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All Graduate Theses and Dissertations Graduate Studies
1971
Recommended Citation
Dabb, Lyle M., "Calcium Carbonate Dissolution and Precipitation in Water: Factors Affecting the Carbonate Saturometer Method"
(1971). All Graduate Theses and Dissertations. 2991.
https://digitalcommons.usu.edu/etd/2991
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ACKNOWLEDGMENTS
I would like to thank Dr. Jerome J . Jurinak for his patience and
I thank Robert A. Griffin and Dr. Sung-Ho Lai for their friendship,
I thank Dr. John J. Hassett for his help when I started this
research.
¥ m fJJt-
Lyle M. Dabb
TABLE OF CONTENTS
Page
INTRODUCTION 1
REVIEW OF LITERATURE 3
LITERATURE CITED 37
VITA 38
LIST OF TABLES
Table Page
Figure Page
Figure Page
Saturometer Method
by
carbonate and dolomite increased. When Mg++ was present in solution the
solubility of calcium carbonate was inc reased more than was the solubil-
ity of dolorrite.
(45 pages)
INTRODUCTION
for determining water quality. Cities are concerned with the degree of
water hardness because hardness limits the use of water for culinary
purposes.
totally favorable even though the removal of Ca++ and Mg++ from solution
reduces the total salt lead. Carbonate precipitation also lowers the
Ca/Na ratio in the water making it less beneficial for subsequent agri-
soil.
His saturation index was computed by subtracting the pH that the water
Saturation Index
Negative values indicate that the water will dissolve calcium carbona t e
with respect to calcium carbonate and negative values indicate that the
highl y-buffered soil, (pHs)' for the actual pH of the poorly buffered
so lub ility of carbonates. This method makes use of the fact that th e
activity.
REVIEH OF LITERATURE
Garrels and Christ (1965), list five equations that are important in
[Ca
-t+ =
] [ C0 ]
-+ Ca-t++ co;
3 10-8 . 3
CaC0 K (l)
3 .._ [Caco ] Caco
3 3
[H+l [Hco;J
H co Hco; + H+ 10-6.4 (2)
2 3
[H co J ~2co3
2 3
[H+l [co;]
10-10.3 (3)
+ co; + H+
Hco; .._
[Hco;J
~co;
[H+] [OH-]
+ H+ + OH
H20 .._ 10-14 . 0 (4)
[H 20] ~20
The above equations show that a number of system variab les are
stood. Garrels and Christ (1965) also outlines five differen t cases or
cerned primarily with case two and to a lesser extent with cases four
and five. These cases show that external variables also play an
i mportant role in determining the f i na l equilibrium s tate o f th e s yst em.
2. The reaction of calci t e in pure water , but with the system open
(1965) gave the follo~;ing list of ion pairs that influenced carbonate
equilibrium in solution.
being more soluble. The concluded that these metastable forms will
develop more readily in the presence of Mg++ and so:. They stated that
tating solid.
ates. Weyl (1967) concluded that the slow kinetics of calcite dissolu -
tion in the presence of Ca++ and Mg++ must be at the liquid-solid inter-
and Panteleva (1937) found that the rate of solution of calcite increased
technique is based upon the fact that the pH of a solution changes when
remains unchanged.
METHODS AND MATERIALS
The method used in this study, for the determination of the solu-
size 13 rubber stopper. The solid phase carbonate and soil additions
were made through an access hole in the stopper. A small hole in the
stopper allowed for the escape of gases . The reaction chamber was sub-
powered by a wate r pump on a Haake E51 temp era ture regulator. The
water pumped through the stirrer also circulated the water in the
stopper. The elec trod e was coupled to a model EUW -301 Heath recording
pH meter.
