(A. G. D. Emerson) Quantitative Forecasting of Pro PDF

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QUANTITATIVE FORECASTING OF PROBLEMS IN INDUSTRIAL WATER SYSTEMS

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FOREWORD
Some calculations in Sections 1.2.1, 1.3.1, 1.5.2, 3.3, 3.4, 4.1.1, 4.4.4, 4.4.6,
4.4.7, and 5.1.4 require the use of tables published in an earlier work cited as
Ref. [8] in the References.
Readers will therefore need to have a copy of that earlier work to hand
before using this book.
Unfortunately, after this book had been drafted, the publishers of Ref. [8]
stated that this earlier work was now out of print. Readers may therefore have
difficulty in obtaining a copy.
To overcome this situation Ref. [8] has been reprinted as a Supplement at
the end of this book. Readers will therefore have all the tables needed, both
from this book and from the supplement, available under one cover.
vii
SYNOPSIS
The operating problems most likely to be encountered in industrial

water systems are:
Fouling by calcium carbonate.
Fouling by calcium sulphate.
Fouling by calcium phosphate.
Corrosion of mild steel.
Corrosion of copper.
Methods are described for calculating the amount of fouling likely to occur,
and the rate at which corrosion is likely to proceed.
These data enable a quantitative forecast to be made of the problems likely
to be encountered in an industrial water system, while the project is still at the
design stage. The information will also be of assistance in investigating problems
experienced in existing systems.
The data are presented in the form of tables to assist operators who are
working on site with portable testing equipment.
The methods described introduce new concepts for the saturation indices of
calcium carbonate, calcium sulphate, and calcium phosphate; for buffer capacity;
and the pitting propensity index.
ix
NOMENCLATURE
( )
[ ]
a
Alk
Thermodynamic activities, expressed as mol/l.

Stoichiometric concentrations, expressed as mol/l.
Fraction of molecules remaining after precipitation.
Total alkalinity
expressed as
Alkalinity to Methyl Orange mg/l in terms
of CaCO3.
Alkalinity to pH 4.5
b Fraction of molecules remaining after precipitation.
B Buffer Capacity
C Total carbon dioxide expressed as mg/l in terms of CaCO3.
C/ Corrosion rate
Ca Calcium hardness expressed as mg/l in terms of CaCO3.
ClR Chlorine residual expressed as mg/l Cl2.
DS Dissolved solids expressed as mg/l as such.
exp Exponential exp (a) = ea.
E Summation of equilibrium constants.
E/ Constant for Suzukis equation.
f Activity coefficient.
I Calcium carbonate saturation index. (Langelier Index)
IL Copper pitting propensity index. (Lucey Index)
Ip Calcium phosphate saturation index.
IS Calcium sulphate saturation index.
K Thermodynamic equilibrium constants.
K Stoichiometric equilibrium constants.
ln Logarithm to base e.
log Logarithm to base 10.
n Number of concentrations.
p Negative log.
pHs Equilibrium pH.
Phos Total phosphate expressed as mg/l in terms of PO4.
Q Weight of calcium carbonate expressed as mg CaCO3.
R Ryznar Index.
xi
xii Quantitative Forecasting of Problems in Industrial Water Systems
SO4
T
V
W
Z
Sulphate expressed as mg/l in terms of Na2SO4.

Temperature C.
Ionic strength.
Vectors.
Weight of calcium carbonate expressed as mg/l CaCO3.
Valency.
INTRODUCTION
This book has been written as a contribution to changing the attitude of mind
when considering problems in industrial water systems. The need for such a
change has been brought about by changes in prevailing economic conditions.
Industrial systems using water for heating or cooling purposes frequently
encounter problems which are associated with the quality of water used. In
former times, when both labour and materials were cheap, it was a relatively
simple matter to discard a system that had encountered problems and build a
new one designed in the light of the experience gained from an old system: in
this way it was hoped to avoid the difficulties previously experienced.
If discarding the system was not considered necessary, some form of chemical
treatment and monitoring might be introduced. If this was not entirely satisfactory
then, with cheap labour available, it was, again, a relatively simple matter to
arrange for periodic manual cleaning of the system to make good the deficiencies
of the treatment. In fact some operators used to boast of the quantity of deposit
removed during such manual cleaning operations. As though it was a matter of
pride, instead of a reflection on the manner in which the system had been
controlled and operated.
But under present day ecomomic conditions such a leisurely approach is no
longer feasible. In the design and operation of industrial water systems it is
important to know in advance what problems are likely to be encountered, and
to be able to give a forecast in quantitative terms.
For one type of system, the steaming boiler, the problem is not too difficult.
For example, a boiler feed water contains X mg/1 of hardness salts: since all the
water entering the boiler is evaporated as steam, all the hardness salts must
remain behind to form scale. Therefore X mg of scale will be formed for each
litre of water evaporated. Expressing the problem in quantitative terms is therefore
a matter of simple arithmetric. For this reason steaming boilers have been
excluded from the discussions in this book.
But for systems involving heat-exchangers (whether for heating or cooling) a
more complex situation exists, depending on the chemical reactions taking place
in the water at various temperatures. The study in this book has been restricted
to heat exchange systems where there is no loss of water by evaporation, or
xiii
xiv
Quantitative Forecasting of Problems in Industrial Water Systems
other means, unless specifically mentioned in special cases. It is also assumed

that there is no change in the chemical characteristics of the water by accidental
ingress of contaminants, or by the loss of dissolved gases by venting to
atmosphere, unless addition of chemicals or loss of gases are specifically
mentioned in special cases. Changes in the chemical characteristics of the water
are limited to those induced by a change of temperature.
The problems most likely to be encountered in the types of systems outlined
above are fouling and corrosion. Fouling is caused by:
Deposition of calcium carbonate.
Deposition of calcium sulphate.
Deposition of calcium phosphate.
These are studied by physical-chemistry methods.
It is appreciated that some fouling may occur by the formation of organic
slimes, which may act as binders for the inorganic deposits mentioned above.
But organic slimes have been excluded from the discussion as their formation is
not amenable to physical-chemistry methods.
The metals of construction most likely to be used in industrial water systems
are mild steel and copper: their rates of corrosion have therefore been included
in the discussion. Other metals may be used from time to time, but mild steel
and copper are regarded as basic: other (often more expensive) metals are
introduced when justified on technical and economic grounds by the operating
conditions existing in an individual system.
Manufacturers of special alloys are sometimes able to indicate how the rate
of corrosion of their materials compare with mild steel or copper under given
operating conditions. Thus, a knowledge of the probable rate of corrosion of the
basic metals can be of assistance in selecting special alloys.
The purpose of the data offered in this book is to enable quantitative forecasts
to be made of the fouling or corrosion likely to be encountered in an industrial
water system, while the project is still at the design stage. A decision can then
be made on the type of water treatment to be adopted, commensurated with the
purpose for which the system is to be used, and its life expectancy.
A discussion on the various types of water treatment that might be considered
is beyond the terms of reference of this book. It is a diagnostic tool utilising the
basic physical-chemistry of water supplies. Water treatment methods may change
from time to time, but the basic physical-chemistry remains unchanged.
However, a forecast of probable operating problems may be used to influence
the choice of a water supply, if several alternatives are available on any given
site.
Introduction
xv
In the case of a small project, or one handling a low grade product, a forecast
of problems as outlined in this book may suffice. But for a large project, or one
handling a sophisticated and expensive product, a trial run on a scale model
may be undertaken before final design details are settled. In such a case an
initial forecast of the problems will enable the trial run to focus on the most
critical conditions likely to be encountered.
In addition, to work at the design stage of a project, the methods described
in this book may be used to assist operators in investigating problems on an
existing system. As this often involves working with portable testing equipment,
the data are presented in the form of tables to facilitate site work.
Contents
Foreword ..........................................................................................
vii
Synopsis ...........................................................................................
ix
Nomenclature ...................................................................................
xi
Introduction .......................................................................................
xiii
1. Calcium Carbonate Fouling .....................................................
1.1 The Ryznar Index ..............................................................................
1.1.1 Origin of Ryznars Work ....................................................
1.1.2 Emergence of the Ryznar Index ........................................
1.1.3 Revised Evaluation of the Ryznar Index ............................
1.1.4 Experimental Errors ..........................................................
1.2 New Data ...........................................................................................
11
1.2.1 Use in the Field .................................................................
13
1.2.2 Margin of Error ..................................................................
16
1.3 The Langelier Index ..........................................................................
17
1.3.1 Use in the Field .................................................................
19
1.3.2 Margin of Error ..................................................................
21
1.4 Choice Between Langelier and Ryznar ............................................
22
1.5 The Special Case of Recirculating Systems ....................................
23
1.5.1 Closed Recirculating Systems ...........................................
23
1.5.2 Open Recirculating Systems .............................................
23
2. Calcium Sulphate Fouling ........................................................
27
2.1 Calcium Sulphate Saturation Index ..................................................
27
2.2 Calculating the Weight of Calcium Sulphate ....................................
28
This page has been reformatted by Knovel to provide easier navigation.
vi
Contents
2.3 Use in the Field .................................................................................
31
32
3. Calcium Phosphate Fouling .....................................................
37
3.1 Calcium Phosphate Saturation Index ...............................................
37
3.2 Calculating the Weight of Calcium Phosphate .................................
41
3.3 Use in the Field .................................................................................
44
48
4. Corrosion of Mild Steel .............................................................
53
4.1 The Ryznar Index ..............................................................................
53
4.1.1 Use in the Field .................................................................
57
4.1.2 The Special Case of the Recirculating System ..................
59
4.2 The Langelier Index ..........................................................................
60
4.2.1 Use in the Field .................................................................
62
64
4.3 Comparison Between the Ryznar Index and Langelier Index ..........
65
4.4 Buffer Capacity ..................................................................................
65
4.4.1 Description of Buffer Effect ...............................................
66
4.4.2 Definition of Buffer Capacity ..............................................
66
4.4.3 Water Analyses and Buffer Capacity .................................
67
4.4.4 Evaluation of Buffer Capacity ............................................
70
4.4.5 Buffer Capacity and Corrosion Rate ..................................
73
4.4.6 Use in the Field .................................................................
73
75
5. Corrosion of Copper .................................................................
77
5.1 Cold Water Systems .........................................................................
77
5.1.1 The Lucey Index ...............................................................
78
5.1.2 An Alternative Approach ...................................................
80
5.1.3 Data Required ...................................................................
80
5.1.4 Effect of Concentration .....................................................
81
5.1.5 Calculating the Index ........................................................
82
5.1.6 Time Scale ........................................................................
84
Contents
vii
5.2 Hot Water Systems ...........................................................................
90
5.2.1 Data on Water Chemistry ..................................................
90
5.2.2 The Role of Residual Chlorine ..........................................
95
5.2.3 Time Scale ........................................................................
95
References ......................................................................................
99
Tables .............................................................................................. 101

Index ................................................................................................ 193
Supplement (Reprint of Ref. 8) ...................................................... 197
Chapter 1
CALCIUM CARBONATE FOULING
The starting point for a study of calcium carbonate fouling is the need for a
method possessing the thermodynamic integrity of physical-chemistry; a method
which is easily applied and will allow the amount of calcium carbonate deposited
to be estimated, or forecast, from an inspection of the chemical analysis of a
water supply.
At present, the literature offers only one parameter linking water analysis
and the amount of calcium carbonate deposited: that parameter is the Ryznar
Index. A study of that Index is, therefore, the logical starting point for the
development of methods for forecasting fouling by calcium carbonate.
1.1. THE RYZNAR INDEX

The Ryznar Index [1] is formally defined as:
R = 2pH S pH
(1)
where pHS is the equilibrium pH described by Langelier [2].

But to understand the significance of the Ryznar Index in relation to the
amount of calcium carbonate deposited, it is necessary to go back to the origin
of Ryznars work and make a reappraisal in the light of recent information that
was not available to him.
1.1.1. Origin of Ryznars Work

Ryznar was investigating, in the laboratories of the National Aluminate
Corporation, Chicago, the effect of scaling inhibitors in reducing, or preventing,
calcium carbonate deposits in industrial water systems. The work involved the
use of a test rig described by Thompson and Ryznar [3]. The basis of the test
rig is shown in Fig. 1. A sample of water to be tested is contained in the header
tank. A fixed volume of water is allowed to flow at a fixed rate through the coil
in the heater tank, which is controlled at any desired temperature. The coil is
detached from the test rig and weighed before and after each run. In this way,
1
Fig. 1. Basis of ThompsonRyznar test rig.
the weight of calcium carbonate deposited is determined, at any selected

temperature, under fixed operating conditions.
At this point it must be emphasised that the conditions existing in the test
rig restricts the application of Ryznars work to those industrial water systems
in which similar conditions apply. That is, once-through, closed systems in which
water enters, passes through to drain, and is subjected only to a temperature
rise. Apart from deposition of calcium carbonate there are no other changes: for
example, incidental ingress of chemicals by contamination, or loss of dissolved
gases by venting to atmosphere. The only chemical changes permitted are those
resulting from the deliberate addition of known reagents to the header tank
before the run starts.
These restrictions apply to all the discussions which follow in this book,
unless there is a direct statement to the contrary.
Using the procedure outlined above, Ryznar determined the weight of calcium
carbonate deposited by a sample of raw water, and compared it with the same
water treated with various inhibitors. In this way he was able to list the inhibitors
Calcium Carbonate Fouling
in their order of merit. By repeating the process for different raw waters Ryznar
was able to provide a more extensive and more informative list of merit for a
range of inhibitors.
Because Ryznars method required only comparative weights of calcium
carbonate, and each experiment was run under fixed conditions, his data records
only the weights of calcium carbonate deposited and not the volume of water
from which they were produced.
Another important point to be taken into account is Ryznars method of
preparing water samples. In the earlier stages of his work he found that the
experimental runs had to be extended over a protracted time, and use large
volumes of water, in order to deposit sufficient calcium carbonate in the coil to
produce a significant weight change.
In order to reduce the time of each run to a manageable length, Ryznar
increased the scaling potential of the waters by increasing their alkalinity. Sodium
carbonate or sodium bicarbonate was added for this purpose. The significance
of this step is discussed later. See Sec. 1.1.4.
1.1.2. Emergence of the Ryznar Index

In the procedures followed by Ryznar it would be an advantage to be able to
forecast, or estimate, from an inspection of the chemical analysis of the water,
the weight of calcium carbonate deposited from a given volume of water at a
given temperature. This information would facilitate the preparation of raw water
samples that would yield a weight of deposit within a range required for a
specific sector of Ryznars investigations.
In pursuit of this objective Ryznar prepared 21 raw water samples which
were passed through the ThompsonRyznar test rig and the weights of calcium
carbonate deposits recorded. The results are set out in Table 1.
The chemical analyses of the water samples were made at atmospheric
temperature (assumed to be a nominal 15 C). From these data Ryznar calculated,
for the temperature (T) in the test rig the equilibrium pH (pHS) as described by
Langelier (loc.cit.).
The equilibrium pH is defined as:
pH S = p[Ca 2+ ] + p[Alk] + pK 2' pK S'
where
and
K 2' =
[ H + ][CO32+ ]
[ HCO3 ]
KS' = [Ca 2+ ] [CO 32 ]
pHS was evaluated from tables by Larson and Buswell [4].
(2)
(3)
(4)
From the values of pHS (at T) and the values of pH (at 15 C) Ryznar
calculated the values of the calcium carbonate saturation index, described by
Langelier (loc.cit.).
(5)
I = pH pHS
The calculated parameters are set out in Table 2.
Because the values of pHS had been adjusted to (T), the temperature in the
test rig, but the values of pH had not (being recorded for 15 C) Ryznar had
broken thermodynamic integrity. But he had no choice since in 1944 there was
no published method for adjusting pH for temperature changes.
In this present reappraisal of Ryznars original work, Eq. (2) has been used
in the modified form:
pH S = p[Ca 2+ ] + p[Alk] + pK 2 pK S + (DS) 0.5 /100
(6)
described by Emerson [5].

Where
and
(H + )(CO32 )
(HCO3 )
(7)
K S = (Ca 2+ )(CO 23 )
(8)
K2 =
Values of p[Ca2+] and p[Alk] have been taken from tables by Manning [6]
and values of pK2 and pKS from tables on pp. 416 and 424 of Hamer et. al. [7].
For this reason the values of pHS, I, and R in Tables 2 and 3 may differ
slightly from those in Ryznars original paper.
A plot of the values of calcium carbonate saturation index (I) against weight
of calcium carbonate (Q) from Table 2 is shown in Fig. 2.
The plot shows a ragged scattering of points with no apparent relationship
between the two quantities. The scattered pattern may be due to:
(i)
(ii)
(iii)
(iv)
Absence of any fundamental relationship between I and Q.

Errors introduced by Ryznar breaking thermodynamic integrity.
Experimental errors in the test rig.
A combination of two or more (i) to (iii).
These matters are discussed later in Secs. 1.1.3 and 1.1.4. But Ryznar assumed
that only (i) was applicable. He abandoned any further investigation of a
relationship between I and Q and began to search for a new, empirical index
that was directly linked to the weight of calcium carbonate deposited. Ryznars
further investigations produced an empirical index:
R = 2pHS pH
(1)
Fig. 2. Plot of Langelier index(I)-v-weight of calcium carbonate(Q).
Fig. 3. Plot of Ryznar index(R)-v-weight of calcium carbonate(Q).
The data in Table 2 has been rearranged to show values of R and the new
parameters are set out in Table 3.
A plot of the values of the Ryznar Index (R) against the weight of calcium
carbonate (Q) from Table 3 is shown in Fig. 3. It will be seen that a smooth
curve can be drawn through the plot to give a neutral point (zero deposit) at
R = 6.2. Ryznars original graph gave the neutral point as R = 6.0. The slight
difference is due to the difference in evaluation mentioned earlier in this section.
A number of proprietary water treatment suppliers have accepted the criterium
(R = 6.0) as a basis for the routine control of systems using their treatment.
There is still a moderate amount of scattering of points in Fig. 3 which may
be due to:
(v) Ryznar breaking thermodynamic integrity.
(vi) Experimental errors in the test rig.
(vii) A combination of both.
Ryznar did not proceed beyond Fig. 3. Having established that a smooth curve
could be drawn linking R and Q, and that a neutral point existed at R = 6.0, he
allowed the matter to rest. He did not, for example, publish any further work on
methods of forecasting, or estimating, the weight of calcium carbonate deposited
using calculations based on his index R.
The objective of this section of this book is to provide methods of forecasting,
or estimating, the weight of calcium carbonate deposited in systems: then clearly
further work must be done on the Ryznar Index if it is to be included in the
methods which follow in this book. It is therefore important to investigate, and
if possible eliminate, errors which may be arising from (v) and (vi) above.
1.1.3 Revised Evaluation of the Ryznar Index

The first step in a revised evaluation of the Ryznar Index is to restore, as far as
possible, the thermodynamic integrity. This can be achieved by using values of
pHS and pH that have both been adjusted to the temperature (T) in the test rig.
The values of pHS have already been adjusted. The values of pH at 15 C
in Tables 13 are converted to temperature T using the method described by
Emerson on pp. 2021 of Ref. [8]. The new values of pH are set out in Table 4,
which is a revised version of Table 3.
A plot of the revised data in Table 4 is shown in Fig. 4. It will be seen that
a smooth curve can be drawn through the plot. This curve is very similar to that
obtained in Fig. 3 (which has been inserted in Fig. 4 as a dotted line for
comparison) but has been displaced to the right in the diagram to give a new
neutral point at R = 7.5.
Fig. 4. Plot of revised Ryznar index(R)-v-weight of calcium carbonate(Q).
It will be a matter for individual water treatment suppliers and plant operators
to decide whether to accept the thermodynamically improved neutral point of
R = 7.5 as a basis for plant control instead of the older, more familiar R = 6.0
discussed in Sec. 1.1.2.
There is still a moderate amount of scattering of points in Fig. 4. In this
respect, Fig. 4 offers no improvement over Fig. 3. This leads to the conclusion
that the scattering is not due to the thermodynamic status of the data. If the
thermodynamic status was a significant explanation there would have been a
marked improvement in the closeness of the fit of the points to the curve on
moving from Fig. 3 to Fig. 4. This conclusion is not altogether unexpected since
the Ryznar Index in Eq. (1) is empirically derived and not the result of a rigid
thermodynamic calculation.
Leading on from this conclusion the next logical step is to consider possible
experimental errors in the test rig.
1.1.4 Experimental Errors

It is considered possible for experimental errors to arise in the test rig for the
following reasons:
(viii) In Sec. 1.1.1, it was explained that Ryznar increased the alkalinity of water
samples by the addition of alkali (sodium carbonate or sodium bicarbonate).
Following such additions time will be required for the ionic species
contributing to the alkalinity and pH of the water to undergo internal
rearrangement and achieve equilibrium. Very little is known about this
time interval, but it introduces the possibility of the onset of precipitation
being delayed. This delay could vary from one water to another and thus
introduces an error when comparing results. Thus the fixed conditions
of the test runs may, in fact, be open to some variation.
(ix) When a water is treated with alkali, to increase the scaling potential,
it passes through a metastable stage where actual precipitation does not
take place. This metastable stage continues until the water is disturbed
and passes into a labile (precipitating) stage by an increase in alkalinity
and/or temperature. Here again, the onset of precipitation may be delayed
leading to a variation in the conditions of the test run. The existence of
the metastable stage is demonstrated in many natural occurring waters,
which have a positive calcium carbonate saturation index (scaling) but
remain stable without precipitation over long periods until the temperature
is raised.
10
(x) The precipitation of calcium carbonate when water is heated takes place
in the bulk of the water. Some precipitate then becomes attached to the
heat exchange surface. (This is in direct contrast, for example, to calcium
sulphate which crystallises on the heat exchange surface). Under these
conditions some of the precipitate may be carried forward with the flow
of water and pass to drain. Thus some of the precipitated calcium carbonate
may be lost and not recorded when the test coil is weighed. Variations in
the recorded weight of calcium carbonate for the reasons just discussed
may be small. But they are significant in comparison with the recorded
weights which amount to a modest number of milligrams.
It may be argued that items (viii), (ix), and (x) are only hypotheses, and pose
the question Can errors of this type actually arise?. The short answer is Yes.
Edwards [9], working in the laboratories of Imperial Chemical Industries Ltd,.
in London, was carrying out investigations very similar to Ryznar using a very
similar test rig. He found that the reproductivity of results was poor. Samples of
water, prepared to the same specification, and put through the test rig on
successive days, gave variable weights of calcium carbonate. It was necessary
to run 5 or 6 tests and take a mean value in order to obtain meaningful results.
Again, a sample of water, treated with inhibitors A, B, C and D, gave results
indicating an order of merit:
A
B
C
D
but on subsequent runs the order changed:
B
A
C
D
A
B
D
C
A
C
B
D
etc.
Again, it was necessary to run 5 or 6 tests and take mean values in order to
obtain meaningful results.
It will be seen from Edwards results that the use of the test rig provides a
screening test capable of indicating broad trends in the amount of calcium
carbonate precipitated (and its reduction by using various inhibitors). But the
results are not sufficiently finely tuned to match parameters calculated on an
accurate thermodynamic basis.
11
To overcome this difficulty the next logical step is to investigate a method for
calculating the weight of calcium carbonate deposited on a thermodynamic basis.
1.2. NEW DATA

The discussions in Sec. 1.1 have extracted from Ryznars work with the test rig
all the information likely to be of value in estimating calcium carbonate
deposition. The next step forward is to provide a method of calculating the
weight of calcium carbonate deposited, instead of using weights obtained from
a test rig. Such a method was not available to Ryznar or Edwards, but is available
now. It has been applied in the following way:
Ten water analyses have been selected which are typical of the raw waters
likely to be available from natural sources, or municipal supplies, for industrial
use. The analyses are set out in Table 5.
The analyses cover the same broad characteristics as the waters used by
Ryznar, with one important exception. Because Ryznar increased the alkalinity
of his waters, his pH values are high (in the 8.0 to 9.0 range, with a few
exceptions). These pH values are higher than those normally found in the natural
waters and municipal supplies available to industry. Therefore in Table 5 a lower
pH range (7.0 to 7.9) has been used.
In the original Ryznar test rig waters were maintained at a temperature of
95 C in 13 cases, at 70 C in 3 cases, and at 50 C in 5 cases. This range of
temperatures is too narrow to cover the range likely to be encountered in actual
plant practice. Therefore in this discussion a temperature range of:
30 C 40 C 50 C
60 C 70 C
80 C
has been selected.

For each of the ten waters at each of the six temperatures the values of pHS,
pH, I, and R have been calculated as described in Secs. 1.1.2 and 1.1.3. From
the values of I, the weights of calcium carbonate (W) have been calculated by
the method described by Emerson on p. 26 of Ref. [8].
W is expressed as mg/1, a unit which is more useful than the original Q
(in mg). Values of W allow weights of calcium carbonate deposits to be calculated
for any volume throughput of water. The results of the above calculations are
set out in Table 6.
In order to obtain a preliminary insight into the relationship between R and
W a plot of values at 30 C, 50 C, and 80 C was made in Fig. 5. It will be
seen that a smooth curve can be drawn for each temperature, and the whole
temperature range covered by a family of curves. It is therefore worthwhile
12
Fig. 5. Plot of revised Ryznar index(R)-v-weight of calcium carbonate(W).
13
exploring the mathematics of Table 6 in further detail. It can be shown by a

detailed mathematical analysis of Table 6 that the relationship between R and W
can be expressed as:
W = exp(AR + B)
(9)
and that for individual temperatures the best fit equations are:
30 C
W = exp(1.75R + 14.79)
(10)
40 C
W = exp(1.66R + 13.80)
(11)
50 C
W = exp(1.47R + 12.54)
(12)
60 C
W = exp(1.13R + 10.28)
(13)
70 C
W = exp(1.17R + 10.33)
(14)
80 C
W = exp(1.24R + 10.65)
(15)
A further examination of Eqs. (10) to (15) shows that the values of A are
linear in relation to temperature and the best fit equation is:
A = 0.015T 2.22
(16)
Similarly, the values of B are linear in relation to temperature and the best
fit equation is:
B = 0.11T + 18.21
(17)
Substituting Eqs. (16) and (17) in Eq. (9) gives a universal equation:
W = exp[(0.015T 2.22)R 0.11T + 18.21]
(18)
For practical purposes it may be easier to use Eq. (18) in the logarithmic
form:
or
lnW = (0.015T 2.22)R 0.11T + 18.21
(19)
logW = (0.007 0.97)R 0.048T + 7.92
(20)
1.2.1. Use in the Field

When applied to practical problems in the field, Eqs. (18) or (19) or (20) will
give the best value of W calculated on the basis of R. The calculated value of W
is the maximum weight of calcium carbonate that can be deposited from 1 litre
14
of water. But in practice in an actual system it could be less for the following
reasons.
(xi) If the water velocity is high, the retention time in the system may be too
low to allow all deposition to be completed within the system.
(xii) Because the precipitation of calcium carbonate takes place in the bulk of
the water (rather than on the heat exchange surfaces) precipitated calcium
carbonate may be carried out of the system by the flow of water.
(xiii) Retention of precipitated calcium carbonate can be influenced by the
roughness of the metal surfaces, and the geometry of the system (e.g. sharp
bends).
(xiv) There may be temperature variations within the system, so that some parts
may not be as high as T. In these lower temperature regions precipitation
will be reduced.
Having listed these points it may be stated that the calculated value of W
represents the highest weight of calcium carbonate that can be deposited, and
thus represents the maximum fouling likely to be encountered.
Another practical aspect that must be considered is the speed and ease with
which Eq. (18), or (19), or (20) can be used by a water technologist. Whether
the technologist is advising a design team on the choice between several possible
water supplies, or carrying out site tests with portable analytical equipment, the
ability to produce a quick answer has obvious advantages. To assist in this, a
table giving values of W against R is set out in Table 7. It is used as follows:
(xv) From a water analysis at atmospheric temperature (15 C) take the values
of Ca, Alk, and DS. Use them to calculate the value of pHS at T by
using Eq. (6) evaluated as described in Sec. 1.1.2. To assist in this
evaluation values of:
p[Ca2+] are given in Table 8
p[Alk] in Table 9
pK2 and pKS in Table 10.
Values of (DS)0.5/100 are calculated by simple arithmetic.
(xvi) From a water analysis at atmospheric temperature (15 C) take the values
of pH and Alk and use them to convert pH to the pH at T, using the
method described by Emerson on p. 20 of Ref. [8].
(xvii) From (xv) and (xvi) calculate the Ryznar Index at T.
R = 2pHS pH
(1)
15
(xviii) In Table 7, locate the sector containing the value of R obtained in (xvii).
Scan the sector heading horizontally and locate the column headed with
the value of R.
(xix) At the left hand edge of the table scan vertically to find T. Now scan
horizontally to meet the column selected in (xviii).
(xx) Where the two intersect is the value of W.
Example
Water analysis at 15 C
Ca = 300 mg/l CaCO3
Alk = 250 mg/l CaCO3
DS = 450 mg/l as such
pH = 7.8.
Temperature in system = 60 C.
Evaluate Eq. (6) as:
p[Ca 2+ ]
= 2.53 from Table 8
p[ Alk ]
= 2.30 from Table 9
pK 2 pK S = 1.40 (10.14 8.74 @ 60 o C from Table 10)

( DS) 0.5
= 0.21
100
pH S
= 6.44 @ 60 o C
From Table 20 at 15 C in Ref. [8]
Alk = 250
pH = 7.8.
gives C = 520.

Alk = 250
C
= 520
gives pH = 7.6 @ 60 C.

R = 2pHS pH = 2 6.44 7.6 = 12.88 7.6
= 5.28 @ 60 C.
In Table 7, locate the sector headed R 5.0 to 5.9.
16
Select the column headed 5.3.

At the left hand edge find T = 60 C.
The vertical column and horizontal line meet at W = 101 mg/l CaCO3.
This figure may be multiplied by the rate of water flow and the time the
plant is on load to give total calcium carbonate fouling.
1.2.2. Margin of Error

Before concluding the discussion of the use of Table 7 it will be useful to try to
access the margin of error likely to be encountered
To make this assessment five waters from Table 5 have been selected as
representative of the range of waters examined. They are Nos: 22, 25, 26, 29
and 30.
Similarly, three temperatures from Table 6 have been selected as representative
of the range of temperatures examined. They are 30 C, 60 C, and 80 C.
Combining these two pieces of data, the values of R and W as recorded in
Table 6 have been listed. The corresponding values of W from Table 7 have
been added alongside. The difference between corresponding values of W have
been listed and expressed as a percentage. The details are set out in Table 11.
In setting up Table 11 the values of W from Table 6 have been taken as the
true value, since they were calculated direct from individual water analyses on
a sound thermodynamic basis.
It will be seen from Table 11 that the errors vary between +50% and 27%.
In an ideal situation the error should be zero. How do the errors arise and what
is their significance?
Equation (18), on which Table 7 is based, is a best fit derived from
Eqs. (10) to (17) which are themselves a best fit to a set of data. Therefore,
there will be cases where the value of a parameter calculated from one of the
equations will be different from the true value.
The errors may be positive or negative, and they will also be cumalative
because any error arising from Eqs. (10) to (15) will be combined with any
errors arising from Eqs. (16) and (17).
It can be shown that the error of +50% mentioned above can be caused by
on error of 0.2 in the value of R, and the error of 27% caused by an error of
+0.5 in the value of R. Errors of this magnitude can be caused by errors of the
order of 0.15 in the values of pHS and pH: errors which are within the tolerance
applicable to normal plant practice.
To assess the significance of the errors in Table 11 it is necessary to compare
them with errors which arise from variations in water analyses due to natural
17
causes. To investigate this aspect, water analyses from two different locations
have been selected. Each water supply possesses characteristics that are likely
to lead to scaling. For each supply, the mean, maximum and minimum analyses
have been recorded. During the progress of any project the normal procedure is
to base calculations for design, operation, and control of a system on the mean
water analysis. But during the working life of the system it will receive water
varying between the minimum and maximum analyses.
To represent these real-life conditions W has been calculated at 30 C, 50 C,
and 80 C for the mean, maximum, and minimum analyses of both supplies. The
difference in values between mean and maximum analyses, and between mean and
minimum analyses have been recorded as errors. The results are set out in Table 12.
It will be seen that the errors recorded in Table 12 vary between +190% and
95%. This range is much greater than those recorded in Table 11. Therefore
Table 7 may be used as a useful working estimate since any errors it may
produce will be far outweighed from those arising from natural causes.
1.3. THE LANGELIER INDEX

It was stated earlier in Sec. 1.1.2 that Ryznar had investigated a possible relationship between Q and I, but had abandoned this line of investigation. In view of
the relationship between R and W subsequently produced in Sec. 1.2 the question
arises Is it possible to produce a similar relationship between I and W ?
To explore this possibility a plot of values for I and W at 30 C, 50 C, and
80 C (as recorded in Table 6) was made in Fig. 6. It will be seen from the plot
in Fig. 6 that a smooth curve can be drawn for each temperature, and that the
whole range can be covered by a family of curves. It is therefore worth exploring
the mathematics of the relationship between I and W in further detail.
It can be shown by a detailed mathematical analysis that the relationship
between I and W can be expressed as:
W = exp(YI + Z)
(21)
and that for individual temperatures the best fit equations are:
30 C
W = exp(4.30I + 0.71)
(22)
40 C
W = exp(3.73I + 0.69)
(23)
50 C
W = exp(3.50I + 0.69)
(24)
60 C
W = exp(2.23I + 1.70)
(25)
70 C
W = exp(2.92I + 0.69)
(26)
80 C
W = exp(2.97I + 0.37)
(27)
18
Fig. 6. Plot of Langelier index(I)-v-weight of calcium carbonate(W).
19
A further examination of Eqs. (22) to (27) shows that the values of Y are
linear in relation to temperature and the best fit equation is:
Y = 0.03T + 5.17
(28)
Similarly, the values of Z are linear in relation to temperature and the best
fit equation is:
Z = 0.0004T + 0.714
(29)
Substituting Eqs. (28) and (29) in Eq. (21) gives a universal equation:
W = exp[(0.03T + 5.17)I 0.0004T + 0.714]
(30)
For practical purposes it may be easier to use Eq. (30) in the logarithmic
form:
or
lnW = (0.03T + 5.17)I 0.0004T + 0.714
(31)
logW = (0.014T + 2.41)I 0.0002T + 0.333
(32)

When applied to practical problems in the field Eq. (30), (31), or (32) will give
the best values of W calculated on the basis of I. The calculated value of W is
the maximum weight of calcium carbonate that can be deposited from 1 litre of
water.
But in practice, in a actual system it could be less for the reasons already
given in items (xi) to (xiv) in Sec. 1.2.1.
Also, as in Sec. 1.2.1, there is a need for a fast and easy method for evaluating
Eq. (30), or (31), or (32). To assist in this, a table giving values of W against I
is set out in Table 13. It is used as follows:
(xxi) From a water analysis at atmospheric temperature (15 C) take the values
of Ca, Alk, and DS. Use them to calculate the value of pHS at T as
already described in item (xv) of Sec. 1.2.1.
(xxii) From a water analysis at atmospheric temperature (15 C) take the values
of Alk and pH and use them to convert the pH to the value at T as
already described in item (xvi) of Sec. 1.2.1.
(xxiii) From (xxi) and (xxii) calculate the Langelier index at T.
I = pH pHS
(5)
20
(xxiv) In Table 13, locate the sector containing the value of I obtained in (xxiii).
Scan the sector heading horizontally and locate the column headed by
the value of I.
(xxv) At the left hand edge of the table scan vertically to find T. Now scan
this line horizontally to meet the column selected in (xxiv).
(xxvi) Where the two intersect is the value of W.
Example
Water analysis at 15 C
Ca = 300 mg/l CaCO3
pH = 7.8.
p[Ca 2+ ]
= 2.53 from Table 8
p[ Alk ]
= 2.30 from Table 9
pK 2 pK S = 1.40 (10.14 8.74 @ 60 o C from Table 10)
( DS) 0.5
100
= 0.21
pH S
= 6.44 @ 60 o C

Alk = 250
pH = 7.8
gives C = 520.

Alk = 250
C
= 520
gives pH = 7.6 @ 60 C.

I = 7.6 6.44 = 1.16.
21
In Table 13, find the sector headed 1.1 to 2.0 and select the column headed
1.2. At the left hand edge find T = 60 C The vertical column and horizontal
line meet at:
W = 114 mg/l CaCO3.
This number, multiplied by the rate of water flow and the time the plant is
on load, will give the total calcium carbonate fouling.
1.3.2. Margin of Error

Before concluding the discussion on the use of Table 13, it will be useful to try
to assess the margin of error likely to be encountered. To make this assessment
the proceedure already described in Sec. 1.2.2 has been adopted. Analyses Nos.
22, 25, 26, 29 and 30 from Table 5 have been taken and temperatures 30 C,
50 C, and 80 C from Table 6.
Combining these two pieces of data, the values of I and W as recorded in
Table 6 were listed. The corresponding values of W from Table 13 were added
alongside. The difference between corresponding values of W were then listed
and expressed as a percentage. The details are set out in Table 14.
In setting up Table 14 the values from Table 6 were regarded as the true
values, since they were calculated direct from individual water analyses on a
sound thermodynamic basis.
It will be seen from Table 14 that the error varies between +36% and 26%.
This is a narrower range than that exhibited by R in Sec. 1.2.2. How do these
errors arise and what is their significance?
The discussion in Sec. 1.2.2 concerning Eqs. (10) to (18), Table 7, and the
errors recorded in Table 11, also apply here concerning Eqs. (21) to (30),
Table 13, and the errors recorded in Table 14. It can be shown that the errors of
+36% and 26% mentioned above, can be caused by errors of 0.04 and +0.06
in the evaluation of I. These errors can arise from errors of the order of 0.03 in
the values of pH and pHS: errors which are well within the tolerance applicable
to the evaluation of these parameters.
As already stated in Sec. 1.2.2 this is an important point which must not be
overlooked when considering the magnitude of errors in the value of W, as a
means of assessing the magnitude of errors in the procedure under discussion.
To assess the significance of errors in Table 14 the procedure already described
in Sec. 1.2.2 has been adopted. The same two waters listed in Table 12 have
been used again and the values of W for values of I at 30 C, 50 C, and 80 C
are recorded. The results are set out in Table 15.
22
It will be seen that the errors recorded in Table 15 vary between + 463% and
100%. This range is much greater than the range recorded in Table 14. Therefore
the errors arising from Table 13 can be ignored as likely to be outweighed by
errors arising from natural causes.
1.4. CHOICE BETWEEN LANGELIER AND RYZNAR

In this book two methods have been developed for estimating the weight of
calcium carbonate deposited in a system. One method is based on the Ryznar
Index (R) and the other on the Langelier Index (I). The existence of two possible
methods of estimation at once raises the question, Which one shall be used?
for any specific problem.
To assist in answering this question selected values of W, based on R and
derived from Table 7, and selected values of W, based on I and derived
from Table 13, are set out together in Table 16. The values based on I have
been taken as the standard: the difference between the values based on R and
the values based on I have been recorded in Table 16 and expressed as a
percentage.
As already stated in Sec. 1.3.1 values of W based on I are considered to be
superior to values based on R. Calculations based on I have a higher
thermodynamic integrity than those based on R. (R is an empirically derived
parameter, and this is considered to be a weak point). Thus values based on I
(Langelier) is the preferred method.
But some water treatment technologists and plant operators may have already
established methods of treatment and control based on R, and would prefer to
continue using R as a basis for estimating W. If this preference is followed, it
will be seen from Table 16 that errors between +38% and 25% may be
encountered. But these degrees of error are small compared with errors likely to
be introduced by natural causes. See Secs. 1.2.2 and 1.3.2.
The final decision will depend on the degree of tolerance that can be accepted
when making a forecast for any given installation.
In the case of a small project, or one handling a low grade product, a
tolerance between +38% and 25% may be acceptable. A calculation for W
based on the value of R would be attractive to a technologist or operator
who already has embedded in his methods of treatment and control calculations
based on R.
But for a large project, or one handling a sophisticated and expensive product,
a more accurate value for W, based on the value for I, will be required.
23
1.5. THE SPECIAL CASE OF RECIRCULATING SYSTEMS

Under the proviso stated in Sec. 1.1.1 the whole of the work discussed up to
this point is restricted to once-through, closed systems. However, as industrial
installations often include recirculating systems, they must now be considered.
1.5.1. Closed Recirculating Systems

Some industrial cooling systems take the form of a primary closed ring in which
water continuously recirculates. Heat, which needs to be dissipated, is absorbed
by the water in a heat-exchanger and then discharged from the water by a second
heat-exchanger which itself is cooled by a secondary cooling system.
In the primary system the volume of water used for the initial filling (or refilling after draining for maintenance) will deposit an initial quantity of calcium
carbonate according to the temperature rise experienced. Once this initial
precipitation has taken place, no more calcium carbonate will be deposited.
The quantity of calcium carbonate can be estimated by the methods already
described, from the analysis of the water and the temperature in the system. In
the calculation, the volume of water in the closed system replaces the flow rate
for a once-through system.
1.5.2. Open Recirculating Systems

The open recirculating cooling system, incorporating an evaporative cooling
tower, is widely used in industry. A special feature of this type of system is the
increase in the concentration of dissolved salts in the recirculating water.
The normal procedure for this type of system is to operate with a predetermined number of concentrations in the recirculating water (by controlled
purging from the system) coupled with treatment with an inhibitor. Each
inhibitor varies in the quantity of calcium carbonate it can hold in solution
before precipitation occurs. This factor determines the optimum number of concentrations to be maintained in the recirculating water. Therefore the number
of concentrations and the dosage of inhibitor are usually given to the plant
operator by the water treatment supplier.
In this context, it will be useful to estimate the weight of calcium carbonate
that will be deposited by a given water in a given plant at a given temperature
if the system is operated at various number of concentrations. This information
will assist in selecting the most appropriate treatment to inhibit fouling, and
the number of concentrations compatible with the selected treatment. Also, this
24
information can be used to justify the cost of treatment by giving an indication

of the loss of thermal efficiency if the system is operated without treatment.
In order to estimate the fouling (whether on the basis of Table 7 or on the
basis of Table 13) it is necessary to modify the methods previously described
for calculating pHS and pH.
pHS
The value of pHS for the make-up water at T, the temperature in the system is
first calculated as in (xv) in Sec. 1.2.1. If the system is to operate with n
concentrations in the recirculating water, the value of pHS in the make-up water
is converted to pHS in the recirculating water by means of the equation described
by Emerson [5]:
pHS
= pHS 2 log n + ( n 0.5 1)
( recirc.)
DS0.5
100
( make up )
(33)
pH
The value of pH in the recirculating water at T, the temperature in the system,
at n concentrations is calculated from the alkalinity of the make-up water
using the method described on p. 27 of Ref. [8].
With the new values of pHS and pH new values of R or I can be calculated
and a new value for W read off from Table 7 or Table 13.
Example
Make-up water analysis at 15 C
Ca = 120 mg/l CaCO3
Alk = 80 mg/l CaCO3
DS = 180 mg/l as such.
Number of concentrations in system = 3.
From Eq. (6)
p[Ca 2+ ]
= 2.92 from Table 8
p[ Alk ]
= 2.80 from Table 9
pK 2 pKS = 1.70 (10.22 8.52 at 40 oC from Table 10)
( DS)0.5
= 0.13
100
pH S
= 7.55 .
25
Convert to recirculating water

pHS = 7.55 2 log 3 + 0.13(30.5 1)
= 7.55 0.95 + 0.13(1.73 1)
= 7.55 0.95 + 0.09
= 6.69.
Alk in make-up water = 80.
In circulating water = 3 80 = 240.
From p. 27 of Ref. [8]
C = 2 Alk = 2 240 = 480.
From Table 63 of Ref. [8]
pH = 8.2
R = 2pHS pH = 2 6.69 8.2 = 13.38 8.2 = 5.18.
From Table 7
W = 159 mg/l CaCO3 for water in system
= 159/3 = 53 mg/l CaCO3 for make-up water.
Alternatively:
I = pH pHS = 8.2 6.69 = 1.51.
From Table 13
W = 490 mg/l CaCO3 for water in system
= 490/3 = 163 mg/l CaCO3 for make-up water.
The values of W in the make-up water may be multiplied by the rate of
adding water to the system and the time that the plant is on load to give the
total calcium carbonate fouling.
In considering the values of W above, the comments in Sec. 1.4 are still
applicable.
Chapter 2
CALCIUM SULPHATE FOULING
The need for discussing calcium sulphate fouling may not, at first, be apparent.
It is therefore useful to outline the circumstances in which calcium sulphate
fouling may be anticipated.
The fouling may be anticipated with water supplies which are high in sulphate.
Typical examples are deep well waters, or saline waters. A similar, but not
identical source, is treated effluent which is offered for industrial cooling
purposes, especially if effluent has been derived from a process involving the
use of sulphuric acid or sulphates.
Waters high in calcium hardness and alkalinity may be treated with sulphuric
acid in order to reduce the alkalinity to a level which will not promote
calcium carbonate fouling. But in doing so, the natural sulphate of the water
may be artificially boosted to a point which will now promote calcium sulphate
fouling.
A similar difficulty may be encountered with waters which will not promote
calcium sulphate fouling in their natural state, but if used in a recirculating
cooling tower (where a concentration effect operates) may be artificially boosted
to a point which will now promote calcium sulphate fouling in the circulating
water.
In the light of the above discussion it is strongly recommended that, whenever
a new system is being designed, or problems in an existing system is under
investigation, the possibility of calcium sulphate fouling should be included. It
should not be assumed, merely by visual inspection of water analyses, that such
fouling will not arise.
2.1. CALCIUM SULPHATE SATURATION INDEX

The calcium sulphate saturation index (IS) is defined by Emerson [10] as:
( DS)0.5
I S = pK p[Ca 2 + ] + p[SO 24 ] +
50
Where
K = (Ca 2+ )(SO 24 ) at equilibrium .

