Oehlberg, Nicholas Peter

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Direct Spectrophotometric Determination of Lead Naphthenate in Linseed Oil

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Loyola University ChicagoLoyola eCommonsMaster's Theses Theses and Dissertations1943Direct Spectrophotometric Determination of LeadNaphthenate in Linseed OilNicholas Peter OehlbergLoyola University ChicagoThis Thesis is brought to you for free and open access by the Theses and Dissertations at Loyola eCommons. It has been accepted for inclusion inMaster's Theses by an authorized administrator of Loyola eCommons. For more information, please contact ecommons@luc.edu.This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 3.0 License.Copyright © 1943 Nicholas Peter OehlbergRecommended CitationOehlberg, Nicholas Peter, "Direct Spectrophotometric Determination of Lead Naphthenate in Linseed Oil" (1943). Master's Theses.Paper 302.http://ecommons.luc.edu/luc_theses/302DIBIO'f SPEC'fROPHOTOMETRIC DETlllBMI:taTIOlf OJ' LlW> liAPHTHElU.TJ: Ill LINSEED OIL BY HI CHOLAS PE!ER OEHLBERG A THESIS SUBMITTED Ill PARTIAL FULFILLMENT OJ' THE Ii:IIQUIRE-Willf.rS J'OR THE D:EGRD OF MASTER OJ' SCilllNCI · Ill LOYOLA UNIVERSITY DlCC:DrBD VITA. Nicholas Peter Oehlberg was born in Chicago, Illinois on October 22, 1909• Be graduated from NiCholas Senn High SChool, Chicago, Illinois in June, 1927. '!he Bachelor of Science degree in Chemist17 was con-ferred b7 Lo7ola Univereit7 in June, 1932. He attended Lo7ola Universit7, graduate school, studJ-ing graduate mathematics from 1932 to 1937• '!he past four 7ears were devoted b7 him to the gradu-ate studJ of chemistq. The author expresses his gratitude to his advisor, Dr. George )(. Schmeing, Chairman of the Department of Chemis-try of Lorola Univers1t7 for his interest, suggestions and guidance, to Reverend Jrancis J. Gerst, s. J., Dean of the Graduate SChool of Lorola Universitr for his helpful criti-cism and assistance, and to Mr· Al Stresen-Reuter of the Frederick Stresen-Reuter Compan, of Chicago for supplJ1Dg chemicals used in this problem• LIST OJ' !ABLES T.AJLE PAGE I AIR IW'ERlmCE READiliGS WITH Pc-4 J'ILTJ:R g. II 50 PERCENT LINSEED OIL AND 50 PERCEIT WIIERAL SPIRITS READINGS USING Po-4 FILTER LIST OJ' GRAPHS GRAPHS PAGE 1 PERCEIT OJ' !RAHSMISSION PLOTTED AGAINST WAVELENGTH WITH AIR AS REFEBEICE 11 2 WG PJl.RCEBT OF TBANSMISSION PLOTTED AGAINST P&CDT OJ' LEAD CONCEBTRlTI ON FOR WAVELDGTHS 400. 420, 44o, 460 .AD 480 12 3 PERCEIT OF TRANSMISSION PLOTTED AGAINST 'IAVELDGTH WITH LINSEED OIL- MINERAL SPIIU TS REJ'EBEICE 13 LOG PDCEN"r OJ TBANSW:SSION PLOTTED AGAINST PERCENT OJ LEAD CONCEif.RlTIOI J'OR WAVELllliGTB 415 14 Quantitative determination of lead in linseed oil for control is a laborious and ttme consuming process. Thia work covers a rapid method for the determination of lead naphthenate in linseed oil that maJ easily be used in similar determinations. The original scope of this report was to cover all lead salts and their solutions used as driers for linseed oil• Investigation showed that the spectrophotometer could not be used for determining the percent of lead for all types under the conditions imposed. Hence data were compiled only on lead naphthenate. !be term "drier" means catalyst. Lead and other metal salts and soaps have a catalytic effect on semi-drying and drying oils, producing an oxidized film. Lead is the first meta11 to be used as a drier for linseed oil. The function of driers is still a ~ster,y2 de-spite the work that has been done. Other metals that perform the function of a drier are cobalt and manganese. Metals that act as driers are used in the form of oxides, salts, or soaps. Soaps commonly used today are the linoleate and resinate. In dissolving the oxide the metal soap of the fatty acid present in the oil is formed. The linoleate is made from a aoluble metal sat and the fatt7 acids of linseed oil. !he resinate is produced from a aoluble metal salt and roain re-acted with l7e. In solution fonn beside the linoleate and resinate, metal naphthenate, produced from petroleam, has found favor due to greater