Langmuir 1987,3, 753-760

753

Surface Properties of Limestones and Their Activation

Products
E. L. Fuller, Jr.*
Plant Laboratory, Martin Marietta Energy Systems, Inc., Oak Ridge, Tennessee 37831

T.R. Yoos
5 Runford Road, Lexington, Massachusetts 02173
Received July 28, 1986. I n Final Form: March 10, 1987
Detailed studies of the thermal activation of commercially available limestones have been carried out
in view of their applicability for cleaning combustion gases of sulfur and nitrogen oxides. The activation
was carried out in vacuo from 450 to 500 C for high-purity Quincy limestone and for a less pure dolomitic
Franklin limestone. The mechanism of carbon dioxide expulsion does not seem to involve an activation
energy and proceeds via a shrinking core mechanism in which the product oxide is comprised of relatively
nonrigid laminae that act to hold nitrogen in the course of sorption experiments at 77 K. Although the
morphology of the generated structure is complex, it does seem to be of the same type throughout the
calcination process and varies only in the amount that is linearly related to the degree of conversion to
the oxide. Natural impurities (aluminosilicates,magnesia, sulfates, etc.) tend to serve as fluxes to promote
sintering of the metastable flexing CaO structure even at these low temperatures. The results of this study
agree well with the data of other laboratory and production-scale studies and provide additional data
regarding the thermochemistry and mechanism of the thermal activation of limestone.

Introduction
Limestone is the most ubiquitous form of calcium carbonate in nature and varies from relatively high purity to
mixtures with other constituents, for example, dolomites.
Current emissions of sulfur oxides (SO3 and SOz, etc.,
generally designated SO,) from the combustion of fossil
fuels are delivering a prohibitiye insult to the environment.
Several programs are currently being studied to remove
the SO, by a reaction employing some form of limestone
or related inexpensive gettering material as shown by reaction 1, where X = 2 or 3, depending upon the degree of
CaC03(s) + SO,(v)

CaSOx+(s) + COz(v)

(1)

o x i d a t i ~ n . ~ This
- ~ process can occur either in the combustion chamber (i.e., fluidized bed combustion or direct
injection) or in the combustion gas stream (stack gas
cleanup). In either instance, efficient, rapid, complete use
of the raw material requires that the starting material must
be of colloidal dimensions to ensure that we are not inundated with the proper gypsum. Reaction 1 proceeds as
a concerted combination of limestone decomposition
CaCO,(s)

CaO(s) + C02(v) + 177.8 kJ/mol (2)

and gypsum formation

CaO(s) + SO,(v)

CaSOx+l(s)

(3)

at the temperature and pressures of the reaction chamber.

If reactions 2 and 3 occur simultaneously, the overall reaction (1) will be kinetically inpeded by the counter currents of the reactant and product vapors, even at temperatures where the bond strengths between the metal
oxide and the respective vapors are weak enough to assure
sufficient mobility on the surface of the intraparticulate
access-egress channels. This idealized depiction is further
(1) Boynton, R. S. Chemistry and Technology of Lime and Limestone;
Wiley: New York, 1980. (For general practical information, the interested reader is recommended perusal of the first edition, 1966).
(2) Slack, A. Enuiron. Sci. Technol. 1973, 4 , 110.
(3) Borgwardt, R.; Harvey, R. Enuiron. Sci. Technol. 1972, 7, 350.
(4) Boynton, R. S. Chemlstry and Technology of Lime and Limestone;
Wiley: New York, 1980;pp 118-125.

complicated by the related reactions that can and will

occur in the complex mixture of the combustion process.
Two major factors that will occur in the porous matrices
of the particles are hydration to form the hydroxide from
the activated limestone
CaO(s) + H,O(v)
Ca(OH)z(s)
(4)

and general blocking of the pores by physical deposition

of both organic and inorganic residues from the combustion processes.
The best use of limestones for the cleanup of combustion
gases, as well as a host of other related processes, depends
on reaction 2, which is cited as activation, calcination,
burning, etc., depending on the expertise of the authors.
Indeed, reaction 2 truly is described as follows:
...This is probably the most basic and the
simplest of all chemical reactions. But, while
it is theoretically very prosaic, there are many
complexities attendant to this reaction. In
spite of incontrovertible scientific data delineating calcination, this process still remains,
to some extent, a technique or an art that only
an experienced lime burner comprehends.l
This work describes a fundamental study to elucidate
the chemistry and structure of the entities involved in the
activation processes more completely and to better define
the kinetics, thermochemistry,and mechanisms so that the
artistry can be defined on a more systematic, scientific
basis. In this manner, we shall provide necessary details
to advance the understanding beyond the following generalities (Boynton, R. s.): ...There are three essential
factors in the kinetics of limestones decomposition: 1.
The stone must be heated to the dissociation temperature
of the carbonates. 2. This minimum temperature (but
practically higher temperature) must be maintained for
a certain duration. 3. The carbon dioxide gas that is
evolved m-ust be removed.
Information pertaining to the chemistry, structure, and
energetics involved in the activation process will provide
the means to advance the field beyond the current empiricism and art. The preceding comments are indicative