27
(34)
(35)
28
Equation (34) may be evaluated by taking values of:

pK from Table 17 (which is based on solubility data for calcium sulphate
by Seidell [11] and Booth and Bidwell [12])
2+
p[Ca ] from Table 8
p[SO2
4 ] from Table 18.
Values of (DS)0.5/50 are calculated by simple arithmetic.
Example
Ca
= 1000 mg/l CaCO3
SO4 = 1700 mg/l Na2SO4

Temperature = 90 C.
2+
From Table 17 pK @ 90 o C = 5.02 From Table 8 p[Ca ] = 2.00
From Table 18 p[SO 24 ] = 1.92
( DS) 0.5
= 1.06
50
4.98
IS = 5.02 4.98 = +0.04.

The positive value of I indicates a water supersaturated to calcium sulphate,
which will cause fouling. If the value was negative there would be no deposition
of calcium sulphate.
Having established a method for calculating IS it may now be utilised to
calculate the weight of calcium sulphate deposited to cause fouling.
2.2. CALCULATING THE WEIGHT OF

CALCIUM SULPHATE
For any given water at any given temperature:
Let initial calcium = A mg/l as CaCO3
(36)
Let initial sulphate = B mg/l as Na2SO4.
(37)
After precipitation of calcium sulphate:

Let fraction of calcium remaining = a
(38)
Let fraction of sulphate remaining = b.
(39)
Calcium Sulphate Fouling
29
Thus:
Final calcium = aA mg/l as CaCO3
(40)
Final sulphate = bB mg/l as Na2SO4.
(41)
From Eqs. (36) and (40):

Loss of calcium = A aA = A(1a) mg/l as CaCO3
136
A(1 a ) mg /1 as CaSO 4
=
100
= 1.36 A(1a) mg/l as CaSO4
(42)
(42a)
(42b)
From Eqs. (37) and (41)

Losss of sulphate = B bB = B(1b) mg/l as Na2SO4
136
B(1 b) mg /1 as CaSO 4
=
142
= 0.96 B(1b) mg/l as CaSO4.
(43)
(43a)
(43b)
Since loss of calcium must be equal to loss of sulphate when both are
expressed in the same unit:
From Eqs. (42b) and (43b):
1.36 A (1 a ) = 0.96 B (1 b)
1.36 A
=
0.96 B
A
1.42 =
B
(1 b)
(1 a )
(1 b)
.
(1 a )
(44)
(44a)
(44b)
For the initial water, the calcium sulphate saturation index may be obtained
by substituting Eqs. (36) and (37) in Eq. (34):
DS0.5
I S = pK pA + pB +
50
(45)
For the final water (i.e. after precipitation of calcium sulphate) the saturation
index may be obtained by substituting Eqs. (40) and (41) in Eq. (34):
DS0.5
I S = pK paA + pbB +
50
(46)
30
But since the water has already precipitated calcium sulphate, and therefore
reached a state of equilibrium, IS has become zero. Thus,
DS 0.5
0 = pK paA + pbB +
50
DS 0.5
( pa + pb)
= pK pA + pB +
50
(46a)
(46b)
Substituting Eq. (45) in Eq. (46b) gives:
0 = I S ( pa + pb )
= I S p( ab)
(47)
(47a)
= I S + log(ab)
(47b)
log(ab) = I S
(47c)
ab = 10 IS
a=
(47d)
10 IS
b
(47e)
(The calculation set out above assumes that the loss of DS by the precipitation
0 .5
of calcium sulphate does not make a significant difference in the value of DS50 ).
Substituting Eq. (44b) in Eq. (47e) gives:
1.42 A
(1 b)
=
B
10 IS
1
(1 b)
=
( b 10 I S )
(1 b)b
=
(b 10 IS )
1.42 A(b 10 IS )
= (1 b)b = b b2
B
1.42 A(b) 1.42 A(10 IS )
= b b2
B
B
1.42 A 1 1.42 A(10 IS )
=0
b 2 + b
B
B
(48)
(48a)
(48b)
(48c)
(48d)
(48e)
31
Expressed in more general terms Eq. (48e) becomes:
1.42Ca 1.42Ca
b 2 + b
(10IS ) = 0
1
SO4
SO4
(49)
Ca
By substituting values for SO4 and IS into Eq. (49), it can be solved for values
of b. Only real, positive values are retained for use: negative or imaginary
values have no physical significance.
The value of b is then substituted in Eq. (43b) to give the loss of calcium
sulphate. The value of b can also be substituted in Eq. (47e) to give a value
for a, which, in turn, can be substituted in Eq. (42b) to give an alternative
figure for the loss of calcium sulphate. Ideally, the two figures for the loss of
calcium sulphate should be identical.
To avoid the time and labour required to solve Eq. (43b), Table 19 has been
Ca
prepared from which values of b can be read off for various values of SO4 and
IS. This offers a procedure suitable for field use.
2.3. USE IN THE FIELD

The procedure outlined below yields a calculated figure for the maximum weight
of calcium sulphate precipitated to cause fouling. In practice, the figure may be
lower due to the effect of restrictions similar to those described in items (xi),
(xiii) and (xiv) in Sec. 1.2.1.
(xxvii). From a water analysis at atmospheric temperature take the values of
Ca
Ca, SO4 and DS. Use them to calculate the ratio SO4 , and the value of IS at T
as described in Sec. 2.1. If IS is negative there will be no fouling and further
calculation is unnecessary.
Ca
(xxviii) In Table 19, run down the left hand edge to find the value of SO 4 .
If the value calculated from the water analysis does not exactly fit the values in
the tables, use the nearest value.
(xxix) Follow that line horizontally across the tables (through 19/1, 19/2,
etc.) to find the column headed with the value of IS. Where the horizontal line
and vertical column meet is the value of b.
Example
Ca = 1000 mg/l CaCO3
SO4 = 1700 mg/l Na2SO4
T
= 90 C
Ca ratio = 1000
1700
SO 4
= 0.59
32
From Table 17
From Table 8
pK @ 90 C = 5.02
p[Ca2+]
= 2.00
From Table 18
p[SO2
4 ]
= 1.92
( DS)0.5
= 1.06
50
4.98
IS = 5.02 4.98 = +0.04.

As the index is positive, the water will deposit calcium sulphate at 90 C.
Ca
In Table 19, find SO4 = 0.6 (the nearest value to 0.59). Scan right to
find IS = 0.04 in Table 19/1. The horizontal line and vertical column meet at
b = 0.96.
From Eq. (43b)
Loss of sulphate = 0.96 1700 (10.96)
= 0.96 1700 0.04 = 65 mg/l CaSO4
From Eq. (47e)
a=
10 0.04 0.91
=
= 0.95
0.96
0.96
From Eq. (42b)

Loss of calcium = 1.36 1000 (10.95)
= 1.36 1000 0.05 = 68 mg/l CaSO4
Ideally the two loss figures should be identical, since they are both expressed
in terms of CaSO4. The difference is due to assuming that the change in DS
on precipitation of calcium sulphate made no significant difference to the value
0 .5
of DS50 (as discussed in Sec. 2.1) and to the values of b in Table 19 being
rounded off to two places of decimals.
For all practical plant purposes the two values are sufficiently close to allow
either value to be used for design or performance forecast purposes.
This value may be multiplied by the rate of water flow through the system
and the time the plant is on load, to estimate the total calcium sulphate fouling.

The comments made in Sec. 1.5 concerning recirculating systems also apply
here. The only item that needs to be discussed in detail is the effect of
33
concentration, in open recirculating systems, on the calcium sulphate saturation

index.
For any given water at any given temperature the calcium sulphate saturation
index is given by Eq. (34):
( DS)0.5
(34)
I S = pK p[Ca 2+ ] + p[SO 24 ] +
50
If the water is now allowed to concentrate n times in an open recirculating

system, the conditions for the circulating water become:
( nDS) 0.5
(50)
( I S ) n = pK pn[Ca 2+ ] + pn[SO 24 ] +
50
( nDS) 0.5
(50a)
( I S ) n = pK p[Ca 2+ ] + p[SO 24 ] + 2pn +
,
50
0
.
5
( DS)
( DS) 0.5
= pK p[Ca 2+ ] + p[SO 24 ] +
( 2pn + ( n 0.5 1)
(50b)
50
50
( DS) 0.5
50
( DS) 0.5
= I S + 2 log n ( n 0.5 1)
50
= I S 2pn ( n 0.5 1)
(50c)
(50d)
The use of Eq. (50d) is illustrated in the following example:

Example
Initial water analysis:
Calcium = 1500 mg/l CaCO3
Alkalinity = 500 mg/l CaCO3
Ca
ratio
SO 4
=
1500
= 0.83
1800
Sulphate = 1800 mg/l Na2SO4

Dissolved Solids = 2800 mg/l as such.
This water is to be treated with sulphuric acid to reduce the alkalinity to 20
mg/l CaCO3, and then used as make-up to a recirculating cooling system at a
temperature of 60 C and operating at a concentration factor of 6.0.
The following changes take place:
Loss of alkalinity = 50020 = 480 mg/l CaCO3
Corresponding gain in sulphate = 480 1.42 = 682 mg/l Na2SO4
New sulphate = 1800 + 682 = 2482 mg/l Na2SO4 .
34
Loss of dissolved solids due to loss of alkalinity = 480 mg/l CaCO3

Gain of dissolved solids due to gain of sulphate = 682 mg/l Na2SO4
Nett gain in dissolved solids = 682 480 = 202 mg/l as such
New dissolved solids = 2800 + 202 = 3002 mg/l as such.
The make-up water to the system therefore becomes:
Ca
ratio
SO 4
Alkalinity = 20 mg/l CaCO3
1500
= 0.60
2482
Sulphate = 2482 mg/l Na2SO4

Dissolved Solids = 3002 mg/l as such
From Table 17
pK @ 60 C = 4.74
From Table 8
p[Ca2+]
= 1.82
From Table 18
p[SO2
4 ]
= 1.76
( DS)0.5
50
= 1.10
4.68
For the make-up water IS = 4.74 4.68 = +0.06

For the recirculating water, Eq. (50d) applies:
30220.5
50
54.79
= +0.06 + 2 0.78 (2.45 1)
50
= +0.06 + 1.56 (1.45) (1.10)
= +1.62 1.60
= +0.02
( I S )n = +0.06 + 2 log 6 (60.5 1)
From Table 19/1

Ca
= 0.60 and ( I S )n = +0.02 gives b = 0.98
SO4
35
From Eq. (43b)

Loss of sulphate = 0.96 6 2482 (1-0.98)
= 0.96 6 2482 0.02
= 286 mg/l CaSO4
This is equivalent to 286
= 48 mg CaSO4 for each litre of water entering the
6
system.
An alternative calculation using Eq. (47e) gives:
a=
10 ( I S )n 10 0.02 0.96
=
=
= 0.98
0.98
0.98
b
Loss of calcium = 1.36 6 1500 (10.98)

= 1.36 6 1500 0.02
= 245 mg/l CaSO4.
This is equivalent to 245/6 = 41 mg CaSO4 for each litre of water entering
the system.
The reason for the differences between the two calculated values for calcium
sulphate fouling has already been discussed in Sec. 2.3. For practical plant
purposes the two values are sufficiently close to allow either value to be used
for design or performance forecast purposes.
Since the fouling has been expressed in terms of water entering the system,
the question may be raised as to why calculations have not been based on the
saturation index of the make-up water and then simply multiplied by 6 (the
value of n).
It will be seen in the Example already worked out that IS = +0.06 for
Ca
the make-up water and SO
= 0.60. Using these values in Table 19/1 gives
4
a value of b = 0.94.
On this basis, the loss of sulphate = 0.96 2482 (10.94)
= 143 mg CaSO4 per litre.
The alternative calculation gives a =
10 0.06
0.94
= 0.93
and loss of calcium = 1.36 1500 (10.93)

= 142 mg CaSO4 per litre.
This appears to be very good agreement. But it cannot be accepted because
calculations based on the make-up water do not allow the full influence of
dissolved solids to be exercised on the ionic equilibria involved in the circulating
water. This leads to loss of thermodynamic integrity, and therefore, the method
cannot be accepted.
Chapter 3
CALCIUM PHOSPHATE FOULING
The need for discussing calcium phosphate fouling arises from the fact that
there has been an increase in the phosphate content of water supplies and hence
an increase in the risk of calcium phosphate fouling in industrial water systems.
The increased use of phosphate fertilisers in agriculture has led to an increase
in phosphate in waterways. Following heavy rain, fertiliser is washed from the
surface of fields into adjoining streams, which in turn feed rivers from which
public water supplies are drawn. This introduction of phosphate into general
water supplies is seasonal, since fertilisers are more usually applied to fields in
Spring, when seed is sown and new crops planted out.
There is also a meteorological factor since the coincidence of heavy Spring
rains with agricultural planting provides a means of washing the surface of
fields at the time fertiliser has been applied.
The use of phosphates in industrial processes and the inclusion of phosphates
in detergents is another source of phosphate entering industrial systems. Effluents
from such processes, which have been treated on site and accepted by a Rivers
Authority for discharge into a stream, will still carry some phosphate. Similarly,
effluent which has been accepted by a local sewage work for treatment, and
subsequently offered to industry for cooling purposes will still carry some
phosphate.
Although step are being taken to reduce the amount of phosphate in water
supplies, complete freedom from phosphate cannot be assumed. It is therefore
recommended that whenever a new system is being designed, or a problem in
an existing system investigated, an assessment of calcium phosphate fouling
should be included. Mere visual inspection of water analysis should not be
accepted as sufficient.
3.1. CALCIUM PHOSPHATE SATURATION INDEX

Following the basis of the definition of the saturation index for calcium sulphate
given in Sec. 2.1, the saturation index for calcium phosphate may be similarly
37
38
defined as:
I p = pKS [3p(Ca 2+ ) + 2p( PO34 )]
(51)
K S = (Ca 2+ ) 3 ( PO 34 ) 2
(52)
where
at equilibrium.
In evaluating Eq. (51) values for calcium can be obtained from a water
analysis, but values for phosphate cannot be obtained so easily. The analytical
test for phosphate gives phosphates in all forms present in the water, whereas
Eq. (51) requires only that portion of the total phosphate present as the
orthophosphate ion. Clearly, some form of conversion is needed.
The necessary conversion has been provided by Green and Holmes [13].
Starting with the equations:
K1 = ( H + )
( H 2 PO 4 )
( H 3PO 4 )
(53)
K2 = (H + )
( HPO 24 )
( H 2 PO 4 )
(54)
K3 = ( H + )
( PO 34 )
( HPO 24 )
(55)
( Phos ) = ( PO 34 ) + ( HPO 24 ) + ( H 2 PO 4 ) + ( H 3PO 4 ) .
(56)
These were re-arranged to give:
( PO34 ) = ( Phos)
( H + )3
+ K1
K1K 2 K3
.
+ K1K 2 ( H + ) + K1K 2 K 3
( H + )2
(57)
Because the expression containing the equilibrium constants is long and

cumbersome it has, in this book, been replaced by the abbreviation:
E=
( H + )3
+ K1
K1K 2 K 3
.
+ K1K 2 ( H + ) + K1K 2 K 3
( H + )2
(58)
Substituting Eq. (58) in Eq. (57) gives:
( PO 34 ) = ( Phos)( E ) .
(59)

I p = pKS [3p(Ca 2+ ) + 2p( Phos) + 2p( E )].
(60)
Calcium Phosphate Fouling
39
For any given water at any given temperature at equilibrium Ip becomes zero
and, for these conditions, Eq. (60) can be written as:
3p(Ca 2 + ) + 2p( Phos) = pK S 2p( E ) .
(61)
Taking values for calcium and Phos from water analyses, and values of KS
from the literature, Green and Holmes calculated values of (E) at equlibrium
conditions. Using these values, and values of K1, K2, and K3 from the literature
in Eq. (58), they then calculated the value of (H+) at equilibrium and hence
obtained pHS. Green and Holmes did not proceed beyond this point as their
main interest was to establish a method for determining the values of pHS as an
aid to controlling phosphate treatments of boiler feed waters.
To facilitate these calculations Green and Holmes set up tables to allow
values of pHS at various temperatures to be read off from analytical values of
calcium and Phos.
In setting up their tables Green and Holmes used values for pK1 based on
Nims [16], values for pK2 based on Bates and Acree [17], and values for pK3
based on Bjerrum and Unmack [18]. The values are set out in Table 20. There
was, however, a problem in evaluating pKS. The literature gave values varying
between 25 and 31. After a review of the literature Green and Holmes selected
a value by Kuyper [19], which they modified in the light of data by Sendroy
and Hastings [20] to give a value of 29.3. This value refers to a temperature of
38 C: there are no experimental data available (nor reliable theoretical data) to
indicate the effect of temperature variations on the selected value of 29.3.
Having to operate with a fixed value for pKS obviously is a weak point in
the procedure.
In establishing Eq. (60) calcium and Phos have both been expressed in terms
of thermodynamic activity. This will lead to an error (usually slight) because
analytical results yield values expressed in terms of stoichiometric concentrations.
Green and Holmes made no correction on this account: they considered such
a correction to be unwarranted in view of the uncertainty over the value
for pKS.
However, it is considered that the necessary corrections should be incorporated
into Eq. (60) in order to preserve thermodynamic integrity. If, and when, new
and improved values for pKS over a range of temperatures become available,
then Eq. (60) will be in a form to use and benefit from the new data.
The corrections may be introduced by applying the theories of Debye and
Huckel [14] and Bronstead and LaMer [15].
(Ca 2 + ) = f Ca [Ca 2 + ]
(62)
40
p(Ca 2 + ) = pf Ca + p[Ca 2 + ]
(63)
2 ( ) 0.5 + p[Ca 2 + ]
= 0.5zCa
(63a)
= 0.5 2 2 ( ) 0.5 + p[Ca 2 + ]
(63b)
2( ) 0 .5
+ p[Ca 2 + ].
(63c)
A similar treatment may be applied to (Phos) by using the valency (z) for
PO3
4 since the analytical tests for Phos are expressed in terms of PO4.
( Phos) = f PO 4 [ Phos]
(64)
p( Phos) = pf PO 4 + p[ Phos ]
= 0.5z 2 PO 4 ( ) 0.5 + p[ Phos]
=
0 . 5 3 2 ( ) 0. 5
+ p[ Phos]
= 4.5( ) 0.5 + p[ Phos ].
(65)
(65a)
(65b)
(65c)
Substituting Eqs. (63c) and (65c) in Eq. (60) gives:

I p = pKS {3p[Ca 2+ ] + 6( )0.5 + 2p[ Phos] + 9( )0.5 + 2 p( E )}
= pKS {3p[Ca 2+ ] + 2 p[ Phos] + 2 p( E ) + 15( )0.5}.
(66)
(66a)
Using the Langelier [2] evaluation:
DS
(where DS is expressed in mg/l)
40000
I p = pKS {3p[Ca 2+ ] + 2p[ Phos] + 2p( E ) + 0.075( DS)0.5 }
(67)
To evaluate Eq. (67) pKS has already been assigned the fixed value of 29.3:
values of p[Ca2+] are given in Table 8: values of p[Phos] are given in Table 21:
values of p(E) are given in Table 22. The value of 0.075(DS)0.5 may be calculated
by simple arithmetic.
Example
Ca
= 250 mg/l CaCO3
Phos = 50 mg/l PO4

DS
= 300 mg/l as such
pH
= 7.8
= 20 C
pKS = 29.3
41
p[Ca] = 2.60
3p[Ca]
= 7.80
From Table 21 p[Phos] = 3.28
2p[Phos]
= 6.56
From Table 22 p(E) = 4.73
2p(E)
= 9.46
DS = 300
= 1.30
0.075(DS)0.5
25.12
From Table 8
Ip = 29.3 25.12 = + 4.18.

As the index is positive, the water will deposit calcium phosphate. Had the
index been zero or negative the water would not deposit calcium phosphate.
At this stage, a word of caution on the interpretation of the index is necessary.
In their original paper Green and Holmes [13] used Eq. (61) to calculate the
equilibrium pH (pHS) for calcium phosphate. If pHS is less than the actual pH,
then precipitation of calcium phosphate will occur. But if pHS is equal to, or
greater than, the actual pH there will be no precipitation of calcium phosphate.
Using the difference between pHS and pH is a useful indicator, and served
the purpose of Green and Holmes, but it is not mathematically identical with
the true saturation index as defined by Eq. (67). The confusion arises because,
in the original concept of a saturation index pioneered by Langelier [2] for
calcium carbonate, the value of I = pH pHS is mathematically identical with
I = pKS (p(Ca) + p(CO3)). But this is not universally true for all molecules.
Thus, although the value of I = pH pHS has been used as a basis for calculations
in Sec. 1.3, it cannot now be used for calculations in this section.
Having established a method for calculating Ip it may now be utilised to
calculate the weight of calcium phosphate deposited to cause fouling.
3.2. CALCULATING THE WEIGHT OF

CALCIUM PHOSPHATE
For any given water at any given temperature:
Let initial calcium = A mg/l as CaCO3
(68)
Let initial Phos = B mg/l as PO 4 .
(69)
After precipitation of calcium phosphate:
Let fraction of calcium remaining = a
(70)
Let fraction of Phos remaining = b .
(71)
42
Thus:
Final calcium = aA mg/l CaCO3
(72)
Final Phos = bB mg/l PO 4 .
(73)

Loss of calcium = A aA = A(1 a ) mg/l as CaCO3
310
=
A(1 a ) mg/l as Ca 3 (PO4 ) 2
300
= 1.03 A(1 a ) mg/l as Ca 3 (PO4 ) 2 .
(74)
(74a)
(74b)

Loss of Phos = B bB = B(1 b) mg/l as PO4
310
B(1 b) mg/l as Ca 3 (PO4 ) 2
190
= 1.63 B(1 b) mg/l as Ca 3 (PO4 )2 .
=
(75)
(75a)
(75b)
Since loss of calcium must be equal to loss of Phos, when both are expressed
in the same unit:
From Eqs. (74b) and (75b):
1.03 A(1 a ) = 1.63 B (1 b)

(1 b) 1.03 A 0.63 A
=
=
.
(1 a ) 1.63B
B
(76)
(76a)
For the initial water the calcium phosphate saturation index may be obtained
by substituting Eqs. (68) and (69) in Eq. (67):
I p = pK S (3pA + 2 pB + 2 p( E ) + 0.075( DS) 0.5 )
(77)
For the final water (i.e. after precipitation of calcium phosphate) the saturation
index may be obtained by substituting Eqs. (72) and (73) in Eq. (67):
I p = pK S (3paA + 2pbB + 2p( E ) + 0.075( DS) 0.5 )
(78)
= pKS (3pa + 3pA + 2pb + 2pB + 2p( E ) + 0.075( DS )0.5 )
(78a)
= pK S (3pA + 2 pB + 2 p( E ) + 0.075( DS) 0.5 ) (3pa + 2pb) .
(78b)
Because the final water will be in equilibrium with precipitated calcium

phosphate Ip must be zero. Thus:
0 = pK S (3pA + 2pB + 2p( E ) + 0.075( DS) 0.5 ) (3pa + 2 pb)
(79)
43

0 = I p (3pa + 2pb)
(80)
= I p ( pa 3 + pb 2 )
(80a)
= I p + log a 3 + log b 2
(80b)
= I p + log a 3b 2
(80c)
I p = log a 3b 2
(80d)
log10 I p = log a 3b 2
(80e)
10 I p = a 3b 2
(81)
10 I p
b2
(81a)
a3 =
10 I p
a = 2
b
0.33
(81b)
(neglecting negative or imaginary roots).

Substituting Eq. (81b) in Eq. (76a) gives:
(1 b )
10 I p

1 2
b
0.33
0.63 A
B
(1 b )
(10 I p )0.33
1
b0.67
(82)
=
0.63 A
B
(1 b)
(b0.67 (10 I p )0.33 )
b0.67
0.63 A
B
(1 b) b0.67
0.63 A
=
B
{b0.67 (10 I p )0.33}
0.63 A 0.67 0.63 A
b 0.67 b1.67 =
b
(10 I p )0.33
B
B
0.63 A 0.63 A I p 0.33

(10 )
= 0.
1
b1.67 + b 0.67
B
B
(82a)
(82b)
(82c)
(82d)
(82e)
44
The discussion covering the development of Eq. (78) through to Eq. (82e)
assumes that the change in DS due to the precipitation of calcium phosphate
will not make a significant difference in the value of 0.075(DS)0.5.
The discussion also assumes that there will be no change in pH to alter the
value of (E). This assumption is justified because the precipitation takes place
in an environment in which the pH is dominated by the relationship between
the alkalinity of the water and the total carbon dioxide content. Since neither
alkalinity nor carbon dioxide are involved in the precipitation of calcium
phosphate, the pH of the water will be buffered to the initial pH.
To utilise Eq. (82e), values of A and B can be obtained from a water
analysis and the value of Ip obtained from Eq. (77) by the method already
described earlier in this section. Equation (82e) may then be solved for b
which can be inserted in Eq. (75b) to give the loss of calcium phosphate.
As Eq. (82e) is complex, Table 23 has been set up to allow values of b to
be read-off from values of Ip and the ratio BA ; or in more general terms the ratio
CaCO3/PO4.
An alternative approach would be to obtain from Eq. (81) an evaluation of
b in terms of a. This evaluation could then be used in a process similar to
that used for Eqs. (82) to (82e) to produce an equation similar to (82e) but
expressed in terms of a.
It can be shown that the equation would read:
0.63 A 2.5 0.63 A 1.5
I
a (10 p ) 0.5 = 0 .
a + 1
B
B
(83)
This equation, like (82e), is complex and would need a new table (similar to
Table 23) to allow Eq. (83) to be evaluated. As Table 23 is already in existence
it is considered that the work involved in preparing a new table for Eq. (83) is
not justified.
3.3. USE IN THE FIELD

The procedure outlined below yields a calculated figure for the maximum weight
of calcium phosphate precipitated to cause fouling. In practice, the figure may
be lower due to the effect of restrictions similar to those described in items (xi),
(xiii), and (xiv) in Sec. 1.2.1.
(xxx) From a water analysis at atmospheric temperature take the values of
Ca, Alk, PO4, DS and pH. Use them to calculate the ratio CaCO3/PO4: to convert
the pH to the value for the temperature in the system (if different from
atmospheric) using the method on p. 20 of Ref. [8]: to calculate the value of Ip
45
using Eq. (67); for the temperature in the system. (If Ip is zero or negative there
will be no precipitation).
(xxxi) In Table 23, find the section containing the value of Ip. Run down the
left-hand edge of the first table in the section to find the value of Ip. (If the
values displayed to not exactly fit the value calculated from Eq. (67) select the
nearest).
(xxxii) Follow the selected value horizontally across the table, proceeding
from table to table in strict numerical order, until the value for CaCO3/PO4 is
found. (If the exact figure is not recorded, select the nearest).
(xxxiii) At the head of the column located in (xxxii) the value of b is
given. Use this to calculate the calcium phosphate precipitated from Eq. (75b).
(Multiply by the rate of flow, and the time the system is on load to give the
total fouling).
(xxxiv) Having precipitated calcium phosphate the water may still be capable
of depositing calcium carbonate to give a mixed fouling. This should now be
checked.
= 0.97 to give the
(xxxv) Take the result from (xxxiii) and multiply by 300
310
deposit in terms of CaCO3. Deduct this from the original Ca figure to give an
amended value. Use this, together with the values for Alk, DS, and pH at the
system temperature to calculate I at the system temperature, as described in
Sec. 1.3.1.
(xxxvi) Use the value of I from (xxxv) to read-off the weight of calcium
carbonate deposited from Table 13.
Example
Ca
= 250 mg/l CaCO3
Phos = 50 mg/l PO4

DS
= 300 mg/l as such
pH
= 7.8 @ 15 C.
What is the fouling at 40 C?

At 15 C
At 40 C
pH = 7.8
C = 312 mg/l CaCO3
C = 312 mg/l CaCO3
pH = 7.7
46
pKs = 29.3
p[Ca2+]
=
2+
3p[Ca ]
=
2p[Phos]
=
From Table 22 p[E] = 4.55
2p[E]
=
DS = 300
0.075(DS)0.5
=
From Table 8
2.60
7.80
6.56
9.10
1.30
24.76
Ip = 29.3 24.76 = + 4.54
Ca
250
=
= 5.0.
PO 4
50
b = 0.01
From Table 23
Final phosphate = 50 0.01 = 0.5 mg/l PO4

Loss of phosphate = 50 0.5 = 49.5 mg/l PO4
310
= 49.5
= 81 mg/l Ca3 (PO4)2 .
190
Loss of calcium = 81 mg/l Ca3 (PO4)2
300
= 81
= 78 mg/l CaCO3.
310
Residual calcium = 250 78 = 172 mg/l CaCO3.
Residual dissolved solids = 300 81 = 220 mg/l as such
p[Ca2+]
= 2.76 from Table 8
p[Alk]
= 2.52 from Table 9
pK2 pKS = 1.70 (10.22 8.52 from Table 10) @ 40 C

DS0.5/100 = 0.15
pHS
= 7.13
pHS
7.13
pH
7.70
= + 0.57 @ 40 C
From Table 13
Total Fouling
W = 20 mg/l CaCO3 (by interpolation)

81 mg/l Ca3(PO4)2
20 mg/l CaCO3.
Example
Ca
= 30 mg/l CaCO3
Phos = 80 mg/l PO4

Alk = 60 mg/l CaCO3
DS
= 100 mg/l as such
pH
= 8.2 @ 15 C.
What is the fouling at 60 C?

At 15 C
At 60 C
Alk = 60 mg/l CaCO3
Alk = 60 mg/l CaCO3
pH = 8.2
C = 121 mg/l CaCO3
C = 121 mg/l CaCO3
pH = 8.0
pKS = 29.3
p[Ca2+] = 3.53
= 10.59
3p[Ca2+]
2p[Phos]
= 6.16
2p[E]
= 7.90
DS = 100
From Table 8
0.075(DS)0.5
0.75
25.40
Ip = 29.3 25.40 = + 3.90

Ca
30
=
= 0.38 .
PO 4 80
From Table 23
b = 0.78
Final phosphate = 80 0.78 = 62 mg/l PO4

Loss of phosphate = 80 62 = 18 mg/l PO4
310
= 18
= 29 mg/l Ca3(PO4)2
190
300
Loss of calcium = 29
= 28 mg/l CaCO3
310
Residual calcium = 30 28 = 2 mg/l CaCO3.
Residual dissolved solids = 100 29 = 71 mg/l as such
47
48
p[Ca2+]
4.70 from Table 8
p[Alk]
2.92 from Table 9
pK2 pKS =
DS0.5
1.40 (10.14 8.74 from Table 10) @ 60 C
0.08
9.10
pH
8.00
= 1.10.
100
pHS
As I is negative there will be no precipitation of calcium carbonate.

Fouling = 29 mg/l Ca3(PO4)2 only.

The comments made in Sec. 1.5 concerning recirculating systems also apply here.
The only item that needs to be discussed in detail is the effect of concentration,
in open recirculating systems, on the calcium phosphate saturation index.
For any given water at any given temperature, the calcium phosphate saturation
index is given by the Eq. (67):
I p = pKS {3p[Ca 2+ ] + 2p[ Phos] + 2p[ E ] + 0.075( DS)0.5 }.
(67)
If the water is now allowed to concentrate n times in an open recirculating

system the condition for the circulating water becomes:
( I p )n = pKS {3pn[Ca 2+ ] + 2pn[ Phos] + 2p[ E ] + 0.075( nDS)0.5 }
= pKS {3pn + 3p[Ca 2+ ] + 2 pn + 2 p[ Phos] + 2p[ E ] + 0.075( nDS)0.5 }
= pKS
{3p[Ca 2+ ] + 2 p[ Phos] + 2p[ E ] + 0.075( nDS)0.5
+ 5pn}
= pKS {3p[Ca 2+ ] + 2 p[ Phos] + 2p[ E ] + 0.075( nDS)0.5 5 log n}.
(84)
(84a)
(84b)
(84c)
The equation cannot be developed beyond this stage, because of the changes
in the pH of the water as it passes round the open recirculating system. Firstly,
there is the change in pH due to the temperature rising from atmospheric to the
ambient temperature in the system.
Secondly, there is the change in pH as the circulating water establishes an
equilibrium with the atmosphere. Thus, the final pH will be different from that
resulting solely from a temperature rise in the system and therefore a different
value of p[E] will be needed to evaluate Eq. (84c).
The use of Eq. (84c) is illustrated in the following example.

Example
Phos
= 40 mg/l PO4
Alk
= 70 mg/l CaCO3
DS
= 200 mg/l as such
pH
= 7.2 @ 15 C
Number of concentrations = 3.
At 15 C
At 45 C and n = 3
Alk = 70 mg/l CaCO3
Alk = 3 70 = 210 mg/l CaCO3
pH = 7.2
C = 2 Alk = 2 210
= 420 mg/l CaCO3
From p. 27 of Ref. [8]
pH = 8.2
From Table 57 of Ref. [8].
pKS = 29.3
p[Ca2+] = 3.10
3p[Ca2+]
=
2p[Phos]
=
2p[E]
=
DS = 200
0.075 (3 200)0.5
=
From Table 8
n = 3 log n = 0.45 5 log n

Ip = 29.3 23.45 = 5.85
Ca
80
=
= 2 .0 .
PO 4 40
From Table 23/6
b = 0.015 (by interpolation).
Final phosphate in system = 3 40 0.015

= 1.8 mg/l PO4.
9.30
6.76
7.80
1.84
25.70
2.25
23.45
49
50
Loss of phosphate = 3 40 1.8

= 118 mg/l PO4
310
= 118
190
= 192 mg/l Ca3 (PO4)2.
Equivalent to
as make-up.
192
3
= 64 mg Ca3(PO4)2 for each litre of water entering the system
Loss of calcium in system = 192 mg/l Ca3(PO4)2

300
= 192
310
= 186 mg/l CaCO3.
Residual calcium in system = 3 80 186
= 240 186
= 54 mg/l CaCO3.
Residual dissolved solids in system = 3 200 192
= 600 192
= 408 mg/l as such.
Alkalinity in system (unchanged) = 3 70
= 210 mg/l CaCO3.
p[Ca2+]
= 3.27 from Table 8
p[Alk]
= 2.38 from Table 9
pK2 pKS = 1.63 (10.20 8.57) from Table 10 @ 45 C

DS0.5/100 = 0.20
pHS
= 7.48
pH
= 8.20
I = pH pHS = 8.20 7.48 = + 1.72.

From Table 13 the value of I = + 1.72 at 45 C falls outside the range of the
table and would appear to indicate calcium carbonate deposited in excess of
620 mg/l.
But this is impossible with a residual calcium in the system of only 54 mg/l.
The anomoly arises from the fact that the Alk/Ca ratio is very high for the
water under discussion.
Clearly, the true value for calcium carbonate deposited will be of the order
of 50 mg/l. A value may be calculated by the method of iteration.
51
If, by way of illustration, it is assumed that there is a nominal precipitation

of 40 mg/l CaCO3, then the final water in the system will contain:
Ca = 14 mg/l CaCO3
p[Ca2+]
= 3.85 from Table 8
p[Alk]
= 2.47 from Table 9
pK2 pKS = 1.63 (10.20 8.57) from Table 10 @ 45 C

DS0.5/100 = 0.19
= 8.14
pHS
pH
I
= 8.20
= pH pHS = 8.20 8.14 = + 0.04.
This value is close enough to the, theoretical, zero for all practical, plant
purposes and therefore 40 mg/l can be accepted as the deposited calcium
carbonate in the system.
= 13 mg/1.
In the make-up water the corresponding figure is 40
3
Total fouling
64 mg Ca3(PO)4
13 mg CaCO3
for each litre of water entering the system as make-up.
Chapter 4
CORROSION OF MILD STEEL
4.1. THE RYZNAR INDEX

At the beginning of this book, under the discussion of fouling by calcium
carbonate, the Ryznar Index was introduced. It was pointed out that Ryznar
had produced his Index as an empirical relationship linking the chemical
characteristics of a water and the weight of calcium carbonate that it would
precipitate under given conditions. It was also pointed out that Ryznar did not
extend his investigations beyond this area. He did not take (what would appear
to be the next logical step) of investigating a possible relationship between his
Index and the rate of corrosion of steel in water.
That gap has now been filled by Finan et al. [21]. Their work involved the
use of a cooling tower test rig, the basis of which is shown in Fig. 7. Water
from the sump is pumped through an electric heat-exchanger in order to obtain
a controlled rise in temperature. The water then passes through a test coupon
chamber in which mild steel and cast iron test coupons are suspended. Weighing
the coupons before and after a test run gives the weight loss due to corrosion
during the duration of the run, and hence the corrosion rate is calculated. Water
leaving the test coupon chamber next passes down a cooling tower where it is
cooled by an upward current of air. Some evaporation losses occur here, causing
an increase in the concentration of salts dissolved in the water. The degree of
concentration is controlled by adjustment of the purge bled from the sump and
the make-up water added.
Using this procedure Finan et al. were able to study the corrosion rates for
a range of natural waters over a range of concentration factors.
The results of this study were not published in the form of tables, giving
details of each test run, but were summarised in the form of a graph. The graph
makes no distinction between cast iron and mild steel. That graph is reproduced
in Fig. 8.
Mathematical analysis of the graph shows that the best fit equation
corresponding to the curve is:
C/ = 0.774 exp (0.458R)
53
(85)
54
Fig. 7. Basis of cooling tower test rig.
Corrosion of Mild Steel
Fig. 8. Plot of Ryznar index(R)-v-corrosion rate(C/ ) mild steel.
55
56
which may be converted to the logarithmic form as:

In C/ = 0.458R + In 0.774
= 0.458R 0.256.
(86)
(86a)
For practical use it will probably be more convenient to use common

logarithms. The conversion is:
2.303 log C/ = 0.458R 0.256
(87)
log C/ = 0.199R 0.111.
(87a)
In Fig. 8, the corrosion rate is expressed in terms of mpy (mils per year = in
103 per year). It is preferred to work in the corresponding SI unit (mm per
year = mm.y1). The conversion is:
log (C/ 39.3) = 0.199R 0.111
(88)
log C/ + log 39.3 = 0.199R 0.111
(88a)
log C/ + 1.594 = 0.199R 0.111
(88b)
log C/ = 0.199R 1.705
(88c)
Before Eq. (88c) can be used in the field, attention must be given to the
temperature at which the values of C/ and R were determined in order to construct
the graph in Fig. 8.
The values for R were based on the analyses of samples of water taken from
the test rig and analysed on the bench at atmospheric temperature. (A nominal
15 C). The values of C/ represent the corrosion rates of mild steel test coupons
maintained at the ambient water temperature in the test rig. This temperature
has not been stated. However, elsewhere in their report, Finan et al. give a
temperature rise of 9 C for a typical industrial cooling system. This figure is in
line with general experience for this type of system. It may reasonably be assumed
that the test rig was set to reproduce conditions existing in typical industrial
systems and therefore the ambient water temperature would be of the order of
9 C above atmospheric temperature. For the purpose of evaluating Eq. (88c) a
nominal system temperature of (25 C) has been assumed. Therefore, before
Eq. (88c) is used the value of C/ must be converted from that for 25 C to that
for 15 C.
Ison and Butler [22] give the temperature coefficient for the corrosion rate
of mild steel in water as:
C/ TC = C/ tC (1 + 0.05 (T t)).
(89)
57
A similar coefficient is indicated by Large [23].

