCO2 DCO2 11
RT dz
where DCO and DCO2 are the diffusivity coefficients for CO and CO2 in the reaction
powder mixture respectively. Based on the foregoing treatment, the conservation
equations for CO may be written as below across the finite element shown in Figure 8:

Rate of mass Rate of mass Net rate of production
0
of CO in at z of CO out at z Dz of CO by reaction
12

Nco S Nco
S RCO S Dz qc 0 13
z zDz
Dividing Equation (13) by S. Dz and taking limit Dz !0 Equation (13) can be

written as:
dNco
RCO qc 0 14
dz
where Nco is flux of CO into the BaSO4 particle, which is
dCco
Nco Dco 15
dz
Substituting Equation (15) in Equation (14), we get
d2 Cco
DCO RCO qc 0 16
dz2
Pco
CCO 17
RT
Substitution of terms from Equation (8) and Equation (16) in Equation (18)
gives the differential equation for conservation of CO as
Dco d2 Pco 21 bK1 Pco2 qc

0 18
RT dz2 1 K2 Pco K3 Pco2
or
d2 Pco 21bRTK1 Pco2 qc

2
0 19
dz Dco 1 K2 Pco K3 Pco2
Similarly, the conservation equation for CO2 is obtained as
d2 Pco2 2b 1 RTK1 Pco2 qc

2
0 20
dz Dco 2 1 K2 Pco K3 Pco2
Equations (19) and (20) are interdependent by the relation as per the assumption
number (6), which may be represented by the equation given below:
Pco2
a 21
Pco
where a is a constant.
Substitution of Equation (21) in Equation (19) and then equating to Equation
(20) gives
0:5 Dco2 =Dco a

b 22
1:0 Dco2 =Dco a
The diffusivity D of gases is inversely proportional to the square root of its

molecular weight. Hence, the ratio (DCO2=DCO) is related to molecular weights of
gaseous species according to the relation given by the equation given below:
p
DCO2 =DCO MCO =MCO2 0:8 23
Substitution of Equation (23) in Equation (22) gives
0:5 0:8a
b 24
1:0 0:8a
or
1:25b 0:5 Pco2

a 25
1 b Pco
The following equation for mass balance on solid carbon in the reaction mixture
is obtained as per Equation (5):
dqc K1 Mc qc Pco2
26
dt 1 I Pco2
where I K3 (K2=K), qc is the mass concentration of carbon, and Mc is the mol-

ecular weight of carbon. Now, the calculation of rate constant K1 in Equation (26) of
the Boudouard reaction is performed as below.
The following dimensionless variables are defined for calculations:
qc Pco2
w ; s t Mc K1 P0CO2 g IP0CO2 ; and c 27
q0c P0co2
Equation (26) may now be written in terms of the dimensionless variables as

dw wc
0 28
ds 1 gc
It is reported that the approximation of 1 gc gc is valid for a wide range of

CO2 CO gas compositions (Grabke, 1966; Rao, 1972).
Hence, Equation (28) may be written as
dw w
0 29
ds g
Integrating Equation (29),
s
ln w C2 30
g
The initial condition is the amount of carbon reacted at the starting time zero.
So,
w 1 at s 0 31
Hence, C2 0
Hence,

s
w exp 32
g
Resubstituting the dimensionless variables from Equation (27) into Equation

(32), we get

qc t Mc K1 Pco2
exp 33
q0c K2 Pco K3 Pco2
Hence,

qc Pco
ln q0
: K 3 K 2 Pco2
c
K1 34
12t
where qc is mass concentration of carbon present per unit volume in the reaction
mixture at time t and qCO is the initial mass concentration (bulk density of carbon)
present in the mixture. The number 12 is the molecular weight of carbon, Mc.
The mass concentration qc of carbon in the reaction mixture at any time may be
obtained from experimental data as shown below.
During the progress of the reaction there is weight loss in the weight of reaction
mixture. The loss is due to two reactions:
1. The conversion of the reaction of barium sulfate to barium sulfide by removal of
oxygen from BaSO4.
2. The carbon reacted by the Boudouard reaction.
total weight loss of the mixture after each run of the experiment DWt 35
For one mole of BaSO4 converted to one mole of BaS
loss in weight 233 169 64g 36
Let Xb be the fractional conversion of BaSO4 in a mixture containing n1 moles of

