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Measurement of pH by

differential conductivity
Information from Endress + Hauser

In the fiercely contested arena of instrumentation for power generation, suppliers are striving to make their instruments easier to use, less
maintenance-intensive and cheaper to acquire.

Technologies have been combined to bring to The conductivity sensor is essentially pieces of efficiently to produce high quality de-ionised
the customer an important control measurement steel (electrodes) with a known surface area and water for use in the steam generation section.
using chemistry and in-house knowledge. a distance between the electrodes. This gives the
The reason for requiring high-quality water with
The measurement of pH in ultra pure water sensor a specific cell constant and application
low impurities stems from the steam generation
application is associated with refilling of range. The larger the surface area and the smaller
and utilisation. When water is evaporated, the
electrolyte reservoirs, salt packed electrodes the distance between the electrodes, the smaller
majority of dissolved components are left as a
or special reference systems. The regular the cell constant becomes. By definition, the cell
precipitate because the water that acted as a
calibration and routine maintenance is a further constant (k) is defined as the distance between
solvent has evaporated. All compounds such
burden on the operating staff. By comparison, the electrodes, divided by the surface area of
as NaCl, CaCO3, MgCO3, NaOH, etc. have
the amount of maintenance required by a pH each electrode:
a specific solubility value. This is the mass of
measuring point compared to a conductivity
k = (L / A) [cm-1] the component that can dissolve in a given
measuring point is vastly different.
amount of water. Example: Ordinary table salt
Electrical conductivity is thus defined as:
For the sake of this article, pH measurement (sodium chloride or NaCl) has a solubility of
will be briefly explained with the focus on X = G . k [S.cm-1] 36,7 g per 100 g of water at 25°C. Marble
conductivity measurement. A pH sensor consists (calcite or calcium carbonate or CaCO3) has a
The unit is defined as Siemens per centimetre
of three basic components: a measuring electrode solubility of 0,0014 g per 100 g of water at 25°C.
[S/cm or Mho/cm].
filled with a buffer solution and separated from If water with a high concentration of impurities
the process with a pH sensitive glass membrane, In all power generation facilities, conductivity is evaporated in a boiler, heavy precipitation
a reference electrode filled with a 3 mol is measured at various points along the water will occur and the boiler tubes will become
potassium chloride (KCl) solution and separated treatment cycle to indicate the condition blocked by the precipitate. Even the use of ultra
from the process with a porous membrane of thereof. The heart of the power generation pure water requires the periodic de-sludge of the
Teflon or ceramic and, lastly, a temperature water treatment cycle is surely the ion exchange boiler to rid it of the accumulated precipitate.
sensor. The two electrodes are electro-chemical columns. The anion, cation and mixed bed or Other components, such as silicate, have the
type electrodes that generate a millivolt (mV) polishing section performs the ion exchange task ability to be carried into the gaseous phase when
potential in the presence of hydrogen (H+) ions. the water is evaporated. This could have major
effects downstream as the silicate precipitates
These electrodes are expendable and need to
on the turbine blades as a glaze. This causes
be calibrated regularly to compensate for the
unbalancing of the turbine and can have
chemical consumption during operation. For
catastrophic results.
the specific resistance of electrolytes, we use the
term “resistivity”. Specific resistance is defined as All of these components, minerals and ions
follows: Where a liquid cylinder with length (l) (impurities) are selectively removed in the
and a cross section of (A) has a resistance of (R) ion exchange section of the water treatment
ohm, the specific resistance is equal to: plant. Ion exchange is the “trading” of similarly
charged ions by the ion exchange resin. This
ρ = R (A / L)
resin is a polymer compound from which
Conductivity, the reciprocal (inverse) value of positive or negative ions are suspended. Cation
the specific resistance, is then equal to: resin suspends hydrogen ions (H+) and anion
resin suspends hydroxide ions (OH-). Like an
For conductivity, we use the Greek letter ĸ
octopus with tentacles, the positive or negative
(kappa).
“tentacles” take similar ions from the water and
ĸ = (1 / R) (L / A) release their respective ions – hence, the term
ion exchange. For example: The sodium ion
Or, introducing conductance G as the reciprocal
in solution is a positively charged ion (Na+).
value of resistance:
Fig. 1: Two conductivity sensors with cation As it passes through the cation exchanger, it
G = (1 / R) exchanger. will bind to the resin and a hydrogen ion (H+),

