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CHEMISTRY 1184 Laboratory Manual for GENERAL CHEMISTRY I

Jim Carroll Roger Hoburg Dana Richter-Egger August 2006

University of Nebraska at Omaha

Table of Contents
Table of Contents ......................................................................................................................................... i Chem1184 SYLLABUS............................................................................................................................... ii Preliminary Operations ............................................................................................................................. iv UNO CHEMISTRY LABORATORY SAFETY RULES, PRACTICES, AND POLICIES ...................... vi Lab Drawer Map ....................................................................................................................................... vii Interpolation 1 Laboratory Notebook.................................................................................. 1 Interpolation 2 Observation of Properties .......................................................................... 5 Project A Observations on Solids ............................................................................................................ 7 Interpolation 3 Numerical Uncertainty ............................................................................ 11 Project B Properties of an Aqueous Sample......................................................................................... 15 Project C Properties of a Liquid Substance.......................................................................................... 23 Project D Inorganic Forms of Copper ................................................................................................... 29 Project E Analysis of Lead in Soil......................................................................................................... 35 Project F Molecular Modeling I............................................................................................................. 39 Interpolation 4 Molecular and Electronic Geometry ....................................................... 39 Interpolation 5 PC Spartan Pro ........................................................................................ 53 Project G Molecular Modeling II........................................................................................................... 57 Project H Introduction to Chromatography ......................................................................................... 67 Project I Chemical Equations................................................................................................................ 73 Project K Introduction to Titrimetry .................................................................................................... 79 Interpolation 7 Nomenclature ........................................................................................... 85 Interpolation 8 Ionic Equations......................................................................................... 87 Project L Qualitative Anion Analysis ................................................................................................... 89 Interpolation 9 Graphing ................................................................................................... 95 Project M Introduction to Calorimetry ................................................................................................. 99 Project N Identification of an Unknown Acid .................................................................................... 105 Index ........................................................................................................................................................ 109

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Chem1184 SYLLABUS
REQUIRED MATERIALS 1. Chemistry 1184 Laboratory Manual 2. Laboratory Notebook meeting the following criteria String or spiral-bound notebook (consider one that is top-bound if you write left-handed) It must have at least 100 pages (50 pairs), each about 8 x 11. Alternate or all pages must be perforated for easy removal. Carbonless paper which makes copies of readable density 3. High-impact, splash-protective, chemical goggles. Select goggles for comfort and good ventilation. You will wear these throughout each period. 4. Calculator 5. Matches (absolutely no lighters) 6. Dish towel or paper towels 7. Small bottle of liquid dish soap 8. Metric ruler These projects and this schedule are designed to build your skills AND to reinforce what you just covered in lecture. The lab and lecture cover the same material, and mutually reinforce each other. Topics are not necessarily introduced at the same time in lecture as in lab and some may appear only in one or the other. Your success in lecture and lab is dependent on your ability to retain knowledge gained in both and to apply it later during and following the current term. If a topic is introduced in lab, your conclusions are expected to arise from lab data, not from lengthy study of text material scheduled for the future. You are also expected to use the textbook as a resource for lab. LETTER GRADES Your final letter grade will be based upon the straight 90, 80, 70, 60 scale (i.e. 100-90 is an A, 90-80 is a B, etc). Plus and minus grades will be given for the upper and lower 3% of each letter grade (no grades of C- will be assigned). Your final grade will be based upon the percentage of all points earned: reports 1040 points, quizzes 100 points, exams 320 and lab practices 80 points = TOTAL of 1460 points. LAB REPORTS Your grade for each project is based on your laboratory notebook (all experimental work, related calculations, class data if specified and conclusions), any graphs drawn and report/data sheets. All components submitted should be the originals, stapled together and turned in at the end of that lab period unless otherwise indicated by your laboratory instructor. Copies of all graphs should also remain attached within your notebook. Points for each project are assessed according to the completeness, correctness and accuracy of your work. More specific guidance is given in the lab manual for most projects. Each project is worth 80 points except the first experiment which is worth 40 points and the last experiment which is worth 120 points. Instructors will deduct 10 points per day late. Consult your instructor no later than the date due if you need an extension. PRE-LAB QUIZZES These 10 point quizzes are available electronically on Blackboard (blackboard.unomaha.edu). They will test your preparedness for each project and must be completed each week before coming to lab. The quiz for project A will not be graded, and the two lowest scores will be dropped this way, you will not be penalized for occasional technology failure (or memory lapse, etc.).

