CHEMISTRY 120A LABORATORY MANUAL

Seventeenth Edition Fall 2011

California State University, Fullerton

Department of Chemistry and Biochemistry

TABLE OF CONTENTS
Grading Information Laboratory Grade Laboratory Reports Academic Honesty
Background Information

1 2 3 4 5 8 9

Why Do Experiments? Safety in the Laboratory Waste Disposal The Laboratory Notebook Quantitative Observations Precision of Measurements Scientific Notation Relative and Absolute Precision Rounding Off Accuracy and Error Averaging Statistical Analysis: the Rule of Four Exploration A1: Is Volume Conserved? Objectives and Introduction Graph of Water Density Procedure Calculations Report Data Sheets

11 12 13 16 20 22 23

25 28 29 34 36 37

Exploration A2: Chemistry of Aluminum Objectives and Introduction Procedure: Formation of an Aluminum Compound Procedure: Displacement Reactions of Aluminum Procedure: Determining the Empirical Formula Calculations Report Data and Results Sheets Exploration A3: An Emission Spectroscope Objectives and Introduction Procedure: Construction of the Spectroscope Procedure: Measurements Calculations Report Exploration A4: Equivalent Mass of an Acid Objectives and Introduction Procedure Report Data and Results Sheet Exploration A5: Preparation and Analysis of a Compound Objectives and Introduction Procedure Analysis of the Compound Calculations Report Data and Results Sheets Appendix Results Reporting Forms

41 47 49 52 58 61 62 65 70 74 76 76 77 80 83-84 85 86 88-89 90-93 93 95 96 99

LABORATORY GRADE
Your work in the laboratory will generate a point total that will be added to your lecture points to generate an overall point total for the course. Consult the syllabus of your lecture instructor for details. The laboratory is worth 200 points, broken down as follows: 1. 2. Laboratory quizzes (25 points each): Laboratory reports and Quality of results: A.1 B.2 A.4 A.5 50 36 25 36 40 187 Laboratory Quizzes (50 points) A quiz testing your preparation and understanding of the laboratory experience will be administered at the beginning of the lab session Weeks 4 and 14. Quality of Results: Your results for each experiment will be graded for accuracy and reproducibility. Accurate and reproducible results require that you take care and pay attention to detail while doing the experiment, and that you develop and master the laboratory and technical skills required for each experiment. Care and good technique will yield good results scores. Laboratory Reports: See the next page for general information concerning laboratory report preparation. In addition, your laboratory manual contains specific instructions for preparing the report for each experiment at the end of the description of that experiment.

Total: 1.

2.

3.

LABORATORY REPORTS
You are required to submit a laboratory report for each experiment. Contents: Each laboratory report should contain three parts: 1.) A copy of the Results Reporting Form for the experiment (see Appendix), filled out neatly and completely. (3 points) 2.) A written narrative, addressing the points described in the instructions for the experiment, see each individual experiment for details (6 points). 3.) A data and calculations section containing the data from your experiment, appropriately organized, and a sample of each different type of calculation you made in obtaining the results from your data (5 points). In addition, your instructor will have the following, which will be graded as part of your report: 4.) The carbon copies of your laboratory notebook pages, turned in to your laboratory instructor at the end of each laboratory period (2 points). Grading: Reports are graded for organization, clarity, readability and completeness. General Rules: Write clearly and concisely. Avoid the use of "I" except when stating your opinion. Do not repeat what is in the laboratory manual. Follow the instructions for each report. Due Dates: Laboratory reports generally are due in the Department Office (MH-580) at 5:00 p.m. on a specified day, usually one week after the completion of the experiment. Consult the laboratory schedule for exact due dates. It is a good idea to plan ahead and write parts of your laboratory report before you have finished the experiment. This will keep you from falling behind and will also help you to understand the experiment while it is still in progress.

ACADEMIC HONESTY
Each laboratory report must be your own individual work. Reports that are group writing efforts or that have been copied from other reports will be given zero credit and may result in disciplinary action for plagiarism. You are encouraged to work together with classmates in doing calculations, analyzing data and arriving at correct interpretations. Nevertheless, you must do the calculations and analysis on your own data and write your own report in your own words. Academic dishonesty includes such things as cheating, inventing false information or citations, plagiarism, and helping someone else commit an act of academic dishonesty. It usually involves an attempt by a student to show possession of a level of knowledge or skill which he or she does not possess. 2011-2013 CSUF catalog, p. 69 Penalties for academic dishonesty are severe. Depending on the incident, the penalty will range from a loss of all possible points for that lab to failure of the entire 5-unit course with documentation of cheating on the students file. Some of the offenses that constitute academic dishonesty are: 1) Plagiarizing the laboratory manual or another person's writing. 2) Turning in someone elses work, be it a full report or just a few comments. 3) Copying, as evidenced by the same mistake on different students' papers. 4) Presenting data in a report that are not on the duplicate notebook pages. 5) Reporting laboratory work that is not on the duplicate notebook pages. 6) Adding to or changing material in one's laboratory notebook after duplicate pages have been submitted. 7) Reporting an experiment that was not actually performed. 8) Reporting work performed in a previous semester.

WHY DO EXPERIMENTS?
Our General Chemistry course includes a laboratory component because all of chemistry is based on observations. You may get the idea from your textbook that chemistry is mostly theory. There is much theory in chemistry, but all chemical theory explains the observations that chemists have made, and theories must agree with experimental observations. In Chemistry 120A, we ask you to complete five explorations. Each of these involves experiments designed to generate data and results of the same sort that chemists obtain when they do research. These explorations differ from chemical research in that the results that you will obtain are already known, whereas research explores the unknown. Still, we expect you to learn how chemists obtain the experimental information that underlies chemical theories. The interplay between theory and observations can be described by a general method, a scientific method. First, a scientist makes observations under controlled conditions (does an experiment). When the scientist has enough results, he or she then proposes a general conclusion regarding these results (frames a hypothesis). If the hypothesis is sufficiently general, the scientist then uses it to deduce what should occur under other conditions (makes predictions). To check the validity of the hypothesis, the scientist then makes more observations (tests the predictions). When the new experiments agree with the predictions, the hypothesis is supported, and enough such support causes it to be accepted as a scientific law. When the experiments do not agree, the hypothesis is incorrect and must be revised. In either case, experiments occupy a central role in any science. They are both the starting point of information gathering and the ultimate test of whether hypotheses are correct. Chemistry provides particularly instructive examples of experiments in science because observations can be made in a chemistry laboratory under controlled conditions. In designing the explorations that constitute the laboratory portion of Chemistry 120A, we had several goals. You can learn much about chemistry as you carry out these explorations. l. 2. You can learn something about how chemists learn. You can learn some facts and laws of chemistry. 4

3. 4. 5.

You can learn some important laboratory techniques. You can learn to work quantitatively. You can learn to think like a scientist.

Every good scientist is an active observer. To become skilled at observations, you must pay attention and ask questions. Why are we doing this particular procedure? What would be the effect of changing a condition? What might go wrong with the procedure? What is the meaning of the observations? Good laboratory workers are always thinking about what is going on, asking questions and modifying their thinking as they go. Form the habit of being an active, questioning laboratory worker. Every good scientist also is a careful record keeper. Complete records must be kept of all procedures and observations. An experiment is no better than the written records of what happened during that experiment. For that purpose, every good experimenter keeps a laboratory notebook, in which all significant observations are written down. Form the habit of recording every observation that might be important.

SAFETY IN THE LABORATORY

Every good scientist takes appropriate safety precautions. A chemistry laboratory is like a freeway -- it is safe for all, provided all understand and obey the rules. But just like a freeway, it can be dangerous for all if anyone ignores the rules. There are basic safety rules for working in the laboratory that are analogous to traffic laws. You are expected to know them and obey them whenever you are working on an experiment. Form the habit of learning safety rules and living by them. Like any other human endeavor that is worth doing, chemistry experiments involve a certain amount of risk, particularly when the unknown is being explored. The Curies, for example, eventually died of cancer brought on by exposure to the radioactivity which they discovered and studied. Nevertheless, risks are minimized and the laboratory made as safe as any other work place when everyone uses caution and common sense. The following are general safety rules that must always be observed.

1. KNOW YOUR EXPERIMENT. The more you know about the procedures and chemicals you are working with, the easier it is to avoid accidents. Read the exploration before coming to the laboratory. Become familiar with a procedure, instrument, or chemical before you do experiments with it. There is no excuse for not knowing as much as possible before beginning to work. 2. ALWAYS BE CAREFUL. Along with ignorance, the worst enemy of safety is carelessness. Care in the laboratory includes staying alert, observing what is going on, and not taking anything for granted. 3. WEAR SAFETY GOGGLES, LAB COATS, CLOSED SHOES. The eye is a marvelous instrument, but it is vulnerable to injury. Accidents in a chemistry laboratory frequently involve flying materials -- splashing liquids, splintered glass, etc. -- which can seriously injure the eyes. Full goggles must be worn at all times in all chemistry laboratories and when picking up materials at the chemicals stockroom. Note: this is not a local rule. State law requires that eye protection must be worn wherever potentially harmful chemicals are stored. We strongly recommend that you not wear contact lenses! They readily absorb chemical vapors that can lead to eye irritation and damage without you realizing it. If you must wear contact lenses, notify your laboratory instructor. 4. KEEP WORK AREAS CLEAN. Chemicals used in the laboratory are safe as long as they are kept in their appropriate place, but they can be very dangerous if allowed to contact the wrong materials. This is particularly true of strong acids and bases and human skin. Chemicals become particularly dangerous when we are unaware of what they are. A spill on a bench top may look like water but be strong acid. Always clean up any spilled material immediately. Mercury spills must be carefully cleaned up using a special air suction apparatus. If you are unfortunate enough to break a thermometer, immediately inform your instructor. Do not try to recover spilled mercury by yourself. 5. LABEL ALL MATERIALS. Any time you are working with more than one substance of similar appearance, there is a possibility of a mix-up. Just as newborn

babies are given name tags to prevent inadvertent confusion, samples in the laboratory should be uniquely identified. 6. DON'T EAT or DRINK. Too many chemicals are harmful when taken internally for it to be safe to eat or drink in the laboratory. 7. WEAR SENSIBLE CLOTHING. High-heeled or open-toed shoes, long floppy sleeves and the like are invitations for accidents to happen. These are prohibited in the laboratory. If you must wear fashionable and/or expensive clothing, wear a protective lab coat or apron over it. If you have long hair, tie it back on lab days. Hair very easily catches fire! 8. BEWARE OF FIRES. Chemistry experiments frequently involve the use of open flames for heating. Always check around you (l) before lighting a Bunsen burner to be certain no one is using a volatile flammable solvent such as acetone, and (2) before using a flammable solvent to be certain no one has an open flame nearby. 9. KNOW WHERE SAFETY EQUIPMENT IS. If you are careful, accidents will be very rare. If they do happen, though, a quick response may be crucial to avoiding disaster. Be sure you know the location of the following, and how to use them: eye wash safety shower fire extinguisher first aid kit emergency telephones all exits

If you get any chemical in your eyes, begin an eye rinse at the eyewash immediately. Eye damage can occur very quickly. 10. BE AWARE OF SENSITIVITY TO CHEMICALS. The chemicals used in General Chemistry are safe for general use, but many chemicals can cause adverse reactions for those who are especially sensitive. If you are pregnant, suffer from allergies, or know of any special sensitivity, please notify your laboratory instructor or the laboratory coordinator before the beginning of laboratory work. If, during a laboratory, you experience unusual symptoms such as persistent itching or shortness of breath, immediately stop what you are doing and consult your instructor. 7

In addition to these general rules, some specific precautions apply when working in the general chemistry laboratory. l. Put nothing in drying ovens unless specifically instructed to. 2. When diluting strong acids, always add the acid to water. Adding water to strong acid can liberate enough heat to boil the solution, causing splattering or "spitting" of hot acid solution in random directions. 3. Handle volatile, toxic, and obnoxious materials in the fume hood. 4. Never return excess chemicals to their original container. Discard excess chemicals in the appropriate waste container. To minimize waste disposal, follow the procedure and do not take more than is needed. 5. Never perform unauthorized or unsupervised experiments. 6. Never pipet liquids by mouth suction. Instead, use a rubber pipet bulb. 7. Never push glass into a stopper without protection. When inserting glass into a stopper, wet the glass with water or glycerol, wrap the glass with a towel, and hold the glass near the stopper. 8. Never taste or smell laboratory chemicals.

