Abstract:
A method for assessing a corrosion inhibitor in a coolant, comprises providing a test kit comprising a first chamber containing an acid buffer and a solvent immiscible therein and a second chamber containing an indicator, the second chamber being in fluid communication with the first chamber and being configured such that retraction of the second chamber draws fluid into the first chamber and advancement forces fluid into the second chamber; drawing a coolant sample into the first chamber; contacting the coolant sample with the acid buffer and solvent in the first chamber and extracting the corrosion inhibitor into the solvent; allowing the solvent and buffer to separate in the first chamber; forcing a portion of the separated solvent into the second chamber; contacting the separated solvent with the indicator in the second chamber, and obtaining a visual indication of the presence of corrosion inhibitor in the coolant sample.

Description:
PRIORITY CLAIM 
     The present application claims priority from PCT/US2009/067836, filed 14 Dec. 2009, which claims priority from U.S. Provisional Applications 61/122,837, filed 16 Dec. 2008, and 61/167,424, filed 7 Apr. 2009, all of which are incorporated by reference. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates generally to a device for evaluating the constituents of a heat exchange fluid having corrosion inhibitors therein. More particularly, the device provides a multi-chambered plunger that allows a multi-part chemical assessment to be carried out in with a minimum of operator inputs. 
     BACKGROUND OF THE INVENTION 
     The systems, apparatus, and methods described herein are particularly suited for determining the constituents of such heat exchange fluids as organic acid technology coolants. Referred to as “extended life coolants,” these heat exchange fluids typically contain carboxylate salts of long-chain alkyl-based organic acids or of aromatic-based organic acids (hereinafter “acid-based corrosion inhibitors”) as corrosion inhibitors. These corrosion inhibitors inhibit corrosion of the metallic surfaces that are contacted by the heat exchange fluid. The organic acid-based corrosion inhibitors are also formulated for longer or extended service lives as compared to inorganic acid-based corrosion inhibitors. The recommended service life for “extended life coolants” (ELC) (under normal driving conditions) is commonly about five years, whereas the recommended service life for conventional coolants may be about two years. 
     Corrosion inhibitors that are suitable for this use are known and include carboxylate salts of long chain alkyl monocarboxylic organic acids (such as 2-ethyl hexanoic acid, octanoic acid, etc.), of dicarboxylic acids (e.g., sebacic acid), or of aromatic organic acids (such as benzoic acids and p-toluic acids). An expanded description of the type of heat exchange fluid that is a subject of the present invention and its application are provided in U.S. Pat. Nos. 5,997,763 (commonly owned with the present application) and 6,475,438. Such heat exchange fluid types are widely used. It is further noted that the subject heat exchange fluids may be aqueous and/or glycol compositions and used for automotive, heavy duty, marine and other industrial applications. 
     The level of corrosion inhibitor(s) present in the coolant may diminish over time. For that reason, it may be desirable to test the coolant in order to determine its continued functionality. There is not currently available a reliable and convenient method or equipment for evaluating heat exchange fluids having corrosion inhibitors therein, so as to, for example, determine the sufficiency of the corrosion inhibitor content to provide ongoing corrosion protection. Analytical methods exist, but such methods typically require equipment, facilities and/or time that are not readily available or convenient to use in the field. Moreover, used heat exchange fluids typically include an array of components, including interferents. These interferents can alter the accuracy of conventional analytical techniques. 
     Thus it is desirable to provide a simple, easy-to-use device that can be used to determine the sufficiency of the corrosion inhibitor content, particularly in the field, where time and operator resources are relatively scarce. 
     SUMMARY OF THE INVENTION 
     In one embodiment of the present invention, a device is provided for evaluating the constituents of a heat exchange fluid having acid-based corrosion inhibitors therein. The invention provides a small, simple, fast, reliable, field-usable, and low-cost device for analyzing fresh, contaminated, and used extended life coolants and assessing their carboxylic acid-based inhibitor content. The device requires a minimum of operator steps and virtually no operator decision-making. Preferred embodiments include a multi-chambered device in which the flow between chambers is controlled by the configuration of the chambers themselves. More specifically, a preferred embodiment includes a device that can be operated merely by sequential retraction and advancement of a single plunger, without the need for manually controlled valves or other flow control methods. 
