Measuring pH in Reagent Grade Water:

This note explains the problems associated with measuring pH in high purity
water. I trust it will provide some insight and answers to this ongoing issue.
We quite often receive complaints or questions regarding problems with the pH
measurement of reagent grade water. The typical complaints reported are; "the pH of my
NANOpure or Easypure water is too low for my method" or "my pH is out of range for
my test." In many cases the analyst will also state; "we have never had this problem
before."
Simply stated, you cannot accurately measure the pH of reagent grade water
under standard bench-top conditions because there is not enough ionic strength in the
water to allow the meter and probe to function properly. Buffer solutions that are used to
calibrate pH meters may have a specific resistance of less than 200 ohms-cm. This is
roughly equivalent to 2400 ppm of total ionic solids as calcium carbonate. Purified
water, depending on source, may have a specific resistance of 200,000 ohms-cm (2.8
ppm) to over 18.0 megohm-cm (<0.03 ppm). Measuring pH in reagent water by standard
methods could be compared to analyzing sub ppb levels of metals by atomic absorption
using 25.0 or 50.0 ppm calibration standards. You will get an answer, but the calibration
is so far out of range for the sample that accuracy is impossible to achieve. In order for
the standard pH meter and electrode to function, a small amount of electrode filling
solution sis released into the sample to be tested. The electrode solution reacts with the
material in the sample to form a conductive bridge that is measured at the bench in an
extremely clean sample container will contain only small quantities of carbon dioxide.
You will get a pH number, but it may only be relevant to the carbon dioxide and electrode
filling solution concentration gradients. The electrode filling solution is more
concentrated than the reagent water sample. This sets up an osmotic pressure gradient
that will tend to force the reagent water into the electrode to dilute the filling solution.
This will also cause drift and inaccurate pH readings. In general, the pH numbers
observed will continue to drift downward as more CO2 is absorbed into the sample.
Even if the meter stabilizes, the accuracy of the reading will be in question. Furthermore,
if the slightest amount of calibration bugger is carried over into the sample, the pH will
reflect the direction of the last buffer. If the sample container has even a minute amounts
of acid or caustic contamination, the pH will also be deflected accordingly. One ppm of
sodium hydroxide or hydrochloric acid can deflect the pH of a reagent water sample by
1.03 units. If a customer reports a pH of 2.0 or 8.5, chances are good that the sample is
contaminated with something other than CO2.
It is important to note that most, if not all of the ionic content of a reagent water
sample exposed to air will consist of carbon dioxide. Carbon dioxide is rapidly absorbed
into reagent water once it is exposed to air. Water collected from an 18.0 megohm-cm

Harfst, W.F., Measuring pH in High-Purity Water. Back to Basics. Oct. 1994 Ultrapure Water.

system may show a resistivity of less than 5.0 megohm-cm by the time it reaches a bench
for testing. This will occur in a matter of seconds. Carbon dioxide dissolved in water
will form carbonic acid. (i.e.; CO2 + H2O = H2CO3). Although a weak acid, carbonic
acid in pure water will tend to produce a lower pH (<7.0 reading). As previously
mentioned, the lower pH reading will most likely manifest itself as a slow downward
drift on a the pH meter. Pure water saturated with carbon dioxide will have a pH of about
4.3. Since carbonic acid is such a weak acid, it can usually be overcome by the addition
of small quantities of buffers. If pH adjustment is required for a method, a buffer, acid or
caustic should be chosen that will not interfere with the lab procedure. In most analytical
techniques, carbon dioxide is not an issue. Most reagents and culture media have enough
buffering characteristics of their own to establish the required pH for the method. If
carbon dioxide is a problem for the application, the published method usually prescribes
boiling or soda lime extraction techniques for removal of the contaminant.
The American Society for Testing and Materials (ASTM) address the irrelevance
of pH in their Type I, II, and III reagent grade water standards. However, they do
specify a pH range for their type IV water as 5.0 to 8.0 pH units. This is also
meaningless. Water with a specific resistance as low as 20,000 ohms-cm can be difficult
to measure accurately due to meter drift. The B/I W.A.T.E.R. program uses a 50,000
ohm-cm cutoff for pH measurement of incoming water samples. This is used more for
screening than actual pH results. If the pH is high or low, than we know that there is a
problem with the customers feed water source.
Probably the most difficult issue surrounding the pH measurement of reagent
water is the inability of regulatory agencies to recognize the problem. For example, the
EPA still calls for a fairly narrow pH range on water used for certain analytical methods.
If you are a required to maintain certification for EPA methods, you must comply with
pH criteria for the application. You end up trying to run pH tests on something that you
really cannot test with any accuracy. In many cases you can get by, but the slightest
contaminant can throw everything out the window. This is normally when the customer
picks up the phone to complain about the water system.
There are several techniques that have been developed to measure the pH of
reagent and high purity water. The simplest form is to add a pinch of salt (NaCL) to an
aliquot sample of the water to be tested. Again, the pH measured will only reflect the
presence of carbon dioxide in the sample. Orion Instruments supplies a reagent water test
kit (pHix Kit) that is available via supply house catalogs for low ionic strength samples.
This method also requires the addition of materials to the sample. Again, the pH value
observed will be relative to the amount of CO2 present. The pinch of salt is probably less
costly. There are pH meters available for use in-line with high purity water systems. I
believe these meters use special microelectronics for calibration and sample reading. I
suspect these meters are also quite expensive. The main point is still whether it is
relevant to the application at hand. In most cases, it is probably meaningless.

Annual Book of ASTM Standards, Vol 11.01 1994, Standard D1193, Specifications for Water page 45.