WASTEDISPOSAL
There are separate containers for different types of waste. Place each kind of waste only in its proper container. Your laboratory procedure describes which container to use for each type of waste that you generate during an exploration. When in doubt, consult your laboratory instructor. Glass waste container is for glass waste. Dont put paper or chemicals in this container! Solid chemical waste container is for solid waste. Dont put glass or liquids in this container! Non-Halogenated Liquid waste container is for organic liquids such as ethanol and acetone. Dont put solids or aqueous solutions in this container! Aqueous waste container is for aqueous solutions that contain toxic materials.

THELABORATORYNOTEBOOK Your laboratory notebook is the most important document in the laboratory, becaise it is where you record all observations that you make while doing explorations. A good laboratory notebook is organized in a way that makes it easy for you to locate and identify an observation that you made at an earlier date. In the General Chemistry laboratory, we expect you to keep a complete notebook, following the rules that are given below. Type of Notebook: You are required to make duplicate copies of all your notebook pages, so your laboratory notebook must produce a duplicate page for each original page. These notebooks have pages in alternating colors. The originals should be on the white pages, duplicates on the yellow or blue pages. Instructor Verification: At the end of each laboratory period, have your instructor date and initial your data pages for that day. Before leaving for the day, turn in the duplicate copies of your data pages to your laboratory instructor. Table of Contents: Reserve the first four pages of your notebook for a table of contents. This table should have four columns: Date, Exploration number, Description, and Page number. The description should briefly identify the procedure. For example, your first entry may be described "Preparation of Solution." Update your table of contents after each laboratory period, so that it always shows all of the data that have been entered in it. Data Pages: At the top of each data page, enter the exploration number and the date. On the first page of each exploration, be sure to begin with the title of the exploration. Your laboratory notebook is the only place where the observations that you make in the laboratory should be recorded. Do not record data or observations on stray pieces of paper or in the laboratory manual.

Types of Data: You should include the following: Numerical data (temperatures, masses, volumes, etc.): identify the data fully, include units, and give the correct number of significant figures. For example: "Mass of empty flask and stopper: 27.4586 g." Observations: record anything that you notice that might turn out to be important. For example: "When the 2 solutions were mixed, a white precipitate formed." "Balance #5 had to be re-zeroed before making this weighing." When in doubt, record an observation. An observation that turns out not to be important can always be ignored, but an unrecorded observation is lost forever. Preliminary calculations: when the procedure calls for you to do a calculation before proceeding, enter the calculation in your laboratory notebook. Comments and speculations: anything that you think of which may help you in interpreting the data and results can be included as a comment. For example: "This calibration doesn't agree with the first one, but I think there were water droplets on the flask walls." Be sure to identify these as opinions by using words like "I think", "Maybe", "It appears", etc. Special Instructions: Write only on the numbered side of the pages. Be sure to use carbon paper to make a duplicate copy of your data or have a notebook with paper that automatically produces a carbon copy. Write only in ink (ball point pen). Never erase errors. If a small mistake is made, draw a line through the mistake and write the correct information above or next to the mistake. If an entire page needs correcting, draw a large X across the entire page and write VOID in large letters. When you void data, write an explanation of why it is invalid. Here are two examples: "The balance was miscalibrated." "I used the wrong reagent in preparing my solution."

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PRECISION OF MEASUREMENTS
Chemistry is a quantitative science. Most of the time, a chemist wants to know not only what is happening but also to what extent (how much). Chemical observations must be expressed as quantitatively as possible. Quantitative measurements have three equally important parts: a numerical value, appropriate units, and a precision. When recording data in your laboratory notebook and when reporting results in your laboratory reports, always include all three of these parts. Of these three parts, precision requires further discussion. Numerical value is self-evident. Units are what allow us to scale a numerical value appropriately (20 miles is quite different from 20 centimeters). Precision is the degree of certainty with which a numerical value is known: "about 20 miles" is a much less precise statement than "21.5 miles." Quantitative scientists have established a basic rule for stating the precision of numerical values: the number of digits recorded for the numerical value expresses the precision of the measurement. As an example of how this rule works, consider measuring the length of a table. You might look at it and estimate, "This is a 2-meter table." The length has been expressed as a one-digit number. Scientifically speaking, this statement means, "This table is more than 1.0, but less than 3.0 meters long." After a crude measurement, you might be able to state the length more precisely as 1.8 meters, meaning that you know the table to be longer than 1.7 but shorter than 1.9 meters. A measurement with a better measuring device might give you a result of 1.83 meters. This means you are stating that the table is greater than 1.82 meters long but less than 1.84 meters long. A very careful measurement with a good tape measure might yield the result, 1.826 meters. Now you are asserting that the table is longer than l.825 but shorter than 1.827 meters. The number of digits in a numerical result is called the number of significant figures. Unless otherwise stated, it is understood that the measurement is precise to within one unit in the last significant figure. Consider, for example, a length that is reported as 1.826 meters. There are four significant figures and we assume, unless told otherwise, that this result contains three certain figures and one doubtful (the last, "6")

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figure. This specific measurement is understood to be 1.826 0.001 meters (i.e. to lie between 1.825 meters and 1.827 meters). Expressing the value in a different unit such as centimeters, 182.6 cm, does not change the number of significant figures (still four). The precision of a measurement depends on the quality of the measuring device used to obtain the measurement. Very sensitive instruments yield measurements of high precision, but less sensitive instruments yield results of lower precision. The analytic balance is the most sensitive instrument that you will use in General Chemistry. The precision of a measurement can also depend on variations in its value. In our example of the table, the table top might be scalloped or fluted, in which case its length would vary by a few centimeters, depending on whether it was measured at a protrusion or an indentation. A scientific example of this kind of fluctuation is the distance between the Earth and its moon. Our moon's orbit is not perfectly circular, so this distance fluctuates with time, varying by about 48,000 kilometers in the course of a month.

SCIENTIFIC NOTATION
Scientists commonly work with very large and small quantities. The diameter of an atom, for instance, is 0.00000000014 meters, and the average distance of the moon from the Earth is 384,000,000 meters. How many significant figures does each of these distances contain? As the numbers are written, it is hard to tell, because all the extra zeros are needed to locate the decimal points. They have nothing to do with the precision of the number. To eliminate the ambiguity created by zeros needed to locate the decimal point, and to shorten the writing of small and large numbers, scientists commonly use a special format, scientific notation, to express these numbers. Scientific notation is based on the fact that any number can be expressed as a number between 1 and 10 multiplied or divided by ten an appropriate number of times. The moon's distance from earth, 384,000,000 meters, can be written as 3.84 x 10 x 10 x 10 x 10 x 10 x 10 x 10 x 10. That looks cumbersome, but we can abbreviate the 8 " x 10" 's as 108 (meaning "multiply by 10, 8 times"): 3.84 x 108 meters. Similarly, an atomic diameter of 0.00000000014 meters can be written as 1.4 10 10 10 10

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10 10 10 10 10 10, abbreviated as l.4 x 10-10 (meaning "divide by 10, 10 times"). (Although it is not needed for scientific notation, 100 has a specific meaning: "multiply by 10, 0 times": 1 x 100 =1). The precision of a number that is written in scientific notation is unambiguous. The number 3.84 x 108 meters means "not less than 3.83 x 108, nor more than 3.85 x 108 meters." Extra zeros now mean extra precision: 3.840 x 108 meters means "not less than 3.839 x 108, nor more than 3.841 x 108 meters."

RELATIVE AND ABSOLUTE PRECISION

The degree of precision in a given experimental value can be viewed in two different ways: as the absolute precision (how big or small is the uncertainty in the value?) or as the relative precision (what is the fractional uncertainty in the value -- how big is the uncertainty relative to the value itself). Each of these ways of looking at precision is important. To illustrate these concepts, we return to our example of the table length. If the table has been measured to be 1.826 meters long, the absolute precision of the measurement is 0.001 meters. The relative precision is 0.001/1.826, or 5 x 10-4. Note that you only have single digit precision in 0.001 so the computed answer is rounded to a single digit, 5 x 10-4, not 5.475 x 10-4. There are several different ways of expressing relative precision: we can state it as 1/1826, or 5 x 10-4, or 0.05% (percent is relative precision x 100), or 5 parts per 10,000. Notice that while absolute precision has the same units as the measured quantity, relative precision is a ratio of two values having the same units and is therefore dimensionless. When you are reporting a measurement, either relative or absolute precision can be used, but when measurements are combined to compute a result, the form of the combination determines which type of precision is more useful. As an illustration, consider the volume and perimeter of the table top whose length we measured earlier. Suppose we find its width to be 0.320 meters (3.20 x 10-1 m). The absolute precision of this width measurement is 0.001 meters, while its relative precision is 1/320, or 0.003 (3 x 10-3). If a measurement of the thickness gives 0.015 meters (1.5 x 10-2 m), the

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absolute precision is 0.001 meters, and the relative precision is 1/15 or 0.067 (or 6.7 x 10-2). Now combine these measurements to determine the perimeter P and the volume V of the table top. Perimeter is P = L + L + W + W = 2(1.826) + 2(0.320) = 4.292 meters; volume is V = L x W x T = 1.826 x 0.320 x 0.015 = 8.76 x 10-3 meters. How precisely do we know each of these computed, or derived, values? The precision of computed results can be found from the precision of individual measurements by considering the largest possible change in each individual measurement. First, consider the table's perimeter. According to the precision of the length measurement, the length might be as large as 1.827 meters, or as small as 1.825 meters. The width might be 0.321 meters, or 0.319 meters. Some of the time, errors will cancel -- the length may be a bit larger than measured, but the width is a bit smaller -but we are interested in how precisely we know the perimeter, so we will assume the worst case. In the worst case, both measurements are off by the maximum amount, in the same direction. Then the perimeter could be as large as 2(1.827) + 2(0.321) = 4.296 meters, or as small as 2(1.825) + 2(0.319) = 4.288 meters. The absolute precision in the perimeter is 0.004 meters. Notice that this is the sum of the absolute precisions of the individual values: 0.001 + 0.001 + 0.001 + 0.001 = 0.004. Applying the same logic to the volume computation, we find that it might be as large as 1.827 x 0.321 x 0.016 = 9.38 x 10-3 cubic meters, or as small as 1.825 x 0.319 x 0.014 = 8.15 x 10-3 cubic meters. The volume is 8.76 x 10-3 0.62 x 10-3 cubic meters, or there is a relative imprecision of 0.62 x 10-3/8.76 x 10-3 = 0.071. Notice that the relative precision for the volume is the sum of the relative precisions of length (5 x 10-4), width (3 x10-3) and thickness (6.7 x10-2): 0.0005 + 0.003 + 0.067 = 0.071 The precision of a composite result can always be determined by the type of analysis described above, but this procedure is tedious. Fortunately the outcome is always the same. For addition and subtraction, the absolute precision of the result is the sum of the absolute precisions of the individual values. For multiplication and division, the relative precision of the result is the sum of the relative precisions of the individual values.