iii LAB EXAMS These 80 point exams will consist of multiple choice, short answer, data calculations and other styles of questions. They are exams and will require solid knowledge of the projects covered and the concepts within. If you prepared for labs, paid attention to lab instructions, understood what you were doing in lab, and knew how to process the data obtained you have a great start, but probably have not done enough to ensure your success. You must pass the nomenclature exam before you will be allowed to do the Anion Analysis Project. If you do not pass the nomenclature exam, you may retake it but your maximum score will be a 70% or 56/80. LABORATORY PRACTICES AND NOTEBOOK A clean, safe work area is a communal responsibility. This duty and proper notebook practices constitute the laboratory practices credit worth 80 points. Instructors will penalize students for deviation from the UNO Chemistry Laboratory Rules, Practices and Policies. Laboratory practices offenses include not wearing safety goggles, not wearing closed-toed shoes and inability to work independently. Students will be asked to leave the lab for particularly hazardous behavior and will not receive credit for the days lab. Notebook offenses include: notes taken in pencil (pencil is OK for graphs); data not placed directly in the notebook; missing data tables or data, incorrect/missing page headings, missing safety information, skipped notebook pages and duplicate pages or notebooks. ATTENDANCE Arrive promptly and prepared for all classes and perform all assigned work as scheduled. (Frequent tardiness or absence is the common cause of grades of F.) If you must be gone, contact your instructor no later than the day you are absent, or leave a message at 554-2651 between 8 a.m. and 4 p.m. To avoid receiving a zero for the project, and quiz if there was one, it must be completed in another lab section that same week. You need permission from both your instructor and the instructor in whose section you wish to work. Making all arrangements for make-up work is the students responsibility. WITHDRAWAL FROM LECTURE You may not audit this class. If you withdraw from lecture, you need your lab instructors permission to remain in lab. Usual criteria are: the semester is over 60% complete, you are able to work independently and your lab work is at least at the B level. Incomplete grades are appropriate only for those with extreme medical or personal problems; they will not be issued for students with outstanding lab reports. ACADEMIC INTEGRITY A zero score will be assigned for any work in which cheating is demonstrable. Higher penalties are possible for obnoxious dishonesty; refer to the Student Handbook. The instructor will notify any individual whose behavior arouses concern, without penalty or prejudice. Those notified should discuss acceptable practices with the instructor. Repetition of the behavior will be taken as demonstration of cheating. AMERICANS WITH DISABILITIES ACT Accommodations are provided for students with verified disabilities. Accommodations must be sought sufficiently in advance to allow arrangements to be made. Contact Services for Students with disAbilities (EAB 117, 554-3872, TTY 554-3799) first. This is the campus office responsible for reviewing documentation provided by students requesting academic accommodations, and for arranging accommodations in cooperation with students and instructors as is needed and consistent with course requirements. If you have emergency medical information to share with your instructor or if you need special arrangements in case the building must be evacuated, please inform your instructor privately ASAP.

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Preliminary Operations
OPERATIONS 1. Description of good laboratory practices and department safety policies. 2. Check-in: Identifying common laboratory equipment. SAFETY POLICY Before you do any laboratory work, the instructor will introduce the Chemistry Department safety policies pertinent to the course. The requirement for use of safety goggles is consistent with Nebraska state law. The policy on treatment of injuries is consistent with By-Laws of the Regents of the University of Nebraska. These safety expenses are the responsibility of the students. In accord with Federal law, Material Safety Data Sheets (MSDS) are available on any reagent supplied for the laboratory. Copies of these are placed in the chemistry library (DSC 336) and are available on the Universitys website http://www.unomaha.edu/ehs/MSDS/MSDSURLs.htm. If you do not find what you need, ask the stockroom supervisor or your instructor. Students with particular chemical sensitivity should notify the instructor, but must check with their doctor for specific advice. While reduction of a specific exposure may be possible, the course is inappropriate for students with previously recognized severe or multiple chemical sensitivities. STUDENT INJURY WHEN STUDENT HEALTH SERVICES (SHS) IS CLOSED. Minor injuries such as small cuts from broken glass and minor burns can be treated by the student as he or she would at home, e.g. with soap, water, and a bandage. If you are unsure of the wound severity, call Campus Security. Security officers are trained in basic first aid and can assist in determining the severity of the injury. An incident report needs to be filled out to document injury events. The report can be downloaded from the UNO web site under Environmental Health and Safety. If any instructor is worried about a student, please email Marcia Adler, SHS. She will call the student the next morning to determine if they need any medical follow up. Major injuries that look like they could use a stitch or retain a glass shard, exposures that could cause a blister or caustic burn-type injury, and any injury or splash to an eye needs immediate attention. The instructor will supply appropriate MSDS and direct the student to his or her private physician or an urgent care facility for prompt evaluation and treatment. The responsibility of the instructor is to recommend appropriate care. The instructor cannot demand it. The incident report will document the recommendation and the student's action. UNO does not pay for classroom injuries -- UNO makes personal health insurance available so that students will be covered when care is needed. When serious life-threatening events occur such as an asthma attack or seizures, call Campus Security. They will call the rescue squad and will assist in the classroom until the squad arrives. Please note that the student can refuse the rescue squad. STUDENT PERSONAL HEALTH INSURANCE When students participate in chemistry laboratory experiences, there are risks involved. We anticipate everyone will be aware of hazards, use caution, and follow procedures, but unforeseen events do occasionally occur. These are the events that the student's personal health insurance is designed to cover. All students enrolled at UNO are offered health insurance. Americans can purchase it at SHS. It is billed with tuition for international students. The cost per semester is less than the minimum charge for a single use of a hospital emergency room.

