Antriprex CE Types

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Technical Information Water Solutions

TI/EVW 0345 e
April 2012 Page 1 of 13

Antiprex® CE types
® = registered Trademark of BASF SE

Antiprex CES Powder


Antiprex CE
Antiprex CE Powder
Antiprex CEX
Antiprex CEX Powder

Organic chelating agents used to control the concentration of metal


ions in aqueous systems
TI/EVW 0345 e April 2012 Page 2 of 13 Antiprex CE types

Content
Page

Properties 3

Chemical nature 3

Chemical and physical data 4

Complex formation 5

Chemical stability 8

Corrosion 8

Applications 9

Cleaners 9

Water treatment 10

Safety 10

Storage 10

Ecological and Toxicological Data 11

Labelling 12

Literature 12

Note 13
TI/EVW 0345 e April 2012 Page 3 of 13 Antiprex CE types

Properties
Nature The active ingredient contained in the Antiprex CE types is ethylenediamine-
tetraacetic acid (EDTA or EDTA-H4) or its salts.

Ethylenediaminetetraacetic acid, C10H16N2O8, is an aminocarboxylic acid


with six functional groups.

HOOC CH2 H 2C COOH

N CH2 CH2 N

HOOC CH2 H 2C COOH

Antiprex CES Ethylenediaminetetraacetic acid (EDTA-H4) in solid form


CAS-No. 60-00-4

Antiprex CE Aqueous solution of the tetrasodium salt of ethylenediaminetetraacetic acid


(EDTA-Na4)
CAS-No. 64-02-8

Antiprex CE Powder Tetrasodium salt of ethylenediaminetetraacetic acid (EDTA-Na 4) in solid form


CAS-No. 64-02-8

Antiprex CEX Aqueous solution of the tetrasodium salt of ethylenediaminetetraacetic acid


(EDTA-Na4), high purity grade
CAS-No. 64-02-8

Antiprex CEX Powder Tetrasodium salt of ethylenediaminetetraacetic acid (EDTA-Na4) in solid


form, high purity grade
CAS-No. 64-02-8
TI/EVW 0345 e April 2012 Page 4 of 13 Antiprex CE types

Chemical and physical data

Unit Antiprex CES Antiprex CE Antiprex CE Antiprex CEX Antiprex CEX


Powder Powder Powder

Physical form White powder Clear, yellowish Slightly yello- Clear yellowish White, crystalline
(visual) Liquid wish powder liquid powder

Molar mass g/mol 292 380 380 380 380


(DIN 32625)

Concentration
(BASF method)*
expressed as % – approx. 40 approx. 87 approx. 40 approx. 84
tetrasodium salt (EDTA-Na4)
expressed as % approx. 100 approx. 31 approx. 67 approx. 31 approx. 65
free acid (EDTA-H4)

Density g/cm3 – approx. 1.30 – approx. 1.28 –


(DIN 51757, 20 °C,
U-tube densitometer)

pH approx. 2.9 approx. 11.5 approx. 11.5 approx. 11.5 approx. 11.2
(DIN 19268, 23 °C, 1% in water) (slurry)

Bulk density g/l approx. 830 – approx. 710 – approx. 780


(ISO 697, 40 mm diam.)

Hazen color – max. 150 max. 150 max. 150 max. 50


(DIN EN 1557) (40% in water) (40 % in water)

Volatile NH3 ppm – max. 80 – max. 80 –


(BASF method)

Calcium binding capacity mg CaCO3/g approx. 350 approx. 110 approx. 230 approx. 110 approx. 230
(BASF method, pH 11) t. q.

Water content % approx. 0.1 approx. 57 approx. 7 approx. 60 approx. 16


(DIN EN 13268)

Viscosity mPa · s – approx. 30 – approx. 20 –


(DIN 53018, 23 °C)

Freezing point °C – < – 30 – < – 20 –


(ISO 3013)

Melting point °C approx. 245 – > 300 – > 300


(ISO 3146) (decomposes) (decomposes)

Solubility in water g/l <1 Miscible in all approx. 600 Miscible in all approx. 600
(BASF method, 25 °C) proportions proportions

The above information is correct at the time of going to press. It does


not necessarily form part of the product specification. A detailed product
specification is available from your local BASF representative.

