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TechNotes
PUREFLOW

The Official Journal of the PFI High Purity Water Conference & Seminar Series

Fall 2013

The Basics of Water Chemistry PART 2 by C.F. “Chubb” Michaud

Summary: In this, the second part of a three-part series, we examine the proper use of a water analysis and traps
to avoid in deciphering it. In the first part, we discussed basic ionization and the value of the Periodic Table of Ele-
ments to the water treatment professional. In Part 3 we’ll discuss the use of chemistry and ion exchange selectivity
to solve certain water treatment problems. Throughout this series, we try to demystify some of chemistry’s com-
plexities to offer you a good grasp of the fundamentals of filtration and ion exchange.

To properly design a water treatment system, particularly with ion exchange and reverse osmosis, it’s neces-
sary to first get both a quantitative and qualitative listing of what the intended feed stream contains. This listing is
known as the water analysis, and a proper interpretation is a must to assure good results. Although the purpose of
an ion exchange system is to remove only the offending ionic components of a feed stream, other factors such as
temperature, total dissolved solids (TDS), pH and trace minerals also play a role and must therefore be considered.
Laboratories usually report a water analysis using certain approved test methods, which give the results in
milligrams per liter (mg/L). This is convenient because 1 mg/L is equal to 1 ppm, or part per million. This number,
however, is in units of weight. Ion exchangers, on the other hand, don’t deal with weight; they deal with ions,
which are the real chemical components we are trying to remove. A milligram of magnesium or calcium does not
contain the same number of ions or ionic equivalents as does sedium or hydrogen. The convention commonly
used is to convert to ppm as CaCO3—calcium carbonate. Confusion arises because both the mg/L value and the
CaCO3 value can and are often reported as ppm. A good practice would be to refer to elemen-
tal components (the analysis) as mg/L and the CaCO3 equivalents (the conversion) as ppm.

CaCO3 as ppm
CaCO3 is an arbitrary name choice. It has a formula or molecular weight (M.W.) of 100
(compared to carbon with a M.W. of 12). Both the calcium (Ca++) and carbonate (CO3=) ions are
divalent. That is, they have a charge value of +2 and -2, respectively (compared to sodium at +1), www.pureflowinc.com
and, thus, an equivalent weight of 50.
 Table 1 Table 2
Conversion Factors for Water Analysis Conversions
Common Water Components Cations mg/L as CaCO3 Anions mg/L as CaCO3
Cations Anions Calcium 60 150 ppm Bicarbonate 220 180ppm
Ca++ 2.50 HCO3– 0.82 Magnesium 4.9 20 ppm Carbonate 5 4ppm
Mg++ 4.10 CO3= 0.83* Sodium 45.9 100 ppm Sulfate 38.5 30ppm
Na+ 2.18 SO4= 1.04 Potassium 2.3 3 ppm Chloride 35.5‘ 50ppm
K+ 1.28 Cl– 1.41 Iron (ferrous) 0.3 0.5 ppm Nitrate 4.3 3.5ppm
Fe++ 1.79 NO3– 0.81 Subtotal 113.4 273.5 Subtotal 303.3 273.5 ignore any items with values below 0.1
Mn++ 1.82 SiO2 0.83 Silica 18 15 ppm. Dividing these corrected totals by
*For ion exchange purposes, it is assumed Total 321.3 288.5 17.1 converts the ppm as CaCO3 values to
that carbonate reacts as the monovalent ion. Temp 68°F | pH 7.6 | Turbidity .5 NTU | Color 35 APHA | Cond 650 umhos grains per gallon (gpg) values. Since the ion
exchange capacity is usually determined
in kilograins (Kgr) per cubic foot, (1 Kgr =
The equivalent weight (eq. wgt.) of any substance is equal to its 1,000 grains), we can now determine the “throughput” capacity in
M.W. divided by its valence. In the case of CaCO3, this is 100 ÷ 2 = 50. gallons per cubic foot (gal/ft3) of resin. Simply divide the grains of
It should be noted neither Ca nor CO3= have an equivalent weight
++
loading into the capacity of the resin.