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Another example will illustrate the application of these rules for precision. A student, asked to determine the density of a non-volatile unknown liquid, filled a 25-mL graduate cylinder until it contained 25.0 mL of liquid. The full cylinder weighed 47.5764 g. Using an eye-dropper, the student carefully removed liquid until the cylinder contained 20.0 mL of liquid, whereupon it weighed 43.0464 g. Consider the various quantities involved in this example. Table I-1 summarizes the measurements, computations, and precisions. The absolute precision of each measured quantity is found directly from the measurement, and the relative precision is the absolute precision divided by the measured value. The precision of each computed quantity is determined by adding the appropriate precisions (absolute or relative) of quantities used in the calculation. The computed precision values in bold face are the ones that we find directly from the measured data, while the other computed precision values are obtained from the bold face values and the value of the quantity.

TABLE I-1: MEASURED AND DERIVED QUANTITIES AND PRECISIONS

QUANTITY initial Cyl. Vol initial Cyl. mass final Cyl. Vol final Cyl. mass MEASURED QUANTITIES VALUE ABS. PRECISION 25.0 mL 0.1 mL 47.5764 g 0.0001 g 20.0 mL 0.1 mL 43.0464 g 0.0001 g REL. PRECISION 1/250 1/475,000 1/200 1/430,000

COMPUTED
QUANTITY vol. transferred mass transferred liquid density VALUE 5.0 mL 4.5300 g 0.9060 g/mL

QUANTITIES ABS. PRECISION 0.2 mL 0.0002 g 0.04 g/mL REL. PRECISION 2/50 = 1/25 1/20,000 1/25 = 0.04

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Specifically, the volume transferred is obtained by subtracting two volumes, so its absolute precision is the sum of absolute precisions of the volumes. The mass transferred is obtained by subtracting two masses, so its absolute precision is the sum of absolute precisions of the two masses. The relative precision for each of these measurements is then obtained from the values of their absolute precision. The density is obtained by dividing mass by volume, so its relative precision is the sum of relative precisions of transferred mass and transferred volume. The sum of 1/25 and 1/20000 is 1/24.9687, which rounds to 1/25 or 0.04. After we find the relative precision of the density, we use it to compute the absolute precision. The absolute precision of the density is (1/25) x (0.9060 g/mL) = 0.04 g/mL. The direct calculation of the maximum and minimum density values again shows the validity of using the shortcut method to find the precision of the calculated result.

ROUNDING OFF
In the above example, the density might be as large as 0.944 g/mL or as small as 0.871 g/mL. It is incorrect to write it as 0.9060 g/mL, which implies that it is known to 0.0001 g/mL. In such cases, the result is rounded off -- non-significant figures are eliminated. Because the uncertainty in the density is in the second decimal place, this result is rounded off to two decimals: 0.91 g/mL. We have still overstated the precision, because 0.91 g/mL implies a precision of 0.01, while the actual precision is 0.04.

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Rounding off one more place and giving the density as 0.9 g/mL would imply an uncertainty of 0.1, which is larger than the actual uncertainty. The convention is to round off until dropping one more digit would result in an uncertainty larger than the actual uncertainty. When the digit following the last significant digit is 5 or greater, the remaining digit is increased by one unit: 0.9060 becomes 0.91. If the digit following the last significant digit is less than 5, the remaining digit remains unchanged: 0.9045 rounded to 2 significant figures is 0.90.

Shortcuts to Precision
Chemists want to spend minimum time determining precision. Every time a chemist makes a measurement, precision and significant figures are a concern, but chemists are more interested in what experiments reveal than they are in significant figures. The first question, then, is "How important is precision for this particular experiment?" An analytical chemist, for example, might be interested in determining the level of a particular carcinogen in a sample of ground water. If the carcinogen is present at only about 1 part per billion, the precision of the measurement must be very carefully stated. On the other hand, a synthetic chemist whose goal is to synthesize new compounds is primarily interested in putting the substance in a bottle. The quantitative yield is important (the higher the yield, the less expensive the product will be), but precise values for this yield are not. When quantitative values are being reported, but their exact values are less important than the qualitative results, the detailed treatment of precision is not needed. Instead, we can use a simple system to determine the appropriate number of significant figures: 1. To determine the number of significant figures in an individual measurement, read the number from left to right, counting all the digits starting with the first one that is non-zero. 300. 3 sig. figs.

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1.00 0.020

3 sig. figs. 2 sig. figs.

2. When adding or subtracting, the number of decimal places in the answer should be equal to the number of decimal places in the number with the fewest places. The number of significant figures is not relevant: 0.12 1.6 11.490 13.2 2 sig. figs. 2 sig. figs. 5 sig. figs. 3 sig. figs. 2 decimal places 1 decimal place 3 decimal places 1 decimal place

Sum:

3. When multiplying or dividing, the number of significant figures in the answer should be the same as that of the quantity with the fewest significant figures:. The number of decimal places is not relevant: 1.365 significant figures: 4 x 2.63 3 / 3.0 2 = 1.2 2

The above example is one where the simplified procedure gives a different result than the more elaborate one. The divisor (3.0) has a relative precision of 1/30, so the result could be stated more precisely than this: the result, 1.19665, could be rounded to 1.20 (1 part in 120) rather than to 1.2 (1 part in 12). If the importance of the result is its quantitative value, 1.20 would be the more appropriate number to report; if its importance is in its qualitative significance, report 1.2. (But don't spend a lot of time worrying about it: either way of reporting is legitimate! What is not legitimate is to report this result as 1.19665.) 4. Calculators do not necessarily give results with the correct number of significant figures. They automatically drop trailing zeroes even when they are significant (try multiplying or adding 3.00 and 5.00 on your calculator) and they may carry extra decimal places even when they are not significant (try dividing 5.00 by 3.00 on your calculator). Even when a calculator is programmed to report a particular

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number of digits, that number of digits may not be the correct number of significant figures. Never believe the number of significant figures on your calculator!

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Precision in Volume Measurements

Volume measurements illustrate both absolute and relative precision. As examples, consider the three volume measurements illustrated in Figure I-1. A liquid in any cylindrical container has a curved surface, as the figure shows. The lowest point on the curved surface, called the meniscus, is the position that we read. We can never read that position exactly but must always estimate it as closely as possible.

Figure I1: Examples of volume measurements. The buret reading is 33.34 mL, the gradiated cylinder contains 30.0 mL, and the beaker contains 37 2 mL The absolute precision of our measurement depends on the diameter and markings on the container. A reading always is more precise than the scale markings, because we can estimate the distance of the meniscus from the nearest mark. In the figure, the buret has a line for every 0.1 mL, and we can estimate with an absolute precision of 0.01 mL. The buret reading in Figure I1 is 33.34 mL. The graduated cylinder in the figure has a larger diameter than the buret, and its markings are every 1 mL. This graduated cylinder is filled to the 30 mL line, but we can estimate that it is not more than 30.1 or less than 29.9 mL, so the absolute precision is 0.1 mL and we record a volume of 30.0 mL. We can estimate the volume of liquid in the 50 mL beaker to the nearest 1 mL, 37 mL, but notice that the beaker is marked 5%. This indicates that

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the lines marked on the beaker are only reliable by this amount. Because 5% of 37 mL is 2 mL, we should report this volume as 37 2 mL. The absolute precision of a volume measurement in the graduated cylinder shown in the figure is 0.1 mL, whether the volume is 30.0 mL or 100.0 mL. The relative precision changes, however, as the amount of liquid in the cylinder changes. The relative precision of a 30.0 mL volume is 0.1/30.0 or 0.003. If the graduated cylinder were filled, on the other hand, the relative precision would be 0.1/100.0 or 0001.

Precision in Mass Measurements

The most precise mass measuring device in the introductory chemistry laboratories is the electronic analytic balance. This balance reads mass digitally with an absolute precision of 0.0001 gram (0.1 mg). However, when a digitally reporting instrument displays a particular number of digits, the uncertainty may be larger than 1 in the last digit to the right. To be sure of the precision of a digital readout, we must measure the same object several times, preferably using different instruments. For example, two balances may read 35.8252 g and 35.8255 g for the mass of the same beaker. In this case, we conclude that the precision of the balances is 0.0003 g, because the "true" mass may have any value between these two measurements. Mass measurements using an analytic balance are more precise than volume measurements using burets. You can measure the volume of 35 mL of water to 0.01 mL using a buret, a relative precision of 3 x 10-4, but you can measure the mass of the same amount of water (about 35 g) to 0.0001 g using an analytic balance. This is a relative precision of 3 x 10-6 , 100 times more precise than the volume measurement.

ACCURACY AND ERROR

Our discussion so far has concentrated on the precision of numerical results, which is the uncertainty in the numerical value. Although precision is very important in quantitative scientific work, the accuracy of a result is even more important because the accuracy indicates how close the result is to the actual or true value.

21

Absolute error (E) is defined to be the difference between the measured (M) and the true (T) values. E=M-T Absolute error can be either positive or negative. Like precision, error can be expressed either as absolute or relative. Relative error (RE) is the ratio of the absolute error to the correct value. RE =

(M T )
T

Think about how scientists can be sure of the true value of any quantity. It's not easy, because every experimental measurement is subject to error, and the usual way of discovering errors is by comparison with a "better" or "truer" value. Although it is almost always necessary to measure with great precision in order to achieve accuracy, precise measurements may not be accurate, particularly if what is actually measured differs for some reason from what it is intended to measure. An everyday example will illustrate this point. A farmer, concerned about whether his crops were receiving enough rainfall, bought 3 precise rain gauges, each capable of registering rainfall to 0.01 mm. He installed two on different sides of his house and one on a fence post beside his fields. After the next rainfall, he read each gauge. Gauge 1, outside his bedroom, registered 55.65 mm; Gauge 2, outside his kitchen, registered 7.45 mm; and Gauge 3, on the fence post, registered 17.78 mm. Although each of these readings was precise to 0.01 mm, they cannot all be accurate. On closer inspection, the farmer found that Gauge l was just at the edge of his roof and had been collecting a significant amount of roof runoff. Gauge 2 was on the downwind side of the house and therefore had been protected from the rain. Only Gauge 3, on the fence post in the open, was both precise and accurate: the true rainfall was 17.78 mm. In chemistry experiments, mistakes in what is measured can cause precise measurements to be in error. A supposedly dry sample that contains some water will have an erroneously high mass. A sample, some of which has been accidentally lost, will have an erroneously low mass. A pressure reading thought to be of only one gas may actually be the total pressure of more than one gas. You should always be alert to the possibility of such errors and do your best to avoid or minimize them.

