Calibration of Volumetric Glassware

Calibration of Volumetric Glassware Introduction This set of laboratory experiments is designed to introduce you to some of the apparatus and operations you will be using during the remainder of this course, including the treatment of data using spreadsheets. While some of the procedures may seem trivial and the results obvious, this is a chance for you to develop good laboratory technique. Volumetric glassware is a class of glass vessels that are calibrated to contain or deliver certain volumes of substances. Graduated cylinders, pipettes (also pipets), burettes (also burets) and volumetric flasks are examples as are beakers and Erlenmeyer flasks. It can be seen from this list that the term "calibrated" can mean "to a varying degree". The manufacturer's stated accuracy of beakers and Erlenmeyer flasks is typically 5% while that for volumetric flasks is generally much higher. In this laboratory experiment, the three types of glassware typically used by an analytical chemist: a volumetric flask, a volumetric pipet and a burets will be calibrated. These tools are used extensively when performing gravimetric and titrimetric Analyses. In order to avoid introducing systematic errors into measurements, each of these instruments must be properly calibrated. And, to reduce the random errors inherent when using these instruments, their proper use must be thoroughly understood. The quality of the measurements obtained from these tools depends heavily on the care taken in calibrating and in using each instrument. Figure 2: Pipettes (http://www.chem.yorku.ca/courses/chem1000/equipment/pipette.html) Figure3: Buret (http://en.wikipedia.org/wiki/file:burette_vertical.svg) Figure 1: Volumetric Flask (http://en.wikipedia.org/wiki/file:brand_volumetric_flask_100ml.jpg) In the most precise work it is never safe to assume that the volume delivered by or contained in any volumetric instrument is exactly the amount indicated by the calibration mark. Instead, recalibration is usually performed by weighing the amount of water delivered by or contained in the volumetric apparatus. The amount of water delivered by or contained in the volumetric apparatus is quantified by mass to effect the calibration. This mass is then converted to the desired volume using the tabulated density of water and the following standard relation: volume = mass / density (1) where volume is measured volume, mass is the mass of water used to fill the volume and density is the density of the water. Department of Cosmetic Science, Chia-Nan University page 1 of 10 02 March, 2015

All volumetric apparatus should be either purchased with a Calibration Certificate or calibrated by an analyst in this manner. Required Reading D.C. Harris, Exploring Chemical Analysis (5th ed., W. H. Freeman, NY, 2013) chapter 2 (Tools of the trade) Systematic Errors Affecting Volumetric Measurements The volume occupied by a given mass of liquid varies with temperature, as does the volume of the device that holds the liquid. 20 C has been chosen as the normal temperature for calibration of much volumetric glassware. Glass is a fortunate choice for volumetric ware as it has a relatively small coefficient of thermal expansion; a glass vessel that holds 1.00000 L at 15 C holds 1.00025 L at 25 C. If desired, the volume (V) obtained at a temperature (T) can be corrected to 20 C by use of: V 20 C = V T [1 + 0.000025 (20 T)] (2) In most work, this correction is small enough it may be ignored. However, the thermal expansion of the contained liquid is frequently of importance. Dilute aqueous solutions have a coefficient of volume thermal expansion of about 0.00025 C -1. Thus, 1.000L of water at 15 C will occupy 1.002L at 25 C. A correction for this expansion is often applied in rigorous calibration procedures. Parallax is another source of error when using volumetric ware. A correction for this expansion must frequently be applied during calibration procedures. Frequently, graduation marks encircle the girth of the apparatus to aid in preventing this artifact by permitting the analyst to align the line of sight. Figure 4: Parallax Error from Incorrect Lines of Figure 5: The Meniscus of Water. sight. (Quantitative Analysis, 4th Ed. by Conway Pierce, Edward L. Haenisch and Donald T. Sawyer; John Wiley & Sons; 1948.) Readings that are taken from a line of sight that is either too high or too low will result otherwise. Department of Cosmetic Science, Chia-Nan University page 2 of 10 02 March, 2015