For a 10 C rise from 15 C to 25 C:
C/ 25 C = C/ 15 C (1 + 0.05 10).
= C/ 15 C (1.5).
(90)
(90a)
Inserting this value in Eq. (88c) gives:

log 1.5C/ 15 C = 0.199R 1.705
(91)
log 1.5 + log C/ 15 C = 0.199R 1.705
(91a)
0.176 + logC/ 15 C = 0.199R 1.705
(91b)
log C/ 15 C = 0.199R 1.881.
(91c)
For general plant use, the equation may be written:

log C/ = 0.2R 1.9.
(92)

To apply Eq. (92) in the field, the following procedure may be used:
(xxxvii) From a water analysis at atmospheric temperature (15 C) take the
values of Ca, Alk, and DS. Use them to calculate the value of pHS at
temperature T (the temperature in the system) using Eq. (6) in Sec. 1.1.2
and following paragraph (xv) in Sec. 1.2.1.
(xxxviii) From a water analysis at atmospheric temperature (15 C) take the
values of pH and Alk and use them to convert to the pH at T, as
described by Emerson on p. 20 of Ref. [8].
(xxxix) From (xxxvii) and (xxxviii) calculate the Ryznar Index at T.
R = 2pH S pH
(1)
(xl) Use the value of R in Eq. (92) to obtain a value of C/ .

(xli) This value of C/ assumes that the relationship between R and C/ is the
same for all temperatures: but this is not so and C/ must be adjusted
for the temperature in the system (T) using Eq. (89).
Example
Calcium = 80 mg/l CaCO3.
Alkalinity = 60 mg/l CaCO3.
Dissolved Solids = 150 mg/l as such
pH = 7.2.
58
Temperature in system = 50 C
p[Ca2+] = 3.10
from Table 8
p[Alk] = 2.92
from Table 9
pK2 pKS = 1.54 @ 50 (10.17 8.63) from Table 10
DS0.5
= 0.12
100
pHS = 7.68 @ 50 C.
At 15 C
At 50 C
Alk = 60 mg/l CaCO3
Alk = 60 mg/l CaCO3
pH = 7.2
C = 140 mg/l CaCo3
C = 140 mg/l CaCO3
pH = 7.1
from Table 20 of Ref. [8]
R = 2pHS pH = 2 7.68 7.1 = 8.26 @ 50 C

log C/ = 0.2 8.26 1.9 (from Eq. 92)
= 1.65 1.9 = 0.25
C/ = 0.56 mm.y1 @ 15 C value.
Convert to 50 C
C/ =
=
=
=
0.56
0.56
0.56
0.56
(1 + 0.05 (50 15))

(1 + 0.05 35)
(1 + 1.75)
2.75 = 1.54 mm.y1.
If the system was constructed from mild steel of 5 mm thickness, failure by

penetration of the metal by corrosion would be anticipated in approximately 3
years ( 1.554 = 3.25).
An alternative way of obtaining the corrosion rate is to read it off from
Table 24.
Locate the section of the table containing the values of R between 8.0 and
8.9. This is found in Table 24/3.
Locate the column headed R = 8.3 (the nearest value to R = 8.26).
At the left-hand edge of the table locate the temperature in the system (50 C).
Scan this line horizontally until it meets the column headed R = 8.3. The
figure at the intersection is the corrosion rate (1.60).
This gives the same failure time for the system. ( 1.561 = 3.13 years)
59
These corrosion rates should be regarded as estimates. The original rates

used by Finan et al. [21] were obtained experimentally from test plates, and are
therefore empirical. Also, they were related to the Ryznar Index, which is itself
an empirical parameter. There is no direct thermodynamic relationship between
the corrosion rate and the Ryznar Index.
4.1.2. The Special Case of the Recirculating System

The discussion so far has been based on once-through system. If a closed system
is employed, utilising a heat-exchanger to shed heat, and IF THE SYSTEM IS
HERMETICALLY SEALED, the water will be maintained out of contact with
oxygen. Any initial corrosion will be stifled.
This situation is unusual and most, so called, closed systems have some
access from atmospheric oxygen via a feed/expansion tank or venting valves
which allow contact with the atmosphere. Under these conditions, with oxygen
available to the system, corrosion will proceed at a similar rate to that already
described.
However, different conditions exist in the open recirculating system using a
cooling tower. In this type of system there is a concentration of dissolved salts
in the circulating water. This modifies the value of pHS as described in Eq. (33)
in Sec. 1.5.2. Also, intimate contact between the circulating water and atmospheric
air in the cooling tower modifies the pH, as described on p. 27 of Ref. [8].
These modified values must be used to calculate the value of R to be used in
Eq. (92).
Example
Dissolved solids = 150 mg/l as such.
pH = 7.2.
Number of concentrations in system = 2
from Table 8
p[Ca2+] = 3.10
p[Alk] = 2.92
from Table 9
pK2 pKS = 1.54 @ 50 C (10.17 8.63) from Table 10
DS0.5
= 0.12
100
pHS = 7.68 for make-up water @ 50 C.
60
In system with n = 2 from Eq. (33)
DS0.5
100
= 7.68 2 0.30 + (1.41 1) 0.12
= 7.68 0.60 + 0.05
= 7.1 .
pHS = 7.68 2 log 2 + (20.5 1)
Make-up @ 15 C
Alk = 60 mg/l CaCO3
pH = 7.2
C = 140 mg/l CaCO3
System @ 50 C and n = 2
Alk = 2 60 = 120 mg/l CaCO3
C = 2 120 = 240 mg/l CaCO3
from page 27 of Ref. [8]
pH = 8.2
R = 2pHS pH = 2 7.1 8.2

= 14.2 8.2 = 6.0.
From Table 24/1 C/ = 0.55 mm.y1
and failure for 5 mm mild steel = 9 years.
4.2. THE LANGELIER INDEX

At the beginning of this book the relationship between the Ryznar Index and
calcium carbonate fouling was discussed in Secs. 1.1 and 1.2. The discussion
was then extended to establish a similar relationship between the Langelier Index
and calcium carbonate fouling in Sec. 1.3.
In the preceeding Sec. 4.1, the relationship between the Ryznar Index and
the corrosion rate for mild steel has been discussed, following the work of
Finan et al. The next logical step appears to be to investigate the possibility of
a relationship between the Langelier Index and the corrosion rate for mild steel.
In order to carry out this next stage of investigation, ten water analyses have
been selected, which cover a reasonably wide range of industrial water supplies.
The Ryznar Index and Langelier Index have been calculated for each water and,
using the Ryznar Index, the corrosion rate for mild steel calculated from Eq. (92).
The relationship between the corrosion rates and the values for the Langelier
Index is then investigated.
The water analyses and associated data are set out in Table 25.
The relationship between the Langelier Index (I) and the Corrosion Rate
(C/ ) at 15 C is shown by the curve in Fig. 9. It will be seen that the general
characteristics of this curve are very similar to those shown in Fig. 8 for the
Ryznar Index.
Fig. 9. Plot of Langelier index(I)-v-corrosion rate(C/ ) mild steel.
61
62
Mathematical analysis of Fig. 9 shows that the best fit equation corresponding to the curve is:
C/ = exp (0.767 I ) 0.359.
(93)
It will probably be more convenient to use this equation in the logarithmic

form:
In C/ = 0.767 I 1.024
(94)
or using common logarithms:

2.303 log C/ = 0.767 I 1.024
log C/ = 0.333 I 0.455.
(95)
(95a)

To apply Eq. (95a) in the field, the following procedure may be used:
(xlii) From a water analysis at atmospheric temperature (15 C) take the values
of Ca, Alk, DS. Use them to calculate the value of pHS at temperature T
(the temperature in the system) using Eq. (6) in Sec. 1.1.2 and following
paragraph (xv) in Sec. 1.2.1.
(xliii) From a water analysis at atmospheric temperature (15 C) take the values
of Alk and pH and use them to convert to the pH at T, as described by
Emerson on p. 20 of Ref. [8].
(xliv) From (xlii) and (xliii) calculate the Langelier Index:
I = pH pHS
(5)
(xlv) Use the value of I to calculate the value of C/ from Eq. (95a).
(xlvi) This value of C/ assumes that the relationship between I and C/ is the
same for all temperatures: but this is not so and C/ must be adjusted for
the temperature in the system (T) using Eq. (89).
Example
Alkalinity = 60mg/l CaCO3.
pH = 7.2.
63
p[Ca2+] = 3.10
from Table 8
p[Alk] = 2.29
from Table 9
DS0.5
= 0.12
100
pHS = 7.68 @ 50 C.
At 15 C
Alk = 60 mg/l CaCO3
pH = 7.2
C = 140 mg/l CaCO3
At 50 C
Alk = 60 mg/l CaCO3
C = 140 mg/l CaCO3
pH = 7.1.
I = 7.1 7.68 = 0.58 @ 50 C

log C/ = 0.333(0.58) 0.455 (from Eq. (95a))
= 0.193 0.445 = 0.252
C/ = 0.56 mm.y1 @ 15 C value.
Convert to 50 C
C/ = 0.56 (1 + 0.05(50 15))
= 0.56 (1 + 0.05 35)
= 0.56 (1 + 1.75)
= 0.56 2.75 = 1.54 mm.y1.
If the system was constructed from mild steel of 5 mm thickness, failure by
penetration of the metal by corrosion would be anticipated in approximately
3 years. ( 1.554 = 3.25).
An alternative method of calculating the corrosion rate is to read it off from
Table 26.
Locate the section of the table containing the values of I between 0.1 and
1.0. This is found in Table 26/1.
Locate the column headed I = 0.6 (the nearest value to 0.58).
At the left-hand edge of the table, locate the temperature in the system (50 C).
Scan this line horizontally until it meets the column headed I = 0.6. The
figure at the intersection is the corrosion rate (1.57).
This gives the same failure time for the system ( 1.557 = 3.18).
These corrosion rates should be regarded as estimates. Although the Langelier
Index is derived by thermodynamic calculations, its calibration to corrosion rates
still depends on the empirical values of Finan.
64

The comments made in Sec. 4.1.2 also apply here. Therefore, it is only necessary
to consider the open recirculating system incorporating a cooling tower.
Again, as already stated is Sec. 4.1.2, the values of pHS must be adjusted to
take account of the concentration factor in the system and before using Eq. (95a).
Example
pH = 7.2.
Temperature in System = 50 C.
Number of concentrations in system = 2
p[Ca2+] = 3.10 from Table 8
p[AlK] = 2.92 from Table 9
DS0.5
= 0.12
100
pHS = 7.68 for make-up water @ 50 C
In system with n = 2 from Eq. (33)
DS0.5
100
= 7.68 2 0.30 + (1.41 1) 0.12
= 7.68 0.60 + 0.05
= 7.1.
pHS = 7.68 2 log 2 + (20.5 1)
Make-up @ 15 C
Alk = 60 mg/l CaCO3
pH = 7.2
C = 140 mg/l CaCO3
from Table 20 of Ref. [8].
System @ 50 C and n = 2
Alk = 2 60 = 120 mg/l CaCO3
C = 2 120 = 240 mg/l CaCO3
from p. 27 of Ref. [8]
pH = 8.2
from Table 63 of Ref. [8].
I = pH pHS
= 8.2 7.1 = 1.1.
Under the operating conditions of the system the water has now achieved
a positive Langelier Index and converted to a scale-forming water. Corrosion
(if any) will be negligible.
65
Before moving on to the next section, it will be interesting to make a

comparison between the values of C/ obtained from the Ryznar Index and the
Langelier Index.
4.3. COMPARISON BETWEEN THE RYZNAR INDEX AND

THE LANGELIER INDEX
In order to make a comparison between the results obtained from the Ryznar
Index and the Langelier Index, four different pairs of values for pHS and pH
and four different temperatures have been selected. The values of R and I have
been calculated for each pair and the values of C/ read off from Tables 24 and 26
respectively. The results are set out in Table 27/1.
It will be seen that there is a difference between the two values of C/ in each
case. The difference increases and becomes more significant as temperatures
increase. It is considered that the explanation lies in the basic characteristics of
R and I.
Five pairs of values for pHS and pH have been selected and the corresponding
values of R and I calculated. The results are set out in Table 27/2. (No temperature
has been recorded as it is not relevant in this case).
It will be seen that the values of I vary over a fairly wide range, whereas
values of R are constant at 8.08.1. This is an indication that I is a more regularly
calibrated parameter than R, and therefore the use of I is preferred. Additionally,
I has the advantage of being obtained by direct thermodynamic calculations,
whereas R is empirically derived.
Some plant operators may prefer to work with R since the values of C/ obtained
from Table 24 are generally higher than corresponding values from Table 26
based on I. The use of R therefore provides an extra margin of safety. However,
using a higher value for C/ may lead to extra or more expensive corrective
treatment and thereby result in a condition of over-kill.
A final decision can only be taken after a careful consideration of the local
conditions prevailing at each plant.
4.4. BUFFER CAPACITY

In the preceding sections, two parameters have been considered for providing a
quantitative forecast of the rate of corrosion for mild steel. The two parameters,
the Ryznar Index and the Langelier Index, both involve the use of the equilibrium
pH (pHS) as defined in Eq. (2). This equation contains a term related to the
concentration of calcium ions in the water.
66
Calculations involving the concentration of calcium ions in the water cease

to be applicable when this item is missing. This state of affairs arises where the
water has been softened by the base-exchange process, or less frequently, has
been softened naturally by the original raw water passing through a layer of
natural zeolite (green sand) in the strata of the ground through which the water
has passed.
An alternative parameter which may be considered for these conditions is
the buffer capacity (sometimes referred to as the buffer value). Large [23] and
Stumm [24] both show that there is a qualitative relationship between the buffer
capacity of a water and the rate of corrosion of cast iron (the lower the buffer
capacity the higher the corrosion rate) but neither worker investigated a
quantitative relationship. Before investigating any possible quantitative
relationship further, it may be helpful to describe buffer effect and buffer capacity.
4.4.1. Description of Buffer Effect

The buffer effect is well known and is described in chemical text books. For the
purpose of this discussion it may be summarised, in general terms, as follows.
When a strong electrolyte is dissolved in water it is completely dissociated
into cations and anions. The change in the alkalinity of the solution on adding
a strong acid/strong base can easily be determined by a simple stoichiometric
calculation. Similarly, the corresponding change in the pH of the solution can
easily be determined by a simple logarithmic calculation.
But when the salt of a weak acid is dissolved in water the anion produced on
dissociation undergoes a secondary reaction with water to form a partially
dissociated anion. This form of anion has the ability to resist or restrict changes
in pH. Thus, while the change in alkalinity following the addition of a strong
acid/strong base remains easily determined by a simple stoichiometric calculation,
the corresponding change in pH can no longer be determined by a simple
logarithmic calculation, because of the anions ability to resist or restrict changes
in pH.
4.4.2. Definition of Buffer Capacity

If was proposed by Van Slyke [25] that the qualitative effect described in the
previous section should be quantified in the following manner.
Original
Solution
Add acid
Original pH
pH0
New pH = pHa
Original alkalinity
Alk0
New Alkalinity = Alka.
67
A change (decrease) in pH = pHa pH0 = d(pH) has produced a change

(decrease) in alkalinity = Alka Alk0
= d(Alk)
Hence a change (decrease) in pH =
d ( Alk )
in alkalinity = d ( pH ) .
d ( pH )
d ( pH )
Original
Solution
Add base
Original alkalinity
Alk0
New Alkalinity = Alkb.
Original pH
pH0
New pH = pHb
= 1 will produce a change (decrease)
A change (increase) in pH = pHb pH0 = d(pH) has produced a change

(increase) in alkalinity = Alkb Alk0
= d(Alk).
Hence a change (increase) in pH =
in alkalinity = d ( Alk ) .
d ( pH )
d ( pH )
= 1 will produce a change (increase)
d ( pH )
d ( Alk )
d ( pH ) is
The ratio
termed the buffer capacity and is defined as the change in
alkalinity per change of 1 unit of pH.
As pH is a logarithm (a pure number) it has no dimensions: but Alk will be
expressed in whatever unit alkalinity is measured. (Mole per litre: equivalent
per litre: mg CaCO3 per litre: etc.). Thus the buffer capacity will be expressed
(for example) as mg CaCO3/litre per unit of pH.
Having developed Van Slykes concept of buffer capacity to this point it is
now possible to move on to its application to water analyses.
4.4.3. Water Analyses and Buffer Capacity

The relationship between water analyses and buffer capacity can best be followed
graphically by means of Fig. 10.
Any given water at any given temperature will have an original alkalinity
(Alk0) and an original pH (pH0) represented by the point 0 in Fig. 10. If a
strong base is now added to the water the alkalinity/pH relationship will follow
the curve 0B. Similarly, if a strong acid is added the alkalinity/pH relationship
will follow the curve 0A.
d ( Alk )
The buffer capacity is defined as d ( pH ) which, in the differential calculus
notation, is the slope of the curve A0B at the point 0 and represented by the
tangent X0Y. If the equation of the curve A0B was known, the slope at point 0
could be calculated. Unfortunately, this equation will not be known and its
experimental determination (especially at elevated temperatures) will be timeconsuming, difficult, and therefore impractical.
68
Fig. 10. Plot of water analyses and buffer capacity.
One way round this difficulty has been offered by Stumm [24] who has
produced the equation:
( H + )( Alk ) ( H + )
K
+
+ ( H + ) + (OH ) .
+ + 2
B = 2.3 +
( H ) + 2K 2 ( H ) + K1 ( H ) + K 2
(96)
In this equation, (Alk) is expressed as equivalents per litre while K1 and K2

are the first and second dissociation constants respectively for carbonic acid.
69
Thus Eq. (96) will give values of B expressed as equivalents per litre per 1 unit
of pH.
Stumm offered Eq. (96) as a means of representing the Van Slyke concept in
terms of water analyses. But there was no detailed mathematical description
showing how Eq. (96) had been deduced.
On first inspection the form and style of Eq. (96) is consistent with it having
been thermodynamically deduced. But it contains a mathematical anomoly.
d ( Alk )
By definition B = d ( pH ) and therefore Eq. (96) is a differential equation

representing changes in alkalinity relative to changes in pH. Such an equation
cannot also contain a term for alkalinity (Alk) on the right hand side. This point
is clearly illustrated by refering to the equation produced by Dye [26].
K (H + )
K2
(H + )
+
+
1
(C ) = ( Alk ) W
( H + ) ( H + ) + 2 K 2
( H + ) K1
(97)
which can be rearranged to give:
( Alk ) =
(H + )
K1
K
(C )
+ W
.
+
K2 (H ) (H + )
+ 1 + + +
( H ) ( H ) + 2 K 2
(97a)
Equation (97a) is a complex expression yielding values of (Alk) in terms

of (C) K1 K2 and (H+). If the equation is now differentiated to give values of
d ( Alk )
it will yield another complex expression in terms of (C) K1 K2 and (H+).
d ( pH )
But in no way will it contain a term for (Alk) on the right hand side. It is for
this reason that, in the absence of any details of its derivation, Eq. (96) is
considered to contain a mathematical anomoly.
On this basis Eq. (96) is considered to lack thermodynamic integrity, but is
retained as an empirical equation since it was used by both Large [23] and
Stumm [24] in establishing a relationship between buffer capacity and the rate
of corrosion of cast iron. In a later section (Sec. 4.4.5) there is a comparison of
these results with the corrosion rate obtained by another method. Therefore it is
important to know the status of Eq. (96) in order to make such a comparison
meaningful.
Evaluating B from Eq. (96) is time-consuming rather than difficult. This will
obviously be a disadvantage if a large number of calculations have to be made.
One method of overcoming the difficulty would be to prepare a series of tables
from which the value of B could be read off for a wide range of alkalinities, pH
values and temperatures. To cover the full range of conditions likely to be
70
encountered in industrial water systems the tables would need to embrace:

Alkalinity
pH
Temperature
10 mg to 500 mg CaCO3 per litre

in steps of 10 mg.
6.0 to 11.9 in steps of 0.2
0 C to 100 C in steps of 5 C.
This range will require a total of 126 tables.

Fortunately, there is no need to prepare these tables. A method is available
for the value of B to be read off from existing tables in Ref. [8].
4.4.4. Evaluation of Buffer Capacity

The method of evaluating buffer capacity can be best described graphically using
Fig. 11.
In this graph the curve A0B is identical with that used in Fig. 10. Any water
at any temperature has an original alkalinity (Alk0) and an original pH (pH0)
represented by the point 0.
A strong base is added to increase the pH by 0.1 unit to pH b. The
corresponding change in alkalinity is an increase to Alkb.
A strong acid is added to decrease the pH by 0.1 unit to pHa. The
corresponding change in alkalinity is a decrease to Alka.
Thus:
Total change in alkalinity = d(Alk) = Alkb Alka.
Total change in pH = d(pH) = pHb pHa.
= pH0 + 0.1 (pH0 0.1)
= 0.1 + 0.1 = 0.2
d ( Alk )
d ( pH )
( Alk b Alk a )
=
0.2
= 5(Alkb Alka).
Buffer capacity = B =
Since Alkb and Alka can be read off direct from the tables in Ref. [8], B is
easily calculated.
In the three examples which follow the value of B is calculated by the method
described above and, for a comparison, the value calculated from Eq. (96) is
also shown. The difference between the two values may be explained by the
fact that Eq. (96) is an empirical equation (as explained in Sec. 4.4.3) whereas
71
Fig. 11. Plot of evaluation of buffer capacity.
the thermodynamic integrity of the tables in Ref. [8] have already been established
in the text of that work.
However, the values calculated from Eq. (96) are of the same order of
magnitude as those obtained from the method described above. Hence the
comparison of corrosion values in Sec. 4.4.5 with those obtained from values of
B from Eq. (96) is acceptable.
72
Example
pH = 7.0
Alk = 100 mg CaCO3/l

At pH = 7.1
T = 15 C
C = 253 mg CaCO3/l
and C = 253
Alkb = 105 mg CaCO3/l

(by interpolation)

Alka = 95 mg CaCO3/l
(by interpolation)
B = 5(Alkb Alka) = 5(105 95) = 5 10
= 50 mg CaCO3/l per unit of pH
(From Eq. (96a) B = 64).
At pH = 6.9
and C = 253
Example
pH = 8.0

At pH = 8.1
T = 15 C
C = 511 mg CaCO3/l
and C = 511

(by interpolation)

(by interpolation)
B = 5(Alkb Alka) = 5(252 248) = 5 4
(From Eq. (96a) B = 17).
At pH = 7.9
and C = 511
Example
pH = 7.5

At pH = 7.6
T = 40 C
C = 318 mg CaCO3/l
and C = 318

(by interpolation)
At pH = 7.4 and C = 318
(by interpolation)
B = 5(Alkb Alka) = 5(153 148) = 5 5
(From Eq. (96a) B = 21).
73
4.4.5. Buffer Capacity and Corrosion Rate

In order to establish a relationship between buffer capacity and corrosion rate
for base-exchange waters, the ten water analyses in Table 25 have been converted
to the analyses that would be obtained following base-exchange treatment.
Although it is often assumed that base-exchange treatment produced a water
with zero hardness, this is not the case. There is an equilibrium between
the water and the base-exchange resin which leaves a trace of residual hardness
in the water. In the present discussion a nominal residual hardness of 2 mg
CaCO3/l has been assigned to each water. The new analyses are set out in
Table 28.
In the same table, new values for pHS and I have been calculated and the
corresponding values of C/ taken from Table 26. Also recorded are the values
for buffer capacity, calculated according to Sec. 4.4.4.
It will be noted in Table 28 that the lower the value of the buffer capacity,
the higher is the value of the corrosion rate. This is in agreement with the
observations of Large [23] and Stumm [24], as already stated at the beginning
of Sec. 4.4.
Exploration of the values recorded in Table 28 shows that a linear relationship
exists between C/ and B/Alk. This is shown in Fig. 12, which indicated a best
fit relationship of:
C/ = 3.89 B / Alk + 0.96.
(100)
For pratical plant purpose this may be rounded-off to:

C/ = 4 B / Alk + 1.
(100a)
This is for base-exchange waters @ 15 C.

Equations (100) and (100a) provide an empirical relationship and therefore,
are of the same status as the Ryznar Index.

Equation (100a) may be used in the field as follows:
(xlvii) From an analysis of a base-exchange water at atmospheric temperature
(nominal 15 C) select the alkalinity and pH value.
(xlviii) From Tables 19 to 24 in Ref. [8] read off the value of C.
(xlix) Move to the tables in Ref. [8] covering the temperature in the system.
Using the alkalinity of the water and the value of C from (xlviii) read
off the new pH.
74
Fig. 12. Plot of corrosion rate(C/ )-v-buffer capacity/alkalinity base exchange water and mild steel.
75
(l) Increase the pH by 0.1 and with the value of C as above read off the
value of Alkb. Similarly, reduce the pH by 0.1 and read the value of Alka.
(li) Calculate the buffer capacity(B) as 5(Alkb Alka).
(lii) Using the value of B and the alkalinity calculate the value of B/Alk and
then use this in equation (100a) to calculate the corrosion rate (C/ ).
(liii) The value of C/ obtained from (lii) assumes that the corrosion rate at the
temperature in the system is the same as at 15 C, which is not the case.
(liv) Apply a temperature correction to convert the value of C/ at 15 C to the
temperature) of the system by using Eq. (89) from Sec. 4.1.
Example
Alkalinity = 200 mg CaCO3/l
System temperature = 40 C.
pH = 7.5 @ 15 C.
At 15 C
C = 433
At 40 C
pH = 7.4.
Increase pH to 7.5
C = 433 Alkb = 205
(by interpolation)
Reduce pH to 7.3
C = 433 Alka = 197
(by interpolation).
B = 5(Alkb Alka) = 5(205 197) = 5 8 = 40

40
B / Alk =
= 0.2
200
C/ = 4 0.2 + 1 = 1.8 mm/yr @ 15 C rating.
Convert to 40 C
C/ = 1.8 (1 + 0.05 (40 15) = 1.8(1 + 0.05 25)
= 1.8 (1 + 1.3) = 1.8 2.3 = 4.1 mm/yr @ 40 C.
An alternative method is to use Table 29.
In Table 29/1 find the column headed B/Alk = 0.2. At the left hand edge find
T = 40 C. Where this line meets the column above read off C/ = 4.05 mm/yr.

The comments made in Sec. 4.1.2 also apply here and, therefore, it is only
necessary to consider a recirculating cooling system incorporating a cooling
tower.
76
The following procedure may be used.

(lv) From the water analysis select the alkalinity of the make-up water @
15 C.
(lvi) Multiply by the number of concentrations (n) to be carried in the system
to obtain the alkalinity of the system water (nAlk).
(lvii) From p. 28 of Ref. [8] calculate C for the system water as twice the
alkalinity (C = 2nAlk).
(lviii) From the tables in Ref. [8], using the values from (lvi) and (lvii) read off
the pH for the system temperature.
(lix) Using this pH value, repeat steps (l) to (liv).
Example
Alkalinity of make-up = 150 mg CaCO3/l
System temperature = 30 C.
Number of concentrations = 3.0.
Alkalinity in system = 3 150 = 450
C in system = 2 Alk = 2 450 = 900.
From Table 39 of Ref. [8] pH = 8.3.
Increase to pH = 8.4 to obtain Alkb = 452.
Decrease to pH = 8.2 to obtain Alka = 448.
B = 5(452 448) = 5 4 = 20.
B / Alk = 20/450 = 0.04.
C/ = 4 B / Alk + 1 = 4 0.04 + 1 = 1.16 @ 15 C rating
Convert to 30 C = 1.16 (1 + 0.05 (30 15)) = 1.16(1 + 0.05 15)
= 1.16(1 + 0.75) = 1.16 1.75 = 2 mm/yr.
From Table 29/1 the value of B / Alk falls off the left-hand edge of the table.
C/ will therefore be less than 2 mm/yr.
Chapter 5
CORROSION OF COPPER
Copper is widely used for pipelines in a variety of industrial systems. Because

of this wide use it is generally assumed that copper is inert and stable with all
types of water likely to be encountered in such systems. But this is not the case.
Under appropriate conditions copper can suffer corrosion.
The track record of this metal shows that it can suffer two forms of corrosion.
One form is designated Type 1 and occurs in cold water systems. The other
form is designated Type 2 and occurs in hot water systems.
5.1. COLD WATER SYSTEMS

Copper used for pipelines in industrial water systems is usually in the halfhard (annealed) state. The conditions under which this class of copper suffers
corrosion in cold water has been described by Campbell [27] and Lucey [28].
These conditions may be summarised as follows:
The copper must carry an ingrained carbon film, due to imperfections in the
annealing process.
The chemical composition of the water must fall within the range that is
capable of initiating corrosion in copper with an ingrained film.
Both conditions must exist together.
From a water-treatment view point it is necessary to be able to forecast
whether any given water falls within the specific range and, if so, to forecast a
time-scale for the progress of the corrosion. Where a water is found to be within
the specific range the plant operator should be warned that the possibility of
corrosion exists, if the copper carries an ingrained carbon film. But this will
not be known in advance as it is impractical to metallurgically examine every
piece of pipework before installation. Any future preventive action will depend
on the local conditions prevailing in the system.
If the time-scale for the progress of the corrosion is very long no further
action may be needed. The probable working life of the system may be shorter
than the time for corrosion to become apparent. However, if corrosion is likely
to become apparent during the working life of the system, the system should be
77
78
kept under observation. (If an ingrained film is not present in the metal, corrosion
will not be initiated). However, if corrosion does appear, the affected pipelines
should be replaced. Complete pipe-runs should be replaced (not merely cutting
out short pipe lengths). In this situation it may be possible to obtain some
compensation from the original pipe supplier (since the carbon film will have
formed during the annealing process). Details of invoices, batch numbers, etc.,
issued at the time of the original purchase should, therefore, be retained.
If the operating conditions of the water system are critical, and no risk of
possible corrosion can be tolerated, then the system should be given an initial
treatment with oxalic acid to remove any ingrained film. This may be achieved
by arranging with the supplier to carry out the acid wash before pipelines are
delivered.
It will be clear from the foregoing discussion that the ability to forecast the
corrosion potential of any water is crucial. A method of making this forecast
has been described by Lucey [29]. He described a procedure for calculating the
Pitting Propensity Index (Lucey Index). If the index is positive, the water is
capable of initiating copper corrosion in the presence of an ingrained film. The
higher the value of the index, the shorter the time-scale. If the index is negative,
corrosion will not be initiated.
5.1.1. The Lucey Index

Luceys method for calculating the Pitting Propensity Index is based on the
study of a large number of case histories. It is, therefore, an empirical method.
Lucey presented his method in the form of a nomogram. This is shown in
skeleton form in Fig. 13.
It will be seen that the nomogram is a complex structure, involving reading
off six vectors on fixed scales and the ruling in of a further eight variable
vectors in order to obtain the final index.
At this point it must be stressed that the Lucey Index is the best method
available at present for forecasting copper corrosion in cold systems. There is
no reason why the original nomogram should not be used by anyone wishing to
work from the original Lucey paper.
However, experience in using the nomogram shows that the following
difficulties may be encountered:
(a) The original nomogram was published on a sheet measuring 21 cm 30 cm.
Accurate working is somewhat difficult on a diagram of this size.
(b) An improvement may be obtained (where full drawing office facilities exist)
by taking an enlarged copy of the original nomogram. But this facility will
Corrosion of Copper 79
Fig. 13. Lucey nomogram for pitting propensity index (IL) skeleton layout.
80
not be available to a technologist working on site with portable testing

equipment.
(c) In any project it is essential to keep a Work Sheet recording all calculations
in case checking is needed. With nomograms (of whatever size) it is necessary
to provide spare copies of the diagrams and rule in the vectors.
In the light of these difficulties it is considered that a case exists for trying
to find an alternative approach. A method which suggests itself is converting
each vector in the Lucey nomogram to an algebraic form. This would yield a
series of equations which could be evaluated by conventional algebra, or allow
for values to be read off from prepared tables. In either case the calculations
could be easily recorded by a normal typewriter, while the use of tables would
be of considerable assistance to a technologist working on site.
5.1.2. An Alternative Approach

Arising from the foregoing discussion an alternative approach is offered below.
At this point it is stressed that the alternative approach in no way denigrates or
devalues Luceys original method. Starting from the same data it seeks to provide
an alternative, algebraic, path to the same end point.
5.1.3. Data Required

pH
As cold systems operate at ambient atmospheric temperature the pH recorded
by a bench test will be the same as that obtaining in the system. There is no
need for a temperature correction of the pH.
Sulphate expressed as SO4 mg/l
If expressed in other terms use the following conversion factors:
S
Na2SO4
3.00
0.68
Sodium expressed as Na mg/l

Na2O
Na2SO4
NaCl
0.74
0.32
0.39
NaNO3
NaHCO3
CaCO3
0.27
0.27
0.45
Nitrate expressed as NO3 mg/l

N
NaNO3
4.42
0.72
Chloride expressed as Cl mg/l

NaCl
CaCO3
0.61
0.71
Dissolved Oxygen expressed as O2 mg/l

If a dissolved oxygen figure is available by direct analysis it may be used. But
for industrial systems, dissolved oxygen is not often included in routine water
analyses. In such case, the dissolved oxygen may be calculated from the water
temperature.
In industrial systems it is rare for water to be pumped direct from a main
into a system. In the UK, it is not permitted and some form of break tank
between the main and the system is mandatory. Therefore water entering the
system will have been held in a river, or a reservoir, or a feed and expansion
tank. In all cases the water will have been exposed to the atmosphere and the
dissolved oxygen will be in equilibrium with the oxygen in the air at ambient
atmospheric temperature.
The dissolved oxygen figure may therefore be taken from data by Truesdale
et al. [30] which, for temperatures up to 40 C corresponds to the equation:
O 2 = ( 24 0.2T )3 10 3 + 0.07T 0.462 .
(101)
Alternatively, the values may be read off from Table 30.
5.1.4. Effect of Concentration

In most cases, the water will pass direct through the system without undergoing
a concentration effect. This will also be true for closed recirculating systems.
However, a concentration effect will be experienced if the water is recirculated
via an open spray pond or an open evaporative cooling tower. In these cases the
values of the items listed above must be adjusted before calculating the Lucey
Index. If the system is operating with a concentration factor of n the values
82
for calculation become:

SO4
Na
NO3
Cl
becomes
becomes
becomes
becomes
nSO4
nNa
nNO3
nCl
Dissolved oxygen does not change because the recirculating water, in the
form of a fine spray, is in continual contact with the air and therefore dissolved
oxygen remains constant.
A change in pH is required in an open recirculating system. To calculate the
change a value for the alkalinity of the water is needed and the procedure is
described on pp. 27 to 29 of Ref. [8]. However, it will be seen from those pages
that for an open recirculating system, operating in clean air and without chemical
additions, the pH will stabilise at 8.3. This value of pH may be used to calculate
the Lucey Index where the above conditions obtain.
5.1.5. Calculating the Index

The method of calculating the Lucey Index which follows, involves evaluating
a series of algebraic expressions (which are termed Vectors) and which
correspond to the geometric steps in the original Lucey nomogram. Vectors are
indicated by the letter V and individual vectors are indicated by a number.
Thus, (V1) (V2) etc. The procedure is as follows:
(lx) Calculate (V1) from sodium as 0.167 Na.
(lxi) Calculate (V2) from nitrate for various values of sulphate as:
Sulphate
07.9 SO4
819.9 SO4
2039.9 SO4
40 and over SO4
(V2)
0.083
0.1
0.125
0.167
NO3
NO3
NO3
NO3
(lxii) Calculate (V3) = (V1) (V2)

(lxiii) Calculate (V4) from sulphate and (V3) as:
( V4 ) = 0.25(SO 4 ) + {(10.2 1.07(SO 4 )}( V3 ) + 25

Alternatively, read off values of (V4) from Table 31.
(lxiv) Calculate (V5) from chloride as:
(V5 ) =
(Cl) 2.196
.
106.66

(lxv) Calculate (V6) from dissolved oxygen as:
( V6 ) = 126 (1 log O2 ).
(lxvi) Calculate (V7) = (V4) (V6).
(lxvii) Calculate (V8) as:
(V8 ) =
(V7 )
.
(V5 ) + 55

(lxviii) Calculate (V9) as:
(V9 ) =
1.852(V6 ) + 246.298(V8 )
.
1.852 + (V8 )

(lxix) Calculate the Lucey Index (IL) from pH as follows:
I L = 0.154(V9 )
(pH 7) 0.33
2.
0.15
Alternatively, read off values of IL from Table 36.

