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FIGURE 1
Misunderstanding of Solubility
What is Actually The nominal volume in the test cham-
Measured ber of the original Bresle patch is 2.5 cm3.
Because it is impossible to predict Considering the volume and solubility of
which salts are present at the surface, an salt, it is possible to dissolve 892.5 mg of
assumption is made in the Bresle method. common salt in the patch. This correlates
The term “measured as sodium chloride” to 7.29 × 105 mg/m2 NaCl. Comparing
indicates that this mixture of salts is inter- this to the IMO regulation of 20 mg/m2,
preted as being only NaCl. Clearly indi- there is a factor of ~36,000 between these
cating how the conductivity is interpreted concentrations. Thus, the solubility of salt
is essential when creating a report. At is not an issue when conducting the test.
present, there are several interpretations A level of 20 mg/m2 NaCl is actually only
in use. Some speak about NaCl while oth- 0.025 mg NaCl in the patch. Even salts
ers mention mixed salts or just chlorides, that are harder to dissolve will be present
and each has a different calculation factor. in such concentrations that should not
provide any solubility problems.
Typical layman’s understanding of salt.
NaCl, Salt, and Soluble iStock photo. Not all salts are equally soluble in
Contaminants water; there is a great difference in solu-
Our vocabulary is full of words that bility. While NaCl can be dissolved to
have a double meaning. If you ask people create this electrolyte by splitting into 357 g/L, its chemical cousin silver
what salt is, they virtually always reply by ions. Within a solution, NaCl is no longer chloride (AgCl) can be dissolved only
referring to the stuff we put on our French present as such; it has split into sodium for 0.00089 g/L. This is stated as the
fries (Figure 1). If you ask, what is “so- and chloride ions. This also indicates that solubility product K sp. At these con-
dium chloride?” they say it is salt. This it is not possible to have just chloride ions centrations, the solution is saturated
statement is true, but, the other way on a surface. and equilibrium is reached between
around is not. Think of it as follows: a cow
is an animal; however, an animal does not FIGURE 2
have to be a cow. The same is true for
NaCl (common salt). NaCl is a salt; how-
ever, salt does not have to be NaCl. Here
the extensive meaning of the word “salt”
starts to cause a problem.
The chemical meaning of the word
salt is a lot broader than the common
word. Salt is a neutral product formed by
a neutralization reaction between acids
and bases. The reaction product is an
ionic compound. This means that when
the product is dissolved in water, it splits
into an anion (negatively charged parti-
cle) and a cation (positively charged
particle). Both the anion and the cation
can be inorganic or organic, as well as
mono- or polyatomic (one or multiple
atoms combined). The breakdown into a
cation and anion produces an electrolyte
in water. Only the products that dissolve
in water and not those that disperse will NaCl in crystal structure as present on surfaces. Fotolia photo.
dissolved and non-dissolved. A dissolved factor that is adjusted during calibration. sured as NaCl. The statement “mea-
salt produces ions and forms an electro- When taking a conductivity reading of sured as sodium chloride,” means that
lyte. The non-dissolved salt does not the solution acquired with the Bresle not only NaCl is measured but also all
produce ions and does not produce an method, all dissolved salts are measured, other dissolved salts.
electrolyte. This means there is no sig- even the small dissolved portion of the To have a traceable result, an easy
VQÅKIV\ QVKZMI[M QV KWVL]K\Q^Q\a -^MV insoluble salts. reference salt has to be selected. NaCl is
calcium carbonate (CaCO3) is a salt, a This electrolyte is what can be mea- chemically a reference salt. Not only is
very insoluble salt, but nevertheless a sured by a conductivity gauge. The it suitable as a reference salt, but it also
salt. It has a solubility of 0.014 g/L. higher the concentration, the higher the is the biggest cause of problems and has
Figure 2 is an illustration of NaCl in its conductivity. The conductivity of an the highest share in concentration, mak-
crystal structure as present on surfaces. electrolyte not only changes by concen- ing it the ideal salt to report. At present,
tration, but also by variation in the ions there are multiple interpretations in use.
