E PA-600/2-76-273a
October 1976
EXPERIMENTAL AND THEORETICAL STUDIES
OF SOLID SOLUTION FORMATION
IN LIME AND LIMESTONE S02 SCRUBBERS
VOLUME I. FINAL REPORT
by
Benjamin F. Jones. Philip S. Lowell, and Frank B. Meserole
Radian Corporation
8500 Shoal Creek Boulevard
Austin, Texas 78766
Contract 68-02-1883
Program Element No. EHE624
EPA Project Officer: Robert H. Borgwardt
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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*	£ — — N ,-,r^
w' i. ?u -
This report describes the results of the theoretical
and experimental program, that Radian conducted to characterize
the coprecipitation of calcium sulfate with calcium sulfite
hemihydrate.
The existence of a coprecipitation product hac been
hypothesized to explain the mechanism by which sulfate could be
precipitated from a scrubber solution subsaturated with respect
to calcium sulfate. Long tern, steady-state operation of lime
and limestone SO: sc'ibb'ing systems with oxidation rates below
20% has been achieved with liquors subsaturated with respect
to all known calcium sulfate solid forms. Nevertheless, sulfate
is measured in the solids precipitated from these systems.
The existence of a calcium sulfate-calcium sulfite
solid solution has been confirmed experimentally and a theoretical
formulation has been established. Calcium sulfite hemihydrate
was precipitated under controlled laboratory conditions from
solutions subsaturated in calcium sulfate. Specific chemical
analysis and infrared spectroscopic techniques xcere used to
identify sulfate in the solids.
The sulfate content in the precipitate was studied
as a function of the relative saturation of calcium sulfate
and the precipitation rate of calcium sulfite hemihydrate.
Also, the effects of high magnesium and chlorides concentrations
anc limestone anc lime dissolution on the sulfate content of
the solids were measured.
ii

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TECHNICAL REPORT DATA
fl'r.jsc rccJ l, : l\ ia: co>r.r!ctinv
EPA-60C/2 - 76-273a f
3. RECIPIENT'S ACCESSION NO.
•I. " 1 Tut AND S7 1 T L E
Experimental and Theoretical Studies of Solid Solution
Formation in Lime and Limestone S02 Scrubbers-
Volume I. Final Report
S. RETORT OATE
October 1976
6. PERFORMING ORGANIZATION CODE
? A.THCRts) Benjamin Yt Jones, Philips. Lowell, and
Frank B. Meserole
8. PfcfiFORMlNG ORGANIZATION REPORT NO.
3 PERFORM'N'G O^OANIZATiON NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Boulevard
Austin. Texas 78766
*0. PRC-GRAM ELEMENT NO.
EHE624
11. CONTRACT/GRANT NO.
68-02-1883
IT. SPONSORING AGENCY NAME. AND ADDRESS
EPA. Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; Through May 1976
14. SPONSORING AGENCY CODE
EPA/600/13^
15. supplementary notes ierl-RTP Project Officer for this report is R.H. Borgwardt,
918/549-8411 Ext 2234, Mail Drop 65.
i 16. abs"*"sact The rep0rt gjves results of a theoretical and experimental study to charac-
; terize the coprecipitation of calcium sulfate with calcium sulfite hemihydrate. A
1 coprecipitation product had been suggested to explain the mechanism by which sulfate
could be precipitated from a scrubber solution subsaturated with respect to calcium
sulfate. Lime and limestone S02 scrubbing systems with oxidation rates below 20%
had been operated long-term at steady state with liquors subsaturated with respect to
all known calcium sulfate solid forms and yet sulfate was measured in the solids.
The existence of a calcium sulfate/calcium sulfite solid solution has been confirmed
experimentally and a theoretical formulation has been established. Calcium sulfite
hemihydrate was precipitated under controlled laboratory conditions from solutions
subsaturated in calcium sulfate. Specific chemical analysis and infrared spectroscopic
techniques were used to identify sulfate in the solids. The precipitate's sulfate content
was studied as a function of the relative saturation of calcium sulfate and the precip-
! itation rate of calcium sulfite hemihydrate. Also, the effects of high magnesium con-
1 centrations and limestone dissolution on the sulfate content of the solids were
; measured.
17. KEY WORDS AND DOCUMENT ANALYSIS
2. DESCRIPTORS
b. iDENTt F 1 E RS/OPEN ENDED TERMS
c. COSATi Field/Group
Air Pollution
Calcium Oxides
Limestone
Flue Gases
Scrubbers
Sulfur Dioxide
Air Pollution Control
Stationary Sources
13B
07B
08G
2 IB
07A
:3. TrMDJ*iCi- STATEMENT
19 SECURITY CLASS i fhn Reportj
Unclassified

Unlimited
20 SECURITY CLASS (This pafic)
Unclassified
22. PRICE
fioi
EPA Fern 2220-1 (9-73)

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ACKNOWLEDGEMENTS
The authors wish to thank Robert II. Borgwardt, EPA's
Project Officer on this contract, for his assistance and
cooperation in the completion of this project. We are indebted
to Larry A. Rohlack for technical assistance in designing and
operating the experimental apparatus and to Donny L. Heinrich
for performing the analytical work.
DISCLAIMER
This report has been reviewed by the Industrial
Environmental Research Laboratory, U. S. Environmental
Protection Agency, and approved for publication. Approval does
not signify that the contents necessarily reflect the views
and policies of the TJ. S. Environmental Protection Agency, nor
does mention of trade names or commercial products constitute
endorsement or recommendation for use.

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TABLE OF CONTENTS
Page
A3STRACT	 i
ACKNOWLEDGEMENTS	 ii
1.0	SUMMARY AND CONCLUSIONS	 1
1.1	Verification of the Existence of
the Calcium Sulfite-Sulfate Solid
Solution	 2
1.2	Quantitative Measurement of the
Sulfate Content of the Calcium
Sulfite-Sulfate Solid Solution	 3
1.3	Development of Sampling Methods
for Slurries Containing High-Liquid
Phase Magnesium Concentrations	 4
1.4	Effect of Relative Saturation of
Calcium Sulfate Hemihydrate	 4
1.5	Effect of the Calcium Sulfite
'Precipitation Rate	 5
1.6	Effect of Magnesium ana Carbonate
Liquid-Phase Concentration on the	!
