769

An Improved Method for Evaluating Detergent Builders

for Water Hardness Control
J.A. McDonell* and A. Liu
Ecolab, Inc., R&D/840 Sibley Memorial Highway, St. Paul, MN 55118

Commercial detergent additives to control water exist for studying scale generation under "realistic"
hardness may act through sequestration, crystal conditions of temperature, salt concentration, etc. (7,8).
growth inhibition, precipitation, or ion exchange. These The use of designed experiments in industry is
builders lower the free hardness (Ca++, Mg ÷+) concen- widespread and well documented (9,10). We report here
tration by different mechanisms. A full factorially the relative water hardness control performances of
designed experiment has been developed to evaluate tripolyphosphate as well as several phosphonates and
builders functioning by the sequestration or crystal polyacrylates using two 2-level full factorial designed
growth inhibition of calcium carbonate or magnesium
hydroxide. The builder's performance is determined by
its ability to prevent precipitation while in the presence
of carbonate and hardness ions. The tests are based on
incubation followed by filtration and determination of A
calcium and magnesium in the filtrate by Inductively
Coupled Plasma (ICP). Variables in the design include
builder concentration, temperature, pH and time.
Regression equations and response surfaces for tri-
polyphosphate and several polyacrylates and phos-
phonates are included.

Approximately 25% of the U.S. population cannot

purchase a phosphate-based detergent. Holland, Italy,
West Germany and Switzerland all have limits on
phosphates in detergents. The search for viable
environmental and economic alternatives in detergents
has continued unabated since the sixties when tri-
polyphosphates were found to cause environmental
problems through eutrophication. These water hard- -~... -~. j ~,4~
"~
ness-controlling agents (detergent builders) are com-
monly used in synthetic detergents to reduce the free
hardness (calcium and magnesium) which in turn is
responsible for reduced cleaning.
Water hardness-controlling agents commonly used O
Q
in the detergent industry are one of three major types
(4): (1) sequestrants/threshold inhibitors such as tri-
polyphosphate, polyacrylates and phosphonates; (2)
precipitant builders such as sodium carbonate, and (3)
ion exchange builders such as zeolites. Of the three the
first is the largest class and the fastest growing. The
experimental methods for assessing their value in water
hardness control include turbidimetric titrations (2),
acidimetric titrations (3) and ion selective electrode
titrations (1,4). The first two have been used for over 20
years and, although they are relatively quick, their
precision and flexibility are limited. Ion selective
electrodes have been used more recently and found to
be very useful in comparing detergent builders (includ-
ing polyacrylates) under similar conditions. Current
electrodes, however, do have their limitations. They
have limited pH ranges and problems with interfering
ions and they require different measurements with two
electrodes to differentiate calcium and magnesium (5,6}.
In addition, since phosphonates are used as electrode
solvents, measurement in the presence of phosphonates
causes electrode drift. Many unpublished procedures
FIG. 1. Perspective plots for calcium in solution in the absence of
*To whom correspondence should be addressed. builder for (A) time and temperature and (]3) pH and temperature,

JAOCS, Vol. 64, no. 5 (May 1987)

770

J.A. MCDONELL AND A. LIU

go
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FIG. 2. Comparison of builders ability to keep calcium and magnesium in solution. (A) and (B) pH 12.5, average "effect" of 49 C (120 F)
and 82 C (180 F) and 50 and 200 ppm builder, i~, 15 min; l , 225 min; (C) and (D) pH 11, 66 C (150 F), 135 rain. i~, 15 ppm builder, l , 125
ppm builder (centerpoints); (E) pH 9.5, average "effect" of 49 C (120 F) and 82 C (180 F) and 15 and 225 rain, [], 5•25 ppm avg.; 11,50/200
ppm avg.

e x p e r i m e n t s . T h e d e s i g n ' s p u r p o s e is t o c r e a t e r e a l i s t i c
conditions of temperature, time, pH and builder
c o n c e n t r a t i o n a n d t o d e v e l o p a n u n d e r s t a n d i n g of
t h e s e r e s p o n s e s u r f a c e s in a n e f f i c i e n t f a s h i o n . T h e
regression analysis and response surface generation
d e t a i l e d in t h i s w o r k w e r e d o n e o n m a i n f r a m e
computers. Several good microcomputer programs
have now appeared which can handle the analysis and
p l o t s , a n d t h e s e w o u l d b e h i g h l y r e c o m m e n d e d for t h e
d e s i g n d e s c r i b e d h e r e i n (11,12).

JAOCS, Vol. 64, no. 5 (May 1987)

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776
J.A. MCDONELL AND A. LIU
REFERENCES
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61:1475 {1984}.
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JAOCS, Vol. 64, no. 5 (May 1987)
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[Received M a y 28, 1986]