Determining Solubility present. The same concentrations of The most common used is the reference
To determine if a salt is soluble, there NaCl or potassium chloride (KCl) pro- to NaCl. Some others are mixed salts
is a chemical rule. In chemistry, a con- duce electrolytes with a different electric and chloride. With the Bresle method,
centration in mg/L is not interesting, conductivity. Conductivity is thus quan- this relates to the respective factors 6, 5,
because of the difference in weight be- titative and qualitative dependent. Tem- and 3.6. Here, factor 6 calculates as
tween different atoms and molecules. The XMZI\]ZMIVLXZM[[]ZMIT[WQVÆ]MVKM\PM NaCl, factor 5 as mixed salts, and factor
amount of molecules is what is of interest measurement. With higher temperature 3.6 to an industry-fantasized possibility
to a chemist. Look at it as bolts and nuts. comes a higher enthalpy. Enthalpy is a of having only chloride ions present.
A bolt is heavier than a nut; to have as measure of the heat content at subatomic Even when test methods are speci-
many bolts as nuts means that you need level. Very simply stated, this means that ÅMLQ\_W]TL[\QTTJM^MZaPMTXN]TQNITT
1 kg of nuts to screw onto 2 kg of bolts. A the hotter a subatomic particle gets, the involved parties stated the salt concen-
chemist looks at a concentration in more active it gets, as does its reactivity tration the correct way. Not stating the
mol/L. The term moles can best be com- and interactivity. A microwave oven does answer with the right interpretation can
XIZML\W\PMLMÅVQ\QWVZMIK\Q^MWZ_WZS- not put heat in your food; it imparts more cause serious differences in the result. If
ing units. In chemistry, the solubility is energy/activity, which in turn produces \PM[XMKQÅKI\QWV[IZMQVKPTWZQLMIVL\PM
stated in three groups: heat. The higher the temperature in a measurement is made as NaCl, there is
A salt is soluble if it dissolves in water solution, the higher the conductivity. I[QOVQÅKIV\LQNNMZMVKM\PI\KIVTMIL\W
to give a solution with a concentration of Modern conductivity gauges are compen- extreme costs caused by unnecessary
at least 0.1 mol/L at room temperature. A [I\MLNWZ\PQ[\MUXMZI\]ZMQVÆ]MVKM<W cleaning.
salt is insoluble if the concentration of an determine conductivity, reference salts
aqueous solution is <0.001 mol/L at room are used. This is done by having a solu- What is the Correct
temperature. Slightly soluble salts give \QWV_Q\PIÅ`MLKWVKMV\ZI\QWVWNIX]ZM Interpretation of Data?
solutions that fall between these extremes. reference salt, usually KCl. Referring to the total salt mixture on
+WVL]K\Q^Q\a Q[ I VWV[XMKQÅK UMI- a surface as NaCl is an interpretation.
Conductivity surement method; it detects all soluble Let us, however, compare it to measuring
The method of measuring the conduc- salts, with all different varieties. The salt \ZINÅKRIU[<PMTMVO\PWNI\ZINÅKRIUQ[
tivity of an electrolyte is not the same as mixture that is found in the measure- not measured, but calculated. It is a
the procedure used to measure conductiv- ment cell usually is not made up of one multiplication of the amount of cars
ity of copper wire. Conductivity is mea- type of salt. This multi-ion electrolyte times their length. You never know,
sured with a sine wave potential across requires an interpretation when the PW_M^MZ _PQKP KIZ[ IZM QV \PM \ZINÅK
\_WLMÅVMLXTI\M[[M\I\ILMÅVMLLQ[\IVKM conductivity has to be reported as a jam, so you don’t know the exact length
from each other. Between these plates, the concentration. This interpretation is one WNMIKPKIZAW]KIVTWWSI\[ITM[ÅO]ZM[
ions in the electrolyte conduct the current of the biggest misunderstandings when in the car industry and calculate an aver-
backward and forward. The size and measuring. The results, according to age car length from this, but what about
distance between the plates determine the ISO 8502-61 and ISO 8502-9,2 have to the old cars? Second, cars are just like salt
cell constant. This constant is also the be reported as mg/m2 soluble salts mea- deposits—region specific. Americans
38 MATERIALS PERFORMANCE November 2009
C O AT I N G S & L I N I N G S
drive Hummers, Europeans drive Mer- Conclusions 2 ISO 8502-9, “Preparation of steel substrates
cedes, and Asians drive the Tata Nano. before application of paints and related
Part1 has presented a general under- products—Tests for the assessment of surface
There is no real comparison and unifor- standing of salts and also explained many cleanliness—Part 9: Field method for the
UQ\a<PM\ZINÅKKWV\ZWTTMZ[NWZ\PMKWI\- misunderstandings. The Bresle test has conductometric determination of water-
ing industry, in this case ISO, gave the been introduced, along with many as- soluble salts” (Geneva, Switzerland: ISO).