BaSO4. Then,
number of moles of BaSO4 converted n1 Xb 37
Hence, the weight loss in the reaction mixture exclusively due to reduction of BaSO4
to BaS is
DWReduction n1 Xb 64 38
So, the weight loss of carbon due to Boudouard reaction is
DWc DWt Wreduction 39

Let
initial weight of carbon in the reaction mixture Wic 40
Hence, fraction of carbon converted
DWc
Fc 41
Wic
Assuming that the total volume of reaction mixture is constant,
qc Wic Wc
42
q0c Wc
The overall reaction for the reduction of BaSO4 may be written as
BaSO4 2C ! BaS 2CO2 43
For two gram-atoms of carbon reacted with one mole of BaSO4, four gram-
atoms of oxygen are lost from the reaction mixture.
Hence,
DWc
oxygen lost for carbon loss of DWc 2Mo 44
Mc
where Mo is the atomic weight of oxygen.

If b, the utilization factor is taken into consideration,
2bDWc
loss of oxygen Mo 45
Mc
So, the total loss of reaction mixture

2bMo
DWt DWc 1 46
Mc
Hence, b may be found from Equation (46) as

3 DWt
b 1 47
8 DWc
Using Equation (47), the utilization factor b may be found from experimental
data.
Using the value of b, the value of a, which is the ratio of PCO2 and PCO, is
calculated from Equation (25).
The total pressure is constant and is equal to 1 atm, i.e.,
PCO PCO2 1:0 48
Hence, simultaneous solution of Equations (25), (47), and (48) gives the value of
Pco and PCO2 for each experimental run.
Calculation of Effective Diffusivity for Reduction Reaction

The reduction reaction takes place by diffusion of CO through the product layer
BaS, as shown in Figure 5.
The rate of diffusion of CO through the product layer is
dCpco
4pr2 De constant Qsay 49
dr
Here, CpCO is the concentration of CO in a single BaSO4 particle.
Boundary Conditions
At r ro
CpCO CCO concentration of CO in mixture of BaSO4 and C
and at r rb
CpCO 0 50
Integrating Equation (49) with the boundary conditions given by Equation (50)
gives
4p De
Q Cp co 51
1=rb 1=r0
The rate of consumption of CO is
dCpco b4p De
4pr2 De Cp co 52
dr 1=rb 1=r0
where b is the stoichiometric coefficient of barium sulfate and is equal to 14.

The initial particle size of barium sulfate, ro, is assumed to be unchanged with
reaction time.
drb
rate of reaction of particle 4pr2b qb 53
dt
where qb is the density of barium sulfate.

Equating Equation (52) and Equation (53), we have
1=4 4p De drb
Cp co 4pr2b qb 54
1=rb 1=r0 dt
Or
Z Z
1=4 De 1 1
Cp co dt r2b drb 55
qb rb r0
Figure 9. A typical plot of z vs. PCO to calculate De. (Figure provided in color online.)
Integrating Equation (55), with the initial condition at t 0 and r b ro, we get

3 De t
Cp co 1 31 Xb 2=3 21 Xb 56
2 qb r20
Let
y 1 31 Xb 2=3 21 Xb 57
Ppco
Cpco 58
RT
Substitution of Equation (57) and Equation (58) in Equation (56) gives
2 R T y r20 qb
De :Pp co zsay 59
3 t
Ppco is PCO, the partial pressure of CO at the surface of barium sulfate
(unreacted), and is calculated from Equation (25) and Equation (48).
Hence, Equation (53) may be written as
z De Pco 60
Thus, from the slope of the plot z versus PCO, the effective diffusivity De of the
reduction reaction is calculated. A typical plot is shown in Figure 9.
Results and Discussion

