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 i

i POLYMERIZATION KINETICS AND EQUILIBRIA OF SILICIC ACID

IN AQUEOUS SYSTEMS
3
Allyn R. Marsh III,l Gerhard Klein" and Theodore Vermeulen 3

Abstract .

The polymerization of silicic acid, or dissolved silica, is

believed to have a major effect in the deposition of silica scale from
geothermal brines. In this research, significant properties o f silica
in aqueous solution have been reviewed, and equilibrium concentrations
and polymerization rates at 25OC have been measured for total SiOp
concentrations from 350 to 900 ppm and pH's from 4 to 10. The results
indicate that polymerization proceeds by a reaction between neutral.
and ionized silicic acid molecules and is strongly dependent on pH.
The acid strength of polymeric silicic acids increases significantly
with molecular weight, producing autocatalysis of the polymerization
process by increasing the amount of ionized acid at any given pH.
Polymerization occurs fastest when there are equal concentrations of
neutral and ionic species.
A comprehensive view o f silicic acid beha or has been developed.
tions and interpretations. Pre-
f scale formation
i icic acid is found
ic and colloidal
S O 2 ) at 25OC.
Low-molecular-weight silicic acid polymers exhibit rapidly diminishing
equilibrium solubilities; for example, [Dimer]/[Monomer]* = 94 M-?.

n
DlSTRlBUTlON OF THIS DOCUMENT IS UNLIMITED
 I

,
~

ii
I

In addition, the standard colorimetric technique for si1 ica

determination, which has been widely misinterpreted in the past, is
extensively examined and its 1 imitations defined.

Master of Science Thesis in Chemical Engineering, University of

Ca 1 i forni a, Berkeley , Ca 1 iforni a.
Now with The Dow Chemical Company, Martinez, California.
2
Sea Water Conversion Laboratory, University of California
1 Field Station, Richmond, California.
, i * 3
Department of Chemical Engineering, University of California,
Berkeley , Ca 1 i fornia .

!
 . .
iii

TABLE OF CONTENTS

Page
Chapter 1. Introduction 1
Geothermal Energy Resources 1
Power Plant Designs 4

Chenlical Nature o f Geothermal Brines 6

Operating' Performance and Scale Formation 8
Problem Areas 13

Chapter 2. Behavior of Silica i n Aqueous Solutions:

LSterature Review 16
The Structure o f Silica and Silicates . 16
Sol ubi 1i t y o f Si 1i ca i n Aqueous Sol utions 17
Behavior o f Si1 ica i n Supersaturated Solutions 23
The Stability o f Colloidal Silica Sols 27
Scale-Formation Pathways 31

Rate-Experiment Procedure 72
Equilibrium Studies 73
 iv

Page
Chapter 4. ,Experimental Results 75
I Equil i brium Results 75
Color-Devel opment Studies 82
I Rate-Run Results 89

Chapter 5. Discussion 109

1

Mechanism of Polymerization 109

! Ionization Behavior of Silicic Acid Polymers 112
Monomer-Dimer Equilibrium 119
Rate Dependence on Total Silica 126
SUmnary 129

Chapter 6. Conclusions and Recommendations 132

Fundamental Points 132
Implications for the Formation of Silica Scale 136
Recomnendations for Further Study 137
General Conclusion 139

Bibliography 140

Appendixes 145
1. Rate Runs: Experimental Data 145
2. Graphs for Unbuffered Rate Runs 158
3. Color-Development Rate Equations 169
4. Proposed Experiment on Heat-Exchanger Fouling 172
 1

L,
Chapter 1

INTRODUCTION

Geothermal Enerqy Resources

With the increasing demand f o r e l e c t r i c a l energy production
and r a p i d l y diminishing supplies o f fuels, the need f o r the develop-

ment o f a l t e r n a t e energy resources has become c r i t i c a l . Geothermal

energy represents one such a1ternate resource which appears a t t r a c t i v e
from both economic and environmental standpoints, and has the poten-
t i a l i n c e r t a i n geographical areas t o a l l e v i a t e the burden o f f o s s i l

f u e l s f o r e l e c t r i c a l energy production. As former Secretary o f the

I n t e r i o r Rogers Morton has stated, " I n t h i s time of c r i t i c a l l y high
energy requirements, the various f u e l s are not a l t e r n a t i v e s t o each
other. We need them a1 1, i n c l u d i n g geothermal" ( S 4 ) .
The development o f geothermal energy i s not without i t s tech-
nological problems. Foremost among these are the management o f geo-
thermal brines containing high l e v e l s o f dissolved solids, and the
prevention of equipment f o u l i n g due t o scale deposits. The o b j e c t i v e
o f t h e present study on the polymerization o f s i l i c i c a c i d i s t o
understand the mechanism and r a t e by which dissolved s i l i c a i n geo-

thermal brines i s a p t t o p r e c i p i t a t e and scale out. However, before

0

proceeding t o t h i s t o p i c , a b r i e f background i n t o the development o f

geothermal energy should prove i n t e r e s t i n g t o the reader and should

identify the groundwork from which t h i s research has sprung.

The presently i n s t a l l e d e l e c t r i c a l generating capacity d e r i v i n g
Lid
energy from geothermal sources i s only 1000 megawatts , roughly a
 2

quarter of one percent of the world's total installed capacity (A9 Ld

and C4). Yet the potential of undeveloped geothermal resources i s ,
vast. The U. S. Geological Survey "has outlined nearly 1,800,000
acres w i t h i n the Western United States and Alaska that are potentially
*
valuable for geothermal energy development, and that may contain an
energy source estimated i n the range of 15 t o 30 thousand megawatts"
(67). (Equivalent electrical capacity represents 10 t o 15 percent of
this resource figure due t o theoretical and practical generating e ffi-
ciencies.) In 1965 White estimated the world's potential heat energy
recoverable from resources up t o three kilometers i n depth to be 23 x
1012 kWh on the basis of equivalent producible electrical energy (M9).
This f i g u r e represents approximately 15 times the U. S. electrical
energy consumption i n 1970, or 1.5 times the world's total energy
consumption i n 1970 (C4).
Rex has estimated that utilization of between one to three per-
cent of the hot water beneath California's Imperial Valley could pro-
duce as much e l e c t r i c i t y as was consumed i n the entire U. s. i n 1970
(A9). The estimates of potential resources by other experts have
differed by many orders of magnitude (M9). However, the one fact that
,
most experts agree on is that geothermal energy represents a viably
recoverable alternate resource, one that ,can make a significant con-
tribution t o the world's energy supply. I

Geothermal systems can be classified into several categories.

Vapor-dominated systems, ds their name implies, give a well-head pro-
duct which is predominately steam and thus ideal for power production.
Except for the possibility of relatively h i g h levels of noncondensible LwJ
gases such as C02 and H2S, which decrease condenser efficiency and
 3

present an environmental hazard (from the standpoint of H2S emission),

"pure" steam systems contain only low levels of dissolved and
entrained solids and thus present relatively minor scale problems.
Operating f a c i l i t i e s a t The Geysers i n California and Lardarello i n
Italy are examples of vapor-dominated systems. I t is no wonder that
these clean sources were among the first geothermal areas developed.
Wells a t Lardarello were first used i n 1904 and are currently produc-
ing a t a r a t e of 400 MW. Pacific Gas and Electric Company began the
first c m e r c i a l l y operating geothermal power plant i n the U. S. at
The Geysers i n 1960 w i t h 12.5 MW o f capacity. he present capacity is
over 300 MW, w i t h 700 MW projected by the end of 1976 (S4). Japan has
a 20 MW plant utilizing a vapor-dominated system a t Matsukawa i n I

Northcost Honshu, which has a projec apacity of 200 Mw (68).

Whereas vapor-dominated syst present the optimum choice for
power plant utilization, only one i n twenty known geothermal systems
produces solely steam (M9). Far more abundant are liquid-dominated
head, typically

mately 17,000 ppm (parts per million) total dissolved solids (M9).
A t h i r d type o f eothermal system characterized by a region
o f hot rock relatively close to the surface b u t without any natural
. '-
 .. . .
. . . .

water source. By injecting water into such a dry formation and remov- LJ
i n g i t from other connected locations, i t is hoped t h a t an a r t i f i c i a l
reservoir can be produced which will yield hot water. The formation
therefore acts like a large heat exchanger supplying heat energy t o
water injected from the surface. If no porous structure exists i n the
rock t o allow the injected water t o percolate through the reservoir,
attempts will be made t o fracture the rock, creating an a r t i f i c i a l
porous structure. Such practices are commonly used i n o i l recovery
when greater reservoir porosity is desired. Although no a r t i f i c i a l l y
stimulated dry-reservoir system is currently being used t o produce
electrical power, tests t o evaluate the idea's f e a s i b i l i t y are current-
l y being made i n New Mexico by the Los Alanos Scientific Laboratory.
If successful, such a r t i f i c i a l systems will markedly increase the num-
ber o f potential geothermal energy sources.
Power P l a n t Designs
Power plants which u t i l i z e steam from vapor-dominated systems
need do l i t t l e more than collect the dry steam from the producing wells
and r u n i t through turbines. Plants u t i l i z i n g two-phase mixtures from
liquid-dominated systems are necessarily more complicated. There are
three basic designs for these geothermal power plants. The design
which is currently being utilized i n operating plants employs a separa-
tor a t the well head t o draw off only a gaseous product, which is sent
t

to+the turbines while the brine is discarded. Variations on this

design u t i l i z e the waste brine from the first separator, and subse-
quently flash i t through a series of separators operating a t lower
pressures t o produce additional steam product. The number of a d d i t i o n a l
stages depends on the i n i t i a l conditions of the brine, b u t i t is seldom
c;
 5

I
(
economical t o use more t h a n three stages.
Typically, geothermal power plants are forced t o u t i l i z e rela-
L
tively low-pressure team (determined by the temperature, depth, and

t
producing capability of the reservqir), operate a t low thermodynamic
efficiency, and consequently employ large quan ies of steam t o pro-
duce relatively small amounts of saleable powe A moment's reflection
\

on the level ofddissolved solids i n typical brines will reveal t h a t

even a relatively small power plant ( i n t e n s of installed capacity)
will bring to the earth's surface rge quantities of solids contained
i n the brines, and these could represent a substantial solid-waste dis-
posal problem if precipitated from solution, to say nothing of the quan-
tities of residual l i q u i d brine. r example, based on the figures
. A

reported e a r l i e r , i f even one percent of the solids i n the Cerro Prieto

brines were to precipitate (Si02 a ng accounts for more than 2.5 per-
cent o f the sol i d s content) t
¶ e daily production
fifteen wells would exceed fifteen tons. To solve this solid waste
thermal p l a n t s provide
dewround reservoir.

-
1

e brine under
ase l i q u i d product

'b,
A t h i r d design currently under study by the Lawrence Livermore
 6

Laboratory involves development of a special two-phase t u r b i n e which u

w i l l employ geothermal brines directly, without prior separation of the
two phases. Because this system uses 100 percent of the well product,
as a higher potential operating efficiency than either of the other
two systems (A1 1) . *

Chemical Nature of Geothermal Brines

As indicated previously, one of the major technological problems
which must be surmounted before geothermal energy can be u t i l i z e d econ-
omically is the problem of scale formation w i t h i n the well, power plant,
or reinjection s i t e . The potential for scale formation is highly de-
pendent on the chemical nature o f the brines, as well a s on their
thermodynamic and hydrodynamic character. As Table 1.1 indicates (W3,
M3, M1, F5), even w i t h i n a given geothermal f i e l d the chemical composi-
tion of brines can vary significantly. The Salton Sea geothermal area
lies only 60 miles northwest of Cerro Prieto, y e t i t s brines are ten
times more concentrated i n total dissolved solids. (The Salton Sea
brines rank among the most saline natural brines i n the world (G7).) By
comparison, Table 1.1 indicates that some of the New Zealand brines are
ten times less concentrated than the Cerro Prieto brines.
The concentration levels of dissolved chemical species are not
only strongly dependent on the temperature (and pressure) of the geo-
thermal reservoir, b u t also on the complex mineral composition of the
reservoir rocks. The chemical composition of product brine is further
complicated by the f a c t that different producing areas vithin the
reservoir may differ significantly i n mineral composition and tempera-
ture. The concentration levels a t the well head also depend on the
degree of flashing and extent of scaling that has occurred as the l i q u i d
 7

L/. - -ppi -
Table 1 . 1
Chemical Compositions of Brines (ppm) from
Various Geothermal Systems
.
Salt Cerro Cerro New New Japan Japan
5 Sea Prieto Prieto Zealand Zealand
Orakei - Broad-
korako 1 ands
IIDNo 1 7 M5 M13 Hole 2 Hole 2 Hole 2 Hole 3
Ref. w3 M3 M3 M1 M1 F5 F5
Temp., OC 340 300 300 200 200
PH 5.2 6.2 8.0 9.1 8.5 7.5 4.3
si02 400 737 1,416 480 840 1,400 606
Na 50,400 I 6,648 8,656 550 1,075 180 250
K 17,500 1,645 2,207 54 223 25 100
ti 21 5 24.8 41 3.1 11.4
Rb 135 0.2 2.2
cs 14 0.3 1.9
Ca 28,000 304 484 1 .o 2.9 6.4 21.4
Sr 400
Ba 235
Mg 54 27.4 17 0.2 2.0 12.6
AS 12 0.8
Fe 2,290 2.0 212
Mn 1,400
fn 540
Pb 102
A1 4.2 0.5 4.3
c1 546 1,044 7.0 9.0
Br 0.8 6.4
I 1 *o 0.3
F N.D. 5.7 7.3 .

kid
 8

brine travels up the well. In sumary, i t i s exceedingly d i f f i c u l t . t o

predict the chemical nature of the brines w i t h o u t detailed data on the
total mineralogic composition of the reservoir (indicating i n particu-
l a r which mineral species are i n equilibrium), the temperature profile
*
i n the reservoir, and the hydrodynamic characteristics of the reservoir
fluid system. In this regard, i t may t u r n out t h a t direct chemical
sampling is the -only re1 iable source of information.
There are several chemical species which notably tend t o precipi-
t a t e from geothermal brines. O f primary concern is s i l i c a , which poses
a significant scaling threat because of i t s rapidly decreasing sol ubi1 -
i t y w i t h decreasing temperature. (Geothermal brines always cool as
they are brought t o the surface.) Silica (Si02) can precipitate w i t h
other cations i n the brines, especially polyvalent cations. Other
comnon scale products are calcium carbonate and calcium sulfate. Un-
like s i l i c a , these species .exhibit solubilities t h a t increase w i t h
decreasing temperature. Nevertheless these species do precipitate,
because the brines can become greatly concentrated i f significant flash-
ing occurs. In addition, significant depressuring w i t h i n the well can
result i n the release of dissolved C02; t h e carbonate ions which form
(Eq. 1) can precipitate subsequently w i t h calcium t o give calcium car-
bona te.
2HC03-& COj= + COP (9) + H20

Other common forms of scale include ferrous sulfide and various metal
oxides.
Operating Performance and Scale Formation
Operating experience i n geothermal power plants t o date seems t o u
indicate t h a t scale formation can occur anywhere w i t h i i i the circulation
 9

L,
loop for geothermal f l u i d s . Operating data from the Matsukawa power
plant i n Japan shows t h a t scale products form everywhere, b u t most
noticeably i n the well-head separators and i n the turbine (04). A par-

I
t i a l analysis o f the scale products i n the well-head separators f o r two
.of Matsukawa's producing wells is own i n Table 1.2 along w i t h the'
chemical composition of thermal waters from those wells (04).

Table 1.2
Scale Products ( X ) i n Matsukawa. We1 1-Head Separators
SiP.J& Aluwo-S -
Na
Well No. 1 17.75 12.20 0.83 0.30 0.21 40.84 3.20 9.25 5.05
Well No. 2 90.45 0.35 0.84 0.59 0.30 2.25 Tr 1.50 0.50

Chemical Composition of Thermal Water (ppm)

5.0 1000- 400- 10- 3 10- 1500- 200- 150-

1500 600 15 40 15 1800 300 200
Well No. 2 400 150- 40-

-
a

gni tude of scale

products was not reported.
LJ

I
 10

This fouling problem seems t o be a strong function o f the moisture con- hi

t e n t o f the steam. Incomplete phase separation and higher l i q u i d con-

t e n t usually r e s u l t i n more scale deposition because the entrained

*
l i q u i d contains s i g n i f i c a n t l y higher l e v e l s o f dissolved s o l i d s (A5).
The chemical composition o f t h e scale varies, depending on the particu-
l a r l o c a t i o n o f i t s deposition, as shown i n Table 1.3 ( S l ) . The r a t e o f
deposition w i t h i n the t u r b i n e seems t o be r a p i d when the scale forms on
clean sur.faces but slows considerably a f t e r a l a y e r has been formed

(04). Additional evidence w i l l be presented i n Chapter 2 which suggests

t h a t preliminary corrosion i s necessary f o r i n i t i a l scale deposition,
a f t e r which the r a t e o f f u r t h e r scale deposition i s markedly reduced

(i2).
Since the q u a n t i t y o f s o l i d s i s much lower i n steam than i n ge'o-
thermal l i q u i d s , power plants u t i l i z i n g vapor-dominated systems are
l e s s susceptible t o scale formation than plants which must separate
steam from l i q u i d brines, o r plants which u t i l i z e brine d i r e c t l y .
Nevertheless, as the above evidence suggests, even steam systems are
subject t o some scaling. Evidence from Lardarello, I t a l y , suggests
s l i g h t scale deposits can form anywhere i n the turbine. Typically,
iron s u l f i d e scale i s prevalent i n the f i r s t rows of blades whereas
l a t e r rows show increasing q u a n t i t i e s o f p a r t i a l l y hydrated amnonium
borates, s i l i c a , and various s i l i c a t e s . I n addition, corrosive etching
by chlorides represents a serious problem t o the d u r a b i l i t y o f mater-

i a l s of construction (A5). Evidence from I t a l y ' s Lago f i e l d indicates

t h a t s i g n i f i c a n t scaling can occur when the steam c a r r i e s q u a n t i t i e s o f
"dragged" o r entrained water. A1 1e g r i n i and Benvenuti (A5) reported
LiJ
that f o r one p a r t i c u l a r well, producing 50 tons per hour o f b r i n e a t
 J

11

a Chemical Anal s of Scale i n the Steam Cycle

atsukawa Power Plant
-
*
( X by weight)
Main Main
Nozzle Nozzle Control Control Stop Stop
1st 2nd 2nd 3rd Valve Valve Valve Valve
Material -Blade
. Blade -
Blade Blade #1 #* -#l - x2
sio2 41.9 39.3 48.94 23.24 29.60 32.16 35.74 17.16
Fe 6.47 6.92 7.59 10.27 7.14 20.32 22.78 39.76

23' 12.23 15.49 17.53 8.95 7.13 7.55 6.32 4.07

CaO 1.40 4.00 2.40 2.60 0.16 0.80 1.00 0.55
MgO ' 0.52 0.89 0.78 0.88 0.21 0.35 0.18
CaS04 10.50 3.80 3.16 4.40 8.3 7.20 2.80

s04
10.70 12.85. 6.32 33.53 31.33 3.97 2.98 3.08
3.29 3.69 2.36 1.63
0.2 0.3

-
i

km t o a holding *

ation. Operating data how t h a t s i g n i f i c a n t q u a n t i t i e s o f scale formed

kb
on the i n s i d e of the 350-mm-diameter steel pipe. Five months a f t e r the
 12

pipe was i n s t a l l e d , scale was 20 mn t h i c k a t the entrance and 3 t o 5 m LJ

t h i c k a t a distance o f 2 km down the pipe. The scale composition v a r i -
Sed with distance, ranging from 85.5% Si02 a t the entrance t o 97.8% a t
.
the e x i t . The scale was allowed t o continue t o b u i l d up u n t i l the f l o w
r a t e through the pipe was c u t i n h a l f , a t which t i y e the p i p e l i n e was
replaced ( Y l ) .
The 60-megawatt power p l a n t a t Cerro P r i e t o (soon t o be .increased
t o 75 MM w i t h the a d d i t i o n o f f u r t h e r wells) was put i n t o operation i n
A p r i l 1973. The p l a n t c u r r e n t l y u t i l i z e s 11 wells which y i e l d a well-
head product o f 25% steam a t 4OO0F and 160 psig. The remaining b r i n e
mixture (75%) i s separated a t the well head and discharged through
p i p e l i n e s several hundred yards i n length t o lagoons which c o l l e c t the
waste brines. A f t e r one year o f operation, there i s no evidence o f
s i g n i f i c a n t scaling i n these o u t l e t pipes. I t was estimated t h a t the

pipes would l a s t between f i v e and ten years before f n u l i n g from scales

made replacement necessary. However, s i g n i f i c a n t scale formation was
observed w i t h i n the producing w e l l s themselves. The scale comprised
mainly carbonates and s i l i c a , and was found t o occur predominately a t
the j u n c t i o n between d i f f e r e n t diameters o f well p i p i n g (C3).
For the Wairakei (New Zealand) geothermal f i e l d , there are con-

siderably more operating data than f o r Cerro Prieto. Ten years o f e v i -

dence there suggests t h a t scale deposition i s n o t a problem f o r t h e i r
t

steam-water mixtures a t pressures between 55 and 75 psig and t h e i r low

concentrations o f t o t a l dissolved sol ids. (See Table 1.1 ; GIai rakei
brines are n o t s i g n i f i c a n t l y d i f f e r e n t from those 1i s t e d f o r Orakeikorako

and Broadlands.) Most waste brines are c u r r e n t l y flashed t o the atmo-

sphere, and there i s no evidence o f s.cale deposition (31). The

u
 13 I
possibility that scale deposits actually do form b u t are eroded by the

c
high discharge velocities is not likely, due t o the boundary layer t h a t
he surface of the pipe walls.' In a few situations where
severe scaling has been observed, the so roblem has been
i
t o particularly slow flows i n which concentrated brines were
d t o cool t o 100°C or less (31 ) .
Problem Areas
,
Based on the operatin t e and a knowledge of geo-
thermal power p l a n t t o identify key areas where
scale formation can present serious threats t o the operating efficiency
o f plants. The well i t s e l f i s a key area. Brines brought t o the sur-
face become cooled and concentrated as large quantities of l i q u i d f l a s h
i n t o steam. The areas w i t h i n the well where significant flashing
occurs are susceptible to scale ventual flow constric-

-
-*

waste brines i n t o porous underground substrata w i t h o u t subsequent

u u p of the injection s i t e . Finally ough scale deposition
from geothmal steam Is minimal compared t o t h a t from l i q u i d brines,
 14

the presence of only small amounts of scale on turbine blades can i1

greatly impair their mechanical performance.
One aspect of the scale-formation problem i n geothermal power
F
plants that has not been discussed yet i s probably the most important
of all- the problem of rate of deposition of scale. Thermodynamics
indicates that precipitation w i l l eventually occur when dissolved
minerals are present a t concentration levels which exceed
b i l i t y limits for a given temperature, b u t does not specify the rate a t
which precipitation w i l l occur. Silica solutions, for example, are
known for their a b i l i t y t o exist i n states of h i g h degrees of supersat-
uration w i t h o u t y i e l d i n g precipitates o r d e p o s i t i n g scales (K5). The
fundamental question then is: Under what conditions will the rate o f
scale formation be slow or fast? And is i t possible t o choose condi-
tions under which the rate will be so slow that deposition will not
occur?
The purpose of the present work is t o investigate the phenomena
o f scale formation, and particularly their rate behavior. Silica has
been chosen as the major subject of investigation, since i t appears
to present the most significant scaling problems, and indeed i s the
primary constituent i n many scales. T h i s study will be fundamental i n
nature, without reference to particular power-generating systems. T

Although a great deal of effort has already been devoted t o study

E

o f aqueous solutions of s i l i c a , the mechanisms of scale formation and

the variables affecting i t s rate have not been treated generally.
Chapter 2 will survey the background knowledge concerning the behavior
of s i l i c a i n dilute aqueous solutions as i t relates to the process o f
i d
scale formation, and will provide a connection between the rate of
 15

L,
s i l i c a scale formation i n geothermal brines and the present study o f
the polymerization r a t e o f s i 1 i c i c acid i n aqueous solutions.

. -
 16

Chapter 2
Lid
BEHAVIOR OF SILICA I N AQUEOUS SOLUTIONS:
LITERATURE REVIEM
, -

The Structure o f S i 1 i c a and S i 1 i c a t e s

Man has studied the chemical nature o f s i l i c a (Si02) and s i l i -

cates f o r thousands o f years, ever since the e a r l y beginnings o f the
glass' and ceramics industry. Several major works have been published

within the l a s t twenty years which present man's knowledge o f s i l i c a

and i t s many forms (11, E l , V l ) . Yet, there are s t i l l many aspects o f
s i l i c a chemistry t h a t are not understood (11). This chapter w i l l touch
upon key aspects o f s i l i c a chemistry, both c e r t a i n and uncertain, which
apply p a r t i c u l a r l y t o the behavior o f s i l i c a i n d i l u t e aqueous solu-
tions.
S i l i c o n dioxide i s a comnon geologic ingredient and comprises
s i x t y percent o f the earth's crust, e i t h e r pure o r combined w i t h other
elements In s i l i c a t e minerals. Pure Si02 e x i s t s i n nature as a complex
three-dimensional s t r u c t u r e i n which every s i l i c o n atom i s bonded t o
four oxygen atoms i n a tetrahedral configuration, and every oxygen atom
i s bonded t o two s i l i c o n atoms ( S 5 ) . I t can e x i s t i n both c r y s t a l l i n e
and amorphous forms: the common c r y s t a l l i n e form i s quartz. (Quartz
e x i s t s as both right-hand o r clockwise-advancing (a-quartz) and l e f t - .
hand (B-quartz) s p i r a l s o f l i n k e d tetrahedra (S3).) Quartz, however, i s
%

o n l y one o f three known c r y s t a l l i n e forms and i s thermodynamically

stable up t o temperatures o f 870°C. Tridymite i s stable fyom 870 t o

1470°C, and c r i s t o b a l i t e i s stable above 1470°C. A l l three forms are
found i n nature below 87OoC, b u t i n such cases, t r i d y m i t e and LL
 , I 17

W cristobalite exist i n thermodynamically unstable states (11). Amor-

phous s i l i c a is a general term for m y non-crys line form of SiOp and
6
includes such species as s i l i c a gel, colloidal s i l i c a , opal, and s i l i c a
glass (KS) . e silicon oxygen tetrahedra are a1 the comnon b u i l d i n g
. blocks o f a l l i l i c a t e minerals as shown i n Table 2.1 (S3, S5).
Solubility of Silica i n Aqueous Solutions
When s o l i d phases of s i l i c a are contacted w i t h water, small
amounts o f the s i l i c a wit1 dissolve and enter the aqueous phase. The
predominent form of d olved s i l i c a i s simple monomeric s i l i c i c acid,
Si(OH), (K5, K2, A l , M4, B4, M5). T h i s acid has the tetrahedral
coordination w i t h oxygen teristic of nearly a l l s i l i c a t e struc-
tures. The -OH groups bo t r a l silicon atom, commonly
termed silanol groups, have a s l i g h t ability to release hydrogen
ions; hence the name s i l i c i c acid. The d i n constant for the
first hydrogen ion ha5 been reported by Ro Erwin (R2) to be
. Greenberg and Price (63) report similar values, 1o-9. 77

ion constant i s
m tetrahedrally bonded
t o four silanol groups is termed monom species can
*
polymerize by forming an oxygen l i n k silicon atoms to
a

than others. Amorphous s i l i c a is more soluble than quartz which i n

..
u 1
t u r n is more soluble tha s t o f the s i l i c a t e minerals ( I t , V3, M5,
lubilities o ca are strong
 18

Table 2.1 i
Structure o f Silicate Minerals
From Stillwell (S5) and Slabaugh and Parsons (S3)
Silicon-
Description Examples Formul a

0-yo
P Orthosilicates-single Garnet
tetrahedra joined by
0
metal ions as i n s a l t s Olivine Mg2S i O4

Two tetrahedra sharinq- Thortvei ti te Sc2Si207

O P
0-Si-0-Si-0 one oxygen-joined to
other Si207 groups by Hemimorphite Zn4(OH)2Si207-H20
A b metal ions
.

Metasil icates-six- Wollastinite Ca3Si309

9iP member rings o f a1 ter-
0’ ‘0 n a t i n g silicon and Beni toi t e BaTiSi30g
oxygen atoms
(%02k;
0’

Larger 12-member rings con- Beryl Be3A1 2Si6018

Rings t a i n i n g a1 ternating
silicon and oxygen
a toms
Si 1icon- Pyroxenes-single Diopside CaMg ( S i03)
Oxygen chain o f si1icon
Chains tetrahedra 1 inked by
oxygen bridges
hub1e Amphiboles-two side-
Chains by-side pyroxene
chains l i n k e d w i t h
oxygen bridges, one
for every four si 1 icon
a toms
Si 1icon- Micas and Clays Kaolinite A12Si205(0H)4
Oxygen
Sheets Muscovite u13Sf3010(OH)2
Three- Feldspars Orthoc 1ase
Dimensional
Structures Anorthite Ca( A1O2I2( Si02l2
L
 19

.. .
I
, ~

functions o f t shown i n Figure 2.1 (K2, A l , M4, M6).