[WT]\QWV)\ZINÅKRIU[\I\MLQVTMVO\PQ[ pects of salt solubility and solution con-
calculated by the length of just one car, a ductivity. Part 2, to be published in the N. FRANKHUIZEN is a commercial technician at TQC,
1949 Cadillac Deville, the length of which Nijverheidscentrum 14, Zevenhuizen 2761JP, The
December 2009 issue of MP, will cover Netherlands, e-mail: nico@tqc.eu. He is chairman
is known worldwide. This means that the sampling procedures, measurement tech- of NEN NC 342.035, The Dutch mirror committee of
IUW]V\WNKIZ[QVIVa\ZINÅKRIU_WZTL- niques, the effect of climate on test results, ISO TC 35, Paint and Varnishes. He has 10 years of
wide can thus be multiplied by a standard and comment on commercially available laboratory experience in the field of chemical
^IT]MIVLITT\ZINÅKRIU[IZM\PMVKWU- test kits. pretreatment and corrosion protection followed by
parable. The same goes with salt mea- work at TQC.
surement—soluble salts in g/m 2 are References
measured as NaCl. 1 ISO 8502-6, “Preparation of steel substrates
before application of paints and related
products—Tests for the assessment of surface
cleanliness—Part 6: Extraction of soluble
contaminants for analysis—The Brestle
method” (Geneva, Switzerland: ISO).
FIGURE 1
FIGURE 2
parameters has to be reported and agreed The combination of the new technique 3 ISO 8502-9, “Preparation of steel
upon by both inspector and customer. and high-quality gauges and patches substrates before application of paints
and related products—Tests for the as-
;]ZNIKM\MUXMZI\]ZMIT[WQVÆ]MVKM[\PM makes these kits especially useful for es- [M[[UMV\WN[]ZNIKMKTMIVTQVM[[¸8IZ\!"
test, meaning that this parameter also tablishing salt contamination. But, what- Field method for the conductometric
needs to be recorded. The lack of these ever procedures are used, it is essential to determination of water soluble salts”
/MVM^I;_Q\bMZTIVL"1;7
recorded values will also render the ac- perform the test properly and to ensure
quired results invalid. that accurate data are obtained.
N. FRANKHUIZEN is a commercial technician at TQC,
Nijverheidscentrum 14, Zevenhuizen 2761JP, The
Conclusions References Netherlands, e-mail: nico@tqc.eu. He is chairman
This article has shown that there is a 1 N. Frankhuizen, “Measuring NaCl, Salt, of NEN NC 342.035, the Dutch mirror committee of
and Soluble Contaminants with Bresle ISO TC 35, Paint and Varnishes. He has 10 years of
lot of science behind proper testing for
Patches—Part 1,” MP "XX laboratory experience in the field of chemical
salt contamination. Inspectors can ben- 36-39. pretreatment and corrosion protection followed by
MÅ\NZWUZMILaUILM\M[\SQ\[\PI\UISM 2 ISO 8502-6, “Preparation of steel work at TQC.
these tests quite simple. Updated Bresle substrates before application of paints
kits are now available with the DSP, en- and related products—Tests for the as-
[M[[UMV\WN[]ZNIKMKTMIVTQVM[[¸8IZ\"
abling inspectors not only to work faster Extraction of soluble contaminants for
but also to produce more accurate results. analysis—The Bresle method” (Geneva,
;_Q\bMZTIVL"1;7