Tips for Correct Use of Volumetric Glassware Pipettes. The pipette is used to transfer a volume of solution from one container to another. Most volumetric pipettes are calibrated To-Deliver (TD) with a certain amount of the liquid remaining in the tip and as a film along the inner barrel after delivery of the liquid. The liquid in the tip should not be blown out. Pipets of the "blow-out" variety will usually have a ground glass ring at the top. And, drainage rates from the pipet must be carefully controlled so as to leave a uniform and reproducible film along the inner glass surface. Measuring Pipets will be gradated in appropriate units. Once the pipet is cleaned and ready to use, make sure the outside of the tip is dry. Then rinse the pipet with the solution to be transferred. Insert the tip into the liquid to be used and draw enough of the liquid into the pipet to fill a small portion of the bulb. Hold the liquid in the bulb by placing your fore finger over the end of the stem. Figure 5: Pipet Usage (Quantitative Analysis, 4th Ed. by Conway Pierce, Edward L. Haenisch and Donald T. Sawyer; John Wiley & Sons; 1948.) Withdraw the pipet from the liquid and gently rotate it at an angle so as to wet all portions of the bulb. Drain out and discard the rinsing liquid. Repeat this once more. To fill the pipet, insert it vertically in the liquid, with the tip near the bottom of the container. Apply suction to draw the liquid above the graduation mark. Quickly place a forefinger over the end of the stem. Withdraw the pipet from the liquid and use a dry paper to wipe off the stem. Now place the tip of the pipet against the container from which the liquid has been withdrawn and drain the excess liquid such that the meniscus is at the graduation mark. Move the pipet to the receiving container and allow the liquid to flow out (avoiding splashing) of the pipet freely. When most of the liquid has drained from the pipet, touch the tip to the wall of the container until the flow stops and for an additional count of ten. Volumetric Flasks. The volumetric flask is used to prepare Standard Solutions or in diluting a sample. Most of these flasks are calibrated To-Contain (TC) a given volume of liquid. When using a flask, the solution or solid to be diluted is added and solvent is added until the flask is about twothirds full. It is important to rinse down any solid or liquid that has adhered to the neck. Swirl the solution until it is thoroughly mixed. Now add solvent until the meniscus is at the calibration mark. Department of Cosmetic Science, Chia-Nan University page 3 of 10 02 March, 2015

If any droplets of solvent adhere to the neck, use a piece of tissue to blot these out. Stopper the flask securely and invert the flask at least ten times. Burets. The Burets is used to accurately deliver a variable amount of liquid. Fill the burets to above the zero mark and open the stopcock to fill the tip. Work air bubbles out of the tip by rapidly squirting the liquid through the tip or tapping the tip while solution is draining. The initial burets reading is taken a few seconds, ten to twenty, after the drainage of liquid has ceased. Holding a white piece of paper with a heavy black mark on behind the burets can highlight the meniscus. Figure 6: take reading on burets (Quantitative Analysis, 4th Ed. by Conway Pierce, Edward L. Haenisch and Donald T. Sawyer; John Wiley & Sons; 1948.) Place the flask into which the liquid is to be drained on a white piece of paper. (This is done during a titration to help visualize color changes that occur during the titration.) The flask is swirled with the right hand while the stopcock is manipulated with the left hand. Figure 7: burets usage during titration (Quantitative Analysis, 4th Ed. by Conway Pierce, Edward L. Haenisch and Donald T. Sawyer; John Wiley & Sons; 1948.) The burets is opened and allowed to drain freely until near the point where liquid will no longer be added to the flask. Smaller additions are made as the end-point of the addition is neared. Allow a few seconds after closing the stopcock before making any readings. At the end-point, read the burets in a manner similar to that above. As with pipets, drainage rates must be controlled so as to provide a reproducible liquid film along the inner barrel of the burets. Department of Cosmetic Science, Chia-Nan University page 4 of 10 02 March, 2015