Solubility is not a strong ure for temperatures below
i

a the critical p o i n t of water. The heat o f s o l u t i o n is 6.0 & 0.15 kcal/

mole for quartz (M4), and 3.35 kcal/mole f o r morphous s i l i c a (M6).
S i l i c a 'is also slightly soluble i n steam. However, a t saturation
pressures, this s is exceedingly low. Kennedy ( K 2 ) states
that:
The solubility of quartz i n saturated vapor i n equi-
1i bri um w i t h q u i d and w i t h crystal 1ine quartz-that i s ,
along the thr -phase boundary-is almost immeasurably
small u n t i l a temperature o f '370OC and pressure o f approxi-
mately 210 atmospheres are reached. From 370oC t o 374.110C
the s o l u b j l i t y i n the vapor phase increases rapidly along
the three-phase boundary, u n t i l at 374.11 the s o l u b
reaches the value o f the l i q u i d a t this temperature
perdent (230 ppm). A t the c r i t i c a l temperature and pres-
sure, the "liquid" and the "vapor" become indistinguishable,
and the solubility curves showing solubility o f quartz i n
liquid and quart vapor meet a t a p o i n t called the lower
critical end-poi f. the system.
Morey and Hessel gesser edy (K2) point out t h a t the s
b i l i t y 'of silica i n water is a strong function o f the f l u i d density.
As seen i n Figure 2.1, the quartz so ty in saturated water reaches
a maximum around 33OoC, and t h e n dro t i c a l tempera-
ng density o f
interval. Figure 2.2 (K2) is a
. on o f constant
a

. gas-phase density is r e a d i l y apparen

ate materials, Morey
and Hesselgesser report owing solubilities a t 5OO0C and 1000
LJ atmospheres: quartz, 2600 ppm;, opaque glass (amorphous s i l i c a ) , 4180
ppm; a l b i t e (sodium feldspar-NaA1Si308) , 770 ppm; and orthoclase
 20

1000

n
E 800
n
P
Y

I
a
i-,
( 0 '
5c
U
c 600
I
cr

400

200

0
0 100 200 300

Temperature ( " C ) t

* c
Figure 2.1 S o l u b i l i t y o f Q u a r t z and Amorphous S
as a F u n c t i o n o f Temperature
D a t a from: Kennedy ( K 2 )
Alexander e t . a l . ( A l )
Morey e t a l . (M5)
b.i
 'b c

G
 22

(potassium fel dspar-KAl S i 308) 760 ppm.

The solubilities of s i l i c a reported i n Figure 2.1 were determined
for essentially neutral solutions. Evidence o f s i l i c a content i n
natural waters suggests that pH has l i t t l e effect i n the range from 2
to 9 (W4, 11). However, Alexander, Heston, and Iler (A1 ) report that
the s o l u b i l i t y of amorphous s i l i c a is dramatically increased for pH's
greater than 9.0. T h i s increase i s most likely due to the-fo
s i l i c a t e anions as s i l i c i c acid monomer ionizes. Thus the
solubility o f silicic acid monomer is independent of pH. B u t , as the
pH of the solution approaches the PKA (the negative 1 garithm, base 10,
o f the acid dissociation constant) for the s i l i c i c acid monomer, the
s i l i c a t e anion concentration increases rapidly, and w i t h i t the t o t a l
amount of s i l i c a i n solution. For example, a t a pH of 10.8, the ratio

..
of s i l i c a t e anions t o neutral s i l i c i c acid molecules i s l O : l , and the
total solubility of s i l i c a is t h u s 11 times the s o l u b i l i t y o f s i l i c i c
acid monomer. Alexander e t a l . ( A l ) found excellent agreement between
this simple model and their experimental data.
On the basis of extensive geologic evidence, the solubility of
s i l i c a i n geothermal reservoirs seems t o be controlled by the s o l u b i l i t y
o f quartz (F2),. T h i s premise has been used t o predict reservoir temper-
atures by observing the quantities of s i l i c a present i n surface waters.
The "si1 ica geothermometer" was developed by Fournier and Rowe (F2) who
achieved good agreement between the estimated and measured maximum tem-
peratures a t depth f o r numerous h o t springs. Their calculations took
into consideration the enhanced si1 ica content i n Surface waters result-
'
ing from flashing that occurred as the brine traveled to the surface.
(Because the s i l i c a solubility i s so low i n steam, nearly a l l the s i l i c a
 o r i g i n a l l y present i n , the l i q u i d a t depth remains i n the l i q u i d p o r t i o n
of the well-head product.) Where no data were available, Fournier and

Rowe were able t o p r e d i c t the amount of steam formed by assuming an

adiabatic passage up the w e l l s thereby b e t t e r c o r r e l a t i n g t h e i r temper-
ature predictions w i t h observed data.
I ’

Assuming t h a t quartz s o l u b i l i t y i s c o n t r o l l i n g andsthat s i g n i f i -

cant q u a n t i t i e s - o f l i q u i d b r i n e can f l a s h on route t o the surface, one
would p r e d i c t tha he s i l i c a content i n residual brines a t the w e l l

head might range from 300 t o 1000 ppm for rese o i r s - t h a t range i n
emperature from 200’ t o 3OO0C (assuming greater than 70% l i q u i d w e l l -

head product). This i s c e r t a i n l y within the ange o f observations for

known geotherma systems. Interestingly, t h uartz sol ubi 1ity does

n o t appear s i g n i f i c a n t l y d i f f e r e n t i n concentrated e l e c t r o l y t e s than i t
n pure water. Fourniec and Rowe (F2), for example, f i n d no s i g n i -
t

f i c a n t d i f f e r e n c e f o r the solubi
solutions . K i tahara (K3) repor

I ,.

W rates o f fresh water,

and lower than e q u i l i b r i u m s o l u b i l i t y levels.)

 24

When the brine cools, i t becomes supersaturated w i t h respect t o

Ll
dissolved s i l i c a . One would then expect s i l i c a to preci
the solubility again corresponds to the quartz solubility a t the lower
temperature. However, geologic evidence (K5, W4) suggests t h a t the
precipitation of s i l i c a from thermal water is determined by the higher
solubil i t y level of amorphous si1 ica (Figure 2.1 ) . For this reason , as
Krauskopf (K5) states, 'I. . . s i l i c a may be carried indefinitely i n
solution i n surface waters a t concentrations f a r i n excess of the solu-
b i l i t y of quartz."
When the concentration o f monosilicic acid i n brines exceeds the
solubility'of amorphous s i l i c a f o r a given temperature, the s i l i c i c acid
' po'lymerites by a condensation reaction between two silanol groups w h i c h
l i n k s silicon tetrahedra together through an oxygen bridge (a siloxane
bond) :
I I I I
-Si-W + Ho-Si- -c -Si-0-Si- + H20
I I I I

The polymerization continues u n t i l the monomeric si1 ica content corres-

ponds to the s o l u b i l i t y value of amorphous silica.* A t this p o i n t the
monomeric s i l i c a i s i n equilibrium w i t h h i g h l y polymerized s i l i c a which
attains a colloidal size. White, Brannock, and Murata (W4) have exten-
sively reviewed the polymerization of s i l i c a i n natural waters. They
s t a t e that :
In supersaturated solutions a t low temperature, mono-
meric s i l i c a polymerizes slowly t o colloidal s i l i c a . The
rate may be almost infinitely slow i n acid water and i n

*Great uncertainty i s indicated i n the geologic and chemical'litera-

ture as to just what form of s i l i c a constitutes "soluble silica". The
convention adopted here equating soluble s i l i c a t o monomeric s i l i c a is
the one most often used. However, i t i s not entirely correct, as will
be shown i n subsequent chapters,.
 25

solutions that are only mod tely supersaturated. The rate

of polymerization is increa by high ptl, h i g h temperature,
rsaturation, and contact w i t h some other
opal--"the naturally occurring form o f
eneral ly w i t h less than 12%water" (K5) .)
of colloidal s i l i c a is favored by h i g h
t a c t w i t h opal.
fed the effect of tempera r e on the nature o f
s i l i c a precipitated from aqueous solutions, and reported: ,
Opal -and gelatinous s i l i c a are formed when s i l i c a is
deposited with-relative rapidity. Opal i s favored by low
temperature. I t occurs a t temperatures as h i g h as 140oC,
b u t i t is unstable and i s converted slowly t o chalcedony o r
quartz. Opal is probably formed from monomeric or, more
' probably, the smaller polymeric molecules o f silica. Evi-
dence is lacking for the direct conversion of gelatinous
s i l i c a to opal a t room temperature. Formation of q u a r t z is
believed to be favored by relati gh temperature, slow
rate of deposition, and low degr upersaturation, and
i s probably formed directly from meri c mol ecul es .
Chalcedony is probably formed fr rs that are rather
strongly supersaturated w i t h respect t o quartz. The rate

s i l i c i c acid i solution. He has studied both the

d i n acid neu- I

rm i s equal t o the equili

,nature, the precipitation of s i l i c a by' cooling'and evapora-

W ion is observed on the aprons of ma
inous s i l i c a is sometimes found i n
springs, and also has been reported from cavities and fis-
sures underground.
 26

The polymerization of s i l i c i c acid involves s p l i t t i n g out a water

b
molecule between silanol groups on two silicon atoms, leaving a silo-
xane 1inkage. Because each monosil icic acid molecule contains four
A
silanol groups (a functionality of four), polymerization w i l l yield a
highly branched polymer structure, as opposed t o straight 1inear chains.
(Flory ( F l ) has shown that branching can occur when the functionality of
the monomer exceeds 2, the minimum necessary for polymerization.) In
highly concent ed solutions of silica (usually greaterthan 0.5% by
weight SiOp), this branching yields an infinite three-dimensional poly-
mer structure which results i n a gel. Less concentrated s i l i c a solu-
tions (more typical of ones found i n nature) yield solutions ("sols") of
colloidal s i l i c a particles. M i t h diameters somewhere i n the range o f
1 t o 100 mu, these particles are remarkably stable under certain condi-
tions (11). Carman (Cl) has given a consistent theory of amorphous
si1 ica structures, including the constitution of colloidal si1 ica
particles formed from the polymerization of s i l i c i c acid. He pictures
these particles as dense spheres containing an amorphous Si02 interior
which results from the complete condensation of silanol groups. The
particle surface is covered w i t h unreacted silanol groups.
The formation of s i l i c i c acid sols is likely t o be an important
intermediate step i n the formation of si1 ica scales from supersaturated -
brines. Therefore, the s t a b i l i t y o f s i l i c a sols is o f fundamental
importance i n hand1 ing geothermal brines. Krauskopf (K5) reports from
geologic evidence that "cclloidal s i l i c a may be precipitated by evapor-
ation, by coprecipitation w i t h other colloids, and by f a i r l y concen-
trated solutions of electrolytes." In comparison to other rates,
agglomeration of a s i l i c a sol by electrolytes i s f a s t a t pH's greater
L
 I , 27

Ld
than 6. Monomeric s i l i c a i n excess of i t s solubility reacts relatively
quickly i n the presence of colloidal s i l i c a , bu is not affected by
b electrolytes except where insoluble metal si1 icates are formed (K5).
Okamoto, Okura, and Goto (03) report that "aluminum has a remark-
*
able effect on the behavior of silica, especially when the l a t t e r exists
lloidal s t a t e , which can be precipitated by a mere trace of
aluminum." The -authors were able to establi i t i c a l ratio of alum-
inum to s i l i c a below which precipitates d i d . They also
observed that i n strongly basic solutlons, a ion reduces the
r a t e o f dissolution. These results are extended to the precipitation of
s i l i c a i n thermal s p gs; the authors s t a t e , d i n g o r on changing
pH, the water becomes supersatured w i t h qnd i t poly-
zes into colloidal form, i n which case i t may be precipitated by
quite a small amount o f aluminum or other trivalent cations, forming a

he effect o f various

he s i l i c a parti-
.

b,
 28

surface becomes positively charged a s i t adsorbs free hydrogen ions.

A t an intermediate pH, the colloidal particles contain no net surface
charge. The position of this so-called isoelectric p o i n t has been a
1
source of widespread controversy. Parks ( P l ) reports t h a t the best
value for the isoelectric p o i n t of silica is 2.0, based on 1

literature survey. On the other hand, Iler (11) has stated that the
apparent isoelectric p o i n t of colloidal si1 ica formed from commercial
'
s i l i c a t e s l i e s between 4 and 5 depending on the age of the sols. The
reason for the discrepancies i n the reported isoelectric points probably
stems from the f a c t that the measurements were influenced by contaminat-
i n g electrolytes i n solution. I t i s also noted t h a t distinctly differ-
ent forms of amorphous s i l i c a were used i n the various experiments.
In high-pH solutions, the negative charge o f s i l i c a colloids pro-
duces a mutual repulsion w i t h resulting stability. If cations are
added to the solution, they can adsorb onto the surface o f the colloids
and reduce the effective charge. Mutual repulsion i s not as strong, and
the sols can agglomerate t o produce larger particles. When the dia-
meters of the aggregated particles exceed 150 - 200 mp, settling gener-
a l l y occurs (11). T h i s type of agglomeration, which is generally char-
acterized by electrostatic interaction, has been termed "coagulation"
by LaMer ( L l ) . Flocculation, on the other hand, acts by a chemical .
bridging mechanism i n which the ends of a separate chemical species
1
adsorb onto two different colloid particles and thereby provide a l i n k .
,'LaMer is careful to d i s t i n g u i s h between these two different processes,
for the resulting precipitates are quite different.
At pH values between 2 and 5, where the sols have seemingly l i t t l e
ge, I l e r claims t h a t electrolytes have l i t t l e effect
LJ
a t t r i b u t e s sol s t a b i l i t y i n t h i s region t o low concentrations o f hydr-

oxide ions which catalyze the ndensation o f two s i l a n o l ' groups t o

y i e l d a siloxane linkage (as w i l l be seen ,shortly when the mechanism o f

polymerization i s discussed). A l l e n and M a t i j e v i c (A6-A8), however,

demonstrated - a t cations do have an appreciable f f e c t on sol s t a b i l -
u l a t e t h a t cations i n s o l u t i o n exchange w i t h hydrogen
face silanol-oxygen atoms. They d t h a t o n l y a small

f r a c t i o n of the surface hydrogens have t o be exc d before i n c i p i e n t

destabil i z a t i i s achieved, an observation whic ees w i t h t h a t o f
Stumm andHahn ( H l ) . A l l e n and M a t i j e v i c a t t r i b u t e stability of

pH, i n t h e absence o f e l e c t r o l y t e s a t i g h t covering

h i c h hydrogen-bond t o t h e s u r f i l a n o l groups and

i c l e s with a p r o t e c t i v e layer. Cations adsorbing on
the surface d i t h i s l a y e r and produce i n s t a b i l i t y .
The r e s u l t s o f A l l e n and M a t i j e v i c i n Figure 2.3
e e f f e c t o f e l e c t r o l y t e concentrati H on c o l l o i d
a b i l i t y regions were establ i s h e hour a f t e r the
1 and e l e c t r o l y t e . Above the the s o l s are
pitate. Below the l i n e stable. With

would also be caused by more conc ed sols while

ons o f s i l i c a would y i e
rom thosc o f Figure 2.3
valent cation e more effective i n causing p r e c i p i t a t i o n than mono-
valent cation Notice t h a t f o r pH's greater than , as l i t t l e as 8

an p r e c i p i t a t e a s o l u t i o n containing 2000 ppm c o l l o i d a l

 I

OE
 . .

sflica. The sol used i n these experiments was Ludox HS (E. I. duPont
ours & Company). The concentration of s i l i c a i n solution was 2000
ppm, the particle diameter was 15 mp, and 'the BET surface area was 210
m2/gm. T h i s diameter and area taken together indicate a particle den-
s i t y of 1.9, slightly less than the density of amorphous s i l i c a , 2.2.
a density of 2.655.)
results show that of the monovalent cations ( L i , Na, K, Cs),
the heavier species are more effective as coagulants; they are less
readily hydrated, and can more effectively neutralize the negative
charge on the colloidal particles (11, A7). Hydrolyzed polyvalent
L
cations (e.9. A1 (OH)? Fe(OH) ) are more effective precipitating
agents than non-hydrolyzed cations (e.g. AI", Fe") (02); and aggrega-
tion of sols by these species can occur by both coagulation and floccu-
chanisms, de ding on the pH range and the state of the
. 1

hydrated species (H1 ). When hydrolyzed cations are present, polymeri-

etween hydroxide groups of the cation and silanol
groups o f the colloid. dging mechanism belongs under t h e
metal hydroxide
species are prevalent. ns are unhydro-

. lyzed, electrostatic a t
"coagulation type" precipitate.
oncentration of on associated w i
salts (ct', so rs t o have no
ity, except i n cases where the anion can complex w i t h t h
form a different adsorbing species, e.g. A l S O i (A8).
kd Scat e-Formation Pathways
A t this stage i t is important to r e l a t e these physical and
 32

chemical observations on the behavior o f s i l i c a i n aqueous s o l u t i o n t o L

scale formation i n geothermal brines. I n the absence o f proven scale-
formation mechanisms, the following mechanisms have been postulated by
L

the author as a basis f o r subsequent experimental study. Figure 2.4

i s a schematic representation o f the conceptualized steps entering i n t o =

the formation o f scale.

S i l i c a dissolves from the r e s e r v o i r rock a t r e l a t i v e l y high tem-
peratures and enters t h e aqueous phase as predominately s i l i c i c a c i d
monomer (Step 1 i n Figure 2.4). The s o l u b i l i t y o f quartz generally
c o n t r o l s the t o t a l s o l u b i l i t y l e v e l o f s i l i c a .
As the s o l u t i o n moves toward the surface and drops i n temperature,
s i l i c a may p r e c i p i t a t e by a v a r i e t y o f mechanisms. I f there are high
concentrations o f metal ions i n t h e brines, r e l a t i v e l y insoluble metal
s i l i c a t e s might p r e c i p i t a t e abruptly. Some metal s i 1 i c a t e s o l u b i l i t i e s
may depend more s t r o n g l y on temperature than t h e quartz s o l u b i l i t y does,

and thus could supersaturate more r a p i d l y upon cooling - Step 2. (Per-

t i n e n t data on m e t a l - s i l i c a t e s o l u b i l i t i e s are lacking, however.) Some
evidence suggests t h a t o n l y s i l i c a t e anions can p r e c i p i t a t e w i t h metal
catidns, and thus pH may be an important f a c t o r (11, K5, 03, W6).
A l t e r n a t i v e l y , i f metal ions (notably i r o n ) are contributed by
t h e presence of corrosion products inside metal piping, metal s i l i c a t e s -
might form on the pipe surface which acts as a stationary nucleation
*
s i t e (Step 2 ' ) . Such effects have been observed i n geothermal wells.
Also, sodium s i l i c a t e has been added t o water systems f o r more than
f i f t y years t o a r r e s t corrosion i n steel piping; the p r o t e c t i v e s i l i c a

scale required has been shown t o form only on an already corroded sur-
1
face (Lehrmn and Shuldener, L2). For i r o n pipes carrying thermal
 e r i z a t i o n --
- -No- -P o-l-y m- ---- --.- I - - s i 0-2 )--" ---
(Low
-

Metal S i l i c a t e S c a l
I

I
I

Reservoir F l u i d R e - E n t r y Zone

*Floc may be present.

.Fi gure 2.4 Sca 1@-Formation Pathways

 34

brines ( a t 86 t o 130°C) from hot springs i n Iceland, Hermannsson (H3)

L
has r e l a t e d s i l i c a - s c a l e formation t o waters t h a t had high dissolved
oxygen content. He suggests t h a t dissolved oxygen i n these waters
f i r s t promotes corrosion o f the pipes which subsequently can promote
the formation o f metal s i l i c a t e scale. The pH o f these Icelandic waters
was 9.3, and the s i l i c a content ranged between 70 and 150 ppm.
Other opportunities f o r scaling a r i s e when geothermal brines
become supersaturated w i t h s i 1 i c a through cooling o r through concen- I

t r a t i o n by vaporization. Geologic evidence suggests t h a t monomeric

s i l i c a w i l l polymerize o r p r e c i p i t a t e u n t i l the amorphous s o l u b i l i l i t y
i s reached, for temperatures up t o 14OOC. Above t h i s temperature amor-
phous s i l i c a i s no longer metastable and i s converted t o - c r y s t a l l i n e
quartz a t an undetermined rate. I t may be t h a t the quartz s o l u b i l i t y

i s c o n t r o l l i n g a t temperatures greater than 140°C. Monomeric s i l i c a may

p r e c i p i t a t e d i r e c t l y from supersaturated solutions i f a c t i v e s i t e s ( i .e.
r e a c t i v e OH groups) are already available. This " p r e c i p i t a t i o n " i s

a c t u a l l y the formation o f a siloxane bond between a reactive'0H group on

the a c t i v e s i t e and one o f the s i l a n o l groups o f the monomeric s i l i c i c
a c i d (Step 3). Previously formed s i l i c a scale, corroded surfaces,

c o l l o i d a l p a r t i c l e s , o r any amorphous s i 1 i c a present could provide an

,
active site.
I f no a c t i v e s i t e s are present, s i l i c i c a c i d w i l l polymeri
s o l u t i o n t o form c o l l o i d a l s i l i c a (Step 4). The c o l l o i d a l s i l i c a may
f u r t h e r polymerize t o p r e c i p i t a t e by i t s e l f i n the form o f a gel
mass (Step S), o r i t may be p r e c i p i t a t e d by the presence of small

amounts of polyvalent cations such as Ca, Mg, Fe, o r A1 (Step 6). The,
p o s s i b i l i t y even e x i s t s t h a t the s i l i c a may not p r e c i p i t a t e a t a l l , but
L
-
 35

U
will instead remain i n solution as the brine passes through the plant
and is reinjected into the ground.
s Uhich one o f these scaling mechanisms prevails will be highly
dependent on the rates o f the individual steps, and these i n t u r n will
*
depend on the temperature and the chemical nature o f the brine. All
the arrows i n Figure'2.4 represent rate processes. If a l l o f the pre-
cipitation rates are slow compared to the residence time o f the brine
i n its circulation loop, no precipitation will occur. The rates that
are fast compared t o this residence time will inevitably contribute to
scale deposition. To predict the locations and characteristics o f
cale formation i t is important t o know the rates of a l l potential
scale-forming reactions, data which today are almost completely lacking.
Steps 3, 4 and 5 i n Figure 2.4 a l l invo he "condensation"
reaction between pairs of silanol groups t o iloxane 1inkages.
f, this polymerization reaction appears t o have a large effect
on the rate o f ica scale deposition from geothermal brines. The
and the perti-

I , and co-workers
,

can be extended
ever, much a d d i -
W tional work is necessary for a full understanding. Vail ( V l ) has
extensively reviewed the precipitation o f low-molecular-weight si1 icate
 36

I
1
ions w i t h metal s a l t s (Step 2), b u t l i t t l e seems t o be known about the
~

I
I
Lid
r a t e o f these reactions. One would tend t o conclude t h a t these reac-
tions, being i o n i c interactions, are r e l a t i v e l y fast. Le
Shuldener (L2) and Woods e t a l . (W6) have s u p e r f i c i a l l y investigated
Step 2 ’ , but a d d i t i o n a l work remains t o be done.
S i l i c a Polymerization: Formation of S i l i c i c Acid Gels
The aggregation o f s i l i c a sols t o form s o l i d gels has been

observed for more than 200 years (11). Thomas Graham, one o f the found-
ers o f the modern f i e l d o f c o l l o i d science, published a paper on the
formation of s i l i c a gels i n 1864 (62, 11). However, o n l y i n - t h e l a t e
1930’s was gel formation a t t r i b u t e d t o the polymerization o f s i l i c i c
a c i d (H4, F3). Subsequently, Carman gave a remarkably c l e a r exposition
on the c o n s t i t u t i o n o f s i l i c a gels ( C l ) . He wrote:
Formation o f s i l i c a gel can be regarded as taking
place i n two stages. In the f i r s t , i n i t i a l l y formed
S i (OH)4 condenses (condensation polymerization reaction
between s i l a n o l groups t o form siloxane bonds) t o c o l l o i d
p a r t i c l e s . I n a d i l u t e s o l u t i o n a f u r t h e r slow increase i n
p a r t i c l e s i z e i s the o n l y subsequent change, but, a t a con-
c e n t r a t i o n of about 1% s i l i c a , these primary p a r t i c l e s are
i n t u r n able t o condense together t o give a very open but
continuous s t r u c t u r e extending throughout the medi urn and
thereby t o bestow a c e r t a i n degree o f r i g i d i t y upon it. I n
I
both stages, the mechanism i s the same, i.e. condensation t o
form Si-0-Si l i n k s ; but i n the f i r s t stage, condensation leads
1 ,to p a r t i c l e s of massive s i l i c a while, i n the second stage,
since i t i s n o t possible t o f i t two p a r t i c l e s accurately
1I together over a common face, t h e numberof S i - 0 - S i l i n k s .
between primary p a r t i c l e s are fewer i n number than those
within the p a r t i c l e s themselves. They are merely s u f f i c i e n t
t o bind adjacent p a r t i c l e s i n a f i x e d p o s i t i o n r e l a t i v e t o %

one another and thereby t o lead t o a r i g i d , highly-porous,

tangled network of branching chains. They are n o t strong
enough t o withstand s t r a i n s produced when the gel i s dried,
SO t h a t adjacent primary p a r t i c l e s break apart and take up
new and more strongly bonded positions i n which each i s
1
joined t o a greater number of neighbors, i.e., t h e gel
undergoes- shrinkage.
C
LJ
I
I
I
 37

... The properties of a gel depend upon its his-

tory, e.g. upon the concentration of the original reagents.
When a gel is formed by mixing concentrated solutions, an
s
immense number o f nuclei are formed close to one another,
so that primary particles are unable t o reach as large a
size a s w i t h more d i l u t e reagents. Even i f the l a t t e r gel
1
is subsequently dried to the same proportion of water, the
larger size of i t s primary particles will give i t a some-
what more weakly bonded structure and coarser texture.
Further, i n the a c t of gelation, t h e more concentrated and
hence more r i g i d gel is unable t o accommodate stresses s e t
up between initiation and completion of gelation. Readjust-
ments o f internal linkages give rise to a spontaneous shrink-
age o r syneresis which i s most marked for concentrated gels.
The polymerization of s i l i c i c acid has been studied extensively by
a variety of techniques. These include measurements of 1i g h t scatter-
ing, freezing-point depression, gel -point time, and depletion o f mono-
s i l i c i c acid concentration w i t h time. The formation o f gels provided
the i n i t i a l evidence of polyme ation, and i t was the first technique
utilized for the study of erization rates.
Silica gels can be p ralizing a soluble sodium (or
potassium) s i l i c a t e solut . Sodium s i l i c a t e solution, a comnon
comnercial product former referred to as "water glass", has wide
industrial application i n detergen es, paper products, s i l i c a
cements, coatin

ht. These solu-

8
tions a r e stabilized a t high metals; the
i n solution is
comnercial products,
1:l.
Ld When a highly alkaline solution of sodium s i l i c a t e i s neutralized
w i t h acid, a solution of lownolecular-weight si i c acids and of the
 38

sodium s a l t o f the a c i d o r i g i n a l i s produced. The i n i t i a l degree o f L/

polymerization o f s i l i c i c a c i d depends on the r a t i o o f Na20 : Si02 i n
the sodium s i l i c a t e solution. Debye and Nauman (01-03) have shown t h a t
1

the degree o f aggregation o f s i l i c a i n sodium s i l i c a t e increases as the

r a t i o o f Na20 t o Si02 decreases. A t the metasilicate r a t i o ( l : l ) , solu- *

b l e s i l i c a t e ions contain a s i n g l e s i l i c o n atom. For a 1:3.3 s o l u t i o n

o f sodium s i l i c a t e , Debye and Nauman (03) have shown by a l i g h t -
s c a t t e r i n g technique t h a t the weight-average molecular weight* i s 325

(compared t o molecular weights o f 60 f o r Si02 and 96 f o r Si(OH)4. Iler

( I 2 ) , i n freezing-point measurements on a s i m i l a r s o l u t i o n prepared from
1:3.3 sodium s i l i c a t e , found a degree o f polymerization** o f 3.25.
Assuming t h a t t h i s corresponds t o a number-average molecular weight* o f
288 (weighted average o f Si302(0H)8 and Si403(OH)10), the r a t i o M /M =
w n
3251288 = 1.13. I f these numbers are correct, the above r a t i o implies
t h a t there i s some d i s t r i b u t i o n o f molecular weights i n a 1:3.3 sodium
s i l i c a t e solution. (A r a t i o o f 1 indicates t h a t a l l the molecules are
t h e same size, i.e. the s o l u t i o n i s monodisperse.)