0743-7463/87/2403-0753$01.50/0 0 1987 American Chemical Society

Fuller and Yoos

754 Langmuir, Vol. 3, No. 5, 1987

I

HONEYWELL RECORDING
I
rHART
I

UNRESTRICTED M U L T I L A Y E R S1 -

I
I

VOLUME F I L L I N G L I M I T

___)

t
/

PORE F I L L I N G AND
MULTILAYER FORMATION

SAMPLE,

L-

FUSED OUARTZ TUBE

FUSED OUARTZ PAN

CYLINDER

U
Figure 1. Schematic diagram of the sorption/activation vacuum
microbalance system used for colloid and surface studies of
limestones and activation products.

of the issues that must be addressed for the use of limestones in the case of current interest. Is it preferable to
inject limestone directly into the combustion chambers and
calcine in situ or precalcine and inject the lime (CaO) for
SO, gettering? In either case, the heat balance involves
between 2.5 and 3.0 million BTU per ton of quicklime. In
both instances, the process involves a vigorous expulsion
of the COz from the rhombohedral calcite crystalline
structure at a rate that increases with increasing temperature. The resultant lime transforms to an increasing
degree to the close-packed cubic (NaC1) structure of the
ealcia with a rate that is enhanced at higher temperatures.
One normally strives for a balance to obtain a material of
high reactivity (high surface area and porosity) with a "soft
burnt" state in contrast to the "hard burnt" or "dead
burnt" material in the vernacular of the trade.'

Experimental Section
Microgravimetric Sorption/Activation System. The experimental data concerning the colloid and surface properties of
the various entities were obtained on a vacuum microbalance
system that has been described in detail e l ~ e w h e r e .Pertinent
~~
points of the sorption/reaction system are given in Figure 1. The
temperature and pressure of the sample chamber can be controlled
accurately a t fixed isothermal and isobaric values over a wide range
(77-1300 K and 104-103 Torr). Such capabilities are required
to best evaluate the kinetics and equilibrium mass values related
to the chemical and physical processes of interest in this report.
The microbalance is left operative on a continuous basis to allow
monitoring of the mass variations and to verify mass invariance
(steady state and/or equilibrium) over prolonged periods (days,
weeks, montha) a t isothermal isobaric conditions. The strip chart
recorder is used in an interpolative manner to visually monitor
states of interest.
A gradient-free, noninductive resistive furnace maintains the
temperature of the sample tube for vacuum activation to fl "C
as long as desired after a rapid heatup. After the desired degree
of decomposition (as measured by the real-time mass loss measurement), the reaction is quenched by removing the furnace and
installing a 77 K, stirred-liquid nitrogen bath around the sample
tube without pressurization above the high vacuum state. This
bath is automatically maintained a t a constant level ( f l mm),
and a vapor pressure thermometer measures the saturation nitrogen pressure and, consequently, the bath temperature quite

02

06

0 4

08

40

P/P,

Figure 2. Generalized schematic representation of nitrogen

adsorption on solids with delineated regions of interest in the
present study of the colloid and surface properties of activated
limestones.
Table 1. Chemical Composition of Limestone Samples As
Determined by X-ray Fluorescence Analysesa
Quincy
Franklin
Franklin
element (-20/+60 mesh) (-12/+30 mesh) (-6/+16 mesh)
Ma
0.139 f 0.030
0.320 f 0.031
0.353 f 0.032
Ai
n
n
0.085 f 0.030
Si
n
0.139 f 0.009
n
P
0.007 f 0.002
0.007 f 0.002
0.009 f 0.002
S
0.000 f 0.002
0.021 f 0.002
0.018 f 0.002
K
0.058 f 0.002
n
n
Ca
39.161 f 0.039
38.814 f 0.039
38.933 f 0.039
Ti
n
n
n
Mn
0.013 f 0.001
0.006 f 0.001
0.006 i 0.001
Fe
0.078 f 0.003
0.121 f 0.003
0.126 f 0.003
Sr
0.0181 f 0.000
0.0440 f 0.000
0.0426 f 0.0005
a Concentration expressed as weight percent based on calibration
curves for seven standard mineral samples [totals do not sum to
100% because major elements (carbon and oxygen) were not included; n denotes negligible concentrations].

accurately (fO.O1 K). High-purity nitrogen gas (99.99g5%) is then

introduced to raise the pressure to the desired value as measured
(and subsequently controlled) by the electronic output from the
capacitance manometer connected to the electrobalance chamber.
This process is incrementally repeated to supply the discrete data
points required to define the curve and shape of the adsorption
isotherm8vgdepicted schematically in Figure 2. This work involved
enough data to define the three regions of interest: (1)from 0.02Po
to
to evaluate monomer capacity by the Brunauer, Emmett,
Teller (BET) or a similar procedure; (2) up to ca. 0.95P0to evaluate
the multilayer sorption and any mesopore condensation in the
pores of the materials; (3) virtual saturation ( P approaching Po,
0.999+ in practice) so that we can determine the limiting factor
caused by the complete filling of the internal reaches of the
particle, if indeed such a phenomenon does occur.
Although this practice does not provide the ultimate detail that
may be desired for complete definition of the porosity and surface
structure, it does provide an economy of time expended and is

(5) Fuller, E. L., Jr.; Agron, P. A. B o g . Vac. Microbalance Tech. 1975,

3, 71.