v CHECK IN You will be assigned an individual drawer containing the standard issue of equipment for the course. At the end of each period all equipment must be returned to the drawer, the drawer locked, and the key returned to the cabinet in the lab. Use the drawer diagram (page vi, after the safety sheets) and supplemental equipment lists to identify all items. Ask your instructor if you are uncertain. You are expected to be able to identify these during the rest of the semester, and will probably be quizzed on them. Unless instructed otherwise, the wash bottle (plastic bottle with spout) should be filled with distilled or deionized water. Look for listed equipment which seems to be missing from your drawer, and chipped or broken glassware. (Porcelain gives a clear ringing when tapped on the counter unless it is cracked; slight cracks may be more easily heard than seen.) Replace all such items at the stockroom window immediately. You must supply a detergent, towels, and matches. You should have a centimeter ruler handy. These and your goggles may be kept in the drawer during the semester. Anything left in drawers after the last laboratory meeting cannot be returned.

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UNO CHEMISTRY LABORATORY SAFETY RULES, PRACTICES, AND POLICIES


A chemistry laboratory is a potentially dangerous place. The practices and policies below are designed and enforced to promote safe conditions. Your lab preparation and behavior must be consistent with these. You will be warned of minor infractions. Lack of awareness of these rules, or serious or repeated infractions will lower your lab grade, and may result in expulsion from the lab with loss of credit. LABORATORY WORK 1. HOURS. To do chemistry, have at least one other person in the laboratory with you. 1000- and 2000-level students do all lab work during scheduled laboratory periods. Students in upper-level labs may work in laboratory outside their scheduled period if they have their instructors specific, written permission. 2. FAMILIARITY. Know what work you are to do. Use Material Safety Data Sheets to acquaint yourself with the properties and hazards of chemicals to be used. Operate no lab equipment until instructed in its use. 3. AUTHORIZED WORK. Perform only designated or authorized experiments, using the materials, amounts, and concentrations called for. Carefully read labels on stock bottles. 4. PREEXISTING HEALTH CONDITIONS. If you have any health conditions which may be adversely impacted by your presence or work in the lab, inform your instructor. You may wish to seek information about reasonable accommodation for persons with disabilities. PERSONAL PROTECTION 5. EYES. Wear chemical splash, high impact protective goggles while anyone is working with chemical reagents. Add a face shield for severe exposure. Prescription glasses (unless deeply tinted or photochromic) or contact lens may be worn under goggles. Initial if you plan to wear contacts: 6. SHOES. Wear closed, comfortable shoes offering spill protection at all times; no sandals. 7. CLOTHING. Wear clothing in lab which is reasonably close-fitting, and which covers you sufficiently to protect against splashes. Laboratory coats or aprons may be used to protect your clothing and skin. 8. HAIR. Confine loose hair sufficiently for safe work, especially near flames and centrifuges. 9. WASHING. Wash your hands with soap and water directly upon leaving the lab. EQUIPMENT 10. FUME HOOD. Confine all sources of irritating mists or vapors to a fume hood in the lab room. 11. GLASSWARE. Use only glassware which is fire polished (no sharp edges) and free of chips or breaks. 12. SAFETY EQUIPMENT. Know the location and appropriate use of: eyewash (splash, irritation), shower (broad splash or burn, burning clothes), bicarbonate (acid spill), dust pan and brush (broken glass), campus security telephone (medical emergency), extinguisher (localized fire), sand (metal fire), fire alarm (big fire). PREVENTIVE PRACTICES 13. COATROOM. Leave coats and other personal belongings (e.g. book bags) in the coatroom. 14. WORK AREAS. Keep your work areas clean. Clean up a spill or breakage before continuing work. 15. TASTING. Leave any food, beverage or snack outside the lab. Drink no water and eat no ice in or from the laboratory. Never taste a laboratory chemical. 16. SMELLING. To note an odor, start with the container well away from the face, waft air towards your face with one hand, and move the container closer only if you note no odor. 17. TUBING. To insert glass tubing or a thermometer into a stopper, lubricate the glass and use an appropriate insertion tool to protect your hands. 18. CHEMICALS. Leave all chemical solutions, materials, and equipment in the lab. Dispose only as directed. ACCIDENTS* * * * In all cases notify the instructor immediately. * * * * 19. BURNS. After contact with chemicals or hot equipment, flush skin with COPIOUS amounts of cold water. 20. EYES. Go immediately to an eyewash to flush chemicals from eyes with water. Continue at least 15 min. 21. BROKEN GLASS. Dispose of broken glass at a designated box in the lab or stockroom, not in paper trash. 22. FIRE. If reasonable, use a wet towel or other means to smother or otherwise contain a fire. 23. MINOR INJURY. First aid is available at Health Services (HS), Milo Bail Student Center. HS will check injuries to identify severity, and attend to students brought to HS due to feeling faint or ill from the lab. 24. SERIOUS INJURY. Major injuries are immediately referred to Campus Security by calling 4-2911. Payment for ambulance transportation and medical treatment is the sole responsibility of the student. By signing this form the student accepts this financial responsibility. I HAVE READ THESE POLICIES AND AGREE TO OBSERVE THEM IN MY CHEMISTRY COURSE. I agree to hold the University of Nebraska at Omaha harmless in any accident that is the result of my own negligence. I understand that employees of the university may, for my own well being, instruct me to follow certain procedures, and I accept sole responsibility for any debts thereby incurred. (Give signed copy to instructor.) Signature _________________________________ Printed Name ______________________________ Date _______________ Student Number ____________ Drawer Number _____