Cleaning of Volumetric Glassware. Cleaning of volumetric glassware is necessary to not only remove any contaminants, but to ensure its accurate use. The film of water that adheres to the inner glass wall of a container as it is emptied must be uniform. Two or three rinses with tap water, a moderate amount of agitation with a dilute detergent solution, several rinses with tap water, and two or three rinses with distilled water are generally sufficient if the glassware is emptied and cleaned immediately after use. If needed, use a warm detergent solution (60-70 C). A burets or test tube brush can be used in the cleaning of burets and the neck of volumetric flasks. Volumetric flasks can be filled with cleaning solution directly. Pipets and burets are filled by inverting them and drawing the cleaning solution into the device using suction. Avoid getting cleaning solution in the stopcock. Allow the warm cleaning solution to stand in the device for about 15 minutes; never longer than 20 minutes. Drain the cleaning solution and rinse thoroughly with tap water and finally 2-3 times with distilled water. Pipets and burets should be rinsed at least once with the solution they are to filled with before use. A General Calibration Procedure As was noted above, volumetric glassware is calibrated by measuring the mass of water that is contained in or delivered-by the device. This mass data is then converted to volume data using the tabulated density of water (See Appendix) at the temperature of calibration. (In very accurate work, the thermometer is calibrated also as an incorrect temperature reading will lead to the use of an incorrect density for water. This, in turn, will give an inaccurate volume calibration.) Finally, this volume data is corrected to the standard temperature of 20 C. This can be accomplished using (1) to describe the thermal volume expansion coefficient of water. Further details concerning calibration of laboratory glassware can be found in the NIST publication The Calibration of Small Volumetric Laboratory Glassware by Josephine Lembeck; NBSIR 74-461. This publication can be found at: http://ts.nist.gov/measurementservices/calibrations/upload/74-461.pdf. In this experiment a volumetric flask, a measuring pipette and a transfer pipette will be using gravimetrically determined water. In each case, the measured mass of the calibrating water will be standardized to 20 C. REAGENTS AND APPARATUS Analytical Balance 100 ml beaker 5 ml pipette 25 ml volumetric flask 50 ml burets thermometer distilled or deionized water Department of Cosmetic Science, Chia-Nan University page 5 of 10 02 March, 2015

PART A - USE OF THE ANALYTICAL BALANCE The analytical balances in the lab are probably the most precise, accurate and reliable pieces of equipment that you will use during the semester. To understand how these balances operate and their limitations you should read the appropriate section in your textbook. Although there are inherent limits in the accuracy and precision of these balances most weighing errors are caused by incorrect handling of the sample. In the first part of this lab you will investigate several potential sources of error. PROCEDURE 1. In this section you will determine the mass of a clean, dry weighing bottle under various conditions. Unless instructed otherwise, you should handle the bottle with your crucible tongs, gloves, or lint-free paper and measurements should be made to the nearest 0.1 mg. Begin by placing the weighing bottle and cap (with cap removed) in the oven for about 5 minutes. Remove and re-mass while warm. Follow the change in its apparent mass for several minutes, reweighing every thirty seconds. Record all masses including the final constant value. 2. After massing the weighing bottle, roll it around in your hand (handle the bottle with your fingers) and then re-mass and compare the two masses. How should weighing bottles be handled on a regular basis? 3. Next, wipe the bottle clean with a dry, lint-free cloth or tissue and reweigh. Record all observations. 4. Hold the weighing bottle and inch from your mouth and breathe on it several times. Re-mass and compare with previous data. 5. Discuss your results in your laboratory write-up. PART B- CALIBRATION OF VOLUMETRIC GLASSWARE Throughout the semester, you will be required to make accurate measurements of volume. The primary means of doing so will be by using either a volumetric pipet, a Mohr pipet, a micropipette, or a burets. Many manufacturers calibrate their glassware so that the true volume is within specified limits of the labeled volume. In cases where particularly accurate measurements are needed, it may be necessary to make a more accurate calibration of your volumetric containers. In this experiment you will calibrate a burets, a volumetric pipet, and a micropipette. PROCEDURE In order to prevent difficulties with access to the analytical balances, please perform all pipetting and volume measurement manipulations at your normal lab station, then transport the bottle to the analytical balance to mass it. 1. If you have any questions concerning the use of any of the volumetric glassware necessary for the experiment, be certain to refer to Chapter 2 in your textbook. Additional information can be obtained from your instructor. A summary of the calibration techniques are provided on pages 40-42 (burets) 43(volumetric flask) and 44-46(pipette). 2. Place about 150 ml of distilled, deionized water in a 250-mL beaker. Place a thermometer in the beaker containing the water and leave it in place through the remainder of the experiment. If the Department of Cosmetic Science, Chia-Nan University page 6 of 10 02 March, 2015