Precipitation Rate of Calcium
Sulfite Hemihydrate	 6
1.7	Coprecipitation of Calcium Carbonate
with the Calcium Sulfite-Sulfate
Solid Solution	 6
2.0	BACKGROUND AND APPROACH	 7	j
3.0	THEORETICAL FRAMEWORK OF THE CALCIUM
SULFITE-SULFATE SOLID SOLUTION	 9
4.0	EXPERIMENTAL APPROACH	 14
4.1	Description of Equipment	 15	¦
4.2	Sampling Techniques Utilized 1
in Kinetic Experiments	 23
iv
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TABLE OF CONTENTS (Cont'd)
Page
4.3	Analytical Techniques		25
4.4	Experimental Calculations		27
5.0	RESULTS		29
5.1 Physical Characterization of the
Calcium Sulfite-Sulfate Solid Solution		41
6.0	DISCUSSION OF RESULTS		51
6.1	Effect of Relative Saturation of
CaSO, -%H£0		58
6.2	Effect of Calcium Sulfite Precipitation
Rate		62
6.3	Comparison of Lime and Limestone Tests
With Clear Liquor Results		64
6.4	Effects of High Levels of Chloride
and Magnesium		64
6.5	Effect of Temperature		65
7.0	REVIEW OF PLANT AND PILOT PLANT DATA		68
8.0	RECOMMENDATIONS		73
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LIST OF TABLES
Pago
TABLE 5-1	LIQUID AND SOLID COMPOSITION DATA
OF EXPERIMENTAL RUNS	 30
TABLE 5-2 SUMMARY 0? MOLAR COMPOSITION OF
LIQUID AND SOLID PHASES OF ALL
EXPERIMENTAL RUNS	 33
TABLE 5-3	SUMMARY OF CALCULATED DATA FOR ALL
EXPERIMENTAL RUNS	 36
TABLE 5-4	LIQUID AND SOLID COMPOSITION DATA
DATA FOR EQUILIBRIUM RUNS	 39
TABLE 5-5	SUMMARY OF RESULTS OF EQUILIBRIUM
RUNS Q-1 THROUGH Q-18	 40
TABLE 6-1	EXPERIMENTAL RESULTS INVALIDATED	 53
TABLE 6-2	EXPERIMENTAL RESULTS FOR CORRELATIONS	 55
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LIST OF FIGURES
Page
Figure 4-1 Schematic Representation of Data
Analysis	 16
Figure 4-2	Equilibrium Extraction Apparatus	 18
Figure 4-3 The Sampling Train Utilized in Equilib-
rium Studies	 20
Figure 4-4 Precipitation Apparatus for Kinetic
Studies	 21
Figure 4-5 Plexiglas Reactor Used in the Kinetic
Studies	 22
Figure 5-1 Infrared Spectra of Pure Calcium Sulfite
Kemihydrate and Calcium Sulfate
Dihydrate	 43
Figure 5-2	Infrared Spectra of Reactor Products.... 44
Figure 5-3 Results of Infrared Quantitative Correla-
tion of Sulfate Mole Fraction with the
Ratio of the Absorbance of the Sulfate
Band (1220 cm *) with the H20 Band
(1620 cm"1)	 47
Figure 5-4 Differential Scanning Calorimetry Pattern
of Precipitated Solids of Kinetic Run 37. 49
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LIST OF FIGURES (Cont'd.)
Page
Figure 6-1 Sulfate Content of Solid Solution as
a Function of CaSCK'^l^O Relative
Saturation in Solution, Clear Liquor
Studies	 59
Figure 6-2 Comparison of Lime and Limestone Experi-
ments with the Clear Liquor Runs	 61
Figure 6-3 Sulfate Content of Solids as a Function
of CaS03'%H20 Precipitation Rate	 63
Figure 6-4 Effect of High Chloride and Magnesium
Concentrations of Sulfate Content of
Solid Solution	 66
Figure 6-5 The Effect of Temperature on Sulfate
Concentration in the Solids	 67
Figure 7-1 Concentration of Sulfate in the Solids
as a Function of the CaS0i*-%H20 Relative
Saturation in the Aqueous Phase	 70
Figure 7-2 Example of Relationship between Sulfate
Mole Fraction and Gypsum Relative Saturation
for Shawnee TCA-Limestone Runs 	 72
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1.0
summary and conclusions
An experimental and theoretical study of tne calcium
sulfite-sulfate solid solution formation has been conducted for
the Environmental Protection Agency (EPA) by Radian Corporation.
Radian has confirmed the hypothesis of R. K. Borgwardt and others
that the sulfate is removed from solution during subsaturated
(CaSO• 2K?0) operation in pilot plant tests by the formation of
a "solid solution" of calcium sulfite and calcium sulfate. The
sulfite oxidation rate has been identiried by Radian as tne
critical control parameter for operation of the S02 scrubber
subsaturated with respect to gypsum.
This report does not contain a complete explanation
of all of the experimental and field data that have been
accumulated relating to the coprecipitatior. of sulfate with
calcium sulfite hemihyarate. Nor is a theoretical expression
offered that accounts for all of the experimental results ob-
tained from this program. The problem may be a result of
several factors including:
•	difficulties associated with control
of all experimental variables and
•	incomplete understanding of all the
factors involved in the phenomenon of
coprecipitation.
The experimental data of this program are presented
in this report along with a critical assessment of the validity
of the data. On the positive side , this study has shown that
the strongest correlating factor relating tc the sulfate content
of the coprecipitate is the relative saturation of calcium
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sulfate hernihydrate in the aqueous phase. This and the
demonstrated absence of a ir.ajor kinetic effect indicate that
the coprecipitation of sulfate with calcium sulfite hernihydrate
is basically an equilibrium controlled process.
This work has successfully shown the existence of a
solid solution of sulfate with calcium sulfite hernihydrate by
direct verification using infrared spectroscopy. A relationship
has also been formulated to predict the sulfate content of the
solids during subsaturated (gypsum) operation based on the solution
composition.
A summary of the results of this program follows.
1.1	Verification of the Existence of the Calcium
Sulfite-Sulfate Solid Solution
Chemical analyses of solids precipitated from solutions
prepared under controlled laboratory conditions to be super-
saturated in CaS0 3*%H20 and subsaturated in CaS0i,'2H20 have
verified the presence of sulfate. Infrared spectral analysis
was also used to confirm the presence of sulfate in the solids.
X-ray diffraction patterns of the sulfate-containing
solids were essentially indistinguishable from the patterns of
pure CaSCh-^HiO. No separate crystalline phase containing
sulfate could be identified by this method.
The infrared spectra not only were used to substantiate
the presence of sulfate in the solids, but also provided direct
evidence of the existence of a coprecipitation product. The ab-
sorption patterns in the 1100-1200 cm": region assigned to the
sulfate ion are quite different for sulfate as a pure gypsum
phase from sulfate in solid solution.