Course/Section _____________

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Lab Drawer Map

Laboratory Notebook

Interpolation 1 Laboratory Notebook


Your notebook is to be a legible record of ALL work done, problems encountered, procedural indications, results observed, calculations and conclusions. Start each project on a new page, with its title and brief proposal. If a project carries over to a new day, place the new date where the continued work begins and the top of the page. Update the table of contents (the first page in your notebook) each week throughout the semester. Put your name and lab section on the outside front cover, to help anyone returning your notebook should you misplace it and consider also adding your e-mail address or phone number. NOTEBOOK USE Make all entries in ink. Cross out a mistaken entry with a single line and write the revised or corrected value next to it, to prevent loss of information. Use full headings for data tables and full labels for single entries; credit is lost for absent or unintelligible entries. Keep your notebook with you as you move around the lab, to enter measurements, procedural changes and observations. Do not take notes which you intend to copy. Since several reports are due on the day the work is done, you have no time to copy. Copying invites error and wastes time; no employer would pay for it. Except for the group report at the end of Project A, your notebook will be graded as evidence of work in progress. Be neat, dont crowd your report or write on the sides of a page. Anything involving procedure must be in the summary. Following the summary, you should have data, which may be in tables, calculations using unit analysis and results. In appropriate places, you should have descriptions of starting materials and final products. Try to make each section stand out and separate it from other sections. Use plenty of room for each section. You may be penalized if it is difficult to follow or read your report. There have been instances where a report was returned to the student to redo. To foster good note-taking, this manual commonly prompts for notebook entries by use of an open box - . (Microsteps for which no entry is expected start with a .) To promote independent thought, you will rarely be given a notebook data format. Though some items from the list below will come up irregularly during the semester, if you fail to enter such items in your notebook, you may loose points. If the project has a sample, record its identification code and label the entry. Describe the samples and reagents supplied to you and products you make. There is little point in describing a colorless water solution which you expected to be colorless, but solid reactants deserves description, even something common such as copper wire. Add anything else you notice during your work, such as slow decomposition, to your initial description. Specify options and changes in procedure. If instructed to do evaporation in an evaporating disk or beaker, note which you chose. Changes in procedure can be personal or class-wide. You may have measured water volume with a 10-mL graduated cylinder. The whole class may be instructed to use mechanical 0.001 g balances rather than electric ones. The notebook should make either change clear. Note pertinent observations. One example is the temperature of the water samples used in density determination. In a less straightforward example, if something suggests your sample became contaminated during the lab, write it down immediately. If no problems develop, the note is still okay. If your result is wrong, youll be in a much better position to explain why. Graphs must have a moderately fine grid (10 lines per inch or finer). Plots may be done in pencil, especially if plotting a curve. When they are returned, attach all graphs (or their photocopies) to notebook pages.