of 50, but the combination does. The eq. wgt. of Ca++ is 20 (M.W. = Example: Determine the proper size of a DI system that will
40 ÷ 2 = 20) and the eq. wgt. of CO3= is 30 (M.W. = 60 ÷ 2 = 30). We handle 20 gpm for 12 hours using the above water analysis. Use
therefore must equate even the Ca++ and CO3= content of water to 6 pounds per cubic foot (lbs/ft3) of HCl for regeneration of cation
the eq. wgt. of CaCO3. We do this by multiplying by a conversion and 7 lbs/ft3 of room temperature caustic (NaOH) for the anion. The
factor (which is derived by dividing the number 50 by the eq. wgt. of literature shows that the cation capacity (at approximately 40 percent
the substance). In the case of Ca++, this is 50 ÷ 20 = 2.5. For CO3= it’s Na and 60 percent alkalinity) to be 27.5 Kgr/ft3. Using a 10 percent en-
50 ÷ 30 = 1.67. We can readily see that most common components gineering downgrade, we have a net design capacity of 24.75 Kgr/ft3
of water will have a different M.W., we’ll have a variety of conversion (27.5 x .9 = 24.75) for the cation. The anion (use a Type II) will have a
factors. Table 1 lists the common elements and their conversion fac- book capacity of 20.3 Kgr/ft3 (with 5 percent silica in the influent) and
tors. A simple water analysis converted from mg/L to ppm as CaCO3 is we will downgrade this by 15 percent for design purposes (multiply
shown in Table 2. .85), which leaves us with 17.25 Kgr/ft3. The engineering downgrade
While the total dissolved mineral content of this water (residual “factor” is a safety factor applied to DI calculations to allow for wear
by evaporation) would measure 435 mg/L, the TDS as CaCO3 is 273.5 and tear, resin loss and some fouling, as well as variations in the feed
ppm (for deionization or DI purposes). One does not add the cation stream over the life of the resin. It is usually 10 percent for cation
and anion values together. For anion determinations, the silica is resins and 15 percent for anion resins.
quoted as an afterthought: “I have 273.5 ppm water with 15 ppm of Since we have an anion load of 16.9 gpg, we will have to remove
silica.” For mixed bed calculations, this is 288.5 ppm water. For soften- 16.9 x 20 x 60 x 12 = 243,360 grains. Dividing this by 17.25 Kgr anion
ing calculations, it’s 10 grain water, and for dealkalization, it’s 10.5 capacity, we see we’ll need 14 cubic feet of anion resin. Since the
grain water. There are 16.0 grains of cations and 16.9 grains of anions cation will have to produce the water required to regenerate the an-
for deionization. ion resin, we must now add that quantity of water to our cation load
before determining the size of the cation exchanger. The total gallons
Every Ion Has a Partner are 20 x 60 x 12 = 14,400. Assuming 75 gal/ft3 of anion resin required
Every ion is assumed to have a counter-ion (as a dancing partner, for regeneration, add to that 1,050—75 x 14. The cation must there-
so to speak). It should be noted that with extreme pH conditions (i.e. fore treat 15,450 gallons (x 16.0 gpg) or 247,200 grains. Dividing this
<4 or >10), there will be an excess of cations or anions, respectively. by our cation rating of 24.75 Kgr, we’ll need 10 cubic feet of cation
Normally, every cation has an anion (with the exception of silica) so resin.
the total cations should equal the total anions (without silica). Silica, Resin capacities are dependent on the water analysis (among
a weakly ionized acid, is presumed to exist (for DI purposes) as H2SiO3 other things) and therefore not constant for every system. The ratios
(silicic acid) and has H+ as its partner. It therefore stands alone. of various ions to one another will cause the resin capacity to vary as
Sometimes the water analysis will be incomplete in that only will the quality of effluent one is targeting. Flow rate per cubic foot
the offending ions (calcium, magnesium, iron, alkalinity, sulfate and will also affect capacity as will temperature of service and regenerant.