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To determine whether the coprecipitate is in
thermodynamic equilibrium with the solution from which it is
grovm cr is a result of kinetic effects, some long-term
equilibration tests were conducted. Solids were allowed to
cone to equilibrium with solutions containing calcium, sulfate
and magnesium concentrations identical to their concentrations
in the solutions from which the solids were precipitated. After
as long as four weeks, the liquid phase was found to be saturated
with calcium sulfite henihvdrate and still subsaturated in
calcium sulfate cihydrate. The sulfate content of the solids
did not change substantially during these tests.
1.2	Quantitative Measurement of the Sulfate Content of
the Calcium Sulfite-Sulfate Solid Solution
An analytical technique was developed during this
program fcr the specific determination of sulfate in solids
typically precipitated in lime and limestone-based SO? scrubbers.
Previously, the sulfate concentration measurements were obtained
by a difference technique. A portion of the sample was analyzed
for total sulfite. A second portion treated to oxidize all of
the sulfite to sulfate was then analyzed for sulfate. The
difference in these two values gives the original sulfate value.
When the sulfate level is low compared to the sulfite concentra-
tion, the error of this technique becomes quite large.
The specific sulfate technique selected for this
program can be used to determine sulfate concentrations in the
range of interest to within ±5% of the actual value, e.g. 10+.5"c.
Infrared analysis was also used to quantitatively
measure the sulfate concentrations in the solid solution samples.
The infrared spectral technique was calibrated by initially
ratioing the solid solution sulfate absorptivity at 1220 cm 1
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to the absorptivity of the water of hydration band at 1620 cm 1.
A correlation was then established relating this ratio to the
sulfate content as determined chemically. Though not as sensi-
tive as the specific sulfate technique, the infrared technique
is much faster and can also be used to distinguish the forms of
sulfate present.
1.3	Development of Sampling Methods for Slurries
Containing High-Liquid Phase Magnesium
Concentrations
One of the difficult problems in characterizing the
solics precipitated from solutions containing high magnesium
concentrations is the contamination of the solids by the high
concentration of dissolved magnesium sulfate. This contamina-
tion results from the adhesion of the liquid phase to the
filtered solids with subsequent crystallization of the magne-
sium sulfate during drying. Sampling and sample handling tech-
niques have been developed which minimize this interference.
1.4	Effect of Relative Saturation of Calcium Sulfate
- Hemihvdrate
The calcium sulfate hemihydrate (CaSOi* •%H20) relative
saturation has been determined to be the most significant
correlating variable associated with the formation of the
calcium sulfite-sulfate solid solution in the laboratory studies
conducted by Radian. These studies have shown that the sulfate
content of the solids, i.e., the sulfate mole fraction of the
precipitated solids, varies most rapidly from 0 to 0.12 as the
calcium sulfate hemihydrate relative saturation ranges from
0 to 0.20. The sulfate mole fraction in the solid solution
rises to 0.16 at a hemihydrate relative saturation of 0.45, the
point at which the solution is also saturated with respect to
gypsum.
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These results are consistent with the theory developed
in e-r.rlv phases of Che experimental program which states that the
equilibrium contribution to the sulfate content of the solid
solution will be a function of the calcium sulfate hemihydrate
relative saturation. The relationship that predicts the sulfate
nole fraction from the relative saturation is given in Equation
1-1.
(1-1)
RSCaSO, ¦	= xCaSO.. • vH.O ' exP (¦ SxCaSO. • %H ? C —
where,
RSCaS0i, • -'H-0 = ttie re^£tive saturation of calcium
sulfate hemihycrate in the liquid
phase, and
x o	r. = z^e Kcle fraction of sulfate in the
UaoU w • -in : «-
solid phase.
1.5	Effect of the Calcium Sulfite PreciDitation P.ate
Experimental results have shown the calcium sulfite
precipitation rate does not have a measurable effect on the amount
of sulfate coprecipitated with calcium sulfite as a solid solution
This was true for precipitation from solutions both high and low m
magnesium concentration-. In other words, kinetic effects co
not appear to be significant in the composition of solid solution
witnin the precipitation range studied, namely 0.001-1.7 milli-
moles/g-min. These results in conjunction with the calcium
sulfate relative saturation data imply that for all practical
purposes the composition of the calcium sulfite-sulfate solid
solution is determined by an equilibrium condition and not
simrlv bv inclusion.
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1.6	Effect of Magnesium and Carbonate Liauid-Phase
Concentration on the Precipitation Rate of Calcium
Sulfite Hemihydrate
Preliminary data from several kinetic experiments show
that liquid-phase magnesium and carbonate ions may inhibit the
precipitation rate of calcium sulfite hemihydrate. Nucleation
in a calcium chloride-sodium sulfite system normally occurs at
a calcium sulfite hemihydrate relative saturation of approxi-
mately 3.0. With the addition of magnesium, calcium sulfite
hemihydrate relative saturations of 8-15 have been observed at
precipitation rates significantly lower than those observed in
the pure system indicating a decrease in the nucleation rate.
The addition of the carbonate ion to a calcium sulfite-sulfate
system required a CaS0 3-%H20 relative saturation of 5.3 to ob-
tain the same precipitation rate measured at a relative satura-
tion of 2.3 in a carbonate-free solution.
The implication of these observations may have a
significant impact on SO2 scrubber system design and warrant
additional experimental studies.
1.7	Coprecipitation of Calcium Carbonate with the Calcium
Sulfite-Sulfate Solid Solution
Qualitative results from infrared spectral analyses
of solids precipitated from liquors containing carbonate indi-
cate that carbonate is coprecipitated with the calcium sulfite-
sulfate solid solution. This is particularly evident in the
I.R. spectra of scrubber solids from Pennsylvania Power &
Light's Sunbury pilot unit where evidence of matrix isolated
carbonate was observed. This coprecipitation of carbonate im-
pacts on the maximum limestone utilization which can be achieved
and may have an effect on the sulfite to sulfate ratio that can
be coprecipitated. Based on these results, additional study of
the coprecipitation of carbonate with the calcium sulfite-
sulfate solid solution is recommended.
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BACKGROUND A;hD APPROACH
Pilot plant studies conducted by EPA. at Research
Triangle Park and full-scale operation at various plants in the
U.S., Japan and England have demonstrated that both lime and
limestone S02 scrubbers can operate unsaturated with respect to
gypsum even under tight "closed-loop" operation. This fact
offers an opportunity, if the phenomenon responsible can be
understood and controlled, to effectively reduce gypsum-scaling
potential which has persisted as cr.e of the principal reliability
problems of lime and limestone flue gas desulfurization systems.
The formation of a "solid solution" of calcium sulfite
and calcium sulfate has been suggested by R. H. Borgwardt and
others as the probable mechanism responsible for the sulfate
purge which leads to unsaturated operation. Several variables
such as sulfate concentration, sulfite precipitation rate anc
concentration of chloride and magnesium have been identified from
field studies as influencing the composition of the solid solu-
tion.