* Determined by potentiometric titration against iron(III)chloride.


** Concentration expressed as EDTA-H(NH 4)3 approx. 50 %
*** Concentration expressed as EDTA-(NH4)3 approx. 48 %
TI/EVW 0345 e April 2012 Page 5 of 13 Antiprex CE types

Viscosity mPa·s
2500

Antiprex CE
Antiprex CEX
2000

1500

1000

500

0
-10 0 10 20 30
Temperature (°C)

Viscosity as a function of temperature

Complex formation The most important property of the Antiprex CE types is their ability to form
water-soluble complexes with polyvalent ions (eg. calcium, magnesium,
lead, copper, zinc, cadmium, mercury, manganese, iron, aluminium) over
a wide pH range from 2 to 13.5. EDTA usually forms 1 : 1 complexes, i. e.
1 mol of EDTA chelates binds to 1 mol of metal ions. The metal ion is com-
pletely enclosed by the ligand. These complexes remain stable, especially in
alkali media and even at temperatures of up to 100 °C.

EDTA has six donor groups and it can form octahedral complexes.

From the law of mass action, the equation for the stability constant K can be
written as follows:

[MeZ(m-n)-]
K=
[Men+] [Zm-]

where

[MeZ(m-n)-] is the concentration of the chelate that is formed


[Men+] is the concentration of free, positively charged metal ions
[Zm-] is the concentration of the ligand anion, in this case EDTA
K is the stability constant for the chelate.
TI/EVW 0345 e April 2012 Page 6 of 13 Antiprex CE types

Logarithmic stability constants (log K) for complexes of EDTA


and selected metal ions

Metal ion log K

Co3+ 41.0

Fe3+ 25.1

Hg2+ 21.8

Cu2+ 18.8

Ni2+ 18.6

Pb2+ 18.0

Cd2+ 16.5

Zn2+ 16.5

Co2+ 16.3

Al3+ 16.1

Fe2+ 14.3

Mn2+ 13.8

Ca2+ 10.6

Mg2+ 8.7

Ba2+ 7.9

Ag+ 7.3

EDTA-H is a tetrabasic acid that dissociates in four steps. The acid


dissociation constants pKa are as follows.

EDTA-H4 pKa1 2.0

EDTA-H3- pKa2 2.6

EDTA-H22- pKa3 6.2

EDTA-H3- pK34 10.3

In aqueous solutions, EDTA competes for metal ions with other anions such
as hydroxide, sulphate, sulphide, carbonate and oxalate that form sparingly
soluble metal salts. The formation of chelates reduces the concentration of
free metal ions [Men+] to such an extent that the solubility products of many
sparingly soluble metal salts are no longer exceeded. The result is that the
salts no longer precipitate or may even redissolve.

The high stability of these complexes prevents metal ions from participating
in typical chemical reactions. For instance, manganese, iron and copper are
no longer able to catalyse the decomposition of peroxide bleach.

Conditional stability constants [log Kcond.] take into account the stability
constant K as well as the acid base dissociation equilibria.
TI/EVW 0345 e April 2012 Page 7 of 13 Antiprex CE types

log Kcond.
18
Ca2+
16 Mg2+
Co2+
14 Ni2+
Pb2+
12

10

0
0 2 4 6 8 10 12 14
pH

log Kcond.
18

16

14

12

10

Cu2+
6 Fe3+
Mn2+
4 Fe2+
Zn2+
2

0
0 2 4 6 8 10 12 14
pH

Conditional stability constants for selected EDTA chelates


TI/EVW 0345 e April 2012 Page 8 of 13 Antiprex CE types

The table below shows the pH ranges in which EDTA forms complexes.

