Desalination, 12 (1989) 275-292

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

215
Electrical Conductivity and Total Dissolved
Solids-What is Their Precise Relationship?
N.R.G. WALTON
Hydrogeochemical Engineer & R.O. Consultant, 25, Eric Lock Road, Shrewsbury SY3 OHQ
(U.K.), Tel.: 0743-723771
(Received J uly 25,1988)
SUMMARY
The ability of RO plants to consistently produce water within the usual 500
mg/l WHO guidelines is a major factor in determining the longer term success
of the plant, and is a principal criterion for guarantee and contractural obli-
gations. However, since total dissolved solids (TDS) is not easily measured,
except under controlled conditions in reputable laboratories, a common alter-
native method is to utilise the simple permeate electrical conductivity (EC)
reading and multiply by a standard correction factor (typically 0.7) to obtain
the required TDS result. This paper demonstrates the considerable problems,
both theoretical and practical, associated (but generally not appreciated) with
these apparently simple measurements and shows that just one simple linear
conversion factor cannot be suitable throughout the range of waters encoun-
tered in the desalination industry, but that several different K factors ranging
from 0.50 to 0.75 need to be used for increasingly saline waters. The apparent
simplicity of the TDS and EC measurements are shown to be illusory and much
care is needed before taking contractural actions based upon these results.
Keywords: desalination, reverse osmosis, distillate, permeate, water quality, quality measurement,
electrical conductivity, total dissolved solids, water chemistry.
I NTRODUCTI ON
Much confusion exists throughout the water industry over this very simple
but important question. I t may come as a surprise to some workers in the de-
salination industry to find that there is unfortunately no simple precise rela-
tionship between these two parameters although workers in every field of water
studies from physical chemistry through electrochemistry, hydrochemistry, soil
and irrigation science, hydrology, geochemistry to marine chemistry each claim
to have the best approximation.
What they are actually using is a tolerable empirical approximation which
appears to hold good within the range of ion concentrations and salinities that
OOll-9164/89/$03.50 0 1989 Elsevier Science Publishers B.V.
276
their particular subject deals with. Thus the theoretical chemists continue to
build on the pioneering works of the early physical chemists, Arrhenius, Ost-
wald, Debye and Hiickel, Onsager, Kohlrausche et al. from early in this century
using ideal solutions and infinite dilutions to formulate absolute definitions
for individual ion behaviors, whilst soil and irrigation scientists get more in-
volved with ionic strength effects due to their interest in the balance between
monovalent and divalent ions, and engineers - preferring a simple on-site rule
of thumb - often simply take the factor of 0.7 so often found on the fixed
scales of commercial electrical conductivity-total dissolved solids (EC-TDS)
meters and think little more about it.
This factor of 0.7 is typically used as the fixed K factor in the well-known
expression
TDS=K.EC
where TDS is in mg/l and EC is in @/cm at 25 C. However there is no fixed
factor and no linear relationship of the above type which is applicable through-
out the water industry for the reasons which will be demonstrated in this paper.
Nevertheless, what can be usefully and practically employed are a few well-
chosen linear K factors to represent distilled waters, natural waters, brackish
waters and seawaters accordingly. A range of K factors is especially required
in the desalination industry because, by definition, the complete range of water
types is dealt with from distilled and fresh natural waters through natural
brackish waters to seawaters and reject brines. The consistent use of just one
K factor (typically 0.7)) even though this is the average value between possible
extremes of 0.5 to 0.9, can lead to errors of up to 30% in TDS estimation from
just this one theoretical simplification alone. This paper goes on to discuss the
many problems and sources of both random and systematic errors associated
with the theory and measurement of both EC and TDS values, which will dem-
onstrate that the simplicity generally associated with these two parameters in
the desalination industry is merely a facade covering a multitude of simplifi-
cations, assumptions, and approximations which have been conveniently over-
looked in the search for the simple K factor.
WHY LI FT THE LI D FROM THI S PARTI CULAR CAN OF WORMS?
The need for greater accuracy in estimating TDS from EC results rather
than using one simple factor to cover all cases is becoming increasingly impor-
tant due to:
(i) Tighter new plant design criteria and specifications.
(ii ) Plant operation efficiency calculations.
(iii ) Contractural specification and guarantee requirements.
(iv) WHO and local health requirements for potable quality water.