Radian has conducted a theoretical and experimental
study to characterize the chemical factors which affect the
formation of the solid solution. The objectives of this study
were tc:
q develop a consistent theoretical basis
for examining field and laboratory data,
• review available field data relative to
unsaturated operation.
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•	develop, if necessary, sampling, sample
handling, and analytical methods which
are consistent with accurate measurement
of sulfite and sulfate in both liquid
and solid phases,
•	study the application cf physical and
analytical techniques which can be
usee to establish direct evidence of
the ccprecipitatior. of sulfate with
calcium sulfite hemihydrate,
o conduct equilibrium studies to establish
whether or not a solid solution will
precipitate from various solutions
near equilibrium,
•	conduct kinetic studies using a lime or
limestone slurry and a clear liquor
characteristic of either lime or lime-
stone scrubbers to determine the effects
of the sulfite precipitation rate,
temperature and scrubber liquor compo-
sition with emphasis on magnesium and
chloride, and
•	develop a theoretical framework for
liquid/solid equilibrium or kinetics
in such a manner that it can be used
for predicting conditions necessary
for unsaturated operation of lime and
limestone scrubbers as a function of
liquor composition and oxidation.
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3.0	THEORETICAL FRAMEWORK Or THE CALCIUM SULFITE-SULFATE
SOLID SOLUTION
Coprecipitation nay be controlled by equilibrium
effects, kinetic effects, or a combination of the two. If a
true solid solution is formed as a result of the coprecipita-
tion of calcium sulfite and calcium sulfate, then fundamental
thermodynamics can be used to describe the equilibrium rela-
tionships which control solid and liquid phase compositions.
On the other hand, if sulfate tends to be incorporated into
the solid phase by inclusion, then the kinetics of sulfite
precipitation should be an important factor. In this latter
case., the sulfate/sulfite ratio in the coprecipitated solids
would be expected to be a direct function of the growth rate
of calcium sulfite solids.
It is important to distinguish between these two
possibilities for the following reasons. If the formation of
a solid solution is the dominant mechanism of coprecipitation,
the system sulfite oxidation rate will determine whether sub-
saturated operation is possible. On the other hand, if kinetic
effects are significant, then system design (in addition to
oxidation control) can be used to optimize coprecipitation
and avoid sulfate scaling.
The existence of a solid solution in equilibrium with
a liquid phase can be described thermodynamically through
t"
chemical potentials. The chemical potential, y.., of the i^-
component in the	phase may be written as.-
¦j. . = u? . + RTIna. .	(3-1)
ij	ij
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aw iv
= the standard state chemical potential,
R = iceal gas constant,
T = the absolute temperature, and
a. . = the activity of the i— component in the
th
j— uhase.
In this analysis, the following designations will
i = 1 «> CaS'C3-^HL0
i = 2 -> CaSCu • -VH?0
j = s =-> Solid
j = I -¦> Liquid
The standard state of the solid phase will be defined as the
pure component. For a solid solution mixture, deviations frox
ideal solutions will be based on mole fractions. Solid phase
activity coefficients,	are defined by Equation 3-2.
ais " °ix:	(3-2a)
a2S = c2x2	(3-2b)
where the x's are the solid phase mole fractions.
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The choice of the hemihydrate of calcium sulfate
as the forn of the solid phase was selected since the calcium
sulfite host matrix is a hemihydrate. This situation can be
imagined by simply replacing a sulfite ion with a sulfate ion.
However, the mathematical formulation could be developed for
the aihydrate of calcium sulfate equally as well. Direct
measurement of the solids subsequently gave a mole ratio of
total S to water of 2:1 which is consistent with the hemihydrate
model.
The activities of CaSOr-'^KiO and CaSCK*%H:>0 in the
liquid phase are defined in Equation 3-3:
2
V " £Ca++ aS0= aH2 0	(3"ja
" aCa-H- aS0= aH 0	(3" 3b)
U	2
The liquid phase is in equilibrium with the solid
phase when the chemical potentials of all components in both
phases are equal. Equating chemical potentials gives
Equation 3-4.
y. - v-o	(3'A)
IS	xl
Substituting the definitions in Equations 3-1 and
3-2 into 3-4 gives Equation 3-5.
^? + RT £n c.x. = w_° o + RT In a.,	(3-5)
is	l 1	1
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Equation 3-5 may be solved for the activities:
ai I
cixi
e
-(u;,-[j/rt
K. IS
(3-6a)
= K-	(3-6b)
The equilibrium cons cant, K^, is the solubility
product constant. This nay be seen by considering the limiting
cases of the pure components and by noting that;
lirn o. = 1.
X-i =1
(3-7)
The relationship between the solid and liquid at
equilibrium for both species is written out in explicit form
in Equation 3-8.
aCa++ aS0= aH,0 K;Cl XCaS03-%K20	(3 8a)
aCa"H" aSOr aH20 K:°2 xCaSO„-3£H;0	(3-8b)
Dividing both sides of Equation 3-8b by the solubilit
product constant, K?, gives Equation 3-9, the left-hand side of
Equation 3-9 is, by definition, the relative saturation of
CaSCU-%H; in the liquid phase.
S' CaSO.^-H.O	32 xCaS0,.%K20	(3"9)

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The mathematical form of the solid phase activity
coefficient can be estimated from the empirical correlation of
the liquid phase calcium sulfate relative saturation with the
sulfate mole fraction in the corresponding solids. The relation
given ir. Equation (3-10) gives the desired functional form to
Equation (3-9),
-V.cn. .«.0 = M + 012 XCaS0.,-%H:0 (3-10)
where the constants n: and ^2 are calculated from the experimental
data.
Substituting this relationship for the activity
coefficient into Equation (3-9) gives:
R-S CaSO.-hY-tO xQ:SO.-%H20'eX?(Cl1 + &2xCaS0. • J2H2(P
The mole fraction of sulfate in the solids can be
calculated from Equation (3-12) given the relative saturation of
calcium sulfate hemihydrate in the aqueous phase from which the
s d»ids are precipitated.
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4.0
EXPERIMENTAL APPROACH
An experimental program was established to characterize
the nature of the mechanism leading to coprecipitation of sulfate
with CaS03-%H20. Controlled experimental conditions were used to
first verify the existence of a coprecipitation product and then
to measure the effects of solution composition. The precipitation
rate and some measure of the sulfate concentration were the primary
variables t.o be studied.
The experimental apparatus and sampling and analytical
techniques used during this program are described in this section.
Additional details are presented in Appendix C.