aolubilit7.3' 4, 5· !he aolution fo~ is usuall7 produced b7 diasolving the proper soap or naphthenate in a petroleam fraction that is known as mineral spirits or into a special fraction. At present lead is dete~ined b7 precipitation aa thiog1Jcolate6, as ozalate7 and as sulfate, and electrol7tical-l7 as oxide Pb02• Jarrett8 has used a semi-colorimetric method in deter.mining cobalt, lead, and manganese, but be did not es-timate the lead colorimetricall7• No references were found in the literature on a spectrophotometric determination of lead in linseed oil although this is a rather obvious meth9d for control of the lead ooncen-tration. Materials used in the following stud7 are: Lead Linoleate (27~ lead) Lead Iaphtbenate Solution (24~ lead) Lead Lino-resinate Solution (24% lead) Frederick Stresen-Reuter, Inc. of Chicago, Illinois - 3 .. Superb Linseed Oil Procter and Johnson of Chicago, Illinois Mineral Spirits Standard Oil of Indiana In order to determine the possibility of comparison of the three lead salts, solutions containing one percent lead as metal were made in linseed oil and in a mixture composed of fift7 percent linseed oil and fift7 percent mineral spirits. These solutions were agee six weeks and then examined. Onl7 lead naphthenate remained dissolved. The lino-leate and lino-resinate solutions contained a lead bearing pre-. cipitate and were considered useless for further stud7 for the spectrophotometer. This test proved the value for the lead naphthenate solution and corroborated previous experimental work. The lino-reainate solution was used in place of the resinate due to claims of greater solubilit7 tban the linoleate, but the precipitates were equal in weight. In considering mineral spirits as the solvent, the fact that it is present in every labo~tory handling linseed oil problems is an important one. Further, it has a low rate of evaporation and solutions made with it can be handled with-out cbage in concentration. Other solvents can be used but -4-they have a faster rate of evaporation. Experimental Procedure Solutions of lead naphthenate in linseed oil were made containing 0.1, 0.2, 0.5, and 1.0 percent lead (as metal). These solutions were diluted to fift7 percent solids by weight w.l th mineral spirits and aged for four weeks as a further cheek on solubility. A pair of test tubes was matched aing the recom-mended dichromate method. These were. carefully marked and used as holders for the solutions in the instrument. Transmission of the solutions was measured on the Coleman Universal Spectrophotometer, using the direct reading from the galTonometer seale. The readings were repeated for cheek. Readings using the Null method were not successful. The data covering the solutions using air as refer-ence are in table I, and those using a reference composed of fift7 percent linseed oil and fifty percent mineral spirits are in table II. In all the tests, a PC-4 filter was used. It is recommended for the wavelength range 4oo to 700 millimicrons. An attempt was made to obtain readings below 415 - 5 .. millimicrons by using a deep purple filter Pc-6, suggested for operation in the range 350 to 4oo millimicrons. Bo readings were obtained. !rial readings of the undiluted solutions were also unobtainable, probably due to the color strength of the oil. No attempt was made to dilute the solutions further. Previous work bas indicated partial separation of the various components in greater dilution. Variations in the instrument readings were finally t·raced to the storage batte17 and were controlled by keeping the battery fully charged. Another variation was traced to the temperature of the solutions. All readings were taken with the solution tem-perature at 250 Centigrade. Discussion of data .An examination of the curves in graph 2 shows the greatest slope for the curve plotting log percent of trans-mission against percent of lead concentration for 4oO milli• microns. The curve for 420 millimicrons is also suitable but would not permit as great an accuracy in determining the per-cent of lead in an unknown as the curve for 40o millimicrons. Using air as a reference