silica) are reported—sodium and chloride are missing. If the analysis In addition, the quantity of regenerant is usually determined by the
appears incomplete, look for the obvious. You can estimate the ppm leakage values (quality) needed, which is what sets the whole thing
as CaCO3 by dividing conductivity (as micromhos, or umhos) by 2.5. in motion. “Leakage,” or what appears to be incomplete removal
In Table 2, we show conductivity as 650 umhos. Dividing by 2.5 gives of unwanted ions, is a result of incomplete regeneration. Keeping
us a TDS of 260 ppm. in mind “complete” regeneration is all but impossible, we choose a
If the totals for cation and anion are not equal, we make them regeneration level producing a leakage we can tolerate as accept-
equal by adding to the sodium (Na ) or chloride (Cl ) values. For
+ - able quality. The engineering of DI systems is a complex science (and,
instance, if the cation total were 15 less than the anion, we would add some say, art) and will not be addressed here.
15 ppm to Na+ as CaCO3 to the cation load. Include the ppm as CaCO3
values for all monovalent cations (K+, NH4+) as part of the Na+ total Softener Loading
and monovalent anions (NO3-) as Cl- totals. We then add silica value to There is more to building a softener than simply measuring
the anion total to get the “total” anion load. This is done after balanc- hardness of the water and setting the dial. Your customer not only
ing the cation and anion totals. wants his or her water softened today, they want it softened tomor-
For the purposes of capacity calculations, it’s generally safe to row, next month and 10 years from now. This means the regeneration
 Table 3
Leakage vs. Total
Dissolved Solids (TDS)
Dosage Chart
TDS of Pounds Trace Metals
procedure must also be a rejuvenation feedwater* of salt While trace metals, particularly heavy metals, may be present at
procedure to keep the unit operating 200 2 very low levels, their toxicity usually dictates that they be reported.
satisfactorily for many years. The water 500 5 Their values are usually reported in micrograms (millionths of a gram)
analysis can help us determine how to 800 10 and written as ug/L (sometimes the letter “u” is substituted for the
do this. 1,200 15 Greek letter “μ” or mu). This value is actually in parts per billion (ppb)
Softener throughput is influenced 1,500 20 and, while its value will probably not affect capacity, its presence may
not only by hardness, but also by TDS, 2,000 25 influence how you design your system. Do not confuse μg with mg.
iron, temperature, flow rate and regen- *Expressed as ppm. It’s a common practice to acid-stabilize a water sample before
eration level and technique. Since TDS sending it off to a lab. The acidification is to prevent precipitation of
and iron will generally be part of the metals due to possible pH changes (from loss of CO2 during warming
water analysis, we’ll look at those. of sample or agitation). Acidification not only prevents precipitation,
Hard water leakage is caused by residual hardness that is left it causes precipitated metals (such as aluminum, iron and lead) to sol-
on the resin after regeneration and bleeds off during the service ubilize. Be suspect if there is a moderate detailing of ppb quantities of
run. Increasing the salt dosage can minimize it. As hard water passes trace metals in the analysis. This sample may have been acidified. The
through a resin bed, the hardness is exchanged for sodium (or potas- raw water may carry these elements as precipitates, which should be
sium). The higher the sodium level (or TDS feed level), the higher the removed by particulate filtration. Take a closer look at the water.
tendency for the softened water to leech hardness back off the resin. Turbidity
This reduces the run length (and thus the capacity) between the Dirty waters can plug and foul ion exchange units, causing chan-
baseline leakage and the breakthrough leakage. Simply knowing the neling and capacity loss. Use a pre-filter if the turbidity values are >5
TDS ahead of time can allow you to avoid costly field calls to remedy NTU (nephelometric turbidity units).