First, the air passed through a fl ask containing glass wool to remove
grease and particulates. The dry air was then passed through a flow-
flow, the air was saturated with water vapor by passing i t through two
gas scrubbers in series. An open flask was then placed in the line to
trap any excess water. The saturated air was dispersed, in the solution
used: A 100 ml sample of a water was pipetted into the r eac tion cham-
ber which was clamped in the wa ter bath over the magnetic stirrer:
then a teflon coated bar was placed in the chamber and the speed of
rotation checked. The rubber stopper containing the sol ution aerato r
was attached. Prior to the insertion of the combination ele ctrode into
through a hole in the stopper and placed in the solution. The dep t h
of the electrode in the solution was adjusted so tha t the stirring bar
would not make contact. Sufficie nt time was allmved for the reaction
water bath before readings were taken. After the aerated solution had
carbonate material was added through the access hole. This addition
as the ending pH. By subtracting the starting pH from the ending pH,
9
The four salts used were: NaCl, a 1:1 salt; Na so , a 1:2 salt;
2 4
Mgso , a 2:2 salt; and MgC1 , a 2:1 salt . These four salts were used
4 2
to determine if sulfate and magnesium ions had any specific effects on
strength. Akin and Lagerwerff (1965) observed that the sulfate ion as
of calcium carbonate.
I = 1/2 L C.
l
zi2
where c1 = concentration of the solution species (+ and ~) and z1 is
crystalline, white, New York); and a calcareous soil (from Vernal, Utah)
and 23°C.
10
of solid added to the aqueous solution affected the value obtaine d from
carbonate and the other water was supersaturated with respect to calcium
amount of calcareous Vernal soil was added and aeration was continued
The data are shown in Figures 1 and 2 . It was observed that the
120 ~ ~ pH
110
100
90
80
70
...."
~ 60
...."'e
E-<
50
40
30
20
soil addi t ion
10
8 8.5
pH
120
llO
100
90
80
70
.,.,
..:"
<lJ
60
.,s
H
so
s.o
40
30
20
soil addition
10
8 8.5
pH
rium faster than the smaller sample weights. From the results of these
data one gram of carbonate material was selected as the sample weight
In Figures 11 through 16, the data show the effect of various salt solu-
against 5 and 6, and also Figures 7 and 8 against 9 and 10, it was noted
beyond the simple ionic strength effect. From their solubility pro-
than calcium carbonate. The data suggest that at the higher concen-
carbonate.
14
Table 1. tlpH values and mmoles of dissolved carbonate for three solid
ca rbonates and four aqueous salt solutions at different ionic
strengths, at 23°C
NaCl
. 00 2 . 95 1. 65 3 . 15 2.33 3 . 02 1.90
Na so
2 4
.oo 2.95 1. 65 3 . 15 2.33 3. 02 1. 90
.05 2 . 50 1. 90 2.69 3 . 50 2 . 46 1. 70
Mgso
4
.00 2.95 1.65 3.15 2.35 3.02 1.90
. 20 2.53 1. 90 2 . 60 2 . 25 2 . 25 .85
MgC1
2
.oo 2 .9 5 1. 65 3.15 2 . 35 3 . 02 1.90
. 05 2 . 98 1. 50 3. 03 1. 60 2.81 . 90
. 10 2. 97 2 . 20 3 . 03 2.50 2 . 79 1. 40
Table 2. llpH values and mmoles of dissolved carb onate fo r three solid
carbonates and four aqueous salt solutions at different ionic
strengths , at l5°C
NaCl
Na so
2 4
.00 2.85 2.00 3.03 3.25 2.75 1.60
Mgso
4
. 00 2.85 2.00 3 .03 3.25 2.75 1.60
MgC1
2
. 00 2.85 2.00 3.03 3.25 2.75 l. 60
8 £:,. Dolomite
() Calcium carbonate
0 Vernal soil
. 05 .10 .20
Ionic strength
6. Dolomite
0 Calcium carbonate
6 0 Vernal soil
11~ 5
.05 .10 . 20
Ionic strength
.6 Dolomite
0 Calcium carbonate
6 0 Vernal soil
11~ 5
.05 . 10 .20
Ionic strength
!:::. Dolomite
() Calcium carbonate
0 Vernal soil
.05 .10 . 20
Ionic strength
/::,. Dolomite
() Calcium carbonate
() Vernal soil
!:::,. Dolomite
O Calcium carbonate
O Vernal soil
D,. Dolomite
() Calcium carbonate
9 () Vernal soil
c. Do l omite
0 Calcium carbonate
6 0 Vernal soil
11~ 5
Figure 10.