Positive values of IL indicate pitting and negative values non-pitting.
In working through the procedure described above, it will be noted that two
of the tables (Tables 35 and 36) have been abridged. Only limited values for
(V9) and IL have been displayed. If these two tables had been completely filled
it would have led to values of IL being obtained which far exceeded the range
produced by Luceys original nomogram. This was considered to be undersirable,
since the purpose of the alternative approach is to follow Luceys original
nomogram as closely as possible. Tables 35 and 36 have therefore been
deliberately abridged in order to keep results within the same range as the original
nomogram.
84
Examples
In order to provide some examples of the calculation of the Lucey Index, five
waters have been selected from Luceys original paper. They represent a
reasonably wide spectrum of values for IL. Each water has been put through the
vector process described above. The results are set out in Table 37.
When making these calculations the values to be used at any stage do not
always fit exactly to the values shown in the tables. In such cases, the nearest
value is usually selected. However, in a few cases the interval between successive
values is sufficiently wide to require interpolation to be used.
It will be seen from Table 37 that the non-pitting waters (Cases 16 and 47)
show some variance between the vector process and the original nomogram.
This is not considered to be of any practical significance. Having determined
that a water was non-pitting Lucey did not proceed with any further calculations
concerning its behaviour in an industrial water system.
Case 14 is a neutral water representing border-line conditions. This will be
considered later when discussing the time-factor for pitting attack.
In the case of the pitting waters (Cases 10 and 8) there is reasonably good
agreement between the vectors and the nomogram.
As already stated at the start of this section, when a positive (pitting) index
has been established it is necessary to calculate a time-scale for the progress of
the attack. This is needed to serve as a warning to the plant operators in case
any given system carries the ingrained carbon film that can initiate pitting.
5.1.6. Time Scale

In setting up a time-scale, Lucey picked three time intervals:
Threshold Time:
The time after a system had started up for the

threshold of attack to commence.
Awareness Time:
The time after a system had started up for the first

physical awareness that attack was in progress. (e.g.
the first signs of pin-hole leaks).
Established Time: The time after a system had started up for the attack
to be well established. (e.g. the system approaching
total failure due to many leaks).
Luceys method for calculating time-scales is based on the study of a large
number of case histories. It is, therefore, an empirical method.
Fig. 14. Lucey nomogram for time scale skeleton layout.
Lucey presented his method in the form of a nomogram. This is shown in

skeleton form in Fig. 14.
It will be seen that the nomogram contains three guidelines: one for
threshold time; one for awareness time; and one for established time. For
any given positive value of IL a vertical projection strikes each of the guidelines
in turn to give three corresponding intercepts on the ordinate axis of the
diagram.
86
Continuing the vector notation used in Sec. 5.1.5 these ordinates are
designated as Vector 10 (V10). Mathematical analysis of the original Lucey
diagram yields the following results:
Threshold (V10) = 98 19(IL).
Awareness (V10) = 161 19(IL).
Established (V10) = 212 19(IL).
For each given value of (V10) a horizontal projection strikes the curve in the
nomogram to give an intercept. A vertical projection from each intercept strikes
the time scale to give the corresponding times. These times are represented by
the letters T, A, and E in Fig. 14.
Mathematical analysis of the original Lucey diagram yields the following
result for the curve:
Time ( years ) = {( V10 )2 /( 2460 11.24 ( V10))}.
Using the vectors described above, the three time-scales may be calculated
for any given positive value of IL.
Alternatively, the time-scales my be read off from Table 38 in which all the
above vectors have been combined.
Examples
In Table 37, the example from the original Lucey Case 10 gave a calculated
value for IL of 6.3. Table 38/1 gives time-scales for this value as:
Threshold
Less than 0.1 year.
Awareness
0.9 year (interpolated).
Established
6.0 years (interpolated).
On this basis, the plant operator would be warned to look out for pin-hole
leaks during the first year of operation, with probable complete failure within
6 years.
The original Lucey value was 7.0, which corresponds to time-scales of:
Threshold
Less than 0.1 year.
Awareness
0.4 year.
Established
4.0 years.
These values are of the same order of magnitude as those given above and
would lead to the plant operator being given warnings in similar terms to those
expressed above.
The margin of error between the two sets of values is acceptable for results
derived from two empirical calculations applied to an industrial system.
In Table 37, the example from the original Lucey Case 8 gave a calculated
value for IL of 3.0. The original Lucey value was identical.
Table 38/1 gives the time-scales as:
Threshold
0.8 year.
Awareness
8.4 years.
Established
33.5 years.
On this basis, the plant operator would be warned to look out for pin-hole
leaks after about 8 years and to expect complete failure in approximately 30
years.
In Table 37, the example from the Lucey Case 14 gave a calculated value for
IL of 0.4. Table 38/1 gives the time scales as:
Threshold
5.7 years.
Awareness
3.2 years.
Established
257.0 years.
On this basis, the plant operator would be advised that it was unlikely that
any leakage would be noticed for approximately 30 years. This time would
probably exceed the working life of the system, so a trouble-free life would be
expected.
The original Lucey value was zero, which would also indicate a probable
trouble-free life for the system.
Before leaving the discussion on time-scales it may be of interest to record
an actual case history.
Case history
A building, fitted with copper cold water systems, carrying mains water from
the local water authority, had experienced no operating difficulties for some
10 years.
It was decided to build an extension to the main building. In view of the past
satisfactory experience with copper systems it was decided to use copper again
in the extension to carry local mains water.
However, as a precaution, the consulting engineer responsible for the design
of building services approached the local water authority and enquired if copper
would be a suitable material to use with the local mains water. He was assured
that copper would be satisfactory.
88
Unfortunately, after the construction of the extension had been completed,

and the new building had been in use for some 2 to 3 years, pin-hole leaks
began to appear in the copper systems.
On investigation it was found that the copper pipework carried ingrained
carbon films. This was traced back to a sub-contractor using sub-standard copper
pipes in an attempt to save costs by using a cheaper material.
When the problem was referred back to the local water authority it was
stated that, during the period of construction of the extension, there had been a
change in the water supplied through the local mains. In order to meet demands
another water supply had been imported into the area and a mixture of old and
imported water now formed the supply to the building. The local water authority
had also noted that, following this change, complaints had begun to reach them
of leakage in copper systems.
The local water authority were unable to offer any further comment at that
time.
The chemical composition of the water supplies involved in this incident are
as follows:
Original
Supply
Imported
Supply
Mixed
Supply
300
190
288
12
33
32
Total hardness
(mg/l CaCO3)
312
223
310
Total alkalinity
(mg/l CaCO3)
250
130
260
Chloride
(mg/l CaCO3)
17
81
37
74
17
Nitrate
(mg/l NaNO3)
30
22
Sulphate
(mg/l Na2SO4)
25
260
53
Calcium hardness
(mg/l CaCO3)
Magnesium hardness
(mg/l CaCO3)
Sodium
(mg/l Na)
Dissolved solids
(mg/l as such)
pH
355
500
7.2
370
7.4
7.3
Carrying out the vector procedures on these analyses gave the following
results:
Lucey Index
1.5
2.0
2.4
Threshold time (years)
3.0
2.0
1.5
Awareness time (years)
18
14
11.5
Established time (years)
85
60
47
The first thing to note about the above analyses is that it is not possible to
make a forecast of the Lucey Index merely by scanning the figures. A full
calculation must be made.
The second thing to note is that the Lucey Index of the mixed supply is not
intermediate between the values for the two component waters, but is greater
than either.
The crucial figures in the above lists are those for the Lucey Index and the
times for the mixed supply. It is clear that with a positive Lucey Index, and
the presence of ingrained carbon films, conditions were favourable for attack on
the copper leading to pin-hole leakage.
But it is surprising to find that the onset of the attack was very much shorter
than the times predicted from Table 38. Why this anomoly?
In the copper systems joints between lengths of pipes, angles and T-joints
were formed by inserting the ends of pipes into outer sleeves which were then
sealed with a ring of solder. Examination of the systems revealed that in a
number of places the soldering had left flux trails on the internal surfaces of the
pipes, and that the incidence of pin-holes was more concentrated in areas adjacent
to the flux trails.
A more detailed examination of these areas was not possible, and the chemical
characteristics of the flux trails are not known. But it may reasonably be assumed
that some substance or substances had been leached from the flux trails by the
flow of water and resulted in the water in the immediate vicinity acquiring a
higher, positive, Lucey Index than the bulk of the supply. This would account
for the aggrevated attack and the awareness of pin-holes after only 2 to
3 years instead of 11 years as predicted.
It is considered that the quantity of leachate need not be very high to produce
the observed effects. For instance, if the leachate was acidic in character, and
90
resulted in a lowering of alkalinity and pH in the immediate vicinity, it can be

shown that a reduction of only 25 mg/l in the alkalinity of the mixed supply
would result in a lowering of the pH to 7.0, with a corresponding reduction of
the awareness time to approximately 1 year.
This illustration is not offered as a definite explanation of the anomoly
encountered, but it does serve to show that only very modest leaching from the
flux trails may be required.
The case history recorded above points up the need for:
Calculating the Lucey Index of the water supply at the design
stage of any project.
Ensuring that copper pipework used is of the highest (carbon
film free) approved standard.
Ensuring a high standard of workmanship in making joints
(with a preference for compression fittings in order to
eliminate flux trails).
5.2. HOT WATER SYSTEMS

Copper used for pipelines in industrial water systems is usually in the
half-hard (annealed) state. But is some countries, particularly Scandinavia,
hard-drawn copper is used.
Copper corrosion in hot water systems is designated Type 2 which has been
described by Campbell [27] and Lucey [28]. The attack is associated with the
presence of an ingrained carbon film in the metal but the process by which the
corrosion proceeds is different from that of Type 1 in cold water systems.
Data on the water chemistry associated with Type 2 corrosion is less than
the corresponding data for Type 1.
5.2.1. Data on Water Chemistry

Much of the data on the water chemistry of Type 2 corrosion in copper systems
has been obtained from the study of domestic hot water systems, or laboratory
experiments which simulate domestic systems. Any parameters which are offered
for the forecasting of copper corrosion in hot water systems are therefore
empirical.
Investigations by Mattsson and Fredriksson [31] into the failures in Sweden
in hot water systems incorporating hard-drawn copper show that pitting occurs
when the following water characteristics exist in the system.
The pH value lies between 5.0 and 7.0.

The bicarbonate concentration is
100 mg/l HCO3 or less.
(This corresponds to a total alkalinity of 83 mg/l CaCO3 or
less for the pH range given above.)
The ratio of [HCO3] : [SO2
4 ] is less than 1.0. (This
corresponds to a ratio of mg/l CaCO3 : mg/l Na2SO4 less
than 1.16.)
The investigations make no reference to water temperatures in the systems.
Therefore it must be assumed that all systems operated at the temperature
commonly used in domestic systems, namely, 60 C (140 F).
Further work by Mattsson [32] shows that even waters which are rated as
non-pitting on the basis of the parameters above, can suffer an erosion effect
and lose their immunity if the linear rate of flow is too high.
Recommended limiting flow rates are given below. If pipework is easily
accessible, so that it can easily be exchanged when damaged, higher flow rates
are permitted.
Type of System
Accessibility
Mains
Exchangeable
Not exchangeable
Branch pipes
Exchangeable
Not exchangeable
Continuous flow
Flow Rate (m/s) at T

10
50
70
90
4.0
2.0
3.0
1.5
2.5
1.3
2.0
1.0
16.0 12.0 10.0

4.0 3.0 2.5
8.0
2.0
2.0
1.5
1.3
1.0
Industrial heat-exchange systems, whether once-through or recirculating, would

be included under continuous flow systems. Systems with an evaporative cooling
tower are excluded. Their operating pH value is likely to be of the order of 8.0.
which is outside the range specified by Mattsson.
It should be noted that the temperatures given in the table above refer only
to the selection and control of linear flow rates. They have no influence on the
water parameters specified by Mattsson earlier in this section.
Investigations by Adeloju and Hughes [33] into the corrosion of copper hot
water systems using Perth (Australia) town supply, gave the analyses for this
92
supply as follows:
Min
Max
pH
6.5
7.5
7.0
Calcium (mg/l Ca2+)
Chloride (mg/l Cl)
44
105
75
15
12
24
88
56
Bicarbonate (mg/l HCO3)

Sodium (mg/l Na+)
Sulphate (mg/l SO2
4 )
Calculated
Mean
Taking the mean analysis, and converting the bicarbonate figure to total
alkalinity as CaCO3 gives 10 mg/l, while converting the sulphate figure to
Na2SO4 gives 9 mg/l. Hence the alkalinity : sulphate ratio is 1.11.
With the mean pH as 7.0 these figures all fall within the Mattsson parameters for a water which will cause pitting. Although the type of copper
pipework used in Perth is not defined, it would appear from the agreement
between the Mattsson parameters and the occurence of pitting, that the use of
the parameters is not necessarily restricted to hard-drawn copper.
In their report on the investigation, Adeloju and Hughes include a review of
four other sites, worldwide, where copper corrosion in hot water systems has
been experienced. Only the briefest details of water analyses are given, and
therefore it is not possible to make any detailed study of any relationship
between water characteristics and the onset of copper corrosion. However, at all
the other four sites, the pH values are greater than 7.0, which suggests that it
may be possible to extend the pH term in the Mattsson parameters beyond the
stated maximum of 7.0. It is not possible to offer any firm explanation for this,
apparent, anomoly: but one explanation which comes to mind is the possibility
that in the cases cited by Adeloju and Hughes the pipework was fabricated from
half-hard copper instead of the hard-drawn in the Mattsson systems. On
this basis there would be a metallurgical difference between the systems.
In their report, Adeloju and Hughes describe the Perth town water as being
high in chlorides. But in the text of the report they indicate that the concentration of the chloride ion did not have a significant effect on the progress of
the corrosion mechanism.
In the four other sites, mentioned earlier, two have chloride ion concentrations of the same order of magnitude as the Perth water, but the other two are
definitely lower. It will be recalled that chloride ion concentration is not

included in the Mattsson parameters.
Investigations by Al-Kharafi et al. [34] into the corrosion of copper in hot
water systems in Kuwait indicate that the presence of an ingrained carbon film
and/or a phosphate film (derived from the water treatment programme in Kuwait)
on the surface of the pipework is necessary for the corrosion to proceed.
The Kuwait water supply consists of a blend of desalinated water and brackish
water (approximately 7%) with pH adjusted to the range 7.6 to 8.7. An average
analysis is:
pH
8.1
Conductivity (mS/m)
35.0
Total alkalinity (mg/l CaCO3)
12.5
15.0
Total hardness (mg/l CaCO3)
93.0
Calcium hardness (mg/l CaCO3)
59.0
Magnesium hardness (mg/lMgCO3)
33.0
Cl)
51.8
Chloride (mg/l
Sulphate (mg/l SO2

4 )
Silica (mg/l SiO2)
75.0
4.0.
The total alkalinity of 12.5 is less than the value of 82 in the Mattsson
parameters. Making the necessary conversions gives the bicarbonate/sulphate
.5
CaCO3
as 12
ratio in terms of Na
111 = 0.11 which is less than the maximum of 1.16
2SO4
in the Mattsson parameters.
The pH range for Kuwait water is higher than the maximum specified in the
Mattsson parameters. This again is support for the suggestion that the pH range
in the Mattsson parameters should be extended when accessing the potential of
a water to cause copper corrosion in hot water systems.
The chloride ion concentration in Kuwait water is of the same order of
magnitude as that for Perth water, but again there is no indication that the chloride
ion plays a significant part in the corrosion mechanism.
Investigations into the corrosion of copper in hot water systems using Tokyo
town supply are covered by four papers: Sato [35] and Baba et al. [3638].
Sato [35] reports that pitting is not dependant on the presence of an ingrained
carbon film on the surface of the metal.
94
Baba et al. [36, 37] with a synthetic water containing:

36.6
Chloride (mg/l Cl)
42.6
Sulphate (mg/l SO2

4 )
76.8
pH
7.0 to 7.8
produced no corrosion at 60 C.
The bicarbonate figure converts to 30 mg/l CaCO3 (which is below the
Mattsson figure of 83) while the sulphate figure converts to 114 mg/l Na2SO4
giving a bicarbonate:sulphate ratio of 0.72 (which is below the Mattsson
ratio of 1.16). The pH is within the extended Mattsson range which has been
suggested earlier in this section. Therefore the water would be expected to show
pitting.
However, when the water was chlorinated, to provide a residual chlorine of
23 mg/l rapid pitting was observed.
In a further series of experiments, Baba et al. [38] took Tokyo tap water as
their basic raw water and then made chemical adjustments to produce four
experimental waters. The analyses are shown in Table 39; the experimental
waters are designated A, B, C, D in the table.
The pH values are within the Mattsson parameter, except for water C, but
from the work described earlier in this section some extension of pH above 7.0
appears to be capable of allowing corrosion to proceed.
The total alkalinities are below the limit of the Mattsson parameter, except
for water D, which is marginally higher by only 3 mg/l.
The bicarbontate : sulphate ratios are below the limit of the Mattsson
parameter, except for water D.
On this evidence it is expected that the experimental waters would produce
pitting at elevated temperatures, with the exception of water D. However, in
a series of experiments; conducted at 60 C; using both hard-drawn and
half-hard copper tubes; maintaining the residual chlorine at the original value
of 1 mg/l; no pitting was observed. But when the chlorine residual was increased
to the range 23 mg/l pitting was observed.
It was noted that the presence or absence of an ingrained carbon film had no
significant effect on the progress of the pitting, and no difference was reported
between hard-drawn and half-hard tubes.
The conclusion from these experiments is that residual chlorine is the critical
factor controlling the progress of the pitting.
5.2.2. The Role of Residual Chlorine

The sterilisation of water supplies is usually achieved by adding chlorine gas,
or hypochloride solution, in sufficient quantity to oxidise all the organic matter
present and leave a residual of free chlorine.
The free chlorine undergoes the following reactions:
Cl2 + H2O = H+ + Cl + HOCl
2HOCl = 2H+ + Cl + ClO2 (chlorite)
HOCl + ClO2 = H+ + Cl + ClO3 (chlorate).
In a series of laboratory experiments Suzuki et al. [39] have demonstrated
that the chlorite ion is the aggressive species which promotes pitting of copper
in hot water systems.
5.2.3. Time Scale

In a further series of experiments Suzuki [40] described a method for estimating
the time for pitting to be initiated by the chlorite ion. His experiments were
made at a fixed temperature of 65 C.
Suzuki expressed his results in the form of an equation:
Time =
Constant ( E/ )
.
Chlorine residual (Cl R )
The constant (E/ ) is a function of:

Temperature
pH (which covered the range 5.5 to 7.5)
Concentration of total anions
(Cl + HCO3 + SO2
4 ).
It can be shown that, for all practical plant purposes, the total anions can be
expressed as
0.65 (dissolved solids).
Mathematical analysis of Suzukis results indicate a relationship:
E/ = g (DS)h
where the values of g and h are dependant on pH.
(103)
96
If the time is expressed as days, and the dissolved solids as mg/l, the smoothed
values of g and h are:
pH
5.5
6.0
6.5
7.0
7.5
*8.0
*8.5
3.9
3.3
2.7
2.1
1.5
0.9
0.3
0.69
0.75
0.82
0.88
0.94
1.00
1.07
* The table has been extrapolated to 8.5 in order to cover the same pH range
as used by Lucey [29] for cold water systems in Sec. 5.1. It is considered that
the values listed are sufficiently accurate for a prediction procedure under
practical, plant conditions.
Using the values listed above, the value of E/ can be calculated for given
values of pH and DS using Eq. (103). If this result is then divided by the chlorine
residual (ClR), expressed as mg/l Cl2, the time (in days) to initiate pitting is
obtained.
Further to the work discussed above, Suzuki visited 9 sites in Japan where
pitting had occurred in hot water systems. He recorded the time taken for failure
of the systems by pitting and compared it with the calculated time for pitting to
be initiated. He was thus able to obtain a ratio:
Failure Time : Initiating Time
The results of this investigation are:
Site NO.
1
2
3
4
5
6
7
8
9
pH
7.2
7.0
7.2
6.0
6.8
6.8
6.1
7.0
6.7
Initiation
Failure
Time (years) Time (years)
1.2
1.3
1.9
1.0
0.7
1.7
0.5
1.1
1.0
2.1
2.4
3.0
2.0
7.5
5.0
2.0
3.2
4.0
Ratio
1.75
1.85
1.58
2.00
10.71
2.94
4.00
2.91
4.00
Mathematical analysis of these results indicate a linear result between pH

and the ratio except for Sites No. 5 and 7 which are out of line from the
remainder. Excluding these two sites, the remainder indicate a relationship:
Ratio = 2.28pH + 18.38.
(104)
As Eq. (104) is a ratio it is independent of the time units used to express the
initiation and failure times.
Having calculated an initiation time, using Eq. (103) it is now possible also
to calculate a failure time from Eq. (104).
The work discussed in this section is summarised in Table 40 which enables
initiation time and failure time to be read off from values of pH, dissolved
solids, and chlorine residual.
Example
pH = 7.5 DS = 150
Initiation Time = 167 days
Chlorine Residual = 1.0

Failure Time = 376 days
From the work described in this section, the following empirical guidelines
are offered in order to assess the probability of pitting attack in the copper
pipework of hot water systems.
An ingrained carbon film on the inner surface of the pipe is required. Some
workers claim that a phosphate deposit (derived from the treatment of the water)
is necessary while other workers claim that pitting can occur in the absence of
any surface film. But the balance of opinion appears to be slightly in favour of
the carbon film. Therefore high standard, film free, pipework should be selected.
There appears to be no evidence to diffentiate between hard-drawn and
half-hard copper in the risk of pitting.
The chemical characteristics of the water in the system must fall within the
Mattsson parameters. However, there is evidence to suggest that the pH value
may exceed the range originally specified by Mattsson.
The risk of pitting is aggrievated if the linear flow rate of the water exceeds
the values recommended by Mattsson.
The presence of free residual chlorine in the water is necessary for pitting to
occur.
The work described in this section has been carried out at temperatures in
the region of 60 C. At higher temperatures the rate of attack would be expected
to be quicker, and at lower temperatures slower. More work is needed over a
reasonably wide range of temperatures to improve the accuracy of forecasting
pitting in industrial systems.
98
The work described has been limited to the water supplies of a few localities
(e.g. Perth, Tokyo) or to synthetic waters which are similar to these supplies.
More work over a wider range of water characteristics is needed to improve the
accuracy of forecasting.
Once-through water systems, or closed recirculating systems, serving industrial
heat exchangers are sufficiently close to domestic hot water systems to allow
the methods described in the section to be used. However, in domestic systems
some residual free chlorine is usually present from the sterilisation of potable
supplies. In industrial systems, free residual chlorine can be avoided since other
chemicals can be used to combat organic pollution; chemicals which are not
permitted for potable water supplies.
Systems incorporating an open cooling tower are excluded. The temperature
of the water in these systems is much lower than in closed systems. And also,
if any form of chlorination is applied, the residual chlorine is stripped from the
water during passage through the tower.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
Ryznar, J. Amer. Waterworks Assoc. 1944, 36, 472.

Langelier, J. Amer. Waterworks Assoc. 1936, 28, 1500.
Thompson & Ryznar, Combustion 1942, 14(5), 41.
Larson & Buswell, J. Amer. Waterworks Assoc. 1942, 34, 1667.
Emerson, J. Soc. Chem. Ind. 1945, 64, 335.
Manning, Upublished I. C. I. Report R93/62/2 (1944).
Hamer, Thurston & Jackson, Industrial Water Treatment Practice Butterworths,
London, 1961.
Emerson, Alkalinity-pH Changes with Temperature for Waters in Industrial Systems
Ellis Horwood, Chichester, 1986.
Edwards, Unpublished I. C. I. Report R628/23/5 (1944).
Emerson, Unpublished I. C. I. Report R93/7/29 (1961).
Seidell, Solubilities of Inorganic and Metal Organic Compounds Van Nostrand,
New York, 1940 and 1952.
Booth & Bidwell, J. Amer. Chem. Soc. 1950, 72, 2567.
Green & Holmes, J. Amer. Waterworks Assoc. 1947, 39, 1098.
Debye & Huckel, Physic. Z. 1923, 24, 285 and 334.
Bronstead & LaMer, J. Amer. Chem. Soc. 1924, 46, 555.
Nims, J. Amer. Chem. Soc. 1934, 56, 1110.
Bates & Acree, J. Res. Nat. Bur. Stds. 1943, 34, 373.
Bjerrum & Unmack, Kgl. Danske Videnskab. Selskab. Matfys. Medd. 1929, 9, 5.
Kuyper, J. Biol. Chem. 1945, 159, 417.
Sendroy & Hastings, J. Biol. Chem. 1927, 71, 783 and 797.
Finan, Harris & Marshall, Materials Performance 1098, 19, Part 3, 2429.
Ison & Butler, Corrosion and Its Prevention in Waters Leonard Hill, London, 1966.
Large, Symposium Internal Corrosion of Iron Mains and Copper Services Inst.
Water Eng. & Scientist (Scientific Sect.) London 22 April 1962. Paper No. 2
pp. 1729.
Stumm, Proc. Am. Soc. Corr. Eng. (J. San. Eng. Div.) Nov. 1960 Sect. SA6. Paper
No. 2657 pp. 2745.
Van Slyke, J. Biol. Chem. 1922, 52, 525.
Dye, J. Amer. Waterworks Assoc. 1952, 44, 356.
Campbell, J. Inst. Metals 1950, 77, 345.
99
100
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
Lucey, Br. Corr. J. 1967, 3, 175.

Lucey, Brit. NonFerrous Metals Res. Assoc. Res. Report. No. A1838, Dec. 1972.
Truesdale, Downing & Lowden, J. Appl. Chem. 1955, 5, 53.
Mattsson & Frederiksson, Br. Corr. J. 1968, 3, 246.
Mattsson, Br. Corr. J. 1980, 15, 6.
Adeloju & Hughes, J. Inst. Corr. Sc. Tech. 1986, 26, 851.
El-Alkharafi, Shalaby & Gouda, Br. Corr. J. 1989, 24, 284.
Sato, Corr. Eng. Japan 1982, 31, 3.
Baba, Kodama, Fujii, Hisamatsu & Ishikawa, Corr. Eng. Japan 1982, 30, 113.
Baba, Kodama, Fujii & Hisamatsu, Corr. Eng. Japan 1981, 30, 161.
Fujii, Kodama & Baba, J. Inst. Corr. Sc. Tech. 1984, 24, 901.
Suzuki, Ishikawa & Hisamatsu, J. Inst. Corr. Sc. Tech. 1983, 23, 1095.
Suzuki, J. Inst. Corr. Sc. Tech. 1984, 24, 429.
SUPPLEMENT
(Reprint of Ref. 8)
ALKALINITY pH CHANGES WITH

TEMPERATURE FOR WATERS IN
INDUSTRIAL SYSTEMS
197
ERRATA TO SUPPLEMENT
Page 12
Line 24 to read:
- - - - - the temperature change of pH to the temperature change
of pK2 - - - - Page 16
Equation (19) to read:
K (H + )
K (H + )
+ 1 + 2+ +
C = ( Alk ) W+
( H ) K1
(H ) ( H ) + 2K 2
Page 17
10 ( pH )
K
K
10 ( pH )
+ 1 + (2pH ) ( pH )
C 10 5 = 2 M 10 5 (WpH )
+ 2K 2
10
10
K1
10
10 ( pH )
K
K
10 ( pH )
+5
C = 2 M 10 5 (WpH )
+ 1 + (2pH ) ( pH )
10
10
10
10
2
K
K
+

1
2

Page 22
Line 16 to read:
- - - - - loss of accuracy to make an easier calculation - - - - -
199
200
Table 66
M
pH
11.0
11.1
11.2
280
290
300
7
18
28
310
320
330
340
350
39
50
60
72
82
360
370
380
390
400
92
103
114
125
135
17
27
38
48
59
410
420
430
440
450
140
157
167
178
189
69
80
90
101
112
7
17
460
470
480
490
500
199
210
221
231
242
122
133
143
154
164
28
38
49
59
70
This section of the table should not be in the grey area, but in the clear
white area, since the values listed are all real positive values
Errata to Supplement 201
Table 76
M 10/ pH 9.4
The listed value of 4 should be in the grey area.
Table 78
M 490/ pH 11.0 should read 10 (no minus sign)
M 500/ pH 11.0 should read 20 (no minus sign)
and both be in the clear white area.
Table 82
M 40/ pH 9.7
The listed value of 12 should be in the clear white area.
Table 113
The whole of the grey area should be labelled
No real, positive, values in this area
Table 116
M 150/ pH 7.9 listed value should read 306
Table 117
TABLES
Table 1. Ryznars original data.
No
Ca
Alk
DS
pH
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
72
72
72
72
70
70
150
150
150
133
133
301
301
301
301
301
301
66
61
68
137
103
132
183
68
169
264
246
280
324
130
322
350
472
535
470
470
550
135
137
142
280
163
190
240
160
380
490
380
420
460
410
760
550
630
690
630
630
700
170
170
185
390
7.90
9.10
9.50
6.70
9.70
9.00
8.90
9.20
9.10
7.65
9.70
7.25
8.65
8.90
8.60
8.55
8.90
8.75
8.70
8.70
8.55
95
95
95
95
95
95
95
95
70
95
95
95
95
95
70
50
50
50
50
70
50
nil
36
105
nil
95
147
117
130
66
4
183
55
325
405
119
74
93
93
4
15
35
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
101
102
Table 2. Ryznars calculated parameters.

No
pH @ 15 C
pHS @ T
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
7.90
9.10
9.50
6.70
9.70
9.90
8.90
9.20
9.10
7.65
9.70
7.25
8.65
8.90
8.60
8.55
8.90
8.75
8.70
8.70
8.55
6.92
6.83
6.69
7.11
6.78
6.52
6.29
6.24
6.47
6.63
6.32
5.89
5.78
5.74
6.06
6.35
6.29
7.42
7.45
7.11
6.89
I = pH pHS
0.98
2.27
2.81
0.41
2.92
3.38
2.61
2.96
2.63
1.02
3.38
1.36
2.87
3.16
2.54
2.20
2.61
1.33
1.25
1.59
1.69
No
nil
36
105
nil
95
147
117
130
66
4
183
55
325
405
119
74
93
53
4
15
35
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Tables
Table 3. Ryznars index data.

No
pH @ 15 C
pHS @ T
R = 2pHs pH
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
7.90
9.10
9.50
6.70
9.70
9.90
8.90
9.20
9.10
7.65
9.70
7.25
8.65
8.90
8.60
8.55
8.90
8.75
8.70
8.70
8.55
6.92
6.83
6.69
7.11
6.78
6.52
6.29
6.24
6.47
6.63
6.32
5.89
5.78
5.74
6.06
6.35
6.29
7.42
7.45
7.11
6.89
5.94
4.56
3.88
7.52
3.86
3.14
3.68
3.23
3.84
5.61
2.94
4.53
2.91
2.58
3.52
4.15
3.68
6.09
6.20
5.52
5.17
nil
36
105
nil
95
147
117
130
66
4
183
55
325
405
119
74
93
53
4
15
35
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
103
104
Table 4. Revised data Ryznar Index.

No
pH @ T
pHS @ T
R = 2pHS pH
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
7.90
8.40
8.80
6.80
9.00
9.20
8.40
8.60
8.70
7.70
9.10
7.30
8.30
8.40
8.40
8.40
8.10
8.60
8.50
8.40
8.30
6.92
6.85
6.69
7.11
6.78
6.52
6.29
6.24
6.47
6.63
6.32
5.89
5.78
5.74
6.06
6.35
6.29
7.42
7.45
7.11
6.86
5.94
5.26
4.58
7.42
4.56
3.84
4.18
3.88
4.14
5.56
3.54
4.48
3.26
3.08
3.72
4.30
4.48
6.24
6.40
5.82
5.42
nil
36
105
nil
95
147
117
130
66
4
183
55
325
405
119
74
93
53
4
15
35
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Table 5. Water analyses for new data.

AT TEMPERATURE 15C
No
Ca
Alk
DS
pH
No
22
150
120
225
8.00
22
23
150
180
270
7.90
23
24
200
160
300
7.90
24
25
200
246
360
7.80
25
26
250
200
375
7.80
26
27
250
300
450
7.70
27
28
300
240
450
7.80
28
29
300
360
540
7.70
29
30
350
280
525
7.80
30
31
350
420
630
7.70
31
Tables
Table 6. Calculated weights of calcium carbonate.

No
pHS
pH
R = 2pHS pH
I = pH pHS
No
0.43
0.50
0.55
0.61
0.63
0.68
0.76
0.82
0.88
0.93
10
20
20
35
30
50
50
80
70
110
22
23
24
25
26
27
28
29
30
31
0.61
0.68
0.68
0.79
0.81
0.76
0.94
1.00
1.06
1.11
15
20
25
40
40
70
60
100
80
130
22
23
24
25
26
27
28
29
30
31
0.71
0.73
0.75
0.94
0.91
1.01
1.09
1.15
1.11
1.21
20
30
30
50
50
80
70
120
90
145
22
23
24
25
26
27
28
29
30
31
TEMPERATURE 30 C
22
23
24
25
26
27
28
29
30
31
7.47
7.30
7.25
7.09
7.07
6.92
6.94
6.78
6.82
6.67
7.90
7.80
7.80
7.70
7.70
7.60
7.70
7.60
7.70
7.60
7.04
6.80
6.70
6.48
6.40
6.24
6.18
5.96
5.94
5.74
TEMPERATURE 40 C
22
23
24
25
26
27
28
29
30
31
7.29
7.12
7.07
6.91
6.89
6.74
6.76
6.60
6.64
6.49
7.90
7.80
7.75
7.70
7.70
7.50
7.70
7.60
7.70
7.60
6.68
6.94
6.39
6.12
6.08
5.98
5.82
5.60
5.58
5.38
TEMPERATURE 50 C
22
23
24
25
26
27
28
29
30
31
7.14
6.97
6.92
6.76
6.74
6.59
6.61
6.45
6.49
6.34
7.85
7.70
7.70
7.70
7.65
7.60
7.70
7.60
7.60
7.55
6.43
6.24
6.14
5.82
5.83
5.58
5.52
5.30
5.38
5.13
105
106
Table 6 (Continued)
No
pHS
pH
R = 2pHS pH
I = pH pHS
No
0.85
0.87
0.92
1.08
1.05
1.15
1.23
1.09
1.35
1.40
25
35
40
65
60
95
85
130
90
100
22
23
24
25
26
27
28
29
30
31
1.10
1.08
1.08
1.24
1.26
1.31
1.39
1.45
1.57
1.56
30
50
50
80
75
115
115
155
125
190
22
23
24
25
26
27
28
29
30
31
1.13
1.25
1.28
1.34
1.38
1.43
1.51
1.57
1.63
1.68
35
60
60
90
85
130
115
170
140
210
22
23
24
25
26
27
28
29
30
31
TEMPERATURE 60 C
22
23
24
25
26
27
28
29
30
31
7.00
6.83
6.78
6.62
6.60
6.45
6.47
6.31
6.35
6.20
7.85
7.70
7.70
7.70
7.65
7.60
7.70
7.40
7.70
7.60
6.15
5.96
5.86
5.54
5.55
5.30
5.24
5.22
5.00
4.80
TEMPERATURE 70 C
22
23
24
25
26
27
28
29
30
31
6.84
6.67
6.62
6.46
6.44
6.29
6.31
6.15
6.19
6.04
7.85
7.75
7.70
7.70
7.70
7.60
7.70
7.60
7.70
7.60
5.83
5.50
5.54
5.22
5.18
4.98
4.92
4.70
4.68
4.48
TEMPERATURE 80 C
22
23
24
25
26
27
28
29
30
31
6.72
6.55
6.52
6.36
6.32
6.17
6.19
6.03
6.07
5.92
7.85
7.80
7.80
7.70
7.70
7.60
7.70
7.60
7.70
7.60
5.59
5.30
5.24
5.02
4.94
4.74
4.68
4.48
4.44
4.24
Tables
107
Table 7. Weight of calcium carbonate deposit (W) from R.

VALUE OF R @ T
T
4.0
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
30
35
40
45
50
55
60
65
70
75
80
2515
1920
1525
1164
925
706
561
428
340
260
206
2107
1620
1297
997
799
614
492
378
303
233
186
1765
1367
1103
954
690
634
431
334
269
209
168
1479
1153
938
731
595
464
378
294
240
187
152
1239
973
798
626
514
403
331
260
213
167
137
1038
821
679
536
444
351
290
229
190
150
124
870
692
577
459
383
305
254
202
169
134
112
729
584
491
393
331
265
223
179
150
120
101
610
493
417
337
285
228
195
158
133
108
91
511
416
355
289
246
200
171
139
119
97
82
30
35
40
45
50
55
60
65
70
75
80
5.0
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
428
350
302
247
213
174
150
123
106
86
74
359
296
257
212
184
151
131
108
94
77
67
301
250
218
181
159
132
115
96
84
69
61
252
211
186
155
137
114
101
84
74
62
55
211
177
158
133
118
99
88
74
66
56
50
177
150
134
114
102
86
77
66
59
50
45
148
126
114
98
88
75
68
58
52
45
40
124
107
97
84
76
65
60
51
47
40
36
104
90
83
72
66
57
52
45
41
36
33
87
76
70
61
57
49
46
40
37
32
30
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
73
64
60
52
49
43
40
35
33
29
27
61
54
51
45
42
37
35
31
29
26
24
51
46
43
38
36
32
31
27
26
23
22
43
38
37
33
31
28
27
24
23
21
20
36
32
31
28
27
25
24
21
21
19
18
30
27
27
24
23
21
21
19
18
17
16
25
23
23
21
20
19
18
17
16
15
15
21
19
19
18
17
16
16
15
14
13
13
18
16
16
15
15
14
14
13
13
12
12
15
14
14
13
13
12
12
11
11
11
11
30
35
40
45
50
55
60
65
70
75
80
30
35
40
45
50
55
60
65
70
75
80
30
35
40
45
50
55
60
65
70
75
80
30
35
40
45
50
55
60
65
70
75
80
108
Table 8. Values of p[Ca2+] from Ca.
0
10
20
30
40
50
60
70
80
90
100
200
300
400
500
600
700
800
900
1000
2000
4.00
3.70
3.53
3.40
3.30
3.22
3.15
3.10
3.05
3.00
2.70
2.53
2.40
2.30
2.22
2.15
2.10
2.05
2.00
1.70
5.00
3.96
3.68
3.51
3.39
3.29
3.21
3.15
3.09
3.04
4.70
3.92
3.66
3.50
3.38
3.28
3.20
3.14
3.09
3.04
4.53
3.89
3.64
3.48
3.37
3.28
3.20
3.14
3.08
3.03
4.40
3.85
3.62
3.47
3.36
3.27
3.19
3.14
3.08
3.03
4.30
3.82
3.60
3.46
3.35
3.26
3.19
3.13
3.07
3.02
4.22
3.80
3.58
3.44
3.34
3.25
3.18
3.12
3.07
3.02
4.15
3.77
3.57
3.43
3.33
3.24
3.17
3.11
306
3.01
4.10
3.74
3.55
3.42
3.32
3.23
3.17
3.11
3.06
3.01
4.05
3.72
3.54
3.41
3.31
3.22
3.16
3.10
3.05
3.00
10
20
30
40
50
60
70
80
90
2.96
2.68
2.51
2.39
2.29
2.21
2.15
2.09
2.04
2.92
2.66
2.50
2.38
2.28
2.20
2.14
2.09
2.04
2.89
2.64
2.48
2.37
2.28
2.20
2.14
2.08
2.03
2.85
2.62
2.47
2.36
2.27
2.19
2.13
2.08
2.03
2.82
2.60
2.46
2.35
2.26
2.19
2.13
2.07
2.02
2.80
2.58
2.44
2.34
2.25
2.18
2.12
2.07
2.02
2.76
2.57
2.43
2.33
2.24
2.17
2.11
2.06
2.01
2.74
2.55
2.42
2.32
2.23
2.17
2.11
2.06
2.01
2.72
2.54
2.41
2.31
2.22
2.16
2.10
2.05
2.00
100
200
300
400
500
600
700
800
900
1.96
1.68
1.92
1.66
1.89
1.64
1.85
1.62
1.82
1.60
1.80
1.58
1.76
1.57
1.74
1.55
1.72
1.54
Tables
109
Table 9. Values of p[Alk] from Alk.
10
20
30
40
50
60
70
80
90
100
200
300
400
500
600
700
800
900
3.70
3.40
3.23
3.10
3.00
2.92
2.85
2.80
2.75
2.70
2.40
2.23
2.10
2.00
1.92
1.85
1.80
1.75
3.66
3.38
3.21
3.09
2.99
2.91
2.85
2.79
2.74
3.62
3.36
3.20
3.08
2.98
2.90
2.84
2.79
2.74
3.59
3.34
3.18
3.07
2.98
2.90
2.84
2.78
2.73
3.55
3.32
3.17
3.06
2.97
2.89
2.83
2.78
2.73
3.52
3.30
3.16
3.05
2.96
2.89
2.83
2.77
2.72
3.50
3.28
3.14
3.04
2.95
2.88
2.82
2.77
2.72
3.47
3.27
3.13
3.03
2.94
2.87
2.81
2.76
2.71
3.44
3.25
3.12
3.02
2.93
2.87
2.97
2.81
2.76
2.71
3.42
3.24
3.11
3.01
2.92
2.86
2.80
2.75
2.70
10
20
30
40
50
60
70
80
90
2.66
2.38
2.21
2.09
1.99
1.91
1.85
1.79
1.74
2.62
2.36
2.20
2.08
1.98
1.90
1.84
1.79
1.74
2.59
2.34
2.18
2.07
1.98
1.90
1.84
1.78
1.73
2.55
2.32
2.17
2.06
1.97
1.89
1.83
1.78
1.73
2.52
2.30
2.16
2.05
1.96
1.89
1.83
1.77
1.72
2.50
2.28
2.14
2.04
1.95
1.88
1.82
1.77
1.72
2.47
2.27
2.13
2.03
1.94
1.87
1.81
1.76
1.71
2.44
2.25
2.12
2.02
1.93
1.87
1.81
1.76
1.71
2.42
2.24
2.11
2.01
1.92
1.86
1.80
1.75
1.70
Table 10. Values of pK2 for

Eq. (7) and pKS for Eq. (8).
PK2
pKS
0
10
20
30
40
50
60
70
80
10.63
10.49
10.38
10.29
10.22
10.17
10.14
10.12
10.12
8.02
8.15
8.28
8.41
8.52
8.63
8.74
8.87
8.99
110
Table 11. Assessment of margin of error (from R).

ERRORS
W
No
Table 6
Table 7
(Table 7)(Table 6)
No
22
30
50
80
7.04
6.43
5.59
10
20
35
15
27
40
+5 (+50%)
+7 (+35%)
+5 (+14%)
22
25
30
50
80
6.48
5.82
5.02
35
50
90
30
66
74
5 (14%)
+16 (+32%)
16 (18%)
25
26
30
50
80
6.44
5.83
4.92
30
50
85
36
66
82
+6 (+20%)
+16 (+32%)
3 (4%)
26
29
30
50
80
5.96
5.30
4.46
80
120
170
73
137
124
7 (9%)
+17 (+14%)
46 (27%)
29
30
30
50
80
5.94
5.38
4.49
70
90
140
87
118
124
+17 (+26%)
+28 (+31%)
16 (11%)
30
Tables
Table 12. Errors for two water supplies (from R).