     In some embodiments, the invention comprises a method for assessing the presence of a corrosion inhibitor in a coolant comprising the steps of a) providing a test kit; b) retracting the second chamber so as to draw a sample of the coolant into the first chamber; c) contacting the coolant sample with the acid and the solvent in the first chamber so as to perform a liquid-liquid extraction of at least a portion of the corrosion inhibitor into the solvent; d) allowing at least a portion of the solvent to separate from the acid solution in the first chamber; e) advancing the second chamber so as to force at least a portion of the separated solvent into the second chamber; f) contacting the portion of separated solvent with the indicator solution in the second chamber so as to obtain a visual indication of the presence of corrosion inhibitor in the coolant sample. 
     The test kit may comprise a first chamber initially containing an acid buffer solution and a solvent, the solvent and the acid buffer being substantially immiscible and the solvent having a specific gravity that is less than that of said buffer solution, the first chamber including a first inlet and means for controlling fluid flow through the first inlet; and a second chamber initially containing an indicator solution and having a second inlet; wherein the second chamber is in fluid communication with the first chamber via the second inlet and the first and second chambers are configured such that retraction of the second chamber draws fluid into the first chamber through the first inlet and advancement of the second chamber forces fluid from the first chamber into the second chamber through the second inlet. 
     The device is such that the steps of the method can be carried out in less than one minute. The second chamber may be slidably received in the first chamber and the test kit may include a base that is capable of supporting the first chamber in an upright position and of sealing the first inlet. The indicator solution is preferably an acid-base indicator. The device is preferably free of manually controlled valves. 
     The present invention provides several advantages. For example, the result is independent of the color of the sample being tested, and the device is simpler than previously known devices. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       For a more detailed understanding of the preferred embodiments, reference is made to the accompanying Figures, wherein: 
         FIG. 1  is a simplified flowchart illustration of the steps carried out by preferred embodiments of the device of the present invention; 
         FIG. 2  is a schematic illustration of one embodiment of a device constructed in accordance with the present invention, in an initial state; 
         FIG. 3  is a schematic illustration of the device of  FIG. 2  after a sample has been collected; 
         FIG. 4  is a schematic illustration of the device of  FIG. 2  after phase separation has occurred; and 
         FIG. 5  is a schematic illustration of the device of  FIG. 2  after the solvent has been contacted with an indicator 
         FIG. 6  is a schematic illustration of a device constructed in accordance with another embodiment the present invention, in an initial state; 
         FIG. 7  is a schematic illustration of one the device of  FIG. 6  after a sample has been collected; 
         FIG. 8  is a schematic illustration of one the device of  FIG. 6  after a first dispensing chamber has been emptied; 
         FIG. 9  is a schematic illustration of one the device of  FIG. 6  after a second dispensing chamber has been emptied; and 
         FIG. 10  is a schematic illustration of one the device of  FIG. 6  after a third dispensing chamber has been emptied. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention provides a method, system, and apparatus for evaluating the constituents of a heat exchange fluid. The systems, apparatus, and methods described herein are particularly suited for determining the constituents of such heat exchange fluids that include organic acid technology coolants. Referred to as “extended life coolants,” these heat exchange fluids typically contain carboxylate salts of long-chain alkyl-based organic acids or of aromatic-based organic acids (hereinafter “acid-based corrosion inhibitors”) as corrosion inhibitors. These corrosion inhibitors inhibit corrosion of metallic surfaces with which the heat exchange fluid comes in contact. The organic acid-based corrosion inhibitors are also formulated for longer or extended service lives as compared to inorganic acid-based corrosion inhibitors. Suitable organic acid-based corrosion inhibitors include carboxylate salts of long chain alkyl monocarboxylic organic acids (such as 2-ethyl hexanoic acid, octanoic acid, etc.), of dicarboxylic acids (e.g., sebacic acid), or of aromatic organic acids (such as benzoic acids and p-toluic acids). 
     Preferred methods for analyzing the fluids are described in commonly-owned co-pending application Ser. No. 11/777,066, which is incorporated herein by reference. As described therein and as illustrated in  FIG. 1 , the preferred analytical method includes the steps of:
         obtaining a sample of the heat exchange fluid (step  10 ), preferably in a predetermined amount;   adjusting the pH of the sample so as to reduce the solubility of target acid-based corrosion inhibitors in the sample (step  12 );   separating the target acid-based corrosion inhibitors from the sample (step  14 ); and   evaluating the separated residue containing the target acid-based corrosion inhibitors (step  16 ).       