( 6 ) Fulier, E. L., Jr.; Holmes, H. F.; Gammage, R. B.; Secoy, C. H.

h o g . Vac. Microbalance Tech. 1972, I , 265.
(7) Fuller, E. L., Jr. Microweighing i n Vacuum and Controlled Enuironments; Czanderna, A. W., Ed.; Elsevier: Amsterdam, 1980.

(8) Gregg, S. J.; Sing, K. S. W. Adsorption, Surface Area, and Porosity; Academic: New York, 1967.
(9) Adamson, A. A. Physical Chemistry of Surfaces; Interscience:
New York, 1976.

Langmuir, Vol. 3, No. 5, 1987 755

Surface Properties of Limestones

Table 11. Comparison of X-ray Powder Diffraction Data for
the Three Limestone Samples t o JCPDS Data for Standard
Calcite and Dolomite"
Calcite Dolomite
Franklin
Quincy
Franklin Franklin -6/+16
JCPDS
JCPDS
5-586
11-78
-20/+60
-12/+30
-6/+16
repeatb

10'

4.03 [5]
3.86 [12]
3.04 [lo01
2.89
2.84 [3]
2.67
2.54
2.50 [14]
2.40
2.28 [18]
2.19
2.10 [18]
2.07
2.02 [15]
1.93 [5]
1.91 [17]
1.88 [17]

3.85 [lo] 3.80 [lo] 3.83 [lo] 3.87 [8]

3.03 [loo] 3.01 [loo] 3.02 [lo01 3.05 [lo01
[loo]
2.88 [tr]'
2.84 [lo] 2.81 141
2.83 [5]
[lo]
[lo]
2.49 [15] 2.47 [15] 2.48 [15] 2.49 [13]
[lo]
2.29 [20] 2.27 [20] 2.28 [20] 2.29 [17]
[30]
2.19 [tr]
2.09 [25] 2.08 [25] 2.09 [20] 2.10 [19]
[5]
1.93 [5]
1.91 [22]
1.88 [15]

1.92 [5]
1.90 [22]
1.86 [20]

1.92 [5]
1.91 [22]
1.87 [22]

40.'

10-2

1.93 [14]
1.91 [22]
1.88 [18]

nValuesare given for d-spacingsand bracketed percent ratios for the

relative diffraction intensities. Joint Committee on Powder Diffraction
Standards, JCPDS, reference values from compilation. bFor a separate
portion of the same mesh fraction showing the presence of dolomite to
be heterogeneous. [tr] denotes minimal detectivity of the dolomite
entities, less than 2 wt % based on measured additions of dolomite to
calcite samples.
amenable to automated control and screening studies of the type
presented here.
Limestone Samples and Their Characterization. Naturally
occurring limestones were chosen for this study from indigenous
mine sources used for commercial supplies much akin to that
which will be required by economic consideration in actual plant
operations. The materials reported here were limited to two
general sources: (1)a relatively pure calcite from the Quincy mine
of Quincy, IL, and (2) a somewhat more heterogeneous material
from the Franklin mine at Crab Orchard, TN. These materials
represent an approximation to the variation one can anticipate
for geomorphologic, chemical, particle size, crystallographic,and
processing variation among the many choices of natural feedstock.
Tables I and I1 show the analytical results performed by the
authors on the specific samples used for subsequent colloid and
surface studies.
Petrographic examinations were used to further characterize
the limestones. Thin sections of the sample grains were prepared
by mounting the grains in epoxy on a glass slide and grinding the
grains to a thickness of 60 pm on a thin-section machine. Onethird of each slice wm dipped into a 10% HCl solution for 1min,
rinsed with distilled water, and subsequently dipped into potassium ferricyanide solution for 3 min. This blue stain detects
iron, which readily substitutes for magnesium in dolomite but
rarely for calcium in calcite. A second staining procedure involves
immersing one-third of each slide into Alizarin Red-S solution
for 30 s, washing it with cold water for 5 s, and blotting the slide
dry. Alizarin Red-S stains calcite red but does not stain dolomite,
thus providing a second visual test for dolomite. The Quincy
limestone proved to be essentially pure calcite crystalline limestone
with fewer than 0.2% of the grains showing any dolomitic behavior. The finer sample of Franklin limestone (-12/+30 standard
mesh size) is almost equally void of dolomite, which is in accordance with previous analyses. The coarser Franklin limestone
sample contains 1-2% dolomite, as determined by grain count.
Some grains were entirely dolomite, while other grains showed
the presence of both calcite and dolomite heterogeneously agglomerated.
In summary, the Quincy limestone and the finer fraction of
the Franklin limestone appear to be quite pure, high-calcium
limestones, and the comer fraction of Franklin limestone contains
up to ca. 2.5% of dolomite. Solely on the basis of these chemical
and mineralogical characterizations, one would not anticipate
appreciable differences in the calcium utilization for sulfur removal.