1
. 05
:.10
Io nic s t reng t h
:
.20
8 "• NaCl
MgCl
2
\1 Na so
2 4
0 Mgso
4
11~ 5
. 05 . 10 . 20
Ion ic str eng th
... NaC1
8
• MgC1
\l Na 2so 4
2
0 MgS0
4
il~ 5
.05 . 10 .20
Ionic strength
Figure 12. Dolomit e additions t o four sal t so luti ons at var ious ionic
strengths , at 23°C .
26
8
... Na C1
• MgC1
'V Na so
2
2 4
0 MgS0
4
il~ 5
. 05 . 10 . 20
Ioni c strength
..• NaCl
MgC1
2
'\'l Na so
2 4
9 .0 MgS0
4
• OS .10 .20
Ionic strength
'If NaCl
• MgC1
\l Na s o
2
2 4
9 0 Mgso
4
. 05 .10 .20
Ionic strength
Figure 15. Dolomite additi ons to four salt solutions at various ion ic
streng ths, at l5°C .
29
y NaCl
• MgC1
\1 Na 2so 4
2
~~~
0 MgS0
4
§
.OS . 10 .20
Ionic strength
The solubility of the carbonates in the Vernal soil was less in any
ate. This was not expected. One possible explanation of the lower
less soluble compound. Olsen and Watanabe (1959) concluded that phos -
calcium ion in the system which acts as a common ion with respect to
calcium carbonate.
ion. This indicated that ~ulf ale len also increased the solubility of
Fi gures 11 and 12, we see that calcium carbonate is more soluble in the
MgSo solution. With the dolomite mineral, the solubility was highest
4
in the waters with Na so and lower in the solution made with Mgso .
2 4 4
This suggests that both Mg++ and so4 increase the solubility of calcium
ral irrigation waters, eight water sources were sampled near Vernal.
the eight water samples were collected June 4, 1970. Chemical data for
the waters are given in Table 4. The carbonate saturometer method (as
described in the Methods and Materials section) was used to obtain 6pH
Negative ~p H values show that the water was supersaturated with respect
to the added solid carbonate. Zero 6pH values were assumed to mean
that the water was at equilibrium with respect to the added solid
carbonate. From the ~pH values given in Table 3, we note that as the
water in Ashley Creek came into the valley, it was undersaturated with
positive ~pH values. Waters two, three, and four were surface waters
that had been stored in Steinaker Reservoir. The measured ~pH values
show that these waters were saturated with respect to the soil carbon-
cates that water quality changes durin~ storage prior to use. Waters
five through eight are drainage waters and have passed through the soil.
6pH values for the different solid carbonate additions, we see that
the soil carbonates are more soluble in any given water than is calcium
32
Table 3 . 6pH values for Vernal soil and calcium carbonate a dditions to
eight natural irrigation wa t ers
Nat ural
Water water Location Soil Caco
t emp OF 6pH 3
6pH
carbonate in that water . The eight waters all followed the same trends
nesium. The only water departing from this trend was water 7. The
seemingly low values for this water could have been the result of pre-
cipitation of carbonate after the readings were made for the composition
readings were made. This could have happened at the high degree of
concentrations. Titration curves were not made for these waters due
solubility.
34
data obtained. The solubility of thr ee solid carbonate mater ials were
of Mg++ and so: in agreement with Akin and Lagerwerff (1965). The
carbonates.
The carbonate saturometer was used t o study the degree of sat ura-
make the results obtained more meaningful, the experimental error must
be reduced.
satura ted air entering the reaction chamber is at room temp erature.
HCl wash and then in deionized water seemed to remov e the carbonate
carbo nate. However, when the same washing pro ced ure was used on
spargers in warm HCl to get a more rapid and comp l ete r eaction between
system may el imi nate the wash i ng problems. However, with the capillary
It has been reported by Brooks, Clark and Thurston (1950) that the
increases . The speed of stirring may also aff ect the amount of carbo-
cons tant.
36
It was obser ved by the author that the starting 6pH values drifted
sligh tly for several days after water solutions were made. Allowing
the water so lutions to stand for several days before using them gave a
water and incubate them. Leach one, with no plant growth. Leach the
seco nd after the same incubation period but '"ith an actively growing
temperature.
the a mount of Ca++ and Mg++ i n solution. Changes in solub ility could be
could be used to check for changes in form before and after precipita-
LITERATURE CITED
Lyle M. Dabb
Master of Science