Under appropriate conditions, neutralized sodium s i l i c a t e solutions

w i l l gel. Hurd and collaborators (H5-H10) have investigated the v a r i -

ables which a f f e c t the r a t e of gelation. They defined the gel t i m e a s

t h e moment a t which a s t i r r i n g rod, suspended a t a 20 degree angle from .

s

*In r e f e r r i n g t o average molecular weight o f a polymer, there are two

s t a t i s t i c a l averaging processes commonly u t i 1ized. The number-averaged
technique uses the number d i s t r i b u t i o n o f p a r t i c u l a r polymeric molecules
as a weighting function i n t h e averaging process. The weight-averaged
technique uses the weight d i s t r i b u t i o n o f polymeric species as the
weighting function.
**The degree o f polymerization equals the number-average molecular weight i d r
divided by the molecular weight o f the average repeat u n i t .
 39

the vertical, fails to fall under its own weight. Other investigators
studying gelation employed equally qual itative techniques; Merrill and
c
Spencer (M2) used the criteria of "loss of uniform flow, the appearance
z of breakage planes when the mixture was tilted, and the adherence of
solid gel to the glass wall," while Moulik and Ghosh (M7) recorded the
time at which a glass sphere failed to fall through a gelling solution.
Although it is difficult to compare quantitatively the results o f these
studies, the reproducibility of the experiments within each study was
quite good.
For any one silica concentration, gel times based on a consistent
gel-point criterion (e.g. the "tilted rod method") correspond to the
same average degree of polymerization, and therefore are inversely pro-
portional to the average rate of polymerization. However, ller (12)
has shown experimentally that consistent gel times for two different
concentrated solutions do not correspond to the same average degree of
polymerization ( 5 .e. same ex'tents of conversion), and therefore the
ratio o f the average polymerization rates .is n the inverse
ratio o f the gel times. Iler compared gelled which had the
e number-average molecular weight, based on odified freezing
* point determination, and fou
rittle, whereas th ons gave gels which
. ly soft and weak."
oint criterion establ i at a specific degree
o f polymerization for dilute concentration, the same gel -point cri ter-
ion will yield a gel time in more concentrated solution that corres-
W
ponds to a lower degree of polymerization. The relationship between
gel-point and degree of polymerization will be discussed in more detail
 40

i n Chapter 5.
The e a r l y gel time studies established a s t r i k i n g dependence on
pH o f polymerization r a t e . Figure 2.5 (M2) presents some t y p i c a l
.
results. I t shows t h a t the r a t e of polymerization i s highest near the

neutral point, and t h a t more concentrated solutions polymerize f a s t e r . I

A1 though not shown i n Figure 2.5, other experimental r e s u l t s i n d i c a t e

t h a t t h e polymerization r a t e reaches a minimum value i n the pH range o f

1 t o 3, and increases a t s t i l l lower pH (H7, 12, A2). Hurd and Sheffer

(H9) have shown t h a t the polymerization r a t e i n the pH range from 4.5
a
t o 6.5 i s proportional t o (OH-) , where CY varies from 0.9 t o 1.7. The
data are d i f f i c u l t t o i n t e r p r e t accurately because the pH o f the poly-

merizing solutions increased during the course o f the reaction. This

'pH r i s e i s t y p i c a l o f g e l l i n g solutions, and Hurd, Frederick, and Haynes
(H6) have attempted t o explain i t by assuming ( i n c o r r e c t l y , as w i l l be
shown) t h a t higher-molecular-weight s i 1 i c i c acids are weaker acids. In
the strongly a c i d i c range, pH - 0.5 t o 0.5, Hurd and Barclay (H7) r e p o r t
t h a t the average polymerization r a t e i s f i r s t - o r d e r i n hydrogen i o n con-
c e n t r a t i o n when H2S04 i s used t o a c i d i f y the sodium s i l i c a t e solution,
and third-order when HC1 i s used. These r e s u l t s suggest t h a t the reac-
t i o n i s catalyzed by c h l o r i d e ion. For polymeritation i n basic medium,
Hurd e t a l . (H10) found a maximum average r a t e a t pH 8.3, above which .
t h e r a t e decreased with hydroxyl i o n concentration t o the 1.7 power

(H8). Above pH 11 no gel formation was observed f o r an SiOp concentra-

t i o n o f 3.8%.

Higher temperatures increase the r a t e o f polymerization, and many

workers have determined an apparent a c t i v a t i o n energy i n the range from
L
0 t o 5OOC.
' By p l o t t i n g the logarithm o f the gel time versus the
41
 42
,

reciprocal o f t h e absolute temperature, good s t r a i g h t l i n e s are LiJ

obtained i n many cases. Nevertheless, such reported " a c t i v a t i o n

energies" a r e n o t t r u e a c t i v a t i o n energies, because they cannot be

associated w i t h a s i n g l e chemical reaction. The apparent a c t i v a t i o n
energies have been found t o depend on pH. Moulik and Ghosh (Ma) r e p o r t
an apparent a c t i v a t i o n energy of 9 kcal/mole a t pH 1.7, i n good agree-
ment w i t h Hurd and Barclay (H7) who r e p o r t a range o f 9-11 kcal/mole

f o r pH's l e s s than 1. For the pH range from 3 t o 5, Hurd e t a l . (H6)

I
r e p o r t the average value of 17 kcal/mole, but t h e i r data show a steady
decrease from 20 kcal/mole t o 15 kcal/mole over t h a t range.
S i m i l a r l y , Munroe e t a l . ( M l l ) , using attainment o f a specified
Young's modulus as a c r i t e r i o n f o r gel time, r e p o r t an apparent a c t i v a -
t i o n energy of 15.2 kcal/mole a t pH 5.6, and 9.4 kcal/mole a t pH 8.2.
Hurd e t a l . (H10) a l s o r e p o r t that, above pH 10.5, gel times increase
w i t h increasing temperature. They o f f e r the p l a u s i b l e explanation t h a t

i polymerization i s r e a d i l y r e v e r s i b l e a t high pH, and t h a t thedepolymeri-

.e.,
t a t i o n r e a c t i o n i s favored a t higher temperature (i polymerization
i s an exothermic reaction). This i s i n accord w i t h the p o s i t i v e heat o f

s o l u t i o n measured f o r amorphous s i l i c a by Morey e t a1 . (M6).

Molecular-Weight Determinations
Disadvantages of the gel-time method are t h a t i t indicates o n l y an .
averaged p o l m e r i z a t i o n rate, and t h a t the c r i t e r i a f o r establishing the
a
gel time a r e h i g h l y empirical. There are many possible condensation
reactions occurring during the course o f gelation, and gel times give

o n l y a macroscopic view of a very complex microscopic process. There-

fore, more q u a n t i t a t i v e methods have been sought. Greenberg (64) noted
t h a t t h e r e f r a c t i v e index o f a s i l i c a s o l u t i o n changes w i t h
Lm
iJ
 43
. .

polymerization, and used this change to monitor the polymerization

rate. He found, for the pH range 9.4 - 10.8, that the rate of forma-
tion of siloxane bonds was inversely proportional to the hydroxide ion

c
concentration. .
Brady e t a1 (85) used a 1ight-scattering technique t o
monitor changes i n the weight-average molecular weight of polymeric
s i l i c a w i t h time, and found the fastest r a t e t o occur a t pH 8. They
also report apparent activation energies of 15.5, 9.6, and 14.6 kcal/
mole a t pH's 5.5, 8.5, and 10.5 respectively. Using similar techniques,
Greenberg and Sinclair. (65) found a maximum r a t e of polymerization a t
pH 8.6, while Debye and Nauman (D4) report a value of pH 7.6. Bechtold
(Bl) reported a s t i l l lower value of pH 5.3 for the maximum rate of
polymerization. These maximum-rate pH values span the range that was
found f o r gel - t i m experiments
Alexander (A2) and I l e r (12) used a freezing-point technique t o
measure changes i n the degree of polyrn tation a t low pH. Alexander
measured a minimum rate o f polymerization a t pH - 2 a t 2OC. He
I

at the point um rate s h i f t e d t o lower PH a t higher

s. T h i s observation was found t o be consistent w i t h the gel-
time results which indicated wer acti.vation energy a t lower pH.
that two different mechanisms were responsible for
I

catalyzed by hydro-
4

strongly acidic

strated their catal t; he reported a minimum rate of this cata-

44
 44

Rate of Decrease of Ronomer Concentration

The experimental techniques cited for the study of silica poly-
merization all suffer from one common drawback-the silica concentra-
tion required is high, greater than 0.5%. This value far exceeds the
ntration limit expected in geothermal brines. There is no evidence ~

that polymerization in dilute solution will behave in a manner analogous

to concentrated solutions, or that one can simply extrapolate trends
found for concentrated solutions. It is therefore advantageous to study
silica polymerization at concentration levels more closely related to
natural systems. Dilute-concentration behavior should permit a closer
f the detailed polymerization mechanisms, which can then be
extended to all concentration ranges.
A number of polymerization studies in dilute solution have been
reported in the literature. The technique utilized measures the
decrease in monomer as a function of time. Its advantage over previous
methods is that it measures the rate o f depletion o f a known reactant,
monosilicic acid, rather than measuring the rate of accumulation o f an
undetermined product, polysilicic acids and colloidal particles. The
disadvantage is the difficulty of preparing pure-monomer starting solu-
tions and measuring only the monosilicic acid concentration in a solu-
tion o f polysil icic acids. The method utilizes a standard colorimetric -
technique for the determination of monosil icic acid which was discovered
by Jolles and Meurath (52) in 1898. Silicic acid monomer will react

with molybdic acid to produce a colored silicomolybdate complex,

H4(SiMo,2040) whose concentration can be determined colorirnetrical ly
(S6). The method is not as straightforward as indicated here, and a
fuller discussion of the proper interpretation of colorimetric data will
L
LJ

'

W
 46

coefficients could be extracted from h i s data which yielded a l i n e a r LJ

Arrhenius p l o t over t h e f u l l temperature range, g i v i n g an energy o f
a c t i v a t i o n o f 10 2 1 kcal/mole. This f i g u r e agrees well w i t h those
-
reported by Munroe e t a1 . (Mll) and Brady e t a1 . (B5). When the cor-
r e c t c a l c u l a t i o n s are performed, Bishop's raw data y i e l d an apparent
second-rder r a t e c o e f f i c i e n t a t 25°C o f 28.3 x liters/mole/sec

(83). Bishop's raw data do i n d i c a t e t h a t there i s a c a t a l y t i c e f f e c t

o f c h l o r i d e ion, as has been suggested previously (H7), b u t here too,
h i s r e s u l t s appear inconsistent .
Polymerization Mechanism and Reaction Order
I t has been i n d i c a t e d t h a t several workers analyzed t h e i r data
according t o a second-order r a t e model. However, the experimental
r e s u l t s as a whole a r e f a r from conclusive as t o the r e a c t i o n order f o r
t h e polymerization o f s i l i c i c acid: estimates have ranged from 1 t o 3
f o r the r e a c t i o n order o f s i l i c i c acid. The data o f Hurd and Sheffer
(H9) and f i l e r r i l l and Spencer (M2) suggest a r e a c t i o n third-order i n
s i l i c a , i n the pH range from 4 t o 6, on the basis t h a t a p l o t o f the
logarithm o f the gel time versus the reciprocal square o f the t o t a l
s i l i c a concentration y i e l d s a s t r a i g h t l i n e . (This reasoning i s over-
s i m p l i f i e d because gel points f o r d i f f e r e n t t o t a l s i 1 i c a concentrations

do n o t correspond t o t h e same average degree o f polymerization, as pre- .

v i o u s l y noted.) However, i n the same pH range, Alexander (A2) observed
t h a t the degree o f polymerization varies l i n e a r l y w i t h time, i n d i c a t i n g
a second-order reaction. I n the acid-catalyzed region, f o r pH's l e s s
than approximately 2.5, Alexander found t h a t the r e a c t i o n r a t e i s t h i r d -
order i n s i l i c a - a r e s u l t t h a t agrees w i t h the observations o f I l e r (12)
V
and Moulik and Ghosh (M7). Katahara (K4) reported t h a t the .
 47

polymerization reaction is second-order i n s i l i c a i n acidic medium, b u t

third-order i n basic medium. On the other hand, a t high pH (above 9 . 5 ) ,
Greenberg's (64) refractive-index data suggest that the rate i s f i r s t -
,order i n s i l i c a . T h i s is i n direct opposition t o the results of
.
Okamoto e t a l . (03) who claim t h a t Goto's ( G l ) empirical kinetic model
suggests a reaction third-order i n si1 ica. o complicate the picture
even more, some authors have confused the total reaction order w i t h the
reaction order o f si1 ica alone (B2).
With regard to the effect of pH, there appears t o be more agree-
ment, however, the reaction order hydroxide ion has not been conclu-
sively established. The bulk of the dat ggest that hydrogen ions
catalyze the reaction below pH 2.5; also a t hydroxide ions catalyze
i n the weakly acidic region, and retard n strongly basic medium.
The pH corresponding to a maximum rate o f polymerization i s a p o i n t of

silicic acid. As

*
egion where the rate is

i n solution. For a t this pH, the numbers of ionized and unionized mole-
W
cules a r e equal. (This view Ss obvi ly over-simp1 ified because
 48

'
polymerization y i e l d s a d i s t r i b u t i o n of molecular sizes f o r which the
L'l
i n d i v i d u a l pKA's w i l l probably d i f f e r . ) Above t h i s pH there are excess
ionized molecules, and below t h i s pH there are excess unionized mole-
*
cules. I n both cases the r a t e o f c o l l i s i o n s between reactants w i l l be
I

reduced, and therefore polymerization w i l l ' be slower. This simple -

mechanism also accounts f o r a r i s e i n pH during polymerization which

has been observed by numerous authors (H6).

I l e r (11) has o f f e r e d an i n t e r e s t i n g t w i s t t o the mechanism shown
i n Equation 2.1 which allows i t t o be extended t o the acid-catalyzed
I

region, where Alexander (A2) has proposed t h a t a s t r u c t u r a l l y d i f f e r e n t

mechanism i s c o n t r o l l i n g . He adopts a hypothesis, . f i r s t suggested by
Treadwell and Wieland ( T l ) and l a t e r r e i t e r a t e d by Weyl (W2), t h a t

$
s i l i c o n may have a coordination number o f s i x w i t h respect t o oxygen

I atoms i n the form o f hydroxyl groups. I n Weyl's words:

W. B. Treadwell and W. Wieland ( T l ) published a study
o f s i l i c i c acids and mentioned the coordination requirements
as a d i s t i n g u i s h i n g feature between the chemistry o f carbon
l and t h a t o f s i l i c o n . ... S i l i c o n has the coordination number
o f f o u r i n s i l i c a t e s , but s i x i n f l u o r o s i l i c a t e s . . . Neither
the authors themselves nor l a t e r workers i n t h i s f i e l d paid
s u f f i c i e n t a t t e n t i o n t o the coordination requirement o f
s i l i c o n as the f a c t o r which i s responsible f o r the poljmeri-
zation. .. Why i s the molecule Si(OH)4' unstable? I t meets
the requirements o f tetravalency o f s i l i c o n and the Si+4
i o n i s surrounded by f o u r 0-2 ions. However, the coordina-
t i o n number o f the S i + 4 i o n i s six, i f the anion i s single
charged, small, o r i f i t has low p o l a r i z a b i l i t y . For t h i s s

reason, s i l i c o n has a coordination number o f s i x w i t h respect

t o fluorine. The OH' group has a great s i m i l a r i t y t o the
F' ion. .. The two. .. are equivalent i n many structures
The i n s t a b i l i t y o f the (monosilicic acid) molecule
Si(0H) i s the r e s u l t o f the incomplete coordination o f
s i l i c o 8 w i t h respect t o OH' ions.
Employing t h i s n o t i o n t o revisual i z e the s t r u c t u r e o f the s i 1 i c a t e
anion, I l e r (11) proposes the following reaction f o r converting s i l i c i c
a c i d monomer t o monosi 1i c a t e ion:
Lid
 49

Lid

. OH
I
HO-Si-OH +..HZ0 + OH-* (2.2)
I
OH I -
OH
*

osilicate ion r s to form an

disilicate ion, i n which each silicon atom has
a coordination o f six. The siloxane bond is subsequently formed as the
two shared silanol groups condense and split out water:

OH
I
HzQ,, ,.OH-' 0,H 9H
.",t i -+ HO- i 0-3 i-OH + OH- + 2H20
3-
HO" ,' OH OH OH
OH (2.3)

temporary coordination o f six:

>

The reaction in strongly

s

lishes an equilibri
bd'
to form a trimer:
 . .
I
50

F
H24 ’ ,‘.OH
I
L
,
a.

F- + H20 t Si(OH)4-- ,Si 8. (2.5a)

HO’ I ‘OH
OH c

F -1
OH OH
+
+ Si(OH)4 + c‘ F-&-O-S\-OH + OH- + w 2 0
dH OH
I
, OH (2.5b)

OHI OH
I :\ OH,
F-Si-0-Si-OH + Si(OH)4 + (HO)4Si:
‘\Op\O-Si(OH)j
dH dH H

* (H0)3-Si-O- ?i-O-Si(OHI3 + F- + Ht (2.5~)

dH

Overall : 3 Si(OH)4- Trimer + 3 H20

I f t h e f i r s t two steps e q u i l i b r a t e q u i c k l y such t h a t the t h i r d step i s
r a t e c o n t r o l l i n g , then the o v e r a l l reaction w i l l apear third-order i n

s i 1 i c i c a c i d concentration and f i r s t - o r d e r i n both hydrogen and f l u o r i d e

i o n concentration. I l e r (13) claims t h a t as l i t t l e as a few parts per
m i l l i o n f l u o r i d e can g r e a t l y enhance the reaction r a t e a t low pH, and

t h a t t h i s c a t a l y t i c effectiveness i s s u b s t a n t i a l l y reduced i f metal ions

-
are present which complex w i t h the f l u o r i d e .
Preview o f the Present Research
The polymerization o f s i l i c i c a c i d plays a fundamntal r o l e i n

the mechanism(s) o f s i 1 ica-scale deposition from geothermal b r i n e

deposition and the r a t e a t which i t occurs

Lr
 51

clearly understand the polymerization process. A1 though this process

has been studied extensively since 1930, the reported f i n d i n g s are
inconsistent, incomplete, and not directly extendable t o the dilute
concentration levels typical of geothermal brines. The effect of pH on
the overall reaction rate is understood imprecisely, as seen by the
widely discrepant values for the reported maximum rate of polymerization.
In this regard, the ionization of s i l i c i c acids is clearly an important
f a c t which has been widely overlooked. Polymerization kinetics i s
another area of widespread disagreement. The mu1tip1 i c i t y of reaction
steps and of polymer structures i n the polymerization procexs virtually
precludes the use of a single reaction rate coefficient and equilibrium
constant t o describe the overall rate o f polymerization. Thus, the
polymerization studies to date give only a qualitative picture of a ‘very
compl ex pol ymerita ti on process.
The present investigation is essentially undertaken as a rate
study o f the condensation reaction between pairs of silanol groups t o
research is t o s p l i t the
parts, and t o
for the effects of pH and
ymerization. Such informa-
ation (and preven-
e a consistent
ehavior under a
of conditions .
 52

Chapter 3

EXPERIMENTAL MEMODS AND PROCEDURES

Scope o f t h e Experiments
Previous investigations o f the polymerization o f s i l i c i c acids
have indicated a strong dependence of the r a t e on pH and on t o t a l s i l i -
con concentration. The r e s u l t s are q u i t e inconclusive, and f u r t h e r
' study i s warranted. The present work e n t a i l s a polymerization r a t e
study o f s i l i c i c a c i d solutions ranging i n pH from 4 t o 10 and i n con-
c e n t r a t i o n from 300 t o 900 ppm t o t a l Si02. A s i n g l e temperature o f
25OC was chosen f o r a ? ? r a t e runs because i t f a c i l i t a t e d the experi-

mental setup and provided the best comparison w i t h previously reported

studies.
The disadvantage of employing a low temperature i n t h i s study i s
t h a t i t i s f a r removed from those i n geothermal brines, and therefore

the specific r a t e r e s u l t s o f the present study cannot be extended

d i r e c t l y t o the r a t e o f s i l i c a polymerization i n geothermal brines.
However, the t r u e objectives o f the present work are t o understand the
behavior o f s i l i c a i n d i l u t e aqueous s o l u t i o n and t o e s t a b l i s h a mech-
anism f o r the polymerization o f s i l i c i c a c i d which accounts f o r the
observed effects of pH and s i l i c a concentration on the o v e r a l l rate. If

a series of elemental chemical reactions can be deduced from a study o f

the macroscopic polymerization process a t one temperature, i t i s usually
a r e l a t i v e l y straightforward matter t o study how each elemental reaction
r a t e changes w i t h temperature and hence understand how the o v e r a l l

reaction r a t e changes w i t h temperature.

 53

LJ S i 1 i c a Determination by the Molybdate Method

There are several methods by which one can monitor ,the r a t e of

polymerization of monosilicic acid. Many o f the proven methods f a l l

under t h e s i n g l e c l a s s i f i c a t i o n of mol ecul ar-wei ght determi nation
L

methods. These f o l l o w the change o f a s t a t i s t i c a l l y averaged property

o f the polymeric s o l u t i o n (Le., molecular weight) w i t h t i m e r a t h e r
than measuring the concentration of any one polymeric species which i s
generally d i f f i c u l t and l e s s informative L i g h t - s c a t t e r i ng techni ques
g i v e q u a n t i t a t i v e information on the weight-averaged molecular weight
o f polymeric molecules i n a s u i t a b l e solvent. The number-averaged
molecular weight can a l s o be obtained from measuring the c o l l i g a t i v e
properties of polymer solutions such as freezing point, b o i l i n g point,
vapor pressure, and osmotic pressure. When applied t o s i l i c a polymeri-
z a t i o n i n f a i r l y concentrated solutions, several standard molecular-
weight monitoring -techniques are s u i t a b l e f o r a r a t e study.
A l t e r n a t i v e l y , t h e o v e r a l l polymerization r a t e o f monosilicic a c i d
canbe measured by observing the r a t e of disappearance o f monomer. This
method depends on t h e a b i l i t y t o measure the concentration of monosilt-
c i c a c i d i n the presence of p o l y s i l i c i c acids, and i s i d e a l l y suited
f o r studies i n v o l ng small . s i l i c a concentrations. There i s an analy-

t i c a l technique which, -to a l i m i t e d degree, has t h i s c a p a b i l i t y , and

h i s so-called molybdate method i s the asis o f the present study.
Because o f i t s importance method w i l l be discussed and

d i n some d e t a i l .
I t has been known f o r more than 75 years t h a t s i l i c a w i l l r e a c t
44 with molybdic a c i d t o y i e l d a yellow complex whose concentration can be
determined spectrophotometrically (52). However, i t was not u n t i 1 25
 , 54

years a f t e r the o r i g i n a l discovery t h a t Dienert and Wandenbuicke (D5)

and Harmon (H2) discovered t h a t only "soluble s i l i c a " and not c o l l o i d a l
c,
s i l i c a would r e a c t w i t h the molybdate. For another 25 years, a contro-
versy persisted i n the chemical and geologic l i t e r a t u r e as t o the .
exact nature o f s i l i c a i n solution, p a r t l y due t o the confusion between
z

the molybdate r e s u l t and gravimetric analyses f o r t o t a l s i 1 i c a (R3).

S i l i c a i n s o l u t i o n was repeatedly placed i n t o one o f two c l a s s i f i c a t i o n s ,
c o l l o i d a l o r "soluble". The l a t t e r r e f e r r e d t o t h a t form o f s i l i c a t h a t
would r e a c t w i t h molybdic a c i d and was generally equated w i t h monomeric

s i 1i c a .
I n 1950 Weitz, Francke, and Schuchard (141) reported t h a t low-
molecular-weight p o l y s i l i c i c acids also r e a c t w i t h molybdic acid, but

a t a slower r a t e than monomer. They found t h a t a t 20°C, monomeric

s i l i c i c a c i d reacted completely i n 75 seconds, dimer reacted completely
i n 10 minutes, and higher polymers reacted much more slowly (A3).
Alexander (A3) found t h a t monomeric s i l i c i c a c i d reacted w i t h excess
molybdic a c i d by a f i r s t - o r d e r reaction whose r a t e c o e f f i c i e n t was 2.3
min" a t 25OC. S i l i c i c a c i d dimer reacted more slowly w i t h molybdate,
b u t a l s o by an apparent f i r s t - o r d e r reaction w i t h a r a t e c o e f f i c i e n t
approximately equal t o 0.9 min". Alexander postulated t h a t dimer
reacts by a two-step sequence o f f i r s t - o r d e r reactions: dimer f i r s t
.
depolymerizes t o monomer, and then monomer reacts w i t h molybdic a c i d t o

y i e l d the colored silicomolybdate complex. The slow depolymerization t

reaction i s the r a t e - c o n t r o l l i n g step f o r the dimer.

Alexander was also able t o show t h a t higher-order p o l y s i l i c i c

acids were very slow t o r e a c t with molybdic acid. His data suggest t h a t
above a c e r t a i n degree of polymerization, molybdic a c i d can react w i t h id
 55

only a limited fraction of the s i l i c a . T h i s fraction of reactive sil-

ita decreases w i t h increasing average molecular weight. The same
behavior was observed by Chow and Robinson (C2) and is consistent w i t h
the e a r l i e r observations that colloidal s i l i c a is unreactive w i t h
molybdate. O'Conner (Ol), has suggested that linear polysilicic acids
depolymerize f a i r l y rapidly i n the presence of molybdate ions. The
r a t e of depolymeri tation is reported1 rst-order i n siloxane bond
concentration ( i n excess molybdate) w i t h a measured rate coefficient
of 1.9 min-l. O'Conner has presented data which .suggests t h a t the rate
of depolymerization per siloxane bond of non-cyclic s i l i c i c acids ( i n
molybdic acid) i s affected only slightly by the degree of polymeriza-
tion up t o hexamer. For example, linear pentamer reacts completely
w i t h molybdic acid and develops 90% o f its color i n 3.5 minutes. This
closely parallels the rate f o r dimer i n solutions containing the same
concentration of si1 icon atoms. O'Conner suggested that higher polysil-
icic acids a r e f a r less reactive, and f n some cases non-reactive, w i t h
molybdic acid because o f their a b i l i t y t o form cyclic and three-
dimensional structures which are seemingly resistent t o depolymeri za-
tion. I t sh be noted that n O'Conner's experiments there: is some
e purity 'of his so-called n-mer solutions, where
n = 2, 3, 4, He prepared these solutio the acid hydrol-
. ysis of chlo ed s i l i c i c acids. B u t i t i s no
acid products c sponded exactly t o h i s chloro reactants ( i .e ,
that depolymeri on o r polymerization did not
ation of the s i l i c i c acids).
u I

Strickland (S6-S8) has performed a thorough investigation on the

1
nature of the silicomolybdate complex. He found the chemical
 56

composition of this complex t o be H4SiMo12040, a strong acid, f u l l y

I
ionized and comparable i n strength to mineral acids (S7). However, the t
silicomolybdate ion is reported by Strickland to have two isomeric
structures, termed a- and 8-silicomolybdata. The former (a) is the *

more stable structure b u t absorbs l i g h t less strongly than the l a t t e r

*
form (8); O’Conner (01) reported a ratio o f extinction coefficients of
1.77 a t 400 my. On the other hand, 8-silicomolybdate is more readily
formed when s i l i c i c acid reacts w i t h molybdate und typical analytical
conditions. The 8-silicomolybdic acid i n i t i a l l y formed is stable for
short periods of time b u t spontaneously decays to the a-form by a first-
, order reaction (S8, 01). Thus the absorption of l i g h t from a solution
of monosilicic acid and molybdic acid reaches a maximum w i t h i n several
minutes, corresponding t o a l l the s i l i c i c acid f u l l y complexed i n the
8-form, and then slowly diminishes t o an asymptotic value as the B-form
is converted into the less strongly absorbing a-form.
The r a t e of conversion of B-silicomolybdate t o a-silicomolybdate
l

is dependent on temperature, pH, and electrolyte concentration.