1 g of EDTA-Na4 or 0.77 g of EDTA-H4 are able to sequester the following


amounts of metal ions, independently of temperature.

mg Metal ion Oxidation- pH range Colour of


number complex

64 Magnesium 2 8.0 – 12.5 Colourless


105 Calcium 2 6.0 – 13.5 Colourless
230 Strontium 2 8.0 – 13.5 Colourless
361 Barium 2 10.0 – 13.0 Colourless
144 Manganese 2 5.0 – 11.0 Colourless
5.0 – 13.0*
147 Iron 2 1.0 – 12.5* Colourless
154 Nickel 2 1.5 – 13.0 Blue
155 Cobalt 2 4.0 – 12.0 Red**
4.0 – 13.5 Violet***
167 Copper 2 1.5 – 11.5 Blue
5.0 – 13.0*
172 Zinc 2 4.0 – 13.0 Colourless
296 Cadmium 2 3.5 – 13.0 Colourless
545 Lead 2 2.0 – 13.5 Colourless
71 Aluminium 3 2.5 – 13.5 Colourless
138 Chromium 3 1.5 – 5.0 Violet
147 Iron 3 1.0 – 5.5 Yellow
550 Bismuth 3 1.0 – 9.0 Colourless

* In the presence of a reducing agent


** At room temperature
*** Appears when heated, persists on cooling

Chemical stability The Antiprex CE types are chemically very stable.

The Antiprex CE types have been shown to be very stable compared to


other organic complexing agents such as citric acid, tartaric acid and
gluconates, especially at high temperatures.

Whereas inorganic sequestring agents (eg. phosphates) may hydrolyse at


high temperatures, Antiprex CE types are stable – even when heated to
200 °C under pressure.

Antiprex CES Powder melt at approx. 245 °C.

Antiprex CE Powder and Antiprex CEX gradually lose their water of crystalliza-
tion at high temperatures and they begin to decompose at approx. 300 °C.

The Antiprex CE types are resistant to strong acids and bases. They are
gradually broken down by chromic acid, potassium permanganate and other
strong oxidizing agents. Stability in the presence of hydrogen peroxide, per-
carbonate and perborate is sufficient for joint application. Nevertheless, we
do not recommend combining Antiprex CE types and peroxides in liquid
formulations.

Substances that release chlorine, such as sodium hypochlorite, have a


highly detrimental effect on the performance of all of the Antiprex CE types,
and some alkaline earth and heavy metal complexes are broken down.

Corrosion The Antiprex CE types stabilize polyvalent metal ions, which means that they
can increase the rate at which metals dissolve. Nevertheless, with the
exception of aluminium, an oxidizing agent such as air always has to be
present for corrosion to take place. Unalloyed steel is prone to corrosion in
media that contain air, but corrosion can be reduced substantially if the pH
is in the alkaline range and can be eliminated almost completely if oxygen
and other oxidizing agents are excluded. With the exception of aluminium,
metals that are cleaned with the Antiprex CE types in the slightly alkaline
range, which is the optimum pH range for the Antiprex CE types, are much
less prone to corrosion than if they are cleaned with acids.
TI/EVW 0345 e April 2012 Page 9 of 13 Antiprex CE types

The Antiprex CE types are capable of dissolving metal oxides such as mag-
netite, and great caution should be taken in cases in which resistance to
corrosion depends the formation of a passive magnetite layer.

The only type of corrosion that has been observed with the
Antiprex CE types is uniform corrosion: pitting or stress cracking have
not been observed in media with a low chloride content. One of the advan-
tages of the Antiprex CE types is that they can be supplied with a very low
chloride content (< 20 mg/kg).

The following information on materials is of a very general nature, because


corrosion depends on many different factors such as exposure to air, gal-
vanic corrosion caused by the presence of different materials and by the
flow patterns of liquids. The compatibility of Antiprex CE types with different
materials needs to be tested in each individual case.

Austenitic stainless steels such as AISI/SAE 321 are very effective for ves-
sels used to store and transport the Antiprex CE types even at temperatures
of 60 – 100 °C.

Ferritic carbon steels such as ASTM A201 Grade B (European Material No.
P265GH) are resistant to Antiprex CEX at temperatures up to 60 °C if the
liquid is blanketed with nitrogen.

Aluminium and aluminium alloys such as AL 7075 T6 (European Material No.


3.4365) are not resistant to the Antiprex CE types, because Antiprex CE is
alkaline and aluminium is quickly corroded by strong bases. The rate of
corrosion depends to a large extent on the pH.

