Minutes of the Committee on Analytical Reagents

General Meeting
Analytical Inorganic Subcommittee
Analytical Organic Subcommittee
New Item Subcommittee

MEMBERS OF THE 2005 ACS COMMITTEE OF THE COUNCIL ON ANALYTICAL REAGENTS

SUBJECT: Minutes of the 5-6 October 2005 Meeting

The meeting was held in the Othmer Conference Room at the ACS HQ in Washington, DC. All members except Bolgar (represented by Cooper), Lowery, Petroski, Re, Rimando, Shah, and Telliard were present. Mary Beth O’Donnell accompanied Lyle Phifer from CHEM SERVICE. Bob Hauserman (ACS Liaison) reported. The next meeting will be at ACS HQ on 19-20 April 2006.

Subcommittees

Analytical Inorganic: Schmidt (Chair), Desai, Foster, Lowery (absent), McBride, Mehta, Moody, Tyner.
Analytical Organic: Re (Chair, absent), Bolgar (absent), Herwehe, Phifer, Piscia, Simon, Wilson.
New Items: Wilson (Chair), Bolgar (absent), Herwehe, McBride, Mehta, Phifer, Piscia, Re (absent), Tyner.
Method Validation: Re (Chair, absent), Foster, Piscia.

Contact Assignments as Section Reviewers of Reagent Chemicals, 10th Edition

Introduction and Definitions

Analytical Procedures and General Directions

Solutions and Mixtures Used in Tests

Specifications for Reagent Chemicals

ACS COMMITTEE ON ANALYTICAL REAGENTS
GENERAL MEETING
6 October 2005
Introductory Remarks and Reports

Greetings. At the opening of the session Paul Bouis announced his official retirement from Mallinckrodt Baker and confirmed his decision to remain as Chair. Paul congratulated the members for their fruitful hard labor in completing the 10th ed. of Reagent Chemicals, and commented on several of our plans to continue the forward movement of the Analytical Reagents Committee.
   (a) It is desirable to incorporate the role of our Reagent Chemicals book in the development of the
ACS vision program. Any ideas for promoting the 10th ed. will be forwarded to Bob.
   (b) The proposed lab training course should be associated with a university and organized around the
materials within Reagent Chemicals, the USP, etc.
   (c) Paul also observed that we need to acquire members who are specialists in the areas cited by Chuck
Wilson in his report of the discussions within the New Items Subcommittee. Observe that traditional
disciplines within chemistry are being hybridized (as likewise are careers).
   (d)Work on the preparation of the 11th ed. begins today.

Membership Appointments: Current 3-year terms are filled as cited below (ACS Yellow Directory 2005).
2007: Anne Coghill, Kishor Desai, Denise Edgren, Loren McBride, Lyle Phifer, Paul Piscia, Nancy Simon, Vanaja Sivakumar.
2006: Christine Foster, John Moody, Wm Schmidt, Wm Telliard, Tom Tyner, Charles Wilson.
2005: Paul Bouis (Chair), Michael Bolgar, Clarence Lowery, Raj Mehta, Michael Re, Robert Thomas.
Associates: Kenneth Herwehe, Richard Petroski, Agnes Rimando, Shirish Shah.
Staff Liaison: Robert W. Hauserman, Director of Publications Dept.
Committee on Committees (ConC): Dr. Milagro Delgado South Florida (2006).

Minutes: No changes within the 20-21 April 2005 Minutes were proposed, and the content was approved by raise of hands with no dissent.

Readers’ Questions: Inquiries continue to be addressed by readers to the Reagent Chemicals section page reviewers and the chair/secretary. Few subjects require posting on the web.