Strickland (S8) reported that the first-order r a t e coefficient a t 20°C
is 2.87 x min’l, butat 100°C the conversion of 6 t o a is complete
i n 20 minutes. (The pH, the i n i t i a l 8-concentra , and the concen-
tration of excess molybdate were not reported.) nner (01) reported
a rate coefficient for the (3 to a conversion of 1.17 x a t 25°C and
.
a pH of 1.5. His molybdate reagent was prepared by the method of 7

Alexander (A3), which was also the method employed f the present
study. Strickland (S8) also discovered that the conversion o
I

a-silicomolybdate is increased a t higher pH and i n the presence of

I
higher electrolyte concentrations , notably sulfate ion. Excess L
 ,
I

57

molybdate retards the r a t e of conversion b u t does not stabilize the 6-

lybdate also diminishes the effect of temperature and
el ectrol yte.
The r a t e of reaction between molybdic acid and nosilicic acid
has also been found t o depend on pH. The reaction i at
hydrogen ion concentrations (1 N) and increases w i t h increasing pH (S7).
The r a t e a t t a i 'maximum betwe PH 1 and 2, a
pH's. The molybdic acid is generally prepa
date s a l t , and i t has been established tha Of added acid
influences the amount of 6-silicomolybdate relative to the amount
of a-silicomolybdate. In solutions . w i t h to l.5 equivalents Of acid
per mole o f MOO;, a-sili
For ratios gre
comolybdate i s
ponds t o the encountered i n most analytical techniques
The simplest molybdate ion, Moo;, is the prevalent species i n
solutions w i t h pH's greater than 6.5 (M10). T h i s ion from
the double dissociation of hydrogens from the dibasic

bi
do-through the formation of oxygen 1inkages betwe e-
cul es .
 I
58

The most l i k e l y s t r u c t u r e f o r the silicomolybdic a c i d as pictured

by Keggin ( K l ) contains a silicon-oxygen tetrahedron a t the center w i t h
f o u r equivalent Mo309H groups attached t o the central oxygens:

oCb3O9Hl

i 0
I
0
I
[HOgMo3] -0-9 -0-Mo -0-Mo-0-Mo
0
I
-OH
IO C M O ~ O6~ H I i d

The OH groups on each o f the terminal molybdenum atoms are strongly

a c i d i c and hence are mostly ionized a t - pH’s corresponding t o the o p t i -
. mum c o l o r development range o f 1 t o 2. Although i t i s d i f f i c u l t t o
, explain why each molybdate chain contains only three molybdenum atoms,

the si1icon:molybdenum r a t i o i s always found t o be 1:12.

l i n e a r , thus explaining the preponderance o f only three-member side

chains which do not f u r t h e r polymerize:

The ionized form o f t h i s a c i d chain can also e x h i b i t a resonance

stability. The c y c l i c side-chain theory has f u r t h e r appeal i n t h a t i t

r e a d i l y accounts f o r isomeric structures which can a r i s e as follows:

A
I
-Si -0-Mo
I
OH 0-MO
”
Po-40’
a

’ 0
‘ - I
I
*.\
-Si-O-Mo=O
dH
Mw%lo=
= 1
P
(hypothetical 6-form) (hypothetical a-form)
 59

L,
From this model of the'silicomolybdate-complex structure, it is
likely that the complex is formed by condensation between silanol
*
groups on the silicic acid molecule and ionized ( - O - ) groups attached
to molybdenum atoms:
OH OH
I I
HO-Si-OH + -0 Mo30i Z HO-Si-0 Mo309 + OH- (3.1)
oh . dH

The reverse reaction is known to occur, in which the silicomolybdate

complex can be destroyed by subjecting t to strong base 6 7 ) .
It has been suggested that polymeric ilicic acids react with
molybdic acid by first depolymerizing to monomer. However, if one pic-
tures the forward polymerization reaction to occur by reaction between
a neutral and an ionized silicic acid molecule to yield a siloxane bond
and a hydroxide.ion, then the reverse reaction must proceed through the
same path, only in reverse. That i s , a hydroxide ion must reac
split a Siloxane bond into a neutral
1 I I
-Si-OH + -Si-0- Z -Si-O-
I \

lybd icic acid solution, pH 1-2, very

ons are present and thus depolymerization should not be
. as has been postulated.

The silicate ion produced

k, very weak acid, quickly reacts with a hydrogen ion to produce an union-
ized siTsno1 group. From the experimental evidence o f Alexander (A3)
 60

and O'Conner (Ol), i t is apparent that this reaction (Eq. 3.2) is

slower t h a n the reaction between a molybdate ion and a monosilicic acid
L
molecule ( E q . 3.1). O'Conner's idea t h a t three-dimensional and cyclic
s i l i c i c acid molecules are unreactive can be employed t o explain why t

molybdate does not react w i t h colloidal or high-molecular-weight s i l i c i c

"
acid mol ecul es .
The analytical technique which measures the s i l i c a i n a solution
by reacting i t w i t h excess molybdate t o form a silicomolybdate complex,
SiMo12040-4, is commonly referred t o as the molybdenum yellow tech-
nique because of the color of the complex t h a t issubsequently formed.
An alternate procedure has been devised i n which the yellow silicomoly-
bdate complex i n i t i a l l y formed is reduced by the addition of a reducing
agent t o form a blue si1 icomolybdous complex. The B-sil icomolybdate
yields a single reduced product while the a-si1 icomolybdate yields two
products depending on the degree of reduction (S7, S8). The standard
molybdenum blue technique occurs i n the following steps (M10): ( a ) The
s i l i c a sample is mixed w i t h the molybdic acid and allowed t o react for
ten minutes ( a t approximately 25°C). ( b ) Strong acid i s then added t o
quench the reaction and prevent the subsequent reduction of the unre-
acted molybdate reagent. (c) A suitable reducing agent i s added t o
convert the B-molybdate complex t o a &molybdous complex whose color is
*

quite stable.
Mullin and Riley (M10) consider that the molybdenum yellow tech- s

nique suffers from the following disadvantages and is therefore less

desirable t h a n the molybdenum blue method: (a) The color is stable for
only 5 minutes, thereafter i t fades due t o the B t o a conversion. (b)
The absorption maximum f o r &si1 icomolybdate complex i s overlapped by Lr
 61

t h a t o f excess molybdate reagent used i n i t s formation, hence the

absorption measurement must be made i n a region where the B-complex

absorbance i s changing r a p i d l y w i t h wavelength. (c) The s e n s i t i v i t y i s

inadequate f o r t h e determination of low s i l i c a concentrations, l e s s

than 0.1 ppm. (d) A t high silicomolybdate concentrations, Beer's Law

i s n o t obeyed, suggesting t h a t more than one form o f the complex i s
present.
I n the present work, the yellow molybdate method was u t i l i z e d ,
and the c r i t i c i s m s o f M u l l i n and R i l e y were not found t o be v a l i d .
The present author disagrees strongly w i t h the statement t h a t the 6-
complex i s o n l y stable f o r f i v e minutes. The present findings are i n
agreement w i t h those o f O'Conner ( O l ) , and i n d i c a t e t h a t the molybdate
method o f Alexander (A3) gives a 6-complex which i s stable f o r up t o 30
minutes a t 25°C. I n fact, In the present study a l l absorbance readings
were made w i t h i n 10 minutes a f t e r t h e i n i t i a l mixing o f s i l i c a w i t h

molybdate reagent. Any molybdenum blue method would require an equal

time f o r yellow c o l o r development before reduction t o the blue color.
The o n l y advantage o f the molybdenum blue method i n regard t o s t a b i l i t y

permit one t o e absorbance readings a t any t i m e

velopment o f t h h e color, r a t h e r than r e q u i r i n g
 62

1 .o 8 I 1 8 I
I I I 1

0.8

0.6

I-
% 0.4

0.2

0.0
360

Wavelength (mu)
?

Figure 3.1 Absorption Spectra for @-Silicomolybdate

and Molybdate Reagent

2 , L
 63
u
absorbance readings due t o slight errors i n the wavelength setting.
(In fact, d u r i n g the course of a l l present experiments, the wavelength
1

was set once a t 400 nm and not readjusted.) In Figure 3.1, Curve 1 is
t the absorbance of the stwtdard molybdate reagent against a reference o f
0.1 N HCl. Curve 2 i s the absorbance o f the same molybdate reagent
containing 8.2 x loo4 moles/liter o f B-silicomolybdate versus a molyb-
date reagent blank. The measurements were made on a Cary 14 scanning
spectrophotometer between the wavelengths o f 350 and 450 mp. The hori-
zontal line a t zero optical density is a double trace of the baseline
for the two runs,
Regarding the sensitivity of the molybdenum yellow method, i t is
true that errors become appreciable below a concentration of 0.1 ppm,
but i n the present experiments, the lowest concentration measured was
2.5 ppm. I t should be noted that in typical experiments, s i l i c a sam-
ples were diluted approximately 50 times i n the normal analytical deter-
mination process. Therefore a sample from a polymerizing solution t h a t
was 0.01 molar total silicon atoms,. would produce upon analysis a
0.0002 molar s ion of B-silicomolybdate complex (provided a1 1 the
i n terms o f equivalent
0 '

>
ncentrations of
c

ticism and has been noted both

.. T h i s f a c t is a
il ica concentra-
* tions, not a major drawback. I t means that concentrations cannot be
ks,
obtained by simply multiplying the recorded optical densities by a
constant factor. Instead a cal ibration curve must be obtained i n i t i a l l y
 64

from which o p t i c a l densities can be r e l a t e d d i r e c t l y t o concentrations. L

T h e - c a l i b r a t i o n curve prepared f o r t h i s present study i s shown i n

Figure 3.2. The deviation from Beer's Law ( s t r a i g h t l i n e ) i s not large,

t

and i s o n l y noticeable at. s i l i c a concentrations above 8.5 ppm (corres-

ponding t o feed-solution concentrations o f 425 ppm s i l i c a ) . The pro- *

cedure f o r obtaining the c a l i b r a t i o n i n Figure 3.2 w i l l be discussed

shortly.
The question arises as t o what s i l i c i c a c i d species c o n t r i b u t e t o
the c o l o r development t h a t reaches a maximum i n f i v e minutes, which was
t h e longest time required t o reach maximum c o l o r development i n most o f
the present experiments. I f a s o l u t i o n sample contained pure monomer,
then a,maximum o p t i c a l density would be expected i n 2 minutes based on
the observations of Weitz e t a l . ( W l ) , Alexander (A3), and O'Conner (01).
I f a s i l i c a sample contains o n l y c o l l o i d a l s i l i c a , which apparently does
not depolymerize i n molybdate a t any observable r a t e , then no c o l o r

would develop. O'Conner has claimed t h a t a 5-minute maximum c o l o r

could contain contributions from a l l low-molecular-weight l i n e a r s i l i -

c i c acids. However, there i s no r e a l way o f knowing precisely what

species c o n t r i b u t e t o the c o l o r development. Unless the maximum c o l o r

i s developed i n 2 minutes, i t i s i n c o r r e c t t o assume t h a t the indicated

s i l i c a concentration i n the i n i t i a l sample was a l l monomer. -
I n Chapter 4 a method w i l l be discussed which permits an estimate
t

t o be made o f the i n i t i a l monomeric s i l i c a content, based on the i n i t i a l

r a t e o f c o l o r development of the 8-silicomolybdate complex. A t that

time evidence w i l l be presented f o r 5-minute maximum readings t o i n d i -

cate t h a t anywhere from .half t o t w o - t h i r d s ~ o f the t o t a l s i l i c o n detected

was i n i t i a l l y i n the form o f monosilicic acid. The remainder o f the

I
 65

Wavelength = 400 m p
Reference = molybdate reagent
 66

detectable si1 ica was present i n diminishing quantities of dimer,

L
trimer, tetramer, etc. A maximum reading i n 4 minutes indicates a
higher percentage of si1 icic acid monomer i n the detectable si1 ica; and
i n the limit, of course, a 2-minute reading indicates that a l l the
analyzed si1 ica was present as monomer.
Thus the conclusion is reached that the maximum molybdate color
reading does not necessarily correspond t o a detection of monosilicic
acid alone, b u t to a weighted sum of the concentrations o f
low-molecular-weight si1 icic acids. (The dimer concentration is
weighted double, the trimer weighted triple, etc.). In the anal
the present experiments, the r a t e o f polymerization of s i l i c i c acid has
been estimated by observing the change w i t h time of the amount of
s i l i c a i n solution that will react w i t h molybdate i n 5 minutes. In
most cases a maximum optical density reading was obtained before t h i s
5-minute dead1 ine. Since the molybdate analysis gives sl i g h t l y more
than just the monosilicic acid concentration i n solution, i t i s incor-
r e c t t o equate the above r a t e to the rate of disappearance of monomer
from the polymerizing solutions. I t i s more correct t o associate the
observed rate w i t h the somewhat more general reaction:

Low-Mol ecular-Weight Highly Polymerized S i 1 ica

S i l i c i c Acids and Colloidal Particles
-
(Colorimetrically deter-
minable i n 5 min. a t 25°C)
f
 67

Experimental Procedures

*
The molybdenum ye1 low method was essentially that of Alexander
Y t modifications. The molybdate reagent was freshly
prepared each day from an ammonium molybdate stock solution, prepared
by dissolving 100 gms of crystalline ammonium molybdate (Mallinckrodt
Analytic Reagent (NH4~6M07024 4Hz0) i n doubly deionized water and
d i l u t i n g to one liter. The molybdate reagent was prepared by mixing
40 ml o f ammonium molybdate stock lution w i t h 100 m l of 1 N HC1 and
500 m l doubly-deionized water and d i l u t i n g to one l i t e r . The resulting
mixture has a r a t i o of acid equivalents to moles of MOO; of 4.41, a pH
o f approximately 1.4, and a concentration of equivalent M o ~ -4~ ofO ~ ~
1.88 x moles/liter. According to Strickland (S6), this solution
i t i a l l y produce only the 8-si1 icomolybdate acid
ed i n polyet polypropylene, o
ntamination w i t h si1 ica from glass.
A l l s i l i c a analyses he following manner: 50

i nd the time was recorded

s stirred vigorously for
t

a Bausch and Lomb Spectronic 20 Colorimeter. Maximum color development

W
(optical density) was usually obse w i t h i n 5 minutes, and this color
remained stable for more than 30 minutes In a l l instances the 100%
,
 68

transmittance p o i n t was established f o r the c e l l containing the molyb-

L+
date reagent alone.
The molybdate c o l o r reaction w i t h s i l i c i c acids was found t o be
t
strongly dependent on temperature. I t i s therefore meaningless t o t a l k
i n terms o f a maximum reading w i t h i n f i v e minutes, without specifying
?

the temperature o f the reaction. For example, monosilicic a c i d r e p o r t -

edly reacts w i t h excess molybdic a c i d i n 2 minutes a t 25OC (A3). At

lower temperatures t h e maximum o p t i c a l density w i l l be developed i n

appreciably longer times. Approximate experiments by the present

author i n d i c a t e an a c t i v a t i o n energy o f 20 kcal/mole f o r the molybdate

c o l o r r e a c t i o n i n the temperature range from 18 t o 3 O O C . The experi-

ments were approximate because the temperature o f the absorption c e l l
was n o t maintained p r e c i s e l y a t the i n i t i a l temperature o f the r e a c t i o n
mixture.
As previously indicated, the i n i t i a l temperature o f the c o l o r
reagent used i n a l l present experiments was 25OC. Color development

samples were placed i n t o €he colorimeter w i t h i n 1 minute a f t e r with-

drawing the 50 m l o f c o l o r reagent from a water bath a t 25°C. Although

the absorbance c e l l s were not thermally regulated, i t i s u n l i k e l y t h a t

the temperature w i t h i n these c e l l s was lowered by more than 1 degree

from the i n i t i a l temperature during the course o f 5 minutes, since the

a

room temperature ranged from 18 t o 22OC. Any tendency f o r the c e l l s t o

cool was also counteracted by the i r r a d i a t i o n o f the c e l l w i t h l i g h t *

(however, t h i s never caused the c e l l s t o heat up). As a f i n a l note

regarding temperature, i t was determined experimentally t h a t the e x t i n c -
t i o n c o e f f i c i e n t f o r the B-silicomolybdate complex a t 400 mp was r e l a -

l y i n s e n s i t i v e t o small changes i n temperature. id

 69

u The standardized curve for concentration versus optical density

was prepared by mixing known concentrations o f sodium metasil icate
crystalline reagent (Na2Si03 9H20) in nized water and measuring
the maximum optical densities developed. It was virtually assured that
all the silica in solution reacted with molybdate to produce the col-
ored complex, because the pH o f the metasilicate solution was greater
than 11, where most o f the silica is in the form o f silicate monomer
ions. When small portions o f this solution (1 ml) were mixed with 50
ml of color reagent, all the silicate ions were converted to silicic
acid at essentially the same pH (1.4) as that o f the molybdate reagent.
The polymerization of silicic ac is very slow at this pH (and degree
o f dilution) so all the silica remains predominately monomer and reacts
completely with the molybdate reagent.
Two experiments were' performed to rify these conclusions.
Sodium hydroxide pellets were added to the metasilicate solution to
se the pH above 13 (peptizing), and the solutions were aged several

again obtained.
ki Preparation o f Si1 icic Acid Solutions
The silicic acid solutions used in the rate experiments were
 70

prepared i n t h e f o l l o w i n g manner: Concentrated s i 1 i c i c a c i d solutions

r e prepared ac i n g t o the method o f Alexander (A4) by

1.9 gms o f pulverized c r y s t a l l i n e sodium m e t a s i l i c a t e (J. T

reagent grade) i n a vigorously s t i r r e d s l u r r y o f 200 m l o f doubly
deionized water, 2 m l o f 1 N HC1, and approximately 75 gm o f moist
hydrogen-form ion-exchange r e s i n (Dowex 50-XB, 20/50 mesh). The acid

s l u r r y was kept a t 2°C i n a 400 m l polypropylene beaker suspended i n

an i c e bath, and the m e t a s i l i c a t e was added slowly over a 5-minute
i o d t o reduce the l i k e l i h o o d o f polymerization. The’mixing was then

continued f o r an additional 10 minutes. According t o Alexander, t h i s

method y i e l d s a s o l u t i o n o f predominantly monosilicic acid, w i t h a

degree o f polymerization o f 1.1. The i o n exchange r e s i n removes the

sodium ions from solution, and the excess a c i d i n s o l u t i o n keeps the

pH a t approximately 2.5 t o prevent premature polymerization. Moist,
r a t h e r than dry, r e s i n was used t o prevent a l a r g e amount o f uptake o f
the i n i t i a l water charge.
From an analysis o f t h i s stock solution, the s i l i c a concentration
was found t o be approximately 10 t o 15% l e s s than would be predicted
(0.0333 moles s i l i c o n / l i t e r ) by assuming the 1.9 gms o f sodium meta-

s i l i c a t e dissolve completely i n 200 m l o f water and 2 m l o f l N HC1.

Possible explanations f o r t h i s are: incomplete dissolution, contribu-
t i o n o f a d d i t i o n a l water from the resin, incomplete s i l i c a analysis, or

loss o f soluble s i l i c a i n t o the s o l i d r e s i n phase. O f these p o s s i b i l i -

t i e s , supplementary experiments r u l e d o u t the f i r s t three, and only the

l a s t one i s tenable. The loss o f some s i l i c a i n the r e s i n was not a

serious problem, because the s i 1 i c a concentration i n t h e stock s o l u t i o n
was always checked c o l o r i m e t r i c a l l y before f u r t h e r sample preparation.
 I 71

A f t e r the 10 minutes o f additional mixing, a measured amount o f

stock s o l u t i o n was decanted and transferred t o a separate beaker, also
suspended i n an i c e bath. This p o r t i o n o f stock was subsequently

=
mixed w i t h a predetermined amount o f d i l u t e base a t elevated tempera-
t u r e t o y i e l d a f i n a l s o l u t i o n o f specified s i l i c a concentration and
pH a t a temperature o f 25°C. The moment o f mixing corresponded t o zero
time f o r the polymerization r a t e experiments. I n the i n i t i a l set o f
experiments, sodium hydroxide* was used t o r a i s e the pH o f the stock
s o l u t i o n t o t h e l e v e l desired f o r t h e r a t e experiments. However the
r e s u l t i n g solutions were inadequately buffered, and pH changes during
the course o f PO r i z a t i o n were considerable. To provide b u f f e r i n g
capacity, .a second s e t o f runs was made i n which sodium acetate and
sodium acetate/ tures were used. A t r i a l procedure
was u t i l i z e d t o ch base should be added t o the measured
stock t o achiev solution f o r t h a t i o n experi-

n of additional stock was t i t r a t e d and d i l u t e d

simultaneously t o the desired pH and concentration endpoint. The
r e s u l t i n g equivalents o f base and amount o f added water were appropri-
I <

he measured stock

c
i n a water bath. In
5

3
The reason f o r f i r s t removing and then adding sodium ions l i e s i n the
desire t o minimize the amount o f excess e l e c t r o l y t e . The stated method
bi contributes f o u r t o f i v e times less Na (and s i m i l a r l y , C1) than would
be contributed by simply n e u t r a l i z i n g sodium m e t a s i l i c a t e w i t h HC1.
There was a l s o t h e desire t o u t i l i z e Alexander's proven method o f
preparation.
I
i
!
,
j '
I
I
72

Rate-Experiment Procedure
To i n i t i a t e the polymerization rate r u n , the measured stock solu-
tion a t 2°C and the heated base solution were quickly mixed i n a 250-ml v

polypropylene erlenmeyer flask w h i c h had previously been placed i n a

*
10-liter water b a t h a t 25 &O.l"C. The temperature of the bath was
thermostatically regulated by a mercury contact thermometer and heated
by a 780-watt submerged coil heater. A t the instant of mixing a stop
watch was started t o monitor the polymerization time, and simultaneously
a "time equals zero" sample was withdrawn for analysis. W i t h sufficient
practice using this experimental technique, an i n i t i a l temperature of
25 t 0 . 5 O C could be obtained. The i n i t i a l pH determination of the
reaction solution was performed following the i n i t i a l s i l i c a t e analysis,
approximately 3 t o 5 minutes a f t e r the s t a r t of the reaction. Most'pH
measurements were made on a Chemtrix type 40 E expanded-scale pH meter
w i t h a combination electrode, standardized w i t h the appropriate Beckman
buffer solution (4, 7, o r 10). A few measurements were made using a
Bec'han Zeromatic pH meter with standard glass and calomel reference
el ectrodes .
To monitor the polymerization rate, l-ml samples were withdrawn
from the reaction solution and quickly added t o 50 ml of molybdate
reagent, freshly pipeted from a reservoir suspended i n the same temper- s

ature bath. The frequency of sampling depended upon the reaction rate
f

which varied widely for different 'experimental conditions. Generally

a given run was sampled 10 t o 15 times d u r i n g the course of reaction
from i n i t i a t i o n t o final equilibrium. pH readings a l l y followed
silicate analyses, b u t occurred a t a somewhat lower sampling frequency. Lf
A l l runs were characterized by a decrease i n the amount o f detectable
 73
u 5 ,

, as much as 85%.
t
s f o r each polymeriz

e solution, withdrawing the Sam

r e d i n s t a n t l y t o a region where the

t i o n conditions, however, the

t few seconds

o f reaction.
h the l-ml sam-

5 l y m e r i t a t i o n runs were termina

ns were established. Here eq
f

r t h e r changes were observed i n

nded periods o f Two sets o f

W
a t room temp oom-temperature

mental setup, an r e s u l t s probably

do n o t d i f f e r s i g n i f i c a n t l y from those t h a t would have been obtained a t
L
25OC. I n the f i r s t s e t of studies, co ntrated s o l u t i
409 ppn Si02,'were each prepared a t pH's o f 7, 8, 9, an 0

t i o n s were sampled i n t e r m i t t e n t l y over a 4 n o n t h period t o e s t a b l i s h

1

an e q u i l i b r i u m c e n t r a t i o n of s i l i c a . I n a second s e t o f
ments, the t o t a l concentration o f s i l i c a was varied o
range. Two se f seven samples each were prepared a t pH's 7

i n which t h e c n t r a t i o n ranged from 200 t o 1800 ppm

equilibrium r u the manner o f preparing the s i l i c a s

s i m i l a r t o the one used f o r the solutions i n the r a t e studies, except

-that o n l y sodium hydroxide was used t o a d j u s t the pH. The solutions
were stored i n polyethylene b o t t l e s w i t h screw caps. As w i l l be shown

i n the next chapter, the s i l i c a concentrations obtained from these

separate e q u i l i b r i u m studies agreed w e l l w i t h the apparent asymptotic
values i n both the buffered and unbuffered r a t e experiments.
 75

L,

w chapter, the experimental r e s u l t s o f t h i s study are pre-

sented i n graphical and tabular form, and an explanation o f the calcula-

t i o n s i s given. The presentation comprises three categories: e q u i l i-

' brium measurements molybdate c o l o r development study nd r a t e runs,

f o r which raw data are tabulated i n Appendix 1. Interpretation o f a l l

ese r e s u l t s i eserved f o r Chapter 5.
E q u i l i brium Results
The f i r s t group o f e q u i l i b r i u m runs i s presented i n Tables 4.la
.and 4.lb.- A l l s i l i c a concentrations a r e expressed i n p a r t s per m i l l i o n

' S i O p . These concentrations were obtained by the molybdate yellow

method and i n d i c a t e the amount o
nvtes , hereafter erred t o as As previously
samples y i el de a maximum c o l o r development i n under 5 min-
. For f r e s h l y prep Mo-detectable s i 1 i c a concentra-

s, 1.1, 1.2, 1.3, and 1.4, were allowed t o age

e time samples 1.1 and d i l u t e d 3:1 w i t h

s 1.2 and 1.4 were d i l u t e d 1:1,

I

i t i o n a l 37 days.

e q u i l i b r i u m s t a t e was t h sides. The undiluted

samples show a polymerization trend marked by a decrease i n the amount

kd I

of Mo-detectable s i l i c a , while the d i l u t e d samples e x h i b i t depolymeri-

z a t i o n as indicated by an increasing l e v e l o f Mo-detectable s i l i c a .
 I 76

Table 4.la iJ
, E q u i l i b r i u m Studies-Set 1, High Concentration
F i r s t Phase o f Aging
I

I n i t i a l Analysis Analysis A f t e r Aginq

Mo-Detectable Si02
(ppm) 2

Total
Sample Si02 Duration
No. Jppm) pH (days) pH Total Un-ionized

1.1 816 10.00 9 10.35 367 80.5

14 10.36 370 79.8
1 1.2 816 9.00 9 9.35 145 107
14 9.05 141 120
1.3 816 8.00 9 8.50 131 126
14 8.11 138 136
1.4 816 7.08 . 9 6.65 122 122
14 6.72 127 127

Second Phase o f Aging*

I n i t i a l Analysis Analysis a f t e r Additional Aging
Mo-Detectable Si02
Ppm)
Additional
Sample Nominal Dura t i o n
No. Total Mo-det. pH (days) pH Total Un-ionized
1.1' 612 275 10.36 37 10.15 293 90
1.2' 408 70 9.05 37 7.90 129 127 *

1.3' 612 104 8.11 37 6.95 125 125

J

1.4' 408 64 6.72 37 6.35 123 123

*Using samples from the f i r s t phase, aged 2 weeks and then d i l u t e d ,

Lid
 77

u For runs a t lower pH, an e q u i l i b r i u m l e v e l o f Mo-detectable s i l i -

c i c a c i d (un t low pH) appears t o elow 130 ppm and above

100 ppm. However, a t high pH, the l e v e l o f detectable s i l i c a i s con-
siderably higher. This can be explained r e a d i l y by a low e q u i l i b r i u m
concentration l e v e l f o r s i l i c i c acids, b u t a high l e v e l f o r s i l i c a t e
anions, as indicated by Alexander e t a l . ( A l ) i n explaining the r a p i d l y

increasing s o l u b i l i t y o f amorphous s i l i c a . A t high pH the s i l i c a t e ions

present i n s o l u t i o n a r e converted i n t o the un-ionized a c i d when mixed
w i t h t h e molybdate c o l o r reagent, and therefore contribute t o the
molybdate c o l o r development.
The t o t a l Mo-detectable si1 i c a concentrations can be adjusted by
d i v i d i n g by the f a c t o r (1 + gA/H+) t o give o n l y the concentration o f
un-ionized s i l i c i c a c i d molecules as shown i n Table 4.la. RA i s an
e f f e c t i v e average a c i d i o n i z a t i o n constant, since the s o l u t i o n sample
contains a mixture o f s i l i c i c acids (monomer, dimer, t r i m e r ) that con-
t r i b u t e t o t h e c o l o r development. A value o f KA o f the
reported d i s s o c i a t i o n constant f o r monomeric s i 1 i c i c acid, has been used I
low about 8.0, where nearly a l l monomeric s i l i c a i s
~

the un-ionized form, t h e c o r r e c t i o n f a c t o r has ~

the other hand, f o r pH's equal t o o r greater than

the recorded pH or the assumed value f o r KA can introduce s i g n i f i -

U
cant e r r o r s i n t h e adjusted concentrations.
l e 4.lb shows the r e s brfum runs i n

which t h e i n i t i a l concentratio a t e l y 50% smaller and the

aging time was increased. gain equilibrium concentrations a r e not

u q u i t e reached, b u t t h e values a f t e r 119 days appear t o be very close

t o a t r u e asymptotic value. For samples 1.6 - 1.8, t h i s l e v e l appears
 78

Table 4.lb La
Equilibrium Studies-Set 1, Low Concentr
I n i t i a l Analysis Analysis A f t e r Aging
t

Total Mo-Detectable Si1 i c a

Sample Si02 Aging Time .o
No. 0 pH (days) pH Total Un-ionized
1.5 409 9.97 12 10.22 354 97.4
19 9.68 327 186*
49 10,20 311 88.7
119 10.10 284 . '94.8

1.6 409 9.00 12 8.95 132 115

19 8.30 136 132
49 7.70 123 122
119 7.55 114 113
1.7 409 8.15 12 7.46 132 131
19 7.00 130 130
49 7.10 119 119
119 7.00 110 110
1.8 409 7 .OO 12 6.47 132 132
19 6.40 128 128
49 6.45 123 123
119 6.33 109 109
*See t e x t for discussion.

fa be approximately 110 ppm-nearly i d e n t i c a l t o the reported s o l u b i l i t y -

o f amorphous s i l i c a a t 20°C. For the high-pH sample, No. 105, the -
adjusted concentration i s lower than 110 ppm, but near it, even though

t h e t o t a l concentration i s much greater. As noted previously, the high-

pti-value deviations from 110 ppm could be due t o pH-measurement errors.