     Step ( 12 ) results in the conversion of at least some (if not substantially all) of the salt form of the target acid-based corrosion inhibitors to its acid form. The acid forms of these corrosion inhibitors are much less soluble in water than the salt form and are, therefore, more susceptible to phase separation or liquid-liquid extraction. The objective of step ( 12 ) is to adjust the pH of the sample so as to at least render the target components susceptible to liquid-liquid extraction from the initial coolant solution, even if a complete physical phase separation has not occurred. In most applications, this requires the target corrosion inhibitor to be rendered at least partially insoluble. 
     According to the present invention, concurrently with its acidification, the sample is placed in contact with a solvent in which the carboxylic acid of the corrosion inhibitor is soluble. This brings about the separation shown as step ( 14 ), which is preferably carried out by liquid-liquid extraction. The carboxylic acid-containing solvent is then placed in contact with an indicator that changes color in the presence of an acid. Preferred embodiments of these steps are described in detail below. 
     Acid-based corrosion inhibitors that can be targeted and assessed using the methods of the present invention include but are not limited to organic acid-based corrosion inhibitors, and more particularly, carboxylate salts of long-chain organic acids such as alkyl monocarboxylic acids and dicarboxylic acids, and carboxylate salts of aromatic based monocarboxylic or dicarboxylic acids. In a typical application, the target corrosion inhibitors of interest may be composed of different groups of corrosion inhibiting compounds, such as groups of carboxylate salts of organic acids. These carboxylate salts may be present at different concentrations and their acidic forms may have different degrees of solubility in the solution. The target groups of compounds will be characterized by different pKa values. For each specific corrosion inhibitor acid, the exact pH at which phase separation initiates will depend on the total concentration of that specific inhibitor, the solubility limit of its protonated form in the solution, and the pKa of the inhibitor. If the pH of the sample is reduced to approximately the pKa value, depending on the concentration (i.e., its solubility limit) of one group of target corrosion inhibitors, that group of target corrosion inhibitors begins to phase separate from the solution and are more susceptible to extraction or separation from the solution. For each specific target corrosion inhibitor, as the total inhibitor concentration is lowered, phase separation is observed to occur at lower pH values. 
     Thus, in the present application, where the intent is to remove the corrosion inhibitors from a fluid sample so that their presence can be detected, the pH is reduced to well below the lowest pKa value of the group of targeted corrosion inhibitors. In the case where the total inhibitor concentration does not exceed the solubility limit of the acid form, phase separation of the inhibitor may not occur. 
     For all inhibitor organic acids, as the pH of the solution is preferably lowered by one, two, three or more pH units below the pKa value of the component of interest, the efficiency of separation is further improved because more of the carboxylate salt is driven by acid-base equilibrium into the carboxylic acid form. This lowering of the pH reduces solubility of the compound of interest in the aqueous solution and thus enables more efficient extraction of the compound, i.e. the carboxylic acid, into the solvent. The relative proportion of acid that is removed from the solution via the liquid extraction depends on the total concentration of the specific inhibitor and the solubility limit for the acid form of the specific inhibitor under consideration. 
     In preferred embodiments, the portion of the sample that is dissolved in the solvent contains the target organic acid-based corrosion inhibitors and excludes corrosive short-chain organic acids and other analytical interferents that would otherwise affect some measurement methods (e.g., titration). The excluded interferents preferably include organic acids that are glycol oxidation products (e.g., glycolic acid or formic acid, and inorganic acid components such as silicates, borates, phosphates, nitrites and nitrates). 
     Referring again to  FIG. 1 , following the separation step, the solvent containing the target acid-based corrosion inhibitors is measured or otherwise evaluated, in step ( 16 ), using one of a number of commonly known analytical methods. As will be described below, the sufficiency of the amount of corrosion inhibitors retained in the heat exchange fluid may be evaluated qualitatively or quantitatively. Suitable measurement methods may involve a titration process and/or chemical reactions. For example, the acidity of the solvent may be analyzed using an acid-base color indicator. In this embodiment, the indication of a color change can be used to indicate that the concentration of acid-based corrosion inhibitors in the sample is equal to, above, or below a predetermined level. 
     Referring now to  FIGS. 2-5 , a preferred system and/or apparatus for carrying out the method described above is a portable, field-ready kit that includes all of the components and prepared solutions necessary for performing the evaluation described above. Using a single field kit, a qualitative analysis can be performed to determine whether the concentration of target corrosion inhibitors in the heat exchange fluid is below or above a predetermined level. 