temperature of the water is not identical to that of the room temperature, allow the water to equilibrate to room temperature. Record the temperature of the equilibrated water. If the temperature of the water changes during the experiment, record the changed temperature. Use the temperature recorded just prior to each mass measurement to do the calculations described later in the experiment. Why are these calculations necessary? How much effect does the temperature of the water have upon the actual delivery of the pipet or burets? Calibration of a burets Burets. Use your cleaned 50mL burets. Note if this is a Class A or other device. Fill the burets with water. Make sure the tip is free of bubbles. Drain into a waste beaker until it is at, or just below, the zero mark. Allow 10-20 seconds for drainage. Make an initial reading to a precision of at least 0.01mL. Test for tightness of the stopcock by allowing the burets to stand for 5 minutes and then re-reading the volume. There should be no noticeable change in the reading. Once the tightness of the stopcock is assured, refill the burets and again drain into a waste until it is at, or just below, the zero mark. Allow for drainage. Touch the tip of the burets to the wall of the waste beaker to remove the pendent drop of water. Make a volume reading. Weigh a receiving container on the Analytical Balance; a 100 ml beaker with Aluminum Foil cover. Drain about 5 ml of water from the burets into the beaker. Allow 10-20 seconds for drainage. Touch the tip of the burets to the wall of the beaker to again remove the pendent drop. Read the burets and weigh the water. Calculate the actual volume of water delivered by the burets in the same manner as outlined above in the procedure on calibrating pipets. Calculate the Correction Factor by subtracting the apparent volume delivered, as given by the burets readings, from the actual volume delivered. Repeat the procedure at least once more. The two Correction Factors should agree within 0.04mL. If they do not, repeat the procedure again. Report the average Correction Factor for 5mL. Repeat this process for 15 ml, 25 ml, 35 ml, and 45 ml delivered. Plot the Average Burets Correction Factor vs. Volume Delivered using Excel or some other graphing software. Calibration of a Volumetric Flask Volumetric Flask. Use your cleaned 25mL volumetric flask. Note if this is a Class A or other device. Calibrate a 25 ml volumetric flask by weighing it empty (and dry) and filled to the mark with distilled water and re-weigh it. Measure the temperature of the water used. Repeat the procedure at least twice more. Calculate the true volume of the flask using the method outlined above. Report the Average, Standard Deviation, and 90% Confidence Interval for this result. Is your result within the listed tolerance for this flask? Perform three replicate measurements for the flask. Calibration of a Pipet Use your cleaned pipet. Note if this is a Class A or other device. Weigh a receiving container on the Analytical Balance; a 100 ml beaker with Aluminum Foil cover. Pipet distilled water into the beaker and reweigh it. Record the temperature of the water used. Department of Cosmetic Science, Chia-Nan University page 7 of 10 02 March, 2015