Ld
 79
_. - . .

W One s t r i k i n g f a c t apparent from the data i n Tables 4.la and 4.lb .

i s that there is a pH decre utions. There appear t o be

f
Some discrepant pH readings .in Table 4.1br notably for the lgth'day,
set of readings i s not sufficient to contradict the
trend. A decrease i n pH w i t h polymerization seems
I
to be the reverse of the situation f o r the formation of s i l i c i c acid
gels, for which numerous studies,, i n c l u d i n g the present one, have
n increase i n pH.
The results of the first set of runs indicated that the level of
detectable s i l i c a i n solution would decrease to an asympt
which corresponds t o the reported solubility of amorphous silica-a '

I I

conclusion previously reached by Krauskopf (K5) In addition, the

equilibrium concentration of un-ionized si1i c i c acid appeared t o be
independent of pH. Because of the experimental scatter i n this set, a
second set of experiments was run. e results of Set 2
Table 4.2, clearly indicate that an equilibrium "solubility" i s

For the low pH s, Nos. 2.1 - 2.6, the f i n a l

ica is remarkably constant, 122.5 Lt 0.4%, for i n i t i a l concentra-
tions of silica t h a t range from 442 t o 1769 ppm, a four-fold range.
Only the lowest concentration (Run 2.7) appears to diso
,
reme sluggishness o the polymerization reaction or t o
I
I

I t is unlikely tha true equi 1 i brium con-

centration. With further aging the concentration o f detectable si1 ica
would probably continue t o show a slow decrease u n t i l a concenteatl'on
LiJ
of approximately 110 ppm ted by the results
 \

80

Table 4..2
Equilibrium Studies--Set 2

I n i t i a l Analysis Analysis A f t e r Aging

*
Tot a 1 Mo-Detectable S i l i c a
~ Sample . 'Conc Aging Time
No. 0 pH (days) pH Total Un-i oni zed 1

2.1 1769 6.70 .34 6.52 125 125

48 6.40 122 ' 122
2.2 1326" 6.60* 34 6.45 128 128
48 6.35 123 123
2.3 1105* 6.43* 34 6.43 128 128
40 6.27 122 122
2 :4 884* 6.30* 34 6.30 131 131
48 6.24 122 122
2.5 663* 6.20* 34' 6.35 123 123
40 6.22 122 122
57 6.22 123 123
2.6 442* 6.13* 34 6.04 134 134
48 5.98 123 123
2.7 221* 6.06* 34 5.75 242. sa 242.5
48 5.25 226. 7a 226.7
2.0 1769 10.00 34 10.5 607 101
48 10.25 596 156
57 10.37 571 121
2 .9 1326" 9.88* 34 10.35 450 99 -
48 10.05 420 151
57 10.20 418 119
2.10 1105.* 9.80* 34 10.10 360 120
48 9.96 319 130
57 9.95 310 . 1.28
'See t e x t discussion.
*Estimated from d i l u t i o n conditions of sample Nos. 2.1 and 2.8. c
 81

Table 4.2 (continued)

i Initial Analysis Analysis After Aging
Total Mo-De tec ta bl e Si 1 i ca
Sample Conc. Aging Time
No . h!?k (days) pH Total Un-ionized
2.11 884* 9.70* 34 10.1 318 106
48 9.90 302 134
57 9.98 302 120
2.12 663* 9.57" 198 114
144 121
113
2.13 111
01 126
2.14 42 142
48 7.55- 136 136

adjusted concent

by diluting por-
ted, the initial

u
 82

because t h e pH o f t h e de-ionized water used t o prepare the d i l u t i o n s

L T

was unknown; a'pH value o f 6.0 f o r the l a t t e r was determined by a l a t e r

measurement.
The measured pH changes f o r Set 2 show the same downward trend
observed f o r S e t 1. For samples 2.8 t o 2.14 i t i s apparent
t h a t the i n i t i a l phases o f polymerization are characterized by a pH

increase. During the course o f polymerization, the pH reaches a m a x i -

mum value and then begins a downward trend. I n only one instance
(sample 2.12) was t h e pH observed f i r s t t o increase and then t o decline
enough t o f a l l below the i n i t i a l value. However, such behavior was
observed a t lower pH's f o r many c l o s e l y monitored, unbuffered r a t e
runs.
Color -0evel o pment Studies
In a l l cases, a n a l y t i c samples o f t h e e q u i l i b r i u m solutions
y i e l d e d maximum o p t i c a l density readings well w i t h i n f i v e minutes. As
Figure 4.1 suggests, the color-development reactions were a l l 97% com-
p l e t e w i t h i n three minutes. The r a t e curves a l l appear t o f o l l o w f i r s t -
order i r r e v e r s i b l e r a t e expressions w i t h r a t e c o e f f i c i e n t s as indicated.
Aged samples a t higher pH produce slower r a t e s o f reaction, except f o r
the peptized sample, which shows the f a s t e s t r a t e o f c o l o r development.

This can be a t t r i b u t e d t o the f a c t t h a t o n l y monomeric s i l i c a e x i s t s a t

t h i s high pH, and thus r e a c t i o n with molybdate i s very f a s t . The other

samples contain varying amounts o f polymeric s i l i c i c acids and ions
which r e a c t less q u i c k l y with molybdate.

The measured r a t e c o e f f i c i e n t f o r the peptized sample i s 2.05

min" a t 24.5OC. Using t h e approximate a c t i v a t i o n energy of 20 kcal/

mole t o adjust t h e 24.5OC reading t o 2SoC, the present value i s id

 83

1.0
.
W
Q)
x
-a0 . 5
E
‘ , o
0
E
3

-
..- 0.2
v)

Q-
0
.05

O C
 84

2.17 rnin-l, o n l y 5.7% lower than the value reported by Alexander (A3),

2.3 rnin”. I t should be noted t h a t the t o t a l Mo-detectable s i l i c a con-

t e n t f o r the peptized No. 2.5 sample i s 4.3% higher than the t o t a l s i l -

i c a content o f sample No. 2.5 (663 ); the difference i s not large.
Another peptized sample, No. 2.12, gave an i d e n t i c a l r a t e c o e f f i c i e n t ,
2.05 min”, and y i e l d e d a detectable concentration o f 659 ppm, near-
p e r f e c t agreement (99.4%) w i t h t h e t o t a l s i 1icon concentration.
Figure 4.1 indicates t h a t the quantity o f Mo-detectable s i l i c a
increases r a p i d l y for pH’s above the reported pK for monosilicic acid.
Neglecting the evidence o f the r a t e o f c o l o r development f o r a moment
(which suggests the presence o f higher-molecularweight si1 i c i c acids),
i t i s seemingly. possible t o explain the increase i n detectable s i l i c a
concentration s o l e l y on t h e basis o f formation o f monosilicate ions.
Ifone considers t h a t t h e t o t a l s i l i c a monomer i s made up of un-ionized
and ionized molecules, then t h e t o t a l s i l i c a can be predicted from a
knowledge o f the un-ionized a c i d concentration, the hydrogen i o n con-

centra tion, and t h e a c i d d i s s o c i a t i o n constant :

To a i d the subsequent analysis, a p o r t i o n o f the e q u i l i b r i u m data i s

presented i n Table 4.3. The 123 ppm Mo-detectable s i l i c a f o r sample
2.5 was present i n s o l u t i o n l a r g e l y as un-ionized s i l i c i c a c i d monomer.
By assuming th,at the e q u i l i b r i u m “ s o l u b i l i t y ” o f un-ionized monomer i s

approximately 0.002 molar o r 120 ppm (SiOp w t . basis), and using the
pH and detectable-silica data i n Eq. 4.19 pK i s calculated and equals

9.795, 9.805, and 9.800 for samples 2;8, 2.9, and 2.11, respectively.

The agreement w i t h the reported value of 9.8 i s excellent. It i s too

u restrictive to consider that the detectable s i l i c a was present entirely
as monomer; i t i s sufficient to assume t h a t the acid ionization con-
stants of the Mo-detectable s i l i c i c acids are a l l practically equal.

Molybdenum-Detectable Silica a t
fferent Total Si1ica Concentrations

Sample No. . pH Total Silica Mo-Detec t a bl e S i 1i ca

- ( ppm) (moles/l i t e r ) 0
2.5 6.22 663 0.00205 123
2.8 10.37 1769 0.00951 571

2.9 0 0.00697 418

2.1 1 9.98 884 0.00503 302

The rate data of Figure 4.1 suggest that the amount of Mo-
detectable s i l i c a was .contributed to by more than just s i l i c i c acid
monomer (ionized o r un-ionized). I t i s possible to estimate the frac-
tion o f detectable s i l i c a present as monomer i n the sample, by compar-
i n g the i n i t i a l slopes of the color-development curves to the slope for

pure monome n a peptized sample. he details of this procedure are

outlined i n Appendix 3. Thus t h e amount of total monomeric s i l i c a is
obtained by mu1 e rate coefficient for the color-development
reaction, k, by si1 ica concentration and d i v i d i n g
*

t for pure monomer, k M = 2.0 (The rate

!ope on a normalized p l o t for a
f i rst -order i rr The results for several samples
W are shown i n Table 4 . Like the concentration of monomer, the
 86

concentration o f polymer (equal to total silica, minus monomer) LJ

increases with increasing pH.

Table 4.4
Calculation of Monomer Content in Aged Samples
A
. Monomer
8

Sample Mo-Detectable Si k k/kM moles/ A-B

No. pH (moles/l i ter) (min-1) 1 iter -
2.5 (pep) 12.5 0.01 159 2.047 1 0.01159 0
2 10.37 0.00951 1.212 0.592 0.00563 0.00388
2.9 18.20 0.00697 1 .303 0.637 0.00443 0.00254
2.11 9.98 0.00503 1.381 0.675 0.00339 0.00164
2.5 6.22 0.00205 1.502 0.734 0.00150 0.00055

(A-B) is the amou'nt of equivalent monomer contributed to the color

development by molecules larger than monomer.

It is interesting that freshly prepared silica samples seldom

yielded a rate coefficient for color development greater than 1.2 min".
The above analysis would thus indicate that these supposed monosilicic
acid solutions actually contained no more than 60% monomer, and thus had I

a degree of polymerization of no less than 1.25. This conclusion dis-

agrees with Alexander's observation that his preparation method (A4)
yields silicic acid solutions with a degree of polymerization o f 1 .l, on
1:
the basis of freezing-point measurements. The inference is that sodium -
i
I
!
metasilicate crystals do not dissolve cohpletely as monomer, but yield
some polymeric acids as well. Greenberg and Sinclair (66) have sug-
gested that COP gas in contact with sodium metasilicate crystals can
cause polymerization in the solid phase. They report that "exposed"
i
 87

sodium metasilicate will dissolve in water to yield some colloidal

particles, whereas sodium metasil icate from freshly opened containers
yields no colloidal silica. Perhaps this observation may explain the
discrepancy between Alexander's observation and the present result.
The total monomeric silica concentrations shown in Table 4.4 can
be separated into ionized and un-ionized concentrations by using equa-
tion 4.1 and assuming Km = When this was done, a curious
result was obtained: The concentration of un-ionized monomer was not
found to be independent of pH, but decreased with increasing pH. This
was a disturbing result because un-ionized monosilicic acid in the pre-
sence of colloidal and amorphous silica should exhibit a constant
equilibrium "solubility" independent of pH. This led the author to
adjust the value of the assumed K,, until a more satisfactory result
was obtained In Table 4.5, two sets o f calculations re shown, for
~(m= 10-9-8and A sensitivity analysis is included for the
second set (smaller Km) i which the pH was varied slightly to achieve
a single constant value the concentration of un-ionized monosil icic
acid. Withfn the tal accuracy o
readily apparent t assuming a pKm o
agree except i ona 1 well with the
un-ionized acid c
m is somewhat
eric silica which
ric and Mo-un
ilibrium. There is obviously an equilibrium which must
exist between monomer, dimer, trimer, etc. in solution. It is apparent
that the equilibrium solubility of amorphous silica as previously
 .
..

Table 4.5 '

Calculations for Acid Dissociation of Monomer

Cal cu 1 a ted = 10-9-8

Total Total
Sample Detectabl e Monomer
No. pH Silica (moles/t) M
- -
M- -M -
M- -M
2.8 10.37 .00951 .00563 .00119 .00444 .00142 .00421 10.34 0.03 .00150

2.9 10.20 .00697 .00443 .00126 .00317 .00148 .00295 10.19 -.01 ,00150

2.11 9.98 .00503 .00339 -,

.00135 .00204 .00154 .00185 10.00 +.02 .00150

2.5 6.22 .00205 .00150 .00150 0 .00150 0 - - .00150

 89

measured by the molybdate method i s actually the sum of a l l detectable

bi
polymeric species i n equilibrium w i t h each other and w i t h amorphous
silica. More attention will be devoted t o this subject i n the follow-
II

i n g chapter, b u t i t i s important t o b r i n g i t t o the reader's attention

., now, to avoid any confusion.
Rate-Run Results
O f the 25 r a t e experiments performed, the f i r s t eleven were i n -
adequately buffered, so similar trials were repeated u s i n g sodium
acetate t o improve the pH control. Table 4.6 lists concentration and pH
conditions for the exp mental runs. For the unbuffered runs, the
. . different pH values represent i n i t i a l , maximum, and f i n a l readings.
In buffered, runs, a t lower concentrations, there was some pH variation
as shown. A t very h i g h (or very low) pH's, unbuffered solutions are
suitably "self-buffered," and no sodium acetate was added t o these
solutions. Several of these runs were grouped i n t o the buffered cate-
gory, even though they contained no special buffering agent.
The results of the 14 buffered rate r u n s , made a t an average
concentration of 870 ppm, are shown i n Figures 4.2, 4.3, and 4.4. The
s are grouped t o s the effect of pH below and above 9 i n Figures
4.2 and 4.3 res , and the effect o f total silicon concentration
igure 4.4. The Mo-detectable si1 ica concentration
divided by the i n i t i a l ntration, o r fraction of total s i l i c a
*
unreacted, is p l e vertical axis versus time i n minutes on the
horizontal axis . The term unreacted s i l i c a i s used t o s g->
nify t h a t si1 ica which npolymerized and the

hsd
 90

Table 4.6
L
Conditions f o r Polymerization Rate Runs

Group 1 (Unbuffered)
T r i a l No. Conc. (ppm S i 0 2 1 pH V a r i a t i o n
1 858 9.00 9.25
+ 9.00 -f

2 411 8.95 -t 9.15 8.60 -f

3 548 8.92 -t 9.10 -+ 8.90

4 791 9.10
5 809 7.55 + 7.44 + 7.55
6 771 6.65 + 7.18
7 793 5.6 + 6.39 + 6.25
8 846 4.10
9 586 8.45 + 8.70 * 8.00
10 585 6.80 + 6.90 -+ 6.50
11 423 8.05 + 7.00

Group 2 (Buffered)
1 847 6.00
2 917 6.67
3 877 6.95
4 864 7.45
5 833 8.00
6 871 9.00
7 872 9.23 + 9.40
8 872 9.48 + 9.65 Unbuffered
9 877 10.0
10 697 8.05
11 535 7.95 + 7.82
* 12 451 8.0 + 7.50
13 359 8.0 + 7.25
14 884 7.55 -* 7.35 Unbuffered
 91 I

LiJ Rate curves which plot concentration on a linear scale and time
on a log scale are known a s Powell plots (F4). The advantage of the

I
Powell plot is that i t gives curves of like shape for different reac-
tion systems which are described by identical kinetic models and differ
. only i n the values of their rate coefficients. For example, two first-
order irreversible reactions whose rate coefficients differ by a factor
of 10 will g i v e identically shaped curves on a Powell plot; the hori-
zontal distance of separation will be ere and equal t o
one logarithmic cycle. Thus two Powell plot curves for identical I
I

reaction systems will be horizontally "parallel,t1 and the ratio o f rate

coefficients will be given by the reciprocal ratio of reaction times a t
any given extent of conversi Identical extents of conversion
do not necessarily correspond to identical "fractions of t o t a l si1 ica
unreacted." T h i s p o i n t will be discussed shortly.)
Rate runs 1 to 5 shown $n Figure 4.2 a l l have a characteristic
sigmoidal shape and are nearly parallel horizontally. (They are steeper
than the Powell plots for first- showing some "auto-
catalysis" which will be discuss ) T h i s i s a consequence
that (1) they a l l c tely the same level of
; (2) they a l l proceed
to the same e detectable s i l i c a , 120 ppm, as shown
by the equilibrium results; and (3) they must a l l proceed by a similar
mechanism. The f i s clear i ndica t ion
that the reacti
Curves 6 ow the same pattern as
curves 1 t o 5, because they were unbuffered. More importantly, curve 6
approaches an asymptotic value well above t h a t of the lower-pH runs.
 92

+ 1'

i
t
Time ( M i n ) ..I

i
I
- j
Figure 4.2 E f f e c t o f pH on t h e R a t e o f
Polymerization -
Lower pH !
I

T o t a l S i l i c o n C o n c e n t r a t i o n = 870 ppm L

Temperature = 2 5 O C

I
I
 93

u
 94

1 .o

0.9

-
0
E
0
0.5

c,
0.4
L
LL

1 10 1000 10,000

Time ( M i n )

.
Figure 4.4 Effect o f Total S i l i c a
C o n c e n t r a t i o n on t h e
Rate o f Polymerization
~

\
I

Temperature = 2 5 O C pH = 8 . 0

L.i
 95

This - i s q u i t e s t e n t w i t h the f a c t t h a t a t pH 9 and above the

e q u i l i b r i u m 'Y f detectable h greater than 120 ppm,

because o f the formation o f s i l i c a t e anions. The curves i n Figure 4.3
c l e a r l y i l l u s t r a t e t h i s point: For higher-pH solutions, the equilibrium
amount o f detectable s i l i c a increases. 'The e i l i b r i u m amount o f
detectable s i l i c a i s obtained by m u l t i p l y i n g the ptotic fractional
values i n t h e graphs by t h e corresponding amount o f t o t a l s i l i c a i n
solution.
G

One might * i n f e r from Figure 4.3 r a t e o f polymerization o f

i

low-molecular-weight s i 1 i c i c acids (Mo-detectable s i 1 i c a ) always

decreases w i t h increas'ing pH above' 9.25. I t w i l l be shown below t h a t

t h f s ' i s o n l y p a r t i a l l y correct; ' t h e p i c t u r e i s complex, since the solu-

t i o n s approch d i f f e r e n t e q u i l i b r i u m l e v e l s o f detectable s i l i c a , o r

d i f f e r e n t e q u i l ib r i m " f r a c t i o n s o f t a1 s i l i c a unreacted." For such

extents o f r e a c t i o n ( o r f r a c t i o n a l

simply comparing the r e a c t i o n times 'To

the same l i m i t i n g amount o f

" f r a c t i o n o f t o t a l s i l i c a unreacted.") Despite t h i s l a c k o f d i r e c t

cornparabil ity, it' i s r e a d i l y apparent t h a t t o t a l s i 1 i c a concentration

 96

has a pronounced effect on the rate of polymerization. For example,

LJ
samples 10 and 13 only differ i n concentration by a factor of two
whereas their rates differ by a factor of a hundred, a truly remarkable
c
effect.
. To obtain comparative r a t e data from the raw data shown i n Fig- .
ures 4.2 t o 4.4 accurately, i t is f i r s t necessary t o convb-t concen-
tration versus time data into extent-of-reaction versus time informa-
tion. If the polymerization reactions were a l l irreversible, this would
be unnecessary. Unfortunatley this is clearly not the case.
purpose o f subsequent comparison, the term "fractional approach t o equi-
librium" will now be defined. Consider a sample which i n i t i a l l y con-
tains 620 ppm detectable s i l i c a a t a pH where virtually a l l the s i l i c a
i s i n the unionized acid form (pH 5 8 ) . The s i l i c i c acid i n this sam-
ple will polymerize u n t i l , a t equilibrium, only 120 ppm s i l i c a remains
detectable. During the course of polymerization, from i n i t i a t i o n to
final equilibrium, 500 ppm of equivalent low-molecular-weight si1 icic
acid polymerized t o such an extent as t o render i t s e l f undetectable by
the molybdate analysis. The reduction of the i n i t i a l detectable s i l i c a
concentration by 500 ppm i s considered t o be a full approach t o equi- i
I
librium. A reduction of the detectable s i l i c a concentration by 250
i
ppm i s termed a 50% approach to equilibrium or a "fractional approach to
. ,

equi 1i br i um" of 0.5. !

For samples a t pH's high enough to contribute significant portions 0 :

of s i l i c a t e ions (greater than 1%total detectable s i l i c s ) , the equili-

brium concentration of detectable s i l i c a is no longer 120 ppm b u t
120 x (1 + 10'9*8/H+). For example a t a pH of 9.8, the equilibrium cy, i
tration o f detectable s i l i c a is 240. Thus, for the sample a t
 97

u pH 9.8 and an i n i t i a l concentration o f 620, the reduction i n s i l i c a con-

c e n t r a t i o n by 250 ppm represents a "fractional approach t o equilibrium"
-
620 370 -250 = 0.658 and not 0.5. I n the analysis o f
Of 620 - 240 - 380
samples which showed a pH change during p erization, the f i n a l pH

i value was used t o c a l c u l a t e the appropriate equilibrium concentration.

(As shown i n Figure 4.2, the m u l t i p l i c a t i o n f a c t o r 1 + 10-9.8/(H+)
accounts f o r the increase i n the t o t a l equilibrium l e v e l of Mo-
detectable s i l i c a due t o a c i d ionization. Since equil ibriuni solutions
o f Mo-detectable s i l i c i c a c i d contain a d i s t r i b u t i o n o f low molecular
weights, the value of 10 represents an experimental l y determined
average o f the low-molecular-weight a c i d dissociation constants.)
A l l r a t e runs o f the present study were recalculated on the basis
o f approach t o e q u i l i b r i u m , with 120 (1 + 10'g*8/H+) ppm taken as the
f

e q u i l i b r i u m concentration i n every case. Figure 4.5, the r e s u l t o f

l a t i o n o f the r a t e runs i n Figures 4.2 and 4.3, shows the e f f e c t
o f pH on t h e time required t o reach various approaches t o equilibrium.

The average t o t a l s i l i c o n concentration f o r a l l runs i s 870 ppm.

Notice t h a t Figure 4.5 i s almost exactly analog s t o the gel t i m e
p l o t s o f e a r l i e r workers (Figure 2.5). Just as i t h gel times, the
time required f o r a c e r t a i n approach t o equilibrium can be considered
-
a
nversely proportional t o t h e average r a t e o f polymerization.
major difference between the gel-time r a t e s and the approach-
i
to-equilibrium r a t e s i s t h a t the l a t t e r are f a r more i n d i c a t i v e o f
polymerization r a t e s f o r pure mo olecuiar-weight

s i 1 i c i c acids.
The important feature o f Figure 4.5 i s t h a t the r a t e o f polymeri-
zation apparently reaches a maximum a t pH's near 9. The maximum
 Fractional Approach t o E q u i l i b r i u m T i m e (Min)

d 0
d 0 0
0 I I l

4
fD
3
U
fD
J
rn
ct
c
J
rn
II

h)
v1
0
0 U
I

86
 99

and shifts towards lower pH's

at higher extents of conversion. Since a higher approach to equilibrium
is accompanied by polymerization between larger polysilicic acid mole-
ts that higher-molecular-weight silicic acids
have their maximum polymerization rates at lower pH's. That is, the
to occur at a higher
exhibits a maximum rate at a

4.5 is the linear relation-

(hereafter referred to as
ATE time) and pH rate region. The slope of
these 1 inear reg is shown on the portion of each curve and
varies from 0.91 ation from 30% to 80%. The
absolute slope values a lose to unity which could strongly sug-
fi rst-order i n hydroxi de
ions in this pH region. The deviation from a true value o f unity is

the polymerization rat

s is obviously due to
 100

two factors. One'is t h a t a t high pH the r e l a t i v e amount o f un-ionized

i c a c i d i s reduced, and since t h i s species i s needed for polymer-

i z a t i o n , the r a t e i s also reduced. The second f a c t o r i s t h a t t h e
reverse reaction, depolymerization, i s f a s t e r a t higher pH. ATE times
i n d i c a t e an average net r a t e of polymerization. When the reverse r a t e
increases
* ,
r e l a t i v e t o the forward rate, the n e t forward r a t e i s reduced.
The e f f e c t o f t o t a l s i l i c a concentration on ATE time i s shown i n
Figure 4.6. As was suggested by the raw data o f Figure 4.4, the average
polymerization r a t e i s c e r t a i n l y a strong function o f the t o t a l s i l i c a
concentration. For gel-time data, i t was found t h a t a p l o t o f t h e gel I
!
I

time against the reciprocal square o f t h e t o t a l s i l i c a concentration

1
yielded a straight line. I n an analogous fashion, the data i n Figure !
I
I
4.6 have been r e p l o t t e d t o show the logarithm o f the ATE time versus
I
t h e logarithm o f t h e t o t a l s i l i c a concentration. The r e s u l t s as
shown i n Figure 4.7 i n d i c a t e approximate s t r a i g h t - l i n e r e l a t i o n s h i p s
I
1
!
!

with slopes as indicated.

I n t h e analysis o f a t y p i c a l E t h order i r r e v e r s i b l e reaction, a
log-log p l o t o f extent o f conversion time versus t h e i n i t i a l concentra-
t i o n y i e l d s a s t r a i g h t l i n e w i t h an absolute slope o f n - 1. Thus, if
.
the averaged s i l i c a polymerization process could be described by a I
I
I
i
simple nth order i r r e v e r s i b l e k i n e t i c model, t h e indicated slopes o f i
I
. I
t h e curves i n Figure 4.7 would suggest reaction orders o f between 6 and I
!
8 i n silica. True r e a c t i o n orders o f thl's magnitude are impossible, as !
i
they would imply the simultaneous c o l l i s i o n o f between 6 and 8 s i l i c i c I
!
a c i d molecules. However, i t i s possible i n a m u l t i s t e p reaction scheme
t o observe an apparent high reaction order based on the observed con- i
!
centrations o f i n i t i a l reactants and f i n a l products. L l
I n Chapter 5, an
t
I

I
 rn

- 0 0
C 3 - h
rD

LO1
 102

,
I I I I
L,
! -
I

n
t 6
.
r
r
Y

aJ
E
c
5
I-
*
W
.
I-
4
*
4
cc
0
3
E
c
CI
.c
L
Q ,2
m
0
4
c
lu
L 1
3
c,
Q
L
0 I I I 1

,8 6.0 6.2 6.4 6.6 6

Natural Logarithm o f Total S i l i c a Concentration

( P P ~s i o 2 )

Figure 4.7 Apparent Reaction Order P l o t

D a t a U n a d j u s t e d f o r pH
v a r i a t i o n (see F i g u r e 4 . 6 )
 103

explanation will be offered for the observance of- these unusually h i g h

c, reaction orders.
The reader w i l l note that the rate runs for buffered samples 10
t
h i b i t significant pH variation s shown i n Figure 4.6.
A drop i n pH has the effect of retarding the reaction r a t e and increas-
e

q ATE times, i n comparison to a constant-pH sample. The data i n

Figure 4.6 appear t o reflect the effect of total concentration a t a con-
s t a n t . pH .O. However, since the pH was not constant, the reaction
times should bexorrected f o r the pH variation w i t h i n a given sample
to obtain a mqre pr si! ,indication oncentration effects, independ-
ent of pH effects. The ATE time data €or buffered runs 10 t o 13 can be
corrected by the f owing empiri

hydroxyl ion from Figure 4.5, and is itself a s l i g h t function of the

reci se correc-

are corrected f o r pH varia-

I

1 -

I
i
I
pRJ
I
 104

l o g p l 6 t o f the corrected d a t Figure 4.9.' The corrected data s t i l l

y i e l d reasonably s t r a i g h t - 1 i n e plots, but the apparent reaction order

i s reduced s i g n i f i c a n t l y . As w i t h the corrected data, the corrected

data i n d i c a t e t h a t the apparent reaction order decreases w i t h i
i n g extents o f conversion (i
.e approaches t o equilibrium) .
Thus far, o n l y the r e s u l t s - o f the "buffered" runs have been pre-
sented. The unbuffered results, which do not d i f f e r s i g n i f i c a n t l y ,
are presented separately i n Appendix 2 along w i t h the predicted
behavior based on the extrapolation o f the buffered r e s u l t s . A I though

the concentration o f sodium acetate used i n the buffered runs was as

high as 1 N, 'the polymerization r a t e does not appear t o have been
affected s i g n i f i c a n t l y by increases i n i o n i c strength. As a general
trend, the buffered runs i n d i c a t e a s l i g h t l y f a s t e r reaction r a t e than

was observed f o r t h e unbuffered runs. Whereas t h i s trend might be

a t t r i b u t e d t o the high l e v e l s o f sodium acetate, i t i s much more l i k e l y
t h a t the pH decrease o f the unbuffered runs produced a decelerating
.effect. The v a l i d i t y o f t h i s conclusion i s evident from a comparison
o f r a t e curves,no.'4 (buffered) and no. 14 (unbuffered) i n Figure 4.2.
The unbuffered r a t e r u n e x h i b i t s a faster. i n i t i a l r a t e o f polymeriza-

t i o n because of i t s higher pH (and s l i g h t l y higher concentration).