     Referring first to  FIG. 2 , an exemplary device  10  for evaluating the concentration of acid-based corrosion inhibitors contained in a heat exchange fluid includes a first chamber  20 , a second chamber  30 , a plunger  40 , and a base  50 . 
     First chamber  20  preferably includes a hollow cylindrical body having an inlet  26  at one end and an open second end. The inner wall of chamber  20  includes a first stop member  22  positioned at a first distance from inlet  26  and a second stop member  24  positioned at a second, greater distance from inlet  26 . Stop members  22 ,  24  may be annular ridges on the inside wall of chamber  20  or any other similar device. A plurality of mixing elements  28  are optionally contained in chamber  20 . Mixing elements  28  may be glass balls or any other small solid objects that will not interact with the chemical components of the present invention. 
     Second chamber  30  is slidably received in chamber  20 . Like chamber  20 , chamber  30  preferably includes a hollow cylindrical body having an inlet  36  at one end and an open second end. The outside diameter of second chamber  30  is incrementally smaller than the inside diameter of chamber  20 , so that a sealing engagement can be formed between the inside surface of chamber  20  and the outside of chamber  30 . The seal may be formed using stop members  22 ,  24 , or using other seal members (not shown). Chamber  30  includes a first stop member  32  at one end, preferably positioned adjacent to inlet  36 , and an optional second stop member  34  positioned at some distance from first stop member  32 . First stop member  32  is disposed on the outside surface of chamber  30  and may form part of the sealing engagement with the inside wall of chamber  20 . Second stop member  34  is disposed on the inside surface of chamber  30 . A plurality of mixing elements  38  are optionally contained in chamber  30 . Mixing elements  38  may be glass balls or any other small solid objects that will not interact with the chemical components of the present invention. 
     Plunger  40  is slidably received in chamber  30 . Plunger  40  preferably comprises a body having a first end  41  and a second end  43 . Second end  43  is provided with seal/stop member  42 , which forms a sliding sealing engagement with the inside surface of chamber  30 . Plunger  40  is preferably sized so that first end  41  closes inlet  36  before or when stop member  42  engages stop member  34 . 
     Before use, chamber  30  is advanced into chamber  20  such that stop member  32  engages stop member  22  and plunger  40  is advanced into chamber  30  such that stop member  42  engages stop member  34  and end  41  closes inlet  36  so that fluid flow between chamber  20  and chamber  30  is prevented. It will be understood that other devices for closing inlet  36  can be used, including but not limited to flapper valves, check valves, and the like. In some embodiments, fluid flow between first chamber  20  and second chamber  30  is prevented by providing an air gap above the liquid surface in chamber  20 , so that an air bubble occupies inlet  36  during the mixing process. Thus, in some embodiments, inlet  36  has a relatively small inside diameter. 
     First chamber  20  is preferably preloaded with an acid solution, shown at  60 , and a solvent, shown at  62 . Acid solution  60  may be a buffer solution. Acid solution  60  and solvent  62  are preferably immiscible and are preferably selected such that the specific gravity of the solvent is less than that of the buffer solution. By way of example only, the acid solution may comprise 0.1N Na 2 HPO 4  in DI water, plus ˜2% concentrated H 3 PO 4  to obtain pH 2.2 and the solvent may comprise dibutyl ether, isopropyl ether, methyl isobutyl ketone, or the like. Second chamber  30  is preferably preloaded with an indicator solution, shown at  64 . Indicator  64  may comprise, for example, 0.1N NaOH in DI water/ethanol 1/3, plus 0.02 wt % bromothymol blue pH indicator. Solvent  62  and indicator  64  may or may not be miscible, as desired. 
     Acid buffers suitable for use with the invention (as the acidifying solution) are generally known. Typically, acid buffers are a mixture of an acid and its salt. Examples of suitable acid buffer systems include HCl/KCl systems (pH=1-2), sodium dihydrogen phosphate/phosphoric acid systems (pH=2-4), potassium tetraoxalate systems (pH=1-2), acetic acid/sodium acetate (pH=3-6), HCl/citric acid systems (pH=1-5). A suitable acid buffer system will have a reactive acid capacity to react with the basic buffers of the ELC coolant systems and neutralize these basic buffers while controlling the pH of the final mixture. The corrosive nature of the acid reagent is thus minimized. 