low capacity or leakage complaints by adjusting the capacity setting
and using a higher salt dose ahead of time. To achieve 5 ppm (or less) Color
leakage during the run, use the salt settings for various TDS values Natural organics (such as tannins) or iron (colloidal, organic or
shown in Table 3. precipitated) may cause color, reported as APHA units. Values for
Soluble iron is exchanged onto a cation exchanger as Fe+2. color below 25 APHA are usually not noticeable by eye. Again, try to
However, with time, it oxidizes to Fe+3 and is not readily removed by determine what is causing the color and install proper pre-filtration.
salt regeneration. If we assign a higher value for iron in determining Softeners do not remove color. Granular activated carbon (GAC) and/
our loading, we will reduce the throughput volume and, therefore, or salt regeneration anion resin can often do the job.
regenerate more frequently.
Temperature
A good practice is to treat each ppm of iron as 1 to 3 grains of
Ion exchange systems are usually intended to function with
hardness. As such, in our sample water analysis, we have 10 grains
water feed temperatures of 50 to 100º F. Higher temperatures can be
loading from hardness and we add 1.5 grains for the iron (total =
detrimental to anion resins in DI systems. A lab-supplied water analy-
11.5). Soluble iron as high as 30 ppm has been successfully treated
sis may list temperature, but it’s meaningless. Rather, check with the
with a standard softener with 10 to 12 pounds of salt/ft3 regeneration
intended installation site if anion exchange enters into the picture.
level. Utilizing a resin cleaner is always a good bet. Citric acid (avail-
Much of the ion exchange process depends upon ions’ ability
able from most chemical suppliers) works well at a level of one pound
to diffuse into and out of the resin bead matrix. This is temperature
per 50 pounds of salt and can be added directly to the brine tank.
dependent and is seriously slowed by cold-water operations. Resin
beds should be at least 50 percent larger in diameter and 100 percent
Water Analysis Traps larger in volume to effectively handle water streams below 40ºF.
There are a few things to watch out for in your calculations:
Conclusions
Hardness and Alkalinity Obtaining and using a good water analysis is essential to the
Frequently a water analysis will report total hardness (TH) and/ proper design of any water filtration system, particularly an ion
or alkalinity (HCO3-) in ppm as CaCO3. For the purpose of designing exchanger. There is much valuable information on a lab analysis that
softeners and dealkalizers, these numbers can be plugged in directly can help you to avoid design errors.
as “loading” values. If, however, the mg/L value is also listed, do the Make sure you understand the water analysis. Check the math
conversion to check their math. to make sure the units add up. Make sure the cations are equal to the
Nitrates and Nitrites anions, and then add in silica to determine total loading.
Nitrate and nitrite are frequently reported in terms of mg/L as N
(nitrogen). This is written as NO3-N and NO2-N. It’s necessary to first Chubb Michaud is the CEO and Technical Director of Systematix Company (founded
in 1982) of Buena Park, CA. He has over 35 years of field experience in water and fluid
convert these values to mg/L as the ion, then to ppm as CaCO3. Since treatment applications and system design and he holds several U.S. Patents on ion
N has a M.W. = 14, and NO3 has a M.W. = 62, it is necessary to multiply exchange processes. Michaud has served on the Water Quality Association Board of
the N value by 62/14 or 4.43 for the NO3 and 3.29 for the NO2. The Directors and Board of Governors. He is a WQA Certified Water Specialist Level VI. He is
maximum contaminant level (MCL) for NO3-N is 10 ppm. This equals currently on the Board of Directors of the Pacific WQA where he has chaired the Techni-
cal and Education Committees for the past 12 years. Michaud has received numerous
44.3 mg/L for NO3 ion and 35.9 ppm as CaCO3. awards in recognition of his technical contributions to the industry. He was inducted
into the PWQA Hall of Fame in 2007. He is a founding member of the Technical Review
Committee for Water Conditioning and Purification Magazine and has authored over
100 technical publications and papers.
 1241 Jay Lane
The Official Journal of the
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