However, as the pH o f t h i s run decreases t o the value f o r the buffered

run, polymerization i s slowed down u n t i l the two runs show i d e n t i c a l

0 '

average r a t e s o f polymerization a t an ATE o f approximately 0.7.

There i s o n l y one previously reported study on s i l i c a polymeriza-
t i o n t o which t h e present r e s u l t s can be compared d i r e c t l y . Bishop

and Bear (82, 63) performed experiments s i m i l a r t o the prese s' i n

which they prepared fresh s i l i c a samples by approximately the same '
 103

explanation w i l l be o f f e r e d f o r the observance o f these unusually high

LJ r e a c t i o n orders.

The reader w i l l note t h a t the r a t e runs f o r buffered samples 10

f
through 13 d i d e x h i b i t s i g n i f n t pH variation, as shown i n Figure 4.6.
I

A drop i n pH has the e f f e c t o f retarding the reaction r a t e and increas-

i n g the ATE times, i n comparison to, a constant-pH sample. The data i n
appear t o r e f l e c t the e f f e c t o f t o t a l concentration a t a con-
8.0. However, since the pH was not constant, the reaction
times should be corrected f the pH v a r i a t i o n w i t h i n a given sample
.
t o obtain a more precise i n d i c a t i o n o f concentration effects, independ-
e n t o f pH e f f e c t s . The ATE time data f o r buffered runs 10 t o 13 can be
corrected by the f o l l o w i n g empirical relationship:

PH-~)~
rded ATE time) ( 10

u i n t h e above c o r r e c t i o n f a c t the apparent r e a c t i o n order f o r

t s e l f a s l i g h t function o f the
simpler but less precise correc-
vera11 precision of
ference which c o r r e c t i o n
method i s used. ..
gure 4.6 a r e corrected f o r pH varia-
8

t a l s i l i c o n concentration
i
' <

8 -
I

I
were observed. The
c o r r e c t i o n prgcedure e f f e c t i v e l y f l a t t e n s the curves a t the lower end of
w s e f f e c t i s i n t u r n r e f l e c t e d i n the log-
 104
4

l o g p l o t o f the corrected data, Figure 4.9. The corrected data s t i l l

LJ
y i e l d reasonably s t r a i g h t - 1 i n e plots, but the apparent reaction order
i s YCduced s i g n i f i c a n t l y . As w i t h the uncorrected data, the
*
data i n d i c a t e t h a t the apparent reaction order decreases w i t h increas-
i n g extents o f conversion (i.e. approaches t o equi 1ibrium) .
Thus far, o n l y the r e s u l t s o f the "buffered" runs have been pre-
sented. The unbuffered results, which do not d i f f e r s i g n i f i c a n t l y ,
are presented separately i n Appendix 2 along w i t h the predicted
behavior based on the extrapolation o f the buffered r e s u l t s . A1 though
the concentration o f sodium acetate used i n the buffered runs was as
high as 1 &, the polymerization r a t e does not appear t o have been
affected s i g n i f i c a n t l y by increases i n i o n i c strength. As a general

trend, the buffered runs i n d i c a t e a s l i g h t l y f a s t e r reaction r a t e than

was observed for t h e unbuffered runs. Whereas t h i s trend might be

a t t r i b u t e d t o the high l e v e l s o f sodium acetate, i t i s much more l i k e l y
t h a t the pH decrease of the unbuffered runs produced a decelerating

effect. The v a l i d i t y of t h i s conclusion i s evident from a comparison

o f r a t e curves no.'4 (buffered) and no. 14 (unbuffered) i n Figure 4.2.
The unbuffered r a t e r u n e x h i b i t s a faster. i n i t i a l r a t e o f polymeriza-
t i o n because of i t s higher pH (and s l i g h t l y higher concentration).

However, as the pH of t h i s run decreases t o the value f o r the buffered -

run, polymerization i s slowed down u n t i l the two runs show i d e n t i c a l
-
average r a t e s of polymerization a t a n ATE o f approximately 0.7.
There i s o n l y one previously reported study on s i l i c a polymeriza-

t i o n t o which t h e present r e s u l t s can be compared d i r e c t l y . Bishop

and Bear (B2, 83) performed experiments s i m i l a r t o the present ones i n
which they prepared f r e s h s i l i c a samples by approximately the same
Lr
 105
1 I I
E
0
.
r
c,
ns
L
c,
E
a
0
t 0
-
n
0
-
n n
Y Y c
a -
0
m
0
F
-
n
P
-a
c
 106

1 I 1 I

. . A.T.E. Slope

8.0

.
r
c 7.0
1E
U

a
E 6.0
c
I-
.
W

I-
. 5.0
U
c
0
4.0
E
c
+r
c
L
rcI 3.0
0)

-
0
A

m
L
2.0
=I
*.,
m
r
1.0

Natural Logarithm o f Total

Silicon Concentration (ppm Si02)

Figure 4.9 Apparent Reaction Order Plot

Adjusted Times for pH = 8.0
 107

technique and measured si1 ica concentrations over s e t intervals' by the

ki
molybdate-bl ue method. They performed a11 their runs u s i n g approxi -
mately 300 ppm- total s i l i c a adjusted t o i n i t i a l PH of 8-54 Their
:
solutions were unbuffered, b u t contained varying concentrations of
added s a l t s and r a t e runs were made a t different temperatures.
Figure 4.10 shows points (marked by 0) from one o f their rate
runs made a t 25°C for a s i l i c a concentration of 257 ppm (System 1 ,
ref. 83). The s o l i d curve is the behavior predicted for a constant pH
of 8.0, from results' of the present study. The steeper slope of the
experimental data reflect a steady decrease i n pH, so that the time
frames of the Bishop-Bear study and the present work are i n good agree-
ment. A time-averaged apparent pH for the experimental data, which
relates them exactly to the
of Figure 4.10. The averaged pH is calculated by the
-
re1a t i on :

")avg )

The calculated pH's are well w i t h i n the range of expected behavior and
quite consistent w i t h &he pH variation in the unbuffered samples of the
present study.
UP s point, 1 en made t o fully interpret

the results of the present e 1 work. I t was f e l t , t h a t this

task could best be accomp
clearly o d'now be foc r 5 which
arranges the obse s study,with previous studies, i n t o a
consistent framework. .
 108

Ld
1 .o

0
0
+,
V 090
a f

ii
L
c
3
Q -80
0
c
F
b
v)

c
c1 -70
0
I-
cc
0

E
0
.60
*F
c1
0
Q
L
LL
.50
8.6

8.4

8.2

B.0

7.8

100 1000 10,000 100,000

Time ( w i n )

F i g u r e 4.10 Compa'rison t o Bishop's D a t a

Data - o
pH = 8 . 0
Conc. = 2 5 7 ppm

. .
 109

b/ Chapter 5

01SCUSSION

Mec hani sm of Polymerization

c

The effect o f polymerization of si1 icic acids

pe of these curves only differs from
plots (Figure 2.5) i n the positi of the maximum
on.. The characteristic shape of
w i t h a polymeriza n reaction mechanism i n v o l v -
i ng the bimol ecul a r between an un-ionized s i l i c i c acid
molecule and an ionize olecule. For illustrati consider the.
effect of hydrogen ion ic rate expres-
sion:

e (5.1)
A maximum rate is a1 concentrations of the
two reactants. his occurs a t the pH equal t o the effective pxA (an
average value) for .the acids i n solutio Below this pH there are
relatively more sun-ionized molecules, so the number of collisions
between"ioni zed and un-ionized species is reduced, and thus the reac-
tion ,rate is reduced. there are more ionized t h a n un-
ionized molecules, and t i kewi se reduced.
his simple model predicts a first-order dependence on hydroxide
ion below the pH of the maximum rate, nd a nearly~symmetrical p l o t of
ri thm o f ,reaction rate versus pH, w i t h the a x i s of symmetry a t
pH = pKA, -for the case of constant total s i l i c a . The fact t h a t sym-
metry is not observed i s due mainly to the increase i n back reaction a t
 110

pH's greater than pKA.

L
The r e a c t i o n pathway visualized f o r siloxane bond ( S i - 0 - S i E )
formation c l o s e l y para1l e 1s the nucleophilic s u b s t i t u t i o n reactions of
4

organic chemistry: A s i l i c a t e anion, with i t s negative charge r e s i d -

i n g on the oxygen atom, penetrates the s i l a n o l (ESi-OH) tetrahedron
surrounding another s i 1 icon atom, and attacks the s i 1 icon atom.
(Since the s i l i c o n atom i s s i g n i f i a n t l y smaller than the oxygen
0 0
atoms-0.40 A compared with 1.40 A - i t i s almost completely shielded by
the oxygen atoms.) As a bond i s formed between the penetrating oxygen
atom and the nucleophilic s i l i c o n atom, a bond between the same s i l i -
con atom and a hydroxide group i s simultaneously destroyed. The s t a t e
o f intermediate bond formation and destruction corresponds t o the a c t i -
vated complex, o r t r a n s i t i o n state, f o r the polymerization reaction:

I n the process o f siloxane bond formation, i t i s possible t h a t

the tetrahedron o f the neutral s i l i c i c a c i d molecule undergoes inver- -
-'
sion so t h a t i n the t r a n s i t i o n s t a t e t h e three non-reacting bonds are ii
I

planar. This p a r t i c u l a r mechanism i s strongly suggested by the depoly- i

merization which occurs i n t h e molybdifte c o l o r reaction, where i t has * iI
been found (A3, 01 , S6-S8) t h a t c y c l i c and h i g h l y branched s i l i c a I
i

polymers depolymerize much more slowly than 1inear polymers. (Here, i

I

molybdate takes the place o f hydroxide i n catalyzing depolymerization.)

:
I t appears l i k e l y t h a t l i n e a r polymers depolymerize f a s t e r because the
!
-OH groups present ( a t l e a s t two t o each S i atom) are unconstrained
L!j
!

I
 111

and can therefore facilitate inversion. By contrast, in the cyclic

b/
structure, the siloxane,bonds are relatively immobile with respect to
tetrahedral inversion. Based on purely geometrical arguments, the
inversion mechanism seems highly plausible.
However, an alternate mechanism is also possible in which the
attacking silicate ion (for the forward polymerization step) merely
replaces a hydroxid roup without inverting the si1 icon-oxygen tetra-
hedron-a mechanism o f displacement. Polymerization and depolymeriza-
tion reactions proceeding by a displacement mechanism should be
essentially unaffected by the number of siloxane bonds per si1 icon
atom. Thus, in order t xplain the experimental results by a dis-
placement model one must postulate that the bonding energy o f a
siloxane bond is strongly dependent on the number o f additional silox-
ane bonds attac to the .parent silicon atom. The analogous behavior
of functional groups attached to an aliphatic car
chemistry, i s familiar Thus, in the depolymeri-
zation of a linear polymer, b y a displacement m nism, it is likely
that hydroxide (or molybdate) attacks terminal silicon atoms selec-
 112

(activated compl ex)

A t low pH, a free hydrogen i o n can bond t o the oxygen atom o f a

I

s i l a n o l group, which tends t o somewhat weaken and lengthen the s i l i c o n -

oxygen bond. I n a subsequent c o l l i s o n step, a s i l a n o l group from

another molecule pushes through t o t h e s i l i c o n atom o f the charged

s i l a n o l , g i v i n g up i t s hydrogen t o the protonated s i l a n o l , and d i s -

lodging the r e j e c t water molecule as a hydronium ion, H30+.
The Si-0 bond t o the protonated s i l a n o l i s weakened and loosened
by t h e extra hydrogen atom, so t h a t less a c t i v a t i o n energy should be

needed t o reach the t r a n s i t i o n state. Also, the need f o r a hydrogen

atom t o t r a n s f e r from one oxygen t o the other makes simple displace-
ment more l i k e l y than inversion. This molecular reasoning agrees w i t h
the r e s u l t s of Alexander (A2) and Hurd and Barclay ( H 7 ) , who found an
a c t i v a t i o n energy o f o n l y 9 kcal a t pH 2, compared w i t h around 15 kca
a t pH 5 (as reported i n Chapter 2).
Ionization. Behavior o f S i 1 i c i c Acid Polymers
. .
The t r u e r a t e of polymerization i s too compl icated t o be descri bed
by a s i n g l e r a t e expression, because i t involves many separate reac-
I
t i o n s between molecules w i t h d i f f e r e n t molecular weights and structures.
For s i m p l i c i t y , however, two types of s i l i c a species can be considered
t o be present-an average-molecular-weight s i 1 i c i c a c i d and an average-
molecular-weight s i l i c a t e ion. For these two species, and an L
,I
 113

appropriately averaged r a t e coefficient, the instantaneous rate of

'c on i s described empirically by a simple second-order rate

Rate = k [A] [A-] ( 5 *4)

where [A] = concentration of an average un-ionized species, and [A'] =

concentration of an average ionized species. Equation 5.4 predicts a

maximum r a t e o f polymerization a t a hydrogen ion concentration equal
to an effective average ionization constant for the mixture o f s i l i c i c
. acids present n the solution.
One-of the oversimplifications of Equation 5.4 i s that i t f a i l s
to account f o r the depolymerization rate, also a function of pH, which
must be subtracted from the gross forward r a t e t o yield a net forward
rate. The rapidly increasing r a t e of depolymerization a t h i g h pH pro-
duces an asymmetrical rve for net polymerization rate versus pH (i.e.,
the r a t e decreases faster -for -pH > pKA than for pH < as shown i n
Figure 4.5. However, he minimum-time pH's for these curves (corres-
ponding to a maximum for the averaged net .rate of polymerization) not
only 1Se below 9.8, t h e for Mo-detectable s i l i c a , b u t also decrease I

with increasing extents of conversion. A. l i n e can be drawn through

these m i n j m u m points, and i t s extrapolation back towards "zero"
brim indicates a maximum-rate pH there of s l i g h t l y
less than 10. consistent w i t h an average pKA of 9.8 t o 9.9
for the i n i t i a l g solution. T h i s pH shift for the minimum ATE
onstants for si1 icic
increasing molecular
Even i f the s i l i c i c acid dissociation constants were a l l equal,
u there would still be a tendency for the maximum-rate pH to s h i f t
 114

I
towards lower pH w i t h increasing conversion, due t o increasing i n f l u -
I'
ence o f the reverse reaction. However, f o r approaches t o equilibrium
o f less than 80%, t h i s pH s h i f t o f the maximum r a t e i s n e g l i g i b l e .
I n considering the pH-shift f o r the minimum ATE time, i t must be
borne i n mind t h a t a pH which gives a maximum averaged r a t e up t o a
given conversion i s higher than the pH t h a t gives a maximum instantan-
eous r a t e a t t h a t conversion.
7 Since Equation 5.4 predicts a maximum i

instantaneous r a t e a t a pH equal t o the averaged pKA, the i m p l i c a t i o n

, . .
i s t h a t the minimum-time pH's i n Figure 4.5 correspond t o pFA's f o r
averaged polymers whose degrees o f polymerization are achieved a t

approaches t o e q u i l i b r i u m l e s s than what i s indicated by each curve.

I n other words, the s h i f t i n pFA w i t h increasing molecular weight i s
even more dramatic than i s apparent from the time-averaged curves o f
Figure 4.5
This conclusion t h a t s i l i c i c acid d i s s o c i a t i o n constants increase
w i t h increasing molecular weight i s f u r t h e r strengthened through q u a l i -

t a t i v e agreement by the experimental r e s u l t s o f other workers. For

example, gel-time p l o t s t y p i c a l l y show a minimum a t pH values near 7
(Figure 2.5). The average degree of polymerization o f s i l i c i c acids i n i

g e l l i n g solutions c l e a r l y i s higher than the average degree o f polymer- I

I

i z a t i o n o f the d i l u t e solutions o f the present study, hence the postu- . 1

I

l a t e d trend f o r increasing a c i d strength w i t h molecular weight i s

- f

substantiated.
The comparison o f minimum-gel -time pH's f o r d i f f e r e n t concen-
t r a t e d solutions provides an i n t e r e s t i n g extension o f the foregoing

analysis. Figure 2.5 shows t h a t the minimum-gel-time pH decreases

i:
with decreasing t o t a l s i l i c a concentration. This can be explained by
 I

115

noting t h a t the gel point occurs a t a higher extent of conversion i n

W
more dilute solutions, as suggested by Carman ( C l ) and demonstrated by
I l e r (12). Qualitatively, this can be explained i n the following
terms: The gel point represents a constant critical amount o f polymer
that has reached "infinite" length. For a smaller t o t a l s i l i c a con-
centration, this c r i t i c a l quantity corresponds to a higher fractional
extent of polymerization and hence to a lower average pK for the total
s i l i c a present.. Consistent w i t h this general behavior, the m i n i m u m
gel time occurs a t a lower pH for more d i l solutions. This provides
strong evidence that the individual (or i n nsic) .acid ionization con-
stants of silanols, f o r different configurations o f the parent S i atom,
can d i f f e r by a factor of over 1000. Thus, a higher average degree of
polymerization again coincides w i t h a lower pH for the maximum average
r a t e of polymerization.
Another piece of experimental evidence also shows t h a t h i g h -
molecular-weight si1 i c i c acids are stronger acids. Isoelectric-point
data f o r colloidal s i l i c a indicate that surface silanol groups are
ionized a t relatively low pH's. Schindler and Kamber (S2) report t h a t
1 groups of colloidal s i l i c a is 6.8
i d monomer, the maximu t e data w i t h
+ increasing amount of pol hous s i l i c a pK form a mono-
tonic sequence, as indica

increashg molecular weig

and 4.2) clearly sh cline i n pH as equilibrium i s approached.
W
This drop can only occur if the highernolecular-weight si1 icic acids
 116

Table 5.1
L
Observed pK Values f o r S i l i c a Acid Forms

System o r Q u a n t i t y Measured pK
I n t r i n s i c K f o r monomer, from $ 10.5*

Time-average pH f o r maximum rates

30% ATE a t 870 ppm Si02 9.2
50% ATE a t 870 pprn Si02 9.0
80% ATE a t 870 ppm Si02 8.7
Gel formation a t 25% conversion t o gel 7.9
Gel formation a t 35% conversion t o gel 7.5
Gel formation a t 60% conversion t o gel 7.0

I n t r i n s i c K f o r t e r t i a r y silanols, from
pK f o r amorphous s i l i c a (S2) 6.8

-
*pK = pKM l o g 4, because monomer contains 4 i n d u s t r i a l
s i l a n o l groups.

being formed are stronger acids. I f a l l s i l i c i c a c i d forms had the

I

same dissociation constants, polymerization would be accompanied by a I

pH increase because the number o f a c i d s i l a n o l groups s t e a d i l y dimin-

ishes. - 1
i
i
I n s i g h t i n t o the pH v a r i a t i o n i n polymerizing solutions i s pro-

vided by considering the simplest o f situations, monomeric s i l i c i c acid - I

I

polymerizing o n l y t o the extent o f dimer. I f no pH change were

observed as the r e a c t i o n proceeds, the f o l l o w i n g r e l a t i o n would hold

f o r the r a t i o o f the dimer t o monomer d i s s o c i a t i o n constants (KD and

Li
 117

+
where CH l c r i t is the unique value o f]'H[ that i s invariant. This
result is derived i n the following way. The ionization equilibria for
monomer and mer, respectively, can be written

(DO) )'H( or (DO) = DTotal Kg

(5.7)
'Total - (D-1 (H+)+ KO

A t constant pH, hence constant (OH-) ance between i n i -

t i a l and final conditions is

M-)o - (M-) = ( (5.8)

Also, the overall mass balance i s

(5.9)

(5.10)
 118

Inverting the two rtght-hand terms, w i t h cancellation of OTotal , gives

Mu1tip1 ication by w(ff+)yields

Re-inversion then yields Equation 5.5.

For a given pH and monomer dissociation constant, Equation 5.5
indicates the value the dimer dissociation constant must have i n order
that the pH not change. If the pH of the solution increases, the
actual i s smaller than the calculated critical value. On the other
hand, if the pH decreases, the actual KD i s larger than the critical
vat ue .
Equation 5.5 brings to l i g h t an interesting consequence: If the
i n i t i a l pH i s greater than p$, the pH of the solution can only i n -
crease. T h i s observation i s not restricted only t o the dimerization
reaction, b u t holds also for the complete s e t of polymerization steps.
Thus, i n any aging sample t h a t i s i n i t i a l l y a l l monomer, the pH will
only show a net increase if the i n i t i a l pH i s greater t h a n PI$. (The
pH may s t i l l reach a maximum value and then decline, but will never drop
below the initial value.) If the i n i t i a l pH i s less than p s , the pH
o f the solution may f i r s t increase and then decrease t o the i n i t i a l
value or below. T h i s semiquantitative model i s i n complete agreement
w i t h the pH behavior of equilibrium runs and unbuffered rate runs
observed i n the present study.
I '
Lj 1
I

I
!
I
!
 - <
119

Finally, the. probable causes of the increase i n aci-d ionization

' tonstant w i t h an increasing degree of polymerization must be consist-
ent. First, f o r linea polymers a t least,' the number of silanol
groups per average polymer molecule i s , g r e a t e r for the higher polymers.
A t a constant intrinsic KO, and a degree of polymerization N, the first
ionization constant (which i s most significant) i s NKO (W7). Second,
i t appears that the major effect 'on
- is a structural one. For
Si(OH)q monomer, KO is (1.26/4) x or 3.15 x For the
"primary" structure -0Si (OH as a dimer, is either the same o r
only slightly grea'ter. For a t e r t i a r y silicon atom (-O)$i(OH), as on
the surface of amorphous s i l i c a , I$i s near 1.6 x for the
secondary form, (-0)2Si(OH)2, may well l i e i n the vicinity of 10-1 0 ,
b u t further investigation of this question will be required.
Monomer-Dimer Equilibrium
In Chapter 4 i t was shown how an approximate monomer concentra-
tion could be obtained ctable si1 ica concentration
the apparent r a t e coef ent. However, the
ference between the concent table s i l i c a and
nted for. T h i s can be done by
ble s i l i c a content

, - + ...
(5.13)

where tmd stands ], [D], [T] are the un-

k, ionized 'concentrations of monomer, dimer .and
. trimer respectively; and
 120

$, KD and KT are the corresponding a c i d d i s s o c i a t i o n constants. Each

term i n t h e summation represents the t o t a l number o f s i l i c o n atoms
c
comprising a p a r t i c u l a r molecular-weight species including both ion-
>
i r e d and un-ionized forms. Equation 5.13 can be s i m p l i f i e d by assuming
t h a t o n l y monomer, dimer, and t r i m e r c o n t r i b u t e t o the molybdate-

detectable s i l i c a . This assumption i s reasonable whenever the t o t a l

Mo-detectable s i 1 i c a concentration i s not much greater than the concen-

t r a t i o n of monomer.
To solve the truncated form of Equation 5.13, i t i s necessary t o

o b t a i n e q u i l i b r i u m expressions which w i l l permit the dimer and t r i m e r

concentrations t o be expressed as functions o f t h e monomer concentra-
tion. For the dimerization reaction, as i n t e r p r e t e d by Equation 5.2,
a mass-action e q u i l i b r i u m expression can be written:

kf
M + M- D + OH- (5.14)
kr

(5.15)

The e q u i l i b r i u m concentration r a t i o , [D]/[M] 2 a constant, w i l l be

indicated as K ( l ) . An e q u i l i brium constant for the trimer-forming

reactions i s s l i g h t l y more d i f f i c u l t t o obtain because t r i m e r can be
formed by two possible reactions:
 121

D t M .
krl'

From these two equations:

(5.18)

With the a i d of the appropriate equilibrium expressions, Equation

5.13 simplifies to

t Y)tX(')
K(2)[M]3
CH+I

(1 &)
4. (5.19)

Equation 5.19 can be further simplified by relating K(2) to K ( ' ) . A

detailed look a t the mechanisms for the two trimer-forming reactions
(Equations 5.16 and 5.17) reveals t h a t ction 5.16, attack by a dimer
ion on a neutral monomer molecule, more closely resembles the dimeriza-

tion.reaction. The conclusion is therefore drawn that K ' and Keq

eq
are nearly equal , and t h u s ,

(5.20)

*
Ma k i
i s a non-linear equation w i t h three unknow
I.
 122

+Ti
3KD ,(’I2
[MI3 (1 -!&)
t (5.21)

The number o f r e l i a b l e data p o i n t s from t h e present study i s

I
l i m i t e d , and therefore a complete regression analysis using Equation

5.21 i s n o t possible. As an a l t e r n a t i v e , the experimental data from

Table 4.4 were used t o o b t a i n approximate values f o r t h e unknown para-
meters by the f o l l o w i n g procedure:

(a) A reasonable value o f KD was assumed.

(b) The data a t low pH (Run 5) were then used t o solve f o r
K ( l ) by Equation 5.21 exactly, because t h e acid-ionization c o r r e c t i v e
terms (1 t KA/H+) could a l l be s e t t o u n i t y .

(c) With t h e data from Run No. 2-11 (adjusted pH, 10.00; t o t a l
S O 2 , 0000503 M), and the newly calcu ated K(’), Equation 5.16 was
aga’in solved t o y i e l d a value f o r KT. With values f o r [MITotal,
[ T ] T ~ Q ~ , KM, KD, and ,K., a weighted-mean-average a c i d d i s s o c i a t i o n

constant was calculated and compared t o the apparent KA f o r

Mo-detectable s i l i c a . I f a close comparison was n o t obtained, a new
value of KD was assumed and steps (a) t o (c) were repeated.
I

(d) With values for a consistent s e t of the parameters ,K, &,

V I

and K ( l ) , t h e f i n a l two data p o i n t s were used t o check the p r e d i c t i n g

accuracy of Equation 5.21.

I n Table 5.2, t h e r e s u l t s o f t h i s c a l c u l a t i o n a l scheme a r e pre-

sented (Case 2). For comparison (Case 1) calculations a r e a l s o shown
i n which a l l the a c i d d l s s o c i a t i o n constants are assumed t o be equal.
 .
c d

Table 5.2
Calculations o f Mol ecular-Weight-Distri b u t i o n f o r
Mo-Detectable S i 1 i c a i n Equilibrium Solutions

Total Mo-Detect Adjusted Total Mo-Detect

Sample No. M M- -r(M) + (M-)]
2.8 .00150 00413 .00388
2.9 0.19 .00150 .00293 .00254
2.11 9.98 .00503 10.00 .00150 .00189 .00164
2.5 6.22 .00150 - 0 .00055

Total Dimer % Er
Sample No. D T T- ' and Trimer Total S i l i c a
2.8 .000446 .001228 .000104 .000720 .002498 -14.53
2.9 .000446 .000870 .000104 .000509 .001929 . - 8.77
2.11 .00164 .000446 .000561 ,0001 04 .000329 .001440 - 3.98
2.5 .00055 .000446 -- .000104 -- .00055 0.00
--I
N
w
(continued)
 .-

Table 5.2 (continued)

Case 2: $ = ,o-9.90 Kg
-- 10'9.75
KT
-- 10-9-57 - = 10-9.82,
K(1) = 94.1, K(21 = 132.9
9 9
' KA

Total Mo-Detect Si Total Dimer X Error i n

Sample No. -[(M) + (M')] D D- T T- and' Trimer Total Silica
2.8 .00388 .0004234 .0016472 .0001266 .000745 .00294 - 9.88
2.9 .00254 .0004234 .0011661 .0001266 .0005278 .00224 - 4.30
2.11 .00164 .0004234 .0007529 .0001266 ,0003370 .00164 0.00
2.5 .00055 .0004234 -- .0001266 -- .00055 0.00

NOTE: K ( l ) and K(') are based on molar concentrations. Calculated values o f

D, D-, T, T-, are g i v e n as monomer-equivalent concentrations.

c
 125

In a l l cases, the dimer and trimer concentrations (ionized and un-

LJ ionized) have been expressed as equivalent moles of monomer. I t is
\ clear that the assumption of increasing acidity w i t h molecular weight
s a better .account for the observed total s i l i c a concentration
than the assumption of invarient acidi For the two highest pH's,
Equation 5.21 the selected parame s predicts t o t a l s i l i c a con-
centrations w the observed total s i l i c a , and the d i s -
crepancies increase w i t h increasing total s i l i c a ( i .e. increasing pH).
T h i s result, although partially fabricated as a result o f the chosen
calculational scheme, is precisely the expected behavior based on the
f a c t that Equation 5.13 resulted from the truncation of higher polymeric
terms from the general form of themass balance equation. As the total
si1ica concentration increases, successively more terms (higher-
weight terms) must be included, otherwise predictions will be
low. I t was partly for this reason that the calculation scheme pre-
viously described was so chosen.
The calculations of Case 2 yield t ollowing results:
9.82, K(') = 94.1, K(' = 132.9, and
 126 .
and Bear (B2). This close comparison i s mainly coincidence, however,
since those authors assumed erroneously t h a t K(’) i s equal t o a l l .
c
higher K’s f o r monomer plus n-mer going t o (n+l)mer, and they also
,
equated t h e i r molybdate-bl ue s i 1 i c a concentrations t o monomer.