WATER ANALYSES
T
MEAN
MAX
ERRORS
MIN
(MAX)-(MEAN)
(MIN)-(MEAN)
NORTHAMPTON (PITSFORD)
15
30
50
80
Ca
Alk
DS
pH
pHS
pH
R
W
pHS
pH
R
W
pHS
pH
R
W
210
124
386
8.10
7.37
8.00
6.74
21
7.04
7.90
6.18
36
6.62
7.90
5.34
55
230
140
466
8.40
7.24
8.30
6.28
43
6.69
6.20
6.72
76
6.27
8.10
4.44
137
Ca
Alk
DS
pH
pHS
pH
R
W
pHS
pH
R
W
pHS
pH
R
W
270
186
435
7.60
7.09
7.50
6.68
21
6.76
7.50
6.02
49
6.34
7.50
5.18
61
310
222
505
7.90
6.97
7.80
6.14
61
6.64
7.70
5.58
88
6.22
7.80
4.64
112
183
96
290
7.90
7.50
7.90
7.10
15
7.17
7.80
6.54
23
6.76
7.80
5.70
3
+22 (+105%)
6 (29%)
+40 (111%)
13 (36%)
+82 (+149%)
52 (95%)
OXFORD (SWINFORD)
15
30
50
80
240
113
365
7.10
7.53
6.90
7.16
2
7.02
6.90
7.14
9
6.50
7.00
6.00
27
+40 (+190%)
19 (90%)
+39 (+50%)
40 (82%)
+51 (+82%)
34 (56%)
111
112

Table 13. Weight of calcium carbonate (W) from I.
VALUE OF I @ T
T
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
30
35
40
45
50
55
60
65
70
75
80
3
3
3
3
3
3
3
3
3
3
3
5
5
4
4
4
4
4
4
4
4
3
7
7
7
6
6
6
5
5
5
5
5
11
10
10
9
9
8
8
7
7
6
6
17
16
15
14
12
12
11
10
9
8
8
26
24
22
20
18
17
15
14
13
11
10
40
36
32
29
26
24
21
19
17
15
14
62
54
48
43
38
34
30
26
23
20
18
94
82
72
63
54
48
41
36
32
27
24
145
124
107
92
78
68
58
50
43
37
32
30
35
40
45
50
55
60
65
70
75
80
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
222
187
159
135
113
97
81
69
58
49
42
340
283
236
197
163
138
114
95
79
66
55
521
427
351
289
235
196
159
131
108
88
72
644
522
423
340
278
202
181
147
118
95
30
35
40
45
50
55
60
65
70
75
80
620
490
395
313
250
199
158
126
707
562
438
344
271
211
166
613
475
308
283
219
655
501
378
289
506
381
502
30
35
40
45
50
55
60
65
70
75
80
Tables
Table 14. Assessment of Margin of Error (from I ).
W
No
22
30
50
80
0.43
0.71
1.13
25
30
50
80
26
(Table 6)
ERRORS
No
(Table 13)
(Table 13)(Table 6)
10
20
35
11
26
42
+1 (+10%)
+6 (+30%)
+7 (+20%)
22
0.61
0.94
1.34
35
50
90
26
54
72
9 (26%)
+4 (+8%)
12 (20%)
25
30
50
80
0.63
0.91
1.38
30
50
85
26
54
95
4 (13%)
+4 (+8%)
+10 (+12%)
26
29
30
50
80
0.82
1.15
1.57
80
120
170
62
163
166
18 (23%)
+43 (+36%)
4 (2%)
29
30
30
50
80
0.88
1.11
1.63
87
118
124
94
113
166
+7 (+5%)
5 (4%)
+42 (+34%)
30
113
114

Table 15. Errors for two water supplies (from I ).
WATER ANALYSES
T
MEAN
MAX
ERRORS
MIN
(MAX)(MEAN)
(MIN)(MEAN)
NORTHAMPTON (PITSFORD)
15
Ca
Alk
DS
pH
210
124
386
8.1
230
140
466
8.4
183
96
290
7.9
30
pHS
pH
RI
W
7.37
8.00
0.63
26
7.29
8.30
1.01
145
7.50
7.90
0.40
11
+119 (+82%)
15 (58%)
pHS
PH
I
W
7.04
7.90
0.86
54
6.96
8.20
1.24
163
7.17
7.80
0.63
18
+109 (+202%)
36 (67%)
pHS
pH
I
W
6.62
7.90
1.28
72
6.27
8.10
1.83
289
6.75
7.80
1.05
42
+217 (+300%)
30 (42%)
50
80
OXFORD (SWINFORD)
15
Ca
Alk
DS
pH
270
186
435
7.6
310
222
505
7.9
240
113
365
7.1
30
pHS
pH
I
W
7.09
7.50
0.41
11
6.97
7.80
0.83
62
7.35
6.90
0.45
nil
+51 (+463%)
11 (100%)
pHS
PH
I
W
6.76
7.50
0.74
26
6.64
7.70
1.06
113
7.02
6.90
0.12
nil
+87 (+335%)
26 (100%)
pHS
pH
I
W
6.34
7.50
1.16
55
6.22
7.80
1.58
116
6.60
7.00
0.40
6
+111 (+201%)
49 (89%)
50
80
Tables
Table 16. Comparison between Langelier and Ryznar.
VALUES OF W
No
22
30
50
80
30
50
80
30
50
80
30
50
80
30
50
80
25
26
29
30
FROM R (TABLE 7)
15
27
40
30
66
74
36
66
82
73
137
124
87
118
124
FROM I (TABLE 13)
ERRORS
No
11
26
42
26
54
72
26
54
95
62
163
166
94
113
166
+4 (+36%)
+1 (+4%)
+2 (5%)
+4 (+15%)
+12 (+22%)
+2 (+3%)
+10 (+38%)
+12 (+22%)
13 (14%)
+11 (+18%)
26 (16%)
42 (25%)
7 (7%)
+5 (+4%)
42 (25%)
22
Table 17. Values of pK for Eq. (34).

T
pK
0
10
20
30
40
50
60
70
80
90
4.62
4.57
4.54
4.52
4.54
4.64
4.74
4.82
4.92
5.02
25
26
29
30
115
116

Table 18. Values of p[SO2
4 ] from SO4.
0
10
20
30
40
50
60
70
80
90
100
200
300
400
500
600
700
800
900
1000
2000
4.15
3.85
3.68
3.55
3.46
3.38
3.31
3.25
3.20
3.15
2.85
2.68
2.55
2.46
2.38
2.31
2.25
2.20
2.15
1.85
5.15
4.11
3.82
3.66
3.54
3.44
3.37
3.30
3.24
3.19
4.85
4.07
3.81
3.65
3.53
3.43
3.36
3.29
3.23
3.19
4.68
4.04
3.80
3.64
3.53
3.43
3.36
3.29
3.23
3.18
4.55
4.00
3.77
3.62
3.51
3.42
3.35
3.28
3.22
3.18
4.46
3.98
3.76
3.61
3.50
3.41
3.34
3.28
3.22
3.17
4.38
3.96
3.74
3.60
3.49
3.40
3.33
3.28
3.21
3.17
4.31
3.92
3.72
3.58
3.48
3.40
3.33
3.27
3.21
3.17
4.25
3.91
3.70
3.57
3.47
3.39
3.32
3.26
3.20
3.16
4.20
3.87
3.69
3.56
3.46
3.38
3.31
3.25
3.20
3.15
10
20
30
40
50
60
70
80
90
3.11
2.82
2.66
2.54
2.44
2.37
2.30
2.24
2.19
3.07
2.81
2.65
2.53
2.43
2.36
2.29
2.23
2.19
3.04
2.80
2.64
2.53
2.43
2.36
2.29
2.23
2.18
3.00
2.77
2.62
2.51
2.42
2.35
2.28
2.22
2.18
2.98
2.76
2.61
2.50
2.41
2.34
2.28
2.22
2.17
2.96
2.74
2.60
2.49
2.40
2.33
2.28
2.21
2.17
2.92
2.72
2.58
2.48
2.40
2.33
2.27
2.21
2.17
2.91
2.70
2.57
2.47
2.39
2.32
2.26
2.20
2.17
2.87
2.69
2.56
2.46
2.38
2.31
2.25
2.20
2.15
100
200
300
400
500
600
700
800
900
2.11
1.82
2.07
1.81
2.04
1.81
2.00
1.77
1.98
1.76
1.96
1.74
1.92
1.72
1.91
1.70
1.87
1.69
Tables
117
Table 19 Values of b from Eq. (49).

Table 19/1
Ca/SO4
VALUES OF IS
(Range 0.01 to 0.10)
Ca/SO4
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.2
0.4
0.6
0.8
1.0
0.99
0.99
0.99
0.99
0.99
0.99
0.98
0.98
0.98
0.97
0.99
0.98
0.97
0.96
0.96
0.98
0.97
0.96
0.95
0.95
0.98
0.96
0.95
0.94
0.93
0.97
0.95
0.94
0.93
0.92
0.97
0.94
0.93
0.92
0.91
0.96
0.94
0.92
0.91
0.90
0.96
0.93
0.91
0.90
0.89
0.95
0.92
0.90
0.88
0.87
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
0.99
0.99
0.98
0.98
0.98
0.97
0.97
0.97
0.97
0.97
0.96
0.96
0.95
0.95
0.95
0.94
0.94
0.94
0.94
0.93
0.93
0.93
0.92
0.92
0.92
0.92
0.91
0.91
0.91
0.90
0.90
0.90
0.89
0.89
0.89
0.90
0.88
0.88
0.87
0.87
0.88
0.87
0.86
0.86
0.86
0.87
0.86
0.85
0.85
0.84
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
0.98
0.98
0.98
0.98
0.98
0.97
0.97
0.96
0.96
0.96
0.95
0.95
0.95
0.95
0.95
0.93
0.93
0.93
0.93
0.93
0.92
0.91
0.91
0.91
0.91
0.90
0.90
0.90
0.90
0.89
0.88
0.88
0.88
0.88
0.88
0.87
0.87
0.86
0.86
0.86
0.85
0.85
0.85
0.85
0.84
0.84
0.84
0.83
0.83
0.83
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
0.98
0.98
0.98
0.98
0.98
0.96
0.96
0.96
0.96
0.96
0.95
0.94
0.94
0.94
0.94
0.93
0.93
0.93
0.93
0.92
0.91
0.91
0.91
0.91
0.91
0.89
0.89
0.89
0.89
0.89
0.88
0.87
0.87
0.87
0.87
0.86
0.86
0.86
0.86
0.85
0.84
0.84
0.84
0.84
0.84
0.83
0.82
0.82
0.82
0.82
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
0.98
0.98
0.98
0.98
0.98
0.96
0.96
0.96
0.96
0.96
0.94
0.94
0.94
0.94
0.94
0.92
0.92
0.92
0.92
0.92
0.91
0.91
0.90
0.90
0.90
0.89
0.89
0.89
0.89
0.89
0.87
0.87
0.87
0.87
0.87
0.85
0.85
0.85
0.85
0.85
0.84
0.84
0.83
0.83
0.83
0.82
0.82
0.82
0.82
0.82
4.2
4.4
4.6
4.8
5.0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
Ca/SO4
VALUES OF IS
(Range 0.01 to 0.10)
Ca/SO4
118

Table 19/2
Ca/SO4
VALUES OF IS
(Range 0.11 to 0.20)
Ca/SO4
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.2
0.4
0.6
0.8
1.0
0.95
0.91
0.89
0.87
0.86
0.94
0.91
0.88
0.86
0.85
0.94
0.90
0.87
0.85
0.84
0.94
0.89
0.86
0.84
0.83
0.93
0.89
0.85
0.83
0.81
0.93
0.88
0.85
0.82
0.80
0.92
0.87
0.84
0.81
0.79
0.92
0.87
0.83
0.80
0.78
0.92
0.86
0.82
0.79
0.77
0.91
0.85
0.82
0.78
0.76
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
0.85
0.84
0.84
0.83
0.83
0.84
0.83
0.82
0.82
0.81
0.83
0.82
0.81
0.80
0.80
0.81
0.80
0.80
0.79
0.78
0.80
0.79
0.78
0.78
0.77
0.79
0.78
0.77
0.76
0.76
0.78
0.77
0.76
0.75
0.74
0.77
0.75
0.74
0.74
0.73
0.75
0.74
0.73
0.72
0.72
0.75
0.73
0.72
0.71
0.71
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
0.82
0.82
0.82
0.81
0.81
0.81
0.81
0.80
0.80
0.80
0.79
0.79
0.79
0.78
0.78
0.78
0.78
0.77
0.77
0.77
0.77
0.76
0.76
0.75
0.75
0.75
0.75
0.74
0.74
0.74
0.74
0.73
0.73
0.73
0.72
0.73
0.72
0.72
0.71
0.71
0.71
0.71
0.70
0.70
0.70
0.70
0.69
0.69
0.69
0.68
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
0.81
0.81
0.81
0.81
0.80
0.80
0.79
0.79
0.79
0.79
0.78
0.78
0.78
0.77
0.77
0.76
0.76
0.76
0.76
0.76
0.75
0.75
0.75
0.74
0.74
0.74
0.73
0.73
0.73
0.73
0.72
0.72
0.72
0.71
0.71
0.71
0.70
0.70
0.70
0.70
0.69
0.69
0.69
0.69
0.68
0.68
0.68
0.67
0.67
0.67
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
0.80
0.80
0.80
0.80
0.80
0.79
0.79
0.78
0.78
0.78
0.77
0.77
0.77
0.77
0.77
0.76
0.75
0.75
0.75
0.75
0.74
0.74
0.74
0.74
0.74
0.73
0.72
0.72
0.72
0.72
0.71
0.71
0.71
0.71
0.71
0.70
0.70
0.70
0.69
0.69
0.68
0.68
0.68
0.68
0.68
0.67
0.67
0.67
0.67
0.66
4.2
4.4
4.6
4.8
5.0
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
Ca/SO4
VALUES OF IS
(Range 0.11 to 0.20)
Ca/SO4
Tables
119
Table 19/3
Ca/SO4
VALUES OF IS
(Range 0.21 to 0.30)
Ca/SO4
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.30
0.2
0.4
0.6
0.8
1.0
0.91
0.85
0.80
0.77
0.75
0.91
0.84
0.79
0.76
0.74
0.90
0.83
0.79
0.75
0.73
0.90
0.83
0.78
0.74
0.72
0.90
0.82
0.77
0.73
0.71
0.89
0.82
0.76
0.73
0.70
0.89
0.81
0.75
0.72
0.69
0.89
0.81
0.75
0.71
0.68
0.88
0.80
0.74
0.70
0.67
0.88
0.79
0.73
0.69
0.66
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
0.73
0.72
0.71
0.70
0.69
0.72
0.71
0.70
0.69
0.68
0.71
0.70
0.68
0.68
0.67
0.70
0.68
0.67
0.66
0.66
0.69
0.67
0.66
0.65
0.64
0.68
0.66
0.65
0.64
0.63
0.67
0.65
0.64
0.63
0.62
0.66
0.64
0.63
0.62
0.61
0.65
0.63
0.62
0.61
0.60
0.64
0.62
0.61
0.60
0.59
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
0.69
0.68
0.68
0.67
0.67
0.67
0.67
0.67
0.66
0.66
0.66
0.66
0.65
0.65
0.64
0.65
0.64
0.64
0.63
0.63
0.64
0.63
0.63
0.62
0.62
0.63
0.62
0.61
0.61
0.61
0.61
0.61
0.60
0.60
0.59
0.60
0.60
0.59
0.59
0.58
0.60
0.58
0.58
0.57
0.57
0.58
0.57
0.57
0.56
0.56
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
0.67
0.66
0.66
0.66
0.66
0.65
0.65
0.65
0.65
0.64
0.64
0.64
0.63
0.63
0.63
0.63
0.63
0.62
0.62
0.62
0.61
0.61
0.61
0.61
0.60
0.60
0.60
0.60
0.59
0.59
0.59
0.59
0.59
0.58
0.58
0.58
0.58
0.57
0.57
0.57
0.57
0.57
0.56
0.56
0.56
0.56
0.56
0.55
0.55
0.54
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
0.66
0.65
0.65
0.65
0.65
0.64
0.64
0.64
0.64
0.64
0.63
0.63
0.63
0.62
0.62
0.62
0.61
0.61
0.61
0.61
0.60
0.60
0.60
0.60
0.60
0.59
0.59
0.59
0.59
0.58
0.58
0.58
0.57
0.57
0.57
0.57
0.56
0.56
0.56
0.56
0.55
0.55
0.55
0.55
0.55
0.54
0.54
0.54
0.54
0.54
4.2
4.4
4.6
4.8
5.0
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.30
Ca/SO4
VALUES OF IS
(Range 0.21 to 0.30)
Ca/SO4
120

Table 19/4
Ca/SO4
VALUES OF IS
(Range 0.31 to 0.40)
Ca/SO4
0.31
0.32
0.33
0.34
0.35
0.36
0.37
0.38
0.39
0.40
0.2
0.4
0.6
0.8
1.0
0.88
0.79
0.72
0.68
0.65
0.87
0.78
0.72
0.67
0.64
0.87
0.78
0.71
0.67
0.63
0.87
0.77
0.70
0.66
0.62
0.86
0.76
0.70
0.65
0.61
0.86
0.76
0.69
0.64
0.61
0.86
0.75
0.68
0.63
0.60
0.86
0.75
0.68
0.62
0.59
0.85
0.74
0.67
0.62
0.58
0.85
0.74
0.66
0.61
0.57
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
0.63
0.61
0.60
0.59
0.58
0.62
0.60
0.59
0.57
0.57
0.61
0.59
0.58
0.56
0.56
0.60
0.58
0.57
0.55
0.54
0.59
0.57
0.56
0.54
0.53
0.58
0.56
0.55
0.53
0.52
0.57
0.55
0.54
0.52
0.52
0.56
0.54
0.53
0.52
0.51
0.55
0.53
0.52
0.51
0.50
0.54
0.52
0.51
0.50
0.49
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
0.57
0.56
0.56
0.55
0.55
0.56
0.55
0.55
0.54
0.54
0.55
0.54
0.54
0.53
0.53
0.54
0.53
0.53
0.52
0.52
0.53
0.52
0.51
0.51
0.51
0.52
0.51
0.50
0.50
0.50
0.51
0.50
0.49
0.49
0.49
0.50
0.49
0.49
0.48
0.48
0.49
0.48
0.48
0.47
0.47
0.48
0.47
0.47
0.46
0.46
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
0.54
0.54
0.54
0.54
0.53
0.53
0.53
0.53
0.53
0.52
0.52
0.52
0.52
0.51
0.51
0.51
0.51
0.51
0.50
0.50
0.50
0.50
0.50
0.49
0.49
0.49
0.49
0.49
0.48
0.48
0.48
0.48
0.48
0.47
0.47
0.47
0.47
0.47
0.46
0.46
0.46
0.46
0.46
0.45
0.45
0.45
0.45
0.45
0.44
0.44
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
0.53
0.53
0.53
0.53
0.53
0.52
0.52
0.52
0.52
0.51
0.51
0.51
0.51
0.50
0.50
0.50
0.50
0.50
0.49
0.49
0.49
0.49
0.49
0.48
0.48
0.48
0.48
0.48
0.47
0.47
0.47
0.47
0.47
0.46
0.46
0.46
0.46
0.46
0.45
0.45
0.45
0.45
0.45
0.44
0.44
0.44
0.44
0.44
0.43
0.43
4.2
4.4
4.6
4.8
5.0
0.31
0.32
0.33
0.34
0.35
0.36
0.37
0.38
0.39
0.40
Ca/SO4
VALUES OF IS
(Range 0.31 to 0.40)
Ca/SO4
Tables
Table 20. Values of pK1 pK2 pK3 for Eq. (58).
T
pK1
pK2
pK3
10
20
30
40
50
60
70
80
2.07
2.10
2.15
2.20
2.26
2.33
2.40
2.47
7.25
7.21
7.19
7.18
7.18
7.19
7.21
7.24
12.56
12.41
12.26
12.13
12.00
11.88
11.77
11.67
Table 21. Values of p[Phos] from Phos.
0
10
20
30
40
50
60
70
80
90
100
200
3.98
3.68
3.50
3.38
3.28
3.20
3.13
3.08
3.03
2.98
2.68
4.98
3.94
3.66
3.49
3.37
3.27
3.19
3.13
3.07
3.02
4.68
3.90
3.64
3.47
3.36
3.26
3.19
3.12
307
3.02
4.50
3.87
3.62
3.46
3.35
3.26
3.18
3.12
3.06
3.01
4.38
3.83
3.60
3.45
3.34
3.25
3.17
3.11
3.06
3.01
4.28
3.80
3.58
3.44
3.33
3.24
3.17
3.10
3.05
3.00
4.20
3.78
3.57
3.42
3.32
3.23
3.16
3.10
3.05
3.00
4.13
3.75
3.55
3.41
3.31
3.22
3.15
3.09
3.04
2.99
4.08
3.72
3.53
3.40
3.30
3.22
3.15
3.09
3.04
2.99
4.03
3.70
3.52
3.39
3.29
3.21
3.14
3.08
3.03
2.98
10
20
30
40
50
60
70
80
90
2.94
2.66
2.90
2.64
2.87
2.62
2.83
2.60
2.80
2.58
2.78
2.57
2.75
2.55
2.72
2.52
2.70
2.52
121
122

Table 22. Values of p(E) for Eq. (67)
TEMPERATURE
pH @ T
10
20
30
40
50
60
70
80
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.83
7.64
7.60
7.26
7.08
6.89
6.70
6.53
6.36
6.18
7.65
7.46
7.27
7.09
6.90
6.72
6.53
6.35
6.18
6.01
7.49
7.31
7.12
6.93
6.74
6.56
6.39
6.21
6.04
5.87
7.33
7.14
6.96
6.78
6.58
6.40
6.21
6.03
5.85
5.69
7.22
6.93
6.70
6.50
6.31
6.13
5.96
5.80
5.65
5.50
7.13
6.87
6.63
6.42
6.28
6.06
5.87
5.71
5.56
5.41
7.00
6.81
6.63
6.43
6.25
6.05
5.85
5.70
5.53
5.35
6.94
6.75
6.55
6.37
6.18
5.99
5.80
5.62
5.45
5.29
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
6.00
5.84
5.68
5.53
5.38
5.24
5.10
4.96
4.84
4.72
5.85
5.64
5.54
5.39
5.25
5.11
4.98
4.85
4.73
4.61
5.69
5.53
5.37
5.22
5.09
4.95
4.82
4.69
4.57
4.45
5.53
5.37
5.22
5.08
4.94
4.80
4.67
4.55
4.43
4.31
5.36
5.21
5.06
4.93
4.79
4.67
4.54
4.42
4.31
4.19
5.26
5.11
4.97
4.82
4.68
4.55
4.42
4.30
4.18
4.06
5.19
5.03
4.87
4.72
4.57
4.43
4.30
4.17
4.05
3.94
5.12
4.95
4.80
4.65
4.50
4.37
4.23
4.10
3.98
3.86
8.0
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
4.65
4.49
4.38
4.27
4.17
4.06
3.96
3.85
3.75
3.65
4.49
4.38
4.27
4.16
4.06
3.95
3.84
3.74
3.63
3.53
4.33
4.22
4.11
4.01
3.90
3.79
3.68
3.58
3.47
3.37
4.19
4.08
3.97
3.86
3.76
3.65
3.54
3.44
3.34
3.24
4.07
3.97
3.86
3.75
3.64
3.54
3.43
3.32
3.22
3.11
3.95
3.88
3.72
3.62
3.51
3.40
3.30
3.20
3.10
3.00
3.82
3.71
3.59
3.49
3.38
3.28
3.17
3.07
2.97
2.87
3.75
3.64
3.53
3.42
3.31
3.20
3.10
3.00
2.90
2.79
Tables
123
Table 22 (Continued)
TEMPERATURE
pH @ T
10
20
30
40
50
60
70
80
9.0
9.1
9.2
9.3
9.4
9.5
9.6
9.7
9.8
9.9
3.55
3.44
3.33
3.23
3.13
3.03
2.93
2.83
2.72
2.62
3.42
3.32
3.22
3.12
3.02
2.92
2.82
2.72
2.62
2.52
3.27
3.17
3.07
2.97
2.87
2.77
2.67
2.57
2.47
2.37
3.14
3.02
2.92
2.82
3.72
2.62
2.52
2.43
2.33
2.23
3.01
2.91
2.81
2.70
2.60
2.50
2.40
2.30
2.20
2.10
2.89
2.80
2.69
2.59
2.49
2.38
2.28
2.18
2.08
1.98
2.77
2.67
2.57
2.47
2.37
2.28
2.18
2.08
1.99
1.89
2.69
2.59
2.49
2.39
2.28
2.19
2.09
1.99
1.89
1.80
10.0
10.1
10.2
10.3
10.4
10.5
10.6
10.7
10.8
10.9
2.52
2.43
2.33
2.23
2.14
2.04
1.94
1.84
1.74
1.65
2.42
2.32
2.22
2.18
2.03
1.93
1.83
1.73
1.64
1.54
2.27
2.17
2.08
1.98
1.88
1.79
1.69
1.59
1.49
1.40
2.13
2.04
1.94
1.84
1.74
1.65
1.55
1.45
1.36
1.26
2.00
1.90
1.80
1.71
1.61
1.51
1.42
1.33
1.24
1.15
1.89
1.79
1.69
1.59
1.49
1.40
1.31
1.21
1.12
1.03
1.80
1.71
1.62
1.53
1.43
1.34
1.25
1.16
1.07
0.98
1.70
1.60
1.51
1.41
1.32
1.23
1.13
1.04
0.94
0.85
124

Table 23. Values of CaCO3/PO4 for selection of values of b from Eq. (82).
Table 23/1
Ip RANGE 0.1 to 1.9
VALUES OF b (RANGE 0.10 to 0.19)
Ip
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
Ip
0.1
0.1
0.2
0.3
0.4
0.5
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
42.10
70.43
16.00
20.33
10.45
34.33
12.58
8.03
130.10
16.25
9.08
6.50
26.75
11.15
7.30
5.58
199.48
32.38
1.1
1.2
1.3
1.4
1.5
14.78
8.30
5.95
4.75
11.08
7.13
5.40
4.43
1.6
1.7
1.8
1.9
Tables
125
Table 23/2
Ip
0.20
0.22
0.24
0.26
0.28
0.30
0.32
0.34
0.36
0.38
Ip
0.1
0.1
0.2
0.3
0.4
0.5
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
8.58
20.33
7.03
25.68
10.50
6.70
52.70
12.18
7.30
5.28
6.80
5.53
4.88
4.50
6.20
4.83
4.00
3.48
4.93
4.03
3.45
3.05
4.13
3.50
3.05
2.75
125.30
22.00
102.00
12.15
21.35
8.40
0.6
0.7
0.8
0.9
1.0
16.18
8.10
5.65
4.38
26.00
9.88
6.18
4.65
3.78
12.85
7.15
5.00
3.98
3.33
8.73
5.70
4.25
3.50
2.98
6.63
4.73
3.70
3.10
2.70
5.35
4.03
3.28
2.80
2.48
1.1
1.2
1.3
1.4
1.5
3.58
3.10
2.75
2.53
3.18
2.80
2.53
2.33
2.85
2.55
2.33
2.15
2.60
2.33
2.15
2.00
2.38
2.18
2.00
1.88
2.20
2.03
1.88
1.78
1.6
1.7
1.8
1.9
126

Table 23/3
Ip
0.40
0.42
0.44
0.46
0.48
0.50
0.52
0.54
0.56
0.58
Ip
0.1
0.1
0.2
0.3
0.4
0.5
32.85
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
13.78
6.63
4.48
42.25
9.23
5.33
3.85
17.30
6.98
4.48
3.38
10.78
5.58
3.85
3.00
30.58
7.78
4.63
3.35
2.68
15.00
6.08
3.93
2.98
2.43
9.80
4.95
3.40
2.65
2.20
7.18
4.15
2.98
2.38
2.00
0.6
0.7
0.8
0.9
1.0
256.58
12.23
6.50
25.63
8.55
5.28
1.1
1.2
1.3
1.4
1.5
4.50
3.55
2.93
2.55
2.28
3.88
3.15
2.65
2.35
2.10
3.43
2.83
2.43
2.15
1.95
3.03
2.55
2.23
2.00
1.83
2.83
2.33
2.05
1.85
1.70
2.48
2.15
1.90
1.73
1.58
2.25
1.98
1.75
1.60
1.48
2.05
1.83
1.63
1.50
1.40
1.88
1.68
1.50
1.40
1.30
1.73
1.55
1.40
1.30
1.23
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.05
1.88
1.78
1.68
1.90
1.78
1.65
1.58
1.78
1.65
1.58
1.48
1.68
1.55
1.48
1.40
1.58
1.48
1.40
1.33
1.48
1.38
1.33
1.25
1.38
1.30
1.25
1.18
1.30
1.23
1.18
1.13
1.23
1.15
1.10
1.05
1.15
1.08
1.05
1.00
1.6
1.7
1.8
1.9
Tables
127
Table 23/4
Ip
0.60
0.62
0.64
0.66
0.68
0.70
0.72
0.74
0.76
0.78
0.1
Ip
0.1
0.2
0.3
0.4
0.5
7.15
3.48
39.35
5.28
2.90
13.95
4.08
2.45
8.08
3.25
2.08
5.53
2.65
1.78
0.2
0.3
0.4
0.5
14.93
9.45
60.18
6.80
18.45
5.28
10.53
4.23
0.6
0.7
0.8
0.9
1.0
5.60
3.53
2.63
2.13
1.83
4.53
3.05
2.35
1.93
1.68
3.75
2.65
2.08
1.75
1.50
3.20
2.33
1.88
1.58
1.38
2.75
2.05
1.68
1.43
1.25
2.38
1.83
1.50
1.30
1.15
2.05
1.63
1.35
1.18
1.05
1.80
1.43
1.20
1.05
0.95
1.55
1.28
1.08
0.95
0.85
1.35
1.13
0.95
0.85
0.78
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.60
1.43
1.30
1.23
1.13
1.45
1.33
1.20
1.13
1.05
1.35
1.23
1.13
1.05
1.00
1.23
1.13
1.05
0.98
0.93
1.13
1.05
0.95
0.90
0.85
1.03
0.95
0.88
0.80
0.80
0.95
0.88
0.83
0.78
0.73
0.85
0.80
0.75
0.70
0.68
0.78
0.73
0.68
0.65
0.60
0.70
0.65
0.63
0.58
0.55
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.08
1.03
0.98
0.85
1.00
0.95
0.93
0.88
0.93
0.90
0.85
0.83
0.88
0.83
0.80
0.78
0.80
0.78
0.75
0.73
0.75
0.73
0.70
0.68
0.70
0.68
0.65
0.63
0.63
0.60
0.60
0.58
0.58
0.55
0.55
0.53
0.53
0.50
0.50
0.48
1.6
1.7
1.8
1.9
128

Table 23/5

Ip
0.82
0.84
0.86
0.88
24.48
5.95
2.68
1.30
0.50
0.1
0.2
0.3
0.4
0.5
4.00
2.15
1.50
13.80
3.03
1.78
1.28
7.00
2.33
1.45
1.08
4.33
1.80
1.18
0.90
2.90
1.40
0.95
0.73
1.98
1.08
0.75
0.58
1.35
0.78
0.58
0.45
0.90
0.55
0.40
0.33
0.53
0.35
0.25
0.20
0.25
0.15
0.13
0.10
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.18
0.98
0.85
0.75
0.68
1.03
0.85
0.75
0.65
0.60
0.88
0.73
0.65
0.58
0.53
0.73
0.63
0.55
0.50
0.45
0.60
0.53
0.45
0.43
0.38
0.50
0.43
0.38
0.35
0.33
0.38
0.33
0.30
0.28
0.25
0.28
0.25
0.23
0.20
0.18
0.18
0.15
0.15
0.13
0.13
0.08
0.08
0.08
0.08
0.05
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
0.63
0.58
0.55
0.53
0.50
0.55
0.53
0.50
0.48
0.45
0.48
0.45
0.43
0.40
0.40
0.43
0.40
0.38
0.35
0.35
0.35
0.33
0.33
0.30
0.30
0.30
0.28
0.25
0.25
0.25
0.23
0.23
0.20
0.20
0.20
0.18
0.15
0.15
0.15
0.15
0.13
0.10
0.10
0.10
0.10
0.05
0.05
0.05
0.05
0.05
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
0.48
0.45
0.45
0.43
0.43
0.40
0.40
0.38
0.38
0.35
0.35
0.35
0.33
0.33
0.30
0.30
0.28
0.28
0.25
0.25
0.23
0.23
0.23
0.20
0.18
0.18
0.18
0.18
0.13
0.13
0.13
0.13
0.10
0.08
0.08
0.08
0.05
0.05
0.05
0.05
1.6
1.7
1.8
1.9
0.1
0.90
0.92
0.94
0.96
0.98
Ip
0.80
Tables
129
Table 23/6
Ip RANGE 2.0 to 5.8

Ip
0.01
0.02
0.03
0.04
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
0.05
0.06
0.07
0.08
0.09
Ip
10.70
6.30
4.70
3.90
3.43
2.0
2.2
2.4
2.6
2.8
10.38
5.70
13.48
6.45
4.35
3.45
10.40
8.70
4.13
3.28
2.80
5.65
4.08
3.28
2.80
2.48
4.28
3.38
2.88
2.53
2.30
3.55
2.98
2.60
2.33
2.15
3.13
2.70
2.40
2.20
2.05
2.85
2.50
2.28
2.10
1.95
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
35.88
11.95
5.98
4.23
3.43
3.80
3.35
2.85
2.55
2.33
2.80
2.60
2.35
2.18
2.05
2.43
2.30
2.13
2.00
1.98
2.20
2.13
2.00
1.90
1.83
2.01
2.00
1.90
1.83
1.78
1.98
1.93
1.83
1.78
1.73
1.90
1.85
1.78
1.73
1.68
1.83
1.80
1.73
1.68
1.63
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
3.00
2.55
2.40
2.26
2.10
2.20
2.05
1.98
1.90
1.86
1.98
1.88
1.83
1.78
1.75
1.85
1.78
1.75
1.73
1.68
1.78
1.75
1.70
1.68
1.65
1.73
1.68
1.65
1.63
1.60
1.68
1.65
1.63
1.60
1.58
1.65
1.60
1.58
1.58
1.55
1.58
1.58
1.55
1.55
1.53
5.0
5.2
5.4
5.6
5.8
130

Table 23/7

Ip
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
Ip
2.0
2.2
2.4
2.6
2.8
304.98
10.15
5.35
3.85
3.10
20.15
7.18
4.48
3.43
2.85
11.63
5.80
3.95
3.15
2.68
8.20
4.90
3.55
2.90
2.53
6.53
4.30
3.28
2.73
2.40
5.55
3.90
3.05
2.58
2.30
4.83
3.55
2.85
2.45
2.20
4.33
3.30
2.70
2.35
2.10
3.93
3.08
2.55
2.25
2.05
3.63
2.90
2.45
2.18
1.98
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
2.65
2.38
2.15
2.00
1.90
2.48
2.25
2.08
1.93
1.83
2.35
2.15
2.00
1.88
1.78
2.25
2.05
1.93
1.83
1.73
2.15
2.00
1.88
1.78
1.70
2.08
1.98
1.83
1.73
1.65
2.00
1.88
1.78
1.68
1.63
1.95
1.83
1.73
1.65
1.58
1.88
1.78
1.68
1.60
1.55
1.83
1.75
1.65
1.58
1.53
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
1.78
1.75
1.68
1.65
1.60
1.73
1.70
1.65
1.60
1.58
1.70
1.65
1.60
1.58
1.55
1.65
1.63
1.58
1.55
1.53
1.63
1.60
1.55
1.53
1.50
1.58
1.55
1.53
1.50
1.48
1.55
1.53
1.50
1.48
1.45
1.53
1.50
1.48
1.45
1.43
1.50
1.48
1.45
1.43
1.40
1.48
1.45
1.43
1.40
1.38
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
1.58
1.55
1.53
1.53
1.50
1.55
1.53
1.50
1.50
1.48
1.53
1.50
1.48
1.48
1.45
1.50
1.48
1.45
1.45
1.43
1.48
1.45
1.45
1.43
1.43
1.45
1.43
1.43
1.40
1.40
1.43
1.40
1.40
1.40
1.38
1.40
1.40
1.38
1.38
1.35
1.38
1.38
1.35
1.35
1.35
1.38
1.35
1.35
1.33
1.33
5.0
5.2
5.4
5.6
5.8
Tables
131
Table 23/8

Ip
0.20
0.22
0.24
0.26
0.29
0.30
0.32
0.34
0.36
0.38
Ip
2.0
2.2
2.4
2.6
2.8
3.38
2.75
2.35
2.10
1.93
2.98
2.50
2.18
1.95
1.80
2.68
2.30
2.03
1.85
1.73
2.45
2.13
1.90
1.75
1.63
2.28
2.00
1.80
1.65
1.55
2.10
1.88
1.70
1.58
1.50
1.98
1.78
1.63
1.50
1.43
1.85
1.68
1.55
1.45
1.38
1.75
1.60
1.48
1.38
1.30
1.65
1.50
1.40
1.33
1.25
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
1.78
1.68
1.60
1.55
1.50
1.70
1.60
1.55
1.48
1.45
1.63
1.55
1.48
1.43
1.40
1.55
1.48
1.43
1.38
1.35
1.48
1.43
1.38
1.33
1.30
1.43
1.38
1.33
1.28
1.25
1.35
1.30
1.28
1.25
1.20
1.30
1.25
1.23
1.20
1.18
1.25
1.23
1.13
1.15
1.13
1.20
1.18
1.13
1.10
1.10
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
1.45
1.43
1.40
1.38
1.35
1.40
1.38
1.35
1.33
1.33
1.35
1.33
1.33
1.30
1.28
1.30
1.30
1.28
1.28
1.25
1.28
1.25
1.23
1.23
1.20
1.23
1.20
1.20
1.18
1.18
1.18
1.18
1.15
1.15
1.13
1.15
1.13
1.13
1.10
1.10
1.10
1.10
1.08
1.08
1.05
1.08
1.05
1.05
1.03
1.03
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
1.35
1.33
1.33
1.33
1.30
1.30
1.30
1.28
1.28
1.25
1.28
1.25
1.25
1.25
1.23
1.23
1.23
1.23
1.20
1.20
1.20
1.18
1.18
1.18
1.18
1.15
1.15
1.15
1.15
1.13
1.13
1.13
1.10
1.10
1.10
1.10
1.08
1.08
1.08
1.08
1.05
1.05
1.05
1.03
1.03
1.03
1.00
1.00
1.00
1.00
5.0
5.2
5.4
5.6
5.8
132

Table 23/9

Ip
0.40
0.42
0.44
0.46
0.48
0.50
0.52
0.54
0.56
0.58
Ip
2.0
2.2
2.4
2.6
2.8
1.55
1.43
1.33
1.25
1.20
1.48
1.38
1.28
1.20
1.15
1.40
1.30
1.15
1.10
1.10
1.33
1.23
1.15
1.10
1.05
1.25
1.18
1.10
1.05
1.00
1.20
1.13
1.05
1.00
0.98
1.18
1.10
1.05
1.00
0.95
1.08
1.00
0.95
0.90
0.88
1.00
0.95
0.90
0.88
0.88
0.95
0.90
0.85
0.83
0.80
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
1.15
1.13
1.10
1.08
1.05
1.10
1.08
1.05
1.03
1.00
1.08
1.03
1.00
1.00
1.00
1.03
1.00
0.98
0.95
0.93
0.98
0.95
0.93
0.93
0.90
0.95
0.90
0.90
0.88
0.85
0.93
0.90
0.90
0.88
0.85
0.85
0.83
0.83
0.80
0.80
0.83
0.80
0.78
0.78
0.75
0.78
0.75
0.75
0.73
0.73
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
1.03
1.03
1.00
1.00
1.00
1.00
0.98
0.98
0.98
0.95
0.95
0.95
0.93
0.93
0.93
0.93
0.90
0.90
0.90
0.90
0.88
0.88
0.88
0.85
0.85
0.85
0.85
0.83
0.83
0.83
0.85
0.85
0.83
0.83
0.83
0.78
0.78
0.78
0.75
0.75
0.75
0.73
0.73
0.73
0.73
0.70
0.70
0.70
0.70
0.68
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
0.98
0.98
0.98
0.98
0.98
0.95
0.95
0.95
0.93
0.93
0.93
0.90
0.90
0.90
0.90
0.88
0.88
0.88
0.88
0.88
0.85
0.85
0.85
0.83
0.83
0.83
0.80
0.80
0.80
0.80
0.83
0.80
0.80
0.80
0.80
0.75
0.75
0.75
0.75
0.75
0.73
0.70
0.70
0.70
0.70
0.68
0.68
0.68
0.68
0.68
5.0
5.2
5.4
5.6
5.8
Tables
133
Table 23/10

Ip
0.60
0.62
0.64
0.66
0.68
0.70
0.72
0.74
0.76
0.78
Ip
2.0
2.2
2.4
2.6
2.8
0.90
0.85
0.80
0.78
0.75
0.85
0.80
0.78
0.73
0.73
0.80
0.75
0.73
0.70
0.68
0.75
0.70
0.68
0.65
0.63
0.70
0.68
0.63
0.60
0.60
0.65
0.63
0.60
0.58
0.55
0.60
0.58
0.55
0.53
0.53
0.55
0.53
0.50
0.50
0.48
0.50
0.48
0.48
0.45
0.45
0.48
0.45
0.43
0.43
0.40
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
0.73
0.73
0.70
0.70
0.68
0.70
0.68
0.68
0.65
0.65
0.65
0.65
0.63
0.63
0.60
0.63
0.60
0.60
0.58
0.58
0.58
0.58
0.55
0.55
0.55
0.55
0.58
0.53
0.53
0.50
0.50
0.50
0.48
0.48
0.48
0.48
0.45
0.45
0.45
0.45
0.43
0.43
0.43
0.40
0.40
0.40
0.38
0.38
0.38
0.38
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
0.68
0.68
0.65
0.65
0.65
0.63
0.63
0.63
0.63
0.63
0.60
0.60
0.60
0.60
0.58
0.58
0.58
0.55
0.55
0.55
0.53
0.53
0.53
0.53
0.53
0.50
0.50
0.50
0.50
0.50
0.48
0.48
0.45
0.45
0.45
0.43
0.43
0.43
0.43
0.43
0.40
0.40
0.40
0.40
0.40
0.38
0.38
0.35
0.35
0.35
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
0.65
0.65
0.65
0.65
0.65
0.63
0.63
0.60
0.60
0.60
0.58
0.58
0.58
0.58
0.58
0.55
0.55
0.55
0.55
0.55
0.53
0.53
0.53
0.53
0.50
0.48
0.48
0.48
0.48
0.48
0.45
0.45
0.45
0.45
0.45
0.43
0.43
0.43
0.43
0.43
0.40
0.38
0.38
0.38
0.38
0.35
0.35
0.35
0.35
0.35
5.0
5.2
5.4
5.6
5.8
134