40-4

1.0

j.2

4.4

j.6

looo/T(

'K)

j.8

2.0

Figure 3. Calculated dissociation pressures for calcium carbonate

and calcium hydroxide.

I
t

-9

-E

DECOMPOSED{

r
.-

&- 7
E

-z

-6

-4
-3

I160

1200

1.240

f.280

1.320

1360

1000/T(OK)

Figure 4. Arrhenius plot for the rate data on activation of Quincy

limestone (=20/+60 mesh) as a function of temperature and
extent of decomposition.

Results and Evaluation

Kinetics and T h e r m o c h e m i s t r y of Limestone Activation. The activation of calcite can be effected over
a wide range of temperatures and pressures, as noted in
Figure 3, based on a standard thermodynamic reference
data.1 The results reported here will be limited to
450-600 "C, where the pumping speed of the vacuum
pumps is not exceeded and t h e rates can be accurately and
conveniently measured. One can monitor t h e rate of gas
evolution, cW(CO,)/dt, either as the mass loss on the
microbalance or by t h e system pressure through t h e relationship

P = (RT/SJ(m(COJ/dt)

(5)

where P is t h e system pressure (Torr), R the gas constant

((Torr I)/(mol K)), T t h e temperature of t h e sample (K),
Sa t h e vacuum pumping speed (72000 L/min), N t h e
evolved carbon dioxide (mol), and t t h e time (min). All
of the values quoted here were determined gravimetrically
with constant monitoring t o ensure t h a t t h e rate of COP
(10) Strehlow, R. A., personal communication.

Fuller and Yoos

756 Langmuir, Vol. 3, No. 5, 1987

-7

I
DECOMPOSED

20

-3
-7

if60

1200

1240
'OOO/T

1.280

1320

P" , CL

1.360

(OK)

Figure 5. Arrhenius plot for the rate data on activation of

Franklin limestone (-12/+30 mesh) as a function of temperature
and extent of decomposition.

0.5

FRANKLIN

CaO, %

Franklin (-12/+30)

of

00
28.9
51.4
70.1
98.7
0.0
23.8
49.2
73.9
95.2

E*, kJ/mol
-182
-184
-164
-284 (-145.9)'
-192.3
-172.3
-159.3

20

40
60
80
100
PERCEN r DECOMPOSITION

m2/g

((CaO))
0.37
25.46
43.96
61.83
89.59
3.35
25.46
46.24
62.83
73.69

Two values related to the two slopes of the corresponding lines

Figure 5 .

Table 111. Activation Energy, E*, and BET Specific

Surface Area for the Calcination of Limestones Based on
the Rate of Mass Loss under Vacuum and in Nitrogen
Sorption, Respectively
BET area,

Quincy (-20/+60)

(20

440

Figure 6. Rate of COz loss for limestones under vacuum at 500

"C related to the degree of decomposition.

1$ 7.5
I

generation did not exceed the pumping speed and did

adhere to its relationship of eq 5. These sensibly constant
rate values are in turn analyzed in the Arrhenius format,
as presented graphically in Figures 4 and 5. These results
show that the activation energy, E* as presented in Table
111, is only slightly dependent upon the degree of calcination and that the magnitude (deduced from the slopes
of the respective linear re1ations)'l is very close to the
thermodynamic enthalpy for the process, as noted in eq
2. In contrast, the activation energy for Franklin limestone
is more dependent upon the degree of calcination, as noted
in Figure 5. The initial values seem to be greater than the
enthalpy at initial calcination and lower temperatures.
The magnitude of the activation falls markedly below the
thermochemical energetics (eq 5) at higher temperatures
and more extensive degrees of calcination. These variations are due to the chemical impurities with only minor
contribution due to the larger particle sizes (as will be seen
in subsequent discussions). We can be assured that the
activation process occurred in essentially a reversible
manner in the thermodynamic sense because no additional
energy was required to overcome an activation barrier
significantly greater than the bond cleavage energy. No
hindrances, such as a diffusional barrier, were encountered
in this relatively mild calcination process. This is most
assuredly not the case in commercial processes where
temperatures ranging up to 1000 "C are employed. However, the present work is useful as a minimal condition
reference for the chemical process alone without the
(11) Moore, W. J. Physical Chemistry; Prentice-Hall: Englewood
Cliffs, NJ, 1972; p 363.