The results obtained from experimental investigations carried out using reactants in
loose powder and pellet form to find the effect of reaction environment, temperature,
molar ratio, and compaction pressure of pellets on the reaction between barium
sulfate and carbon are discussed in detail. In addition, the inferences drawn from
the application of the mathematical model to experimental data about the

rate-controlling step are also discussed.
Effect of Reaction Environment

Experiments in Vacuum
When experiments were conducted under vacuum, it was observed that there was no
formation of BaS product, as found by chemical analysis and X-ray diffraction. This
result confirms that there is no reaction between barium sulfate and carbon in the
absence of air. Hence, it is concluded that the reaction proceeds through gaseous
intermediates.
Experiments in Air
It was observed that in all experiments, the percentage conversion attained a
maximum value and then dropped steeply with time afterwards. Typical plots show-
ing the trend of conversion degree with time are shown in Figure 10.
Conversion increases with time due to the formation of BaS in the mixture as the
reaction proceeds with time as expected. The fall in conversion is attributed to the
dilution of CO and CO2 gases by diffusion into the surrounding atmosphere, thereby
causing the surrounding air to react with BaS to form BaSO4.
Experiments in Nitrogen
The experiments conducted under nitrogen environment also showed a similar trend,
but the rate of fall in degree of conversion is considerably reduced, as shown in
Figure 11. It is inferred that due to a significant decrease of air concentration in
the vicinity of BaS, the rate of reaction with air is decreased. Hence, the rate of fall
was reduced.
Figure 10. General trend of conversion vs. time graph.

Figure 11. Conversion-time plots to study the effect of nitrogen environment.
Effect of Reaction Parameters

Temperature
The conversion of BaSO4 to BaS increased with temperature for all experiments.
Typical plots for a few experimental conditions are shown in Figure 12. It is also
observed that the time for maximum conversion of BaS decreased with temperature,
as shown in Figure 12. The overall reaction is endothermic in nature and hence
Figure 12. Conversion-time plots to study the effect of temperature on percent conversion and
optimum reaction time.
Figure 13. Conversion-time plots to study the effect of molar ratio.
the increase in temperature results in improved conversion degree for selected

reaction time.
Molar Ratio
The percentage of conversion to BaS increased with molar ratio of carbon to BaSO4
in comparison to that under stoichiometric conditions with other conditions
Figure 14. Conversion vs. time graph to study the effect of compaction pressures.
Table III. Relationship between compaction pressure and porosity
S. No. Compaction pressure (kg=cm2) porosity

1 10 0.42
2 20 0.39
3 30 0.36
4 40 0.35
remaining constant. The plots of conversion versus time showing the effect of molar
ratio are presented in Figure 13. The conversion is expected to increase due to the
increased availability of CO for the reduction reaction with BaSO4. However, the
trend in the degree of conversion is the same as that observed for experiments conduc-
ted under atmospheric condition in air.
Compaction Pressure
When the reactant mixture is compacted into pellets and reacted, the degree of con-
version is found to increase in comparison to that in the loose powder system under
similar reaction conditions, as shown in Figure 14. However, the degree of conversion
was found to increase up to 30 kg=cm2, beyond which there was marginal decrease in
conversion.
The degree of conversion increased due to the increased closeness between the
reactants and also due to the slow rate of diffusion of air into the pellets. However,
the degree of conversion is observed to increase up to a compaction pressure of
30 kg=cm2, after which there was a marginal decreasing trend, as seen from the data
obtained at a compaction pressure of 40 kg=cm2. This is attributed to the decrease in
effective diffusion of CO to the reactive sites because of reduced porosity. The
relationship between compaction pressure and porosity is presented in Table III.
Experiments in Moving Bed Reactor

The conversions obtained in the experiments conducted in a moving bed reactor
under different temperature conditions are similar to those obtained in batch experi-
mental studies using reactants in pellet form. The comparison is presented in Table II.
Accordingly, it is concluded that the results obtained and inferences drawn from
batch experimental results are also directly applicable for continuous production.
Application of Mathematical Model Equation