Books and Web Sales Report: Bob Hauserman reported the final sales figures for the 9th edition hardback
to be approximately 2,628 copies – representing about $400,000 in revenue. From April 2005 through July 2005 we sold 11 9th edition combos which breaks down as follows:

3 – member combos	1 – institutional combo	2 – non-member web only
4 – non-member combos	0 – member web only	1 – institutional web only

Life to date figures:

101 – member only	19 – institutional combo	25 – non-member web only
74 – non-member only	10 – member web only	14 – institutional web only
243 – total (179 domestic, 64 foreign)

Bob noted that his boss wants the members to know how very well the 10th ed. turned out. Also special thanks are due Anne and Betsy for their tremendous job in assembling the final product. As planned, the hardcopy was highlighted at the recent ACS meeting, and approval for the preparation of the electronic copy was granted priority quickly. Meanwhile an 8-page brochure was distributed to the members of the committee featuring the book as “New from The American Chemical Society & Oxford University Press”. Bob urged that members forward information to him for sending the brochure to the names suggested. Bob also reported that the US Division of Oxford has persuaded the European Division to handle sale of the 10th ed. (the practice of this company). This observation resulted in some discussion of the problem for poor nations in procuring our book.

Bob reported that Oxford is not involved in the development of the Web copy and associated materials.
He also observed that the trend is to print technical and scientific books on line (on demand). This practice
could eventually lead to the disappearance of traditional hard copy.

Following Bob’s report Lyle Phifer inquired about current handling of hotel reservations for our meetings.
Bob will send travel office information to all members. He also stated that a continental breakfast will be served before the opening meeting on Wednesday and a full breakfast, before the general meeting on Thursday.

Development of a “Strategic Plan” for a 2 to 3-year period. Paul and Bob have begun work on this project. Time consuming participation of members will be avoided as much as possible. Development of the proposed lab course will be included here.

Revision of Operating Procedures. Paul submitted an edited copy of his revision of the 1994 text. The copy will be attached to these minutes in the Agenda Book for the next meeting.

Reports of Subcommittees. Reports for Analytical Inorganic, Analytical Organic, and New Items were
delivered by the chairs and by Russ Cooper who volunteered for Nancy Simon who had to depart early. See
minutes.

Action on Specifications. For convenience of consideration Chuck reviewed one organic reagent together with a number of inorganic reagents in the meeting of the Inorganic Subcommittee: 1,3-Benzenediol (Page 198, 10th ed.). The printed spec for melting point is 110-112°C. It was proposed to harmonize our lower limit with the USP: 109°C, and this unanimous recommendation was presented in the general meeting. The Committee voted to accept this recommendation without dissent. No changes for specs of other reagent chemicals were presented. 10th ed. Supplement

MINUTES OF SUBCOMMITTEES
ANALYTICAL INORGANIC SUBCOMMITTEE
5 October 2005

Members: Schmidt (Chair), Desai, Foster, Lowery, McBride, Mehta, Moody, Tyner.

Heavy Metals General Test: Replacement of the catchall test by summation of individual metals. This development involves such problems as determination of the history of contaminants in a given reagent chemical and sudden changes of pattern of contamination in sources. Paul will continue to think through the options available for heavy metals testing, and report at the April 2006 Meeting. Continued by Bouis

Heavy Metals General Test (Pages 27-30, 9th ed. with supplement revision for 10th ed.): Desai submitted a proposed revision of the general procedure as already incorporated in the manuscript for the 10th ed. (see copy in Agenda for 04.05). The subcommittee did not choose to adopt the entire rewrite, but agreed that dilution buffer should be employed in general procedure for the 10th edition Concept of the revision was unanimously adopted, and Kishor was assigned to submit a rewrite using dilution buffer. His entire copy of 5-06-05 previously attached to an email is reproduced below. Kishor 10th ed. Supplement

Heavy Metals (as Pb)
The heavy metals test is designed to limit the common metallic impurities (Ag, As, Bi, Cd, Cu, Hg, Mo, Pb, Sb, and Sn) that produce colors when sulfide ion is added to slightly acid solution that contain them. In this test, such heavy metals are expressed “as lead” by comparing the color developed in test solution with that developed in lead standard/control solution. The optimum condition for proper performance of the test are: pH of solution between 3 and 4, total volume of 50 mL, use of pH 3.5 ammonium acetate dilution buffer solution, use of freshly prepared hydrogen sulfide water, and use of standard/control containing 0.02 mg of lead ion (Pb). These conditions are rarely modified in the individual procedures, and it will be only after a method validation that the method modification would be suitable for the individual reagent. The color- comparison should be made; using matched 50-mL color –comparison tubes, by viewing vertically over a white background. In some instances, an appropriate amount of the sample is added to the standard, there after called the control (see page 91), because the color developed in the test may be effected by the sample being tested. In other instances, no such effort occurs and the standard may be prepared without any of the sample. In general, the individual standard procedure provide only for the preparation of the sample solution. The reminder of the test directions, being the same for all reagents, is provided in this chapter.