Silicon carbide and tungsten carbide are suitable materials for pump seals.
Nickel- bound tungsten carbide seals are resistant to Antiprex CE at
temperatures of up to 100 °C.

Applications The Antiprex CE types are used sequester free metal ions in aqueous
systems.

They are used to soften water and to remove traces of alkaline earth and
heavy metals.

Stoichiometric amounts of Antiprex CE types are required to complex metal


ions. Solutions are clear after they have been treated with chelating agents,
and they do not need to be filtered or decanted.

The Antiprex CE types can be used to solubilize precipitated metal salts and
hydroxides. Traces of free metal ions are always present in equilibrium with
salts, even if these salts are very sparingly soluble. If these free ions are
chelated, the equilibrium is gradually displaced in favour of the soluble
chelates.

The rate at which precipitates dissolve depends on their crystal structure


and age, and on the temperature. Increasing the temperature can help to
increase the rate at which precipitated solids dissolve. Old, dried-on scale
has to be treated with Antiprex CE types over a longer period, and we would
recommend applying 1 g/l more than the stoichiometric amount in this case.

Cleaners The Antiprex CE types can be employed in all types of cleaner formulations.
They prevent hardness ions and heavy metal ions from precipitating. Inor-
ganic solids of this type can form scale and deposits in tanks, pipes, and
nozzles and on hard surfaces. The Antiprex CE types boost the performance
of the surfactants contained in cleaner formulations and ensure that their
performance remains undiminished during the whole cleaning process.

Scale that consists of calcium carbonate, calcium phosphate or calcium


oxalate can be formed in pipes and heat exchangers at high temperatures in
various industrial processes. The Antiprex CE types can be added to cleaner
formulations remove this type of scale. The rate at which the scale dissolves
can be increased by increasing the cleaning temperature.
TI/EVW 0345 e April 2012 Page 10 of 13 Antiprex CE types

Water treatment Antiprex CE types are very effective for treating water to prevent scale and
deposits of calcium carbonate, calcium sulphate and calcium phosphate
from forming in boilers, evaporators, reverse osmosis membranes, heat
exchangers and filters, etc. They can also be used to remove scale.

The Antiprex CE types are every effective for cleaning equipment of this
type, because they are less corrosive than other cleaners. They have the
advantage over acids that no potentially disruptive CO 2 is formed when
calcium carbonate is dissolved.

The following table shows the amounts of Antiprex CE required to soften


1 litre of water containing 1 mmol of Ca2+ ions/l at 20 °C*.

1 mmol Ca2+ ions/l


(DIN 53910, Part 1)

Antiprex CES approx. 295 mg


Antiprex CE approx. 955 mg
Antiprex CEX Powder approx. 450 mg

* The standard unit of water hardness in Germany according to DIN 53910,


Part 1, is mmol of Ca ions per litre of water, but other units are still in use
internationally.

1 mmol/l of Ca ions = 5.6° German hardness = 10.0 ° French hardness


= 7.0 ° English hardness (° Clark) = 100 ppm CaCO3

1 ° Clark (English hardness) corresponds to 0.01 g CaCO/0.7 l water


(= 0.143 mmol Ca ions/l)

1 ° German hardness corresponds to 0.01 g CaO/l water


(= 0.178 mmol Ca ions/l)

1 ° French hardness corresponds to 0.01 g CaCO /l water)


(= 0.1 mmol Ca ions/l)

In the United States, water hardness is sometimes expressed in ppm.


1 ppm CaCO = 0.001 g CaCO /l water = 0.01 mmol Ca ions/l.

Example The amount of Antiprex CE Powder required to soften 100 l of


water with a hardness of 2 mmol Ca ions/l (= 200 ppm CaCO
= approx. 14 ° Clark) is 450 x 2 x 100 x 0.001 g = 90 g
Antiprex CE Powder.

Safety
We know of no ill effects that could have resulted from using the
Antiprex CE types for the purpose for which they are intended and from
processing them in accordance with current practice.

According to the experience we have gained over many years and other
information at our disposal, the Antiprex CE types do not exert any harmful
effects on health, provided that they are used properly, due attention is
given to the precautions necessary for handling chemicals, and the informa-
tion and advice given in our Safety Data Sheets are observed.