The experimental studies were divided into the following
areas:
0 selection and development of sampling anc
analytical methods which are consistent
with the accurate measurement of sulfite
and sulfate in both the liquid and solid
phases,
•	a series of experiments at lew sulfite
precipitation rates to establish whether
or not a solid solution will precipitate
from solutions near equilibrium,
•	a series of experiments at higher precipita-
tion rates to determine if kinetic effects
are significant,
m investigation of the effects of:
dissolved magnesium
temperature
ionic strength (NaCl),
dissolving limestone and lime
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# investigation of the applicability of	f
selectee physical techniques in the identi-	•
fication, characterization and measurement
of the solid solution.
Results of this program are compared to results
obtained in field studies to obtain a consistent theoretical
framework for predicting conditions necessary for unsaturated	r
operation (gypsum) of lime and limestone scrubbers. A schematic
flew of the correlation of all available data is shown in Figure
4-1.
A . 1	Description of Equipment
r
Experimental equipment utilized during this program
consisted of two equilibrium apparatuses, a kinetics reactor
and appropriate sampling trains for each.
Earlv Phase Equilibrium Apparatus
i
The first equilibrium apparatus constructed was designed	1
to establish whether a solid solution would precipitate from
various solutions near equilibrium and to establish a quantitative
relationship between the equilibrium liquid and the solid phase
compositions.
t
This equilibrium apparatus consisted of a closed-loop	1
system in which water could be removed from a solution containing
calcium sulfite and calcium sulfate by means of evaporation. The
evaporated water was condensed and passed through a calcium sulfite
saturator and then the solution was sent back to the precipitation
vessel. Evaporation was regulated by solution temperature and
system vacuum control.
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LITCRATURE
PHYSICAL
review
MEASUREMENT
CHARACTERIZATION
or
SOLID
SOLUTION
FORMATION
1	
THEORETICAL'
FRAMEWORK
data
FIELD
ANALYTICAL
STUDIES
KINETIC
EQUILIBRIUM
STUDIES
PROCEDURES
PROCESS
DESIGN
CORRELATION.
DATA
FIGURE 4-1.
SCHEMATIC REPRESENTATION OF DATA ANALYSIS

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This experimental approach in the equilibrium studies
was terminated in the early phases of the test program due to
the impracticality of long experimental run tines (one to four weeks).
Oxidation and other operational problems also prevented the
practical application of this equilibriurn approach over the re-
quired run tir.es .
Ecuilibration Apparatus
This equipment, Figure 4-2, was designed to obtain
equilibrium data from solids grown during the kinetics phase oi
this project:. The solids were equilibrated with a liquor similar
to that i: which it was grown, thus allowing the relative influence
cf the equilibrium and kinetic effects on the sulfate content of
the solids to be separated and quantified.
An experimental apparatus was designed and constructed
to accommodate six experimental runs simultaneously at a con-
trolled temperature in an inert atmosphere. A large plexiglas
box was fabricated and served as the enclosure. Heat lamps
connected to a temperature controller and thermistor system
maintained the enclosure at a controlled temperature while two
fans circulated nitrogen to minimize temperature gradients within
the box. Thermometers suspended from the top of the box at
several locations were used to monitor the temperature. Nitrogen
entered the enclosure on the back side of the fans providing a
constant oxygen purge cf the enclosure.
Plexiglass cylinders with an internal volume of 570 ml
were charged with appropriate solids and liquors. These solu-
tions then were thoroughly mixed on a tumbling device designed
especially for horizontal rotation of the cylinders at a constant
-17-

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i h n n m i s t o n
rilEflMOMIITCn
- T H L n M O M [• T I- n
TEMP t: H A T U 11 b
	I'
cnNTnoLirn
I	
HF AT
J A M P
pU n gc
CIRCULATING
TANG
PLE X I - GL A S
BOX
670 ML
P t. F X I - G I AS
I VCSSCI.S
0 O1 r LE
FIGURE 4-2. EQUILIBRIUM EXTRACTION APPARATUS

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speec for long periods of time. Ceramic cylinders were used within
the containers to produce grinding to expose new surfaces of the
crystals for dissolution and precipitation. Additional details
of this experimental technique are contained in Appendix C.
A sampling procedure was designed to ensure consistent
and accurate, nieasurenents of sulfite and sulfate in both the
liquid and solid phases. A pictorial representation of the
sampling train utilized in these equilibrium studies is shown
in rigurc 4-3. Temperature and pH measurements of the equili-
brated solutions were taken just prior to sample collection.
Rapid liquid phase sampling to provide an aqueous sulfite sample
and a diluted filtrate sample was accomplished by usir.g a peri-
staltic pump anc a 47 mm filter. All sampling lines were kept
as short as possible and a constant purge of nitrogen was
directed at the sample port in the vessel at all tines during
sampling to minimize any liquid contact with air. After
collection of the two liquid samples, the equilibrated solids
were obtained by filtration of the slurry. The filtration was
done ir. a nitrogen atmosphere.
Kinetic Apparatus
The kinetic apparatus, shown in Figures 4-4 and
4-5, served as a precipitation device to quantify the influence
of solution composition on the formation of the coprecipitate.
with this flow-through system, experimental conditions such as
temperature, calcium sulfite precipitation rate and relative
saturation of calcium sulfate can all be varied independently
to simulate the reactor compositions necessary for this study.
-19-

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N? I'UHGb
10
0
1
COMBINATION B
Fl. FCTPODE I
riLTrn
[© ©_ ~~U (O) {o
I-T
METER
5 7 0 ML
PLL.X1-GLAS
VESSEL
-------
p ®
PARASTALTIC
PUMP AND CONTROLLER
ROTOMETER
PA^ASTALTIS PJV>

CONTROLLED
TEMPERATURE
BATH
f.^lNOFR D^IV^
PA3A3IAI Ti:
SAMPLE
CO
UH MONITOR
PARASTALTIC pump
AND CONTROLLER
FIGURE 4-4. PRECIPITATION APPARATUS FOR KINETIC STUDIES
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I
STIRRER
SUPPORT
STIRRER
T HERMOMETER
•-STIRRER
S HAFT
PROPELLOR
baffle
baffle
PROPELLOR
PLEXI'GLAS
REACTOR
FILTER
FIGURE PLEXIGLAS REACTOR USED IN THE KINETIC STUDIES
-22-
K
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The primary components of Che kinetics apparatus are:
•	a continuous liquid/slurry feed system,
•	a reactor,
•	a grinder,
•	a continuous mixed product removal system
and
•	a pH monitor.
The continuous liquid/slurry feed system provided two well-defined
feed streams to the reactor where precipitation occurred. A
continuous mixed product removal system and grinder were incor-
porated into the kinetics apparatus in order to maintain a constant
slurry density and particle size in the reactor. The pH of
the reactor effluent was monitored in a flow-through cell immediately
downstream of the filter.