Table 23/11

Ip
0.80
0.82
0.84
0.86
0.88
0.90
0.92
0.94
0.96
0.98
Ip
2.0
2.2
2.4
2.6
2.8
0.43
0.40
0.38
0.38
0.38
0.38
0.35
0.35
0.33
0.33
0.33
0.33
0.30
0.30
0.30
0.30
0.28
0.28
0.25
0.25
0.25
0.23
0.23
0.23
0.23
0.20
0.20
0.18
0.18
0.18
0.18
0.15
0.15
0.15
0.15
0.13
0.13
0.13
0.10
0.10
0.08
0.08
0.08
0.08
0.08
0.05
0.05
0.05
0.03
0.03
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
0.35
0.35
0.35
0.35
0.33
0.33
0.33
0.30
0.30
0.30
0.28
0.28
0.28
0.28
0.28
0.25
0.25
0.25
0.23
0.23
0.20
0.20
0.20
0.20
0.20
0.18
0.18
0.18
0.18
0.18
0.15
0.15
0.13
0.13
0.13
0.10
0.10
0.10
0.10
0.10
0.08
0.08
0.08
0.08
0.08
0.03
0.03
0.03
0.03
0.03
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
0.33
0.33
0.33
0.33
0.33
0.30
0.30
0.30
0.30
0.30
0.28
0.28
0.25
0.25
0.25
0.23
0.23
0.23
0.23
0.23
0.20
0.20
0.20
0.20
0.20
0.18
0.18
0.18
0.18
0.15
0.13
0.13
0.13
0.13
0.13
0.10
0.10
0.10
0.10
0.10
0.08
0.08
0.08
0.08
0.08
0.03
0.03
0.03
0.03
0.03
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
0.33
0.33
0.33
0.33
0.33
0.30
0.30
0.30
0.30
0.28
0.25
0.25
0.25
0.25
0.25
0.23
0.23
0.23
0.23
0.23
0.20
0.20
0.20
0.20
0.20
0.15
0.15
0.15
0.15
0.15
0.13
0.13
0.13
0.13
0.13
0.10
0.10
0.10
0.10
0.10
0.08
0.08
0.08
0.08
0.08
0.03
0.03
0.03
0.03
0.03
5.0
5.2
5.4
5.6
5.8
Tables
135
Table 23/12
Ip RANGE 6.0 to 9.8

Ip
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
Ip
6.0
6.2
6.4
6.6
6.8
2.00
1.95
1.85
1.80
1.75
1.73
1.75
1.70
1.68
1.65
1.70
1.68
1.65
1.63
1.60
1.65
1.65
1.60
1.60
1.58
1.63
1.60
1.58
1.58
1.55
1.58
1.58
1.55
1.55
1.53
1.55
1.55
1.53
1.53
1.50
1.53
1.53
1.50
1.50
1.50
1.50
1.50
1.48
1.48
1.48
6.0
6.2
6.4
6.6
6.8
7.0
7.2
7.4
7.6
7.8
1.75
1.70
1.63
1.68
1.68
1.65
1.63
1.60
1.60
1.60
1.60
1.60
1.58
1.58
1.58
1.58
1.58
1.55
1.58
1.55
1.55
1.55
1.53
1.53
1.53
1.53
1.53
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.48
1.48
1.48
1.48
1.48
1.45
1.45
1.45
1.45
7.0
7.2
7.4
7.6
7.8
8.0
8.2
8.4
8.6
8.8
1.63
1.63
1.63
1.60
1.60
1.58
1.58
1.58
1.58
1.58
1.55
1.55
1.55
1.55
1.55
1.55
1.55
1.55
1.53
1.53
1.53
1.53
1.53
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.48
1.48
1.48
1.48
1.48
1.48
1.48
1.48
1.45
1.45
1.45
1.45
1.45
1.45
1.45
8.0
8.2
8.4
8.6
8.8
9.0
9.2
9.4
9.6
9.8
1.60
1.60
1.58
1.58
1.58
1.58
1.58
1.55
1.55
1.55
1.55
1.55
1.55
1.53
1.53
1.53
1.53
1.53
1.53
1.53
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.48
1.48
1.48
1.48
1.48
1.48
1.48
1.48
1.45
1.45
1.45
1.45
1.45
1.45
1.45
1.45
1.45
1.43
9.0
9.2
9.4
9.6
9.8
136

Table 23/13

Ip
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
Ip
6.0
6.2
6.4
6.6
6.8
1.48
1.48
1.48
1.45
1.45
1.48
1.45
1.45
1.45
1.43
1.45
1.45
1.43
1.43
1.43
1.43
1.43
1.40
1.40
1.40
1.40
1.40
1.40
1.38
1.38
1.40
1.38
1.38
1.38
1.38
1.38
1.38
1.35
1.35
1.35
1.35
1.35
1.35
1.33
1.33
1.33
1.33
1.33
1.33
1.30
1.33
1.30
1.30
1.30
1.30
6.0
6.2
6.4
6.6
6.8
7.0
7.2
7.4
7.6
7.8
1.45
1.45
1.45
1.45
1.45
1.43
1.43
1.43
1.43
1.43
1.43
1.40
1.40
1.40
1.40
1.40
1.40
1.38
1.38
1.38
1.38
1.38
1.35
1.38
1.38
1.38
1.35
1.35
1.35
1.35
1.35
1.35
1.33
1.33
1.33
1.33
1.33
1.33
1.33
1.33
1.30
1.30
1.30
1.30
1.30
1.30
1.30
1.28
1.28
1.28
7.0
7.2
7.4
7.6
7.8
8.0
8.2
8.4
8.6
8.8
1.43
1.43
1.43
1.43
1.43
1.43
1.43
1.43
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.38
1.38
1.38
1.38
1.38
1.38
1.38
1.38
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1.33
1.33
1.33
1.33
1.33
1.33
1.33
1.33
1.30
1.30
1.30
1.30
1.30
1.30
1.30
1.28
1.28
1.28
1.28
1.28
8.0
8.2
8.4
8.6
8.8
9.0
9.2
9.4
9.6
9.8
1.43
1.43
1.43
1.43
1.43
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.38
1.38
1.38
1.38
1.38
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1.33
1.33
1.33
1.33
1.33
1.30
1.30
1.30
1.30
1.30
1.30
1.30
1.30
1.30
1.30
1.28
1.28
1.28
1.28
1.28
9.0
9.2
9.4
9.6
9.8
Tables
137
Table 23/14

Ip
0.20
0.22
0.24
0.26
0.28
0.30
0.32
0.34
0.36
0.38
Ip
6.0
6.2
6.4
6.6
6.8
1.30
1.30
1.28
1.28
1.28
1.28
1.28
1.28
1.25
1.25
1.23
1.23
1.23
1.23
1.23
1.20
1.20
1.18
1.18
1.18
1.15
1.15
1.15
1.15
1.15
1.13
1.13
1.13
1.13
1.13
1.10
1.10
1.08
1.08
1.08
1.05
1.05
1.05
1.05
1.05
1.03
1.03
1.03
1.03
1.03
1.00
1.00
1.00
1.00
0.98
6.0
6.2
6.4
6.6
6.8
7.0
7.2
7.4
7.6
7.8
1.28
1.28
1.28
1.28
1.28
1.25
1.25
1.25
1.25
1.25
1.23
1.20
1.20
1.20
1.20
1.18
1.18
1.18
1.18
1.18
1.15
1.15
1.15
1.15
1.15
1.13
1.10
1.10
1.10
1.10
1.08
1.08
1.08
1.08
1.08
1.05
1.05
1.05
1.05
1.05
1.03
1.03
1.03
1.03
1.03
0.98
0.98
0.98
0.98
0.98
7.0
7.2
7.4
7.6
7.8
8.0
8.2
8.4
8.6
8.8
1.28
1.28
1.28
1.28
1.28
1.23
1.23
1.23
1.23
1.23
1.20
1.20
1.20
1.20
1.20
1.18
1.18
1.18
1.18
1.18
1.15
1.15
1.15
1.13
1.13
1.10
1.10
1.10
1.10
1.10
1.08
1.08
1.08
1.08
1.08
1.05
1.05
1.05
1.05
1.05
1.00
1.00
1.00
1.00
1.00
0.98
0.98
0.98
0.98
0.98
8.0
8.2
8.4
8.6
8.8
9.0
9.2
9.4
9.6
9.8
1.28
1.28
1.28
1.25
1.25
1.23
1.23
1.23
1.23
1.23
1.20
1.20
1.20
1.20
1.20
1.18
1.18
1.18
1.18
1.18
1.13
1.13
1.13
1.13
1.13
1.10
1.10
1.10
1.10
1.10
1.08
1.08
1.08
1.08
1.08
1.05
1.05
1.05
1.05
1.05
1.00
1.00
1.00
1.00
1.00
0.98
0.98
0.98
0.98
0.98
9.0
9.2
9.4
9.6
9.8
138

Table 23/15
Ip
0.40
0.42
0.44
0.46
0.48
0.50
0.52
0.54
0.56
0.58
Ip
6.0
6.2
6.4
6.6
6.8
0.98
0.95
0.95
0.95
0.95
0.93
0.93
0.93
0.93
0.93
0.90
0.90
0.90
0.90
0.90
0.88
0.88
0.85
0.85
0.85
0.83
0.83
0.83
0.83
0.83
0.80
0.80
0.80
0.80
0.80
0.78
0.78
0.78
0.78
0.75
0.73
0.73
0.73
0.73
0.73
0.70
0.70
0.70
0.70
0.70
0.68
0.68
0.68
0.68
0.68
6.0
6.2
6.4
6.6
6.8
7.0
7.2
7.4
7.6
7.8
0.95
0.95
0.95
0.95
0.95
0.93
0.93
0.93
0.93
0.93
0.90
0.90
0.88
0.88
0.88
0.85
0.85
0.85
0.85
0.85
0.83
0.83
0.83
0.83
0.83
0.80
0.80
0.80
0.80
0.80
0.75
0.75
0.75
0.75
0.75
0.73
0.73
0.73
0.73
0.73
0.70
0.70
0.70
0.70
0.70
0.68
0.68
0.68
0.68
0.68
7.0
7.2
7.4
7.6
7.8
8.0
8.2
8.4
8.6
8.8
0.95
0.95
0.95
0.95
0.95
0.93
0.93
0.93
0.93
0.93
0.88
0.88
0.88
0.88
0.88
0.85
0.85
0.85
0.85
0.85
0.83
0.83
0.83
0.83
0.83
0.80
0.80
0.80
0.80
0.80
0.75
0.75
0.75
0.75
0.75
0.73
0.73
0.73
0.73
0.73
0.70
0.70
0.70
0.70
0.70
0.68
0.68
0.68
0.65
0.65
8.0
8.2
8.4
8.6
8.8
9.0
9.2
9.4
9.6
9.8
0.95
0.95
0.95
0.95
0.95
0.93
0.93
0.93
0.93
0.93
0.88
0.88
0.88
0.88
0.88
0.85
0.85
0.85
0.85
0.85
0.83
0.83
0.83
0.83
0.83
0.80
0.80
0.80
0.80
0.80
0.75
0.75
0.75
0.75
0.75
0.73
0.73
0.73
0.73
0.73
0.70
0.70
0.70
0.70
0.70
0.65
0.65
0.65
0.65
0.65
9.0
9.2
9.4
9.6
9.8
Tables
139
Table 23/16
Ip
0.60
0.62
0.64
0.66
0.68
0.70
0.72
0.74
0.76
0.78
Ip
6.0
6.2
6.4
6.6
6.8
0.65
0.65
0.63
0.63
0.63
0.60
0.60
0.60
0.60
0.60
0.58
0.58
0.58
0.58
0.58
0.55
0.55
0.55
0.55
0.55
0.50
0.50
0.50
0.50
0.50
0.48
0.48
0.48
0.48
0.48
0.45
0.45
0.45
0.45
0.45
0.43
0.43
0.43
0.43
0.40
0.38
0.38
0.38
0.38
0.38
0.35
0.35
0.35
0.35
0.35
6.0
6.2
6.4
6.6
6.8
7.0
7.2
7.4
7.6
7.8
0.63
0.63
0.63
0.63
0.63
0.60
0.60
0.60
0.60
0.60
0.58
0.58
0.58
0.58
0.58
0.55
0.55
0.55
0.55
0.55
0.50
0.50
0.50
0.50
0.50
0.48
0.48
0.48
0.48
0.48
0.45
0.45
0.45
0.45
0.45
0.40
0.40
0.40
0.40
0.40
0.38
0.38
0.38
0.38
0.38
0.35
0.35
0.35
0.35
0.35
7.0
7.2
7.4
7.6
7.8
8.0
8.2
8.4
8.6
8.8
0.63
0.63
0.63
0.63
0.63
0.60
0.60
0.60
0.60
0.60
0.58
0.58
0.58
0.58
0.58
0.53
0.53
0.53
0.53
0.53
0.50
0.50
0.50
0.50
0.50
0.48
0.48
0.48
0.48
0.48
0.45
0.45
0.45
0.45
0.45
0.40
0.40
0.40
0.40
0.40
0.38
0.38
0.38
0.38
0.38
0.35
0.35
0.35
0.35
0.35
8.0
8.2
8.4
8.6
8.8
9.0
9.2
9.4
9.6
9.8
0.63
0.63
0.63
0.63
0.63
0.60
0.60
0.60
0.60
0.60
0.58
0.58
0.58
0.58
0.58
0.53
0.53
0.53
0.53
0.53
0.50
0.50
0.50
0.50
0.50
0.48
0.48
0.48
0.48
0.48
0.45
0.45
0.45
0.45
0.45
0.40
0.40
0.40
0.40
0.40
0.38
0.38
0.38
0.38
0.38
0.35
0.35
0.35
0.35
0.35
9.0
9.2
9.4
9.6
9.8
140

Table 23/17

Ip
0.80
0.82
0.84
0.86
0.88
0.90
0.92
0.94
0.96
0.98
Ip
6.0
6.2
6.4
6.6
6.8
0.33
0.33
0.33
0.33
0.33
0.28
0.28
0.28
0.28
0.28
0.25
0.25
0.25
0.25
0.25
0.23
0.23
0.23
0.23
0.23
0.20
0.20
0.20
0.20
0.20
0.15
0.15
0.15
0.15
0.15
0.13
0.13
0.13
0.13
0.13
0.10
0.10
0.10
0.10
0.10
0.08
0.08
0.08
0.08
0.08
0.03
0.03
0.03
0.03
0.03
6.0
6.2
6.4
6.6
6.8
7.0
7.2
7.4
7.6
7.8
0.33
0.33
0.33
0.33
0.33
0.28
0.28
0.28
0.28
0.28
0.25
0.25
0.25
0.25
0.25
0.23
0.23
0.23
0.23
0.23
0.20
0.20
0.20
0.20
0.20
0.15
0.15
0.15
0.15
0.15
0.13
0.13
0.13
0.13
0.13
0.10
0.10
0.10
0.10
0.10
0.08
0.08
0.08
0.08
0.08
0.03
0.03
0.03
0.03
0.03
7.0
7.2
7.4
7.6
7.8
8.0
8.2
8.4
8.6
8.8
0.33
0.33
0.33
0.33
0.33
0.28
0.28
0.28
0.28
0.28
0.25
0.25
0.25
0.25
0.25
0.23
0.23
0.23
0.23
0.23
0.20
0.20
0.20
0.20
0.20
0.15
0.15
0.15
0.15
0.15
0.13
0.13
0.13
0.13
0.13
0.10
0.10
0.10
0.10
0.10
0.08
0.08
0.08
0.08
0.08
0.03
0.03
0.03
0.03
0.03
8.0
8.2
8.4
8.6
8.8
9.0
9.2
9.4
9.6
9.8
0.33
0.33
0.33
0.33
0.33
0.28
0.28
0.28
0.28
0.28
0.25
0.25
0.25
0.25
0.25
0.23
0.23
0.23
0.23
0.23
0.20
0.20
0.20
0.20
0.20
0.15
0.15
0.15
0.15
0.15
0.13
0.13
0.13
0.13
0.13
0.10
0.10
0.10
0.10
0.10
0.08
0.08
0.08
0.08
0.08
0.03
0.03
0.03
0.03
0.03
9.0
9.2
9.4
9.6
9.8
Tables
141
Table 24. Corrosion rate (C/ ) as mm.y1 for mild steel from R.
Table 24/1
VALUES OF R @ T
(Range 6.0 to 6.9)
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
5
10
15
20
0.10
0.15
0.20
0.25
0.11
0.16
0.21
0.26
0.11
0.17
0.22
0.28
0.12
0.17
0.23
0.29
0.12
0.18
0.24
0.30
0.13
0.19
0.25
0.31
0.13
0.20
0.26
0.33
0.14
0.21
0.28
0.35
0.15
0.22
0.29
0.36
0.15
0.23
0.30
0.38
5
10
15
20
25
30
35
40
0.30
0.35
0.40
0.45
0.32
0.37
0.42
0.47
0.33
0.39
0.44
0.50
0.35
0.40
0.46
0.52
0.36
0.42
0.48
0.54
0.38
0.44
0.50
0.56
0.39
0.46
0.52
0.59
0.42
0.49
0.56
0.63
0.44
0.51
0.58
0.65
0.45
0.53
0.60
0.68
25
30
35
40
45
50
55
60
0.50
0.55
0.60
0.65
0.53
0.58
0.63
0.68
0.55
0.61
0.66
0.72
0.58
0.63
0.69
0.75
0.60
0.66
0.72
0.78
0.63
0.69
0.75
0.81
0.65
0.72
0.78
0.85
0.70
0.77
0.84
0.91
0.73
0.80
0.87
0.94
0.75
0.83
0.90
0.98
45
50
55
60
65
70
75
80
0.70
0.75
0.80
0.85
0.74
0.79
0.84
0.89
0.77
0.83
0.88
0.94
0.81
0.86
0.92
0.98
0.84
0.90
0.96
1.02
0.88
0.94
1.00
1.06
0.91
0.98
1.04
1.11
0.98
1.05
1.12
1.19
1.02
1.09
1.16
1.23
1.05
1.13
1.20
1.28
65
70
75
80
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
VALUES OF R @ T
(Range 6.0 to 6.9)
142

Table 24/2
VALUES OF R @ T
(Range 7.0 to 7.9)
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
5
10
15
20
0.16
0.24
0.32
0.40
0.17
0.25
0.33
0.41
0.18
0.26
0.35
0.44
0.18
0.27
0.36
0.45
0.19
0.29
0.36
0.48
0.20
0.30
0.40
0.50
0.21
0.32
0.42
0.53
0.22
0.33
0.44
0.55
0.23
0.35
0.46
0.58
0.24
0.36
0.48
0.60
5
10
15
20
25
30
35
40
0.48
0.56
0.64
0.72
0.50
0.58
0.66
0.74
0.53
0.61
0.70
0.79
0.54
0.63
0.72
0.81
0.57
0.67
0.76
0.86
0.60
0.70
0.80
0.90
0.63
0.74
0.84
0.95
0.66
0.77
0.88
0.99
0.69
0.81
0.92
1.04
0.72
0.84
0.96
1.08
25
30
35
40
45
50
55
60
0.80
0.88
0.96
1.04
0.83
0.91
0.99
1.07
0.88
0.96
1.05
1.14
0.90
0.99
1.08
1.17
0.95
1.05
1.14
1.24
1.00
1.10
1.20
1.30
1.05
1.16
1.26
1.37
1.10
1.21
1.32
1.43
1.15
1.27
1.38
1.50
1.20
1.32
1.44
1.56
45
50
55
60
65
70
75
80
1.12
1.20
1.28
1.36
1.16
1.24
1.32
1.40
1.23
1.31
1.40
1.49
1.26
1.35
1.44
1.53
1.33
1.43
1.52
1.62
1.40
1.50
1.60
1.70
1.47
1.58
1.68
1.79
1.54
1.65
1.76
1.87
1.61
1.73
1.84
1.96
1.66
1.80
1.92
2.04
65
70
75
80
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
VALUES OF R @ T
(Range 7.0 to 7.9)
Tables
143
Table 24/3
VALUES OF R @ T
(Range 8.0 to 8.9)
8.0
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
5
10
15
20
0.25
0.38
0.50
0.63
0.26
0.39
0.52
0.65
0.28
0.41
0.55
0.69
0.29
0.44
0.58
0.73
0.30
0.45
0.60
0.75
0.32
0.47
0.53
0.79
0.33
0.50
0.66
0.83
0.35
0.52
0.69
0.86
0.36
0.54
0.72
0.90
0.38
0.57
0.76
0.95
5
10
15
20
25
30
35
40
0.75
0.88
1.00
1.13
0.78
0.91
1.04
1.17
0.83
0.96
1.10
1.24
0.87
1.02
1.16
1.31
0.90
1.05
1.20
1.35
0.95
1.10
1.26
1.42
0.99
1.16
1.32
1.49
1.04
1.21
1.38
1.55
1.08
1.26
1.44
1.62
1.14
1.33
1.52
1.71
25
30
35
40
45
50
55
60
1.25
1.38
1.50
1.63
1.30
1.43
1.56
1.69
1.38
1.51
1.65
1.79
1.45
1.60
1.74
1.89
1.50
1.65
1.80
1.95
1.58
1.73
1.89
2.05
1.65
1.82
1.98
2.15
1.73
1.90
2.07
2.24
1.80
1.98
2.16
2.34
1.90
2.09
2.28
2.47
45
50
55
60
65
70
75
80
1.75
1.88
2.00
2.13
1.82
1.95
2.08
2.21
1.93
2.06
2.20
2.34
2.03
2.18
2.32
2.47
2.10
2.25
2.40
2.55
2.21
2.36
2.52
2.68
2.31
2.48
2.64
2.81
2.42
2.59
2.76
2.93
2.52
2.70
2.88
3.06
2.66
2.85
3.04
3.28
65
60
75
80
8.0
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
VALUES OF R @ T
(Range 8.0 to 8.9)
144

Table 24/4
VALUES OF R @ T
(Range 9.0 to 9.0)
9.0
9.1
9.2
9.3
9.4
9.5
9.6
9.7
9.8
9.9
5
10
15
20
0.40
0.58
0.79
0.99
0.42
0.62
0.83
1.04
0.44
0.65
0.87
1.09
0.46
0.68
0.91
1.14
0.48
0.71
0.95
1.19
0.50
0.75
1.00
1.25
0.53
0.79
1.05
1.30
0.55
0.83
1.10
1.38
0.58
0.86
1.15
1.44
0.60
0.90
1.20
1.50
5
10
15
20
25
30
35
40
1.19
1.38
1.58
1.78
1.25
1.45
1.66
1.87
1.31
1.52
1.74
1.96
1.37
1.59
1.82
2.05
1.43
1.66
1.90
2.14
1.50
1.75
2.00
2.25
1.58
1.84
2.10
2.36
1.65
1.93
2.20
2.48
1.73
2.01
2.30
2.59
1.80
2.10
2.40
2.70
25
30
35
40
45
50
55
60
1.98
2.17
2.37
2.57
2.08
2.28
2.49
2.70
2.18
2.39
2.61
2.83
2.28
2.50
2.73
2.96
2.38
2.61
2.85
3.09
2.50
2.75
3.00
3.25
2.63
2.89
3.15
3.41
2.75
3.03
3.30
3.58
2.88
3.16
3.45
3.74
3.00
3.30
3.60
3.90
45
50
55
60
65
70
75
80
2.77
2.96
3.16
3.36
2.91
3.11
3.32
3.53
3.05
3.26
3.48
3.70
3.19
3.41
3.64
3.87
3.33
3.56
3.80
4.04
3.50
3.75
4.00
4.25
3.68
3.94
4.20
4.46
3.85
4.12
4.40
4.68
4.03
4.31
4.60
4.89
4.20
4.50
4.80
5.10
65
70
75
80
9.0
9.1
9.2
9.3
9.4
9.5
9.6
9.7
9.8
9.9
VALUES OF R @ T
(Range 9.0 to 9.9)
Tables
145
Table 24/5
VALUES OF R @ T
(Range 10.0 to 10.9)
10.0
10.1
10.2
10.3
10.4
10.5
10.6
10.7
10.8
10.9
5
10
15
20
0.63
0.95
1.26
1.58
0.66
0.99
1.32
1.65
0.69
1.04
1.38
1.73
0.73
1.09
1.45
1.81
0.76
1.13
1.51
1.89
0.79
1.19
1.58
1.98
0.83
1.25
1.66
2.08
0.87
1.31
1.74
2.18
0.91
1.37
1.82
2.28
0.96
1.43
1.91
2.39
5
10
15
20
25
30
35
40
1.89
2.21
2.52
2.84
1.98
2.31
2.64
2.97
2.07
2.42
2.76
3.11
2.18
2.54
2.90
3.26
2.27
2.64
3.02
3.40
2.37
2.77
3.16
3.56
2.49
2.91
3.22
3.74
2.61
3.05
3.48
3.92
2.73
3.19
3.64
4.10
2.87
3.34
3.82
4.30
25
30
35
40
45
50
55
60
3.15
3.47
3.78
4.10
3.30
3.63
3.96
4.29
3.45
3.80
4.14
4.49
3.63
3.99
4.35
4.71
3.78
4.15
4.53
4.91
3.95
4.35
4.74
5.14
4.15
4.57
4.98
5.40
4.35
4.79
5.22
5.66
4.55
5.01
5.46
5.92
4.78
5.25
5.73
6.21
45
50
55
60
65
70
75
80
4.41
4.73
5.04
5.36
4.62
4.95
5.28
5.61
4.83
5.18
5.52
5.87
5.08
5.44
5.80
6.16
5.29
5.66
6.04
6.42
5.53
5.93
6.32
6.72
5.81
6.23
6.64
7.06
6.09
6.53
6.96
7.40
6.37
6.83
7.28
7.74
6.69
7.16
7.64
8.12
65
70
75
80
10.0
10.1
10.2
10.3
10.4
10.5
10.6
10.7
10.8
10.9
VALUES OF R @ T
(Range 10.0 to 10.9)
146

Table 24/6
VALUES OF R @ T
11.0
11.1
11.2
11.3
5
10
15
20
1.00
1.50
2.00
2.50
1.05
1.57
2.09
2.61
1.10
1.64
2.19
2.74
1.15
1.72
2.29
2.86
25
30
35
40
3.00
3.50
4.00
4.50
3.14
3.66
4.18
4.70
3.29
3.83
4.38
4.93
45
50
55
60
5.00
5.50
6.00
6.50
5.23
5.75
6.27
6.79
65
70
75
80
7.00
7.50
8.00
8.50
11.0
11.4
(Range 11.0 to 11.9)

11.5
11.6
11.7
11.8
11.9
1.20
1.80
2.40
3.00
1.26
1.88
2.51
3.14
1.32
1.97
2.63
3.29
1.38
2.06
2.75
3.44
1.44
2.16
2.88
3.60
1.51
2.27
3.02
3.78
5
10
15
20
3.44
4.01
4.58
5.15
3.60
4.20
4.80
5.40
3.77
4.39
5.02
5.65
3.95
4.60
5.26
5.92
4.13
4.81
5.50
6.19
4.32
5.04
5.76
6.48
4.53
5.29
6.04
6.80
25
30
35
40
5.48
6.02
6.57
7.12
5.73
6.30
6.87
7.44
6.00
6.60
7.20
7.80
6.28
6.90
7.53
8.16
6.58
7.23
7.89
8.55
6.88
7.56
8.25
8.94
7.20
7.92
8.64
9.36
7.55
8.31
9.06
9.52
45
50
55
60
7.32
7.84
8.36
8.88
7.67
8.21
8.76
9.31
8.02
8.59
9.16
9.73
8.40
9.00
9.60
10.20
8.79
9.41
10.04
10.67
9.21
9.86
10.52
11.18
9.63
10.31
11.00
11.69
10.08
10.80
11.52
12.24
10.57
11.33
12.08
12.84
65
70
75
80
11.1
11.2
11.3
11.4
11.5
11.6
11.7
11.8
11.9
VALUES OF R @ T
(Range 11.0 to 11.9)
Tables
147
Table 24/7
VALUES OF R @ T
T
12.0
12.1
12.2
12.3
12.4
(Range 12.0 to 12.9)

12.5
12.6
12.7
12.8
12.9
5
10
15
20
1.58
2.37
3.16
3.95
1.66
2.48
3.31
4.14
1.74
2.60
3.47
4.34
1.82
2.72
3.63
4.54
1.90
2.85
3.80
4.75
1.99
2.99
3.98
4.98
2.09
3.13
4.17
5.21
2.19
3.28
4.37
5.46
2.29
3.43
4.57
5.71
2.40
3.59
4.79
5.90
5
10
15
20
25
30
35
40
4.74
5.53
6.32
7.11
4.97
5.79
6.62
7.45
5.21
6.07
6.94
7.81
5.45
6.35
7.26
8.17
5.70
6.65
7.60
8.55
5.97
6.97
7.96
8.96
6.26
7.30
8.34
9.38
6.56
7.65
8.74
9.83
6.86
8.00
9.14
10.28
7.19
8.38
9.58
10.78
25
30
35
40
45
50
55
60
7.90
8.69
9.48
10.27
8.28
9.10
9.93
10.76
8.68
9.54
10.41
11.28
9.08
9.98
10.89
11.80
9.50
10.45
11.40
12.35
9.95
10.95
11.94
12.94
10.43
11.47
12.51
13.55
10.93
12.02
13.11
14.20
11.43
12.57
13.71
14.85
11.98
13.17
14.37
15.57
45
50
55
60
65
70
75
80
11.06
11.55
12.64
13.43
11.59
12.41
13.24
14.07
12.15
13.01
13.88
14.75
12.71
13.61
14.52
15.43
13.30
14.25
15.20
16.15
13.93
14.93
15.92
16.92
14.60
15.64
16.68
17.72
15.30
16.39
17.48
18.57
16.00
17.14
18.28
19.42
16.77
17.96
19.16
20.36
65
70
75
80
12.0
12.1
12.2
12.3
12.4
12.5
12.6
12.7
12.8
12.9
VALUES OF R @ T
(Range 12.0 to 12.9)
Table 25. Water analyses for Langelier index/corrosion relationship for mild steel.
No
Ca
Alk
DS
pH
pHS
@ 15C
(Eq. 6)
R
@ 15C
(Eq. 1)
I
@ 15C
(Eq. 5)
C/
@ 15C
(Eq. 92)
32
33
34
35
36
37
38
39
40
41
50
50
100
100
150
150
200
200
250
250
30
70
60
140
100
200
140
260
180
320
120
180
240
360
375
525
510
690
645
855
6.50
6.60
6.80
6.90
7.10
7.00
7.20
7.10
7.30
7.20
8.86
8.50
8.29
7.96
7.93
7.67
7.70
7.46
7.51
7.31
11.22
10.40
9.78
9.02
8.76
8.34
8.20
7.82
7.72
7.42
2.36
1.90
1.49
1.06
0.83
0.67
0.50
0.36
0.21
0.11
2.21
1.51
1.14
0.80
0.71
0.59
0.54
0.46
0.44
0.38
148

Table 26. Corrosion rate (C/) as mm.y1 for mild steel from I.
Table 26/1
(Range 0.1 to 1.0)
VALUES OF I @ T
T
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
5
10
15
20
0.20
0.29
0.39
0.49
0.21
0.32
0.42
0.53
0.23
0.34
0.45
0.56
0.25
0.37
0.49
0.61
0.27
0.40
0.53
0.66
0.29
0.43
0.57
0.71
0.31
0.46
0.61
0.76
0.33
0.50
0.66
0.83
0.36
0.54
0.72
0.90
0.39
0.58
0.77
0.96
5
10
15
20
25
30
35
40
0.59
0.68
0.78
0.88
0.63
0.74
0.84
0.95
0.68
0.79
0.90
1.01
0.74
0.86
0.98
1.10
0.80
0.93
1.06
1.19
0.86
1.00
1.14
1.28
0.92
1.07
1.22
1.37
0.99
1.16
1.32
1.49
1.08
1.26
1.44
1.62
1.16
1.35
1.54
1.73
25
30
35
40
45
50
55
60
0.98
1.07
1.17
1.27
1.05
1.10
1.26
1.37
1.13
1.24
1.35
1.46
1.23
1.35
1.47
1.59
1.33
1.46
1.59
1.72
1.43
1.57
1.71
1.85
1.53
1.68
1.83
1.98
1.65
1.82
1.98
2.15
1.80
1.98
2.16
2.34
1.93
2.12
2.31
2.50
45
50
55
60
65
70
75
80
1.37
1.46
1.56
1.66
1.47
1.58
1.68
1.79
1.58
1.60
1.80
1.91
1.72
1.84
1.96
2.08
1.86
1.99
2.12
2.25
2.00
2.14
2.28
2.42
2.14
2.29
2.44
2.59
2.31
2.48
2.64
2.81
2.52
2.70
2.88
3.06
2.70
2.89
3.08
3.27
65
70
75
80
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
VALUES OF I @ T
(Range 0.1 to 1.0)
Tables
149
Table 26/2
(Range 1.1 to 2.0)
VALUES OF I @ T
T
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
5
10
15
20
0.42
0.62
0.83
1.04
0.45
0.68
0.90
1.13
0.49
0.73
0.97
1.21
0.53
0.79
1.05
1.31
0.57
0.85
1.13
1.41
0.61
0.92
1.22
1.53
0.66
0.99
1.32
1.65
0.72
1.07
1.43
1.79
0.77
1.16
1.54
1.93
0.88
1.25
1.66
2.08
5
10
15
20
25
30
35
40
1.25
1.45
1.66
1.87
1.35
1.58
1.80
2.02
1.46
1.70
1.94
2.18
1.58
1.84
2.10
2.36
1.70
1.98
2.26
2.54
1.83
2.14
2.44
2.75
1.98
2.31
2.64
2.97
2.15
2.50
2.86
3.22
2.31
2.70
3.08
3.47
2.49
2.91
3.32
3.74
25
30
35
40
45
50
55
60
2.08
2.28
2.49
2.70
2.25
2.48
2.70
2.93
2.43
2.67
2.91
3.15
2.63
2.89
3.15
3.41
2.83
3.11
3.39
3.67
3.05
3.36
3.66
3.97
3.30
3.63
3.96
4.29
3.58
3.93
4.09
4.65
3.85
4.24
4.62
5.01
4.15
4.57
4.96
5.49
45
50
55
60
65
70
75
80
2.91
3.11
3.32
3.53
3.15
3.38
3.60
3.83
3.40
3.64
3.88
4.12
3.68
3.94
4.20
4.46
3.96
4.24
4.52
4.80
4.27
4.58
4.88
5.19
4.62
4.95
5.28
5.61
5.01
5.36
5.72
6.08
5.39
5.78
6.16
6.55
5.81
6.23
6.64
7.06
65
70
75
80
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
VALUES OF I @ T
(Range 1.1 to 2.0)
150

Table 26/3
VALUES OF I @ T
(Range 2.1 to 3.0)
2.1
2.2
2.3
2.4
2.5
2.6
5
10
15
20
0.90
1.35
1.80
2.25
0.97
1.45
1.93
2.41
1.05
1.57
2.09
2.61
1.13
1.70
2.26
2.83
1.22
1.83
2.44
3.05
1.32
1.98
2.64
3.30
25
30
35
40
2.70
3.15
3.60
4.05
2.90
3.38
3.88
4.34
3.14
3.66
4.18
4.70
3.39
3.96
4.52
5.09
3.66
4.27
4.88
5.49
45
50
55
60
4.50
4.95
5.40
5.85
4.83
5.31
5.79
6.27
5.23
5.75
6.27
6.79
5.65
6.22
6.78
7.35
65
70
75
80
6.30
6.75
7.20
7.65
6.76
7.24
7.72
8.20
7.32
7.84
8.36
8.88
2.1
2.2
2.3
2.8
2.9
3.0
1.43
2.14
2.85
3.56
1.54
2.30
3.07
3.84
1.66
2.49
3.32
4.15
1.79
2.69
3.58
4.48
5
10
15
20
3.96
4.62
5.28
5.94
4.28
4.99
5.70
6.41
4.61
5.37
6.14
6.91
4.98
5.81
6.64
7.47
5.37
6.27
7.16
8.06
25
30
35
40
6.10
6.71
7.32
7.93
6.60
7.26
7.92
8.58
7.13
7.84
8.55
9.26
7.68
8.44
9.21
9.98
8.30
9.13
9.96
10.79
8.95
9.85
10.74
11.64
45
50
55
60
7.91
8.48
9.04
9.61
8.54
9.15
9.76
10.37
9.24
9.90
10.56
11.22
9.98
10.69
11.40
12.11
10.75
11.51
12.28
13.05
11.62
12.45
13.28
14.11
12.53
13.42
14.32
15.22
65
70
75
80
2.4
2.5
2.6
2.7
2.8
2.9
3.0
VALUES OF I @ T
2.7
(Range 2.1 to 3.0)
Tables
151
Table 26/4
VALUES OF I @ T
(Range 3.1 to 4.0)
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
4.0
5
10
15
20
1.94
2.90
3.87
4.84
2.09
3.13
4.17
5.23
2.25
3.38
4.50
5.62
2.44
3.65
4.87
6.09
2.63
3.94
5.25
6.56
2.84
4.25
5.67
7.09
3.06
4.59
6.12
7.65
3.30
4.95
6.60
8.25
3.57
5.36
7.14
8.93
3.86
5.78
7.71
9.64
5
10
15
20
25
30
35
40
5.81
6.77
7.74
8.71
6.26
7.30
8.34
9.38
6.75
7.88
9.00
10.13
7.31
8.52
9.74
10.96
7.88
9.19
10.50
11.81
8.51
9.92
11.43
12.76
9.18
10.71
12.24
13.77
9.90
11.55
13.20
14.85
10.71
12.50
14.28
16.07
11.57
13.49
15.42
17.35
25
30
35
40
45
50
55
60
9.68
10.64
11.61
12.58
10.43
11.47
12.51
13.55
11.25
12.38
13.50
14.63
12.18
13.39
14.61
15.83
13.13
14.44
15.75
17.06
14.18
15.59
17.01
18.43
15.30
16.83
18.36
19.89
16.50
18.15
19.80
21.45
17.85
19.64
21.42
23.21
19.28
21.20
23.13
25.06
45
50
55
60
65
70
75
80
13.55
14.51
15.48
16.45
14.60
15.64
16.68
17.72
15.75
16.88
18.00
19.13
17.05
18.26
19.48
20.70
18.38
19.69
21.00
22.31
19.85
21.26
22.68
24.01
21.42
22.95
24.48
26.01
23.10
24.75
26.40
28.05
24.90
26.78
28.56
30.35
26.99
28.91
30.84
32.77
65
70
75
80
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
4.0
VALUES OF I @ T
(Range 3.1 to 4.0)
Table 27. Comparison between Ryznar and Langelier.