The increasing use of RO and ED desalination systems makes this review of
the EC-TDS relationship more pertinent due to the reliance of both plant
design and membrane performance and guarantees upon good product EC-
TDS results - especially when dealing with brackish water desalination. Fur-
thermore, the almost universal reliance on a current WHO limit of 500 mg/l
TDS for potable water, brings the manufacturers of one-pass seawater RO
desalination plants close to the limits, since at typically 99% membrane salt
rejection rates, standard seawater RO permeate will contain around 330 mg/l
TDS and Arabian Gulf seawater around 450 mg/l TDS. Reliance upon EC-
TDS conversion factors then becomes critically important for performance
guarantee evaluation, since the direct measurement of TDS is not easily and
accurately carried out without controlled laboratory conditions and skilled
technicians.
The need for a quick and simple conversion from EC to TDS arises from the
dichotomy between design standards and operational utility. All standard val-
ues for the degree of mineralisation of waters are expressed in the absolute
terms of TDS, which is not a parameter which is readily measurable. The re-
lated value of EC is however simply and conveniently measured by on-line
variable resistance devices which can be coupled to recorders and alarms etc.
for continuous monitoring of plant performance. The difficulty is to find a
simple relationship between these two related measurements without gross
oversimplification making the chosen factor or expression too erroneous.
This paper will demonstrate that the true precise relationship between these
two parameters throughout the range of natural water salinities is almost im-
possibly complicated, whilst at the other extreme the use of just one simple K
factor is a gross oversimplification which leads to potentially large errors. It is
however possible to compromise by defining several K factors which can be
applied in the correct circumstances to give a very good approximation of TDS
from an EC result, thereby maintaining the operational simplicity and utility
of EC readings.
TOTAL DI SSOLVED SOLI DS (TDS) -DEFI NI TI ON AND MEASUREMENT
What is TDS?
Superficially this question appears to be self evident, but this hides a number
of important points both theoretical and practical. The question of what is
dissolved and what is not has long been a difficult question in the water
industry, since particles, ions and molecules exist throughout an entire size
spectrum both individually and in larger polymeric agglomerations, through
colloidal suspensions to visible particulate matter. The dividing line between
what is truly dissolved and what is in colloidal suspension or agglomeration
can only be drawn by reference to a specific filter mesh size.
Since micron-sized colloidal particles are evident under a simple microscope,
the line had to be drawn at the sub-micron size and the figure of 0.45 pm has
tended to become the internationally accepted standard in the water industry
for deciding what is in true solution or dissolved matter and what is partic-
ulate matter. This dividing line came about largely arbitrarily as a matter of
practical necessity since 0.45 pm was the smallest pore-size filter paper com-
mercially available in the 1960s and early 1970s when these matters were being
deliberated internationally.
Sampling problems
Having defined dissolved, what about the practical difficulties associated
with collecting a 0.45 pm filtered water sample?
I t is very often not practicable to filter the sample on site, so any filtration
(if carried out at all) generally takes place in the laboratory after many hours
or days later. I n this time interval, a whole range of physical, chemical and
biological activities can take place in the sample bottle, e.g.
(i) Oxygenation of sample can lead to precipitation of previously dissolved
species like iron and sulphide.
(ii) Degassing of CO, can give a raised pH which will upset the carbonate
equilibria and may precipitate CaCO,.
(iii) Biological decay of dissolved NO; ions which may subsequently degas
as volatile NH3 or N2 gases.
(iv) Biological utilisation of COz, dissolved organic matter and PO:- ion
uptake.
(v) Agglomeration of micro-colloids originally smaller than 0.45 pm.
Many of these biological changes can be slowed down to relative insignific-
ance by storing the sample in the cold and dark immediately after collection
and prior to analysis. However, the overall error potential is such that samples
should ideally be filtered in situ at the time of collection, then kept in a refrig-
erator prior to analysis, which should ideally be within 24 h of sample collection
and filtration.
Analytical problems
The standard TDS measurement is normally carried out by evaporating an
accurately weighed water sample in a platinum crucible to dryness at lBOC,
followed by cooling in a dessicator and weighing the residue to constant weight.
Theoretical problems associated with this are:
(i) The bicarbonate equilibrium is upset by the rise in temperature, and 50%
of the original bicarbonate ion dissolved in the water is lost as CO, gas when
CaCO, scale precipitates viz.
2HCO,-CO;- +CO,+H,O
219
Since bicarbonate is often a dominant ion in most fresh natural waters, this
can be the source of very large errors unless corrected for.
(ii) Upon precipitation of the dissolved salts during evaporation, some water
of crystallisation can be incorporated into the crystal structure, which will then
be weighed as solid material. Using a temperature of 180 C rather than the
originally lower temperature of 110C helps to minimise this problem, but
when significant quantities of sulphate salts are present, as in brackish waters
and seawater, the calcium and magnesium sulphates tend to retain some water
of crystallisation, even at 180 C.