-1'
/

I /
o

20

40

60

BOTTOM SCREEN MESH NUMBER

Figure 7. Initial decomposition rates of limestones under vacuum

at 500 "C related to the size of the particles.
stringent physical barriers of heat and mass transfer that
are encountered in the more "brute force" processes.
The decomposition at fixed temperature (i.e., 500 "C)
follows the classical exponential relationship
(6)
(dC/dt) = (dC/dt),=oe-kc
where C represents the concentration of the product CaO,
expressed as a percentage in the context of Figure 6. The
numerical value of the rate constant k (evaluated as the
slope of the linear logarithmic relation) is virtually the
same for both samples, indicating a very similar reaction
mechanism. The displacement shown in Figure 6 results
from the more rapid decomposition of the finer particles
of the Quincy sample. A more informative relation is given
in Figure 7, which shows the consistency between samples
and that the theoretical extrapolation to "zero mesh" is

Surface Properties of Limestones

Langmuir, Vol. 3, No. 5, 1987 757

280

240
240

200
200

460

1-8

:1

s
t

160

-zP

420

PERCENT
DECOMPOSITION

L.

'

OI

E 120

80
80

40

0
0

P/P,

Figure 8. Nitrogen sorption isotherms of Quincy limestone

( ~ 2 0 / + 6 0mesh) at 77 K after various degrees of thermal activation in a vacuum microbalance chamber.

consistent with a virtual infinitely slow decomposition rate

for extremely large crystals of limestone. These relationships result from the cooperative effects within the limestone crystals where synergetic relations exist in that each
C02unit senses how many CaO units have been generated
and is less prone to exit for greater degrees of calcination.
This is in direct contrast to the statistical (mass action)
control of noninteractive systems where the rate is proportional to the number of COz units remaining ( A ) and
the order of the reaction ( n ) :
dC/dt = kA"

Sorption Analyses for Surface Area and Porosity

of Quincy Limestone. Nitrogen sorption isotherms were
constructed on the samples at selected degrees of activation
by quenching under vacuum from the activation temperatures to 77 K by removing the furnace and installing a
liquid nitrogen cryostat around the tube where the sample
is suspended a t a depth 12 cm below the liquid nitrogen
level, which is controlled automatically at f 2 mm. This
liquid is continuously stirred with a flow of nitrogen purge
gas. The bath temperature and saturation vapor pressure,
Potare monitored continuously with a dedicated vapor
pressure thermometer (capacitance manometer) and incorporated in all calculations. In this manner, the desired
CaO/CaC03 composition was maintained without recarbonation or hydration from the very low, albeit finite,
residual gas concentrations of the 104-Torr static base
vacuum. The cold walls of the quartz hangdown tube
served as excellent getters during the course of the isotherm construction.
When the sample is allowed to subsequently warm to
ambient temperatures, some of the cryogenically sorbed
water does flash to the sample and is entirely driven off
as the sample temperature is increased through the
200-300 OC regime depicted in Figure 3. In this manner,
we can be assured that the microbalance system provides
us with adequate, precise data for the quoted quantitative
speciation.
Nitrogen sorption isotherms for Quincy limestone, given
in Figure 8, are normalized to the inherent amount of

20

40

60

80

100

PERCENT DECOMPOSITION

Figure 9. Isobaric nitrogen sorption capacity of Quincy limestone

at 77 K as a function of the degree of activation.

calcium oxide present in the sample, based on sample

weight and chemical purity analysis (presented in bracketed format, (CaO), in this discussion). This methodology
avoids the pitfalls associated with the proposed practice12
of normalizing to the sample weight, which varies linearly
with the degree of activation (up to 40% of the original
weight upon total activation). At this writing, we have
opted to avoid the practice of normalizing to the actual
amount of CaO formed because the data of Figure 8 would
essentially form a single sigmoidal curve caused by the
linear isobaric relations shown in Figure 9. These interpolated data show that the sorption processes are virtually
identical for all degrees of activation and for all degrees
of coverage of the active adsorption sites. The finite
sorption capacity at saturation (denoted as the S isobar
in Figure 9) seen for P = Poin Figure 8 indicates that the
sorption is limited to the internal reaches of the particles
and that there has been virtually no fragmentation,
spallation, or related processes occurring in the activation
processes. Evidently, the carbon dioxide is expelled from
the limestone particles, and the adsorbed nitrogen is held
on the voided intraparticulate volume. Thus, the classical
interpretation of the adsorption isotherm in terms of flat,
open, free surfaces will be somewhat in error. Nevertheless,
we present the following discussion because alternatives
are not readily available, and this seem to be the accepted
practice even though the model is not strictly tenable.
Following accepted practice and tradition,8vgJ2J3the
low-pressure data of Figure 8 and 9 can be analyzed in the
rectilinearking format of the BET treatment,14as depicted
graphically in Figure 10. The extensive linear region with
respect to the pressure axis is somewhat misleading because this covers only a very limited range of adsorption
when expressed in terms of the extensive measure, r
[mg(N2),mol(N2),cm3(STP),etc.]. We are virtually forced
(12) Sing, K. S. W.; Everett, D. H.; Hall, R. A. W.; Moscou, L.; Pierotti,
R. A.; Rouquerol, J.; Siemieniewska, B. Pure Appl. Chem. 1985, 57,
m-m.
- - - - - -.
(13) Mikhail, R. Sh.;Hanifi, S.; Abo-El-Enein, S. A.; Good, R. J.; Irani,
J.; J. Colloid Interface Sci. 1980, 75, 74.
(14)Brunauer, S.; Emmett, P. H.; Teller, E. J. Am. Chem. SOC.1938,
60, 309.