Storage Antiprex CE and Antiprex CEX should not be stored at temperatures below
0 °C, because this can cause them to precipitate. It can be reconstituted by
heating it briefly to 40 – 50 °C and stirring.

Antiprex CE is easily capable of being pumped at temperatures down


to – 10 °C.

Antiprex CE Powder is hygroscopic, and so it should be kept in tightly


sealed containers. The Antiprex CE types supplied in powder form have a
shelf life of two years, provided they are stored in their original packaging
and kept tightly sealed.
TI/EVW 0345 e April 2012 Page 11 of 13 Antiprex CE types

The Antiprex CE types supplied in liquid form have a shelf life of one year in
their tightly sealed original packaging.

We would recommend storing the Antiprex CE types supplied in liquid form


in tanks made from AISI 316 Ti or AISI 321 stainless steel.

Ecological and Toxicological Data The toxicological and ecological properties of EDTA have been evaluated in
detail by the authorities of the European Community [1]. In addition, publicly
accessible documents include the report by the Dutch Institute for Health
and Environment [2] and the WHO Guidelines for drinking-water quality [3].

EDTA does not fulfill the criteria of easy biological degradability according
to standard OECD tests, yet biological decomposition has been proven
under suitable conditions—higher retention times, low alkaline pH, or
adapted bacterial flora [1, 4a, 4b], i. e., conditions that are found in nature.
Biological decomposition was also proven directly for EDTA complexes-
calcium, manganese, and zinc [5, 6].

Photochemical decomposition of the EDTA complexes of iron, cobalt, and


manganese is also known [1], and FeEDTA in particular is significantly pres-
ent in the environment under slightly acidic conditions [7]. Photooxidation of
EDTA under real conditions-natural river water with no deliberate addition of
iron, natural sunlight — has also been confirmed on numerous occasions [7,
8, 9].

EDTA has been reported within the ppb range in many waters in Europe.
However, the amounts found in the environment are clearly lower than the
amount used [1]. This can be explained by the proven photochemical and
biological decomposition. As described under REACH, EDTA can be evalu-
ated as “widely biologically degradable” [10].

EDTA is not to be classified as “persistent,” according to REACH.

Furthermore, EDTA can be destroyed directly in wastewater treatment by UV


oxidation [11].

EDTA only has low aquatic toxicity; within the EU risk assessment, a PNEC
of 2,200 μg/L was established. This value is approx. 100 – 1,000-fold above
presently typical values for EU waters [1].

The remobilization of heavy metals by EDTA has been intensively discussed


and evaluated. It is only conceivable under extreme conditions, given that
the exchange of metals proceeds relatively slowly. EDTA is preferentially
found in the water phase low in heavy metals, and hardly at all in the sedi-
ment phase rich in heavy metals; heavy metals frequently occur tightly
bound in the environment. Typically, the respective metal complex already
forms when EDTA is used, at the latest in the wastewater system, where
ZnEDTA frequently predominates. No correlation between EDTA and heavy-
metal content of waters in the environment could be proven [1, 7, 12].

The absorption of EDTA across the food chain should also be evaluated as
uncritical. EDTA is a toxicologically well evaluated substance [1] and has
been used medically in chelation therapy for many decades. It is not easily
absorbed by the digestive tract and quickly excreted through the urine [13,
14]. In many countries, EDTA is permitted as a food additive.

Due to its high polarity and good water solubility, it does not accumulate in
the food chain, and the amounts absorbed through food and drinking water
are typically 1,000-fold under digestible amounts.
TI/EVW 0345 e April 2012 Page 12 of 13 Antiprex CE types

Labelling Please refer to the latest Safety Data Sheets for detailed, up-to-date
information on classification, labelling and product safety.