22

AVERAGING
One way to avoid accidental mistakes in measurement is to repeat an experiment several times and then report the average of several measurements as the most reliable result. In such replications of experiments, in addition to precision and error we can also define the average or mean value and the deviation of individual values from this average value. The average value (A) is the sum of all individual values divided by the number of values (N): A=
M N

(The symbol - the Greek capital letter sigma - means "add up all the individual values of"). The deviation (D) of each individual value is the absolute value (i.e. always positive) of the difference between the value and the average. D = |M - A| This is the absolute deviation. If we divide an absolute deviation by the measured value, we obtain the relative deviation, Drel: Drel =
D M

We can average a set of deviations to obtain an average deviation (Dav): Dav =

D N

The average of the relative deviations is the Relative Average Deviation, RAD, which you will be asked to calculate in several of the reports for Chemistry 120A: RAD =
Drel N

The average deviation and relative average deviation are good measures of precision, because they reflect the uncertainty in a whole set of measurements. We return to our (now wiser) farmer friend for an example of these concepts. The farmer has bought a fourth rain gauge (being skeptical of all of them) and has installed one at each corner of his field. After the next storm, he checks all four gauges,

23

finding readings of 60.52, 60.48, 60.78, and 60.54 mm. Table I-2 summarizes the measurements and their deviations from the average. Table I-2 Deviations in Measured Rainfall Gauge Units: 1 2 3 4 Sum Average Reading mm 60.52 60.48 60.78 60.54 242.32 60.58 Absolute Deviation |M-A| mm 0.06 0.10 0.20 0.04 0.40 0.10 Relative Deviation 103(|M-A|)/A Parts per 1000 (ppt) 1.0 1.6 3.3 0.7 6.6 1.6

The average absolute deviation is 0.10 mm, and the average relative deviation is 0.0016 or 1.6 ppt (parts per thousand), or 0.16%. Because the absolute deviations are only precise to about 1 part in 10 (0.01 mm out of about 0.1 mm), each relative deviation is rounded off to 2 significant figures.

STATISTICAL ANALYSIS: THE RULE OF FOUR

Sometimes, in a set of measurements, one result deviates greatly from the other results. If the large deviation is due to known experimental error, exclude the result (Remember the farmer's first placement of his rain gauges.) Many times, however, the cause of a large deviation is not known. In such a case, a statistical test can be applied to find out whether the result should be retained or rejected. The easiest test is the "Rule of Four". For the Rule of Four to be valid, the set must include at least four values. The average (mean) value is calculated without including the value which deviates the most, and the average deviation is computed for the set without this value. Then the deviation

24

of the excluded value is evaluated; if it is greater than four times the average deviation, its exclusion is statistically valid. Conversely, if its deviation is less than four times the average deviation, the result must be included in the set as a valid measurement, and the mean value and average deviations must be obtained for the entire set. Applying the Rule of Four to the data in Table I-2, we temporarily exclude the reading with the highest deviation, that from Gauge 3. This gives the results shown in Table I-3: Table I-3 Adjusted Rainfall Deviations Gauge Units 1 2 4 Sum Average 3 Reading mm 60.52 60.48 60.54 181.54 60.51 60.78 Absolute Deviation mm 0.01 0.03 0.03 0.07 0.02 0.27

The average deviation of the three remaining values is only 0.02 mm, and the deviation of the Gauge 3 reading, 0.27 mm, is more than four times that. On statistical grounds, we are justified in rejecting the Gauge 3 reading and reporting the rainfall as 60.51 0.02 mm.

25

EXPLORATION A1 IS VOLUME CONSERVED?

OBJECTIVES Science is built on sets of general laws. Some of these laws involve conservation. Energy is conserved. Usually, mass is conserved. How about volume? Your objective in this exploration is to determine whether volume is conserved. To determine this, you will learn how to make quantitative measurements of both mass and volume. INTRODUCTION Consult your textbook, Sections 1.5 and 1.6, for more details about measurements and density. Is volume conserved? This question must be answered by experiments. We can theorize all we like, but no theory will tell us what actually exists in nature. Chemistry textbooks describe theories that predict behavior, but all the concepts described in a textbook are based on observations and experiments done by generations of chemists. You probably already know one of the fundamental laws of nature having to do with mass: mass is neither created nor destroyed in physical or chemical processes. This is an example of a conservation law. We say that mass is conserved. You will explore whether volume is also conserved. In other words, when two liquids are mixed together, is the new volume always equal to the sum of the volumes of the individual samples? In order to study any property like mass or volume, we must have techniques for making quantitative measurements. Because mass and volume are everyday properties, you already know something about how to measure them. Bathroom scales measure mass, and measuring cups measure volume. To explore volume conservation, however, you need to measure masses and volumes with higher accuracy than everyday measuring devices allow. In this exploration, you will learn to

26

use precision scientific tools for measuring mass and volume. An analytic balance measures masses with high accuracy, while volumetric glassware measures volumes accurately. Bathroom scales and analytic balances both work by weighing - that is, by measuring the amount of gravitational force that a mass exerts. Force is directly proportional to mass (f = ma), so force measurements can be converted to masses, provided we know the proportionality. Whereas a bathroom scale measures mass only to the nearest half-pound, a quality analytic balance can measure to 0.0001 g (0.1 mg). Using the conversions, 1 pound = 454 g and 1 mg = 0.001 g (10-3 g), we can see that an analytic balance is over 2 million times more precise than a bathroom scale. Volumetric glassware and measuring cups both work by measuring height. Each has been carefully manufactured so that when full, it contains a known volume of liquid. In the case of measuring cups, we fill "to the brim" or to a mark etched on the cup. In the case of volumetric glassware, we always fill to some prescribed mark. You will use two types of such glassware: volumetric flasks, which contain known volumes of liquid, and volumetric pipets, which deliver known volumes of liquid. Each of these is very simple: it is nothing more than a piece of glassware with a line scribed on it. Nonetheless, they allow the measurement of volumes with high precision and accuracy. Analytic balances are more versatile than volumetric glassware, because the analytic balance measures masses over a continuous range with high precision and accuracy. Each volumetric flask and volumetric pipet, in contrast, can accurately and precisely measure just one fixed volume. For volumes other than the fixed volume, it is more convenient to measure mass and find a way to convert to volume. Density provides a connection between mass and volume. Experiments have shown that the ratio of mass to volume of any pure liquid or solid is a constant, provided that temperature does not change. This ratio is defined to be the density d, given by the equation, m d= Equation A1-1 V Density commonly is expressed in units of g/mL or g/cm3 (1 mL = 1 cm3), so it will be convenient to measure masses in grams and volumes in milliliters.

27

Equation A1-1 links three quantities. If you know any two of these three quantities, you can calculate the third. To determine density, you can weigh a sample of known volume, then calculate density using Equation A1-1. If you weigh a container filled with a liquid of known density, you can use a rearranged version of Equation A1-1 to calculate the volume: V=
m d

Equation A1-2

Accurate mass determinations actually involve two mass measurements. When you weigh an object, you compare the gravitational force on the balance pan plus the object to the force on the balance pan alone. To obtain the mass of a liquid sample, you compare the mass of a container filled with liquid to the mass of the empty container. mobject = m2 - m1 Many analytic balances permit the mass reading to be pre-set to read zero for the comparison mass. This is called taring the balance. When this is done, the second mass reading gives the mass of the object directly (When you zero a bathroom scale before stepping on it, you are taring the scale). Taring sets m1 = 0, giving mobject = m2 - m1 = m2 - 0 = m2 Equation A1-2 provides a way of determining volume to high precision. If the density of a liquid is accurately known, you can use mass measurements and Equation A1-2 to determine the volume of any particular container. Water is the most convenient liquid to use for such measurements. It is inexpensive, non-toxic, and its density has been very accurately measured. To apply Equation A1-2, however, we must measure the temperature as well as the mass, because the density of water varies slightly with temperature, as Figure A1-1 (next page) shows.

28

0.999

Density (g/mL)

0.998

0.997

0.996

0.995 5 10 15 20 Temperature (C) 25 30 35

Figure A1-1: Density of water as a function of temperature

SEQUENCEOFEXPERIMENTS Part A: Estimate whether liquid volumes are conserved. Part B: Calibrate a 10-mL Volumetric Flask to determine its precise volume. Part C: Calibrate a 5-mL Transfer Pipet to determine the precise volume it delivers. Part D: Determine precisely the density of an Unknown liquid. Part E: Quantitatively determine whether liquid volumes are conserved.

29

PROCEDURE
Precaution: no open flames are permitted during this experiment! Cleaning: The first time you use a piece of glassware, clean it by washing with soap and water, then rinsing thoroughly with tap water, and finally rinsing with about 5 mL of deionized water from your wash bottle. Once you have clean glassware, you need not clean it again during this exploration, because none of the liquids contaminates glassware. Drying: When the procedure calls for dry glassware, add 2-3 mL of acetone to the clean glassware, swirl to wet all surfaces, and then discard the acetone in the acetone waste bottle. Dry the outside of the glassware with a paper towel. Dry the inside by inserting a Pasteur pipet attached to the house vacuum and drawing air through until the glassware is dry. Do not blow air through the glassware, because compressed air contains oil droplets that will contaminate the glassware!

PartA:PreliminaryStudyofVolumeConservation
1.) Clean your 10-mL graduated cylinder and one test tube. Invert them in a 250mL beaker containing a paper towel and allow them to drain. Rinse your metal spatula with deionized water. 2.) Using your wash bottle, add 5.0 mL of deionized water to your 10-mL graduated cylinder. Pour this liquid into the clean test tube. Again using your wash bottle, add another 5.0 mL of deionized water to your 10-mL graduated cylinder. Pour the water from the test tube back into your 10-mL graduated cylinder, stir thoroughly with your metal spatula, and then read and record the total volume. Discard the water in the graduated cylinder. 3.) Again, add 5.0 mL of deionized water to your 10-mL graduated cylinder, and then pour it into the clean test tube.

30

4.) Obtain an acetone wash bottle. Rinse your 10-mL graduated cylinder with about 3 mL of acetone, swirl to wet all the surfaces, then discard the liquid in the acetone waste bottle. 5.) Now add 5.0 mL of acetone to your 10-mL graduated cylinder. Add the water from the test tube to the acetone in the graduated cylinder, stir the liquid mixture thoroughly with your metal spatula, and then read and record the total volume. Discard this liquid in the waste bottle marked "acetone waste." Answer the following questions as comments in your notebook, and give your reasoning. Note: Comments should appear on both the original and the carbon copy of your notebook pages. A.) When you mixed two volumes of the same liquid (water) was the resulting volume close to or equal to the sum of the two volumes? B.) Is the sum of the two volumes within the range of uncertainty with which you can read volume using the 10 mL graduated cylinder? C.) Answer the same questions when two different liquids (water and acetone) are mixed. D.) Does it appear to you that volume is conserved when the same liquids are mixed? When different liquids are mixed?

Part B: Volumetric Flask Calibration

The quantitative determination of whether volume changes when two different liquids are mixed requires the calibration of a volumetric flask (Part B) and a pipet (Part C). 1.) Place about 11 mL of deionized water in your clean 10-mL graduated cylinder. Let it stand so that its temperature will equilibrate with that of the lab. 2.) Clean and dry a 10-mL volumetric flask and stopper. After drying, handle them only with a paper towel or Kimwipe, because oil from your hands can change the mass of the flask. Do not handle the flask any more than is necessary. 3.) Zero an electronic analytic balance, and then weigh the stoppered flask to the nearest 0.0001 g (0.1 mg). Record this mass.

31

5.) Using a Pasteur pipet and rubber bulb, fill the flask with deionized water until the bottom of the meniscus is exactly even with the mark. (See Figure A1-2). Adjust the water level with the Pasteur pipet, being careful that no water droplets adhere to the walls of the flask above the mark Figure A1-2: Proper location of liquid level when a volumetric container has been correctly filled to the mark.

5.) Stopper the flask and reweigh to the nearest 0.1 mg, using the same balance as for the weighing in step 2. Handle the flask with a paper towel or Kimwipe to prevent fingerprints. 6.) Return the sample to the graduated cylinder. temperature of the water to the nearest 0.5 oC. Measure and record the

7.) Repeat steps 1-6 four more times to obtain five sets of data. Note: It is essential that you dry your volumetric flask for each trial. Rinse with acetone and draw a vacuum through it using a Pasteur pipet. DO NOT BLOW HOUSE AIR INTO THE FLASK.