     In general, any readily available acid capable of reducing the pH of the sample fluid may be used as the acidifying solution instead of an acid buffer. Acids such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid (i.e. 0.1 molar to 1 molar in concentration) may be used. 
     Referring again to  FIG. 2 , base  50  is preferably sufficiently stable to support device  10  in an upright position. To that end, base  50  may include a receptacle  52  sized to receive the inlet  26  of chamber  20 . In some embodiments, the inside of receptacle  52  and the outside of inlet  26  may be provided with mating threads, luer taper fittings, snap fittings, or other similar sealing device (not shown) therebetween so that base  50  may also function as a cap or closure for chamber  20 . It will be understood that a valve or similar device can also be included to control the flow of fluid through inlet  26  if desired. In such an embodiment, it is not necessary for base  50  to function as a cap. 
     Because the present device provides a visual output and depends in part on visual verification of the process steps, it is preferred that the components of the device, and in particular chambers  20  and  30 , be constructed of a clear or at least partially transparent material. 
     Operation 
     When it is desired to use device  10  to assess a sample of fluid, base  50  is removed from chamber  20  and a sample of coolant is drawn into chamber  20  by retracting chamber  30  until stop member  32  engages stop member  24 , as shown in  FIG. 3 . By way of example only, the distance between stop member  22  and stop member  24  may be such that the volume of sample obtained in this manner is about 1 ml. If necessary, cap  50  is then replaced and the device is preferably shaken so as to cause thorough mixing of the sample, acid solution  60  and solvent  62  in chamber  20 . If present, mixing elements  28  enhance the contact between the solutions. A mixture, shown at  70  in  FIG. 3 , is temporarily formed in chamber  20  during this process. Because the pH of the acid solution is low, salts of the corrosion inhibiting compounds are converted to their carboxylic acid forms, which have reduced solubility in the aqueous phase. At the same time, the carboxylic acids are soluble in the solvent, with the result that some of the corrosion-inhibiting compounds migrate into the solvent. 
     If the cap is not already in place, chamber  20  is then placed in base  50 , and the mixture is allowed to rest. As shown in  FIG. 4 , during the rest period, the carboxylic acid-containing solvent solution  74  separates from the mixture  72  containing the sample and the acid solution. In most instances, separation is sufficiently complete in 30 to 120 seconds. It has been found that a visual determination that separation is complete is sufficiently precise to allow for meaningful assessment of the coolant sample. 
     Once the solvent has separated from the aqueous phase in chamber  20 , chamber  30  is advanced into chamber  20  until stop member  32  again engages stop member  22 . With cap  50  in place or inlet  26  closed by other means, movement of chamber  30  within chamber  20  forces a portion of the solvent phase, which is uppermost in chamber  20 , to enter chamber  30 , which in turn causes plunger  40  to retract along chamber  30  so as to accommodate the additional fluid volume in chamber  30 . The amount of solvent solution  74  that enters chamber  30  is preferably less than the total amount of solvent, so as to ensure that the mixture in chamber  30  is not contaminated with the sample/acid solution  72 . 
     Once inside plunger  40 , solvent solution  74  mixes with the indicator solution there, forming a sample indicator solution  76 . The presence of sufficient organic acid in the solvent phase will neutralize the base, causing the sample indicator solution to become acidic and change color. If the amounts, compositions, and concentrations of the solutions provided with the device are selected appropriately, the presence or absence of a color change in the indicator solution can be used as an indicator of the presence or degree of degradation of the corrosion inhibitor. 
     For example, a color change may indicate that the concentration of acid inhibitors in the sample is in excess or equal to a predetermined threshold concentration. This predetermined threshold amount preferably corresponds to the desired threshold or minimum concentration of acid inhibitors in the heat exchange fluid in use. It should be noted that any appropriate indicator may be used for indicating or detecting the threshold concentration of acid inhibitors. 
     The preferred method described above is particularly advantageous over prior art methods of testing extended life coolant/heat exchange fluids to determine the content of acid-based corrosion inhibitors. In the above-described method, the long-chain alkyl and the aromatic organic acids, such as the carboxylic acid-based corrosion inhibitors, are excluded from the rest of the sample, and particularly from corrosive short-chain organic acids and other acidic interferents. In this way, after separation, measurement of organic acids will only detect the targeted organic acids (i.e., the target corrosion inhibitors). The measurement will not be affected or interfered by inclusion of short-chain organic acids and other acidic interferents, including inorganic acids. 