Each component of the kinetics apparatus was periodically
checked to ensure that consistent and accurate measurements of
the individual test parameters were being maintained. Additional
details of the kinetics apparatus are given in Appendix C.
4.2	Sampling Techniques Utilized in Kinetic Experiments
The sampling train and procedures were designed to
obtain consistent and accurate measurements of the composi-
tions of both the liquid and solid phases. All sampling
lines and fittings were nalgon and teflon to minimize chemical
changes in the samples. For the most part sampling provisions
were incorporated in the experimental apparatus flow system
(see Figure 4-4).
-23-
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I
Feed scream samples were obtained by diverting the
feed liquors through three-way stopcocks located in front of
the reactor into prepared sample bottles. The reactor effluent
liquor passed through the pH monitor and was collected for
analysis. Precipitated solids were recovered from the reactor
by filtering a portion of the slurry removal stream.
Sufficient samples were taken during each run to
characterize the streams entering and leaving the reactor.
Diluted filtrate samples were taken from the two feed streams
and the reactor effluent after the line-out period of approxi-
mately three solids residence times. Aqueous sulfite samples
were taken in a similar fashion and were used with the pH
measurements to monitor the approach to steady state. Periodic
slurry samples were taken and filtered to obtain the weight
percent solids in the reactor. After the system had been operated
for three solids residence times, the reactor solids were
collected, washed and dried.
!
A sampling procedure was developed to minimize	i
contamination during sampling of the solids from high magnesium
sulfate liquid phase concentrations. Basically this technique
consists of a rapid separation of the precipitated solids
from the liquid phase. This separation was achieved with a
pressurized filtering system using polycarbonate filter membranes.
The solids are then twice slurried in a saturated calcium	^
sulfite solution and filtered. Next the solids are rinsed
with acetone and allowed to dry in an inert atmosphere.
Detailed descriptions of this and other sampling techniques are
included in Appendix C.
F
i
-24-
I
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-r. 3	Analytical Technique
The analytical methods used during this program are
breifly discussed in this section. A more detailed description
of each procedure is included ir. Appendix D.
For the most part the analytical techniques used were
those previously selected and modified by Radian for S02 scrubber
slurry analyses. A more sensitive sulfate procedure for solids
analysis was developed especially for this program.
Chemical Analysis of Liquid Phase Samples
Calcium, sodium and magnesium analyses on the filtered
feed and reactor effluent streams were performed by atomic ab-
sorption spectroscopy. Liquid phase sulfite measurements were
made using an iodometric back titration with sodium arsenite.
The end point of the titration was determined amperimetrically.
Aqueous sulfate concentrations were measured by
substracting the sulfite concentration from a total sulfate plus
sulfite measurement. The latter value was obtained by first
oxidizing the sulfite to sulfate and then measuring the resultant
total sulfate. The sulfate analytical procedure consists of an
initial cation exchange process followed by an evaporation step
at 75°C. The resulting sulfuric acid is then titrated with a
standard NaOH solution to determine the quantity present.
The chloride analyses of the aqueous samples were made
using a pcter.tiometric titration technique using a standardized
silver r.i:ra:s solution as the titranc. Carbonate analyses
were made by first acidifying the solution. A nitrogen sweep
gas was then passed through the acidified solution. The C02
content of the sweep gas was measured with a noncisoersive
infrared analyzer.
-25-
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Analytical Techniques for Solids Characterization
Both chemical and instrumental techniques were used
to determine the chemical composition of the solids precipitated
in the laboratory studies. These techniques were also applied
to some solids field samples from lime- and limestone-based SC2
scrubbing units. Specific chemical analyses of the solids were
made to determine the calcium, sulfate and sulfite concentration
Magnesium, chloride and carbonate analyses of the solids were
run periodically. Additional characterization of the solids
was accomplished using such instrumental techniques as infrared
spectroscopy, differential scanning colorimetry, X-ray diffraction
and thermogravimetry.
The specific sulfate, sulfite and carbonate analyses
were carried out directly on a portion of the sample. The
remaining chemical species were determined subsequent to the
dissolution of a portion of the sample. The solids were dissolved
in an acidic peroxide solution. Aliquots of this solution were
then analyzed for calcium, magnesium, sodium, chloride and total
sulfur using the same procedures described for the liquid phase
analyses.
A specific sulfate analytical procedure was developed
during this program to accurately measure the sulfate concentra-
tions in the precipitated solids. A weighed quantity of solid
samples was dissolved in an oxygen-free acidic solution.
COi was bubbled through the solution to remove the sulfite as
SOz. Once the dissolution was complete the solution was removed
and the sulfate level was determined by the ion-exchange, titri-
metric sulfate method. This technique provided improved accuracy
ir. the sulfate determinations over the concentration range en-
countered in ccprecipitate solids.
-26-
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The presence of large excesses of calcium carbonate
with the coprecipitate solids tends to cause some error in this
sulfate determination. This situation developed during some
of the limestone slurry tests where low utilization was encountered
Additional characterization of the solids was done
using infrared spectroscopy (IR), differential scanning colorimetry
(DSC), X-ray diffraction, and thermogravimetric analysis (TGA).
Infrared spectroscopy was used to qualitatively and quantitatively
measure the sulfate in the solid solution samples. The presence
of gypsum ir. the solids was identified by IR, DSC or X-ray
diffraction.
X-ray diffraction was used to measure the crystalline
phases present in the precipitated solids. However, the
diffraction Datterns for the solid solution samples were indis-
tinguishable from that of Dure calcium sulfite hemihydrate.
The dehydration temperatures as well as the quantities
of water lost from the solids were determined using DSC and TGA
methods.
4.4	Experimental Calculations
This section contains a brief description of the
calculations utilized in the data analysis of the experimental
runs. Liquid phase calculations included computation of the
activities of each of the ions and relative saturations of
calcium sulfite hemihydrate and calcium sulfate hemihydrate
and dihydrate by Radian's aqueous ionic equilibrium program.
The calcium sulfite precipitation rate was calculated from
inlet and effluent aqueous sulfite concentrations and flow rates.
-27-
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Solid phase calculations included the determination
of the sulfate and sulfite mole fractions of the precipitated
product based on the chemical analysis of the solids. The sulfite
precipitation rate was also calculated from the measured
slurry removal rate, weight percent solids and the solids analysis.
The sulfate precipitation rate was based on- the sulfite preci-
pitation rate and the sulfate to sulfite ratio in the solid.
These rates were normalized by dividing by the mass of the
seed crystals in the reactor.