PartC:PipetCalibration
Note: The upper limit of electronic balances is 105 g. 1.) Clean a 50-mL Erlenmeyer flask, wipe the outside dry, and invert it on a paper towel to allow it to drain. Fill a 250-mL beaker with about 200 mL of deionized water.

32

2.) Clean your 5-mL pipet. Fill it about 1/2 full with soapy water, seal it with your fingers at both ends, and shake. After a minute, drain the pipet (do not blow). Repeat the process. Then rinse the pipet with tap water (3 times), deionized water (3 times), acetone (once), and deionized water (3 times). The water should drain without leaving drops on the pipet walls. If drops still adhere, Consult your instructor to determine how to clean your pipet with NOCHROMIX. 3.) You can deliver very precisely the same volume each time if you master pipetting, but reproducibly delivering the same volume requires practice, otherwise your data will be neither accurate nor precise. Use a pipet bulb to draw water from the 250mL beaker into the pipet until the level is above the pipet mark. Use your fingertip to control the pipet as you drain it to the mark while holding it vertical. Once the pipet is at the mark, let it drain by gravity (do not shake or blow out the liquid). 4.) Weigh your clean 50-mL Erlenmeyer flask to the nearest 0.1 mg. Measure and record the temperature of the water in the 250-mL beaker. Using your 5-mL transfer pipet, transfer a 5 mL sample of deionized water to this flask. Weigh it again to the nearest 0.1 mg, using the same balance for this and subsequent weighings. This is the first calibration of the pipet. 5.) Measure and record the temperature of the water in the 250-mL beaker. Using the same pipet, add another 5 mL of deionized water to the Erlenmeyer flask and then weigh it. Repeat with three additional samples of deionized water, recording the water temperature and weighing after each addition. This gives a total of five additions, so the flask should contain 25 mL of deionized water.

PartD:DensityofanUnknownLiquid
1.) Obtain from the solutions stockroom (SLC-242) a yellow box containing your unknowns for the semester. It will include an unknown liquid for Experiment A1. Use this liquid in the following procedure and in Part E. 2.) Dry your 10-mL graduated cylinder. Carry out steps 1-6 of procedure B using your unknown liquid instead of deionized water. Return the liquid to the graduated cylinder after each

33

trial. It is essential to dry your volumetric flask at the start of each trial. Repeat the procedure three times. From the mass differences and the calibrated volume of your 10-mL volumetric flask, calculate the density of the unknown liquid, to four significant figures. If your three results do not agree to within 1%, repeat the procedure once more. 3.) Discard the liquid in your volumetric flask and any liquid remaining in the 10mL graduated cylinder in the Organic Liquid Waste container. The liquids used in this procedure are organic materials that are injurious to the biosphere. Do not pour them down the sink!

Part E: Additivity of Volumes

1.) Clean and dry your 10-mL graduated cylinder and 10-mL volumetric flask. Fill your 50-mL beaker about half full of deionized water. Using your 5-mL transfer pipet, add a 5 mL sample of deionized water to the volumetric flask. Stopper and weigh to the nearest 0.1 mg. 2.) Transfer about 11 mL of your unknown liquid into your 10-mL graduated cylinder. Using a Pasteur pipet and rubber bulb, add the unknown liquid to the volumetric flask until the meniscus coincides with the line. 3.) Stopper the flask, invert it several times to mix thoroughly, allow it to stand for 2-3 minutes and then observe the liquid level in the flask. Using a Pasteur pipet and rubber bulb, add additional unknown liquid until the liquid level is again at the line. 4.) Repeat step 3 until the liquid level remains at the line after mixing and standing. Then reweigh the flask and record the mass. 5.) Discard this liquid mixture in the waste bottle labeled "Non-Halogenated Liquid Waste". Repeat Part E to obtain a second set of data. If the results from the two sets of data do not agree, repeat again to obtain a third set of data.

34

CALCULATIONS
Calculations for Part B: as follows: Compute the mass of water in the flask for each trial mwater = mfull flask - mempty flask Use the water temperature and Figure A1-1 to find the density of water at this temperature. Read the density from the graph to the correct number of significant figures. Use the mass of the water and its density to compute the volume of the flask. Vflask =
mwater dwater

Record this result with the correct number of significant figures. You measured 5 the mass of water with an accuracy of 0.1 mg out of 10 g (1 part in 10 ), and you can read the density of water to 0.0001 g/mL (1 part in 104), so each calculated volume should be reported with a precision of 1 part in 104. Calculate the average volume of your experimental values. Vflask, average =

(Vtrial 1 + Vtrial 2 + ..... )

Number of trials

Determine and report the absolute deviation and relative deviation of each measurement. Absolute Deviation = Vflask - Vflask, average Relative Deviation =
Absolute Deviation Average Volume

Also, calculate the average deviation and relative average deviation (RAD). These deviations are a measure of the uncertainty of the volume determinations. Average Deviation =

(Deviationtrial 1 + Deviationtrial 2 + ..... )

Number of trials

Relative Average Deviation =

(Rel. Dev.trial 1 + Rel. Dev.trial 2 + ..... )

Number of trials

Use the rule of four (pp. 23-24) to discard any volume that is not statistically valid. Calculate the average volume from the statistically valid data. Use this average value in all calculations that call for the volume of your volumetric flask.

35

Calculations for Procedure C: Calculate the pipet volume for each trial. You will have five separate values. Compute the average volume delivered and the deviation of each individual value from this average. Use the rule of four (pp. 23-24) to discard any statistically invalid measurements. Calculate the average volume of your pipet using all statistically valid data. Use this statistically valid average value in all calculations that call for the volume of your 5-mL transfer pipet. For each addition of water in part C, compute the mass of water delivered by the pipet. mwater = mflask, with 5 mL added - mflask, prior to adding 5 mL Use the water temperature and Figure A1-1 to find the density of the water at this temperature. Read the graph to the correct number of significant figures and record the density reading in your notebook. Use the mass and density to calculate the volume delivered by the pipet: Vpipet =
mwater dwater

Calculate the pipet volume to the correct number of significant figures. Take the average of your experimental values. Vtrial 1 + Vtrial 2 + ..... Vpipet, average = Number of trials

Also determine and report the absolute deviation and the relative deviation of each measurement as well as the relative average deviation (see p. 34). Calculations for Procedure D: Compute the density of your liquid from the mass data and the average flask volume from calculation B: mliquid = mfull flask - mempty flask dliquid =

mliquid Vflask, average

Calculate and report the average of your determinations, the absolute and relative deviations of the individual results, the average deviation, and the RAD. Calculations for Procedure E: The calculation of volume change on mixing uses the results of earlier calculations. The volume of water is equal to the calibrated

36

volume of your transfer pipet. The volume of your unknown liquid is found from the mass difference between step E1 and E4 and the density of your liquid, which you calculated in part D: m mE1 Vliquid = E4 dliquid The initial volume is the sum of these two volumes: The final volume is the volume of your volumetric flask. change Vmix is the volume of the flask minus the initial volume: Vmix = Vflask, average - Vinitial After computing Vmix, convert your result to percent change: % change = 100%
Vmix Vflask, average

Vinitial = Vpipet + Vliquid Thus, the volume

Report Vmix and the percentage change with the correct number of significant figures.

REPORT
RESULTS REPORTING FORM: Attach a completed copy of the form in the Appendix. WRITTEN NARRATIVE: In no more than one typewritten page, state your conclusions concerning the conservation of volume, describe the evidence that leads you to these conclusions, and state how reliable you think your conclusion is. (Could your experiments be in error? By how much?) DATA AND CALCULATIONS: Construct and print out an Excel spreadsheet organized according to the data sheets that appear on the following pages. QUALITY OF RESULTS: There are 20 results points in this experiment: calibration of the volumetric flask, 4 points; calibration of the pipet, 4 points; density of the unknown liquid, 6 points; and volume change on mixing, 6 points.

37

EXPLORATION A1 IS VOLUME CONSERVED? DATA AND RESULTS SHEETS PARTBCALIBRATIONOFTHEVOLUMETRICFLASK

Trial mass (flask empty) mass (flask & water) mass (water) ____ ____ 1 ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ 2 ____ ____ ____ ____ ____ ____ 3 ____ ____ 4 ____ ____ ____ ____ ____ ____ 5 ____ ____ ____ ____ ____ ____

water temperature (oC)

water density (from graph) ____ flask volume average flask volume absolute deviation average absolute deviation relative deviation ____

relative average deviation (RAD)

average flask volume from statistically valid data

38

PART C CALIBRATION OF THE PIPET

Trial mass (before addition) mass (after addition) mass (water added) water temperature (oC) 1 ____ ____ ____ ____ 2 ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ 3 ____ ____ ____ ____ ____ ____ 4 ____ ____ ____ ____ ____ ____ 5 ____ ____ ____ ____ ____ ____

water density (from graph) ____ pipet volume average pipet volume absolute deviation ____

average absolute deviation ____ relative deviation ____ ____ ____ ____ ____ ____ ____

relative average deviation (RAD)

average pipet volume from statistically valid data

39

PART D DENSITY OF AN UNKNOWN LIQUID

Trial 1 2 ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ ____ 3 ____ ____ ____ 4 ____ ____ ____ 5 ____ ____ ____

mass (flask empty) ____ mass (flask + unknown) mass (unknown liquid)

average flask volume from part B density of unknown liquid ____ average density of unknown liquid absolute deviation average absolute deviation relative deviation ____

relative average deviation (RAD)

average density of unknown liquid from statistically valid data

40

PART E DETERMINING IF VOLUME IS CONSERVED

Trial mass (flask + 5 mL water) _____ _____ 1 ______ ______ ______ _____ ______ _____ _____ _____ ______ ______ ______ ______ ______ ______ ______ ______ ______ ______ 2 ______ ______ ______ 3

mass (flask + water + unknown liquid) mass (unknown liquid) _____

average density of unknown liquid (from D) volume of unknown liquid average pipet volume (from C) initial volume (water + unknown liquid) final volume (average V of flask, from B) Vmix average Vmix percent change average percent change _____ _____

41

EXPLORATION A4 EQUIVALENT MASS OF AN ACID

OBJECTIVES
The mole is the currency of chemistry, and chemists often have to analyze substances using mole calculations. One important way to do this uses chemical reactions that proceed quantitatively. In this exploration, you will make use of acid-base neutralization and its quantitative measurement by means of titration. The objectives are to learn how to make accurate quantitative chemical measurements and carry out acid-base analysis with an accuracy of better than 0.5%. You will standardize a solution and use that solution to analyze an unknown substance.