(iii) Heating to 180 C can partially decompose organic matter and will drive
off any volatile material present, although these effects are likely to be small.
Practical problems associated with the TDS measurement include:
(i) The common substitution of a porcelain or other dish/crucible due to the
expense of platinum. This can result in errors due to precipitation of salts
within the pores of the porcelain which become difficult to remove, and the
hydration-dehydration cycle of the porcelain itself gives weighing errors at
different temperatures.
(ii) The common substitution of loo-105 C instead of 180 C as the final
evaporating temperature due to the general availability of water-baths but not
such ready availability of controlled heating mantles for the higher tempera-
tures. The increased presence of water of crystallisation, especially in sulphate
salts, will cause errors in TDS weighings.
(iii) Sputtering of water sample during heating allows carry-over of salts
with the water and into aerosols.
(iv) For low TDS samples, the accuracy in weighing, even with a good elec-
tronic balance will lead to significant errors, e.g. a lo-mg/l TDS water sample
will involve the weighing of just 1 mg of dried residue from the standard 100
ml sample; an error of up to 30% is quite conceivable here, just in the weighing
alone. Of course larger samples can be evaporated, but time can then become
a difficult problem for the laboratory.
(v) The availability of good laboratory facilities and skilled analysts will
have an important effect on the final TDS result, with error potentials up to
40% not uncommon on the lower TDS waters. Even finger-marks on the dish
can add a significant sweat-film at the sub-mg level and the inclusion of dust
particles is always a constant problem unless the greatest care is taken.
(vi) Actual TDS evaporation measurements are not always carried out, es-
pecially if a full chemical analysis is required at the same time; the TDS is then
often calculated by adding together all the major cations:
Na++K++Ca2++Mg2+, and major anions: HCO; + SO:- + Cl- + NO, in
mg/l. Minor ions like Sr+, F-, Br-, I -, Fe2+ are rarely included but, except
for Br- in seawater, their omission is usually insignificant. However, neutral
dissolved solids like Si02 and organic material can be a significant source of
error in low TDS waters if they are not analysed for and included in the total
analysed ions.
280
Sometimes a TDS evaporation measurement is included alongside a full water
analysis. I n such cases it is interesting to compare the measured value with the
calculated value of TDS. Differences of the order of 50% are not uncommon in
potable waters. This gives some idea of the error magnitude that can be asso-
ciated with individual TDS results due to a combination of some or all of the
three theoretical and six practical problems listed above, and possibly others
not listed here.
Thus using an actual TDS measurement as an absolute standard against
which to judge an EC reading, is not always superior or beneficial. There are
often times when the use of a good EC reading multiplied by the appropriate
K factor is a better way of obtaining the TDS than by analysing for it. The
important thing here is to use the correct K factor, since using the common 0.7
factor will generally not give a better result than the TDS evaporation method.
ELECTRI CAL CONDUCTI VI TY (EC) - DEFI NI TI ON, THEORY AND
MEASUREMENT
Background and definition
Theories of electrical conductivity of ions in solution were developed to-
wards the end of the last century, building upon the pioneering works of Ohm
and Faraday to formulate expressions for the electrical conductance of solu-
tions, analogous to those developed in the electrical industry for electrical re-
sistivity of solid matter. Hence the term specific conductance (or conductiv-
ity) of a solution was developed as the simple reciprocal of specific electrical
resistance (or resistivity ) . This involves an expression relating the resistance
or conductance of a specific item within fixed dimensions.
Specific electrical conductance (SEC) was the originally accepted term, but
often became shortened to electrical conductance, which implies an incorrect
inverse connection with electrical resistance, rather than resistivity. Thus con-
ductivity or electrical conductivity (EC) is now the generally accepted term
for this measurement, although specific conductance is still used by the more
academic workers.
Electrical conductivity (EC), as its name implies, is a measure of the ability
of a conductor to carry an electric current. The EC of an electrolyte or aqueous
solution is a summation of the current-carrying ability of every ion present and
is dependent upon the number of ions per unit volume of solution and the
mobilities with which each ion is able to move under the influence of the ap-
plied electrical potential. Since the temperature dependence of EC is critical
(about 2% per 1 C), either the exact temperature of measurement or, more
commonly, the EC result corrected to the standard thermodynamic reference
temperature of 25 o C must be quoted. This is conveniently written as EC,,.