2 NOTEBOOK STRUCTURE

Laboratory Notebook

For each experiment, your notebook should have the following items. The first four must be complete before coming to pre-lab. Headings complete for each page used, including lab section e.g., Chem 1184-002 Experimental summary due at the beginning of pre-lab and limited to one page. See the example on the following page. o Purpose given in lab manual o Procedural summary a brief summary of procedure and data analysis plans Safety (begins second page) list all concerns and how they are to be addressed Data tables prepare anticipated tables following example on pages 3. Observations and Data o Describe starting materials and final products. Any unknown must have an ID listed in the report. o All data collected for multiple runs must be entered directly into a data table (preprepared when anticipated). The tables will contain all pertinent data and results. o All calculations must be shown immediately below the table for each type of result. Where calculations are repetitive (same process/equation, only the numeric values are different) you should show only one SAMPLE calculation. Calculations must have the correct number of significant figures and units. They should also be carried out using unit/dimensional analysis. You will lose points for mistakes and omissions in your calculations. For example, in Project B you need to show only one of the calculations for a standard deviation in detail in your report. o Points are awarded for all data reported correctly, (sample) calculations and results. Precision and accuracy are evaluated. o Numeric values must have a proper label and units i.e. the volume of NaOH was 37.19 mL unit label o If you are not making multiple runs, then all data and results must be properly labeled and arranged in an orderly fashion. Your report will be evaluated on neatness and orderliness, so use ample space and write legibly using ink. Post-lab questions there may be questions to be answered, so be aware of them and answer fully. Discussion a brief reflective statement should communicate the degree of success achieved for the experiment and the quality of the results. Conclusion a brief statement of what is now known as a result of having done the experiment; may be qualitative and/or quantitative in nature. This may also involve comparison to expected results.

If a project carries over to a new day, place the new date where the continued work begins and at the top of the page. Remember, start each project on a new page, with its title and brief proposal. At the end of the semester you will submit your notebook for evaluation. The attachments and one copy of each page must be part of a bound notebook.

Laboratory Notebook

Observation of Properties

Interpolation 2 Observation of Properties


QUALITATIVE AND QUANTITATIVE PROPERTIES Objects have different attributes - size, shape, mass - and properties. Properties are the characteristic qualities of matter - ways in which matter behaves differently, largely independent of the attributes of specific objects. People use many words describing properties. Just think of all the words to describe colors. Our comparatively weak vocabulary for describing tastes hampers communication of these. Described properties such as color, odor and taste are qualitative. Other properties generally reported qualitatively include: luster (shiny/dull) surface texture (rough/smooth) tackiness (sticky/slippery) transparency/opacity phase (gas, liquid, solid). Reproducibility - the expectation that others would get about the same result if they repeated your work - is critically important in science and technology. Poor reproducibility of qualitative properties limits their usefulness. For example it takes years of training for food scientists to give reproducible descriptions of odor and taste. Reproducible numerical measurement can be learned comparatively quickly, or done by instruments. Instead of describing the overall impression of color, an instrument evaluates relative brightness at specific hues which combine to give our visual impression of color. Numerically measured properties are quantitative. Many properties are reported qualitatively or quantitatively, as appropriate to specific cases. Properties (besides color) most likely to be of interest in this project include: acidity or basicity in water crystal habit (characteristic form) hardness particle size (coarse/fine) solubility in a given liquid wettability Other examples are: conductivity, elasticity, flammability, magnetic susceptibility, stability in air, strength, and, for metals, malleability and ductility. Solubility is a property expressing the extent to which two substances form a homogeneous mixture - a solution. If you add solid to water and get a clear mixture, the solid has broken into pieces too small to scatter visible light. The mixture is termed homogeneous. The solid has become a solute mixed in the solvent (water), making a solution. If you add solid to water and get a cloudy mixture, you have formed a suspension. The mixture is heterogeneous. Homogenized milk - mixed so the cream does not separate - is heterogeneous to chemists. Milks cloudiness indicates it is a colloidal suspension. During solubility tests if you get a mixture which remains cloudy after thorough mixing, call it a suspension in your notebook and add no more solid. For solubility tests, use small portions of solid. Mix solute and solvent well. Be patient with observations, because dissolution may be slow. For example, though caffeine solubility in water is over two grams per 100 mL at 25C and it dissolves quickly in hot water, its dissolution in cold water may seem negligible for several minutes. Solubility of solids is often reported as mass per volume solvent in g/100 mL. Simple solubility measurement is quantitatively so unreliable - due to possibly incomplete dissolution for