Fuller and Yoos

758 Langmuir, Vol. 3, No. 5, 1987

90

80

is 990

70

60

/
3 030

0 026

30
0 018

20
0 52
10
3006

a/ /
/

O b
0

0
038

016

324

C32

040

F/ao

Figure 10. BET plots for the sorption of nitrogen on Quincy

limestone (e20/+60 mesh) after various degrees of vacuum ac-

tivation.

to report BET surface area values in order to have a

comparative measure of the adsorption reactivity of our
samples because the practice has become so widely applied
for similar systems (see Table 111). The reader is warned
to temper his image of the physical arrangement of the
sorption sites and to not anticipate the presence of this
extent of square meters for sorption and/or subsequent
reaction for scrubber cleanup of combustion gases.
In accordance with the data of Figure 9, the calculated
BET sorption capacity is seen to vary in proportion to the
degree of calcination, as shown for Quincy limestone in
Figure 11. The area units are included by tradition and
could equally well be expressed in more general stoichiometric extensive terms; that is, the BET surface area of
90.8 m2/g(CaO)corresponds to 0.0373 mol(N2)/mol(CaO).
Thus, we see that the BET monolayer values are stoichiometrically equivalent to expulsion of 26.8 COz molecules to provide a site for each of the sorbed nitrogen
molecules within the CaO/CaC03 particles at the respective reduced chemical potential (reduced pressure, ca.
O.lPo).In addition, the limited sorption capacity of 284
mg(N2)/g(CaO)is equivalent to 0.355 mol(NJ/mol(CaO),
which corresponds to 2.82 CaO units coordinated to each
bound nitrogen molecule in the said matrix. Such a high
stoichiometric ratio decreases confidence in the assumptions inherent in the BET and related models: (1) the
surface exists as a rigid array of ions somewhat in registry
with the bulk substrate, (2) there is no physical impediment within distances that will preclude multilayer formation, and (3) the substrate is energetically inert, and
virtually all of the energy change is involved in modification of the sorbate Nz.
In actuality, virtually all of the data presented here are
in direct contradictions to all of the tacit assumptions
presented above, and they point out the pitfalls of applying
simplified models to systems that are obviously more
complex. It is probably far more realistic to model the
strudture of these activated limestones in terms of models
used for gels, zeolites, clays, etc., where
For strongly curved cavity walls of molecular
dimensions and for volume filling of these

COCO,

40

60

80

IO0

PERCENTAGE DECOMPOSITION

COO

20

Figure 11. Calculated BET equivalent surface area as a function

of decomposition for Quincy and Franklin limestone after various
degrees of vacuum activation.

cavities, the significance of the term surface

area also needs consideration. Such surface
areas are widely referred to in the literature.
However, what is involved in these estimates
is not the true surface area of the cavity wall
but the area that would be covered by the
number of guest molecules which completely
fill the intracrystalline pores if these molecules
were removed and placed in a close-packed
monolayer upon an equivalent area.15
For the conditions that prevail in these systems, one must
also question the structural rigidity of the walls that
contain the bound sorbate in the inner reaches of the
activated materials.16 These materials are comprised of
thicknesses of only a few molecules, at most, and cannot
be expected to have strengths of the magnitude encountered in macroscopic systems. Such structures surely flex
to some degree as the pores (both micropores, 0-2 nm, and
mesopores, 2-100 nm) are filled/generated in the course
of the sorption process. Virtually all methods of calculating
pore size distributions assume tacitly that these pores exist
in a fixed geometric array.
Sorption Analyses for Surface Area and Porosity
of Franklin Limestone. Qualitatively, the results for
Franklin limestone are very similar to those reported for
the Quincy limestone, as noted in Figure 12. The sorption
isotherms are all of the sigmoidal character akin to those
of Figure 8 for the purer Quincy limestones, even to the
extent that there is a finite sorption capacity at saturation
in each case. The major discrepancy is that there is a
sintering phenomenon in play for the Franklin calcite in
which the sorption capacity is diminished below the linear
proportionality noted for the Quincy limestone activation.
This result is noted in the calculated BET monolayer capacity of Figure ll and, to an even greater degree, in the
saturation uptake (noted in the difference between the S
(15) Barrer, R. M. Zeolites and Clay Minerals as Sorbents and Molecular Seiues; Academic: New York, 1978; p 158.
(16) Rouquerol, F. Etude par Adsorption Gazeuse de la Texture des
Solides Diviaes (application a la glucine, a lalumine et a differents gels
et oxydes) Ph.D. Thesis, Docteur es Sciences Physiques, Universite de
Paris, 1965.