The absolute units for EC are mhos/cm, although for practical purposes
pmhos/cm are commonly used. However, the mho (or reciprocal ohm) has now
281
TABLE I
Typical EC,, values of natural waters
Water type Approximate
EC @S/cm)
at 25C
Ultra-pure water 0.05-0.5
Distilled waters l-10
Rain waters 5-50
Potable waters 50-1000
Brackish waters 2000-20,000
Saline waters 20,000-40,000
Seawaters 40,000-60,000
Brines 60,000+
been directly replaced by the Siemens, thus @/cm are now the usual units for
the expression of EC, with natural waters having the typical values as illus-
trated in Table I .
Theoretical background
The measurement of EC,, always involves the combined measurement of
two or more ions. To express conductivity as an absolute property of individual
ions, use is made of a parameter called the equivalent (or molar) conductance
(A) of each ion, which is defined as
A= 1000% in S cm/equiv. (or mol)
where EC,, is expressed in its absolute units of S/cm at 25 C and C is the
concentration of the ion in chemical equivalents per litre or mol per litre.
Since chemical normalities and equivalents are now being phased-out in the
current mood for international standardisation of units, the concentration
nowadays is expressed by mol/l.
Thus, the A value becomes molar conductance rather than equivalent con-
ductance as in the past. Molar conductivities approach a limiting upper value
with increasing dilution, so that a parameter A, -the molar conductance at
infinite dilution - can be defined for each individual ion. I n practice, infinite
dilution is approached at around 10m4 M for many simple salt solutions, with
corresponding EC& values around 10 ,&/cm.
Tables of A, values can be found in any high school physical chemistry text
book, but a few relevant examples are listed in Table I I . From such tables of
A, values, theoretical results for the conductivity of dilute solutions can be
directly calculated as follows:
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TABLE II
Examples of typical molar conductances of common ions
Ion Molar conductance
(S cm*/mol) at
25C (/i,)
K+ 73.5
Na+ 50.1
H+ 349.8
Cl- 76.3
OH- 198.0
HCO, 45.4
TABLE III
Calculated and measured values for ECzs of a range of concentrations of standard KC1 solutions,
illustrating the change in K value for more concentrated solutions
KC1 solution concentration
mdl
Molarity
Electrical conductivity
Calculated Measured
W/cm) W/cm)
TDS/EC
(K)
7.455 1O-4 14.98 16.8 0.503
74.55 10-3 149.8 146.9 0.507
745.5 10-2 1498.0 1408.9 0.529
7455 10-l 14,980 12,856 0.580
74,550 1.0 149,800 111,342 0.670
For example, the approximate EC of a 10 A3 A4 standard KC1 solution can be
calculated from the data in Table I I , as follows:
EC& = (73.5+76.3)~106~1/1000~10-3=149.8 @S/cm
Similarly a 10m4 M KC1 solution would have EC,, =14.98 @/cm, and so on.
Actually measured standard values for these solutions are however slightly
different as illustrated in Table I I I .
Theoretical relationship with TDS
Table I I I clearly shows the non-linearity of the TDS-EC relationship even
for a series of standard single salt KC1 solutions, where concentrations greater
than 10m3 M show increasingly large deviations reaching 26% at 1 M concen-
tration. Similar results are obtained using other single salt electrolyte solu-
tions. However, natural waters contain a mixture of various different salts and
the depression of EC& with increasing total salt concentration then becomes
283
even greater due to both physical and electrical ionic interactions. The bicar-
bonate ion in particular has a rather low molar conductance, and since it is
often a dominant ion in natural (fresh) water systems, it often exerts a marked
depressive effect on the conductivity of fresh water, so that the TDS/EC re-
lationship (K value) increases dramatically.
For example, to take an extreme case, a 10V3 M solution of NaHC03 will
have an approximate EC,, calculated from the data in Table I I of
(50.1+45.4)~106~1/1000~10-3=95.5$3/cm
and since the TDS of such a solution is 84 mg/l, the TDS/EC relationship or
K value =0.88, which is the upper extreme value for any natural water system.
Thus, it can be clearly seen that both increasing concentration and different
ionic composition, even in single salt solutions, can have a marked effect on
the TDS-EC relationship. Consequently, the relationship or K value cannot
be considered to be either fixed or linear, although the natural mix of ions in
natural water systems allows the extreme values of single-salt solutions to be
neglected.
Temperature effects
The main physical effect of temperature is to increase ionic mobility at higher
temperatures through decreasing the viscosity of the solution.