Table 27/1
T
pHS @ T
pH @ T
R@T
C/ from Table 24
I@T
C/ from Table 26
20
30
40
50
7.0
8.5
9.6
10.2
6.5
7.2
7.8
8.0
7.5
9.8
11.4
12.4
0.50
2.01
5.40
10.45
0.5
1.3
1.8
2.2
0.66
1.70
3.22
5.31
152

Table 27/2.
pHS
pH
7.5
7.8
8.0
7.3
7.0
7.0
7.5
8.0
6.5
6.0
0.5
0.3
0
0.8
1.0
8.0
8.1
8.0
8.1
8.0
Table 28. Water analyses for buffer capacity/corrosion relationship for mild steel.
No
Ca
Alk
DS
pH
pHS
@ 15C
(Eq. 6)
I
@ 15C
(Eq. 3)
C/
@ 15C
(Eq. 26)
Alkb
4.4.4
Alka
4.4.4
B
4.4.4
No
42
43
44
45
46
47
48
49
50
51
2
2
2
2
2
2
2
2
2
2
30
70
60
140
100
200
140
260
180
120
120
180
240
360
375
525
510
690
645
855
6.50
6.60
6.80
6.90
7.10
7.00
7.20
7.10
7.30
7.20
10.26
9.90
9.99
9.66
9.81
9.55
9.70
9.46
9.61
9.41
3.76
3.30
3.19
2.76
2.71
2.55
2.50
2.36
2.31
2.21
6.36
4.50
4.17
2.95
2.85
2.54
2.44
2.17
2.09
1.93
33
76
65
150
105
210
145
270
185
330
25
63
55
133
95
190
135
250
175
310
40
65
50
85
50
50
50
100
50
100
42
43
44
45
46
47
48
49
50
51
Tables
153
Table 29. Corrosion rate (C/) as mm.y1 for mild steel in base exchange waters from B/Alk.
Table 29/1
B/Alk @ T
(Range 0.1 to 1.0)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
5
10
15
20
0.70
1.05
1.40
1.75
0.90
1.35
1.80
2.25
1.10
1.65
2.20
2.75
1.30
1.95
2.60
3.25
1.50
2.25
3.00
3.75
1.70
2.55
3.40
4.25
1.90
2.85
3.80
4.75
2.10
3.15
4.20
5.25
2.30
3.45
4.60
5.75
2.50
3.75
5.00
6.25
5
10
15
20
25
30
35
40
2.10
2.45
2.80
3.15
2.70
3.15
3.60
4.05
3.30
3.85
4.40
4.95
3.90
4.55
5.20
5.85
4.50
5.25
6.00
6.75
5.10
5.95
6.80
7.65
5.70
6.65
7.60
8.55
6.30
7.35
8.40
9.45
6.90
8.05
9.20
10.35
7.50
8.75
10.00
11.25
25
30
35
40
45
50
55
60
3.50
3.85
4.20
4.55
4.50
4.95
5.40
5.85
5.50
6.05
6.60
7.15
6.50
7.15
7.80
8.45
7.50
8.25
9.00
9.75
8.50
9.35
10.20
11.05
9.50
10.45
11.40
12.35
10.50
11.55
12.60
13.65
11.50
12.65
13.80
14.95
12.50
13.75
15.00
16.25
45
50
55
60
65
70
75
80
4.90
5.25
5.60
5.95
6.30
6.75
7.20
7.65
7.70
8.25
8.80
9.35
9.10
9.75
10.40
11.05
10.50
11.25
12.00
12.75
11.90
12.75
13.60
14.45
13.30
14.25
15.20
16.15
14.70
15.75
16.80
17.85
16.10
17.25
18.40
19.55
17.50
18.75
20.00
21.25
65
70
75
80
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
B/Alk @ T
(Range 0.1 to 1.0)
154

Table 29/2
B/Alk @ T
(Range 1.1 to 2.0)
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
5
10
15
20
2.70
4.05
5.40
6.75
2.90
4.35
5.80
7.25
3.10
4.65
6.20
7.75
3.30
4.95
6.60
8.25
3.50
5.25
7.00
8.75
3.70
5.55
7.40
9.25
3.90
5.85
7.80
9.75
4.10
6.15
8.20
10.25
4.30
6.45
8.60
10.75
4.50
6.75
9.00
11.25
5
10
15
20
25
30
35
40
8.10
9.45
10.80
12.15
8.70
10.15
11.60
13.05
9.30
10.85
12.40
13.95
9.90
11.55
13.20
14.85
10.50
12.25
14.00
15.75
11.10
12.95
14.80
16.65
11.70
13.65
15.60
17.55
12.30
14.35
16.40
18.45
12.90
15.05
17.20
19.35
13.50
15.75
18.00
20.25
25
30
35
40
45
50
55
60
13.50
14.85
16.20
17.55
14.50
15.95
17.40
18.85
15.50
17.05
18.60
20.15
16.50
18.15
19.80
21.45
17.50
19.25
21.00
22.75
18.50
20.35
22.20
24.05
19.50
21.45
23.40
25.35
20.50
22.55
24.60
26.65
21.50
23.65
25.80
27.95
22.50
24.75
27.00
29.25
45
50
55
60
65
70
75
80
18.90
20.25
21.60
22.95
20.30
21.75
23.20
24.65
21.70
23.25
24.80
26.35
23.10
24.75
26.40
28.05
24.50
26.25
28.00
29.75
25.90
27.75
29.60
31.45
27.30
29.25
31.20
33.15
28.70
30.75
32.80
34.85
30.10
32.25
34.40
36.55
31.50
33.75
36.00
38.25
65
70
75
80
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
B/Alk @ T
(Range 1.1 to 2.0)
Tables
155
Table 29/3
B/Alk @ T
(Range 2.1 to 3.0)
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
5
10
15
20
4.70
7.05
9.40
11.75
4.90
7.35
9.80
12.25
5.10
7.65
10.20
12.75
5.30
7.95
10.60
13.25
5.50
8.25
11.00
13.75
5.70
8.55
11.40
14.25
5.90
8.85
11.80
14.75
6.10
9.15
12.20
15.25
6.30
9.45
12.60
15.75
6.50
9.75
13.00
16.25
5
10
15
20
25
30
35
40
14.10
16.45
18.80
21.15
14.70
17.15
19.60
22.05
15.30
17.85
20.40
22.95
15.90
18.55
21.20
23.85
16.50
19.25
22.00
24.75
17.10
19.95
22.80
25.65
17.70
20.15
23.60
26.55
18.30
21.35
24.40
27.45
18.90
22.05
25.20
28.35
19.50
22.75
26.00
29.25
25
30
35
40
45
50
55
60
23.50
25.85
28.20
30.35
24.50
26.95
29.40
31.85
25.50
28.05
30.60
33.15
26.50
29.15
31.80
34.45
27.50
30.25
33.00
35.75
28.50
31.35
34.20
37.05
29.50
32.45
35.40
38.35
30.50
33.55
36.60
39.65
31.30
34.65
37.80
40.95
32.50
35.75
39.00
42.25
45
50
55
60
65
70
75
80
32.90
33.25
37.60
39.95
34.30
36.75
39.20
41.65
35.70
38.25
40.80
43.35
37.10
39.75
42.40
45.05
38.50
41.25
44.00
46.75
39.90
42.75
45.60
48.45
41.30
44.25
47.20
50.15
42.70
45.75
48.80
52.85
44.10
47.25
50.40
53.55
45.50
48.75
52.00
55.25
65
70
75
80
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
B/Alk @ T
(Range 2.1 to 3.0)
Table 30. Dissolved oxygen (O2 mg/l) for

water in equilibrium with atmospheric air.
Temperature
(T C)
0
5
10
15
20
25
30
35
40
Dissolved Oxygen
(O2 mg/1)
14.16
12.37
10.89
9.61
8.82
8.09
7.50
7.00
6.54
156

Table 31. Values of vector 4 (V4) from (V3) and SO4
Table 31/1
VALUES OF (V3)
(Range 10.0 to 5.5)
SO4
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
SO4
10
28.80
28.73
28.67
28.60
28.54
28.47
28.41
28.34
28.27
28.21
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
31.07
33.43
35.83
38.26
40.70
43.16
45.62
48.08
50.55
53.03
55.51
57.99
60.47
62.95
65.44
67.92
70.41
72.90
75.39
31.01
33.38
35.79
38.22
40.67
43.12
45.48
48.05
50.53
53.00
55.48
57.96
60.44
62.93
65.41
67.90
70.39
72.88
75.37
30.96
33.34
35.75
38.18
40.63
43.09
45.56
48.03
50.50
52.98
55.46
57.94
60.42
62.91
65.39
67.88
70.37
72.86
75.35
30.91
33.29
35.71
38.15
40.60
43.06
45.52
48.00
50.47
52.95
55.43
57.91
60.40
62.88
65.37
67.86
70.35
72.84
75.33
30.85
33.24
35.76
38.11
40.56
43.03
45.49
47.97
50.44
52.92
55.40
57.89
60.37
62.86
65.35
67.84
70.33
72.82
75.31
30.80
33.20
36.63
38.07
40.53
42.99
45.46
47.94
50.42
52.90
55.38
57.86
60.35
62.84
65.33
67.82
70.31
72.80
75.29
30.74
33.15
35.68
38.03
40.49
42.96
45.43
47.91
50.39
52.87
55.35
57.84
60.33
62.82
65.31
67.80
70.29
72.78
75.27
30.69
33.10
35.54
37.99
40.46
42.93
45.40
47.88
50.36
52.84
55.35
57.82
60.30
62.79
65.28
67.77
70.27
72.76
75.25
30.64
33.06
35.50
37.96
40.42
42.89
45.37
47.85
50.33
52.82
55.30
57.79
60.28
62.77
65.26
67.75
70.25
72.74
75.23
30.59
33.01
35.36
37.92
40.39
42.86
45.34
47.82
50.30
52.79
55.28
57.77
60.26
62.75
65.24
67.73
70.23
72.72
75.21
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
SO4
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
SO4
VALUES OF (V3)
(Range 10.0 to 5.5)
Tables
157
Table 31/2
VALUES OF (V3)
(Range 5.0 to 0.5)
SO4
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
SO4
10
28.14
28.08
28.02
27.95
27.89
27.82
27.75
27.69
27.62
27.56
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
30.53
32.97
30.97
65.22
67.71
70.20
72.70
75.19
30.48
32.92
35.38
37.84
40.32
42.80
45.28
47.76
50.25
52.74
55.23
57.72
60.21
62.70
65.20
67.69
70.18
72.68
75.17
30.43
32.87
35.33
37.80
40.28
42.76
45.25
47.73
50.22
52.71
55.20
57.69
60.19
62.68
65.17
67.67
70.16
72.66
75.15
30.37
32.83
35.29
37.77
40.25
42.73
45.22
47.70
50.19
52.69
55.18
57.67
60.16
62.66
65.15
67.65
70.14
72.64
75.14
30.32
32.78
35.25
37.73
40.21
42.70
45.19
47.68
50.17
52.66
55.15
57.65
60.14
62.64
65.13
67.63
70.12
72.62
75.12
30.27
32.73
35.21
37.69
40.18
42.66
45.15
47.65
50.14
52.63
55.13
57.62
60.12
62.61
65.11
67.61
70.10
72.60
75.10
30.21
32.69
35.17
37.65
40.14
42.63
45.12
47.62
50.11
52.61
55.10
57.60
60.09
62.59
65.09
67.58
70.08
72.58
75.08
30.16
32.64
35.13
37.61
40.11
42.60
45.09
47.59
50.08
52.58
55.08
57.57
60.07
62.57
65.07
67.56
70.06
72.56
75.06
30.11
32.59
35.08
37.58
40.07
42.57
45.06
47.56
50.06
52.55
55.05
57.55
60.05
62.55
65.04
67.54
70.04
72.54
75.04
30.05
32.55
35.04
37.54
40.04
42.53
45.03
47.53
50.03
52.53
55.03
57.72
60.02
62.52
65.02
67.52
70.02
72.52
75.02
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
SO4
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
SO4
35.42
37.88
40.35
42.83
45.31
47.79
50.28
52.76
55.25
57.74
60.23
62.73
63.73
VALUES OF (V3)
(Range 5.0 to 0.5)
158

Table 31/3
(Range 0 to 5.0)
VALUES OF (V3)
SO4
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
SO4
10
27.50
27.44
27.37
27.31
27.24
27.18
27.11
27.05
26.98
26.92
26.85
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
30.00
32.50
35.00
37.50
40.00
42.50
45.00
47.50
50.00
52.50
55.00
57.50
60.00
62.50
65.00
67.50
70.00
72.50
75.00
29.95
32.45
34.96
37.46
39.96
42.47
44.97
47.47
49.97
52.47
54.97
57.48
59.98
62.48
64.98
67.48
69.98
72.48
74.98
29.89
32.41
34.92
37.42
39.93
42.43
44.94
47.44
47.94
52.45
54.95
57.45
59.95
62.45
64.96
67.46
69.96
72.46
74.96
29.84
32.36
34.87
37.39
39.89
42.40
44.91
47.41
49.92
52.42
54.92
57.43
59.93
62.43
64.93
67.44
69.94
72.44
74.94
29.79
32.31
34.83
37.35
39.86
42.37
44.88
47.38
49.89
52.39
54.90
57.40
59.91
62.41
64.91
67.42
69.92
72.42
74.92
74.42
29.73
32.27
34.79
37.31
39.82
42.34
44.84
47.35
49.86
52.37
54.87
57.38
59.88
62.39
64.89
67.39
69.90
72.40
74.90
29.68
32.22
34.75
37.27
39.79
42.30
44.81
47.32
49.83
52.34
54.85
57.35
59.86
62.36
64.87
67.37
69.88
72.38
74.88
29.63
32.17
34.71
37.23
39.75
42.27
44.78
47.30
49.81
52.31
84.82
57.33
59.84
62.34
64.85
67.35
69.86
72.36
74.86
29.57
32.13
34.67
37.20
39.72
42.24
44.75
47.27
49.78
52.29
54.80
57.32
59.81
62.32
64.83
67.33
69.84
72.34
74.85
29.52
32.08
34.62
37.16
39.68
42.20
44.72
47.24
49.75
52.26
54.77
57.28
59.79
62.30
64.80
67.31
69.82
72.32
74.83
29.47
32.03
34.58
37.12
39.65
42.17
44.69
47.21
49.72
52.24
54.75
57.26
59.77
62.27
64.78
67.29
69.80
72.30
74.81
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
SO4
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
SO4
VALUES OF (V3)
(Range 0 to 5.0)
Tables
159
Table 31/4
(Range 5.5 to 10.0)
VALUES OF (V3)
SO4
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
SO4
10
26.79
26.72
26.66
26.59
26.53
26.46
26.40
26.33
26.27
26.20
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
29.41
31.99
34.54
37.08
39.61
42.14
44.66
47.18
49.70
52.21
54.72
57.23
59.74
62.25
64.76
67.27
69.77
72.28
74.79
29.36
31.94
34.50
37.04
39.58
42.11
44.63
47.15
49.67
52.18
54.70
57.21
59.72
62.23
64.74
67.25
69.75
72.26
74.77
29.31
31.90
34.46
37.01
39.54
42.07
44.60
47.12
49.64
52.16
54.67
57.18
59.70
62.21
64.72
67.23
69.73
72.24
74.75
29.25
31.85
34.42
36.97
39.51
42.04
44.57
47.09
49.61
52.13
54.65
57.16
59.67
62.18
64.69
67.20
69.71
72.22
74.73
29.20
31.80
34.37
36.93
39.47
42.00
44.54
47.06
49.58
52.10
54.62
57.14
59.65
62.16
64.67
67.18
69.69
72.20
74.71
29.15
31.76
34.33
36.89
39.44
41.97
44.51
47.03
49.56
52.08
54.60
57.11
59.63
62.14
64.65
67.16
69.67
72.18
74.69
29.09
31.71
34.29
36.85
39.40
41.94
44.48
47.00
49.53
52.05
54.57
57.09
59.60
62.12
64.63
67.14
69.65
72.16
74.67
29.04
31.66
34.25
36.82
39.37
41.91
44.44
46.97
49.50
52.02
54.54
57.06
59.58
62.09
64.61
67.12
69.63
72.14
74.65
28.99
31.62
34.21
36.78
39.33
41.88
44.41
46.95
49.47
52.00
54.52
57.04
59.56
62.07
64.59
67.10
69.61
72.12
74.63
28.93
31.57
34.17
36.74
39.30
41.84
44.33
46.92
49.45
51.97
54.49
57.01
59.53
62.05
64.56
67.08
69.59
72.10
74.61
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
SO4
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
SO4
VALUES OF (V3)
(Range 5.5 to 10.0)
160

Table 32. Values of vector 5 (V5) from Cl.
Chloride
(Cl mg/1)
5
10
15
20
25
30
35
40
45
50
55
60
Vector 5 (V5)
0.32
1.47
3.59
6.75
11.01
16.43
23.06
30.91
40.04
51.46
62.21
75.30
Table 33. Values of vector 6 (V6) from O2.

Dissolved Oxygen
(mg/1)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Vector 6 (V6)
126.00
88.07
65.88
50.14
37.93
27.95
19.52
12.21
5.77
0.00
5.22
9.98
14.36
18.41
22.19
Tables
161
Table 34. Values of vector 8 (V8) from (V5) and (V7).

Table 34/1
VALUES OF (V7)
(Range 100 to 55)
(V5)
100
95
90
85
80
75
70
65
60
55
(V5)
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
1.82
1.81
1.81
1.80
1.79
1.79
1.78
1.78
1.77
1.76
1.75
1.74
1.72
1.71
1.69
1.68
1.67
1.64
1.61
1.59
1.56
1.54
1.43
1.33
1.25
1.15
1.11
1.05
1.00
0.95
0.91
0.87
0.83
1.73
1.72
1.71
1.71
1.70
1.70
1.69
1.69
1.68
1.67
1.67
1.65
1.64
1.62
1.61
1.60
1.58
1.56
1.53
1.51
1.48
1.46
1.36
1.27
1.19
1.12
1.06
1.00
0.95
0.90
0.86
0.83
0.79
1.64
1.63
1.62
1.62
1.61
1.61
1.60
1.60
1.59
1.58
1.58
1.57
1.55
1.54
1.53
1.51
1.50
1.48
1.45
1.43
1.41
1.38
1.29
1.20
1.13
1.06
1.00
0.95
0.90
0.86
0.82
0.78
0.75
1.55
1.54
1.53
1.53
1.52
1.52
1.51
1.51
1.50
1.50
1.49
1.48
1.47
1.45
1.44
1.43
1.42
1.39
1.37
1.35
1.33
1.31
1.21
1.13
1.06
1.00
0.94
0.89
0.85
0.81
0.77
0.74
0.71
1.45
1.45
1.44
1.44
1.43
1.43
1.42
1.42
1.41
1.41
1.40
1.39
1.38
1.37
1.36
1.34
1.33
1.31
1.29
1.27
1.25
1.23
1.14
1.07
1.00
0.94
0.89
0.84
0.80
0.76
0.73
0.70
0.67
1.36
1.36
1.35
1.35
1.34
1.34
1.33
1.33
1.33
1.32
1.32
1.30
1.29
1.28
1.27
1.26
1.25
1.23
1.21
1.19
1.17
1.15
1.07
1.00
0.94
0.88
0.83
0.79
0.75
0.71
0.68
0.65
0.63
1.27
1.27
1.26
1.26
1.25
1.25
1.25
1.25
1.24
1.23
1.23
1.22
1.21
1.20
1.19
1.18
1.17
1.15
1.13
1.11
1.09
1.08
1.00
0.93
0.88
0.82
0.78
0.74
0.70
0.75
0.67
0.64
0.61
0.58
1.18
1.18
1.17
1.17
1.16
1.16
1.16
1.16
1.15
1.14
1.14
1.13
1.12
1.11
1.10
1.09
1.08
1.07
1.05
1.03
1.02
1.00
0.93
0.87
0.81
0.76
0.72
0.68
0.65
0.70
0.62
0.59
0.56
0.54
1.09
1.09
1.08
1.08
1.08
1.07
1.07
1.07
1.06
1.06
1.05
1.04
1.03
1.03
1.02
1.01
1.00
0.98
0.97
0.95
0.94
0.92
0.86
0.80
0.75
0.71
0.67
0.63
0.60
0.65
0.57
0.55
0.52
0.50
1.00
1.00
0.99
0.99
0.99
0.98
0.98
0.98
0.97
0.97
0.96
0.96
0.95
0.94
0.93
0.92
0.92
0.90
0.89
0.87
0.86
0.85
0.79
0.73
0.69
0.65
0.61
0.58
0.55
0.60
0.52
0.50
0.48
0.46
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
(V5)
100
95
90
85
80
75
70
65
60
55
(V5)
VALUES OF (V7)
(Range 100 to 55)
162

Table 34/2
VALUES OF (V7)
(Range 50 to 0)
(V5)
50
45
40
35
30
25
20
15
10
(V5)
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
0.91
0.91
0.90
0.90
0.90
0.89
0.89
0.89
0.88
0.88
0.88
0.87
0.86
0.85
0.85
0.84
0.83
0.82
0.81
0.79
0.78
0.77
0.71
0.67
0.63
0.59
0.56
0.53
0.50
0.48
0.45
0.43
0.42
0.82
0.82
0.81
0.81
0.81
0.80
0.80
0.80
0.80
0.79
0.79
0.78
0.78
0.77
0.76
0.76
0.75
0.74
0.73
0.71
0.70
0.69
0.64
0.60
0.56
0.53
0.50
0.47
0.45
0.43
0.41
0.39
0.38
0.73
0.72
0.72
0.72
0.72
0.71
0.71
0.71
0.71
0.71
0.70
0.70
0.70
0.68
0.68
0.67
0.67
0.66
0.65
0.63
0.63
0.62
0.57
0.27
0.53
0.50
0.47
0.44
0.42
0.40
0.38
0.36
0.35
0.33
0.64
0.63
0.63
0.63
0.63
0.63
0.62
0.62
0.62
0.62
0.61
0.61
0.60
0.60
0.59
0.59
0.58
0.57
0.56
0.56
0.55
0.54
0.50
0.47
0.44
0.41
0.39
0.37
0.35
0.33
0.32
0.30
0.29
0.55
0.54
0.54
0.54
0.54
0.54
0.53
0.53
0.53
0.53
0.53
0.52
0.52
0.51
0.51
0.50
0.50
0.49
0.48
0.48
0.47
0.46
0.43
0.40
0.38
0.35
0.33
0.32
0.30
0.29
0.27
0.26
0.25
0.45
0.45
0.45
0.45
0.45
0.45
0.44
0.44
0.44
0.44
0.44
0.43
0.43
0.43
0.42
0.42
0.42
0.41
0.40
0.40
0.39
0.38
0.36
0.33
0.31
0.29
0.28
0.26
0.25
0.24
0.23
0.22
0.21
0.36
0.36
0.36
0.36
0.36
0.36
0.36
0.36
0.35
0.35
0.35
0.35
0.34
0.34
0.34
0.34
0.33
0.33
0.32
0.32
0.31
0.31
0.29
0.27
0.25
0.24
0.22
0.21
0.20
0.19
0.18
0.17
0.17
0.27
0.27
0.27
0.27
0.27
0.27
0.27
0.27
0.27
0.26
0.26
0.26
0.26
0.26
0.25
0.25
0.25
0.25
0.24
0.24
0.23
0.23
0.21
0.20
0.19
0.18
0.17
0.16
0.15
0.14
0.14
0.13
0.13
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.17
0.17
0.17
0.17
0.17
0.17
0.16
0.16
0.16
0.16
0.15
0.14
0.13
0.13
0.12
0.11
0.11
0.10
0.10
0.09
0.09
0.08
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.07
0.07
0.06
0.06
0.06
0.05
0.05
0.05
0.05
0.04
0.04
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
(V5)
50
45
40
35
30
25
20
15
10
(V5)
VALUES OF (V7)
(Range 50 to 0)
Tables
163
Table 34/3
VALUES OF (V7)
(Range 5 to 50)
(V5)
10
15
20
25
30
35
40
45
50
(V5)
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.09
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.07
0.07
0.06
0.06
0.06
0.05
0.05
0.05
0.05
0.04
0.04
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.18
0.17
0.17
0.17
0.17
0.17
0.17
0.16
0.16
0.16
0.16
0.15
0.14
0.13
0.13
0.12
0.11
0.11
0.10
0.10
0.09
0.09
0.08
0.27
0.27
0.27
0.27
0.27
0.27
0.27
0.27
0.27
0.26
0.26
0.26
0.26
0.26
0.25
0.25
0.25
0.25
0.24
0.24
0.23
0.23
0.21
0.20
0.19
0.18
0.17
0.16
0.15
0.14
0.14
0.13
0.13
0.36
0.36
0.36
0.36
0.36
0.36
0.36
0.36
0.35
0.35
0.35
0.35
0.34
0.34
0.34
0.34
0.33
0.33
0.32
0.32
0.31
0.31
0.29
0.27
0.25
0.24
0.22
0.21
0.20
0.19
0.18
0.17
0.17
0.45
0.45
0.45
0.45
0.45
0.45
0.44
0.44
0.44
0.44
0.44
0.43
0.43
0.43
0.42
0.42
0.42
0.41
0.40
0.40
0.39
0.38
0.36
0.33
0.31
0.29
0.28
0.26
0.25
0.24
0.23
0.22
0.21
0.55
0.54
0.54
0.54
0.54
0.54
0.53
0.53
0.53
0.53
0.53
0.52
0.51
0.51
0.51
0.50
0.50
0.49
0.48
0.48
0.47
0.46
0.43
0.40
0.38
0.35
0.33
0.32
0.30
0.29
0.27
0.26
0.25
0.64
0.63
0.63
0.63
0.63
0.63
0.62
0.62
0.62
0.62
0.61
0.61
0.60
0.60
0.59
0.59
0.59
0.57
0.56
0.56
0.55
0.54
0.50
0.47
0.44
0.41
0.39
0.37
0.35
0.33
0.32
0.30
0.29
0.73
0.72
0.72
0.72
0.72
0.71
0.71
0.71
0.71
0.70
0.70
0.70
0.69
0.68
0.68
0.67
0.67
0.66
0.65
0.63
0.63
0.62
0.57
0.53
0.50
0.47
0.44
0.42
0.40
0.38
0.36
0.35
0.33
0.82
0.82
0.81
0.81
0.81
0.80
0.80
0.80
0.80
0.79
0.79
0.78
0.78
0.77
0.76
0.76
0.75
0.74
0.73
0.71
0.70
0.69
0.64
0.60
0.56
0.53
0.50
0.47
0.45
0.43
0.41
0.39
0.38
0.91
0.91
0.90
0.90
0.90
0.89
0.89
0.89
0.88
0.88
0.88
0.87
0.86
0.85
0.85
0.84
0.83
0.82
0.81
0.79
0.78
0.77
0.71
0.67
0.63
0.59
0.56
0.53
0.50
0.48
0.45
0.43
0.42
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
(V5)
10
15
20
25
30
35
40
45
50
(V5)
VALUES OF (V7)
(Range 5 to 50)
164

Table 34/4
(Range 55 to 100)
VALUES OF (V7)
(V5)
55
60
65
70
75
80
85
90
85
100
(V5)
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
1.00
1.00
0.99
0.99
0.99
0.98
0.98
0.98
0.97
0.97
0.96
0.96
0.95
0.94
0.93
0.92
0.92
0.90
0.89
0.89
0.86
0.85
0.79
0.73
0.69
0.65
0.61
0.58
0.55
0.52
0.50
0.48
0.46
1.09
1.09
1.08
1.08
1.08
1.07
1.07
1.07
1.06
1.06
1.05
1.04
1.03
1.03
1.02
1.01
1.00
0.98
0.97
0.85
0.94
0.92
0.86
0.80
0.75
0.71
0.67
0.63
0.60
0.57
0.55
0.52
0.50
1.18
1.18
1.17
1.17
1.16
1.16
1.16
1.16
1.15
1.14
1.14
1.13
1.12
1.11
1.10
1.09
1.08
1.07
1.05
1.03
1.02
1.00
0.93
0.87
0.81
0.76
0.72
0.68
0.65
0.62
0.59
0.57
0.54
1.27
1.27
1.26
1.26
1.25
1.25
1.25
1.25
1.24
1.23
1.23
1.22
1.21
1.20
1.19
1.18
1.17
1.15
1.13
1.11
1.09
1.08
1.00
0.93
0.88
0.82
0.78
0.74
0.70
0.67
0.64
0.61
0.58
1.36
1.36
1.35
1.35
1.34
1.34
1.33
1.33
1.33
1.32
1.32
1.30
1.29
1.28
1.27
1.26
1.25
1.23
1.21
1.19
1.17
1.15
1.07
1.00
0.94
0.88
0.83
0.79
0.75
0.71
0.68
0.65
0.63
1.45
1.45
1.44
1.44
1.43
1.43
1.42
1.42
1.41
1.41
1.40
1.39
1.38
1.37
1.36
1.34
1.33
1.31
1.29
1.27
1.25
1.23
1.14
1.07
1.00
0.94
0.89
0.84
0.80
0.76
0.73
0.70
0.67
1.54
1.54
1.53
1.53
1.52
1.52
1.51
1.51
1.50
1.50
1.49
1.48
1.47
1.45
1.44
1.43
1.42
1.39
1.37
1.35
1.33
1.31
1.21
1.13
1.06
1.00
0.94
0.89
0.85
0.81
0.77
0.74
0.71
1.64
1.63
1.62
1.62
1.61
1.61
1.60
1.60
1.59
1.58
1.58
1.57
1.55
1.54
1.53
1.51
1.50
1.48
1.45
1.43
1.41
1.38
1.29
1.20
1.13
1.06
1.00
0.95
0.90
0.86
0.82
0.78
0.75
1.73
1.72
1.71
1.71
1.70
1.70
1.69
1.69
1.68
1.67
1.67
1.65
1.64
1.62
1.61
1.60
1.58
1.56
1.53
1.50
1.48
1.46
1.36
1.27
1.19
1.12
1.06
1.00
0.95
0.90
0.86
0.83
0.79
1.82
1.81
1.81
1.80
1.79
1.79
1.78
1.78
1.77
1.76
1.75
1.74
1.72
1.71
1.69
1.68
1.67
1.64
1.61
1.59
1.56
1.54
1.43
1.33
1.25
1.18
1.11
1.05
1.00
0.95
0.91
0.87
0.83
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
(V5)
55
60
65
70
75
80
85
90
85
100
(V5)
VALUES OF (V7)
(Range 55 to 100)
Tables
Table 35. Values of vector 9 (V9) from (V6) and (V8).
Table 35/1
VALUES OF (V8)
(Rangel 1.85 to 1.40)
(V6)
1.85
1.80
1.75
1.70
1.65
1.60
1.55
1.50
1.45
1.40
(V6)
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
111
113
116
118
121
123
126
128
131
133
136
138
141
143
146
148
109
111
114
116
119
121
122
126
129
132
134
137
139
142
144
147
107
109
112
115
117
120
121
125
127
130
133
135
138
140
143
145
148
105
107
110
113
115
118
119
123
126
128
131
134
136
139
141
144
147
103
105
108
111
113
116
117
121
123
126
129
132
135
137
140
143
145
148
101
103
106
109
111
114
115
120
122
125
128
130
133
136
138
141
144
146
99
101
104
107
109
112
113
118
120
123
126
129
131
134
137
139
142
145
148
96
99
102
105
107
110
112
116
119
121
124
127
130
132
135
138
141
143
146
94
97
100
103
105
108
109
114
117
119
122
125
128
131
133
136
139
142
145
147
92
95
97
100
103
106
107
112
115
117
120
123
126
129
132
135
137
140
143
146
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
(V6)
1.85
1.45
1.40
(V6)
Values of (V9) in this area lead to very

high, positive, values of IL which fall
outside the original Lucey nomogram and
indicate conditions favourable to intense
pitting.
1.80
1.75
1.70
VALUES OF (V8)
1.65
1.60
1.55
1.50
(Rangel 1.85 to 1.40)
165
166

Table 35/2
VALUES OF (V8)
(Range 1.35 to 0.90)
(V6)
1.35
1.30
1.25
1.20
1.15
1.10
1.05
1.00
0.95
0.90
(V6)
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
89
92
95
98
101
103
107
110
113
115
118
121
124
127
130
133
136
139
141
144
147
87
90
93
96
99
102
105
107
110
113
116
119
122
125
128
131
134
137
140
143
146
84
87
90
93
96
99
102
105
108
111
114
117
120
123
126
129
132
135
138
141
144
147
82
85
88
91
94
97
100
103
106
109
112
115
118
121
124
127
130
133
136
139
142
145
148
79
82
85
88
91
94
97
101
104
107
110
113
116
119
122
125
128
131
134
138
141
144
147
77
79
82
86
88
92
95
98
101
104
107
111
114
117
120
123
126
129
133
136
139
142
145
148
73
76
79
83
86
89
92
96
99
102
105
108
111
115
118
121
124
127
131
134
137
140
143
147
70
73
77
80
83
86
90
93
96
99
103
106
109
112
116
118
122
125
129
132
135
138
142
145
148
67
70
74
77
80
84
87
90
93
97
100
103
106
110
113
117
120
123
126
130
132
136
140
143
146
64
67
70
74
77
81
84
88
92
94
97
101
104
107
111
114
118
121
124
128
131
134
138
141
144
148
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
(V96)
1.35
0.90
(V96)
Values of (V9) in this

Area lead to very high, positive,
Values of IL which fall outside the original
Lucey nomogram and indicate conditions favourable
To intense pitting.
1.30
1.25
1.20
VALUES OF (V8)
1.15
1.10
1.05
1.00
(Range 1.35 to 0.90)
0.95
Tables
Table 35/3
VALUES OF (V8)
(V6)
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
(V6)
0.85
0.60
0.55
0.50
0.45
0.40
(V6)
60
57
53
49
45
41
64
60
57
53
49
45
67
64
60
57
53
49
71
67
64
60
57
53
74
71
67
64
60
56
77
74
71
68
64
60
81
78
75
71
68
64
84
81
78
74
71
68
88
85
82
78
75
72
91
88
85
82
79
75
95
92
89
86
82
79
98
95
92
89
86
83
101
99
96
93
90
87
105
102
99
97
94
90
108
106 103
100
97
94
112
109 107
104
101
98
115
113 110
107
105
102
119
116 114
111
108
106
122
120 117
115
112
109
125
123 121
118
116
113
129
127 125
122
120
117
132
130 128
126
123
121
136
134 131
129
127
124
139
137 135
133
131
128
143
141 139
137
134
132
146
144 142
140
138
136
Values of
146
144
142
140
149
147
145
143
(V9) in this
area lead to very high
149
147
positive values of IL which fall outside the
original Lucey nomogram and indicate
conditions favourable to intense pitting.
37
41
45
49
53
56
60
64
70
72
75
80
83
87
91
95
99
103
107
110
114
118
122
126
130
135
137
141
145
149
33
37
41
49
48
53
56
60
64
68
72
76
80
84
88
92
96
100
104
107
111
115
119
123
127
131
135
139
143
147
28
32
36
40
24
48
52
56
60
64
68
72
76
80
84
88
92
96
100
104
108
113
117
121
125
129
133
136
141
145
23
27
31
36
40
44
48
52
56
60
64
68
73
77
81
85
89
93
97
101
105
110
114
118
122
126
130
134
138
142
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
149
147
125
0.45
0.40
(V6)
0.85
0.80
0.80
0.75
0.75
0.70
(Range 0.85 to 0.40)
0.70
VALUES OF (V8)
0.65
0.65
0.60
0.55
(Range 0.85 to 0.40)
0.50
167
168

Table 35/4
VALUES OF (V8)
(Range 0.35 to 0.00)
(V6)
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
(V6)
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
18
22
27
31
35
39
43
48
32
56
60
64
69
73
77
81
85
90
94
98
102
106
111
115
119
123
127
132
136
140
144
13
17
21
26
30
34
39
42
47
52
56
60
64
69
73
77
82
86
90
95
99
103
107
112
116
120
125
129
133
138
142
7
12
16
20
25
29
34
38
43
47
51
56
60
65
69
73
78
82
87
91
95
100
104
109
113
117
122
126
131
135
139
1
6
10
15
20
24
29
33
38
42
47
51
56
60
65
69
74
78
83
87
92
96
101
105
110
114
119
123
128
132
137
5
0
5
9
14
18
23
28
32
37
42
46
51
55
60
65
69
74
79
83
88
92
97
102
106
111
116
120
125
129
134
11
6
2
3
8
13
17
22
27
32
36
41
46
51
55
60
65
70
74
79
84
89
93
98
103
108
112
117
122
126
131
18
13
8
-3
2
7
11
16
21
26
31
36
41
45
50
55
60
65
70
75
80
84
89
94
99
104
109
114
118
123
128
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
(V6)
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
(V6)
VALUES OF (V8)
(Range 0.35 to 0.00)
Tables
169
Table 35/5
(Range 0.00 to 0.45)
VALUES OF (V8)
(V6)
0.00
0.05
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
33
27
22
17
12
7
2
3
9
14
19
24
29
34
40
46
50
55
60
65
70
75
81
86
92
96
101
106
111
116
122
(V6)
0.00
0.05
0.10 0.15 0.20

40
35
30
25
19
14
9
3
2
7
12
18
23
28
34
39
44
49
55
60
65
71
76
81
87
92
97
102
108
113
118
49
43
38
33
27
22
16
11
5
0
5
11
16
22
27
33
38
44
49
54
60
65
71
76
83
87
93
98
103
109
114
0.25
58
52
47
41
35
30
24
19
13
7
2
4
9
15
21
26
32
37
43
49
54
60
65
71
78
82
88
93
99
105
110
67
62
56
50
44
38
33
27
21
15
10
4
2
8
14
19
25
31
37
42
48
54
60
66
73
77
83
89
95
100
106
0.10 0.15 0.20
0.25
VALUES OF (V8)
0.30 0.35
0.40
0.45
(V6)
88
82
76
70
64
57
51
45
39
33
27
20
14
8
2
4
10
17
23
29
35
41
47
54
61
66
72
78
84
91
97
100
93
87
81
74
68
61
55
49
42
36
30
23
17
10
4
2
9
15
21
28
34
41
47
55
60
66
72
79
86
92
105
99
92
87
79
72
67
59
53
46
39
33
26
20
13
6
0
7
13
20
27
33
40
48
53
60
66
73
79
86
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
0.30 0.35
0.40
0.45
(V6)
77
71
66
60
54
48
42
37
30
24
18
12
6
0
6
12
18
24
30
36
42
48
54
60
67
72
78
84
90
96
102
(Range 0.00 to 0.45)
170

Table 35/6
(Range 0.50 to 0.95)
VALUES OF (V8)
(V6)
0.50 0.55
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
105
98
91
84
77
71
64
57
50
43
36
29
23
16
9
2
5
12
18
25
32
39
46
53
60
66
73
80
(V6)
0.50 0.55
0.60 0.65
0.70
0.75
0.80
0.85
0.90
0.95
(V6)
102
95
87 101
79 93
72 85
64 77
56 69
48 61
41 53
33 45
25 37
18 29
10 21
2 13
5
5
13
3
21
11
29
19
36
27
44
35
52
43
59
51
100
92
84
75
67
58
50
42
33
25
16
8
0
9
17
26
34
42
99
90
82
73
64
55
46
38
29
20
11
2
6
15
24
33
107
98
89
80
70
61
52
43
33
24
15
6
4
13
22
106
97
87
77
67
58
48
38
29
19
9
1
10
105
95
85
75
64
54
44
34
23
13
3
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
0.60 0.65 0.70
0.75
0.80
0.85
0.90
0.95
(V6)
Values of (V9) in this area lead to very high

negative values of IL which fall outside the
original Lucy nomogram and indicate
conditions favourable to non-pitting
104
97
90
83
76
68
61
54
47
40
33
26
19
12
5
3
10
17
24
31
38
45
52
60
67
74
103
96
88
81
74
66
59
51
44
37
29
22
14
14
77
0
8
15
22
30
37
45
52
59
67
VALUES OF (V8)
(Range 0.50 to 0.95)
Tables
171
Table 35/7
(Range 1.00 to 1.45)
VALUES OF (V8)
(V6)
1.00
1.05
1.10
1.15
1.20
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
104
93
83
72
61
50
39
28
17
103
92
80
68
57
45
34
102
89
77
65
52
100
87
74
98
(V6)
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
1.40
1.45
25
20
15
10
5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
Values of (V9) in this area lead to

very high negative values of IL which
fall outside the original Lucey nomogram
and indicate conditions favourable to
non-pitting.
VALUES OF (V8)
1.25
1.30
(V6)
1.35
(Range 1.00 to 1.45)
1.40
1.45
(V6)
172

Table 36. Values of Lucey index (IL) from (V9) and pH.
Table 36/1
VALUES OF (V9)
pH
150
148
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
pH
146
144
(Range 150 to 132)

142
140
138
136
134
132
pH
13.0
12.7
12.4
12.2
11.9
11.7
11.5
11.3
11.2
11.0
13.0
12.7
12.3
12.0
11.9
11.6
11.4
11.2
11.0
10.9
10.6
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
143
132
pH
High, positve
positivevalues
valuesof
ofIILLininthis
thisarea
areafall
fall
outside the original Lucey nomogram and
pitting.
150
148
12.9
12.9
12.8
12.6
13.0
12.8
12.6
12.5
12.3
12.9
12.7
12.5
12.3
12.2
12.0
12.9
12.6
12.4
12.2
12.0
11.9
11.7
13.0
12.7
12.5
12.2
12.0
11.8
11.6
11.5
11.3
146
144
142
140
138
136
VALUES OF (V9)
(Range 150 to 132)
Tables
Table 36/2
(Range 130 to 112)
VALUES OF (V9)
pH
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
pH
130
128
126
124
122
120
118
116
114
112
pH
12.6
12.0
11.6
11.2
10.9
10.6
10.3
10.1
9.8
9.6
9.4
9.2
9.1
8.9
12.3
11.7
11.3
10.9
10.6
10.3
10.0
9.8
9.5
9.3
9.1
8.9
8.8
8.6
12.8
12.0
11.4
11.0
10.6
10.3
10.0
9.7
9.5
9.2
9.0
8.8
8.6
8.5
8.3
12.5
11.7
11.1
10.7
10.3
10.0
9.7
9.4
9.2
8.9
8.7
8.5
8.3
8.2
8.0
12.1
11.3
10.7
10.3
9.9
9.6
9.3
9.0
8.8
8.5
8.3
8.1
7.9
7.8
7.6
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
120
118
116
114
112
pH
High, positive values of IL in thia area

intense pitting.
12.7
12.4
12.1
11.8
11.6
11.3
11.1
10.9
10.7
10.6
10.4
12.8
12.4
12.1
11.8
11.5
11.3
11.0
10.8
10.6
10.4
10.3
10.1
12.9
12.5
12.1
11.8
11.5
11.2
11.0
10.7
10.5
10.3
10.1
10.0
9.8
12.6
12.2
11.8
11.5
11.2
10.9
10.7
10.4
10.2
10.0
9.8
9.7
9.5
12.9
12.3
11.9
11.5
11.2
10.9
10.6
10.4
10.1
9.9
9.7
9.5
9.4
9.2
130
128
126
124
122
VALUES OF (V9)
(Range 130 to 112)
173
174