INTRODUCTION
Refer to your textbook, Section 4.6, for more details about acid-base reactions and the technique of titration. In titration, the amount of a substance in a sample is determined by measuring the volume of a solution of known concentration (the standard solution) required to react completely with the substance. A buret is used to deliver and measure the standard solution. The point of a titration at which exactly enough titrant has been added is the stoichiometric point. The end point of a titration is the point when there is an abrupt change in some property of the reaction system, such as a change in the color of an indicator. In a good titration, the end point is also the stoichiometric point. A standard solution may be prepared directly, by preparing a precisely known volume of solution containing a precisely weighed amount of a compound of known purity. When this is not convenient, standardization can be done by titrating a precisely weighed amount of a compound of known purity with the solution that is to be standardized. In the titration of an acid by a strong base, hydroxide ions (OH-) react with acidic hydrogen atoms. At the stoichiometric point, the moles n of hydroxide added exactly equals the moles n of acidic hydrogen atoms initially present. n hydroxide ion = n acidic hydrogen We do not measure amounts of moles (n) directly. Instead, we measure mass (m) and volume (V). The molar mass (MM) and concentration (M) provide connections between these measured quantitites and the amount in moles:

42

n=

m MM

and

n= MV

One mole of a substance may generate one or more moles of hydronium ions or hydroxide ions. Whereas one mole of HCl will consume one mole of hydroxide ions, one mole of sulfuric acid, H2SO4, will consume two moles of hydroxide ions. We define a new quantity, the equivalent mass (EM) of an acid, to be the mass in grams that reacts with one mole of strong base. The units of equivalent mass are g/eq. The equivalent mass of an acid is related to the molar mass through the number of acidic hydrogen atoms that the acid contains: EM =
MM # of acidic H

Here are two examples illustrating the concept of equivalent mass. 1) reaction of acetic acid with hydroxide ions: CH3CO2H (aq) + OH- (aq) CH3CO2- (aq) + H2O (l) Each acetic acid molecule contains one acidic hydrogen atom, so one mole of this acid reacts with one mole of hydroxide ion. The equivalent mass of CH3CO2H is numerically the same as its molar mass: EM =
60 g / mol MM = = 60 g/eq # of acidic H 1 eq/ mol

2) reaction of oxalic acid with hydroxide ions: H2C2O4(aq) + 2 OH- (aq) C2O42- (aq) + 2 H2O (l) Each oxalic acid molecule contains two acidic hydrogen atoms, so one mole of oxalic acid reacts with two moles of hydroxide ions. In this case, the equivalent mass is one-half the molar mass: EM =
90 g / mol MM = = 45 g/eq # of acidic H 2 eq / mol

The usefulness of equivalent mass is that we can calculate it from the results of a titration, without knowing how many acidic hydrogen atoms an unknown substance contains. Suppose that titration of a known mass (macid) of an acidic substance with a solution of strong base of known concentration (Mbase) requires volume Vbase to reach the stoichiometric point. The number of moles of acidic hydrogen atoms is the mass of acid divided by the equivalent mass, so the equality at the stoichiometric point is: n hydroxide ion = n acidic hydrogen
Mbase Vbase =

macid EM acid

Equation A4-1

Rearranging gives an expression for the equivalent mass in terms of measured quantities: 43

EM acid =

macid Mbase Vbase

Equation A4-2

In this exploration, you will use acid-base titrations to determine the equivalent mass of an unknown acid. You will first standardize a solution of NaOH to determine its molarity, titrating it against a known mass of an acid that is a primary standard. A primary standard is a pure compound that can be weighed accurately and then titrated. The primary standard reacts completely and in only one way with the titrating reagent. Your primary standard is potassium hydrogenphthalate (KHC8H4O4). This salt dissolves in water to yield potassium ion (K+) and the hydrogenphthalate ion (HC8H4O4-). The hydrogenphthalate anion has only one acidic hydrogen atom, and it reacts completely and cleanly with OH-: HC8H4O4-(aq)+ OH-(aq) H2O(l) + C8H4O42-(aq) The equivalent mass of KHC8H4O4 is therefore numerically the same as its molar mass, 204.23 g/mol. After standardizing your NaOH solution, you will use it to titrate a known mass of unknown but pure acid. After titration, the mass of the acid, the volume of the titrant (NaOH), and the molarity of the titrant will all be known, so you can calculate the equivalent mass of the unknown acid.

PROCEDURE
Solution disposal: The solutions used in this exploration are not toxic. Dispose of them in the sink with a tap water rinse. I. Preliminary Procedures: 1.) At the beginning of the laboratory period, fill your 500-mL plastic storage bottle with deionized water. Transfer this water to your largest beaker and heat until the water boils. As soon as it boils vigorously, discontinue heating, cover loosely with Al foil, and allow the water to cool until the beaker can be handled without discomfort. While the water cools, carry out steps 2-7. 2.) Clean and dry a weighing bottle. 3.) Check the color of the solid drying agent in your desiccator. It should be blue. If it appears pink, take the desiccator to the solutions stock room and exchange the drying agent for a fresh supply. 4.) You should have vials of unknown acid and potassium hydrogenphthalate in your box of unknowns. Transfer the KHC8H4O4 into the clean, dry weighing bottle, put the uncovered bottle 44

and its stopper (do not stopper the weighing bottle) inside a 250-mL beaker labelled with your name and section number, cover loosely with Al foil, and dry it in the oven at 110 oC for at least an hour. 5.) Store the vial of unknown acid, capped, in your desiccator. NOTE: DO NOT DRY YOUR UNKNOWN. Record your unknown number in your lab notebook. 6.) Mount your buret in a buret clamp, so it is in fully vertical position. Check the buret for cleanliness by filling with deionized water and allowing it to drain. If droplets adhere on the walls, consult your instructor for the appropriate cleaning procedure. When your buret is clean, fill it about halfway with deionized water. Read and record the buret reading. Then open the stopcock slowly and allow ten drops to fall from the buret. Close the stopcock, read and record the new buret reading. From the volume difference, calculate the size of one drop for your buret. 7.) Calculate the approximate molarity of the NaOH solution that you are going to prepare. The stock solution is about 50% by mass NaOH (MM = 40 g/mol), and the density of this solution is about 1.5 g/mL. You will dilute 5 mL of this solution to about 500 mL. Also calculate the mass of potassium hydrogenphthalate, KHC8H4O4, (MM = 204.23 g/mol) that will be neutralized by 20 mL of this NaOH solution. What is the correct number of significant figures for these results? Show your calculations to your laboratory instructor and verify that they are correct before proceeding further. The approximations calculated for the NaOH stock solution concentration, give the estimated amount of KHP that you will use in the first titrations. The KHP mass that you weigh out, and the molar mass of KHP, are known precisely, so the titrations against KHP will allow you to calculate exact NaOH concentration in the stock solution instead of approximate values. Once the exact value of the NaOH concentration in stock solution is known, then the NaOH stock solution will be used to titrate your unknown acid to allow calculations of its equivalent mass. 8.) When the beaker of boiled water from step 1 is cool enough to handle without discomfort, pour about half the water into your 500-mL storage bottle. Add approximately 5 mL (graduated cylinder accuracy) of the NaOH stock solution, then add the remaining water and cap the bottle. Mix this solution thoroughly by inverting the storage bottle and shaking many times (approximately thirty) so that the solution is perfectly homogeneous. Thorough mixing is essential for good results. This is your standard base solution. Keep it capped except when you are transferring it to your buret (this prevents absorption of carbon dioxide from the atmosphere). 9.) Remove your weighing bottle containing potassium hydrogenphthalate from the oven and let it cool (lid still off) in your closed desiccator. Once it is cool, cap the weighing bottle and keep it in your desiccator with its cap on except when actually weighing (this prevents absorption of water by the potassium hydrogenphthalate). II. Weighing and Titration Procedures: Weighing: Each solid sample must be weighed on weighing paper to the nearest 0.1 mg. Tare the balance and weighing paper, add solid KHC8H4O4 until you have the appropriate mass calculated in Part 1, Step 7, then record that mass. Transfer the solid quantitatively to a clean

45

125-mL Erlenmeyer flask, then return the weighing paper to the balance, reweigh, and record the new mass. The mass of solid in the Erlenmeyer flask is the difference between these two recorded masses. Add to the Erlenmeyer flask about 30 mL of deionized water and 2-4 drops of phenolphthalein indicator. Titration: To avoid spillage, always transfer standard NaOH solution from your storage bottle to a clean, dry 50-mL beaker and use this to fill and refill your buret. Do this transfer immediately before filling, as base solution that stands in contact with air becomes contaminated with carbon dioxide. Transfer no more than 25 mL of solution at a time, in order to conserve your solution. Before beginning titrations, rinse your buret with a few mL of standard base. Then fill it so the volume of titrant is more than 25 mL. Allow about 1 mL to drain out. Make sure no bubbles appear in the tip; consult your instructor if you see bubbles. Read and record this volume to the nearest 0.01 mL. Titrate each sample to the first, pale pink color that persists upon thorough mixing. Caution: Dark pink means you overtitrated! When you get near the endpoint (pink color disappears slowly), add base dropwise with swirling. If you believe that one additional drop will exceed the endpoint, you can add a partial drop by opening the stopcock just long enough for a droplet to form on the buret tip. Touch the tip to the side of the titration flask to transfer the partial drop, and swirl the flask to mix the partial drop with the solution. After the endpoint is reached, rinse the sides of the flask using a squeeze bottle filled with deionized water (to be sure that none of the sample was splashed on the sides). If the color disappears, you have not yet reached the true endpoint. At the end of the titration, record the buret reading to the nearest 0.01 mL. Standardization: Titrate at least four KHC8H4O4 samples. The first sample mass should be within 10% of your calculated amount for 20 mL of base. Subsequent samples should have a mass that you expect to require 22-24 mL of base, based on your calculated molarity from your initial titration. After each titration, calculate the molarity of your NaOH solution. If the results of the first two titrations disagree by more than 5 ppt (parts per thousand: 5 ppt is 0.5%), consult your instructor before proceeding with the third titration. Continue doing standardizations until you have 3 results that agree within 5 ppt. Use these three to compute the molarity of your standard base and label your storage bottle accordingly. Equivalent Mass: Titrate at least four samples of unknown acid. For the first titration, use a mass within 10% of 0.15 g (0.135-0.165) (Do not waste time by attempting to have a mass of exactly 0.1500 g.) From the result of this "pilot" titration, calculate the mass that will require 22 mL of titrant. (You can use simple proportions to get this result!). For subsequent titrations, use a sample mass within 10% of this value. To get full points for results, you must have at least three "good" titrations that agree within 5 ppt! Solid disposal: Any unused solid can be disposed of by washing down the sink with tap water.

46

REPORT
RESULTS REPORTING FORM: Attach a completed copy of the form in the Appendix. WRITTEN NARRATIVE: In no more than one typewritten page, describe how each part of the procedure in this exploration is important for obtaining accurate results. Comment on whether or not the equivalent mass that you obtained for your acid is a reasonable one (The unknowns are organic acids; you may wish to consult reference sources such as the Handbook of Chemistry and Physics). DATA AND CALCULATIONS: This consists of three parts: 1.) Complete an Excel spreadsheet that is constructed according to the layout on the following page. 2.) Provide a clear and organized set of sample calculations. Provide a sample calculation for each unique type of calculation, but do not show all calculations. For example, if you carried out four trials of one type, show only the calculations for the first trial. Organize the sample calculations in a clear, coherent and well-labeled fashion. Part of your grade will depend on your organization and clarity. 3.) Report the error limits on your value for the standard base molarity. Determine these error limits by assuming you can weigh to a precision of 0.0001 g and the buret can be read to a precision of 0.01 mL. Use the data for your first trial to estimate the error limits. See the Quantitative Observations section at the start of this manual. QUALITY OF RESULTS (20 points): Your three best values for the equivalent mass of your unknown will be graded on a 0-5 basis. In addition, your reported average value will be graded on a 0-5 basis. If you report more than three values, the three that give you the highest point total will be graded.

47

 EXPLORATIONA4:EQUIVALENTMASSOFANACIDDATAANDRESULTSSHEET

A. Standardization
Trial Mass of KHC8H4O4 Titration Volume of NaOH Molarity of NaOH Solution Average Molarity Absolute Deviation Average Absolute Deviation Relative Average Deviation (ppt) _________ ________ ________ I ________ _________ _________ II ________ ________ ________ ________ ________ ________ _________ III IV

_________________ ________ _________ ________ _________

B. Analysis of the Unknown Acid

Unknown Number Trial Mass of Unknown Titration Volume of NaOH Moles of acidic H atoms I _________ _________ _________ _________ II ________ ________ ________ ________ ________ _________ ________ ________ ________ ________ _________ III IV

_________________ ________ _________ _________________ _________________

Equivalent Mass of Unknown_________ Average Equivalent Mass Absolute Deviation

Average Absolute Deviation Relative Average Deviation (ppt)

48

EXPLORATION A5 PREPARATION AND ANALYSIS OF A COMPOUND

OBJECTIVES
Chemists make new substances and then have to analyze them. You have already carried out explorations involving simple synthesis and analysis. Now you will combine these two basic chemical procedures, the way a research chemist might. Your objectives are to make a substance, isolate it, purify it, and determine what it is. You will determine its chemical composition (empirical formula) by a combination of mass determinations, volumetric procedures, and deductive reasoning.

