Fr~mniusZe~ehriftfiir

Fresenius Z. Anal. Chem. 297, 320-322 (1979)

9 by Springer-Verlag 1979

Education in Analytical Chemistry at the Royal Institute of Technology, Stockholm* Folke Ingman Dept. of Analyt. Chemistry, The Royal Institute of Technology, S-100 44 Stockholm, Sweden

Ausbildung in Analytischer Chemic am KiJnigl. Institut t'ur Technologic in Stockholm Zusammenfassung. Nfihere Einzelheiten fiber Vorlesungen, Praktika und Prfifungen in Analytischer Chemic am Institut ffir Technologic werden mitgeteilt. Summary. Details are given on lectures, practical exercises and examinations in Analytical Chemistry at the Royal Institute of Technology, Stockholm. Key words: Analytische Chemic; Ausbildung am Inst. f. Technologic, Stockholm

In the 1st year, 96 students are admitted in September. After taking courses in mathematics and inorganic chemistry during autumn, Analytical Chemistry is introduced in January. The course is fairly concentrated, its duration is 6 weeks, and there is a written examination immediately after the course. In the 3rd year, 24 more students are admitted, who have started their education in chemistry at the University but who want to give their education a more technical direction. The second course is not as concentrated as the first one, its duration is about 11 weeks and several other subjects are taught at the same time. The advanced course in Analytical Chemistry is open to choice for the students. It is normally chosen by students specialising in chemistry or biochemistry and the number of students has recently been 1 5 - 25/year. The course is given during autumn of the 4th year and is of 9 weeks duration. During spring of the 4th year, a few students choose to do their special project in Analytical Chemistry. This * Presented at Euroanalysis III conference, Dublin, August 20-25, 1978

0016-1152/79/0297/0320/$01.00

project comparises scientific work on a limited subject during 3 months and results in a written report. The students graduate after the 4th year. Details of the courses are compiled in the following. First Course (compulsory) nominally 96 students

"Classical" analytical chemistry Lectures 4h Analytical calculations 10 h Exercises 112 h Written examinations 1h Oral examination 0 Literature. J. S. Fritz and G. H. Schenk: Quantitative analytical chemistry, 3rd ed. Boston: Allyn & Bacon 1974. - Detailed laboratory manual. The aim of the course is to teach basic Analytical Chemistry including standard laboratory operations. The written examination consists of two parts: 1. Theory, each student choosing three of six questions. No aids are allowed. 2. Calculation, which is taken after completion of the theoretical part. Any aids (e.g. the text book) except such containing solved problems may be used and the problems are designed to show the students' ability to obtain information from the book. The problems are chosen from stoichiometry, titrimetry, absorption spectrophotometry and extraction analysis. First Course Exercises

1. Complexometric titration of PB(II) with EDTA using methyl thymol blue as indicator. 2. Determination of Ni(II) gravimetrically by precipitation with dimethyl glyoxime. 3. Gravimetric determination of sulphate ions in presence of Fe and Cu by precipitation of BaSO 4 after absorption of Fe and Cu on a cation exchanger. 4. Determination of Ca by titration with KMnO~ solution after precipitation as C a C 2 0 4.

F. Ingman: Education in AC at the Royal Institute of Technology 5. Determination of hydrochloric acid and maleic acid in mixture by potentiometric titration on a metrohm potentiograph. 6. Gas-chromatographic determination of ethyl acetate in aqueous solution. 7. Spectrophotometric determination of orthophosphate with ammonium molybdate and Sn(II) chloride. 8. Determination of Mn in steel by spectrophotometry. 9. Analysis of an alloy. Second Course (compulsory) nominally 120 students

Instrumental analysis Lectures Exercises Written examinations Oral examinations

21 h 28 h 1 0

32l Chemical calculation Exercises Written examination Oral examination

28 h 84 h 1 1

Literature. G. W. Ewing: Instrumental analysis, 4th ed. New York: McGraw-Hill Book Co. 1975. - A. Ringbom: Complexation in analytical chemistry. New York: Wiley/Interscience 1963. The course starts with an introduction to the concept of conditional constants and side reaction coefficients, which is then applied to titrimetry, ion exchange and extraction analysis. Different instrumental methods of analysis are then treated with special emphasis on comparison of the methods and their ability to solve different analytical problems. The laboratory exercises are carried out individually by the students. Advanced Course Exercises

Literature. G. W. Ewing: Instrumental analysis, 4th ed. New York: McGraw-Hill Book Co. 1975. Laboratory manual. The aim of the course is to teach the principles of modern instrumental analysis. There are not sufficient resources to permit individual exercises in this course. Therefore, the students are divided into groups of three and the exercises are given the form of demonstrations carried out by the teachers who are specialized in the different instrumental methods. Second Course Demonstrations

1. Ion-selective electrodes. 2. Potentiometric titration in non-aqeous media. 3. Atomic-absorption spectrophotometry (Perkin Elmer 300). 4. Flame-emission spectrophotometry (Eppendofff). 5. X-ray diffraction and fluorescence analysis. (Philips equipment). 6. Optical emission spectroscopy (ARL 26000). 7. Evaluation of analytical data and control of analytical instruments using electronic computers (HP 2114, DEC 10). 8. Gas chromatography (HP 5750). 9. Gas chromatography - mass spectrometry (HP 5750-LKB 9000). 10. IR- and UV-spectrophotometry (BeckmanInstruments). Advanced Course (open to choice). 15 students 1977/78 Choice and criticism of methods Lectures 42 h