Observation of Properties

example - that the result should be reported descriptively, qualitatively. In other words, even one significant figure (See Interpolation 3.) may not be justified. Acids and bases have been recognized since the first millennium A.D., long before any acidbase theory. Behaviors empirically associated with acids are sour taste, tendency to react with - and dissolve - carbonate rocks and active metals, and neutralization of bases. Bases tend to taste bitter, precipitate metal ions from solution, and neutralize acids. Certain vegetable dyes change color with change in solution acidity, and these dyes have long been used to indicate solution acidity quickly and safety - without tasting! These indicator dyes are conveniently available impregnated in paper strips. The dye litmus is so common that many who have never studied chemistry recognize the term litmus test. Indicator dyes generally have only two forms with different colors. Individual dye particles have one color or the other. Test papers have either color or, in a narrow range of acidities for each indicator, a blend of both colors due to the presence of both forms of indicator. The advantages to litmus are that it stores well and that its region of change between forms occurs at the acidity of neutral water. PRACTICE PROBLEMS 1. At Halloween one might worry about the fire resistance of the materials in a costume. What would make a measurement of fire resistance more qualitative; more quantitative? 2. The solubility of a certain solid in water is 3 mg/10 mL. If you put 5 mg into 10 mL and shake a long time, you form a uniform white haze in the tube. Does that mean the solid is insoluble in water? 3. An indicator is yellow in acidic solution and red in neutral, and basic solution. What color and what acidity do you expect if both form of the indicator are present in a solution?

Observation of Solids

Project A Observations on Solids


OBJECTIVE Record observations on a solid sample, compare those observations to identify other people with the same sample and compose a joint description of the material. SKILLS REHEARSED 1. Starting a laboratory notebook 2. Qualitative observation and description of properties 3. Use of graduated cylinder and metric volumes 4. Use of microspatula and sense of small metric masses 5. Efficient mixing in a test tube 6. Use of comparator and reticle and sense of metric lengths 7. Personal communication of scientific data BACKGROUND Samples used in this project may all be purchased in some form at your grocery store. They include: a) acetylsalicylic acid (aspirin), b) caffeine (coffee, colas), c) calcium carbonate (antacid, limestone), d) calcium hydrogenphosphate (polishing agent in toothpaste), e) calcium dihydrogenphosphate monohydrate (in baking powder), f) citric acid (fruit, flavoring, soft drinks for acidity), g) cream of tartar (potassium hydrogentartrate, leavening acid), h) disodium hydrogen phosphate (in cheese, evaporated milk; ham curing; hot cereals), i) ferrous gluconate (iron supplement), j) hydroxyapatite (close to calcium phosphate, teeth, anticaking agent in table salt), k) magnesia (magnesium oxide, antacid), l) sodium chloride (salt, for flavoring, preservation), m) tetrasodium diphosphate (thickener in chocolate milk), n) sodium hydrogen carbonate (sodium bicarbonate, for leavening, cleaning), o) sodium laurylsulfate (detergent), p) sodium palmitate (soap), q) starch (a polymer in pasta, potatoes, bread), r) sucrose (table sugar), s) vanillin (flavoring extracted from vanilla bean), t) vitamin C (ascorbic acid, in fruit). Consumer products are almost always mixtures, while the samples in this project are pure substances, so you will probably not correctly recognize your sample. You are not expected to. Your instructor will not identify your sample until after you turn in your group report. In later projects you will gain experience with ways to improve identification success. Comparing quantitative properties with lists will be done in Projects C and M. Testing chemical properties, such as heat of reaction, is related to Projects I and L. Making specific chemical tests for part of a substance, such as phosphate, will be done in Project K. Measuring chemical changes quantitatively is part of several projects, starting with Project D. Estimation of a small mass - The size of 2 mg (0.002 g) of solid (on a microspatula blade) is between that of a lower case o and a capital O. Mixing in a test tube - Hold the top of the tube tightly with the thumb and index finger of your less-dominant hand. Flick the bottom of the tube strongly toward you. Repeating this motion quickly should generate a vortex (tornado-like funnel) which reaches the bottom of the tube. This is a safe, effective way to get good mixing, which is important for valid solubility estimates.