Two general test procedures are provided. Method one is to be used unless otherwise specified in the individual standard. This method is used, generally, for those substances that yield clear, colorless solution under specified test conditions. Method 2 is used generally, only for certain organic compounds.

Unless otherwise directed in the individual specification, the test shall be carried out as follows.

Procedure. Test in a well-ventilated fume hood.

pH 3.5 Ammonium Acetate Dilution Buffer: Dissolve 5.0 g of ammonium acetate in about 450 mL of water in a 500 mL beaker. Using a pH meter, while stirring, adjust the pH to 3.5 with slowly adding glacial acetic acid or with ammonium hydroxide (10% NH3) as needed. Dilute to 500 mL with water and store in a plastic bottle.

To each of the tubes containing the test solution and the standard/control solution, add 5.0 mL of freshly prepared hydrogen sulfide water, and dilute with pH3.5 ammonium acetate dilution buffer to 50 mL and mix. Any brown color produced within 5 min in the test solution should not be darker than that produced in the standard/control solution.

• When a control solution is specified in the individual specification and a direction is given therein to add a weight of lead ion (Pb), no further lead shall be added. Proceed to the dilution of pH adjustment, as necessary.

Method 2
Test Solution. Transfer the quantity of substance specified in the individual specification to a suitable crucible, add sufficient sulfuric acid to wet the sample, and carefully heat at a low temperature until thoroughly charred.
(The crucible may be loosely covered with a suitable lid during the charring.)
Add to the carbonized mass 2 mL of nitric acid and 0.25 mL of sulfuric acid, and heat cautiously 0until white fumes of sulfur trioxide are no longer evolved. Ignite, preferably in a muffle furnace, at 500 to 600°C until the carbon is burned off completely. Cool, add 4 mL of 6 N hydrochloric acid, and cover. Digest on a hot plate (=100°C) for 15 min, uncover, and slowly evaporate on the hot plate to dryness. Moisten the residue with 0.05 mL of hydrochloric acid, add 10 mL of hot water, and digest for 2 min. Add ammonium hydroxide (10%) dropwise, until the solution is just alkaline, and dilute with water to 25 mL. Adjust the pH of the solution to between 3 and 4 (by using a pH meter) with 1 N acetic acid or with ammonium hydroxide (10%) as needed, dilute with pH 3.5 ammonium acetate dilution buffer solution to 40mL, and mix.

Standard/Control Solution. To 20 mL of water, add 0.02 mg of lead ion (Pb), and dilute with water to 25mL. Adjust the pH (within 0.1 unit) to the value established for the test solution (by using a pH meter) with 1N acetic acid or ammonium hydroxide (10% NH3) as needed, dilute with pH 3.5 ammonium acetate dilution buffer solution to 40mL, and mix.

To each of the tubes containing the test solution and the standard/control solution, add 5.0 mL of freshly prepared hydrogen sulfide water, and dilute with pH3.5 ammonium acetate dilution buffer to 50 mL and mix. Any brown color produced within 5 min in the test solution should not be darker than that produced in the standard/control solution.

* * * * *

Specific Items

Ammonium Acetate (Page 147, 10th ed.): The pH adjustment in Method 1 for Heavy Metals was examined in the context of Ammonium Molybdate below, and found to need no change in 10th ed. Drop

Ammonium Molybdate (Page 165, 10th ed.): Heavy Metals, Method 1. Final solution volumes require adjustment to be equivalent. Assigned to Chuck to rewrite. Assigned Chuck Wilson

Cyclohexanone: Water (Page 283, 10th ed.): Trial runs of coulometry vs. current KF procedure. Raj has determined that the KF procedure does work. The committee decided to retain the current test, and cease additional testing of coulometry. Drop