Measuring Pipette. Fill a 10 ml measuring pipette with deionized water, then drain it to ensure that no droplets remain on the inner walls. If droplets remain, clean the pipette thoroughly and repeat. Fill the pipette and deliver approximately two milliliters into the weighed bottle. Estimate all volume readings to the nearest 0.01 ml. Cap the bottle and reweigh. Repeat this procedure for samples of 4, 6 and 8 ml. Perform three replicate measurements for the pipette. Transfer Pipette. Fill a 10 ml transfer pipette with deionized water and drain to ensure that no droplets remain on the inner walls. If droplets remain, clean the pipette thoroughly and repeat. Fill the pipette to the fill line and deliver the total volume of liquid into a dry bottle. Cap the weighing bottle and reweigh. Perform three replicate measurements for the pipette. Repeat the procedure at least 2 more times. Dry the beaker and re-weigh it for each replication. (Are you pipetting consistently and correctly?) Calculate the apparent mass of the water delivered for each time you pipet. From this mass, and the density of water at the given temperature (See Appendix), calculate the volume of the water delivered. Correct the volume to 20 o C. Calculate the Average, Standard Deviation and 90% Confidence Interval for your calibration result. Is your result within the listed tolerance for this pipet? (See Appendix. What is the better question to ask?) Appendix - Density of Water Temperature ( o C) Density (g/ml) 10 0.9997026 11 0.9996084 12 0.9995004 13 0.9993801 14 0.9992474 15 0.9991026 16 0.9989460 17 0.9987779 18 0.9985986 19 0.9984082 20 0.9982071 21 0.9979955 22 0.9977735 23 0.9975415 24 0.9972995 25 0.9970479 26 0.9967867 27 0.9965162 28 0.9962365 29 0.9959478 30 0.9956502 Department of Cosmetic Science, Chia-Nan University page 8 of 10 02 March, 2015

Appendix - Tolerances for Class A Volumetric Glassware at 20 o C Pipets Volumetric Flasks Burets Capacity (ml) Tolerances (ml) 0.5 0.006 1 0.006 2 0.006 5 0.01 10 0.02 20 0.03 25 0.03 50 0.05 100 0.08 Capacity (ml) Tolerances (ml) 5 0.02 10 0.02 25 0.03 50 0.05 100 0.08 250 0.12 500 0.20 1000 0.30 2000 0.50 Capacity (ml) Tolerances (ml) 5 0.01 10 0.02 25 0.03 50 0.05 100 0.20 With the exception of Graduated Cylinders, the Tolerances for Class B devices is typically twice that of a Class A device. (ASTM E694) Department of Cosmetic Science, Chia-Nan University page 9 of 10 02 March, 2015

Discussion Prepare a Laboratory Report as described previously. Present all measured data in the report together with the expected data. Describe and explain the relationships between the two sets of data. Include good-quality figures and tables to substantiate your discussions. Include a quantitative error analysis in your discussion. Compare your assessment of the various volumetric glassware accuracy values to the manufacturer's stated values. Report Include answers to the following questions: 1. Are the true volumes of your burets, pipette and volumetric flask within Class A tolerance (consult the text for tolerances)? 2. For burets, pipette and volumetric flask, is the deviation of the true volume from the nominal (labeled) volume greater or less than your error? Discuss. 3. Suppose that the error in maintaining and determining the temperature of the water was ± 1 o C. Repeat the computation of the volume of the pipette, propagating the uncertainties of determining the mass of water delivered (your standard deviation) and that of the density of water (based on ± 1 o C). 4. Perfect conditions for performing an experiment never exist. List and discuss the relative importance of experimental conditions that may have affected your calibrations. Possibilities: reproducibility of weighing, constancy of laboratory temperature, cleanliness... 5. The water used in your calibration was quite pure. Suppose, however, that impure water containing some salt was inadvertently used instead of pure water and that the impure water had a density of 1.00117 g/ml at the temperature of your calibration. Recalculate the volume of your volumetric flask. Department of Cosmetic Science, Chia-Nan University page 10 of 10 02 March, 2015