Rate Dependence on Total S i l i c a

The t r u e r e a c t i o n order f o r s i l i c i c a c i d i n the polymerization
process has been a source o f uncertainty f o r many previous investiga-

tors. The mechanism of Equation 5.2 suggests a second-order dependence

on s i l i c a , but t h i s c l e a r l y does not correspond t o what was observed
i n Figures 4.6 -‘4.9. The trend observed i n Figure 4.8, f o r example,
was t h a t the apparent r e a c t i o n order decreases with increasing conver-
sion, from 7.0 a t a 10% conversion t o 4.8 a t a 90% conversion. These
high values f o r t h e apparent reaction orders are i n d i c a t i v e o f an auto-
c a t a l y t i c effect i n t h e polymerization process; the r a t e o f disappear-
ance o f monomer seems t o be catalyzed by the formation o f polymer
products.

To i l l u s t r a t e t h i s phenomenon, consider a normal second-order

reaction, 2A-B.k The r e a c t i o n s t a r t s out w i t h a maximum r a t e o f
conversion o f A t o B, k[A]: , and c o n t i n u a l l y decreases as the q u a n t i t y

o f reactant decreases. However, t h i s i s not the case f o r the disappear-

ance o f monosilicic a c i d during the e a r l y stages o f polymerization.
Here, a p l o t o f approach t o equilibrium versus time on a l i n e a r scale
yields a straight line. This i s i n d i c a t i v e o f a constant r a t e period
where a tendency f o r t h e reaction r a t e t o diminish due t o the depletion
o f reactants i s opposed by an accelerating e f f e c t produced by the

accumulation of polymer which catalyzes the reaction. Acceleration o f

L d
the polymerization process therefore depends on t h e l e v e l o f polymer
 127

formed. For solutions w i t h higher i n i t i a l concentrations of monomer,

LJ polymer i s b u i l t up more quickly, consequently the acceleration occurs
a t an e a r l i e r stage of conversion.
Figure 5.1 clearly demonstrates the effect of autocatalysis. The
runs shown were replotted from Figure 4.4 w i t h time expressed on a
\
The most interesting features of these curves i s that
the maximum reaction r a t e i s shown to occur well a f t e r polymerization
has been initiated and to remain constant over a significant portion of
 127a
.
4
0
L

"
j
0
0
F

0,
0
0
co
0
CI
0 0
.
(D
 128

weight and gives r i s e to t h e autocatalysis.

W
I t i s w e l l t o supplement t h e mathematical explanation j u s t given
by a c l a r i f y i n g verbal explanation: Since a s i l i c a t e anion i s a neces-
sary c o n s t i t u e n t f o r polymerization t o occur, increasing the l e v e l o f

- s i l i c a t e anions w i l l increase t h e r a t e o f f u r t h e r polymerization, pro-

vided t h e r a t i o o f anions t o neutral molecules i s l e s s than u n i t y .

Because higher-molecular-weight s i 1 i c i c acids are stronger acids, the

polymerization process produces ( f o r a time) more s i l i c a t e ions than i t

uses up. These new anions, i n turn, contribute t o the polymerization

process. The trend i s i n t h e d i r e c t i o n of maximum-polymerization
r a t e conditions, where there are equal concentrations o f s i 1 i c i c acids
and s i l i c a t e ions i n solutions.
There i s an i n t e r e s t i n g consequence o f t h i s theory. Autocata-
l y t i c effects were observed i n the present experiments because pH's
o f t h e buffered solutions were lower than the e f f e c t i v e pi'$,'s o f the
s i l i c i c acids i n t h e solutions. For t h i s situation, polymerization
r e s u l t s i n a more equal number o f un-ionized and ionized a c i d molecules
and therefore an fncreased polymerization rate. I f , however, the r a t i o
of ionized t o un-ionized a c i d molecules i s greater than u n i t y (i
.e., the
pH i s greater than o r equal to t h e e f f e c t i v e pi$ f o r the s i l i c i c acids

present), instead the r e a c t i o n r a t e w i l l slow down w i t h increasing

conversion. I f i t were possible to adjust t h e pH continuously during
the course of polymerization so that t h e ionized t o un-ionized concen-
t r a t i o n r a t i o was always constant, t h e reaction r a t e should e x h i b i t a
pure second-order e f f e c t ( i n s i 1 tca) .
\

W
The'experimental r e s u l t s i n Figures 4.6 - 4.9 indicate that the
degree o f autocatalysis decreases with increasing extents o f conversion
 129

the apparent reaction order decreases). This observation is

W
consistent w i t h the above discussion. Referring t o Equation 5.1,
bsol Ute slope of the reaction rate curve versus pH decreases
rapidly as p approaches pFA. That is, when the ratio of ionized t o
un-ionized molecules is very small (as when pH<<pKA), s l i g h t increases
i n the level o f s i l i c a t e anions w i l l have the greatest effect i n
accelerating further polymerization. As polymerization proceeds, and
lowers the pKA of the s i l i c i c acid i n solution, i t reduces the differ-
ence between pKA and pH ( i f the solution is buffered the pH is
assumed to be constant). Autocatalys i s is reduced because continuing
pFA decreases have a smaller accelerating effect. The pH for the runs
i n Figure 4.4 was 8.0, well below the effecti\ie pKA o f the s i l i c i c acid
i n solution a t i n i t i a l extents of conversion. However, for ATE = 808,
the minimum pH of the curve i n Figure 4.5 is not much larger than 8.0.
Therefore, the apparent r a t e dependence o pH i n Figure 4.8 f o r the
80% ATE curve is significantly lower than t h a t for the 30%ATE curve.

oncentration on the rate of

by a second-order reac-
tion between a nd an ionized s i l i c i c
ecule, provided one also a es that the acidic strength of
acid increases w i t h molecu i g h t . T h i s assumption i s
. mental evidence:

itation rate shifts

ng extents of conversion.
(b) The pH .of most unbuffered polymerizing solutions decreases
LJ i s less .than the i n i t i a l prA.
 130

(c) The pKA for silanol groups on the surface of colloidal par- i
t i c l e s has been reported t o be 6.8.'
(d) The pH for minimum gel times l i e i n the neutral range (pH
7 to 8), and shift toward lower values for less concentrated solutions.
(e) The equilibrium concentration o f monomer a t h i g h pH suggests
a value a f p$ = 9.9. The average PKA for low-molecular-weight s i l i c i c
acids (Mo-detectable s i l i c a , of which monomer represents 60% o r greater)
is 9.8.
From a molecular viewpoint, the idea t h a t larger s i l i c i c acid molecules
are stronger acids is reasonable. Two probable causes for this are the
larger number of silanol groups per molecule, and the enhanced acidity
of a silanol group when more than one siloxane bond i s attached t o i t s
parent silicon.
The model which has been presented provides consistent explana-
tions for nearly a l l o f the observed behavior of s i l i c a i n solution.
I t connects the observations for s i l i c a i n both dilute and concentrated
'
solutions, and places them into a consiste.nt framework. Discrepancies
i n both the reported reaction orders and the pH's for maximum polymer-
ization rates can now be systematically explained. As an example, the
I

i n i t i a l average degree of polymerization for the s i l i c a i n solution,

I
!
although seldom noted i n previous experiments, has a pronounced effect
on the macroscopically observed behavior.
The model, however, is not yet quantitative, and cannot be used
to predict accurately the polymerization behavior of s i l i c a i n aqueous
I

media. There are innumerable possible polymerization reactions involv-

ing s i l i c i c acids o f unknown acid strengths, degrees of branching, and
extents of cyclization; therefore, the number of unknown rate
!
 131

coefficients and equilibrium factors is also large. More quantitative

LJ
information about acidities, structures, rates, and equilibria of the
different s i l i c i c acids is vitally important.
The eventual attainment of a successful kinetic model depends on
continued research t o unravel the chemical mysteries of polysil i c i c
acids. In the final chapter, several suggestions are offered for
add i t i ona 1 study .
 132

Chapter 6

CONCLUSIONS AND RECOMMENDATIONS

.

This chapter summarizes the major conclusions o f this study. In

the first of three sections, conclusions on the behavior of s i l i c i c
acid i n aqueous solution will be presented. T h i s section w i l l include
new inferences stemming from the results of the present experimental
work, as well as important f i n d i n g s of previous workers. The second
section will briefly relate these conclusions t o the problem of s i l i c a -
scale formation i n geothermal brines. In the final section, recommend-
ations will be offered for the direction of additional work which must
be performed t o f u l l y understand the problem of silica-scale formation.
Fundamental Poi n t s
(1) Monosilicic acid i n aqueous solution will polymerize when
its concentration exceeds sane equilibrium value which is an increasing
function of temperature. Polymerization is characterized by the 1i n k -
ing together of two silicon-centered-oxygen tetrahedra by the sharing
of a c m n oxygen atom. The polymerization reaction is regarded as
condensation polymerization, because a water *molecule i s s p l i t out
uhen two silanol groups combine to produce a siloxane bond.
(2) Solid amorphous s i l i c a represents the ultimate polymeric
form (noncrystalline) o f monosil i c i c acid. When solid amorphous s i l i c a
is contacted w i t h water, the concentration of nonosilicic acid builds
up i n solution toward i t s equilibrium value. As i n any reversible
chemical system, during the course of net depolymerization, monosil icic
acid will be continually repolymeriring; so that, a t equilibrium, the Li
n
 133

rates of polymerization and depolymerization are equal. The repoly-

L, mertzation o f monomer occurs mainly, although not exclusively, as a
recondensation of monosilicic acid onto the sol i d amorphous silica.
Some of the monosilicic acid polymerizes w i t h i t s e l f or other s i l i c i c
acids i n solution to form polymeric s i l i c i c acids. The small polymers
i n i t i a l l y formed can i n t u r n polymerize w i t h each other or more mono-
mer and continue to. grow. Eventually,' a maximum concentration o f
polymer is reached because the rate of further polymerization just
equals the rate of depolymerization o f the polymer formed. When s o l i d
amorphous s i l i c a "dissolves" i n water, equilibrium 5s established such
that the amount of monomer comprises a large portion of the total
s i l i c a i n solution.
(3) When a Ion o f monosilicic acid b supersaturated,
by either a decrease i n temp ture, evaporative concentration, o r neu-
tralization of monosilicate anions, a n forward polymeri zati on takes
place such that equilibrium is restored. In the absence of any s o l i d
amorphous s i l i c a ( i uding colloi particles), the monomer will
polymerize i n solution, and the concentration of polymer may b u i l d up
to relatively h i g h levels without precipitating. ( I f colloidal s i l i c a
is ion will occur p a r i l y as a condensation of
monomer onto t h

iop), the entire solution will form a s o l i d gel. At

ess than t h i ncentra tiori
r i z a t i o p can result i n
the format ion o f h i g h -mol ecul a r -wei gh t par ti cl es o l l o i d a l size
b/ which a r e soluble under certain conditio owing to hydrogen bonding
 134

and ionic interactions occurring i n aqueous soluti

(4) The polymerization reaction (siloxane bond-forming reaction)
proceeds by the reaction of a neutral s i l i c i c acid molecule w i t h a
si1 icate ion.
(5) The strength of s i l i c i c acids increase
molecular weight ( i .e., KA increases w i t h increasing molecular weight).
(6) The acid dossociation constant for monosilicic acid i s
l0'9.9

(7) The average acid dissociation constan

lution of low-molecular-weight si1 icic acids (
1009.8

( 8 ) The maximum r a t e of polymerization as a m function of pH

occurs a t a pH equal to the average pKA (= pi$,) for the s i l i c i c acid i n
solution. As the average degree of polymerization increases, the maxi-
mum r a t e point shifts t o lower pH's.

(9) For pH-buffered solutions, the apparent overall reaction

order i n s i l i c a , n, for the polymerization of low-molecular-weight
s i l i c i c acids is greater t h a n 2 when pH c pKA, and less than 2 when
pH > PKA.

(10) The equilibrium constant for the dimeri

- = 0.00748. The concentration ratio, [D]/[M] 2 is
Keq [M][M-]
constant equal t o 94 liters/mole.
(11) The solubility of un-ionized monosil.icic acid
independent of pH, and equal to 0.0015 moles/l i t e r
*
(12) The approximate monomer : dimer : trime
equilibrium solutions for pH's less than 10 i s 45 : 1. With t h i s
 135

d i s t r i b u t i o n , therefore, 75% of the total silicon is present as mono-

mer, 20% as dimer and 5% as linear trimer. The d i s t r i b u t i o n is likely
to s h i f t towards higher percentages of monomer w i t h increasing temper-
a ture.
(13) Monosilicic acid reacts w i t h excess molybdate color reagent
(as prepared by Alexander's method ( ) by an apparent first-order
irreversible reaction whose rate coefficient a t 24.5OC i s approxi-
mately 2.05 min-'. The yellow color i s stable for a t least 15 minutes.
The energy of activation for the color reaction is approximately 20
kcal/mole for the temperature interval from 18 t o 3OOC.
(14) Linear silicic acid polymers will depolymerize i n the pre-
sence of molybdate reagent and contribute t o the concentration o f
detectable s i l i c a . Cyclic and highly branched polymers do not depoly-
merize readily i n the p nce of molybd eagent.
(15) The polymerization reaction is exothermic; the heat of solu-
tion (depolymerization) o f amorphous s i l i c a is 3.35 kcal/mole, which
. - .

suggests that the heat of siloxane bond formation by water removal is

i l l therefore decrease
 136

Implications for the' Formation of Silica Scale

(1) The potential for scaling exists whenever the concentration
of monosilicic acid exceeds the equilibrium solubility limit for amor-
phous s i l i c a a t the temperature of the solution. ( T h i s is true pro-
vided amorphous s i l i c a i s a metastable phase a t the temperature i n
question.)
(2) In general, s i l i c a scale formation w i l l be much more rapid
i n neutral and alkaline brines than i n acidic brines. I t i s unlikely
that the naturally occurring pH's will ever be high enough t o retard
scale formation by reducing the concentration of un-ionized species.
Thus the observed r a t e of formation should continually increase w i t h
increasing a1 kal i n i ty.
(3) Except i n instances of high degrees of supersaturation,
scaling probably occurs by a stepwise condensation of monosilicic acid
molecules onto a surface which contains bonded OH groups capable of
liberating hydrogen ions. The OH groups can be silanol groups i f a
s i l i c a layer is already present, or the hydroxide layer of a corroded
metal surface. I f no corrosion of the metal surface has occurred, a
s i l i c a scale is much less likely t o form. The rate of deposition of
silica will depend on the degree of ionization of the surface silanol
groups or other hydroxyl groups. Assuming the pKA of these groups is 1

greater than 6, scale deposition will be relatively slow a t pH's below

< ,

5. The density of the scale fonned will depend on the rate of deposi-
. .

tion. Very slow rates will produce dense scales ( i .e., scales w i t h
low moisture contents).
(4) In highly supersaturated solutions, polymerization of si1 ica c, i

in.solution will be most rapid i n neutral and alkaline solutions.

 137

LJ There is a likelihood .that this polymerization will result i n the co-

precipitation of colloidal s i l i c a w i t h metal cations. Metal silicate
precipitates will be more prevalent i n brines containing significant
portions of polyvalent cations. Aluminum and iron are potentially the
strongest precipitation accelerators.
(5) For a given degree of supersaturation, the rate of scale
fornation will be a strong function of temperature.
Recommendations for Further Study
The present resea h has helped to define the behavior of s i l i c a
i n aqueous solution. I t has focused upon the polymerizing nature o f
s i l i c i c acid, and has identified a'mechanism which accounts q u a l i t a -
tively ,for much of the previously observed behavior o f s i l i c a over a
wide range of conditions, I t has identified the probable scale-
formation mechanisms , nd has indicated how different chemical and
physical conditions- will influence the rate of scale formation. How-
ever, a great deal of additional work needs t o be done before the
problem of scale formation i s ' understood sufficiently t o define appro-
priate measures that
The foremost o tive o f future research into the problem of

conditions under which they occur. Care should be exercised i n the

proper simulation of geothermal brine I t is not advisable t o u t i l i z e
W
actual geothermal brfnes i n a r t i f i c i a l t e s t systems, for such f l u i d s
 138

may have undergone an irreversible chemical transfonnation during the

interval from i n i t i a l collection t o eventual reuse. I t may also be
misleading t o simply dissolve pure amorphous s i l i c a i n water. The
best simulation procedure, then, a1 though certainly the most d i f f i c u l t ,
would be t o u t i l i z e actual reservoir rock samples from the geothermal
,area of interest, and to partially dissolve these i n water a t h i g h
temperature .
Once an appropriate a r t i f i c i a l brine is "synthesized," a wide
variety of physical situations could be simulated t o yield meaningful
Information on scale formation. Such t e s t simulations might include:
flashing i n the well, phase separation, operation of b r i n e heat trans-
f e r equipment, deposition of scale on clean versus corroded surfaces,
etc. The results of this present study can be employed as useful
guidelines i n defining and setting up these experiments. One particular
system is discussed briefly i n Appendix 4 as an example of the k i n d of
practical information that can be gained from simulation-type studies.
I n i t i a l simulation studies w i l l hopefully provide detailed
information on the mechanisms of silica-scale formation under geo-
thermal operating conditions. Subsequent. study should then be devoted
to establishing the rate of scale development and understanding the
factors t h a t influence it. Here, the research program should probably
follow two distinct paths. One would involve a comprehensive schedule
of continued simulation to determine empirically the rate of scale
development under various operating conditions. The other would entail
a detailed chemical study of the various scale-formation reactions t o
obtain a kinetic model t o predict the rate of scale formation.
In this regard, kinetic data on the polymerization of monosilicic
 139

acid w i t h either a corroded surface, an amorphous s i l i c a surface, or

'bi
other s i l i c i c acids i n solution would be of considerable interest.
Such studies could be performed i n i t i a l 1 low temperatures, b u t
eventual scale-up to higher temperatures is essential. In conjunction
. w i t h this study, i t is particularly important t o determine quantita-
tively the dependence o f acid strength on molecular size. In addition,
efforts should be made t o understand the molecular structure of
colloidal s i l i c a , gels, and hard amorphous s i l i c a scales. With such
information available, significant strides would have indeed been made
towards the understanding o f silica-scale formation. Ultimately, once
the si 1ica -scal e problem i s suf f icierr t l y understood , the appropriate
corrective action can be taken.
General Conclusion
In connection w i t h geothermal energy development, the present
research project has explored the problem of silica-scale formation i n
the perspective of what i s known about the aqueous chemistry of s i l i c a .
New experimental data and theoretical deductions have been added t o \ \

previously ex n i n g need for extensive a d d i -

tional information on si1ica the combined effort
o f many i n d i v to these complex
problems, geo w i t h sufficient
success t o i m

w
 ~

,j
140

BIBLIOGRAPHY

A1 Alexander, 6. B., Heston, W. M., and I l e r , R. K., 3. Phys. Chem.,

-
58, 453 (1954) .
A2 Alexander, 6. B., J. Am. Chem. SOC., -
76, 2094 (1954) .
A3 G. B., 3. Am. Chem. Soc., -
75, 5655'(1953).
A4 Alexander, 6. B., J. Am. Chem. SOC., -
75, 2887 (1953).
A5 -
A l l e g r i n i , 6. and Benvenuti, G., Geothermics Special Issue No.
2, (U.N. Symposium on t h e Development and U t i l i z a t i o n o f Geo-
.
thermal Resources, Pisa, 1970) , Vol 2, Part 1, 865 (1970).
A6 Allen, L. H. and Matijevic, E., 3. C o l l o i d and I n t e r f a c e Sci.,
33 420 (1970).
-9

A7 Allen, L. H. and Matijevic, E., 3. C o l l o i d and I n t e r f a c e Sci-.,

31 287 (1969).
-9

A8 Allen, L. H. and Matijevic, E., J . C o l l o i d and I n t e r f a c e Sci.,

-
35, 66 (1971).
A9 Anderson, 3. H. , "Thermal Wells f o r Power Production," a paper
presented a t t h e A.1.Ch.E. national meeting, Dallas, Tex.,
Feb. 20-23, 1972.
. A10 Ashley, K. D. and Innes, W. B., -
Ind. Eng. Chem., 44, 2857 (1952).
A1 1 Austin, A. L., Higgins, 6. H., and Howard, J. H., "The Total
Flow Concept for Recovery o f Energy from Geothermal Hot Brine
Deposits," UCRL-51366 TID-4500, UC-51, prepared under A.E.C.
Contract No. W-7405-Eng-48, Apri 1, 1973.
s,532 (1955).
I ,

81 Bechtold, 14. F., J. Phys. Chem.,

82 Bishop, A. D. and Bear, J. L:, Thennochim. Acta, 3, 399 (1972). - I
I
B3 Bishop, A. D., Ph. D. Dissertation, Univ. o f Houston (1967). = I
84 Brady, E. L., J. Phys.. Chem., 57. 706 (1953). i
- ,

B5 Brady, A. P., Brown, A. G., and Huff, H., J. C o l l o i d Sci., -

8,
252 (1953).
. c1 Carman, P. C., Trans. Faraday SOC., 36, 964 (1940).
I

c2 Chow, D. T. and Robinson, R. J., Anal. Chem., -

25, 646 (1953).
I

c3 Comisidn Federal de Electricidad, P r i v a t e Comnunication, Cerro

Ll :
Prieto, Mex., Jan. 1974.
!
 141

u c4 of Energy in an Industrial Society," in

. H. Freeman and Co., San Francisco, 83-94,

- D1 n, R., 3. Chem. Phys., -

17, 664 (1948).
02 P., 3. Phys. Chem., 53, 1 (1949).
I D3 Debye, P. and Nauman, R., J . Phys. Chem.,%, 1 (1951).
04 Debye, P. and Nauman, R., 3 . Phys. Chem., 65, 10 (1961).
D5 Dienert, F. and Wandenbuicke, F., Compt. rend., 176,1478 (1923).
El Eitel, W., The Physical Chemistry o f Silicates, Chicago Univ. ,
hicago, 1954
F1 . J.9 J . Am. hem. Soc., 63, 3083 (1941).
F2 Fournier, R. 0. and Rowe, J . J . , Am. 3. Sci., 264, 685 (1966).
F3 , J. Phys. Chem., 901 (1937).
F4 Frost, A. A. and Pearson, R. G., Kinetics and Mechanisms, Second
Ed., New York: John Nil
F5 Fujii, Y. and Akeno, T., Geothermics
(U.N. Symposium
-
Special Issue No. 2,
the Development and Uti1 ization of Geothermal
Resources , Pisa 2, Part 2, 1416 (1970).
G1 Gofo, K., J . Phys. 1007 (1956)
62 (1 964).
63 Greenberg, S. A. and Price, E. W., J . Chem. 9 61,1539
(1957).
64

66
. 67
68
H1

LJ H2
 142

H3 -
Hermannsson, S. , Geothermics Special Issue No. 2, (U.N. Sympo-
slum on t h e Development and U t i l i z a t i o n o f Geothermal Resources,
. L-
Pisa, 1970), Vol. 2, P a r t 2, 1602 (1970).
H4 Hurd, C. B., Chem. Rev., E, 403 (1938). e

H5 Hurd, C. B. and M i l l e r , P. S., J . Phys. Chem., -

X, 2194 (1932).
H6 Hurd, C. B., Frederick, K. J . , and Haynes, C. R., 3. Phys. Chem., v-

-
42, 85 (1938).
H7 Hurd, C. B. and Barclay, R. W., J. Phys. Chem., -
44, 847 (1940).
H8 Hurd, C. B. and Marotta, A. J., J . Am. Chw. SOC., 62, 2767
( 1940) .
H9 Hurd, C. B. and Sheffer, H. E., J . Phys. Chem., 45, 588 (1941).
H10 Hurd, C. B., Pomatti, R. C., Spittle,, J. H., and Alois, F. J.,
J . Am. Chem. SOC., 66, 388 (1944).
I1 I l e r , R. K., The C o l l o i d Chemistry o f S i l i c a and S i l i c a t e s ,
Cornell Univ. Press, I t h i c a , New York, 1955.
I2 I l e r , R. K., 3. Phys. Chem., '57, 604 (1953)..
I3 f l e r , R. K., J. Phys. Chem., -
56, 680 (1952).
31 -
James, R., Geothermics Special Issue No. 2, ( U . N . Symposium on
the Development and U t i l i z a t i o n o f Geothermal Resources, Pisa,
.
1970), Vol 2, P a r t 2, 1676 (1970).
52 Jolles, H. and Neurath, F., 2. angew. Chem., 11,893 (1898).
K1 Keggin, J . F., Proc. Roy. SOC. (London), A144, 75 (1934).
K2 Kennedy, G. C., Econ. Geol., -
45, 629 (1950).

K3 Kitahara, S., Rev. Phys. Chem. o f Japan, 30, 115 (1960).

K4 Kitahara, S., Rev. Phys. Chem. o f Japan, 30, 131 (1960). t

K5 Krauskopf, K. B., Geochim. e t Cosmochim. Acta, -

10, 1 (1956).
*

L1 LaMer, V. K., J. C o l l o i d Sci., -

19,' 291 (1964).
L2 Lehrman, L. and Shuldener, H. L., Ind. Eng. Chem., 44, 1765
7

(1952).
M1 -
Mahon, W. A. J., Geothermics Special Issue No. 2, (U.N. Sympo-
sium on the Development and U t i l i z a t i o n o f Geothermal Resources, (+!
I

PSsa, 1970), Vol. 2, P a r t 2, 1310 (1970).

 143

M2 M e r r i l l , R. C. and pencer, R. W., J. Phys. and C o l l o i d Chem.,

h, -
54, 806 (1950). '
M3 Molina, B. R. and
2, (U.N. Symposium
-
eothermics Special Issue No.
t and U t i l i z a t i o n of Geo-
* thermal Resources, Pisa, 1970), Vol, 2, Part 2, 1377 (1970).

M4 Morey, 6. W., Four R. O . , and Rowe, J. J., Geochim e t

*
Cosmochim. Acta, 16, 1029 (1962).
M5 Morey, 6. W., Fournier, R. O . , and ROW& J. J., J. Geophys. Res.,
69 1995 (1964).
-9

W. and Hesse . M., Econ. G e o L 46, 821 (1951).

N., J . Indian Chem. Soc., E,801
SOC., 9,907

inera1 Resources ,

, 12, 162 (1955).

J . Res., -
27B,

01 O'Conner, T. L., J. Phys. Chem., 65, 1 (.1961).

02 Okamoto, G., 0 dG Geochim. e t Cosmochim. Acta,
-'
12 123 (1957)
03 O'Melia, C. R. umm, MI, J . ColloSd and
437 (1967).
04 Otawa, 1. and Fujii, Y.,

-
.

t h e Development and U t i 1i z a t i o n o f Geothermal Resources, P i sa,

hi 1970) Vol. 2, P a r t 2, 1546 (1970).
 144

s2 Schindler, P. and Kamber, H. P., Helv. Chim. Acta, -

51, 1781
(1968) .
s3 Slabaugh, W. H. and Parsons, T. D., General Chemistry, John Wiley
and Sons, Inc., New York, 1966.
s4 Southern California Edison Co., "In Search of Steam," 1974.
S5 Stillwell, C. W., J. Chem. Educ., -
10, 667 (1933).
S6 Strickland, J. D. H., J. Am. Chem. SOC., -
74, 872 (1952).
s7 Strickland, J. D. H., J. Am. Chem. SOC., 74, 862 (1952).
_.

s8 Strickland, J. D. H., J. Am. Chem. SOC., -974 868 (1952).