Solid and liquid mass balances across the reactor
were calculated to evaluate the reliability of the data collected
for each experimental run. Total solid and liquor inlet molar
rates were calculated and compared to total outlet solid and liquid
molar rates. Agreement within expected experimental error of
the total inlet and outlet mass rates supported the accuracy of
the measured flowrates and chemical analyses. The calcium,
sulfite, and sulfate precipitation rates based on liquid analyses
were compared for consistency with the corresponding precipita-
tion rates based on solids analyses. Detailed equations used in
calculations are presented in Appendix C.
-28-
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5.0	RESULTS
This section presents the results of the experimental
studies designed to characterize the formation of the calcium
sulfite/sulfate coprecipitation phenomenon. Results of the
physical techniques used to identify, characterize and measure
the solid solution are also presented. The qualitative and
quantitative effects of the following variables on the solid
solution composition were evaluated:
•	relative saturation of calcium sulfate
hemihydrate,
•	calcium sulfite precipitation rate,
•	lime and limestone slurries,
•	magnesium concentration,
•	temperature, and
•	ionic strength or sodium chloride
concentration.
The experimental results of these parameter studies were inter-
preted within the framework of the theoretical relations describ
previously. Namely, the activity product of the aqueous phase
calcium sulfate was correlated to the sulfate content of the
precipitated solids. The precipitation rate had no measurable
effect on the amount of sulfate incorporated into the solids.
A summary of the analytical results as well as the
calculated values for the experiments conducted during this
program are presented in Tables 5-1, 5-2, 5-3, 5-4 and 5-5.
-29-
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TABLE

LIQUID
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TABLE
Run
f>nl r	Number
7/(11/7'. F S
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k in
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lo/ni/7r» k- I'.
10/70/7'.	K-1r»
10/77/7S	K If.
10/7 1/7'.	K- 17
10/77//',	K-in
IO/7R//'»	K-»9
10/70/7"»	K • 70
1 1 /0«/7%	K 71
1 I/II'.//'.	K 77
11/u'/7'¦	r-jj
(cont ilined)
SUMMRY C
Temp.
	Eli		CO
ft. 77	'.f,
7.71
7.RR	/,o
R.'.O	/, \
R. 111	/,'»
R.'i/	'.9
n.7()	'i
R.70	Ml
nil	'»9
R.or,	/i9
i. m	f,9
R.(19	A 9
R.I?	il'
7.10	A9
n.'.n	/.9
n.R	/.r.
8 . IH	'-7
R.OR	AR
n.OR	4R
R.no	vi
7.90	6')
R.10	/»n
R.S7	Sfl
R.R7	S?
MOLAR COMPOSITION OF LiqUIJ>_AND SOIJD PIIASF.n OF ALL LXPF.RIMKNTAL RUNS
I <">. 1
r. in
». 7'I
1.17
R. V.
9. in
n.o
17.7
II./
9. i
17.1.
17 0
11.1
I.IS
I . I 1
I l.R
1 . 9
19.9
17. 1
17.1
I 7.4
17. n
17.P
F.I f I urn I I.I »I <| An;i I y ^rnim. 1 r i/ I 11 n )
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0. I
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0.
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10.'.
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7 7
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M . f.
M.R
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7'. '.
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79 f.
70.1
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17.f»
11.R
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91
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in. 7
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10. n
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17. 1
n.o
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11.9
11.7
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119
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r. f. I
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M	f. .1'.
a;
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70	r, .or,
7-)	7 . HI
77.11
17
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1
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Run
l)>il e NuhMti
x!L
Temp.
* »
I I /!«/?'»
1 1/711 /7S
17/01/7"
17/01/7S
i7/oi//s
17/07/7%
17/07/7'.
17/OS/7'.
1 7/os//s
l?/o«/r»
1 7/nn/7 "»
17/17/r.
I 7 / 19 / 7 r»
1 7/77/75
17/10/7'.
17/11/7".
1 7/ 11 //"t
1 /07/7ft
7/o7/;r»
2/oi/7ft
7/oi//ft
7/OA/7ft
?/in/7ft
7/1 7/7ft
7/17/7
7/17//
7/17/7
K -7'.
K 7ft
K 7/
k- 7A
K 79
K- HI
K 11
K- 17
K- n
K 1A
K IS
K 17
k • M
K-
K-All
K-AI
k-A7
K AA
K-AS
K-Aft
K-A7
K AA
K A9
K - SO
V SI
K • S7
K S »
fl.A'>
h.07
fi. 1?
7.90
r.. n i
fi. 11
ft. 17
ft. 11
s.<»n
ft. (HI
fi. 17
S.9A
ft. 17
5.fti
ft.77
r.. ftO
S. 7*
f.. 71
ft. IP
ft. ?n
ft. 70
ft. 74
ft. 21
7.9S
v jn
n. 11
a. in
so
Aft
so
'•7
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so
in
so
so
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so
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a a
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SO
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A 9
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si
so
AO
A 1
A 9
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n. r i
71 .0
?n. n
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17.1
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17.6
11.0
17.0
1 7.ft
17.1
11.1
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29.7
7V'»
70. 1
7S. 7
77. 7
7 A . ft
77. 7
10. R
7S.9
9 S 1
1.07
9.0|
ft.9/
Ft I In.
is.n
7 A A
ftl.O
I '.ft.
1 / ».
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1 MA
7H .
'.ft. 7
A ft. R
9A . fl
7000.
ftO.
77R.
101.
7»0.
1 IS.
ftO. 7
AA.
AO.
A S. A
AO.
A A . A
AO. A
A I . 0
A?. A
A I. ft
front" Inupd)
TABI.K 3-2 (rnntimiod)
U'lul.l
Mbl'_!	
An.i I ysrs (r»in
CI '
no
7ft. 0
A 7. ft
9ft. A
9 1.0
ia . n
7ft. S
A1.9
HR.A
7 V A
7ft . 01
ftSft.
17.fi
S9A .
S/9.
ft 19.
SI8.
7ftft.
Al 1
inA.
ft 1A.
SAO.
nsi.
A 1. I
A I O
AO f,
l'l. ft
I«s/l Wvt)
r.o,
r:o,,
in
11
r.«« i i.i a»« »i
_!!&''
i:o
n.
I . A 9
1. r.ft
A. ftn
i /
7.A1
11.1
10.1
nr.
K. 1
7.0
ft ft
ni. s
S.12
SO. ?
2 1. A
V.. ft
IS. I
17.1
1A . 9
10. 1
17.9
10. 1
7 . ft'l
1 . 90
I .*A
1
1 A A
11.1
A . SS
1A . 0
7 V
VI A
1/.A
ft 1. r.
7ft. I
7A.R
19.7
A 7 7 .
71 .ft
177.