N,N-Dimethylformamide (Page 295) Water: The procedure in the new edition was changed to coulometry from KF in the 9th ed. Although the sample size in the 10th ed. is small for coulometry, no change will be made. 10th ed. retention

Dithizone (Page 287, 9th ed.; Page 304, 10th ed.): Assay. Change of method will be developed in response to Moody’s email. Assigned to Chuck. Assigned Chuck Wilson

Hydrofluoric Acid (9th ed., Page 337; 10th ed., Page 356): Fluosilicic Acid. Consider the last sentence “One milliliter of 0.1 N sodium hydroxide corresponds to 0.0036 g of H2SiF6.” See also the 16 April 04 memo which wrongly states that “0.0036” should be “0.0072”. On the basis of this memo the change was made on the Web for a 9th ed. supplement However, the error was found before the printing of the 10th ed.; hence both 9th ed. and 10th ed. are correctly printed. Raj Drop

Lead Subacetate (Page 393, 10th ed.): Nitrate. Item was introduced at the meeting by Kishor. Note below the preparation of Blank Solution C that the paragraph contains superfluous directions beginning in line 4
with ”Set a spectrophotometer…” Delete this and all remaining material through the end of the paragraph.
This text is included in the general instructions on pages 38-39. Kishor Desai 10th ed. Supplement

Lithium Chloride (Page 374, 9th ed,; Page 397, 10th ed.): Nitrate. Raj distributed a protocol dated 15 April 2005 wherein brucine sulfate is used instead of phenoldisulfonic acid. Tom and Chuck were assigned to check the protocol. The matter will be settled after public issue of the 10th ed. Raj has also considered the inclusion of chlorate in the spec. Raj Mehta & Tom Tyner 10th ed. Supplement

Manganese Chloride Tetrahydrate (Page 419): Sulfate. Note that a factor of “0.412” should be inserted in the equation for the percent sulfate calculation. As printed, the result yields the percent of Barium Sulfate. 10th ed. Erratum

Mercuric Oxide, Red (Page 429); Yellow (Page 430): Production source to meet Insoluble in dilute HCl spec. Vendors check their sources; Chuck cannot find any. Assigned Chuck & other vendors

Potassium Phosphate Tribasic (Page 553, 10th ed.): Hydrate vs. anhydrous products. See Chuck’s email dated Sept. 21, 2005. Form in 10th ed. is anhydrous or heptahydrate, but all producers are supplying as n-hydrate, and Chuck suspects suppliers are marketing n-hydrate as heptahydrate. Confirm and revise specs for current products, if needed. Assigned to Wilson & other vendors

Sodium Iodide (Page 596, 9th ed.; Page 539, 10th ed.): Barium Test. Raj originally reported the possibility of changing test to AA. Work is ready; add to 10th ed. supplement. Apply also to Potassium Iodide (Page 539) which Raj has checked; Tom will also check. This action caused the members to support systematic conversion of the barium test to AA throughout Reagent Chemicals wherever suitable and easy to manage. Raj and Tom 10th ed. Supplement

Sodium Tungstate Dihydrate (Page 656, 10th ed.): Molybdenum. Explore AA to replace current test after publication of the 10th ed. Lowery et al

Zinc Acetate Dihydrate (Page 694 9th ed.): Lead test. Raj has run this test by AA. Hence the lead can be tested by the same procedure as for zinc metal and the other zinc salts. The change can be made in the first supplement for the 10th ed. Raj 10th ed. Supplement

1,3-Benzenediol (Page 199, 10th ed.): See General Meeting.Minutes: Harmonization of ACS and USP. 10th ed. Supplement

ANALYTICAL ORGANIC SUBCOMMITTEE
Fall Meeting October 5, 2005

Members present: Herwehe, Phifer, Piscia, Simon
Russ Cooper (representative from Accustandard in place of Bolgar)
Mary Beth O’Donnell – Visitor from ChemService
Members absent: Bolgar, Edgren, Petroski, Re, Teilliard Wilson (attended Analytical Inorganic Subcommittee meeting).

Simon substituted for Re as chair for the meeting.