The well known approximation of the effect of temperature upon EC of about
2% per 1 o C is a very general average which is reasonable enough when used
on a mixed-ion natural water at approx. I fr 15 C from the international stan-
dard of 25 C. However, each individual ion has its own often very different
temperature coefficient, which varies with both concentration and absolute
temperature, with especially large departures (up to ten times) from the 2%
approximation evident in very cold and very hot water, where viscosity changes
and dissolved CO, ionisation rates change rapidly.
Many workers have attempted to fit empirical cubic and quartic equations
to describe the observed variations in EC with temperatures. However, in prac-
tice, general agreement suggests that the simple linear equation:
EC,,
=EC,[1+0.022(25-t)]
i.e., a 2.2% per 1 C temperature change is the most useful practical application
for temperature correction within ambient natural temperatures for most
mixed-ion natural waters.
I t should be noted that most commercially available EC meters make use of
this simple relationship to electronically correct for temperature deviations
from the standard 25 C by applying an automatic 2% per 1 C correction. How-
ever, one should beware of older meters which may temperature-correct to the
previous 20 C standard temperature which will give an immediate 10% error
284
to the EC reading if this fact is not noticed. The writer came across an inter-
esting example in one Middle-Eastern country where alarm was occasioned by
the latest annual country-wide wellwater salinity (EC) survey which indicated
a 10% rise in virtually all water well EC readings. I t was sometime before this
universal EC rise was attributed to the change from an old 20 C standard
temperature meter to a new 25 C standard meter.
pH effects
Pure water itself is not a conductor of electricity, since it exists in a molec-
ular rather than ionic structure. However, there is always a very slight ioni-
sation tendency in water as given by the ionic product of water K,= lo-l4 at
25C. i.e.,
H,O=H++OH-:
K _ [H+I [OH+ I = lo-14 mol/]
,+.- FL01
This gives an EC of about 0.05 @/cm, an exceptionally low value. However,
at especially high ( >9) or low ( <5) pH values, the EC of water becomes
significant. e.g., at pH 5, H+=10m5 M. Now since An+ =349.8 mho cm/mol
(Table I I I ), which is about five times higher than the molar conductance of
other cations, due to its very small size and high mobility, its EC contribution
would be
Similarly at high pH values, say pH 9, ( [H+ ] =lo- M), since K, =10-14,
[H+] [OH-] =10-14, therefore [OH-] =10-14/10-g=10-5 M and non- is
similarly several times larger than other anions at 198.0 mho cm2/mol (see
Table I I I ), then the EC of pH 9 water at 25 C can be calculated as
198.0. 106/103. 10m5M =1.98 @/cm
However, since virtually all waters used and produced within the desalination
industry normally lie within the natural water pH range of 5-9, the contribu-
tion to EC measurements of non-neutral, ionised water molecules is evidently
very small and generally negligible.
Undesirable electrical effects
Polarisation
The inevitable polarisation problems associated with passing electric cur-
rents through aqueous solutions of electrolytes are largely overcome by the use
of alternating currents (AC) of moderate frequency, typically 1000 Hz.
285
AC frequency
The typical moderate AC frequencies (1000 Hz) used in many ordinary com-
mercial EC meters is necessarily a compromise between the need to minimise
polarisation in high EC waters and reduce the capacitance effects which be-
come increasingly significant in low EC waters. Higher AC frequencies (2000-
4000 Hz) are often used in salinometers for oceanographic work to minimise
polarisation potential, whilst EC meters especially designed for use with dis-
tilled, de-ionised and high purity waters typically operate at 60-100 Hz to min-
imise capacitance errors. At very high frequencies (co. 10,000 Hz) however,
the inter-ionic forces break down and conductivity again approaches the high
assymptotal values reached at infinite dilution.
Capacitance
The capacitance effect is directly related to the frequency of measurement
and the length of cable between measuring cell and meter. Thus for broad-
spectrum EC meters with a fixed frequency of around 1000 Hz, it is advisable
to keep cable lengths to less than about 20-30 m to minimise capacitance prob-
lems. More sophisticated broad ranging instruments include a variable null-
balancing capacitor to allow for increased accuracy especially at low ( < 100
@/cm) conductivities, where capacitance errors can reduce the measured con-
ductance by up to 10%.
I mpedance
Boundary layer impedance is set up on the surface of the measuring elec-
trodes due to polarisation effects. This can either be reduced by using an ap-
propriate measuring frequency for the salinity of the water to be measured or
more practicably, by changing the size and material of the cell electrodes. De-
positing platinum-black on the surface of platinum electrodes or using spe-
cially prepared graphite-carbon electrodes with a cell of the appropriate size,
can significantly reduce impedance and reactance effects on conductivity
measurements.