INTRODUCTION
Consult your textbook, Sections 3.6, 4.5, and 4.7, for more details about formula determination, synthesis, and redox reactions. This exploration combines synthesis, purification, and analysis (determination of an empirical formula). You will prepare a green compound containing potassium, iron, oxalate and waters of hydration, purify it by crystallization, and then analyze it. Experiments will let you compute grams and moles of iron and oxalate per gram of the compound. Then you can determine the moles of potassium per gram of compound using the requirement that the compound be electrically neutral. Once you know the grams of iron, oxalate, and potassium per gram of compound, you can determine the water content by difference. Then you can find mole ratios and convert these ratios into an empirical formula. You will analyze for oxalate by doing redox titrations. Oxalate is quantitatively oxidized by potassium permanganate (KMnO4). Five moles of oxalate react with two moles of permanganate, according to this net reaction: 16 H3O+(aq) + 2 MnO4- (aq) + 5 C2O42-(aq) 2 Mn2+(aq) + 10 CO2(g) + 24 H2O(l)

49

First you will standardize a KMnO4 solution by titrating known samples of Na2C2O4 with permanganate solution. Then you will titrate samples of your compound with the standard permanganate solution in order to determine the moles of oxalate per gram of the green compound. Knowing moles of oxalate per gram, you can also calculate grams of oxalate per gram of the green compound. You will analyze for iron gravimetrically, utilizing a unique light-driven redox reaction. Light reduces all the iron in your green compound to Fe2+ ions, and some oxalate is oxidized to carbon dioxide. The remaining C2O42- combines with Fe2+ to form FeC2O4.2 H2O, a canary-yellow insoluble solid. 2 Fe3+(aq) + 3 C2O42-(aq) + 4 H2O(l) 2 FeC2O4.2 H2O (s) + 2 CO2(g) You will collect and weigh the yellow FeC2O4.2 H2O solid. From the mass of the solid, you can calculate the number of moles of solid, which is also its number of moles of iron. Knowing the moles of iron and the mass of the original compound that was decomposed, you can calculate the moles of iron per gram of the green compound. Knowing moles of iron per gram, you can also calculate grams of iron per gram of the green compound. You will deduce the moles of potassium per gram of the green compound from the requirement that the compound be electrically neutral. This analysis is similar to the one that you carried out on the aluminum compound in Exploration A2. This green compound contains K+, Fe3+, and C2O42- ions, so the requirement for electrical neutrality is:
mol C O2 mol K+ 2 4 3 =2 g of compound g of compound mol Fe3+ g of compound
light

Eq. A5-1

Knowing moles of potassium per gram, you can also calculate grams of potassium per gram of the green compound. You will deduce the amount of water in the green compound by difference. The sum of the grams per gram values must equal one, so:

3+ 2- + g of H O g of Fe g of C O g of K 2 2 4 Eq. A5-2 g of compound = 1 g of compound g of compound g of compound

50

Once the moles of each component per gram of compound is known, you can determine the empirical formula from the mole ratios, rounding as needed.

PROCEDURE
At the beginning of the first lab period, discard the potassium hydrogenphthalate in your weighing bottle. Rinse the weighing bottle with deionized water, place it (uncapped) in a 250mL beaker labeled with your name and section number, and dry it in the oven for 10 minutes. Remove it from the oven, allow it to cool, and then transfer your sodium oxalate (in your unknowns box) into this bottle. Place the uncapped weighing bottle back in your 250-mL beaker labeled with your name and section number, and dry it in the oven at 110oC for at least one hour. Before the end of the period, transfer the uncapped weighing bottle to your desiccator for storage. You will use the dried sodium oxalate in Part II C.

PART I: PREPARATION OF THE COMPOUND

A. Formation of the compound: 1.) Weigh 6.0 g of K2C2O4H2O on any convenient balance. Transfer the solid into a clean 125mL Erlenmeyer flask and add 12 mL (graduated cylinder) of deionized water. Heat this mixture over a Bunsen burner, stirring occasionally with your glass stirring rod, until the solid dissolves completely (the solution should not boil). 2.) Measure 4.0 mL (graduated cylinder) of 2.5 M FeCl3 solution, add it to the Erlenmeyer flask, and mix thoroughly with your glass stirring rod. 3.) Place the flask in an ice bath and allow it to stand until the solution forms a large quantity of green crystals.

51

B. Purification of the compound

1.) Pour off the liquid above the green crystals, removing as much liquid as you can without losing any of the solid. Add 12 mL of deionized water to the flask, and heat the flask over a Bunsen burner until the solid redissolves. Then place the flask in an ice bath. 2.) Add 2-3 mL of deionized water to a test tube, and place the test tube in the ice bath to cool. 3.) Assemble your suction filtration apparatus. Wet the filter paper with deionized water and turn on the suction briefly to draw the water through. 4.) When the cold flask contains a large amount of green crystals, stir it thoroughly, turn on the suction to your filtration apparatus, and pour the mixture onto the Bchner funnel. After all the liquid has passed through, rinse the solid with the cold water from the test tube. 5.) Turn off the suction, transfer the Bchner funnel to the rinsing setup in a hood, and rinse twice with small quantities (several mL each) of acetone. Then return the Bchner funnel to your suction apparatus, resume suction, and continue suction for at least 10 minutes to partially dry the solid. 6.) While you are waiting, clean, dry, and weigh your larger screw-capped vial. Record the mass. 7.) Transfer the solid to a large piece of filter paper on a watch glass, spread the solid out, and cover with a second piece of filter paper. Blot with the filter paper, and if the filter paper becomes visibly wet, stir the solid around and blot with an additional piece of filter paper. Store the compound between the two pieces of paper in your locker until the next laboratory period. 8.) At the beginning of the next laboratory period, transfer the solid to the screw-capped vial and weigh vial plus solid. Record the mass. Label the vial with your name and section number, wrap the sample bottle in aluminum foil to protect the compound from light, and store in your locker when not in use.

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PART II: ANALYSIS OF THE COMPOUND

A. Analysis of the compound for iron
Note: while Step 2 is being carried out, proceed with Parts B and C. 1.) Weigh about 1.1 grams ( 10%, weighed to 0.1 mg) of your compound on weighing paper. Quantitatively transfer the weighed compound to a test tube and add 20 mL (graduated cylinder) of 10% (by volume) acetic acid. Label the test tube with your name and section number. Stir the mixture with a glass stirring rod (no policeman), and LEAVE THE STIRRING ROD IN THE TEST TUBE. 2.) Place the test tube in a test tube rack exposed to direct or diffuse sunlight (your instructor will tell you the proper location). DO NOT STOPPER THE TEST TUBE, BECAUSE CO2 GAS IS EVOLVED DURING THE REACTION. 3.) Check your test tube about once every hour, stirring it gently to insure that the solution is well mixed. As the reaction proceeds, gas bubbles will form; this is carbon dioxide being released in the reaction. The reaction will take several hours to go to completion, so the irradiation will have to be done during two laboratory periods. At the end of the first period, stir the mixture thoroughly with your stirring rod. Then leave it to stand until the next laboratory period. Continue the exposure to sunlight during the second laboratory period. The reaction should be completed during this period. The reaction is complete when the solution is nearly colorless, a yellow precipitate is present, and there is no green solid remaining. 4.) Accurately weigh (0.1 mg) a 7 cm piece of filter paper. Form the filter paper into a cup fitting snugly inside your Bchner funnel (recall exploration A2). The filter paper should extend above the bottom of the funnel and around its entire circumference. Assemble the funnel containing the filter paper in your filter flask and wet the filter paper with deionized water using your wash bottle. Turn on the suction to the filter flask and GENTLY press the filter paper down with your fingers until it contacts the funnel bottom completely. BE CAREFUL NOT TO TEAR THE FILTER PAPER DURING THIS OPERATION.

53

5.) Using your stirring rod, stir the solution and precipitate in the test tube thoroughly. Then pour it onto the filter paper, using the stirring rod to transfer as much of the precipitate as possible. Add several mL of deionized water to the test tube, stir thoroughly with your stirring rod, and rinse the precipitate on the filter paper with this solution, being careful to transfer the last of the precipitate in the process. Repeat this process only once if all the precipitate has not yet been transferred. Repeated rinses will cause large errors in the determination since iron(II) oxalate is slightly soluble in water. In the fume hood set up for acetone rinse by suction filtration, add about 4-5 mL of acetone to the test tube, mix thoroughly and pour over the filter paper. Finally, rinse the entire filter paper with acetone from a wash bottle. DO NOT USE ACETONE AT THE BENCH BECAUSE OTHERS MAY BE USING BUNSEN BURNERS. 6.) Continue suction on the filter flask for 10-15 minutes. Then discontinue suction, remove the filter paper, place it in a beaker labeled with your name, cover with a watch glass, and place the beaker in the drying oven at 60 C for 1 hour. NOTE THAT THIS IS A DIFFERENT TEMPERATURE THAN BEFORE, AND DO NOT LEAVE THE BEAKER IN THE OVEN OVERNIGHT. Store the covered beaker in your locker until the next laboratory period. Then weigh the filter paper and precipitate.

B. Preparation of standard potassium permanganate solution

Clean your 500-mL plastic storage bottle by rinsing it three times with small quantities of deionized water. Do not use soap and water or acetone for cleaning. These leave a residue that will react with permanganate! Prepare 500 mL of potassium permanganate solution by transferring 35 mL (graduated cylinder accuracy) of stock permanganate solution into the 500mL storage bottle and filling with deionized water to within 1 inch of the top of the bottle. Cap the bottle and mix thoroughly by inverting and shaking the bottle about thirty times.

C.Titrationsusingpotassiumpermanganate
Note: Your first titration should be a blank. Then do three standardizations and three titrations of your compound. Do an additional standardization after completing the titrations of your compound. The procedure for both types of titration is the same, as described in steps 1-3 below.

54

Blank: (Do only once). Deionized water and the dilute sulfuric acid used to prepare the sample solution for titration may contain some impurities that react with permanganate ion, so you must perform a blank titration. Follow the titration procedure on a solution that contains 50 mL deionized water, 5 mL of 6M H2SO4, and 1 ml of concentrated H3PO4 .This titration should take no more than a few drops to reach the endpoint. Record this small volume. Subtract this volume from the volume of permanganate solution required to titrate each sample solution. Standardization: Follow the titration procedures used for Analysis (see below) for both the standardization of the permanganate solution against sodium oxalate and the titration analysis of your compound. Remember to heat the contents of the flask to 80oC before titration with permanganate solution. Repeat standardization titrations until your molarities of permanganate solution agree within 5 ppt (0.5%). Remember that there are 2 MnO4- (permanganate) ions for every 5 C2O42- (oxalate) ions at the stoichiometric point (see net ionic equation on first page of Exploration A5) when calculating molarity of the permanganate solution. See the Data and Results sheet to guide you on the molarity calculation for the permanganate solution. For your first standardization titration, weigh approximately 0.15 gram (within 10%, weighed to the 0.1 mg) of the dried sodium oxalate. For subsequent titrations, use a proportional mass of dried sodium oxalate that requires between 22 and 24 mL of titrant. Titration: For your first titration on your compound, weigh a sample of your compound of about 0.15 gram (within 10%, but weighed to 0.1 mg). For subsequent titrations, use a mass that requires between 22 and 24 mL of titrant. The filling procedure for KMnO4 is the same as that used for standard base. Transfer about 25 mL of solution to a clean, dry beaker and then pour this solution into your buret. 1.) Set up your buret clamp on a ring stand. Rinse your buret twice with 5 mL portions of your standard permanganate solution and then fill it to within 1 mL of the top. Drain about 0.5 mL out, make sure there are no bubbles in the buret tip, and read and record the initial buret volume to the nearest 0.01 mL.

