Chem 2 /Analytical Chemistry/ CIT Experiment I 5 GAS CHROMATOGRAPHIC ANALYSIS OF nALKANES INST RUMENT:- Varian 3400 Gas Chromatograph

CHEMICALS:- Hexane, Heptane, octane, nonane, decane and mixtures of these alkanes in diethylether (solvent). OPERATING CONDITIONS:DSQ Injector Temp.: 20OOC 12/ / Qt at Detector Temp: 200OC Column Temp: (i) 709C isothermal (ii) 5OOC to 1309C at SOC per minute Temperature programming Column: GPSP 2100 (10%) - (non polar packed column) Carrier Gas: nitrogen Carrier Gas Flow: 60 cm3/min. Attenuation: 32 Range: 9 OBJECTIVES (1) To investigate the reproducibility of sample injection i (2) To compare the isothermal and temperature programmed analysis of a \ mixture of hexane, heptane, octane, nonane and deeane. l (3) To identify and quantitate alkanes in the solution mixtures provided. Procedure Part (1) (a) Prepare a solution of heptane in ether by pipetting 1.0 cm3 of heptane into a 50.0 cm3 volumetric flask and diluting to volume with ether (CARE! Use ether only in fume cupboard and away from all sources of heat). Stopper the

tlask and invert a number of times to ensure complete mixing. Rinse the microlitre syringe provided with the prepared heptane solution. Inject 1 ul of 69

Chem 2 I/Analytical Chemistry! CIT the heptane solution and wait for the heptane peak to elute (this should take about 2 minutes). Note: the ether will elute before the heptane peak and should take less than a minute to elute. When the heptane peak has eluted, press reset to obtain the report of the chromatogram. Repeat the injection 6 more times and obtain the report ofthe chromatogram after each injection. Part (2) (a) You are provided with a solution mixture of all the 5 individual alkanes which is 20% (v/v) in each alkane. Prepare a solution of this mixture in ether by pipetting 5.0 cm3 of the mixture into a 50.0 cm3 volumetric flask and diluting to volume with ether, Stopper the flask and invert a number of times to ensure complete mixing, (b) Mnse the syringe well with the solution mixture prepared in (a) and inject lul under the isothermal conditions used in (part I) and wait for the peaks to elute. Note: this will take up to 20 minutes - check with your instructor that all peaks have eluted before proceeding. The peaks elute in the order ether, hexane, heptane, octane, nonane and decane. When the sixth peak i.e. decane has eluted press reset and obtain the report of the chromatogram. (c) Consult your instructor on how to change from isothermal to the temperature programme outlined in the OPERATING CONDITIONS. (d) Repeat the analysis carried out in (b). The peaks still elute in the same order

but note the differences in the 2 chromatograms. Part (3) (a) You are provided with 3 unknown solutions (labelled A, B and C) each of these contain a number of the alkanes. Prepare a solution of each unknown in ether by pipetting 5,0 cm3 into a 50.0 cm3 volumetric flask and diluting to volrune with ether (great care is required to avoid cross contamination during this procedure). Stopper the tlask and invert a number of times to ensure complete mixing. Each of these prepared unknowns should be analysed under the conditions used in part (2)(d) i.e. l ul injection and temperature programmed analysis. It is important to rinse the syringe several times with a particular unknown prior to the injection of the l ul sample into the gas 70

Chem 2 /Analytical Chemistry! CIT chromatograph. lt should also be noted that after each injection of an unknown you must wait until after the retention time of decane (established in part (2)(d)) before proceeding to analyse the next unknown. Analyse each unknown and if time permits, repeat each analysis. Treatment of Results Part (l) Tabulate the retention time and the peak area (integration cotmts) values for the repeat analysis of heptane in part (l) of the procedure, and calculate the average and the relative average error for both area and retention time eg. retention times: 7.50, 7.46, 7.56, 7.78, 7.32 min.

average I 7.52 min individual error = .02, .06, .04, .26, .20 average error : .58/5 = .ll6 relative average error = (.116/7.52) X 100 . p `/{L: Part (2) t Tabulate the retention times ofthe 5 alkanes as determined in part 2 of the procedure for both the isothermal analysis and the temperature programmed analysis. __ `%lot a graph of (i) the retention times of the alkanes vs the number of carbon ` J atoms in the alkanes i.e. 6, 7, 8, 9, l0.Vand (ii) log of the retention times ofthe alkanes vs the number of carbon atdms in the alkanes. These plots should be carried out using the data obtained from the isothermal analysis only. \,. Part (3) Identiy and quantify the alkanes in the unknowns A. B & C, studied under temperature programmed conditions Qualitative analysis Obtain the closest match between the retention time of each peak in each of 2 _ the unknowns (ignore very small peaksras these are probably dueto V contamination of the samples) and the retention times established for each 7l

Chem 2 /Analytical Chemislry/ CIT alkane in part ofthe procedure (i.e. under temperature programmed

conditions). List the alkanes in each of the unknowns. This is how qualitative analysis is commonly carried out in gas chromatographic analysis. Quantitative analysis The concentrations ofthe alkanes in each of the unknowns can be estimated by the method of area normalisation. Quantitative analysis is achieved in gas chromatographic analysis by use of peak area data since the size of a chromatographic peak is directly related to the amount of a component which gives rise to that peak. However this will only give accurate results if the detector responds equally to all the alkanes. lf the detector does respond equally to all alkanes then a mixture of alkanes of \ equal concentration would give the same area for each alkane peak in a chromatogram of the mixture. You can check this by comparing the areas of the alkane peaks in the chromatogram of the 20% (v/v) mixture established in part (2)(d) of the procedure. You will probably find that the peaks do not have identical areas and consequently the detector does not respond equally to the alkanes under investigation. To use the area normalisation method in this case requires that we multiply the area of an alkane peak in the chromatogram of the unknown by a number called a response factor. The resulting area is called the corrected area . i.e. Area x Response Factor = Corrected Area We then use the corrected area to calculate the concentration of each alkane in each unknown mixture. To calculate the response factors for each alkane, use the area data obtained from the chromatogram of the 20% (v/v) mixture established in part (2)(d) of the procedure (i.e. the temperature programmed mixture of all alkanes) as follows: Response factor for (each) alkane Z area of alkane peak

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Chem 2 /Analytieal Chemistry! CIT Note: The octane peak is taken as a reference or internal standard and by definition has a response factor = 1.00; This means that an alkane with a peak area greater than that of octane will giveiajesrpnsefactprjisQtland an alkariivfth a peak area less that of octane @11 give a response factor >1.00. Q. K Now galculate a corrected area foreagijtlkaner inkeach of the unknowns, (what weuare egimgighere ag the areasiliat would be obtained if the detector responded equally to all alkanes). i.e. Area x Response Factor Z Corrected Area l \ Finally use the areanrlrnalisationuforjnula todetermine the concentration of each alkane in each of the unknowns A, B and C: Corrected area of a particular alkane in unknown X 100 = concentration of Sum of corrected areas of all alkanes in the unknown particular alkane (% in uriknown) Using this method calculate the concentration (% v/v) of each of the alkane in t each ofthe unknowns A, B and C and clearly tabulate your results. 73