Table 36/3
(Range 110 to 92)
VALUES OF (V9)
pH
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
pH
110
108
106
104
102
100
98
96
94
92
pH
11.5
10.7
10.1
9.7
9.3
9.0
8.7
8.4
8.2
7.9
7.7
7.5
7.3
7.2
7.0
11.2
10.4
9.8
9.4
9.0
8.7
8.4
8.1
7.9
7.6
7.4
7.2
7.0
6.9
6.7
10.9
10.1
9.5
9.1
8.7
8.4
8.1
7.8
7.6
7.3
7.1
6.9
6.7
6.6
6.4
10.6
9.8
9.2
8.8
8.4
8.1
7.8
7.5
7.3
7.0
6.8
6.6
6.4
6.3
6.1
10.3
9.5
8.9
8.5
8.1
7.8
7.5
7.2
7.0
6.7
6.5
6.3
6.1
6.0
5.8
10.0
9.2
8.6
8.2
7.8
7.5
7.2
6.9
6.7
6.4
6.2
6.0
5.8
5.7
5.5
12.8
9.7
8.9
8.3
7.9
7.5
7.2
6.9
6.6
6.4
6.1
5.9
5.7
5.5
5.4
5.2
12.5
9.4
8.6
8.0
7.6
7.2
6.9
6.6
6.3
6.1
5.8
5.6
5.4
5.2
5.1
4.9
12.2
9.1
8.3
7.7
7.3
6.9
6.6
6.3
6.0
5.8
5.5
5.3
5.1
4.9
4.8
4.6
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
108
106
104
102
100
98
96
94
92
pH

intense pitting.
11.8
11.0
10.4
10.0
9.6
9.3
9.0
8.7
8.5
8.2
8.0
7.8
7.6
7.5
7.3
110
VALUES OF (V9)
(Range 110 to 92)
Tables
Table 36/4
(Range 110 to 92)
VALUES OF (V9)
pH
90
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0 11.9
7.1 8.8
7.2 8.0
7.3 7.4
7.4 7.0
7.5 6.6
7.6 6.3
7.7 6.0
7.8 5.7
7.9 5.5
8.0 5.2
8.1 5.0
8.2 4.8
8.3 4.6
8.4 4.5
8.5 4.3
pH
90
88
86
84
82
80
78
76
74
72
pH
12.5
9.4
6.3
5.5
4.9
4.5
4.1
3.8
3.5
3.2
3.0
2.7
2.5
2.3
2.1
2.0
1.8
13.0
12.2
9.1
6.0
5.2
4.6
4.2
3.8
3.5
3.2
2.9
2.7
2.4
2.2
2.0
1.8
1.7
1.5
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
74
72
pH

intense pitting.
11.6
8.5
7.7
7.1
6.7
6.3
6.0
5.7
5.4
5.2
4.9
4.7
4.5
4.3
4.2
4.0
11.2
8.1
7.3
6.7
6.3
5.9
5.6
5.3
5.0
4.8
4.5
4.3
4.1
3.9
3.8
3.6
10.9
7.8
7.0
6.4
6.0
5.6
5.3
5.0
4.7
4.5
4.2
4.0
3.8
3.6
3.5
3.3
10.6
7.5
6.7
6.1
5.7
5.3
5.0
4.7
4.4
4.2
3.9
3.7
3.5
3.3
3.2
3.0
10.3
7.2
6.4
5.8
5.4
5.0
4.7
4.4
4.1
3.9
3.6
3.4
3.2
3.0
2.9
2.7
10.0
6.9
6.1
5.5
5.1
4.7
4.4
4.1
3.8
3.6
3.3
3.1
2.9
2.7
2.6
2.4
12.8
9.7
6.6
5.8
5.2
4.8
4.4
4.1
3.8
3.5
3.3
3.0
2.8
2.6
2.4
2.3
2.1
88
86
84
82
80
78
76
VALUES OF (V9)
(Range 90 to 72)
175
176

Table 36/5
(Range 70 to 52)
VALUES OF (V9)
pH
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
pH
70
68
66
64
62
60
58

fall outside the original Lucey nomogram and
pitting.
13.0
12.7 12.4
11.9 11.6
8.5
83.8
8.8
5.7 5.4
4.9 4.6
4.3 4.0
3.9 3.6
3.5 3.2
3.2 2.9
2.9 2.6
2.6 2.3
2.4 2.1
2.1 1.8
1.9 1.6
1.7 1.4
1.5 1.2
1.4 1.1
1.2 0.9
70
68
12.7
12.1
11.3
8.2
5.1
4.3
3.7
3.3
2.9
2.6
2.3
2.0
1.8
1.5
1.3
1.1
0.9
0.8
0.6
12.8
12.4
11.8
11.0
7.9
4.8
3.9
3.4
3.0
2.6
2.3
2.0
1.7
1.5
1.2
1.0
0.8
0.6
0.5
0.3
12.8
12.4
12.0
11.4
10.6
7.5
4.4
3.6
3.0
2.6
2.2
1.9
1.6
1.3
1.1
0.8
0.6
0.4
0.2
0.1
0.1
12.8
12.5
12.1
11.7
11.1
10.3
7.2
4.1
3.3
2.7
2.3
1.9
1.6
1.3
1.0
0.8
0.5
0.3
0.1
0.1
0.2
0.4
66
64
62
60
VALUES OF (V9)
56
12.8
12.5
12.2
11.8
11.4
10.8
10.0
6.9
3.8
3.0
2.4
2.0
1.6
1.3
1.0
0.7
0.5
0.2
0.3
0
0.2
0.4
0.5
0.7
13.0
12.8
12.5
12.2
11.9
11.5
11.1
10.5
9.7
6.6
3.5
2.7
2.1
1.7
1.3
1.0
0.7
0.4
0.2
0.1
0.3
0.5
0.7
0.8
1.0
58
56
(Range 70 to 52)
54
52
pH
12.9
12.7
12.5
12.2
11.9
11.6
11.2
10.8
10.2
9.4
6.3
3.2
2.4
1.8
1.4
1.0
0.7
0.4
0.1
0.1
0.4
0.6
0.8
1.0
1.1
1.3
12.8
12.7
12.4
12.0
11.9
11.6
11.3
10.9
10.5
9.9
9.1
6.0
2.9
2.1
1.5
1.1
0.9
0.4
0.1
0.2
0.4
0.7
0.9
1.1
1.8
1.4
1.6
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
54
52
pH
Tables
Table 36/6
VALUES OF (V9)
pH
(Range 50 to 32)
50
48
46
44
42
40
38
36
34
32
pH
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
13.0
12.7
12.6
12.4
12.1
11.9
11.6
11.3
11.0
10.6
10.2
9.6
8.8
5.7
2.6
1.8
1.2
0.8
0.4
0.1
0.2
0.5
0.7
1.0
1.2
1.4
1.6
1.7
1.9
13.0
12.8
12.7
12.5
12.3
12.1
11.8
11.6
11.3
11.0
10.7
10.3
9.9
9.3
8.5
5.4
2.3
1.5
0.9
0.5
0.1
0.2
0.5
0.8
1.0
1.3
1.5
1.7
1.9
2.0
2.2
12.7
12.5
12.4
12.2
12.0
11.8
11.5
11.3
11.0
10.7
10.4
10.0
9.6
9.0
8.2
5.1
2.0
1.2
0.6
0.2
0.2
0.5
0.8
1.1
1.3
1.6
1.8
2.0
2.2
2.3
2.5
12.4
12.2
12.1
11.9
11.7
11.5
11.2
11.0
10.7
10.4
10.1
9.7
9.3
8.7
7.9
4.8
1.7
0.9
0.3
0.1
0.5
0.8
1.1
1.4
1.6
1.9
2.1
2.3
2.5
2.6
2.8
12.1
11.9
11.8
11.6
11.4
11.2
10.9
10.7
10.4
10.1
9.8
9.4
9.0
8.4
7.6
4.5
1.4
0.6
0
0.4
0.8
1.1
1.4
1.7
1.9
2.2
2.4
2.6
2.8
2.9
3.1
11.8
11.6
11.5
11.3
11.1
10.9
10.6
10.4
10.1
9.8
9.5
9.1
8.7
8.1
7.3
4.2
1.1
0.3
0.3
0.7
1.1
1.4
1.7
2.0
2.2
2.5
2.7
2.9
3.1
3.2
3.4
11.5
11.3
11.2
11.0
10.8
10.6
10.3
10.1
9.8
9.5
9.2
8.8
8.4
7.8
7.0
3.9
0.8
0
0.6
1.0
1.4
1.7
2.0
2.3
2.5
2.8
3.0
3.2
3.4
3.5
3.7
11.1
10.9
10.8
10.6
10.4
10.2
9.9
9.8
9.4
9.1
8.8
8.4
8.0
7.4
6.6
3.5
0.4
0.4
1.0
1.4
1.8
2.1
2.4
2.7
2.9
3.2
3.4
3.6
3.8
3.9
4.1
10.8
10.6
10.5
10.3
10.1
9.9
9.6
9.4
9.1
8.8
8.5
8.1
7.7
7.1
6.3
3.2
0.1
0.7
1.3
1.7
2.1
2.4
2.7
3.0
3.2
3.5
3.7
3.9
4.1
4.2
4.4
10.5
10.3
10.2
10.0
9.8
9.6
9.3
9.1
8.8
8.5
8.2
7.8
7.4
6.8
6.0
2.9
0.2
1.0
1.6
2.0
2.4
2.7
3.0
3.3
3.5
3.8
4.0
4.2
4.4
4.5
4.7
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
pH
50
48
46
44
42
40
38
36
34
32
pH
VALUES OF (V9)
(Range 50 to 32)
177
178

Table 36/7
VALUES OF (V9)
(Range 30 to 12)
pH
30
28
26
24
22
20
18
16
14
12
pH
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
10.2
10.0
9.9
9.7
9.5
9.3
9.0
8.8
8.5
8.2
7.9
7.5
7.1
6.5
5.7
2.6
0.5
1.3
1.9
2.3
2.7
3.0
3.3
3.6
3.8
4.1
4.3
4.5
4.7
4.8
5.0
9.9
9.7
9.6
9.4
9.2
9.0
8.7
8.5
8.2
7.9
7.6
7.2
6.8
6.2
5.4
2.3
0.8
1.6
2.2
2.6
3.0
3.3
3.6
3.9
4.1
4.4
4.6
4.8
5.0
5.1
5.3
9.6
9.4
9.3
9.1
8.9
8.7
8.4
8.2
7.9
7.6
7.3
6.9
6.5
5.9
5.1
2.0
1.1
1.9
2.5
2.9
3.3
3.6
3.9
4.2
4.4
4.7
4.9
5.1
5.3
5.4
5.6
9.3
9.1
9.0
8.8
8.6
8.4
8.1
7.9
7.6
7.3
7.0
6.6
6.2
5.6
4.8
1.7
1.4
2.2
2.8
3.2
3.6
3.9
4.2
4.5
4.7
5.0
5.2
5.4
5.6
5.7
5.9
9.0
8.8
8.7
8.5
8.3
8.1
7.8
7.6
7.3
7.0
6.7
6.3
5.9
5.3
4.5
1.4
1.7
2.5
3.1
3.5
3.9
4.2
4.5
4.8
5.0
5.3
5.5
5.7
5.9
6.0
6.2
8.7
8.5
8.4
8.2
8.0
7.8
7.5
7.3
7.0
6.7
6.4
6.0
5.6
5.0
4.2
1.1
2.0
2.8
3.4
3.8
4.2
4.5
4.8
5.1
5.3
5.6
5.8
6.0
6.2
6.3
6.5
8.4
8.2
8.1
7.9
7.7
7.5
7.2
7.0
6.7
6.4
6.1
5.7
5.3
4.7
3.9
0.8
2.3
3.1
3.7
4.1
4.5
4.8
5.1
5.4
5.6
5.9
6.2
6.3
6.5
6.6
6.8
8.1
7.9
7.8
7.6
7.4
7.2
6.9
6.7
6.4
6.1
5.8
5.4
5.0
4.4
3.6
0.5
2.6
3.4
4.0
4.4
4.8
5.1
5.4
5.7
5.9
6.2
6.4
6.6
6.8
6.9
7.1
7.8
7.6
7.5
7.3
7.1
6.9
6.6
6.4
6.1
5.8
5.5
5.1
4.7
4.1
3.3
0.2
2.9
3.7
4.3
4.7
5.1
5.4
5.7
6.0
6.2
6.5
6.7
6.9
7.1
7.2
7.4
7.4
7.2
7.1
6.9
6.7
6.5
6.2
6.0
5.7
5.4
5.1
4.7
4.3
3.7
2.0
0.2
3.3
4.1
4.7
5.4
5.5
5.8
6.1
6.4
6.6
6.9
7.1
7.3
7.5
7.6
7.8
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
pH
30
2.8
26
24
22
20
18
16
14
12
pH
VALUES OF (V9)
(Range 30 to 12)
Tables
Table 36/8
(Range 10 to 8)
VALUES OF (V9)
pH
10
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
7.1
6.9
6.8
6.6
6.4
6.2
5.9
5.7
5.4
5.1
4.8
4.4
4.0
3.4
2.6
0.5
3.6
4.4
5.0
5.4
5.8
6.1
6.4
6.7
6.9
7.2
7.4
7.6
7.8
7.9
8.1
6.8
6.6
6.5
6.3
6.1
5.9
5.6
5.4
5.1
4.8
4.5
4.1
3.7
3.1
2.3
0.8
3.9
4.7
5.3
5.1
5.7
6.1
6.4
6.7
7.0
7.2
7.5
7.7
7.9
8.1
8.2
8.4
6.5
6.3
6.2
6.0
5.8
5.6
5.3
5.1
4.8
4.5
4.2
3.8
3.4
2.8
2.0
1.1
4.2
5.0
5.6
6.0
6.4
6.7
7.0
7.3
7.5
7.8
8.0
8.2
8.4
8.5
8.7
6.2
6.0
5.9
5.7
5.5
5.3
5.0
4.8
4.5
4.2
3.9
3.5
3.1
2.5
1.7
1.4
4.5
5.3
5.9
6.3
6.7
7.0
7.3
7.6
7.8
8.1
8.3
8.5
8.7
8.8
9.0
5.9
5.7
5.6
5.4
5.2
5.0
4.7
4.5
4.2
3.9
3.6
3.2
2.8
2.2
1.4
1.7
4.8
5.6
6.2
6.6
7.0
7.3
7.6
7.9
8.1
8.4
8.6
8.8
9.0
9.1
9.3
5.6
5.4
5.3
5.1
4.9
4.7
4.4
4.2
3.9
3.6
3.3
2.9
2.5
1.9
1.1
2.0
5.1
5.9
6.5
6.9
7.3
7.6
7.9
8.2
8.4
8.7
8.9
9.1
9.3
9.4
9.6
pH
10
VALUES OF (V9)
pH
5.3
5.0
5.1
4.8
5.0
4.7
4.8
4.5
4.6
4.3
4.4
4.1
4.1
3.8
3.9
3.6
3.6
3.3
3.3
3.0
3.0
2.7
2.6
2.3
2.2
1.9
1.6
1.3
0.8
0.5
2.3 2.6
5.4 5.7
6.2 6.5
6.8 7.1
7.2 7.5
7.6 7.9
7.9 8.2
8.2 8.5
8.5 8.8
8.7 9.0
9.0 9.3
9.2 9.5
9.4 9.7
9.6 9.9
9.7 10.0
9.9 10.2
4.7
4.5
4.4
4.2
4.0
3.8
3.5
3.3
3.0
2.7
2.4
2.0
1.6
1.0
0.2
2.9
6.0
6.8
7.4
7.8
8.2
8.5
8.8
9.1
9.3
9.6
9.8
10.0
10.2
10.3
10.5
4.4
4.2
4.1
3.9
3.7
3.5
3.2
3.0
2.7
2.4
2.1
1.7
1.3
0.7
0.1
3.2
6.3
7.1
7.7
8.1
8.5
8.8
9.1
9.4
9.6
9.9
10.1
10.3
10.5
10.6
10.8
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
pH
(Range 10 to 8)
179
180

Table 36/9
(Range 10 to 28)
VALUES OF (V9)
pH
10
12
14
16
18
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
4.1
3.9
3.8
3.6
3.4
3.2
2.9
2.7
2.4
2.1
1.8
1.4
1.0
0.4
0.4
3.5
6.6
7.4
8.0
8.4
8.8
9.1
9.4
9.7
9.9
10.2
10.4
10.6
10.8
10.9
3.8
3.6
3.5
3.3
3.1
2.9
2.6
2.4
2.1
1.8
1.5
1.1
0.7
0.1
0.7
3.8
6.9
7.7
8.3
8.7
9.1
9.4
9.7
10.0
10.2
10.5
10.7
10.9
3.4
3.2
3.1
2.9
2.7
2.5
2.2
2.0
1.7
1.4
1.1
0.7
0.3
0.3
1.1
4.2
7.3
8.1
8.7
9.1
9.5
9.8
10.1
10.4
10.6
10.9
3.1
2.9
2.8
2.6
2.4
2.2
1.9
1.7
1.4
1.1
0.8
0.4
0
0.6
1.4
4.5
7.6
8.4
9.0
9.4
9.8
10.1
10.4
10.7
10.9
2.8
2.6
2.5
2.3
2.1
1.9
1.6
1.4
1.1
0.8
0.5
0.1
0.3
0.9
1.7
4.8
7.9
8.7
9.3
9.7
10.1
10.4
10.7
11.0
pH
10
12
14
16
20
22
24
26
28
pH
2.5
2.2
1.9
1.6
1.3
2.3
2.0
1.7
1.4
1.1
2.2
1.9
1.6
1.3
1.0
2.0
1.7
1.4
1.1
0.8
1.8
1.5
1.2
0.9
0.6
1.6
1.3
1.0
0.7
0.4
1.3
1.0
0.7
0.4
0.1
1.1
0.8
0.5
0.2 0.1
0.8
0.5
0.2 0.1 0.4
0.5
0.2 0.1 0.4 0.7
.2
0.1 0.4 0.7 1.0
0.2
0.2 0.5 0.8 1.1 1.4
0.6 0.9 1.2 1.5 1.8
1.2 1.5 1.8 2.1 2.4
2.0 2.3 2.6 2.9 3.2
5.1 5.4 5.7 6.0 6.3
8.2 8.5 8.8 9.1 9.4
9.0 9.3 9.6 9.9 10.2
9.6 9.9 10.2 10.5 10.8
10.0 10.3 10.6 10.9
10.4 10.7 11.0
10.7 11.0
11.0
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
High, negative values of IL in thia area

non-pitting.
18
VALUES OF (V9)
20
22
24
26
(Range 10 to 28)
28
pH
Tables
Table 36/10
(Range 30 to 48)
VALUES OF (V9)
48
pH
5.5
1.0
0.7
0.4
0.1 0.3 0.6 0.9 1.2 1.5 1.8
5.6
0.8
0.5
0.2 0.1 0.5 0.8 1.1 1.4 1.7 2.0
5.7
0.7
0.4
0.1 0.2 0.6 0.9 1.2 1.5 1.8 2.1
5.8
0.5
0.2 0.1 0.4 0.8 1.1 1.4 1.7 2.0 2.3
5.9
0.3
0 0.3 0.6 1.0 1.3 1.6 1.9 2.2 2.5
6.0
0.1 0.2 0.5 0.8 1.2 1.5 1.8 2.1 2.4 2.7
6.1 0.2 0.5 0.8 1.1 1.5 1.8 2.1 2.4 2.7 3.0
6.2 0.4 0.7 1.0 1.3 1.7 2.0 2.3 2.6 2.9 3.2
6.3 0.7 1.0 1.3 1.6 2.0 2.3 2.6 2.9 3.2 3.5
6.4 1.0 1.3 1.6 1.9 2.3 2.6 2.9 3.2 3.5 3.8
6.5 1.3 1.6 1.9 2.2 2.6 2.9 3.2 3.5 3.8 4.1
6.6 1.7 2.0 2.3 2.6 3.0 3.3 3.6 3.9 4.2 4.5
6.7 2.1 2.4 2.7 3.0 3.4 3.8 4.0 4.3 4.6 4.9
6.8 2.7 3.0 3.3 3.6 4.0 4.3 4.6 4.9 5.2 5.5
6.9 3.5 3.8 4.1 4.4 4.8 5.1 5.4 5.7 6.0 6.3
7.0 6.6 6.9 7.2 7.5 7.9 8.2 8.5 8.8 9.1 9.4
7.1 9.7 10.0 10.3 10.6 11.0
7.2 10.5 10.8
7.3
7.4
7.5
High, negative values of IL in thia area
7.6
7.7
7.8
non-pitting.
7.9
8.0
8.1
8.2
8.3
8.4
8.5
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
pH
pH
30
30
32
32
34
34
36
36
VALUES OF (V9)
38
38
40
40
42
42
44
44
46
46
(Range 30 to 48)
48
pH
181
182

Table 36/11
(Range 50 to 68)
VALUES OF (V9)
pH
50
52
54
56
58
60
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
2.1 2.4 2.7 3.0 3.3

2.3 2.6 2.9 3.2 3.5
2.4 2.7 3.0 3.3 3.6
2.6 2.9 3.2 3.5 3.8
2.8 3.1 3.4 3.7 4.0
3.0 3.3 3.6 3.9 4.2
3.3 3.6 3.9 4.2 4.5
3.5 3.8 4.1 4.4 4.7
3.8 4.1 4.4 4.7 5.0
4.1 4.4 4.7 5.0 5.3
4.4 4.7 5.0 5.3 5.6
4.8 5.1 5.4 5.7 6.0
5.2 5.5 5.8 6.1 6.4
5.8 6.1 6.4 6.7 7.0
6.7 6.9 7.2 7.5 7.8
9.7 10.0 10.3 10.6 10.9
3.6
3.8
3.9
4.1
4.3
4.5
4.8
5.0
5.3
5.6
5.9
6.3
6.7
7.3
8.1
pH
50
62
3.9
4.1
4.2
4.4
4.6
4.8
5.1
5.3
5.6
5.9
6.2
6.6
7.0
7.6
8.4
64
4.3
4.5
4.6
4.8
5.0
5.2
5.5
5.7
6.0
6.3
6.6
7.0
7.4
8.0
8.8
66
4.6
4.8
4.9
5.1
5.3
5.5
5.8
6.0
6.3
6.6
6.8
7.3
7.7
8.3
9.1
High, negative, values of IL in thia area

non-pitting.
52
54
56
VALUES OF (V9)
58
60
62
64
66
(Range 50 to 68)
68 pH
4.9
5.1
5.2
5.4
5.6
5.8
6.1
6.3
6.6
6.9
7.2
7.6
8.0
8.6
9.4
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
68 pH
Tables
Table 36/12
(Range 70 to 88)
VALUES OF (V9)
pH
70
72
74
76
78
80
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
5.2 5.5 5.8 6.1 6.4 6.7

5.4 5.7 6.0 6.3 6.6 6.9
5.5 5.8 6.1 6.4 6.7 7.0
5.7 6.0 6.3 6.6 6.9 7.2
5.9 6.2 6.5 6.8 7.1 7.4
6.1 6.4 6.7 7.0 7.3 7.6
6.4 6.7 7.0 7.3 7.6 7.9
6.6 6.9 7.2 7.5 7.8 8.1
6.9 7.2 7.5 7.8 8.1 8.4
7.2 7.5 7.8 8.1 8.4 8.7
7.5 7.8 8.1 8.4 8.7 9.0
7.9 8.2 8.5 8.8 9.1 9.4
8.3 8.6 8.9 9.2 9.5 9.8
8.9 9.2 9.5 9.8 10.1 10.4
9.7 10.0 10.3 10.6 10.9
pH
70
82
84
7.0 7.3
7.2 7.5
7.3 7.6
7.5 7.8
7.7 8.0
7.9 8.2
8.2 8.5
8.4 8.7
8.7 9.0
9.0 9.3
9.3 9.6
9.7 10.0
10.1 10.4
10.7 11.0
86
88
pH
7.6 8.0
7.8 8.2
7.9 8.3
8.1 8.5
8.3 8.7
8.5 8.9
8.8 9.2
9.0 9.4
9.3 9.7
9.6 10.0
10.0 10.3
10.3 10.7
10.7
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5

non-pitting.
72
74
76
78
VALUES OF (V9)
80
82
84
86
(Range 70 to 88)
88
pH
183
184

Table 36/13
(Range 90 to 108)
VALUES OF (V9)
pH
90
92
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
8.3
8.5
8.6
8.8
9.0
9.2
9.5
9.7
10.0
10.3
10.6
11.0
8.6
8.8
8.9
9.1
9.3
9.5
9.8
10.0
10.3
10.6
10.9
pH
90
94
96
98
100
102 104
106 108
pH
8.9
9.2 9.5
9.1 9.4 9.7
9.2 9.5 9.8
9.4 9.7 10.0
9.6 9.9 10.2
9.8 10.1 10.4
10.1 10.4 10.7
10.3 10.6 10.9
10.6 10.9
10.9
9.8
10.0
10.1
10.3
10.5
10.7
11.0
10.1
10.3
10.4
10.6
10.9
11.0
10.4 10.6 11.0

10.6 10.9
10.7 11.0
10.9
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5

non-pitting.
92
94
96
VALUES OF (V9)
98
100
102
104
106
(Range 90 to 108)
108
pH
Table 37. Examples of calculating Lucey index (IL).
ORIGINAL
LUCEY CASE NO:
10
14
16
47
pH
7.7
7.3
7.8
8.0
7.5
SULPHATE
mg/l SO4
190
61
99
58
18
SODIUM
mg/l Na
18
15
37
22
11
NITRATE
mg/l NO3
nil
37
28
37
37
CHLORIDE
mg/l Cl
22
23
42
37
22
OXYGEN
mg/l O2
7.5
9.4
7.0
14.0
7.2
(V1)
0.167 Na
0.167 18
3.01
0.167 15
2.51
0.167 37
6.18
0.167 22
3.67
0.167 11
1.84
For SO4 190

0.167 NO3
0.167 0
nil
For SO4 61
0.167 NO3
0.167 37
6.18
For SO4 99
0.167 NO3
0.167 28
4.68
For SO4 58
0.167 NO3
0.167 37
6.18
For SO4 18
0.1 NO3
0.1 37
3.7
(V2)
Tables
185
186
Table 37. (Continued)
10
14
16
47
3.01 0
3.01
2.51 6.18
3.67
6.18 4.68
1.5
3.67 6.18
2.51
1.84 3.7
1.86
(V4)
Table 31
Table 31/2
72.62
Table 31/3
39.75
Table 31/2
50.08
Table 31/3
39.82
Table 31/3
29.79
(V5)
Table 32
8.88
8.88
35.48
27.00
8.88
(V6)
Table 33
15.71
2.89
19.52
18.41
10.27
72.62 15.71
56.91
39.75 2.89
36.86
50.08 19.52
30.56
39.82 (18.41)
39.82 + 18.41
58.23
29.79 19.52
10.27
(V8)
Table 34
Table 34/1
0.90
Table 34/2
0.59
Table 34/2
0.33
Table 34/1
0.71
Table 34/2
0.16
(V9)
Table 35
Table 35/2
92
Table 35/3
62
Table 35/4
56
Table 35/3
55
Table 35/4
37
IL
Table 36/3
6.3
Pitting
Table 36/5
3.0
Pitting
Table 36/5
0.4
Slight Pitting
Table 36/5
0.3
Non Pitting
Table 36/6
1.6
Non Pitting
7.0
Pitting
3.0
Pitting
zero
Non Pitting
1.0
Non Pitting
3.0
Non Pitting
(V3)
(V1) (V2)
(V7)
(V4) (V6)
Table 36
Original Lucey
Nomogram
ORIGINAL
LUCEY CASE NO:
Tables
Table 38. Time-scales from values of (IL).
Table 38/1
TIME-SCALES (Years)
IL
THRESHOLD
AWARENESS
ESABLISHED
IL
0.2
0.4
0.6
0.8
1.0
6.3
5.7
5.0
4.5
4.6
35.7
32.0
28.7
25.9
23.3
361.7
257.0
196.0
156.2
128.1
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
3.5
3.1
2.7
2.3
2.0
21.1
19.0
17.2
15.5
14.0
107.4
91.4
78.7
68.5
60.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
1.7
1.5
1.2
1.0
0.8
12.7
11.5
10.3
9.3
8.4
53.0
47.0
14.8
37.4
33.5
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
0.7
0.5
0.4
0.3
0.2
7.5
6.8
6.0
5.4
4.8
30.0
27.0
24.4
22.0
19.9
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
0.1
0.1
4.3
3.8
3.3
2.9
2.5
17.9
16.2
14.6
13.2
12.0
4.2
4.4
4.6
4.8
5.0
2.2
1.9
1.6
1.4
1.1
10.8
9.7
8.8
7.9
7.1
5.2
5.4
5.6
5.8
6.0
1.0
0.8
0.6
0.5
0.4
6.3
5.7
5.0
4.5
4.0
6.2
6.4
6.6
6.8
7.0
5.2
5.4
5.6
5.8
6.0
Values in this
area are less
than 0.1 years
6.2
6.4
6.6
6.8
7.0
IL
THRESHOLD
AWARENESS
ESABLISHED
TIME-SCALES (Years)
IL
187
188

Table 38/2
TIME-SCALES (Years)
IL
THRESHOLD
AWARENESS
ESABLISHED
IL
0.3
0.2
0.1
0.1
3.5
3.1
2.7
2.3
2.1
7.2
7.4
7.6
7.8
8.0
8.2
8.4
8.6
8.8
9.0
1.7
1.5
1.2
1.0
0.8
8.2
8.4
8.6
8.8
9.0
9.2
9.4
9.6
9.8
10.0
0.7
0.5
0.4
0.3
0.2
9.2
9.4
9.6
9.8
10.0
10.2
10.4
10.6
10.8
11.0
0.1
0.1
10.2
10.4
10.6
10.8
11.0
7.2
7.4
7.6
7.8
8.0
Values in these areas are all less

than 0.1 years
11.2
11.4
11.6
11.8
12.0
11.2
11.4
11.6
11.8
12.0
12.2
12.4
12.6
12.8
13.0
12.2
12.4
12.6
12.8
13.0
IL
THRESHOLD
AWARENESS
ESABLISHED
TIME-SCALES (Years)
IL
Tables
Table 39. Water analyses for Tokyo corrosion experiments.
Tokyo Tap
Water
(ex.R.Tone)
Experimental Waters
A
pH
Total alkalinity (mg/l CaCO3)
Total hardness (mg/l CaCO3)
Calcium hardness (mg/l CaCO3)
Magnesium hardness (mg/l CaCO3)
Chloride (mg/l Cl )
Sulphate (mg/l SO42 )
Residual chlorine (mg/l Cl1 )
7.0
40.8
67.6
48.4
18.8
19.2
37.9
1
7.0
25.0
64.6
51.4
13.2
39.9
76.2
3
6.9
33.9
67.8
48.8
19.0
26.2
39.3
2
7.9
52.0
68.2
48.8
19.4
163.1
38.0
3
6.9
85.1
68.2
49.0
19.2
32.0
37.1
3
Bicarbonate : Sulphate
0.73
0.22
0.58
0.92
1.55
Ratio
mg/l CaCO3 mg/l Na2SO4
Table 40. Time-scales for copper pitting in hot systems.

Table 40/1
RESIDUAL CHLORINE mg/l Cl2

0.5
1.0
1.5
2.0
TIME (days) TIME (days) TIME (days) TIME (days)

pH
DS
INIT
FAIL INIT FAIL INIT FAIL INIT FAIL
DS
pH
5.5
20
40
60
80
100
150
200
250
300
350
400
450
500
62
100
132
160
188
248
302
352
400
444
486
528
568
362
584
771
934
1098
1148
1764
2056
2336
2593
2838
3083
3317
20
40
60
80
100
150
200
250
300
350
400
450
500
5.5
pH
DS
INIT
FAIL INIT FAIL INIT FAIL INIT FAIL
pH
DS
31
50
66
80
94
124
151
176
200
222
243
264
284
281
292
385
467
549
724
882
1028
1168
1296
1419
1542
1659
21 123
33 293
44 257
53 310
63 368
83 485
101 590
117 683
133 777
148 864
162 946
176 1028
189 1104
16
25
33
40
47
62
76
88
100
110
122
132
142
93
146
193
234
275
362
444
514
584
648
712
771
829

0.5
1.0
1.5
2.0
189
190

Table 40/2
0.5
1.0
1.5
2.0

pH
DS
INIT FAIL INIT FAIL INIT FAIL INIT FAIL
DS
pH
6.0
20
40
60
80
100
150
200
250
300
350
400
450
500
62
104
142
176
208
282
352
414
476
534
590
644
698
291
489
667
827
978
1325
1654
1940
2237
2510
2773
3027
3250
31
52
71
88
104
141
176
207
238
267
295
322
349
146
244
334
414
489
663
827
973
1119
1255
1387
1513
1640
21
35
47
59
69
94
117
138
159
178
197
215
233
99
165
221
277
324
442
550
649
747
837
926
1011
1095
16
26
36
44
52
71
88
104
119
134
148
161
175
75
122
169
207
244
334
414
489
559
630
696
752
823
20
40
60
80
100
150
200
250
300
350
400
450
500
6.0
6.5
20
40
60
80
100
150
200
250
300
350
400
450
500
62
112
156
196
236
328
416
500
580
658
734
810
882
221
399
555
698
840
1168
1481
1780
2065
2342
2613
2884
3140
31
56
78
98
118
164
208
250
290
329
367
405
441
110
199
278
349
420
584
740
890
1032
1171
1307
1442
1570
21
37
52
65
79
109
139
167
193
219
245
270
294
75
132
185
231
281
388
495
595
687
780
872
961
1047
16
28
39
49
59
82
104
125
145
165
184
203
221
57
97
139
174
210
292
370
445
516
587
655
723
797
20
40
60
80
100
150
200
250
300
350
400
450
500
6.5
pH
DS
INIT FAIL INIT FAIL INIT FAIL INIT FAIL
pH
DS

0.5
1.0
1.5
2.0
Tables
Table 40/3
RESIDUAL CHLORINE mg/1 Cl2
0.5
1.0
1.5
2.0

pH
DS
INIT FAIL
INIT FAIL INIT FAIL INIT FAIL
DS
pH
7.0
20
40
60
80
100
150
200
250
300
350
400
450
500
68
108
154
148
142
346
444
542
636
728
818
908
996
140
261
373
479
586
817
1074
1311
1539
1762
1980
2197
2410
29
54
77
99
121
173
222
271
318
364
409
454
498
70
131
186
240
293
419
537
656
770
881
990
1099
1205
19
36
51
66
81
115
148
181
212
243
273
303
332
46
87
123
160
196
278
358
438
513
588
661
733
803
15
27
39
50
61
87
111
136
159
182
205
227
249
36
65
94
121
148
211
269
329
385
440
496
532
603
20
40
60
80
100
150
200
250
300
350
400
450
500
7.0
7.5
20
40
60
80
100
150
200
250
300
350
400
450
500
50
96
140
184
278
334
436
538
640
738
838
936
1034
113
216
315
414
513
752
981
1210
1440
1661
1886
2106
2327
25
48
70
92
114
167
218
269
320
369
419
468
517
56
108
158
207
257
376
491
605
720
830
943
1053
1163
17
32
47
61
76
111
145
179
213
246
279
312
345
38
72
106
137
171
250
326
403
479
554
628
702
776
13
24
35
46
57
84
109
135
160
185
210
234
259
29
54
79
104
128
189
245
304
360
416
473
527
588
20
40
60
80
100
150
200
250
300
350
400
450
500
7.5
pH
DS
INIT FAIL
INIT FAIL INIT FAIL INIT FAIL DS
pH

0.5
1.0
1.5
2.0
RESIDUAL CHLORINE mg/1 Cl2
191
192

Table 40/4
0.5
1.0
1.5
2.0
TIME (days)
TIME (days)
TIME (days) TIME (days)

INIT FAIL INIT FAIL
DS
PH
pH
DS
INIT FAIL
INIT
FAIL
8.0
20
40
60
80
100
150
200
250
300
350
400
450
500
36
72
108
144
180
270
360
450
540
630
720
810
900
72
144
216
288
360
540
720
900
1080
1260
1440
1620
1800
18
36
54
72
90
135
180
225
270
315
360
405
450
36
72
108
144
180
270
360
450
540
630
720
810
900
12
24
36
48
60
90
120
150
180
210
240
270
300
600
24
48
72
96
120
180
240
300
360
420
480
540
600
300
9
18
27
36
45
68
90
118
135
158
180
203
225
600
18
36
54
72
90
136
180
226
270
316
360
406
450
225
20
40
60
80
100
150
200
250
300
350
400
450
500
8.0
8.5
20
40
60
80
100
150
200
250
300
350
400
450
500
14
32
48
66
82
128
174
220
268
316
366
414
464
25
56
84
116
144
224
305
385
469
553
641
725
812
7
16
24
33
41
64
87
110
134
158
183
207
232
12
28
42
58
72
112
152
193
235
277
320
362
406
5
11
16
22
27
43
58
73
89
105
122
138
155
9
19
28
39
47
75
102
128
156
184
214
242
271
4
8
12
17
21
32
44
55
67
79
92
104
116
7
14
21
30
37
56
77
96
117
138
161
182
203
20
40
60
80
100
150
200
250
300
350
400
450
500
8.5
pH
DS
INIT FAIL
INIT
FAIL
INIT FAIL INIT FAIL
DS
pH

0.5
1.0

1.5
2.0
Index
Index terms
Links
A
alloys
xiv
B
boilers
xiii
buffer capacity
xi
ix
65
73
calcium
xi
25
60
xii
27
62
ix
37
64
xiv
41
88
1
42
92
16
44
93
18
53
19
57
21
59
calcium carbonate
xi
xii
ix
xiv
16
18
19
21
25
27
41
45
48
50
51
53
60
calcium phosphate
xi
ix
xiv
37
41
42
44
45
48
calcium sulphate
xi
ix
xiv
10
27
35
37
carbonate
xi
xii
ix
xiv
16
18
19
21
25
27
41
45
48
50
51
53
60
chlorine
xi
94
chlorine residual
xi
94
96
97
cold systems
78
80
copper
xi
ix
xiv
77
78
87
97
corrosion
xi
71
ix
73
xiv
77
53
78
55
90
56
58
63
69
corrosion of mild steel
ix
53
xiv
11
14
28
D
deposition
193
194
Index terms
Links
E
Edwards
10
11
16
21
22
39
87
field
13
19
31
44
56
57
62
73
fouling
ix
31
xiv
32
1
35
14
37
16
41
21
44
23
51
27
53
38
39
41
40
41
60
61
error
F
28
60
G
Green & Holmes
H
heat exchangers
98
L
Langelier
xi
17
22
Langelier index
xi
17
22
60
Lucey
xi
77
89
90
96
Lucey index
xi
78
81
89
90
margin of
16
21
65
87
Mattsson
90
97
Mattsson parameters
92
93
97
mild steel
ix
65
xiv
74
53
organic
xiv
95
98
organic slimes
xiv
10
55
56
58
60
21
65
90
97
P
parameters
63
195
Index terms
Links
phosphate
xi
ix
xiv
37
41
42
44
93
97
pitting
xi
ix
78
79
83
84
90
propensity index
xi
ix
78
79
23
27
32
48
59
64
75
81
82
91
98
recirculating systems
23
32
33
48
81
98
Ryznar
xi
59
1
60
6
65
14
73
17
22
53
55
57
Ryznar index
xi
12
14
22
53
55
57
59
60
65
73
saturation
xi
41
ix
42
4
48
27
29
33
35
37
saturation index
xi
42
4
48
27
29
33
35
37
41
slimes
xiv
R
recirculating
steel
ix
xiv
53
55
58
60
63
65
74
sulphate
xi
82
xii
88
ix
92
xiv
10
27
28
37
80
systems
ix
xiii
xiv
23
32
33
37
87
48
95
56
59
70
77
78
80
81
84
95
13
19
31
44
57
62
73
78
80
82
84
86
T
time scales
U
Use in
V
Van Slyke concept
66
vectors
xii

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Published by

World Scientific Publishing Co. Pte. Ltd.

British Library Cataloguing-in-Publication Data

QUANTITATIVE FORECASTING OF PROBLEMS IN INDUSTRIAL WATER SYSTEMS

The operating problems most likely to be encountered in industrial

Thermodynamic activities, expressed as mol/l.

xii Quantitative Forecasting of Problems in Industrial Water Systems

Sulphate expressed as mg/l in terms of Na2SO4.

Quantitative Forecasting of Problems in Industrial Water Systems

other means, unless specifically mentioned in special cases. It is also assumed

1. Calcium Carbonate Fouling .....................................................

1.1 The Ryznar Index ..............................................................................

1.1.1 Origin of Ryznars Work ....................................................

1.1.2 Emergence of the Ryznar Index ........................................

1.1.3 Revised Evaluation of the Ryznar Index ............................

1.1.4 Experimental Errors ..........................................................

1.2 New Data ...........................................................................................

1.2.1 Use in the Field .................................................................

1.2.2 Margin of Error ..................................................................

1.3 The Langelier Index ..........................................................................

1.3.1 Use in the Field .................................................................

1.3.2 Margin of Error ..................................................................

1.4 Choice Between Langelier and Ryznar ............................................

1.5 The Special Case of Recirculating Systems ....................................

1.5.1 Closed Recirculating Systems ...........................................

1.5.2 Open Recirculating Systems .............................................

2. Calcium Sulphate Fouling ........................................................

2.1 Calcium Sulphate Saturation Index ..................................................

2.2 Calculating the Weight of Calcium Sulphate ....................................

This page has been reformatted by Knovel to provide easier navigation.

2.4 The Special Case of Recirculating Systems ....................................

3. Calcium Phosphate Fouling .....................................................

3.1 Calcium Phosphate Saturation Index ...............................................

3.2 Calculating the Weight of Calcium Phosphate .................................

3.3 Use in the Field .................................................................................

3.4 The Special Case of Recirculating Systems ....................................

4. Corrosion of Mild Steel .............................................................

4.1 The Ryznar Index ..............................................................................

4.1.1 Use in the Field .................................................................

4.1.2 The Special Case of the Recirculating System ..................

4.2 The Langelier Index ..........................................................................

4.2.1 Use in the Field .................................................................

4.2.2 The Special Case of the Recirculating System ..................

4.4 Buffer Capacity ..................................................................................

4.4.1 Description of Buffer Effect ...............................................

4.4.2 Definition of Buffer Capacity ..............................................

4.4.3 Water Analyses and Buffer Capacity .................................

4.4.4 Evaluation of Buffer Capacity ............................................

4.4.5 Buffer Capacity and Corrosion Rate ..................................

4.4.6 Use in the Field .................................................................

4.4.7 The Special Case of the Recirculating System ..................

5. Corrosion of Copper .................................................................

5.1 Cold Water Systems .........................................................................

5.1.1 The Lucey Index ...............................................................

5.1.2 An Alternative Approach ...................................................

5.1.3 Data Required ...................................................................

5.1.4 Effect of Concentration .....................................................

5.1.5 Calculating the Index ........................................................

5.1.6 Time Scale ........................................................................

This page has been reformatted by Knovel to provide easier navigation.

5.2 Hot Water Systems ...........................................................................

5.2.1 Data on Water Chemistry ..................................................