55

2.) Weigh the sample to be titrated, and transfer the solid to a clean 250-mL Erlenmeyer flask. Add 50 mL (graduated cylinder) of deionized water, 5 mL (graduated cylinder) of 6 M H2SO4, and 1 mL (graduated cylinder) of concentrated H3PO4. The H2SO4 provides an excess of hydronium ions, and H3PO4 acts as a catalyst that speeds up the redox reaction. 3.) Heat the solution to 80 C. Transfer the flask to the titration setup and begin adding KMnO4 solution, swirling the flask as you add. Titrate the solution with permanganate until you first see a permanent pink color in the mixed solution that lasts after thorough mixing. The pink color is due to a slight excess of permanganate ion, which is present in the system after all of the oxalate ions have been oxidized to CO2. During the titration, be sure that permanganate is added directly into the solution with good mixing. The acid concentration may fall too low if the solution is not well mixed or if the permanganate is added down the side of the titration flask. When permanganate reacts in a region that is low in acid concentration, MnO2 may form instead of Mn2+, giving erroneous results.

CALCULATIONS
1.) Calculate the molarity of your standard potassium permanganate solution from the titration results for sodium oxalate. 2.) Calculate the empirical formula of your compound as described in the introduction. a.) Determine moles/g and g/g of oxalate from the permanganate titrations. b.) Determine moles/g and g/g of iron from the iron oxalate precipitate. c.) Determine moles/g and g/g of potassium using Equation A5-1. d.) Determine g/g and moles/g of water using Equation A5-2. e.) Divide through by moles/g of iron to convert your results to one iron atom per formula unit (Do this even if it gives less than 1 for any of the other amounts). f.) Report the subscripts for potassium and oxalate to two decimals and the number of hydrated water molecules to one decimal. g.) Round each value to the nearest integer; do not multiply through to clear fractions, even if the values are not close to integers. Calculate the molar mass based on these rounded values.

56

4.) Calculate the mass of your purified product from the masses recorded in Part I.B, steps 6 and 8. Convert to moles using the moles of iron per gram of compound that you determined in Step 2b. Calculate your percent yield of the compound, assuming that iron is the limiting reactant and that each mole of iron should yield one mole of product.

57

REPORT
RESULTS REPORTING FORM: Attach a completed copy of the form in the Appendix. WRITTEN NARRATIVE: In no more than one typewritten page, describe what happens to iron and oxalate in each step of the exploration in which a chemical change occurs. Include balanced chemical reactions. Comment on whether or not the empirical formula that you obtained for your compound is a reasonable one (you may wish to consult reference sources such as the Handbook of Chemistry and Physics). DATA AND CALCULATIONS: Construct an Excel spreadsheet organized according to the layout on the following pages. Provide a clear and organized set of sample calculations. Include a sample calculation for each unique type of calculation, but do not show all calculations. For example, if you carried out four trials of one type, you need show only the calculations for the first trial. Organize the sample calculations in a clear, coherent and well-labeled fashion. Part of your grade will depend on your organization and clarity. QUALITY OF RESULTS: Your results are worth 24 points: 3 points for the yield of product, 3 points for the molarity of KMnO4, 18 points for the empirical formula.

58

EXPLORATION A5 - PREPARATION AND ANALYSIS OF AN IRON COMPOUND DATA AND RESULTS SHEETS
I:PreparationandYieldoftheCompound 1.) Mass of Sample Vial Plus Product 2.) Mass of the Empty Sample Vial 3.) Mass of Product _________ _________ _________

II: Analysis of the Compound

A. 1.) Sample Mass 2.) Mass of Filter Paper Plus Precipitate 3.) Mass of Filter Paper 4.) Mass of FeC2O42 H2O Precipitate (A3 A2) 5.) Moles of FeC2O42 H2O Precipitate (A4/MM) 6.) Moles of Iron Per Gram of Compound (A5/A1) 7.) Mass of iron/ g compound (A6 x MM Fe) AnalysisoftheCompoundforIron _______________ _______________ _______________ _______________ _______________ _______________ _______________

59

B.StandardizationofKMnO4 1.) Blank volume: _____________ Trial 2.) Mass of Na2C2O4 (g) 1 _________ ________ ________ ________ ________ ________ _________ _________ ________ _________ _________ _________ 2 _________ _________ _________ _________ ________ 3

3.) Moles of oxalate (B2/MM Na2C2O4) _________

2 4.) Moles of permanganate ( ) X (B3) _________ 5

5.) Net Volume of MnO4- (mL) (Subtract B1) 6.) Molarity of KMnO4 (B4x1000)/B5 7.) Average Molarity of KMnO4 Absolute Deviation Average Absolute Deviation Relative Average Deviation (ppt) C. TitrimetricAnalysisoftheCompoundforOxalate Trial 1.) Mass of Sample 2.) Net Volume of MnO4- (mL) (Subtract B1) 3.) Moles of C2O42- (5/2)(B7 x C2/1000) 4.) Moles C2O42-/g compound (C3/C1) 1 _________ _________ _________ _________ _________ _________

2 _________ _________ _________ _________

3 _________ _________ _________ _________

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5.) Average Value (moles oxalate/g compound): Absolute Deviation Average Absolute Deviation Relative Average Deviation (ppt)

_________ _________ _________

_________ _________ _________

6.) Mass oxalate/g compound (moles/gram x MM C2O4):_________ D DeterminationofEmpiricalFormula _______________ _______________ _______________ _______________

1.) Moles of Potassium Per Gram Compound (Eq. A5-1) 2.) Mass potassium/g compound (moles/gram x MM K) 3.) Mass of water per gram of compound (Eq. A5-2) 4.) Moles of Water Per Gram Compound (D3/ MM H2O)

Unrounded Empirical Formula of Compound: K____ Fe (C2O4)_____ ___ H2O (report to 2 decimal places) Rounded Empirical Formula of the Compound: K___ Fe (C2O4)___ _____ H2O (integral values) 5.) Molar mass of compound calculated from the rounded formula: _________ E DeterminationofYield

Moles of FeCl3 used ___________ Moles of iron in product (I.3 x A6) % Yield of Product ___________ ___________

61

Appendix:

Results Reporting Forms

62

CHEMISTRY 120A RESULTS REPORTING FORM - EXPLORATION A-1

Instructions: Copy this sheet, fill it out completely, and staple it to the front of your laboratory report. Do NOT place this sheet as part of your Data and Calculations section. FIRST NAME__________________ LAST NAME_______________________ SECTION NUMBER________ LAB INSTRUCTOR_____________________ A. Volume of the 10-mL Volumetric Flask (Part B) Trial flask volume 1 ____ 2 ____ 3 ____ ____ ____ ____ ____ 4 5 ____ ____

average flask volume (five significant figures) absolute deviation ____ ____

B. Volume of the 5-mL Pipet (Part C) Trial pipet volume 1 ____ 2 ____ ____ ____ ____ ____ 3 ____ 4 ____ ____ 5

average pipet volume (three significant figures) absolute deviation ____ ____

C. Density of Unknown Liquid ( Part D) Liquid Unknown Number: ________ Average Density: ______

D. Volume change on mixing (Part E) Average Vmix (mL): _______ Average Percent Change ______%

63

CHEMISTRY 120A RESULTS REPORTING FORM - EXPLORATION A-2

Instructions: Copy this sheet, fill it out completely, and staple it to the front of your laboratory report. Do NOT place this sheet as part of your Data and Calculations section. FIRST NAME__________________ LAST NAME_______________________ SECTION NUMBER________ 1.) Yield of Product: mass purified compound ____________ percent yield ____________ LAB INSTRUCTOR_____________________

Calculate the percent yield using the molar mass of your empirical formula. 2.) Molar Mass of Aluminum (three significant figures) acidic trial: molar mass aluminum basic trial: molar mass aluminum 3.) Moles of Components per Gram of Compound moles of aluminum per gram compound moles of sulfate per gram compound moles of potassium per gram compound moles of water per gram compound ____________ ____________ ____________ ____________ ____________ ____________

4.) Empirical Formula (report unrounded values to two places): Based on 1 mole of Al3+ moles K+: _________ moles H2O: moles SO42-: _________ _________ Based on 2 moles of SO42moles K+: _________ moles H2O: moles Al3+: _________ _________

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CHEMISTRY 120A RESULTS REPORTING FORM - EXPLORATION A-3

Instructions: Copy this sheet, fill it out completely, and staple it to the front of your laboratory report. Do NOT place this sheet as part of your Data and Calculations section. FIRST NAME__________________ LAST NAME_______________________ SECTION NUMBER________ LAB INSTRUCTOR_____________________

I. Wavelengths of Hg lines
(nm) blue ________ green __________ yellow ________

II. Fluorescent lights (List all that you

observed)
color: wavelength: _______ _______ _______ _______ _______ _______ _______ _______ _______ _______

III. Rare gas emission lines

(List each color and wavelength) Neon Argon Krypton Xenon __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________ __________

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CHEMISTRY 120A RESULTS REPORTING FORM - EXPLORATION A-4

Instructions: Copy this sheet, fill it out completely, and staple it to the front of your laboratory report. Do NOT place this sheet as part of your Data and Calculations section. FIRST NAME__________________ LAST NAME_______________________ SECTION NUMBER________ LAB INSTRUCTOR_____________________

A. Molarity Determination for NaOH (report four best values)

Trial Molarity of NaOH Average Molarity Absolute Deviation Average Deviation 1 _______ 2 ______ 3 ______ 4 ______

_______ _______ ______ ______ ______

_______ ______

Relative Average Deviation (parts per thousand)

B. Equivalent Mass of Unknown Acid (report four best values)

Unknown Number Trial Equivalent Mass Average Equivalent Mass Absolute Deviation Average Deviation _______ 1 _______ 2 ______ 3 ______ 4 ______

_______ _______ ______ ______ ______

_______ ______

Relative Average Deviation (parts per thousand)

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CHEMISTRY 120A RESULTS REPORTING FORM - EXPLORATION A-5

Instructions: Copy this sheet, fill it out completely, and staple it to the front of your laboratory report. Do NOT place this sheet as part of your Data and Calculations section. FIRST NAME__________________ LAST NAME_______________________ SECTION NUMBER________ 1.) Yield of Product Mass of Purified Compound ____________ Percent Yield ____________ (Use your value for moles of iron per gram of sample to calculate the percent yield.) 2.) Molarity of KMnO4 Average Molarity _________ 3.) Moles of components per gram of compound Moles of iron per gram compound Moles of oxalate per gram compound Moles of water per gram compound Moles of potassium per gram compound 4.) Empirical formula (based on Fe3+-= 1) Report unrounded values to two places K+ _______ C2O42-________ H2O________ ____________ ____________ ____________ ____________ RAD (ppt): ______ LAB INSTRUCTOR_____________________

Molar mass based on rounded empirical formula ___________

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