An additional impedance (and capacitance) effect is associated with long
cable lengths, especially in highly conductive waters where the cable resistance
then becomes of a similar magnitude to the electrolyte resistance being mea-
sured. I n this instance an increase in measuring cell dimensions (see below)
is required to increase the measured electrolyte resistance and thereby de-
crease the significance of the cable resistance.
Overall electrical effects
There are inevitably interactive effects between the electrical factors of fre-
quency, capacitance, impedance and reactance, although it is only really nec-
essary to take account of these factors at very low or very high conductivities,
where the compromise electronics built into the standard broad-spectrum EC
286
meter designed to give good results at economic prices, start to give increasing
error potential. For accurate measurement of EC at <50 @/cm or >50,000
@/cm it is advisable to use measuring systems dedicated to these extreme
values since they will incorporate the different frequencies, capacitance cor-
rection, change in cell size, etc., which is necessary to maintain accuracy at
these extremes. For instance, marine chemists and oceanographers often use
specially designed EC measuring systems called salinometers. Apart from
reading directly in resistance (ohms) and salinity (ppm NaCl) these operate
at higher frequencies, utilise larger measuring cells and contain a more accu-
rate non-linear temperature correction facility to enable more accurate con-
ductivity readings to be obtained in seawater.
Measuring cell dimensions
The usual measuring (1.0 cm) cell contains electrodes of a fixed size and
arrangement, so that the electric current is passing through exactly 1.0 cm3 of
water. Any slight deviations from this rigidly fixed volume are compensated
for by a factor known as the cell constant, which for a 1.0 cm3 cell, normally
has a factor of between 0.85 and 1.15 depending upon manufacturing toler-
ances. This factor is usually marked onto the measuring cell itself, for manual
correction or on some meters it can be corrected for by an internal compen-
sation resistor which, when set to the value of the cell constant, will automat-
ically correct the EC reading.
Each new cell will have its own individual cell constant, as determined by
the manufacturer from its EC& readings in a series of standard solutions.
This cell constant correction facility present on some EC meters can be used
as a standardisation control for recalibration when fouling or abrasion may
have altered the effective cell constant, although great care is needed during
any restandardisation procedure due to the possibility of contamination of the
standardising solutions, even with distilled water.
The use of a l.O-cm measuring cell, although common, is not universal. Once
again it is an operational compromise. The measurement of low EC ( <100
@/cm) waters is more accurately obtainedusing a O.l-cm cell, whilst the mea-
surement of high EC water ( >20,000 @/cm) requires the use of a 10.0 cm cell
for greater precision and accuracy. This is due to the fact that an error in the
typical Wheatstone bridge resistance measurement is set up if the measured
resistance strays too far from any standard value, since the added resistance
of very dilute solutions effectively occurs as the reciprocal effect of parallel
resistors rather than the additive effect of series resistors. Changing the size
of the measuring cell can help to maintain a similar resistance over very large
changes in salinity, with a consequent reduction in measurement error.
281
Other practical problems with EC measurements
(i) The simple trapping of an air-bubble between the measuring electrodes
is a surprisingly common cause of erroneously low EC results, since the air
bubble occupies a portion of the fixed volume of the EC cell, thereby reducing
the measured conductivity.
(ii) Fouling of the electrode surface - particularly in on-line measurement
cells - also commonly leads to decreasing EC values with time. Small amounts
of filmy organic substances like oils or surfactants are often the cause of sim-
ple, cleanable fouling incidents. Longer term damage can be done by erosion
and corrosion of the electrode surfaces, or even poisoning as when sulphides
contact platinum electrodes and lead to serious electrode malfunctions with
time.
(iii) Range-switching innacuracies are particularly frustrating in most av-
eragely-priced EC meters, with over- or under-reading of typically up to 10%
when switching from one decade-range resistor to another. The answer to this
is to recalibrate with the appropriate KC1 standard solution each time the dec-
ade range is changed, although this is often impractical. However, process con-
trol instrumentation rarely requires range-switching once correctly set, so this
problem afflicts mainly the laboratory and other multi-purpose and portable
meters.
(iv) Some meters are fitted with very loose calibration or cell-constant
switches which are too easily knocked or moved during use and necessitate
recalibration, which may be very difficult if in isolated field locations.
(v) The presence (or absence) of the important temperature compensation
facility is often incorrectly understood. I t is sometimes thought that one must
set the dial to the temperature at which one wishes to report the result, i.e.
25 C, instead of the actual water temperature. This obviously can lead to very
large errors at the rate of about 2% per lo C.