1. X-ray diffraction and fluorescence analysis (Philips Equipment). (Analysis of ash from a garbage-burning station). 2. Optical emission spectroscopy (ARL 12-channel direct reading spectrometer, Spectroscandia IDES instrument, and plasmatherm ICP-unit). 3. Ion-selective electrodes for silver and fluoride determination. 4. Determination of water according to Karl Fischer. 5. Flow-injection analysis. Optimization of the conditions for the determination of phosphate. 6. Flameless atomic-absorption spectrophotometry. Determination of lead in blood plasma. (Perkin Elmer 403 with graphite cuvette unit). 7. Determination of copper in sea water by anodic stripping voltammetry. Comparison of different modern voltammetric techniques. (PAR 174 A). 8. Spectrophotometry in the infared (Beckman equipment). 9. Gas chromatography (Hewlett-Packard 5750). 10. Gas chromatography-mass spectrometry (GCHewlett-Packard 5750, MS-LKB 9000). 11. Inorganic mass spectrometry (AEI MS 702). Determination of trace metals in a detergent. Examination in Analytical Chemistry, Advanced Course 26th November 1977. Time: 9 a.m. - 1p.m. Aids. Anythingbut solvedexamplesor conversationwith other students. Directions. Choosefiveof the problems. If solutionsare givento more than fiveproblems only the first fivewill be considered. 1. Calculatethe conditionalprotonation constantsfor EDTA in a solution containing0.133moles per litre of barium chloride at an

322 ionic strength I = 0.4 (the constants found in the tables are valid at I = 0. l). Give a rough picture of the titration curve for a titration of 25.0ml of 0.01 M E D T A (0.133 M BaC12) with 0.01 M N a O H , p H = f(VN~oH), 2. A 0.01 M solution of copper ions m a y be titrated with E D T A solution according to the literature. a) In a weakly alkaline solution by using murexide as indicator and N H + as a buffer (CNH3+NI41= 0,01 M). b) In a weakly acidic solution by using 1-(2-pyridylazo-)-2naphthoI(PAN)as indicator and hexamethylenetetramine as a buffer. Suggest a suitable p H for the determination in both cases. Which one of the methods gives the smallest systematic titration error assuming that the titration can be finished exactly when 50 ~ of the indicator has changed colour? The answer should be justified by appropriate calculations. 3. A 0,01 M solution of Bi(III) containing 0.1 moles per litre of potassium chloride m a y be titrated with E D T A using pyrocatechol violet as indicator, At what p H should the titration be performed, and what will the titration error be assuming that pBi in the end point can be determined to whithin +_ 0,5 logarithmic units? 4, Th(IV) can be determined in the presence of La(III) by titrating with polyamino-polycarboxylic acid T T H A , Supposing that both the concentration of Th and the concentration of La is 0,01 mole/litre, suggest a suitable p H for the determination and a suitable indicator, 5. Suggest a method for the separation of uranium(IV) from thorium(IV) by ion exchange. Specify type of method - batch or column filtration - type of resin, milieu (pH etc). 6. Derive the Gran-function for the titration of metal ion M with ligand L according to the equation M+L=ML on the assumption that M can be measured with an ion selective electrode obeying the nernst equation. The titration is to be carried on beyond the equivalence point, 7. How m a n y milligrams of calcium fluoride can be dissolved in 100 ml of 0.05 M hydrochloric acid? 8. To 100 ml of a solution being about 1 0 - 3 M with respect to Sn(II), 10.0 ml of a 0.0200 m EDTA-solution were added and pH was adjusted to 5,5. The excess of E D T A was then backtitrated using lead nitrate solution and methylthymol blue as indicator. W h a t is the resulting relative titration error for the determination of Sn?

Fresenius Z. Anal. Chem., Band 297 (1979) 9. Heavy metals in natural waters do participate, not only in equilibrium reactions (precipitation, complex formation etc.) with different ionic species in the water (C1 , PO43 -, N T A etc.) but also in redox reactions. The redox properties of different natural waters m a y be quite different, ranging from oxygen rich waters having high pe values (5 + 15) to waters poor in oxygen, forming a "sulphide environment" having low pe values ( - 5 + -10). Consider a "model lake" having a total iron content of 10 8moles per litre and containing 10-6 moles per iitre of N T A (nitrilotriacetic acid). The p H of the lake water is 7.5. Which ionic species will dominate in the water at different pe values? The following ionic species should be considered: Fe 2+, Fe 3 + Fe2+-NTA, Fe3+-NTA and Fe3+OH -NTA. The reactions and constants are: Krea(Fe 2+ + 2 e - = Fe) = 1014"9 M 2 K~.~d(Fe3 + + e - = Fe z +) = 10-13.o M K(Fe 2 - + N T A = Fe z +-NTA = 108.8 M - 1 K(Fe 3 + + N T A = Fe 3 +-NTA = 10 ~s'9 M - 1 K(Fe 3 + + O H + N T A = Fe 3 + O H - - N T A ) = 109.9 M - 1 1ogc~NTAtm 2.3 at p H = 7.5 do the calculations for pe values - 5,0 and 5. pe = - l o g [ e - I = E/(RTF

l l n 10) E/0.060 V.

10. A t the national swedish environment protection board, there is interest in being able to trace the propagation of heavy metals (particularly copper and zinc) originating in the paint used on the bottoms of tankers laid up in Brofjorden bay. There have been suggestions that "tea bags" filled with an ion-exchange resin be hung out at suitable locations in the bay in the environment of the tankers, the idea is that the heavy metal ions would be enriched over a period of time. If all the bags were then collected simultaneously and analysed, the results could form a basis for getting an idea of the time averages of the concentration gradients in the surrounding waters. Do you think that the method would work according to plan? Assume that the water has the same composition as N o r t h Sea water, and Dowex 50X8 is used as the ion-exchange resin. Modify the method to yield the desired results. Do the calculations for Cu 2 + ions. Received October 2, 1978