Elektron May 2005 17


also positively charged, will be released. In due to the extraordinarily high conductivity of
the anion exchanger, the negatively charged the hydrogen ion (H+). In the model used, the
chloride ion (Cl-) will bind to the anion resin and conductivity of the hydrochloric acid (HCl) is
a hydroxide ion (OH-), also negatively charged, three times higher than the conductivity of the
will be released in its place. The hydrogen ion sodium chloride (NaCl).
(H+) and the hydroxide ion (OH-) will combine Thus, the conductivity ĸacid after the cation
to form pure water H2O. Thus, an impurity in exchanger corresponds to three times the value
the water (NaCl) was exchanged to form pure before the cation exchanger. The conductivity
water H2O. ĸdirect before the cation exchanger is composed
of the contribution from the sodium hydroxide
Chemical background on pH by differential
(NaOH) and from the sodium chloride (NaCl)
conductivity
that is 1/3 ĸacid. Thus, the concentration of the
Whenever an electrolyte dissolves in water, the sodium hydroxide is proportional to the direct
electrolytes dissociate into positively charged measured conductivity, minus one third of
cations and negatively charged anions. NaCl the post cation exchanger conductivity. With
(salt), HCl (acid) and NaOH (base) will be used retrospect to the molecular conductivity of
as examples. Strong electrolytes (e.g. NaOH) the sodium hydroxide (243 S/cm per mmol/
dissociate completely, weak electrolytes (e.g. l), it yields the concentration of the sodium
acetic acid, CH 3 COOH, or as an extreme hydroxide as:
Fig 2: Diagram from Guideline VGB-R 450L
example, pure water, H2O) dissociate only Appendix. NaOH = (ĸdirect - (ĸacid /3))/243 mmol/l
partially. In the ultra pure water process, chlorine And the pH value will be:
There is a precisely defined relationship
ions (Cl-) and sodium ions (Na+) derive from pH = 14 + log [NaOH] * measured in mol/l
between the H+ and the OH- ions in water. This
impurities, such as sodium chloride (NaCl). pH = 11 + log [NaOH] measured in mmol/l
relationship is defined by the formula of the law
In addition, sodium ions (Na + ) also form pH = 11+ log ((ĸdirect - (ĸacid /3))/243)
of mass action and results in the equilibrium
alkaline additives, such as caustic soda (sodium pH = 11 – log 243 + log (ĸdirect - (ĸacid /3))
constant “K”.
hydroxide or NaOH). The measurement of pH = 8,60 + log (ĸdirect - (ĸacid /3))
conductivity is done with a dual channel device, For water and diluted solutions at 25 °C: (*According to DIN 1313, [G] means the
the Mycom S CLM 153 from Endress + Hauser. Kw = [total H+ concentration] numerical value of the large G)
One conductivity sensor measures the direct x [total OH- concentration] This yields us with the measured parameter,
conductivity (ĸdirect) and the second conductivity = 10-13.997 mol²/l² without the direct measurement thereof.
sensor measures the same sample after it has
As in the case of the pH value, it is easier to work The measurement is not susceptible to the
passed through a small cation exchanger. This
with the negative common logarithm: contaminations typically associated with pH
second measured value is referred to as ĸacid,
systems. On pH systems where loss of electrolyte
the so-called acid conductivity. With reference pH = -log H+ causes system failings, this type of indirect
to the explanation of the functioning of an ion e.g. - log10 [10-7 mol H+] measurement provides the solution. There
exchanger, any Na+ ions that are present in the = 7 pH, i.e. -log10 [10-13.997 Kw] are of course some limitations and conditions
form of NaCl will be exchanged for H+ ions to = 13.997 pKw that would prevent the system from working
form HCl. properly. Typically, the conditioning of the
In the pH determination by differential boiler feed water should be alkaline-based,
To understand the pH calculation from conductivity, a specific model, constituted by with sodium hydroxide (NaOH) or NH4OH
this differential conductivity measurement, an alkalising agent and specific impurity, is according to the VGB guideline. Furthermore,
it is necessary to revise the mathematical used. In the model of the German Vereinigung the impurities that are present should consist
methods behind pH measurement. The term der Großkraftwerksbetreiber e.V. (Association of predominantly of sodium chloride (NaCl), as
“pH” is derived from the Latin “potentio Power Station Enterprises) and implemented on the first impurities that break through the ion
hydrogenium” that means strength of hydrogen. the Endress + Hauser Mycom S CLM 153, the exchanger columns consist mainly of NaCl.
It is mathematically defined as the negative alkalising agent is sodium hydroxide (NaOH) There should be minimal phosphates present
logarithmic function of the concentration of the and the impurity is sodium chloride (NaCl). in the water for water softening. As a guide, the
hydrogen ions in solution, or: The pH is a result of the sodium hydroxide phosphates should be less than 0,5 mg/l. As a last
concentration CNaOH. Further, chemistry condition, if the pH exceeds 8, the concentration
pH = -log [H+]
states that the conductivity of the acid (e.g. of impurities must be small in comparison to the
So, why is it necessary to have a scale of 0 - 14 to HCl) is three times higher than the conductivity alkalising agent.
define the minimum and maximum values? of the corresponding salt (e.g. NaCl). This is From the above, it is clear that it is possible to
determine pH in ultra pure water with differential
conductivity measurement.

Bibliography
[1] Brush-up 2000, by Klaus Stellmacher
[2] Perry’s Chemical Engineer’s Handbook 6th Edition,
by Don Green & Robert H. Perry
[3] Endress + Hauser Conducta, by - Dr. D Köngeter
(internal presentation)
[4] V G B T e c h n i s c h e V e r e i n i g u n g d e r
Grosskraftwerksbetreiber E.V. – Richtlinie VGB-
R450 L

Contact Grant Joyce, Endress+Hauser,


Tel (011) 262-8031,
grant.joyce@za.endress.com ‰

18 Elektron May 2005

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