Surface Properties of Limestones

280

Langmuir, Vol. 3, No. 5, 1987 759

I;

//

Figure 14. Graphical comparison of the calcite structure (a) and

the cubic calcia (sodium chloride, cubic) structures (b) arranged
to a highlight the laminar nature of each.

20

40

60

80

100

P/P,

Figure 12. Sorption isobars for nitrogen on Franklin limestone

(-12/+30 mesh) at 77 K after various degrees of activation.
-

20

40

60

80

100

PERCENT DECOMPOSED

Figure 13. Second-order effect on nitrogen sorption deficiency

for the sintering of activated Franklin limestone.

line of Quincy samples and the S curve for Franklin samples in Figure 12). This sintering process is seen to be a
second-order effect, as presented in Figure 13, and seems
to be generally effective over the entire pressure range.
There is a general loss of capacity overall, with no obvious
closure of a specific range of pores or elimination of unique
sorption sites.

Discussion and Comparison

At this juncture, we note that the sorption capacity, Z,,
of activated limestones can be empirically expressed in the
mathematical form
2, = a

+ bf -cf

(7)

where the constants a , b, and c are finite, albeit negligible

in some cases, and relate the sorption capacity to the
fraction of the vacuum activation, f (percent vacuum activation/100).

The nonlinear effect of the sintering (defined here simply as sorption activity loss) is also detected in the spread
and nonconstancy of the activation energy for Franklin
limestone, as presented in Table 111. The combined sintering/activation process occurs with a lower activation
energy at higher degrees of calcination as compared to the
activation process alone at lower degrees of activation.
When the sintering process is absent (Quincy limestone),
the activation energy is constant for all degrees of activation.
The expression of eq 7 is somewhat general and allows
one to understand the nature of activation of limestones.
The a term is the inherent sorption capacity of the
unactivated limestone particles and is related to the particle size, particle roughness, inherent porosity of the
particles, etc. Furthermore, correlations related to sieve
screen sizes, such as those presented here, must account
for the adherence of fine particles to the larger particles
just allowed past the mesh size. The generation term, b,
is a direct extensive measure of the amount of sorption
sites opened for nitrogen by the expulsion of carbon dioxide in the activation process. This quantity relates to
the dual mechanisms that transpire in the mass transport
of the gas from the calcite matrix and the simultaneous
restructuring to the calcia structure. This work indicates
that the restructuring is not complete to the cubic calcia
structure for the vacuum activation at 400-500 "C and that
the structure remains somewhat open or, at least, remains
somewhat flexible to allow egress of sorbed nitrogen into
the inner reaches, even at cryogenic temperatures (77 K).
This process is best visualized when one recognizes the
similarities of the rhombohedral calcite structure and the
cubic calcia structure in the form presented by Bishopl8
(see Figure 13). Both structures are seen to be comprised
of laminae of calcium ions and anions. In this context, the
vacuum activation process is seen to involve only the
thermal activation of the carbonate ion to a degree that
it dissociates to release a carbon dioxide entity that can
(probably by alternating association/dissociation steps as
sequential sites) be transported and expelled through the
slit-shaped intralaminar channels. These channels do not
rigidly close behind the expelled carbon dioxide and are
either open for or are prized open by the sorbed nitrogen
in subsequent evaluation of surface area and porosity.
High-temperature calcination leads to marked sintering
where these interlaminar channels are completely and irreversibly closed by the formation of strong calcium/oxide
ionic bonds producing lime with only a few square meters
per gram.l
The c parameter of eq 7 is related to the impurity content of the limestone and is a loss term that seems to arise
because of the sintering of the internal sorption sites. The
work of Mikhial et
showed that this second-orderterm
is virtually absent for the vacuum activation of high-purity
limestone (Iceland spar) and the the enhancement factor,
b, is quite comparable to that we have found for Quincy

760

Langmuir 1987, 3. 760-768

limestone. [These investigators found an apparent surface

area of 80 f 8 m2/g(CaO) for vacuum activation at 620 C.]
The impurities in the Franklin limestone (magnesia, aluminosilicates, sulfates, iron, strontia, etc., as shown in
Table I) serve as fluxes and/or channel blockers in the
activation process. The sintering is enhanced at higher
temperatures where Heating a t 700 OC for various durations leads to higher percentage decomposition, and, as
shown by SEM, fragmentation and recrystallization that
take place to an advanced stage.13 In the case of this
report, where the vacuum activation was carried out below
ca. 600 C, there is little or no fragmentation, and virtually
all of the nitrogen sorption is due to the layer structure
of the adsorbent and to the penetration of the adsorbed
phase between the 1ayers,13as noted for c1ays,l6gels,17and
related systems.lg
The mechanism of thermal activation of limestones
depends upon several factors:
1. Temperature of the Sample. If the activation is
carried out in vacuo, one is not limited to the case where
...CaC03 does not decompose below 500 oC...,Zoand the
thermodynamically limiting behavior is obtained. When
(17)Fuller, E. L.,Jr. J. Colloid Interface Sci 1967,33,47.
(18)Bishop, A. C. An Outline of Crystal Morphology; Hutchison,
1967.
(19)Everet. D. H. In T h e Solid-Gas Interface; Flood, E. A., Ed.;
Marcel Dekker: New York, 1967.
(20) Glasson, D. R.; ONeil, P. In Characterization of Porous Solids;
Greg, S. J., Sing, K. S. W., Stoeckli, H. F., Eds.; The Society of Chemical
Industry: London, 1979;p 351-357.