     In addition, the present invention provides an indication of coolant composition that is not dependent on the color or appearance of the original coolant sample. It has been found that the dyes typically used in coolant compositions are not soluble in the solvent phase  62 , and thus do not interfere with the color of the indicator  64 . 
     It is not uncommon for consumers to mix extended life coolants with other heat exchange fluids. A common mixture may include short-chain organic acids, which are formed unintentionally by oxidation of glycol, and inorganic corrosion inhibitors along with long-chain organic acid-based corrosion inhibitors. Hybrid extended-life coolants also contain a mixture of inorganic and long-chain organic acid-based corrosion inhibitors. In one preferred method, only the corrosion inhibitors that render the heat exchange fluid to be “extended life” are detected. Accordingly, in a quantitative measurement, the amount of “extended life” additives or coolant required to replenish the mixture and preserve its extended life can be determined. 
     The method, system, and apparatus described above provide a reliable, field ready and convenient method for analyzing the heat exchange fluids. The system and apparatus described above are particularly useful for original equipment manufacturers (OEMs), fleet owners, and automotive shops (e.g., truck stops or fast lube facilities). One benefit of the described method, systems, and apparatus, is that it provides a quick, efficient, and accurate quantitative field method for determining the residual content of target acid-based corrosion inhibitors in either fresh, contaminated, or used extended life heat exchange fluids. The method may be used to determine the concentration of acid-based corrosion inhibitors in order to determine the heat exchange fluid&#39;s utility for continued use or, alternatively, to determine how much of any fresh corrosion inhibitors may be added to maintain the heat exchange fluid&#39;s utility. 
     Because the present device requires only retraction and depression of a single plunger and no control or decision steps, it is extremely simple to use. Accordingly, it is contemplated that the invention will be particularly beneficial to OEM&#39;s, fleet owners, the automobile service industry, and every day automobile owners. The mechanic, maintenance personnel, or car owner can accurately determine the concentration or level of acid-based inhibitors present in heat exchange fluid samples or whether the concentration or level in the heat exchange fluid is above or equal to a predetermined minimum threshold. With this information, the same personnel can determine the sufficiency of the heat exchange fluid for continued use and/or determine how much, if any, of fresh coolant must be added to maintain the utility of the coolant. 
     In an alternative embodiment of the invention, the separation can be carried out using a multi-chambered device as illustrated in  FIGS. 6-10 . This embodiment is also described in U.S. application Ser. No. 61/122,837, which is incorporated herein by reference in its entirety. 
     A preferred system and/or apparatus for carrying out the method described above is a portable, field-ready kit, as shown schematically in  FIG. 6 . Such a “field kit” may include all the components and prepared solutions necessary for performing the general evaluation method described above. Using a single field kit, a qualitative analysis can be performed to determine whether the concentration of target corrosion inhibitors in the heat exchange fluid is below or above a predetermined level. 
     Referring now to  FIG. 6 , an exemplary system  100  for evaluating the concentration of acid-based corrosion inhibitors contained in a heat exchange fluid includes five variable-volume chambers  111 ,  211 ,  311 ,  411 ,  511 . Chambers  111 - 311  are dispensing chambers and preferably each comprise a barrel  112 ,  212 ,  312  and a corresponding plunger/piston  113 ,  213 ,  313 , whereas receiving chambers  411  and  511  each preferably comprise a barrel  412 ,  512  and a handleless piston  413 ,  513  (shown in phantom). Chambers  111 - 511  may comprise or resemble conventional syringes or any other suitable mechanism for controllably collecting, holding and releasing fluids. For example, it will be understood that dispensing chambers  111 - 311  may be constructed in any manner that allows them to be easily manually operated. Thus, by way of example only, instead of plungers the volume of each chamber may be reduced by means of a thumbwheel or the chambers themselves may comprise compressible containers. 
     The volume of chamber  511  is preferably equal to the sum of the volumes of chambers  211  and  311 . In preferred embodiments, the area of piston  513  is greater than the area of piston  413 , and more particularly at least twice as great as the area of piston  413 . In some embodiments, the volumes of chambers  211  and  311  are equal. The volume of chamber  411  is preferably equal to the volume of chamber  111  plus the volume of a predetermined amount of indicator solution. 