The rate constant K1 for the Boudouard reaction is calculated at different tempera-
tures using Equation (34). The effective diffusivity De of the reduction reaction is
calculated from the slope of the plot z versus Pco, as per Equation (60).
The calculated values of rate constant K1 and the effective diffusivity for loose
powder system are presented in Table IV. The activation energies for the reactions
are found from the slopes of the plots of lnK1 versus 1=T and ln De versus 1=T.
The activation energy for the Boudouard reaction is found to be 0.33 105 and that
for reduction is found to be 2.32 105 J=mole.
Table IV. Values of rate constant K1 and effective diffusivity De for loose powder
system
S. No. Temperature ( C) K1 (mol=atom cm2 min) De cm2=min

1 900 0.00364 4.03 103
2 950 0.00569 1.51 102
3 1000 0.00706 0.08
4 1050 0.00873 0.293
5 1100 0.00984 0.55
Table V. Activation energy with compaction pressure of pellets
Compaction pressure Boudouard reaction Reduction reaction

S. No. (kg=cm2) (J=mole) (J=mole)
1 10 0.316 105 04 105
2 20 0.302 105 0.945 105
3 30 0.298 105 0.836 105
4 40 0.3 105 0.835 105
The activation of energy of the Boudouard reaction is found to be lower than

that of the reduction reaction because the rate of diffusion through the product layer
of BaS is slower than the rate of formation of CO. Thus, it may be concluded that
the diffusion of CO through BaS is the rate-controlling step.
The activation energy of the reduction reaction is found to decrease with
increase in compaction pressure. The activation energy of the reduction reaction
under different compaction pressures of the pellet is given in Table V.
The decrease in activation energy with increase in compaction pressure is due to
the increased rate of reaction because of the closeness of the reactant particles and
also to the reduced diffusion of air through the pellet surface.
Conclusions
1. The air present in the interstices of the reaction mixture is sufficient and necessary
to initiate the reaction. Subsequently, the reduction reaction of BaSO4 to BaS
proceeds faster, giving higher conversion in the absence of air.
2. The percentage of conversion of BaSO4 to BaS increases with temperature,
compaction pressure (up to 30 kg=cm2), and molar ratio of carbon to BaSO4.
3. It is recommended that the production of BaS be done using the reactant mixture
in the form of pellets.
4. The activation energy of the Boudouard reaction is lower than that of the
reduction reaction, confirming that the reduction reaction between CO and
BaSO4 is the rate-controlling step in the overall reaction mechanism.
5. The optimum conditions for continuous production of BaS at laboratory scale
under atmospheric air conditions are found to be a temperature of 1100 C, a
compaction pressure of 30 kg=cm2, and reaction time of 7 min.
Acknowledgments
The authors thank Ms. S. K., Barium Chemicals, Hyderabad, for supply of materials
for the studies and P. Victor, B. Swetha, Anil Kumar, Deepthi, Dr. T. Sankarshana,
and Dr. D. Jaya Prakash of University College of Technology, Osmania University,
Hyderabad, for their help in experimentation.
Nomenclature
B stoichiometric coefficient of carbon monoxide
C1, C2, C3 integration constants
CCO concentration of carbon monoxide at any radius
CCO0 concentration of carbon monoxide at the surface of BaSO4 particle
CCO2 concentration of carbon dioxide at any radius
CCO20 concentration of carbon dioxide at the surface of BaSO4 particle
De effective diffusivity, cm2=s
DCO diffusivity of carbon monoxide in the pores of the sample, cm2=s
DCO2 diffusivity of carbon dioxide in the pores of the sample, cm2=s
K1, K2, K3 rate constants for Boudouard reactions
MC molecular weight of carbon
MCO molecular weight of carbon monoxide
MCO2 molecular weight of carbon dioxide
Mo atomic weight of oxygen
n1 initial number of moles of BaSO4, mole
PCO partial pressure of carbon monoxide in the mixture, atm
PCO2 partial pressure of carbon dioxide in the mixture, atm
Q a constant.
R universal gas constant, cm3-atm=g.mol.K
RCO rate of formation of carbon monoxide
RCO2 rate of formation of carbon dioxide
r radius of particle at any time, cm
rb radius of barium sulfate particle, cm
r0 initial radius of BaSO4 before reduction reaction, cm
T temperature, K
t time of reaction, min.
DWt total weight lost during reaction time t, g
DWc weight loss of carbon, g
Wic initial amount of carbon in reaction mixture, g
DWReduction weight loss due to reduction reaction, g
Xb conversion of BaSO4 to BaS, %
y 13(1-Xb)2=3 2(1-Xb)
2
z 3 RTyr0 qb
2 t
Greek letters
a ratio of partial pressure of carbon monoxide in the mixture to partial
pressure of carbon dioxide
b utilization factor
c Pco2
0
P co2
g K2PCO K3PCO2
q0c initial mass concentration of carbon in the mixture, g=cm3