Item 1. Pyrogallol
Piscia: Reported that the major impurity in pyrogallol is di-pyrogallol. Has collected analytical procedures from several sources. Restek was a source of a method for phenolic compounds. Agilent markets a DB-FFAP column that can be used for these analyses. Paul will distribute these procedures to members of the committee so that a couple of methods can be selected for testing.
(Edgren volunteered at the fall meeting to work on the method in the future.)
Action Item: Committee members should select a couple of methods to test and start developing a verification procedure. Herwehe and Cooper are taking the lead in developing a verification method.

Item 2. Glycerol
The analysis for glycerol is similar to the analysis for pyrogallol. If we develop a method for pyrogallol, we will be well on the way to having a method for glycerol. It was noted at the spring meeting that a DB-FFAP column would be suitable for both pyrogallol and glycerol.
(Edgren volunteered to look at EP method at spring meeting.)
Action Item: When a method is selected for pyrogallol, it will be tested for use with glycerol.

Item 3. Aldehydes and ketones
Wilson was unable to test the derivatization of aldehydes and ketones as part of an analysis for aldehydes and ketones. DNPH (dinitro phenyl hydrazine - DNPH - a derivatization agent for carbonyls) is on the list for the New Items Committee.
It was emphasized at the meeting that LC/MS is the preferred method for doing these analyses.
Action Item: Request references for the use of DNPH as a derivatizing agent for aldehydes and ketones from Re. Further action on validating a method using DNPH in analyses for aldehydes and ketones is contingent on receiving references from Re.

Item 4. Proprionic, Formic and Monochloroacetic Acid
Wilson was not able to test the use of DNPH as a derivatizing agent for these compounds.
Further action on validating a method using DNPH in analyses for these acids is contingent on receiving references from Re. (See Aldehydes and Ketones)

Item 5. Organophosphorus pesticides
Method verification for the 15 organophosphorus pesticides in the 10th edition was done by Phifer’s lab. Validation was to have been done by Re’s lab. Other organophosphorus pesticides that could be included are unstable and require the use of diazomethane to determine decomposition products. These compounds are widely used specifically because they decompose in the environment and standards for these compounds are needed. These analyses are of concern because both the compounds to be analyzed and the derivatizing agent are hazardous materials. Phifer’s lab has determined that the use of diazomethane is the best analytical procedure and the committee felt that the method submitted by Phifer’s lab should be included in Reagent Chemicals.
Action Item: Obtain validation of the method for the 15 compounds in the 10th edition from Re.
Action Item: Obtain methods for analysis of unstable organophosphorus pesticides from Phifer.
Action Item: Herwehe volunteered to validate the method using diazomethane for the unstable organophosphorus pesticides.

Item 6. Explosives and metabolites
The verifications of methods GCFID-EXP1 and GCMS-EXP1 have been completed by Bolgar’s labs and the data have been submitted to Re.
Action Item: Obtain validation data from Re. The validation procedures being sought from Re are for the GC compounds.
Action Item: The LC compounds were not included in the above. A LC/MS is required to identify the decomposition products. Herwehe volunteered to Cooper that he would attempt using his LC/MS to do the identification work.

Item 7. Haloacetic acids and methyl esters
Action Item: Check with Re for validation of procedures for methyl ester that were included in the 10th edition.

NOTE:
There are three methods that are at the stage where validation is required. These are:
(a) organophosphorus pesticides,
(b) explosives and explosive metabolites, and
(c) methyl esters of haloacetic acids.
Herwehe is validating (a).
Phifer volunteered to validate either (b) or (c) [his lab verified (a)].
Re might be a source of validation data for (b).
Re might be a source of validation data for methyl ester analysis in ( c).
Validation assignments can be arranged after available data is obtained from Re.

Item 8. 95% Ethanol
Report not available from Edgren.
Phifer’s lab submitted data from TCD analysis of 95% ethanol. Phifer did not recommend the use of TCD for the analysis, i.e., not as a method specified for determining the percent water. The Karl Fisher titration is preferred. The TCD could be suggested as an alternative to determining percent water by difference.
Action Item: We need to include both volume and weight percents of water in alcohol in Reagent Chemicals.