the activation is carried out at higher temperatures, the

process is complex with various degrees of shattering and
sintering.
2. Pressure (Carbon Dioxide Chemical Potential)
in the Gas Phase above the Solid CaC03/Ca0 Sample
As Controlled by the Pumping System. The decomposition rate in vacuo depends on the temperature variation of the free energy change (enthalpy) of the process.
3. Purity of the Sample. Impurities tend to serve as
fluxes to enhance low-temperature sintering and to close
off access to the inner reaches of the activated oxide.
4. Amount of Reaction with Reaction Gases. Water,
carbon dioxide, sulfur dioxides, etc., all react to modify the
structure of the activation products. Studies with the
vacuum microbalance system allow one to control or, in
this instance, eliminate these reactions and to study the
activation process alone.
5. The activation process can be defined in terms of
simple, straightforward kinetic parameters. The process
is first order in the amount of oxide formed, with little or
no excess energy of activation, at least in vacuo a t temperatures ranging up to 650 C.
6. The morphology of the activation can be described
mathematically as a shrinking core generation of active
sorption sites for pure materials, increasing capacity of
virtually identical topology. Impurities tend to introduce
a second-order loss term caused by sintering or channel
blocking.
Registry No. SO,, 12624-32-7; N2-,7727-37-9.

Stability, Critical Thickness, and the Time of Rupture of

Thinning Foam and Emulsion Films
A. Sharma and E. Ruckenstein*
Department of Chemical Engineering, State University of New York at Buffalo,
Buffalo, New York 14260
Received November 3, 1986. I n Final Form: March 11, 1987
A theory is developed to predict the critical thickness of rupture and the lifetimes of the tangentially
immobile foam and emulsion films. The theory accounts for the stabilizing effects of film thinning on
the growth of the surface corrugations and leads to an explicit expression for the critical thickness as a
function of the velocity of thinning, amplitude of the surface corrugations, viscosity, surface tension, and
Hamaker constant. The predictions of the theory are in both qualitative and quantitative agreement with
the experimentally obtained critical thicknesses. The comparison of the theory with the data for critical
thickness confirms an independent experimental observation that the velocity of film thinning depends
inversely on the film radius (and not on the square of the film radius as predicted by Reynolds law of
film thinning). The stabilization due to drainage is found to be significant in determining the lifetimes
of thin films, and the importance of this effect increases as the wavelength of the perturbation increases.
The present theory in conjunction with the data for critical thickness predicts the lifetimes of foam films
that are in agreement with the experimental data. Further, the Hamaker constant that is obtained by
fitting the experimental data to the present theory is in excellent agreement with its predictions from the
Lifshitz theory.
powder coating,s paper ~ o a t i n gthin
, ~ solid films used in
I. Introduction
microelectronics,1 and the corneal tear film.11J2 In esThe intermolecular forces induce the instability of thin
films in such diverse settings as foams and emul~ions,l-~ sence, a thin film becomes unstable when the destabilizing
deformation of biological membra ne^,^,^ electrostatic
(1)Vrij, A. Discuss. Faraday SOC.1966,42,23.
(2)Scheludko, A. Adu. Colloid Interface Sci. 1967,1, 391.
(3) Ivanov, I. B.; Dimitrov, D. S. Colloid Polym. Sci. 1974,252,982.
(4)Manev, E.; Scheludko, A.; Exerowa, D. Colloid Polym. Sci. 1974,

(7) Maldarelli, C.; Jain, R. K. J. Colloid Interface Sci. 1982,90, 263.

(8) Cross, J. A. In Surface Contamination; Mittal, K . L., Ed.; Plenum:
New York, 1979;Vol. 1! p 89.
(9)Babchin, A. J.;Clish, R. L.; Warren, D. Adu. Colloid Interface Sci.

1981,14, 251.
(10)Ruckenstein, E.; Dunn, C. S. Thin Solid Films 1978,51, 43.
(11)Sharma, A,; Ruckenstein, E. Am. J . Optom. Physiol. Opt. 1985,
62,246.
(12)Sharma, A.;Ruckenstein, E. J . Colloid Interface Sci. 1986,111,
8.

0743-7463/87/2403-0760$01.50/0 0 1987 American Chemical Society