Observation of Solids

Using litmus paper for pH testing - Use a clean stirring rod to transfer a drop of solution to a test paper held in the air. (Papers placed on counters often give false readings due to contamination.) Do this with both blue and red strips. If the sample is insoluble, touch strips of dry paper to a small portion of sample moistened with water on a watchglass. In your notebook first write the indicator color produced. Then interpret the observation in terms of the solution acidity indicated. Acid solutions turn blue litmus paper to red. Solutions which are appreciably basic turn red litmus to blue. If no change is apparent, compare the test strip with one to which you added (neutral) distilled water. Neutral solutions may leave both red and blue litmus unchanged, or may change both to a mixture of both colors. Measuring particle size - A comparator, Figure 1, is a low-power magnifier. Look through the lens (narrower end), and turn its housing to focus the reticle etched on the larger face. A reticle is a pattern of scale lines. Place a tiny portion of solid on a clean surface. Hold the comparator just above the solid. Use the 0.50.5 mm grid to estimate particle size. Use a piece of lens tissue to clean the comparator before returning it. SAFETY
Figure 1 Comparator

Keep chemicals off your hands. Rinse off anything that spills on your skin. Wash your hands when leaving the lab. Do not taste the samples supplied; they are supplied in a concentrated form which may cause a problem. Avoid dust inhalation. Prevent eye injury or irritation. Wear what eye protection you have while anyone is working with chemicals or breakable equipment. Approved goggles are required for later lab work. PREPARATIONS NOTEBOOK Your notebook is to be a legible record of work planned, problems encountered, procedural indications, results observed, calculations and conclusions. You must have a bound notebook, with alternate pages which tear out easily, solely for this laboratory. Notebook entries must be in ink. To encourage and aid anyone to return your notebook, place your name on the outside front cover. On the cover or inside, add information such as your lab section, lab instructor, e-mail account or telephone number. To aid use of your notebook, place a table of contents on the first page or other conspicuous place. Many laboratory notebooks have numbered pairs of pages. If your notebook is unnumbered, use carbon paper to number pairs of pages consecutively from 1 to 20 (40 pages in all). Have this ready before the Project B pre-lab meeting. Your instructor may require particular features or format for your notebook. All instructors require that you take notes in ink, keep notes in duplicate, and that the top of each page contain the notebook page number, the date or dates when notes were entered, the project title or letter, and your name. Enter these on the first page of notes and its copy. Start your notebooks table of contents with Project A.

Observation of Solids

PROCEDURE Obtain a tube containing your sample from the instructor. Enter the identification code from the tube into your notebook and label this entry. Do parts 1 through 6 in any order. 1. Particle Size (see TECHNIQUES) If the particles are too small to measure, record the size as less than 50 m, one tenth the reticle spacing. 2. Solubility Test Use a 10 mL graduated cylinder to measure about 5 mL distilled water. (Fill your distilled water wash bottle from the goose-neck tap at the sink on the wall.) Transfer this to an 18x150 mm (large) test tube. Transfer about 2 mg solid to the water. (see TECHNIQUES) Observe how well water wets the solid and whether the solid floats or sinks in water. Mix well. (see TECHNIQUES) Observe how much solid remains after 30 s, including both the solid which settles in the tube and the solid which remains in suspension (Properties Interpolation). If the solid dissolves quickly, start over with 1 mL water or less and 2 mg solid. As long as the solid dissolves quickly, add increasingly large portions. Observe how much solid remains after three minutes or more. If the solid dissolves completely, add another 2 mg. Keep track of how much dissolves. Use your observations to describe the samples solubility, as: insoluble, slightly soluble (the first portion dissolves incompletely), moderately soluble (more than the first portion dissolved completely), or highly soluble (at least ten portions dissolve). Save the mixture of sample and water for acidity testing. 3. pH Test (acidity/basicity) Test the acidity or basicity of your sample using red and blue litmus test papers from your drawer. (see TECHNIQUES) 4. Qualitative Description Describe the sample color. Describe three other qualitative properties of your sample. Examples are given in the Properties Interpolation. Describe at least one other property which might differentiate your sample from others. For example, if the solid is crystalline, use a microscope to view and describe its shape. Before proceeding to step 8, return the sample tube to the instructor. You need to have recorded the properties of your solid well enough to identify it from your notes. COMMUNICATING WITH OTHERS Communication with others is helpful in formulating ideas. It is essential if findings are to be useful to others. Communication and recognition of the work of others have been hallmarks of science. Alchemists were pre-scientific, in that they worked secretively. As a scientist, you will learn in this course by speaking and listening to others doing similar work; you are encouraged to discuss your work with others in the lab. Scientists whose work is based on or parallels previous work are responsible for crediting the other authors. You must acknowledge in your reports anyone with whom you work as a partner or whose results you use. At the end of this project you are asked to use your work and that of others in a coauthored report. You must name the other authors. This is to be the only coauthored work this semester. Duplicate work in later reports will be treated as copying. It will be penalized.