Literature [1] EU Risk Assessments „Edetic acid (EDTA),“ Volume 49, 2004 and
„Tetrasodiumethylenediaminetetraacetate (Na4EDTA),“ Volume 51, 2004
[2] RIVM Report No. 6017822028, 2009

[3] „Edetic acid (EDTA) in Drinking water,“ Background document for


development of WHO Guidelines for Drinking-water Quality, 2003

[4a] Van Ginkel CG and Geerts R: Full-Scale Biological Treatment of Indus-


trial Effluents Containing EDTA in Nowack B, Van Briesen JM, Biogeo-
chemistry of Chelating Agents, ACS Symposium Series 910, 2003

[4b] Henneken L, Klüner T, Nörtemann B, Hempel DC: Abbau von EDTA mit
freien und immobilisierten Bakterien, Wasser Abwasser Vol 135(6)
1994, 354. (Decomposition of EDTA with free and immobilized bacteria,
water, and wastewater)

[5] Nörtemann B: Biodegradation of Chelating Agents: EDTA, DTPA, PDTA,


NTA, and EDDS in Nowack B, Van Briesen JM, Biogeochemistry of
Chelating Agents, ACS Symposium Series 910, 2003

[6] Satroutdinov AD, Chistyakova TI, Dedyukhina EG, Minkevich IG: Micro-
bial Degradation of DTA: New EDTA-Degrading Bacterial strains in
Nowack B, Van Briesen JM, Biogeochemistry of Chelating Agents, ACS
Symposium Series 910, 2003

[7] Kari FG and Giger W: Speciation and Fate of Ethylenediaminetetraac-


etate (EDTA) in Municipal Wastewater Treatment, Wat. Res. Vol 30(1)
1996, 122 – 134

[8] Metsärinne S, Tuhkanen T and Aksela R: Photodegradation of ethylene-


diaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid
(EDDS) within natural UV radiation range. Chemosphere 45 (2001)
949 – 955

[9] Virtapohja JS: Environmental Fate and Effects of Chelating Agents used
in the Pulp and Paper Industries in Division of Environmental Chemistry
Preprints of Extended Abstracts, Vol 40(1) 2000, 439 – 441

[10] ECHA, Guidance on information requirements and chemical safety


assessment, Part C and Chapter R.11: PBT Assessment, as well as
Chapter R.7b: Endpoint specific guidance.

[11] Wirsing F, Sörensen M: Wasserwirtschaft Wassertechnik Vol. 11 – 12


2004, 54 – 55. (Water supply and distribution, Water technology)

[12] Lorenz J: Remobilisierung von Schwermetallen aus ruhenden Gewäss-


ersedimenten durch EDTA und NTA bei aerober und anaerober Wasser-
phase in Wissen- schaftliche Berichte des Forschungszentrums Karl-
sruhe FZKA 5977 1997. (Remobilization of heavy metals from resting
aquatic sediments by EDTA and NTA in the aerobic and anaerobic
water phase, Scientific Reports of the Karlsruhe Research Center
FZKA, 5977, 1997)

[13] Durbin PW, Schmidt CT: Predicting the kinetics of chelating agents in
man from animal data in Health Physics Vol. 57(1) 1989 165 – 174.

[14] Powell JJ, Burden TJ, Greenfield SM, Taylor PD, Thompson RPH:
Urinary excretion of essential metals following intravenous calcium diso-
dium edetate: an estimate of free zinc and zinc status in man in Journal
of Inorganic Bio- chemistry 75 1999 159-165.

[15] R. Svoboda; C. Lehr; H.-G. Seipp


Power Plant Chemistry 6 (2004), p. 197
TI/EVW 0345 e April 2012 Page 13 of 13 Antiprex CE types

[16] F. Kostroun, et. al.


VGB Kraftwerkstechnik 75, Vol. 9, 1995 p. 819 – 823

[17] A. Langer, et. al.


VGB Kraftwerkstechnik 68, Vol. 9, 1988, p. 945 – 947

Note
The data contained in this publication are based on our current knowledge
and experience. In view of the many factors that may affect processing
and application of our product, these data do not relieve processors from
carrying out their own investigations and tests; neither do these data imply
any guarantee of certain properties, nor the suitability of the product for
a specific purpose. Any descriptions, drawings, photographs, data, pro-
portions, weights etc. given herein may change without prior information
and do not constitute the agreed contractual quality of the product. It is
the responsibility of the recipient of our products to ensure that any
proprietary rights and existing laws and legislation are observed.

April 2012

Europe
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Tel.: +33 1 4964-5000 Carl-Bosch-Straße 38 Tel.: +44 1274 41 70 00
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