a straight line is not -6-plotted, indicating that Beer's law does not hold. This type of eurve has been reported in the literature for carotene as satisfacto 17• Using a reference of fift7 percent linseed oil and fift7 percent mineral spirits, onl7 one point is obtained for 0.1 percent lead concentration (!.able II). It is at 415 milli• microns. Log percent of transmission is plotted against percent of lead concentration for this wavelength in Graph 4. Again the curve shows that Beer's law does not hold. A comparison of Graph 2 and Graph 4 shows that the air reference me\hodfor 4oo millimicrons is more ahcurate than the mixed standard method for 415 millimicrons. Conclusions Use of the Coleman Univeraal Spectrophotometer for the direct determination of lead Daphthenate ma7 be considered as a rapid and accurate control method. The air reference method is recommended over the lin-seed oil - mineral spirits reference method. Suggestions for further work fork could be done with the spectrophotometer using lead naphthenate with other vegetable oils. The determination of cobalt and manganese naphthenates in T&rious oils could be - 7-run and these resulta correlated to this investigation to de-termine whether a method for the determination of the three drier metala, cobalt, lead and manganese, could be found. -s-lUlFERENCES 1. J. Fritz, Farben Zeitung, !1. 755, 801, 8o6 (1938) 2. Nicholson, Industrial and Engineering Chemistry, ~. 1175-79 (1942) 3• Gardiner and Waddell, Industrial and Engineering Chemistry, ll.· 629 (1941) 4. Harkness and Brmm, Industrial and Engineering Chemistry, 3b 499 (194o) 5• "Facts about Buodex", Juodex Products Co, Inc., Elizabeth, New Jerse7 6. Long and Fgge, Industrial and Encineering Chemiatr7, gQ_, 809-11. (1928) 1• Diener and Wertbsn, Prpceedings of the American Societ7 for Testing Metals, 30 Part II 924 (1930) 8. Jarrett, J., Oil and Color Cham!ata Association, !i• 29 (194o) -9 ... TABLE ONE .A.IR REfERENCE WITH Pc-4 FILTER PERCDT OF LEAD (.A.S METAL) 0.1 0.2 0.5 leO 380 21.4 19.2 .. .. 400 27·9 24.4 19·3 15.6 420 42.8 37·8 30.8 24.6 440 6o.4 54.2 46.4 40.0 460 75·1 68.6 62.6 54•5 480 ~.9 80.0 74.8 67.8 500 91·3 88.3 84.0 78.2 520 96·5 93·1 89.8 85·5 540 98e2 96.0 95·0 90.0 560 98·5 96.0 93·0 580 .. 100.0 98·5 95·0 600 -... 99·0 96·5 620 -100.0 96·3 640 -100.0 96.0 66o - -99·0 95·0 680 -98.0 94.0 700 - - - --ro-TABLE TWO 5~ LINSEED OIL AND 5~ MIJERAL SPIRITS STANDARD Pc-4 FILTER PERCENT OF LEAD (AS METAL) 0.1 0.2 0.5 1.0 415 94.8 83·5 66.5 52.0 420 .. 87.8 70.0 56.0 430 -92·3 78.2 64.3 44o -99·0 84.5 72·0 450 ... -90.0 78·5 lt-60 -.. 94.6, 84.9 470 - -96·5 88.8 480 -98·3 92.0 490 -.. 99·5 94·3 500 99·0 95·8 510 - - -97·0 520 .. -.. 98.0 530 - - -98.2 54o - - -99·0 550 - -... 99·3 560 -w ... '/D -'10-~-if()O I soo s.ro W A V ~ "-liNG- I H AI~ R~t=IER.If"NC/f" PC -1./ Fl L.. Tt:R.. G-I~APH I f-a-AI~ R £f:lf"R ~ Ne if'" pe,"' ~="I" r~R.. G-R.,4PI-J Z, 1 I I I (), I 0. J... l), ~ I, 0 P£~ Ct:NT i../Z"AD CON<!.t:NTR.ArloN .. 13 - ~ .... ~ ...... ~ ~ ..[ <t~~ ~~ ~ ~ ~ tt) ~ (I( ~ tt(' ...... =t lv ll Q., ~ ll ~ ~ ...... 14 ~ ~ ~ ~ \b e ~ "" ~ ~..... ....J I ~ /v()ISS'tWSN~li..L. ~ --.o lc, -~ 1.) <:) -:"'( lei .;::) -~ (;) ~ \!, <:)~ -~~ ~l.t( <:) -" ~I ,~ "') > '< ~ J()-9-1-- ~~-t..JNS~IE"D ()11....- 11/N£~~1... SPII'<.IT5 1(£F~~ ~N~Jf I I ( 0./ t),.J.. ().,s-P~R. <!~NT J....~AO Pe-lf. F/1.. TE"I( G/(A-PH 'I I /,0 CON<!ENT!e.A- Tl~/\1 Approval Sheet 'l'he thesis submitted by Mr. ~icholas :t. uehlberg he.s been ree.d a.nd approved by three members of the Department of Ghe~istry. The fine.l copies have been examined by the eli-rector of the thesis and the s igne.ture w·hich appears· below v;'rifies the fact that eny necessary chELnbes ~1e.ve been incorporated, and tha-i; the thesis is r.ow given f'ine.l e.a·rove.l wi_ th reference to content, form, B.nd cnech&.nice.l accuracy. 'l'he thesis is therefore accepted in p: rtii:d i'ul-fillment of the requirements for the Lei:.ree of .:ia.ster of Arts. b£1%. J/ /f?~J De.te 

Direct Spectrophotometric Determination of Lead Naphthenate in Linseed Oil

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