CHEM 3216 Written Midterm 3 (Fall 2023)

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Georgia Institute Of Technology *

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3216

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Chemistry

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Feb 20, 2024

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Name: CHEM 3216 CHEM 3216 Module 3 Written Exam Exam Instructions o This exam consists of four (4) sections and has ten (9) pages. Please ensure you have all pages. o Please put your full name on the front page and initials on all other pages . o You will have a total of 50 minutes for this exam. o You are allowed to bring one (1) single-sided 8.5 x 11 inch crib sheet. This can be either handwritten or printed. No additional notes or sheets are permitted. o You are permitted to use any calculator. Ensure that any stored data is cleared before the exam begins. o Please ensure that all electronic devices, except for your calculator, are turned off and stored away. Best of luck! 1 Fall 2023 | Midterm 3
Name: CHEM 3216 Question 1: Chromatographic Theory (25 pts) The data below is for a reversed-phase liquid chromatography separation using a packed column. The resulting chromatogram and peak table are also provided. Peak Retention Time, t R (min) Width, W (min) Color Nonretained (Marker Peak) 3.2 -- Brown #1 5.7 1.2 Blue #2 6.5 0.6 Orange #3 8.0 0.8 Green 2 Fall 2023 | Midterm 3 Property Number Units Length of packing, L 15.0 cm Flow rate, u 0.50 mL/min V M 1.5 mL V S 0.15 mL
Name: CHEM 3216 #4 8.5 1.2 Red #5 9.7 1 Purple a. For Peak #1 ( Blue ), find the number of theoretical plates ( N ). (2 points) b. For Peak #1 ( Blue ), find the retention factor ( k ). (2 points) c. Calculate the selectivity factor ( α ) between Peak #3 ( Green ) and Peak #4 ( Red ). (2 points) d. Calculate the resolution ( R s ) between Peak #3 ( Green ) and Peak #4 ( Red ). (2 points) e. Calculate the length of column necessary to separate Peak #3 ( Green ) and Peak #4 ( Red ) with a resolution of 2.5. (6 points) 3 Fall 2023 | Midterm 3
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Name: CHEM 3216 f. Referring to the van Deemter equation, explain why using extremely low flow rates lead to high plate heights. (5 points) g. The figure below shows the plate height ( H ) as a function of linear flow rate ( u ). Each trace illustrates a column with different particle size. Referring to the terms of the Van Deemter equation, explain why the adoption of smaller particles led to lower and flatter curves. (6 points) 4 Fall 2023 | Midterm 3
Name: CHEM 3216 Question 2: Liquid Chromatography Instrumentation and Optimization (30 pts) a. Draw and label a block diagram for a partition liquid chromatography system. (8 points) b. Draw and label a diagram of a laser-induced fluorescence detector AND list one pro and one con of this detector. (8 points) c. Many texts recommend setting the retention factor of the last eluting peak in an LC separation to k = 5 . What impact would increasing the retention factor further have on resolution and retention times? Defend your answer mathematically. (5 points) 5 Fall 2023 | Midterm 3
Name: CHEM 3216 d. Using a 70:30 water:acetonitrile solvent mixture with a polarity index of 8.88, the last eluting peak had a retention factor of 3.0. What polarity index would be required to adjust the retention factor to 5.0? (4 points) e. After optimizing the retention factor of the last eluting peak, we can further improve resolution by improving the selectivity factor ( α ). Explain how the solvent selectivity triangle helps with this goal. (5 points) 6 Fall 2023 | Midterm 3
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Anode Cathode Name: CHEM 3216 Question 3: JPL OWLS Ocean World Instrument (CE-LIF-ESI-TOF-MS) (25 pts) The Jet Propulsion Laboratory is developing a sophisticated capillary zone electrophoresis instrument that is equipped with a laser-induced fluorescence detection system and an electrospray ionization mass spectrometer. a. Using a combination of drawings and words, describe the chemistry occurring on the capillary surface that leads to electroosmotic flow. (5 points) b. For each of the ions on the diagram provided below, draw arrows indicating the direction and relative magnitude of the inherent electrophoretic mobilities and the net mobility (taking into account electroosmotic flow). (5 points) 7 Fall 2023 | Midterm 3
Name: CHEM 3216 c. Using a combination of drawings and text, describe the process of electrospray ionization. (5 points) d. Using a combination of drawings and text, describe how a time of flight mass analyzer separates ions with different m/z . (5 points) e. Calculate the time of flight for a peptide with mass 999 Daltons. Assume the acceleration voltage was 15,000 V and the field-free flight path was 1.5 meters. Also assume that MALDI was used for ionization, so the peptide will be in the form [M+H]+, with a single charge. (5 points) 8 Fall 2023 | Midterm 3
Name: CHEM 3216 Question 4: GC-ECD-EI-Quadrupole-MS (20 pts) a. Explain how an electron capture detector works. (6 points) b. Electron ionization (EI) and chemical ionization (CI) are two common ionization methods used in gas chromatography-mass spectrometry. Explain how CI differs from EI. (4 points) c. Explain how a quadrupole acts as a mass filter to allow only a narrow range of m/z to reach the ion transducer at any given time. (6 points) 9 Fall 2023 | Midterm 3
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Name: CHEM 3216 d. Assume two analytes, fluoxymesterone (monoisotopic mass = 336.21) and 4- chlorodehydromethyltestosterone (monoisotopic mass = 334.17), coelute from the GC column. What resolving power (resolution) would our mass analyzer need to separate the molecular ions (M +* ) of these species? (4 points) 10 Fall 2023 | Midterm 3