17 V
7 17.
7S7.
700.
707.
I 1 A .
MM.
A S. A
9 1.
7.R
A . '.ft
7. 0*i
7 . V.
7.7/
ft. nr.
ft. HA
ft ;n
?.s%
7. in
A . 70
7. 1ft
n.f,7
n. 7 7
7. 7S
7. 1
7. IS
ft. A1
/. 79
7 . ;s
7. 7A
S . SR
7 17
/. 17
1. Oft
/./•*»
7. 1ft
7. 1A
7. M
*1 ftf, 7 AO
0 7
l>.
1)7S
07S
OS 7
O 77
0	IS
1	A
07
O 1
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ha I c
Ifi.n
NomiIh'T
iliL
Toiip.
C<:)
c.»
K 'ft
K 'iH
K-MI
K-fil
K (>?
K r,i
k - I n
K <>'>
K f.f.
K r» 7
K-ftn
K-f»9
k- 7n
k- ;i
n.7fl
f.. 7 '»
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r». 71)
s.f.9
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S. 70
-i.9»
v mi
van
v 79
f>7
7.91
R. 17
M
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51
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7. 7f»
7'.
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7.0
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M«<- «:<»I I«l•: tro r.o lilfli |o I Iwrsf«»nr Hi »l
TABI.F) 5-2 (cont inucd)
i < i it*.-in
H.i* _
in.R
f,r,. r,
7o.>.
i/n.
1 in
v,n.
I'.70.
no.
117.
117.
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?<».
ft ft .ft
f, i. r.
I f '| ii (<1 An .i I y'
	(¦
M.I).
M
7n;
N.I).
M f>
ft lfc
'AU,
n n.
(mm.• 1 I I I I | )
co"i so" : t»
>11 'I An;t I y.r-r- (imm I / j; t im )
IB.4
in.7
M I).
r». 2
m.B
N.t>.
ft.)
i. r>
f*. 7
N.n.
7 *» 1
7. on
1. 7(t
\n.n
7f). r>
17.«
1 9 ft
97.
IB. 7
1 '»'».
I'.B
I'.9
97.
. 70
. 73
7.7/.
n
I '.
I'l
n
v
M
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700
f,'.7
'.7 7
4'ifl
7
9
9
In
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n -in
7. v.
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n. nr.
0.R'I
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1.r,	\
n. -»7
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67 7 . f>t
0I"7 7 7 7
fi . 7
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v v*
1 . 70
117
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III'
f.
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I I «l t»i 1 f 11 «• .mi i I \	it «• in u « iir.il r ,
-------
TAM.K 5-3. SUMMARY OF CALCULATED DATA VOR ALL EXPEP.fMI-NTAL RUNS
Hit p
Run
Nni'iU^i
I.I 'l«tor
rvpg'
HL
Tr""|'
_QJ_
i
LO
l
7/0 1/ 7 '
7 / I fl / 7 r»
7/?9/r»
n/o'i/ 7s
n/n/7*
«/."!//'»
0/«r./7S
9/17/7S
«> / K. / 7 '»
9/1 ///'i
i/;'»//r»
/7*»
HI/01/7S
io/i) i/;1*
10/70/75
10/77/ 7<>
10 / 7 J / 7 '>
10/77/7'
10/?fl/7^
10/7*1/ 7S
I I/ 1/7S
I l/A/7',
I- '»
K ft
1- 9
r. lo
t 11
K-.'
K 1
k r,
K - n
v- 9
k-11>
K-II
K I?
K- I 1
K-I'i
*• r»
K If.
K • I 7
K IR
K-|9
K-70
r. ?i
K 77
K 71
C.I.,
I..
c I
r I
c . I..
i: I.,
i 1..
r.i„
I .

Af.
a'
an
A \
AO
a 9
am
vi
A 9
A 9
A 9
A9
'.I
4
6
A
AR
AR
AR
A 9
a 9
10
JJJLll
~.	n r,
;.a'»
i. r»
n. v;
l in
7. 7'.
MJO
7 99
* RO
A. nf,
7.R0
1. 7f1
S7
1. ir.
0.	A 1
i). m
1.Rl
A . A n
~.(11
71
A.'»1
A.
7. 77
7. M
n	r»	I vr S.itui.il Iimi
"O,	SO.,	ro-. M
(to '') (|o ')	• 7ii2o c.iso,, Vi':" 11.t«t
n. ?%
10
t,. ?r.
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A.'>R
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7. V.
7 . 10
7.?n
7_71
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7.M
7.r»a
7. A "»
7.S9
7 . ?9
7. r>A
1.77
7. 77
7. r>r»
7.91
7. f.r,
7. f»f.
1. 77
i. r»
0. 97
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71
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77
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.79
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. 77
. 77
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0
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I . 7H
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<»'. 1
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.or, A
".iii mi >•
I'l ' I |- I I II I
i: ti r-
^imiii • I ' • / [• ¦' I mJI_ _«
n. ii«' i
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t>'»7
li'.f.
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TAIJLIi
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n/mm
H/7i>//',
17/01/?',
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I7/OS/7'.
17/imm
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1?/l?/r>
i7/i«>/r.
i2/;2/r»
i?/ m/;r»
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l?/it/r.
I
2/07/76
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7/0 1/7*
7/04/7ft
7/
k in
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K •(*}
K
K
K-r,f>
K hi
r-'iR
K '.y
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K	'1
K	' '
K	r. I
j-cri
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r«-ni|i
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chl_!1
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n.-'.o
ft.117
ft. 17
7 . 90
ft.HI
ft il
ft. I?
ft. n
rt, <>n
ft. fin
r,. i?
6. 17
ft. 72
"».ftO
V 71
fi. ia
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ft, ?o
ft, 74
*•-7|
7.9r»
R . 70
* ! 1
fl. Ill
4ft
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r>d
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41
t,n
vi
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so
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fron! I ni»rf1)
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K
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(1111) £,r'n\^L?i!L t ,iNO., 7ll?n I.I1:* r,.
? ,nn
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t,\n
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4.47
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n.ii r	Hniiiln-r l/]M*	
TAJU.K 5-j |c().uiiuic(l)
7t?'.n
1/1o/ /
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VI'i/7
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1/71/7
1/11/7
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*	A / 0 *> / 7
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1*17 J11
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k- r>r.
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K-r, i
K-ftin
K»fi'i
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7
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TAH1/E 3-4. I.ICJUID AN!) SOLID COMPOS I'll ON DATA TOR K(}U I I.I HKAT ION RUNS
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TAHU5 r)-r'>. SUMMARY OF Rl-SUI.TS 01- K(}U 11.1 NR I HM RUNS <}-I TIIROIICll Q- I K
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