     Dispensing chambers  111 ,  211 ,  311  are preferably connected in parallel to an extraction device  350 , which may be a membrane, sorbent, or the like, as described above. Likewise, receiving chambers  411 ,  511  are preferably connected in parallel downstream of extraction device  350 . One or more of the chambers and in particular chamber  311  may be releasably connected to the system, so as to allow chamber  311  to be used for collection of the sample to be assessed. 
     As illustrated in  FIG. 6 , before usage of the device, chamber  311  preferably contains a predetermined volume of an acidifying solution or buffer that will reduce the pH of the sample fluid below a predetermined level. The volume of acidifying solution or buffer is preferably smaller than the total volume of chamber  311  so that there is room in chamber  311  to also accommodate a sample volume in addition to the acidifying solution or buffer. Chamber  211  contains a wash solution as described in detail below. Chamber  111  contains a solvent, again as described in detail below. 
     Operation 
     When it is desired to assess a sample of coolant, chamber  311  may be removed from the kit and used to collect the desired sample. If chamber  311  is preloaded with a volume of acid or buffer, the sample may be drawn into chamber  311  and allowed to mix with the preloaded liquid. In preferred embodiments, chamber  311  is sized such that its total volume is equal to sum of the initial volume of acidifying solution and the desired sample size, so the chamber  311  is full after the sample has been collected, as shown in  FIG. 7 . 
     In the case where the sample is being assessed for the presence of acid-based corrosion inhibitors, the pH of the resultant acidified sample in chamber  311  is preferably below about 6 and, more preferably, within the range of about 2 to about 4. In this way, the target corrosion inhibitor organic acids in the sample fluid are rendered insoluble, or substantially insoluble, in the acidified sample. 
     Acid buffers suitable for use with the invention (as the acidifying solution) are generally known. Typically, acid buffers are a mixture of an acid and its salt. Examples of suitable acid buffer systems include HCl/KCl systems (pH=1-2), sodium dihydrogen phosphate/phosphoric acid systems (pH=2-4), potassium tetraoxalate systems (pH=1-2), acetic acid/sodium acetate (pH=3-6), HCl/citric acid systems (pH=1-5). A suitable acid buffer system will have a reactive acid capacity to react with the basic buffers of the ELC coolant systems and neutralize these basic buffers while controlling the pH of the final mixture. The corrosive nature of the acid reagent is thus minimized. 
     In general, any readily available acid capable of reducing the pH of the sample fluid in the preloading step as desired may be used as the acidifying solution instead of an acid buffer. Acids such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid (i.e. 0.1 molar to 1 molar in concentration) may be used. These concentrated acids will also neutralize the basic ELC coolant media and reduce the pH for the intended purpose. The use of these acids will require, however, that operating procedures are specifically implemented, and operating equipment designed, for the handling of corrosive materials. 
     Chamber  311  is designed to enable coolant and acidifying solution to be mixed just prior to, or during, manual injection of the acidified sample into the extraction device. In preferred embodiments, the resulting mixture is injected into the extraction device by depressing plunger  313 , as illustrated in  FIG. 8 . Because chambers  111  and  211  are already full at this point, no fluid flows into them. Instead, the contents of chamber  311  flow into extraction device  350 . If the extraction device is an SPE cartridge, the pH-adjusted sample is preferably injected into the extraction device  350  at a rate that is sufficiently slow to allow adsorption of target organic acids from the acidified sample onto the SPE cartridge. In this process, most of the heat exchange fluid and water-soluble components of the fluid (including corrosive short-chain organic acids and inorganic acids) pass through the SPE cartridge. 
     Fluid flowing out of extraction device  350  flows into line  322 . Because there is preferably no valving in line  322 , fluid pressure at the entrances to receiving chambers  411  and  511  will be substantially the same. However, because the area of piston  513  is greater than the area of piston  413 , the pressure of fluid flowing out of extraction device  350  will apply a greater force to piston  513  than to piston  413 , causing it to move sooner and faster than piston  413 . In addition, the interface between piston  513  and the inside wall of chamber  511  may be designed to have lower coefficients of static and/or dynamic friction than the interface between the piston  413  and the inside wall of chamber  411 , so that piston  513  is still more likely to move farther than piston  413 . These differences between chambers  411  and  511  cause the majority of the fluid to enter chamber  511 , as illustrated in  FIG. 8 . 