T1 Treadwell, W. D. and Wieland, W., Helv. Chim. Acta, -
13, 842
( 1930) .
V1 Vait, J. G., Soluble Silicates, Their Properties and Uses, Holt
Reinhold and Co., New York, 1952.
hf1 Irleitz, E., Francke, H. and Schuchard, M., Chem. Zeit., -
20, 256
(1950) .
hf2 Weyl, W. A., "A New Approach t o Surface Chemistry and t o Hetero-
geneous Catalysis," Mineral Industries Exp. Sta. B u l l . No. 57,
Pennsylvania State College (1951).
w3 White, D. E., -
Econ. Geol., 63, 301 (1968).
w4 White, 0. E., Brannock, W. W., and Murata, K. J.., Geochim. e t
Cosmochim. Acta, -
10, 27 (1956).
w5 Wills, J. H., Encyclopedia of Chemical Technology, eds. K i r k ,
R. E. and Othrner, D. F., Interscience Encyclopedia, Inc., New
York, Vol. 12, 303 (1954).
W6 Wood, J. M., Beecher, J., and Lawrence, P. S., Corrosion, 3,
1 7 t (1957).
w7 Wall, F. T., and Butts, E. H., Jr., 3. Chem. Phys., -
17, 1330
(1949).
Y1 Yanagase, T., Suginohara, Y. and Yanagase, K., Geothermics -
Special Issue No. 2, (U.N. Symposium on the Development and
Utilization of Geothermal Resources) Vol. 2, Part 2, 1619 (1970).
 144a

ACKNONLE DGMENTS

I wish t o express ~IY sincere appreciation o Professor Theodore

Vermeulen whose unselfish devotion of time was instrumental i n the
successful completion of t h i s thesis. I w i s h also t o extend special
thanks t o Gerhard Klein, who continually provided helpful suggestions
and asked thought-provoking questions i n the course of this research,
and t o Professors A. 0 . K. Laird, Scott Lynn, and M. Gopala Rao whose
invaluable i n p u t s t o the content of this thesis are respectfully
acknowledged. Among a l l the other people who helped me d u r i n g the
course of this research, Felix Tsai and Ignacia Huang both provided
invaluable assistance through their wise counsel and continual probing
i n an unbiased pursuit f o r uncompromising answers to d i f f i c u l t research
problems. I also gratefully acknowledge the support of the office and
technical s t a f f of the University's Sea Water Conversion Laboratory a t
the Richmond Field Station, and financial support from the Atomic
Energy Commission (now the Energy Research and Development Administra-
tion). Lastly, I wish t o express my heartfelt thanks t o the secre- ,
I

t a r i e s who masterfully created a finished. thesis from a jungle of

penciled-in legends and corrections and of crossed-out sentences ,
the figures).
 145

,
APPENDIX 1
bi RATE RUNS: EXPERIMENTAL DATA

. WFtERfO R 4 t f RUN 1

- 8 rne
6. C 5

6.00
--. .-... . - ... - . .- . .. . . ..
.. .,---- ....-.*- -_-.- -.. . (IWFERED RATE RUN 3

- -.-e. ..STOCK SOLUTION

f RE SIN SLURRY1
- HETASIL.rG*
10901
HCL,W.lN.
2
UATERrML.
200
,

- --
-..-.
-
SCIPLE
---- - -_--.
- . --!?3
STOCKrPL.
- .-.
HCL;ML.rH;
. -
'-NAOHmuL.rN.
12.5 0.05-
NAOACrML . t k *
22.0 2,
WATCRvYL.
65.5

---.-- -- TRA&SFIIITANCE READINGS (1 Y L I I S O ' E l . PEACFNT 1

-- , -- - . ---. I. COLOR OEVELOP,YENT T WnF ( SEC i

30*"-xS 60 75 90 120. 159. 180. 2 4 0 , 3 0 3 . L O U & ?p
',STOCK 55.0 46.5 37.8 33.3 30.2 26.2 24.0 23.5 22.4 21.7 21.3
REACTIOY
..?..4e.v. HI N . ~ . --" -4s. 5 3 9 . s . ... 32.0
--.5
10
0
_____ 5+.0
45.0
4800
3 9 - 3 35.0
42.5 38.3
28.0 2 5 . 8
28.0 31.8
31.8 29.7
3508
24.7 23.7 23.2
25.1 2 4 . 2 23.6
29.0 27.7 27.3
- --. 15 58.3 50.5 45.2 11.1 34.5 32.,3
38.2 30.8 29.4 24.3
20 60.0 51.6 46.2 42.3 39.5
36.3 3403 34.0 33.0 32.5
--3o ---. 58.5 53.2 49.1 42.8 40.5
46.5 3U.5 37.5 37.1
70,O-62.0 57.0 53.5 50.0
47.6 45.8 45.5 b4.5 4L.O 6.95
-
--PO " - 71.5 65.0 60.6 57.5 S3.0 51.7 50.8 50.5 5 0 . 5
90 76.s 70.5 66.5 64.0 61.8 59.5 58.4 58.0 5t.2 57.2
.- 420
180
-
. 77.0 t2.5
76.0
4903 56.5 64.5 62.2 63.5
72.8 71.0 69.5 67.5 66.8
t 0 . 5 6C.O 60.1
66.0 6 5 . 5 6 5 . 5 60 9Q
t 4 P - -.- .---- ..- w* -.. .
0 .._.- 7005-4900 68.4 68.2- 6 8 . 0 67.5 ..
 147
,
 i

WFFEREO R A T € RW 7

... .-. ... T R A N S W l l T A l C F R F A O I N G S t 1 M L o l 5 0 *Lo RCACENT)

-. COLOR DE VF LClPCEW T I NE f $Et J

30 45 60 75 90 120- 150. LUG. 2400 300. ObWN LLCN L S Y h PH
STOCK 44.0 34.5 29.3 25.8 23.7 21-1 20.0 19.5 19.0 l 8 . d 18.6
REACT ION
... TARE* WIN. . .
0 25.6 23.0 22.5 Fa25
. . - . 2.5
S
.............. - . _ 40-S 38.0 37.8
46.C 44. 7 +3.2
1.s - . -- - _- 48.0 47.0 46.5
-,,as 10
...... __ - ..____. . . - :.-- . ...._.___. . . . . S1.3
52.0 50.5
51.1
50.3
51.3
9-49

20 S3.6 52.4 5Z.C S-3L!

30 . . . . 5’1.0 sc.5 56.4 9.4.)
4s 57.c s4.4
. . 120
60
76.0 72.0 60.0 6 5 0 s 63.5 61.4 60.5 60.0 59.5 59.5
st.4 51.0 F.43
59.0 S0.7 9.5=
.-,_19 4~ MRS
"its - .- . . . . ... -. -.- . 63.0
65.8
b2.3
,
9.45
9.9s
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- - 6UFFEREO R41E R U h 8

LOW PH

. . . . . . . . . . . . . -_...-_
p
-----w45 ............ 9.65

--. 60 -_-
. .90 ............
9.75

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 149

_-
-.. - - - - _ -.. . 9 --....--. - -. - . .-
--.- ST.OCK SrJLtlfICN
{RESIN SLURkY)
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(59
' ,
t-
.- T_+NSFI TTANCE READINGS ( 1 ML .IS0 ML REAGENT

OEVELOPYEYT T I M E t SET. I
5 9 0 1 2 0 , 150. i a o - 210. 300. ~ O W N P H
0 0 29.2 2 6 . 0 2 4 . 3 23.4 2 2 . 4 2 2 . 0 21.7

5!5-0-'46;0 39. 05
-.. 32.4 28.6 26.0 24.7 23.4 21.3 9.96
-8 34.6 30.9 2d.8 27.5 25.9 25.0
00 34.8 31.0 29.7 27.5 25-3 24.8
20 57.0 48.5 43.0 39.3 36.0 32.4 30.3 29.0 27.7 26. I 10*@5
-bo-'--- 58.5 50.3 4405 10-5 37.4 33.5 31.5 33.5 29.3 28.5
3 5 0 3 . 4 8 0 5 44.5 40.6 36-3 33.5 32.1 30.9 30.0 10 005
6 3 ; 5 54.5 48.5 4 4 . 9 41.3 36.8 34.1 32.9 30.5 '
61.-0.5203 46.5 6 2 . 5 3905 35.9 3 4 - 0 32.0 32.1 31.9 9.95
90 62.0 54.0 48.0 44.3 41.5 31.9 34.2 35.4 34.5 33.5 10 000
I20 .62.5 54.5 48.5 k4.0 41.9 38.4 36.5 3 5 - 6 34.6 34.2 LO. 00
62.0 53.3 411-3 44-S 41.7 38.5 3 6 - 9 36.3 35.6 34.8 10oC5

---- 4 RES I N SLURRY

CL-1 R o kATERrPL.
2 200
 150

--. --
--. TIPIES WIN,
0
- 43-00'3500 31.5 '29.2 27.5 25.5--24.5'23.5 23.C 22.5 7-95
- 10
20-
47.0-37o5 33.5
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3305 28.5 26.5 25.4 24.8 23.3 2 3 . 9
32.3 30.5 20.5 27.8 27.5 27.2 27.0
---. 30 52.0 45.0 41.0 38.5 36.5 34.9 33.8 33.3 32.8 32.6 7. es
45 --- 57.0 50.0 46.0 43.5 42.0 40.4 39.5 39.0 38.7
38-1
--bo-. 6105 55.5 51.5 49.0 4703 4507 44.8 4405 4 4 . 0 43.7
. 75' 62.5 56.3 52.8 51.3 4905 48.3 47.8 47.5 4 7 . 2 47.3
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--i-20-- - 67.0 61.0 57.5 56.0 54.5 53.0 52.4 52.1 S l . 8 52.9 7.82
150 68.5 53.0 60.0 s8.o 56.8 5s.e 54.8 54.7 54.7
--& 80'--- - 7010 64.5 61.5 59.5 58.5 57.0 -- 55.5 5 5 - 0 56.0
240 71.0 66.0 62.5 61.0 5C.8 5.8.8 58.1 5 7 - 8 5 7 . 5 57.5
-3'60--- - 71.5 67.0 64.0 62.2 41.3 63.0 5 9 ; s 59.2 5 8 - 7 59.5 7. e2
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------- - 50 - - -. . . 18 0.03 50 2 82
.-_----- .-- -.TRANSMITTAKCE READINGS ( 2 ML./SO PL. RFAGFhf)

- - -
30 45
COLOR DEVELOPMENT T l P E ( S E C I
60 15 90 1230 150. I d & 2 4 0 . 30C. 1Owk PH
- STOCK 49.0 43.0 34.4 30.5 27.8 24.4 21.0 22.5 21.8 2c'- 5
REAC T I DN
... l H E I -nI N -. . __ . . .- - . .
,--e 0 - --.-.42.0 31.5 27.2 25.5
29.7 23.3 22.5 22.3 21 00 7.98
15 42.0 94.0 27.2 25.5
29.8 23.8 23.2 22.6 22.2 21-6
--.- 30 _. . 4305 36.6 28.5 26.7
31.3 24.6 23.6 23.0 22.3 7.40 s
45 45.7 3 3 0 4 30.5 28.8
37.8 26.7 2S.6 25.3 24.8 2C.6
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- 300 2 40

360
-
61.5 55.3 5 1 - 7 49.4 4708
6-4.0 57.U 54.0 51.7 S0.0
55.5 5305 52.1
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4 8 . 5 47.7
50.7 30.0
44.7 44.4 45.9
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7-65
7.t5
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2 9 HRS 560 2 7. so
, t c s nus 5Q07 7-50

.- ._ .
 t

151

-__.STOCK
REACT I O N - - -
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-- IIHE,
0
KIN.-
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10 53.5-45.5 40.0 36.5 34.2 31.3 29.8 29.4 28.7 28.5
20-'--55.0 47.0 41.2 37.7 35.3 320'1 30.7 29.7 29.3 28.5
- 30 54.0 46.0
45- --- .5500 46.5
41.0 37.2 34.6 31.7 30.2 29.5 28.8
41.0 37.0 34.0 31.3 2 9 . 5 29.5
28.7
28.5
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--
90-'-
120
i5o
54.0 46.0
54.0 45.0
----
55.0 47.0
40.7 31.0 34.5 31.0
40.0 36.0 33.5 3108 30.5 29.5
4106 37.8 3503 32.3 33.5 30.0 29.5
29.5 28.9
25.C
29.6
28.5
29.2
.
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---z;io-
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S3.0 45.5 43.5 37.0 34.9
300 C 29.8
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31. 9 30.5 29.8 29.8
21-#KS--66.0 58.6 54.5 51.9 49.8 47.2 45.8 45.8 44.8 45.0 7 -40
.e-
29.5 HRS 68.0 61.8 5?.S-55,0 5?.0-51.0 50.0 49.5 4 8 . 5 48.5
45 HRS * - . 51.8 7.10
191' 69 H~sZ S .--_-71.5 6-- -_
5.5.-. 6 2 o - P , S 9 r S 58.0 56.0.54.9-5407 54.3 54.5
s9.5
7.35
7.25
-
--.
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 152

I
I
i

--.- STMK SOLUTION

( R E S I N SLURRY 1
- HETASLL.
1,902
et. HCLvYL.1 he WdTERvHLo
2 2 00

. ---
-_ --3.0- '..as-- - .COLCR.
OEVELOPMFNT T (ME ( f E C 1
60 75 90 120. 1500 130. 2 4 0 . 300.-lOYh 25CN PH
STOCK
-RkAC T I ON---
51.5-42~5-36,5, 33r4-29.5 ?$.0_ 23-0.5 ______
2205--21.9-
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70.0 66.4 63.0 61.5
55.0 56.7 55.8
58.9 5 7 . 9 5702
55.0 54.6 5 4 0 3
5 6 . 5 55.5 5 5 . 4
52.9 9-13
5 4 . 4 9.18
-. 60.....--._ 77.0 11.8 68.0 65.5 63.7 61.5 60.5 59.8 58.4 58.4 57.8 57.1 9.17
90 i7.0 71.6 68.0 65.5 63.5 61.4 60.5 55.5 59.4 58.9 5 7 . 9 5 7 . 5 9.1s
-r_.??- . - 78.0 7 2 . 8 69.8 67-55 45.5' 63.5 62.5 52.3 61.0 6 0 . 5 60.1 59.6 9.25
2 70 78.0 73-3 70.0 67.5 66.3 63.5 61.9 62.0 61.8 6 L . E 61.3 9.1 R
------ 20 HRS -- 82,,!_7-8.0-7_5-0 0_.7_?.-0 71.3 -69o-k 68.4-67.5 67.0 66.5 6608 9 098
 153

.__.-

28.1 9. 10
47 08 - ..
53.0
s5.5
5T. 1
57.7
60.5
.. . ....
 154

-_I_ -- STOCK SPLUTION

4 RES1 N SLURRY 1
- METASILIIG.
1.902
HCLvHLolN.
2
bATER rWLo
20 0

----.- TRANSHITTANCE REAOINGS ( 1. ML./50 YL. REAGENTJ

-- -

-s--- .
,
1
0 ' 5 2 . 0 -43.5 38.0
71.3 64.5 60.0
3405 32.0 29.2 27.0
57.3 54.8 51.8 51.0
25.0 25.C
50.5 50.1
25.0 24.5
49.8 48.8
24.0 ? e 5 5
41.7
- 30
60-'-'
7t3.5.73.5
--
78.0 73.5 70.5
69.5 61.0 65.0 62.8 61.4
66.0 66.5 64.5 153.0
60.7 60.2
C2.5 61.7
59.5
61.5
sa.6 58.5 7.40
t J . 7 5907 7.+5
-.PO--- ..82.0
. 77.8 74.5 7 2 . 1 . 7 0 . 6 68.5 66.9 46.5 66.0 6506 6 6 . 0 65.6 7.42
120 82.5 78.0 75.1 73.0 71.5 63.5 67.8 67.0 67.4 67.2 67-5
-2E - 81.5 76.5 74.0 72.0 70.7 59.5 68.6 68.0 t 7 . 9 67.7 67.7 7.55
2+ NRS 06.5. 83.0 R0.S 76.9 77.8 76.4 74.8 7407 74.5 74.6 73.9

.--. .-

-
. --_ . STCCK SOLUrlClN
(RESIN SLURRY)
- M E T A S I L ~ I G . HCLiML.1No
1.900 2
MATERIMLO
200

11%. H1N.
0 - - 4 9 . 0 4015
I _

35.5 32.3 30.0 27.9 26.2 25.7 25.5 25.5 2 5 . 1 6.65

- 3IS
0'" 59.0 53.6
- & 2 . 5 53.5
44.8
40.0
40.5 3705
43.8 40.6
33.4 30.6 2S.6
36.7 34.6 3403
28.5 27.7 2 7 . 5 15.65
3303 32.3 32.1
- 60 67.0 59.0 53.5
Po- --- .57.5 69.0 ' 5 5 . 4
53.3 47.8
52.0 49.8
44.5 4L.S 40.5
46.6 44.6 4 3 . 6
39.5 3 9 0 5 35.5 6 . 7 0
42.9 4 2 . 8 42.5
- a20
150---
70.0 63.0 58.2
72.5 66.0 6 1 0 5
55.0 52.6
58.5 56.5
50.2 48.7 48.0
154.5 52.5 51.5
47.3 47.1 46.0 6 - 6 5
51.3 51.3 5 0 . 5
-- 2 10
270- -. -
75.0..-69.5
. 65.0
-61.0
62.8 63.6
65.0 63.5
51.7 57.3
61.5 60.8 60.0
5 6 . 6 50.4 5t.C t o 70
59.5 5 3 . 5 59.0 6.57
360 73.0 t9.9 67.9 65.0 64.0 C3.S C3.5 C2.9 52.4 b o 9 5
T3.S'HRS-85.3 81.3 78.5 76.8 75.1 7305 72.8 72.4 12.2 72.0 72.5 7 - 1 8
 156

--_-. -.STOCK SnLUTlON

tRESIFi SLURRY 1
- METASIL.*h.
. 1.900
WCL,CIL. 1N.
2
hATER*CrL.
230
--. .
SAAPLE -
-_
STOCK,ML.' HCL,HL.*N. NIOHINLOIN; NAOIIC rML. *N. kATFR*ML.
-.--I -- ----__
75 -----.-- . - ..4.6 - 2 . P:02 .---- 100

T R A N S ~ ! T T - ~ C ~ , R E A O I N CtS1.5 HL./SO ML -
._
---. COLOR DEVELOP3FNT TIME f SEC)
30"--45 . '60 75 90 120. 150. 183. 240. 300. l C Y N PH
-- REACT
STOCK -54.0
103
4 4 . 0 - 3 6 . 5 32.5 29.5 26.0 24.5 22rO 22.2 2203

--. T I W I w_ll--
0 5 3 ~ ' 0 - 4 3 ; 0 ~ 3 7 ~ 0 ' 3 3 .30.0
0 26.3 24.5'2400 23.6 23.; 2 2 . 4
- 15
30----68.5-61.3
63.0
Sb.6 48.9 45.0 42.3 33.8
56.0 52.5 50.3 47.1
37.3 35.5 39.6 35.5 35.0
4 5 0 3 4 5 0 5 4 4 . 5 44.5
8.45

8.65
-- 45.-
60
- -- 13.5 66.2 61.5 58.1 56.0 56.7
7 3 . 0 ~ ' 4 7 . 5 62.5 58.9 56.9 5 4 . 4
52.3 51.8 52.0 52.9 51.5
53.5 52.0 52.3 52.3 51.a 8.68
--r;+-- 77.0 73.a 66.5 63.5 61.5 59.3 5 8 . 5 56.2 5 t . a 55.e 5 5 . 5
7 9 . 5 ' 7 2 . 8 6 8 0 5 ' 6 5 . 3 63.5 60.5 59.7 58.5 58.4 5 E . O 57.2 3-13
- 150 -_----
1a0
12.3 6 8 0 8 6 5 . 6 63.5 61.5
78..0"72.5 68.1 00.3 64.5 62.4
65.0 59.0 58.5 5 5 . 5 5 S . l
61.5 63.0 59.0 59.5 59.2 8.69
-- 20 URS 81.5 75.7 71.9 '69.2 67.3 65.3 63.0 53.5 62.9 6 2 . 8 63.0 7-90
64'HdS-'80.2 75.5 72.0 69.4 67.8 65.5 6 4 - 8 65.5 t5.O 65.0 6 4 0 2 @.OC
.___ ___ -
_.___ -
. . . . ... . . . .. .._ --
..--
.I.... .- ... .. . . . . . .

----. --- 30---45"' COLOR OEVELOPWNT T I P 5 ( S E C )

60 75 90 120. 153. 18C. 240. 333. lOPN PP
STOCK 54.0 44.5 38.2 - ..34.0 31-0 27.4 25.5 24.5 23.4 22.1 22.7
- - ----- -
T I H E * HIN.
-
--e
.

-
@' 5 2 - 0 42.5.3508 31.5 28.2 24.7 22.9 22.7 2 2 0 0 21.6 21.6 6.80
- 1s
30- --
50.0 41.0 35.0
.51.0 t 2 . S 37.0
31.9
33.0
28.2
33.0
24.7 23.4
26.6 25.0
22.3 21.1 21.5
24.1 23.2 2 3 . 0
21.1
23.3 6.90
- 60 54.0 43.5 3 9 0 5
9s-.-' 53.0 46.8 3 e . 8
35.2
35.0
32.0
32.3
28.9 2 7 . 2
29.5 2R.5
25.6 25.2'24.e
26.4 25.9 25.0
24.7
25.5
6-SC

120 44.0 16.0 40.2 36.5 33.8 30.9 29.2 28.3 28.C 2 7 . 9 24.8 6-90
--180'- - - 57.0 43.8 43.6 40.0 31.0 31.5 30.5 29.7 30-0 33.0 6.LC
240 59.0 51.0 415.0 43.0 40.6 3708 360s 34.5 34.0 33.0 33.7 6.53
*-305-"-'-4t;O 5 5 . 0 48.5 45.3 43.0 41.2 38.5 38.5 37. ? 37.5
-- - . -
121 H R S 82.0 7705 7405
_.
72.3 70.b 69.9 68.0 57.8 67.8 7-35

--.---- . . - .- -..--_- - -
.. _ - - .. _-.. _..--.. - - -_----. -~
_"

,
 157

CCV SCIlUTICN
( R E S l N SLURRY)
- MET~S~L~IG
1.901
PCLrHL.1N.
.
2
WATERINLO
200

c
--TRANSMITTANCE READINGS f 1 NLe/50 HL .REAGENT t

-. ..-. - .----
30 .-is“
COLOR OEVELOPYENT T I H E ( S E C I
60 75 90 120. 150. 180. 2 4 0 . 3 0 3 . 1OHN PH
-.--$StOCK 51.5 42.3 36.0 31.8 29.2 25.9 24.3 23.0 22.5 22.3
RE4Cr I Ok
-.?fwi* H1N. .
0 53.0 45.6 36.8 34.5 32.3 29.0 27.7 25.4-‘24.5 24.4 24.4 8-06
1
,,: - _.. ._5010 41.0 36.0 32.3 30.0 27.3 25.5 24.3 23.5 23.5 23.6
30 5C.S 41.8 36.0 32.5 30.2 27.5 26.0 24.9 24.6 26.7 24 07 7 .SP
--.-- .--. 50.0
.... 41.0 35.5 32.0 29.7 25.8 25.5 25.5 24.9 24.8 24 -7 8-05
136 4905 41.0 36.5 33.5 31.3 28.8 27.5 26.7 26.5 26.5 Z t 02 e. cs
-rgo,, _ .-
53.0 45.2 40.5.37.z 35.0 32.7 31.0 30.3 29.0 29.e 30 05 8 -05
270 57.5 50.0 45.5 42.3 40.2 37.8 36.9 35.6 35.5 3L.5 35.0 8-95
- - --f .
360
540
-.-- 61.0
64-C
- 53.2
5607
48.6
52.0
45.8 43.6
49.4 47.4
41.3 40.2 3404 39.5
45.3 4405 43-4 42.9
Z9.5
43.4
35.5
4 2 09
7.90
7.65
-c-- .720 66.5 58.7 54.5 51.4 49.9 47.5 46.5 45.0 44.5 44.2 k4.5 1-30
23 tiHS--?t.O 65.5 61.257.9 55.9 53-5 51.8 51.3 50.8 50.7 7. C O
3.0 *.S.-?2.0 65.5- 61.5. 58.8 5 7 0 1 54.9 53.9 52.8 52.4 52.3
,
,
158

APPENDIX 2
GRAPHS FOR UNBUFFERED RATE RUNS

1.0

E
3
c
0.8
i
A
c
P
c
J
cf
w

c
u
(D
0
L
n
n
=s
c
c 0.4
0
(Fig. 4.6)
(Fig. 4.8)

0.2

Run 1
Conc = 858 pprn
pH = 9.0 + 9 . 2 5 + 9.00
A d j u s t e d pH = 9.0
159
 160

1 .( I I
L,
-
i

0.8

x
0
4 0.6
0
L
P
n
e
r-
4
E
0
.c
e,
0 0.4
4
L
LL

0.2

0 I
A
n -- AUdnjaudsjtuesdt e d I
(Fig.
(Fig.
4.6)
4.8)

1 10 100 1000 ?

Time (min)

. Run 3
C o n c = 548 ppm
pH = 8 . 9 2 -+ 9.10 -+ 8.90
Adjusted pH = 9 . 0
. I

L-
 161

&

.
r
F

.-
Time ( m i n ) .

Cone = 791 ppm

W
 162

1 .o I

II
I

0.8
E
3
c
L
a
c
P

0.6
0
+,

c
V
I . Q
0
L
n
P
U
P
0.4
Q
c
0
.p
c,
V
Q
L
LL

0.2

Time (min)

Run 5
Conc = 8 0 9 ppm
pH = 7 . 5 5
A d j u s t e d pH = 7 . 5
 163

u 1.0
I
I I
/
 164

I I

0 - Adjusted (Fig. 4.8)

E
a 0.0 - A0
c

/
L
a
c
c
c
=I
u- 4 0
w
0
+,
0.6 -
c
30
&
Q.
-
n
e
P
rrJ
E
0.4 -
0
.rr
e,
0
e
8
L
-
L

n o I

I
0 t-- I

10 100 1000 10,000

.e

Time (min)

Run 7
Conc = 793 ppm
pH = 5 . 6 -c 6.39 .+ 6.25
A d j u s t e d pH = 6 . 0
 165
I

I
I

I
 166

1.0 I I

E
3
.
r
L
0.8
a
.
r
P
.
r
I
0-
W

0
&
t 0.6
0
Q
0
L
P
U

0.4

0.2
o - Experimental Points
Predicted- Points:
A - Unadjusted .(Fig. 4.6)
Cl - Adjusted (Fig. 4.8)

0
10 100 1000 10,000

Time ( m i n ) i

Run 9
Conc = 587 ppm
pH = 8.45 + 8.70 + 8.0
Adjusted pH = 8.6
 . ,.
167
1

1 .o
W
0 - Experimental Points
Predicted Points:
k b - Unadjusted
-
a Adjusted

0
c,
0.6
c
0
Q
0
L
P
P
e

0
.
r
c,
0
CQ
L
LL

/
0.2
 I 168

1 .o

o - Expcrimental Points
Predicted Points:

0.8
A
U --
Unadjusted
Adjusted I 0

E
J
c
L
a
.c
*
.
r
-
3
CT
W

0 0.6
*,

c
u
m
0
L -
n
P
U
c
Q
c
0.4 -
0
c
i,
0
4
L
-
LL

0.2 -

09 I I
C
10 100 1000 10,000

t
lidme (min)

Run 11
Conc = 423
pH = 8.0 + 7.0
A d j u s t e d pH = 7 . 5
L
 169

APPENDIX 3
COLOR-DEVELOPMENT RATE EQUATIONS
I Part 1. R t e of Color Develo nt: Ana’lysis f o r Monomer

Assume the f o l l o w i n g r e a c t i o n s o ur i n t h e molybdate

k analysis
.- First
Monomer . > r Complex
Order
nomer m n c e n t r a t i o n
I n i t i a l monomer c o n t e n t o f sample

o n c e n t r a t i o n of molybdate complex

MT table s i l i c a concentration
k* = First o r d e r r a t e c o e f f i c i e n t f o r t h e
apparent i r r e v e r s i b l e reaction
= Apparent f i r s t o r d e r r a t e c o e f f i c i e n t
kaPP
from experimental d a t a

Assumed c o l o r development r e a c t i o n : dM* = k*[M1]

A c t u a l c o l o r development d a t a y i e l d s s t r a i g h t l i n e on semilog
 170

Therefore, kappMT = k*M10 L

k
t app 'M
0 k* T

Part 11. Simple Case: Detailed Calculation t

Assume ( a ) Initial solution contains only Monomer, M l S and

and Dimer, Mp3. '
(b) Dimer depolymerizes to monomer by first-order
irreversible reaction whose rate coefficient

kd k*
M2 + 2M1 4 M*

Rate equations:

dM2 =
dt OkdM2

dM1 =
at
dM* k*M1 (7)
aT
Initial condition: M10 + 2Mp0 = MT (8)

-kdt c

Solution to Eqn. 5: M2 = M20e (9)

Solution to Eqn. 6:

-k*t + 2kdM20 [e O k d t - e -"*'I

H1 = MIOe k*-kd
 171

Solution to Eqn. 7:

ations 11 and 12 to both be satisfied,

e f a c t that kd i s not a constant for
t h e color development curves shown in Figure 4.1 indicates
t h a t the corresponding samples did contain i gher-mol ecular-
r. Lower values of kaPP
solutions indicating
,ined higher p
 172

APPENDIX 4
PROPOSED EXPERIMENT ON HEAT-EXCHANGER FOUL1 NG L!
The following i s an abbreviated description of an experiment
a
designed to simulate the operation of a brine-isobutane heat exchanger,
yielding pertinent information on the potential problem o f heat- r

transfer reduction due t o s i l i c a scaling.

A synthetic brine from a constant-temperature reservoir, satur- .

ated w i t h monomeric s i l i c a , is pumped through a heat exchanger i n which

. '
the temperature is reduced continuously over a long section of pipe.
During the course of passage through the heat exchanger, the degree of
supersaturation w i l l continually increase, and therefore the d r i v i n g
force f o r precipitation w i l l continually increase. Brine samples should
be taken a t intermediate stages along the heat exchanger path t o deter-
mine the degree of polymerization for s i l i c a i n solution. The brine
flow r a t e i n the heat exchanger should be appropriately controlled
along w i t h the cooling duty load, to permit varying brine residence
times a t a particular degree of supersaturation. The pH o f the h i g h -
temperature monomer reservoir can also be varied.
Removable sections of heat exchanger will permit periodic examin-
ation for solid scale deposition as a function of supersaturation.
Such removable sections can be made of uncorroded or corroded metals to -
b

determine what effect this has on the rate of deposition. With such a
s
system, a considerable amount of practical data can be obtained. With
s l i g h t modification, this apparatus can be used to t e s t deposition
behavior under partially flashing conditions, typical of wells and
phase separators.
L