(vi) The use of older meters which have their internal temperature compen-
sation fixed on the old British standard water temperature of 2OC, leads to
an immediate 10% error on all readings reported or understood to be standar-
dised at the international standard of 25 C.
SUMMARY OF EC AND TDS MEASUREMENT PROBLEMS
Having read the article so far, the reader may never feel quite the same about
the once ever-so-simple dip and read EC result and may look a little more
closely at any given TDS result. However, the writer intends only to point out
the degree of potential errors due to both theory and practice inherent in any
given EC or TDS result, so that a little operational tolerance and flexibility is
obtained between clients, consultants and contractors over their sometimes
288
fixed attitudes towards stated limits for plant operational guarantees and per-
formance certification.
For example, the writer has been involved in several instances when reverse
osmosis product waters appeared to lie outside the almost universal WHO limit
of 500 mg/l TDS within the guaranteed lifetime of the membranes. I n each
case, the plants were relatively small <500 m3/d and so had no on-site labo-
ratory. On-line EC meters, corroborated with hand-held portable EC meters,
gave readings of around 800-900 (us/cm which was reading 560-630 mg/l on
the lower TDS scale of the same meters.
These meters had a fixed scale conversion of TDS =0.7 x EC which is a fairly
common, but terribly misleading, facet of many commercial EC meters.
Arguments ensued between clients, consultants and contractors over guar-
anteed performance etc., etc., and even external analysis for TDS did not ini-
tially resolve the matter due to conflicting results obtained from different
laboratories.
I f the EC meters are all correctly standardised, and can all agree on an EC
reading -t 5%, then by using the correct conversion K factor of 0.55 for RO
permeate waters, the correct TDS results of 440-495 could then be realised
and hopefully agreed upon by all concerned.
RELATI ONSHI P OF EC WI TH TDS FOR THE DESALI NATI ON I NDUSTRY
Having now carefully defined both EC and TDS and outlined the many the-
oretical and practical problems associated with their measurement, the need
to define a good simple working relationship between EC and TDS is still re-
quired to be able to reconcile the plant TDS design and international standard
requirements with the EC operational readings obtained.
Since there is definitely no simple relationship between these parameters
across the range of waters encountered in the desalination industry, and since
complicated mathematical predictions which suit academics, theoreticians and
computers are of little use to the majority of workers in the industry, the best
alternative is to produce a series of K values for different ranges of salinities.
The correct way to do this is to take a series of samples of the water in
question to a reputable laboratory and measure the EC and TDS a number of
times until good precision and accuracy are statistically achieved, and then to
take the ratio of the average values to obtain a best possible K factor. Of
course, all the precautions such as filtration and bicarbonate correction for
TDS measurements, and calibration and standarisation of EC measurements
as listed in this paper need to be adhered to, to be sure of getting good, accurate
results. Only then can the actual K factor for that particular ionic-mix water
be relied upon.
However, since most desalination plants utilise fairly predictable water types,
the K factors can be approximated in advance as shown in Table I V.
TABLE I V
Suggested K factors for use with different desalination water types
Water type Typical EC&
(@J /cm )
K factor
Distillate l-10 0.50
RO permeate 300-800 0.55
Seawater 45,000-60,000 0.70
Reject brines 65,000-85,000 0.75
The reason for the predictability of the TDS-EC relationship for these water
types is due to the overwhelming predominance (cu. 90% ) of just two ions in
all these waters, namely Na+ and Cl-, and the increasingK factor with salinity
reflects the hindrance of ionic mobility by the crowding effect of these ions at
higher concentrations.
The major variability of EC with TDS comes with fresh, potable and brack-
ish waters which contain a variety of dissolved salts, sometimes with
Mg (HCO, )2 or Ca (HCO, )z predominant and sometimes CaS04, NaHCO, or
NaCl as the dominant salt present. The complex ion-pairing and physical (size )
and electrical (charge) interactions which take place in solutions of these salts
make any simple TDS-EC relationship impossible. However, many natural
waters do contain a fairly well-balanced blend of the eight major ions, and so
extremes of interaction due to large size or high charge effects are often bal-
anced down so that most natural waters have K values which vary between
0.55 and 0.85. This of course is where the much used value of 0.70 comes in as
simply the average between these two extremes.
However, from the desalination point of view, it is generally brackish waters
with EC ranging from 2000-20,000 @/ cm which are of interest and these waters
rarely have a K factor below 0.60 or above 0.67 due to the chemical evolutionary
sequence of most brackish ground waters. Consequently, a good average K value
of 0.63 has been found to satisfy most brackish Middle East groundwaters with
salinities in the range of 2000-20,000 mg/l as TDS.