Item 9. “Fishy” Methanol
Action Item: Members of the committee are willing to analyze “fishy” methanol if Mallinckrodt Baker would provide samples.

Item 10. Phthalates
O’Donnell is working on these compounds. Of the 42 compounds that could be included in the book, approximately 20 are pure; the others are sold as technical grade. The committee suggested that the 20 pure compounds be included because they are “analytical reagents” and because they are included on the EPA phthalate list.

Item 11. Diphenyl ethers
These poly brominated ethers are used as flame retardants. The committee suggested that compounds in this class that are on the EPA list should be considered for inclusion in Reagent Chemicals.

Phifer brought the advertisement by YAVONAE for a skincare product to the attention of the committee. The ad claims that “This product is certified as 100% pure by the American Chemical Society.” The article was submitted to Hauserman.

The committee responded to a request by William F. Carroll, Jr., President of the ACS, for suggestions of how the society could help universities hard-hit by recent hurricanes in the Gulf Coast states. The suggestion was made that electronic versions of the 10th edition of Reagent Chemicals might be given to schools such as Tulane University and Xavier University of Louisiana.

NEW ITEM SUBCOMMITTEE MEETING MINUTES
Fall 2005

The 10th edition of "Reagent Chemicals" was published and included 32 new items. A list of the new items is attached. There are three remaining items we wish to keep open and continue for consideration. They are as follows:

Barbituric acid; This item is used as a reagent for cyanide determinations and is a viable consideration for mining and environmental analytical uses. We have reissued the monograph with a sensitivity determination for the detection of cyanide. A copy of the revised standard is available. EMD will perform validation and send samples to JT Baker for inter-lab evaluation. The sensitivity test is qualitative and should not involve extensive validation work.

2, 4 Dinitrophenylhydrazine; DNPH is used as a derivitizing reagent for the detection of aldehydes and ketones. It is currently being evaluated by the Organics Subcommittee for HPLC applications for solvents that currently have polarographic determinations. The standard already includes a sensitivity determination for aldehydes and ketones. EMD will validate the procedure and send inter-lab sample to JT Baker. A copy of the standard is available.

Lanthanum nitrate; This reagent is submitted but needs validation work to be accepted. The item is used as an ionization suppressant in AAS. JT Baker will conduct the validation and submit inter-lab sample to EMD. A copy of the standard is available.

Potential new items for inclusion in future editions were evaluated for reagents in the Life Sciences sector. A list was generated from the past that identified potential new items. From this list there were a significant number of items already listed in the book. We will review the list and determine for each reagent if a specific used qualification section needs to be added for use in this field. Possible considerations include low water solvents and nuclease free tested reagents. A list of identified reagents is available and we will report at the Spring meeting possible actions for future publications.

Of the reagents listed in potential new Life Science products. We generated a list of potential items that did not include antibiotics, microbiology components or amino acids and derivatives. We compiled a list of more than 40 items that could be considered potential new items. Most are biological buffers, organic acids and reagents. We will start with this list and work forward for priority consideration. If time allows we will look at other items. The list is available.

A review of potential specifications was conducted to establish a starting point for specific reagents. In line with our operating procedures, we tried to verify that there were two suppliers for each reagent and at least two suppliers who guaranteed the specific test.

Also we looked for the highest available quality. This is only a starting point and can not be construed as an official listing. It is only a guide to be considered. If the Committee acquires individuals with specialized expertise we may want to revaluate the listing. Also, individual sponsors may want to revise the listing. A file for each potential new item is available.

As an ad hoc discussion the committee meeting evolved into a generalized discussion on the future format of the book and the need for moving in the direction of Bioscience applications. It was a consensus agreement that new technologies and activity in the realm of analytical chemistry is rapidly evolving in this direction and the committee should definitely add such items to the book. Whether the book can handle the increased volume is a consideration but considering the principle and service to the analytical community we should add life science reagents and worry about details of publishing the book in the future when we determine what course of publication will be adapted, WEB based or hard print. It was also established that additional testing applications will need to be implemented, i.e. electrophoresis and fluorescence spectrophotometry. It was also determined that pKa values will be only listed as physical/chemical properties instead of specifications with ranges.

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