qc mass concentration of carbon in the mixture at time t, g=cm3
s dimensionless time, t McK1Pco2
qc
w q0c
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Chemical Engineering Communications

ISSN: 0098-6445 (Print) 1563-5201 (Online) Journal homepage: http://www.tandfonline.com/loi/gcec20

SOLID-STATE REACTION BETWEEN BARIUM

J. S. N. Murthy & P. Vishnu Vardhan Reddy

To link to this article: http://dx.doi.org/10.1080/00986445.2011.631204

Published online: 05 Jun 2012.

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Download by: [EPFL Bibliothque] Date: 30 August 2016, At: 03:56

Solid-State Reaction Between Barium

Keywords Barium sulfate; Barium sulfide; Carbon; Diffusion; Reaction; Solid

Address correspondence to J. S. N. Murthy, Vignana Bharathi Institute of Technology,

In comparison to the number of studies on gas-solid reactions, there are a limited

generation of gaseous products. Reduction of metal oxides is a common example for

MeOs Cs ! Mes COg 4

Kinetic Studies with Reaction Mixture in Loose Powder Form

Figure 1. Plan of the experiments and scope of experimental data.

Experiments Under Atmospheric Condition

Table I. Scope of experimental data

Experiments in Nitrogen Environment

Experiments Under Vacuum

Figure 2. X-ray diffractogram of pure barium sulfide.

Figure 3. X-ray diffractogram of reacted sample.

Kinetic Studies with Reaction Mixture in Compacted Pellet Form

Experiments in Atmospheric Condition

Experiments in Nitrogen Environment

Experiments in Moving Bed Reactor

Figure 4. X-ray diffractogram of reacted sample in nitrogen.

Figure 5. X-ray diffractogram of reacted sample in vacuum.

Estimation of Conversion by Chemical Analysis

% Conversion from % Conversation from

Development of Mathematical Model

Kinetics of Boudouard Reaction

Mechanism of Reduction Reaction of Barium Sulfate

BaSO4 s 4COg ! BaSs 4CO2 g 2

Figure 6. Reduction of single BaSO4 particle.

Figure 8. Reaction system finite element in the reaction mixture.

Dividing Equation (13) by S. Dz and taking limit Dz !0 Equation (13) can be

where Nco is flux of CO into the BaSO4 particle, which is

Dco d2 Pco 21 bK1 Pco2 qc

d2 Pco 21bRTK1 Pco2 qc

Similarly, the conservation equation for CO2 is obtained as

d2 Pco2 2b 1 RTK1 Pco2 qc

0:5 Dco2 =Dco a

The diffusivity D of gases is inversely proportional to the square root of its

Substitution of Equation (23) in Equation (22) gives

1:25b 0:5 Pco2

where I K3 (K2=K), qc is the mass concentration of carbon, and Mc is the mol-

Equation (26) may now be written in terms of the dimensionless variables as

It is reported that the approximation of 1 gc gc is valid for a wide range of

Resubstituting the dimensionless variables from Equation (27) into Equation

For one mole of BaSO4 converted to one mole of BaS

loss in weight 233 169 64g 36

Let Xb be the fractional conversion of BaSO4 in a mixture containing n1 moles of

number of moles of BaSO4 converted n1 Xb 37

So, the weight loss of carbon due to Boudouard reaction is

DWc DWt Wreduction 39

initial weight of carbon in the reaction mixture Wic 40

Hence, fraction of carbon converted

The overall reaction for the reduction of BaSO4 may be written as

BaSO4 2C ! BaS 2CO2 43

where Mo is the atomic weight of oxygen.