Fig. 1 gives a generalised view of the change in K factor with increasing
salinities for different water types. The dominant HCO, ion concentration of
many fresh waters gives the very steep rise in K value at low concentrations,
whilst the increasing importance of SOi- in brackish waters maintains K val-
ues well-above the single mono-valent KC1 standard line, whereas the fall-off
in Kvalue between 1000 to 10,000 mg/l TDS is due to the dominance of inter-
ion interference causing reduced EC values at higher TDS values. I t is in this
region where K factors can have the highest variability due to the opposing
effects of increased physical resistance and ionic interactions at higher con-
centrations, and the disproportionate ratio of divalent to monovalent ions.
290
0.4
loo lb
I
IO2
I
IO
I
IO
I
IO5
TOS (mdl)
Fig. 1. Plot of TDS against K values showing fields of dominance for different water types.
Fig. 1 also shows that the waters important to the desalination industry
occupy very limited fields on the diagram and generally follow the exponential
trend of the NaCl line. Their limited positions on this field diagram clearly
illustrate the progressive increase in K values for increasing salinity waters,
but within very limited ranges, which indicates the proposed use of the four
different K values for the four different desalination water types.
CONCLUSI ONS
(i) The measurement of both TDS and EC has been shown to be neither
theoretically as simple nor operationally as straightforward as is often assumed.
(ii) Both results contain a host of simplifications, assumptions and poten-
tial errors that can easily give rise to total error factors in excess of 30% unless
the most careful background investigations, calibrations and cross-checkings
are carried out within reputable laboratories.
(iii) The relationship between EC and TDS has been shown to be neither
simple nor linear although because of the actual complexity of the precise re-
lationship a practical compromise has been suggested utilising four different
K factors - one for each water type encountered in the desalination industry.
291
(iv) The use of just one K factor for all water types cannot be justified since
errors of up to 25% can be introduced from just this one approximation alone.
(v) The common use of a standard K factor of 0.7, which is chosen as an
average between the possible extremes of 0.5 and 0.9, and is often to be found
in the direct transformation of EC readings to TDS results on the face of many
commercial EC meters, is very misleading and, particularly in the product water
side of desalination plants where it is most important, will give immediate
errors of some 25%.
(vi) The non-recognition of the large error inherent in this direct transfor-
mation of EC to TDS, can be the cause of contractural arguments as specifi-
cations and guarantees can appear to be broken when the normal (WHO) 500
mg/l product TDS limit is apparently breached at an EC& value of only 715
@/cm instead of the more realistic value of 910 $S/cm.
(vii) The many other factors involved in obtaining good EC and TDS re-
sults, particularly electronic simplifications and compromises within commer-
cial EC meters and analytical errors in TDS results, have been described to
give an overall appreciation of the problems and errors inherent in each of
these results, suggesting that a more cautious approach to result-interpreta-
tion should be pursued.
(viii) The temperature effect on EC has been shown to be different for each
individual ion present, although it is concluded that the use of the standard
approximation of 2.2% per 1 C is good enough for most mixed-ion waters within
+15 C of the 25 C standard reference temperature. However, the correct use
of the temperature compensator and the awareness of older meters internally
compensating to the old standard of 20 C has been pointed out as an important
source of often unnoticed error.
(ix) The theoretical basis for the recommended substitution of four individ-
ual K factors for use in different stages of desalination plants has been pre-
sented, and is considered to be the simplest and most practically useful method
of obtaining a TDS estimation from an EC result. These factors can be pre-
sented with some certainty in the desalination industry, because the water
types involved are generally very predictable and are overwhelmingly com-
posed of the two simple ions of Na+ and Cl- even in the distillate-permeate
product waters.
(x) The recommended appropriate K factors are:
Distillates, with EC,, of l-10 @/cm, K=0.50
Permeates, with EC,, of 300-800 pS/cm, K= 0.55
Seawaters, with EC& of 45-60 mS/cm, K= 0.70
Brines, with ECz5 of 65-85 mS/cm, K~0.75
(xi) Thus the linear formula
292
with TDS in mg/l and EC&, in @S/cm can still be used for estimating TDS
from EC by substituting the appropriate K factor, and the result can then often
be more accurate than the error-prone direct TDS measurement.
(xii) For the WHO limit of 500 mg/l TDS, the corresponding limiting EC&
reading for permeate waters will be 500/0.55 =910 @/cm which is some 27%
higher than the figure of 715 @/cm obtained by straightforward conversion
using the standard K= 0.7 single factor.