     Referring again to  FIG. 6 , chamber  211  contains a predetermined volume of wash solution, which may comprise water that has been acidified to a desired pH. For example, the pH of the water may be in the range of about 3 to 4. The wash solution is preferably selected to have a pH that is not so low as to cause error in a subsequent analytical procedure but not so high as to cause the corrosion inhibitor organic acids to re-dissolve. The wash solution may be prepared by diluting a strong acid, such as hydrochloric acid, to a low concentration in distilled water, or by any other suitable technique, such as are known in the art. 
     The wash solution is used to rinse the SPE cartridge or other extraction device and to wash away water-soluble acids, salts, and buffer components and separate them from the corrosion inhibitor organic acids, which remain in the extraction device. Thus, when plunger  213  is depressed fully as shown in  FIG. 9 , the fluid from chamber  211  flows through extraction device  350 . Again, the fluid flows into line  322  and applies equal pressure at the entrances to chambers  411  and  511 . Again, the majority of the fluid enters chamber  511 , as shown in  FIG. 9 . 
     Finally, plunger  113  may be depressed so as to cause dispensing chamber  111  to inject a solvent into line  320 . Any organic solvents or organic solvent mixtures that can desorb and dissolve the organic acid ELC compound from extraction device  350  may be used as the solvent. Suitable organic solvents include alcohols such as methanol, ethanol, and isopropanol. Other polar organic solvents such as acetone and tetrahydrofuran are also suitable provided these are applied in an appropriate manner. 
     The organic solvent elutes the target organic acids (i.e., corrosion inhibitors of interest) from extraction device  350 . However, at this point, chamber  511  is completely or nearly completely filled with the contents of chambers  311 ,  211 , and the sample fluid. Thus, the eluent comprising solvent and dissolved/desorbed compounds is forced to flow into chamber  411 , as shown in  FIG. 10 . As mentioned above, chamber  411  contains a predetermined amount of an indicator, which mixes with the solvent as plunger  113  is depressed and the solvent flows through extraction device  350  and into chamber  411 . 
     In one embodiment, chamber  411  holds a prepared solution of a base (e.g., 0.1 molar sodium hydroxide in water) (a “standardized base solution”) and a suitable acid-base color indicator, such as are known. The entire device  100  can be shaken or inverted several times to mix the contents of chamber  411 . In some embodiments, chamber  411  may be removed from the test kit, capped, and then shaken to mix the organic solvent solution and the indicator/base solution. This ensures a quantitative reaction between the eluted organic acids in organic solvent and the base. 
     A color change indicates that the concentration of acid inhibitors in the eluent is in excess or equal to a predetermined threshold concentration. This predetermined threshold amount preferably corresponds to the desired threshold or minimum concentration of acid inhibitors in the heat exchange fluid in use. It should be noted that any appropriate indicator may be used for indicating or detecting the threshold concentration of acid inhibitors. 
     Because the present device requires only sequential emptying of the dispensing chambers  111 - 311 , without any additional control steps, the present method is relatively simple. Accordingly, it is contemplated that the invention will be particularly beneficial to OEM&#39;s, fleet owners, the automobile service industry, and every day automobile owners. The mechanic, maintenance personnel, or car owner can accurately determine the concentration or level of acid-based inhibitors present in heat exchange fluid samples or whether the concentration or level in the heat exchange fluid is above or equal to a predetermined minimum threshold. With this information, the same personnel can determine the sufficiency of the heat exchange fluid for continued use and/or determine how much, if any, of fresh coolant must be added to maintain the utility of the coolant. 
     It should be noted that the methods, systems, and apparatus described herein may be applicable to fluids other than the heat exchange fluids specifically described herein. Likewise, the evaluating methods described herein may be performed manually or, by using an automated system and/or apparatus. 
     The foregoing description is presented for purposes of illustration and is not intended to limit the invention (as defined by the following claims) to the form described. Although several embodiments of the testing method, system and apparatus have been shown or described, alternative embodiments will be apparent to those skilled in the chemical, instrumentation, and other relevant art. For example, the various evaluation methods may be employed to evaluate other heat exchange fluid compositions not described herein. Moreover, the evaluation methods may be employed in conjunction with use of other testing components or arrangements. The embodiments described are further intended to explain the best mode of practicing the invention and to enable others skilled in the art to utilize the invention in such, or other, embodiments.