10

Observation of Solids

5. Group Formation Two others in the lab section have the same substance as you. (With 14, 17, 20 or 23 students there will be one group of two; with one less, there will be two groups of two.) Take your notebook around to discuss properties with other students. Use your observations to find the other two students who have your substance. Record their first and last names, and their sample identification codes in your notebook. Report as a group to the instructor to determine if your group is correct and record their answer, correct or not. (If the group is incorrect you are on you own to try again (the instructor will not say who is misplaced. You may ask questions concerning your observations.) When the group is correctly identified resolve any inconsistencies within the groups observations. (Your instructor will return your sample tube if needed. If you find an error in your previous observation, draw a single line through that entry.) Draft and edit a single joint report of the sample properties. The report must incorporate the observations of all those with the same sample and be edited by the group until all are satisfied. Reports should meet the specifications for any general communication. They should be organized to accomplish an objective and edited for proper grammar and spelling. While simple labels are fine for a notebook entry, complete sentences are required for a formal report. No minimum length requirement is specified, but the report does need to cover all tests done. CLEAN-UP Return your sample tube to the instructor with all remaining uncontaminated solid. Flush solutions to the sink. Place used, insoluble solid in the trash. Clean all tubes, rinse with distilled water, and replace in your drawer. Wipe up the microscope area and your bench. Lock your drawer and return the key to the cabinet. You must submit the notebook pages for this project before the end of lab time. EVALUATION Evaluation is based largely on completeness: page heading, reasonable observation of at least the properties requested, identification of your reporting group, and the coauthored report. Incomplete, inconsistent, or ambiguous notes may be penalized. Because your group should edit its collective work, you will not have a chance to resubmit your report for a better grade. (If one of your group is submitting an independent - different - report, this must be explained in writing to the instructor.)

Numerical Uncertainty

11

Interpolation 3 Numerical Uncertainty


What is the right answer? may not be a simple question to answer. In a laboratory, a result might be poor because a raw measurement was poor or because calculations using the measurement were poor. Because the way numbers are written has scientific meaning, the result might be poor just because it is written, as in 34 mL when in fact 34.00 mL is meant. All three (measurement, calculation and presentation) are necessary to accurately communicate the right answer. Study of your lecture text gives considerable practice in calculation. Before you submit lab reports, check your work for faulty set-up and careless calculations, which produce gross error. This interpolation introduces you to other types of error through the concepts of uncertainty and significant figures. UNCERTAINTY Repeated measurements, even those done with great care, will not be exactly the same and will not all equal the true value. The deviation or difference between a measured value and the true value1 is due to the uncertainty in the measurement. Uncertainty can be separated into two components: accuracy and precision (your lab work will be graded according to one or both of these qualities several times in this course). The most valuable measurements have the smallest deviations; however, measurements without deviation or a deviation of zero have little to no value. When the same measurement is made repeatedly, Figure 2, they are typically spread fairly evenly above and below the mean (average). The difference between the mean and the true value is the accuracy. Accuracy is largely dependant on bias (systematic error) which includes operator error (an action which makes all results high or low), equipment error (if the instrument or equipment gives consistently high or low results) and method error (if the instructions lead all operators to get consistently high or low results). However, if the bias is small compared to the random error, the random error may also decrease the accuracy.

Figure 2 Distribution of repeated measurements

The narrowness of the spread of individual values about the mean is the precision. Probably the most common measurement of precision is the standard deviation. High precision, which is good, corresponds to a small standard deviation. The amount of precision (or imprecision) is due to random error. Random error can be minimized but never eliminated. Therefore, it is bad to report a standard deviation of zero, because that indicates it is unknown. It is better to have large standard deviation than none at all but best for it to be small. The scientific approach to random error is to characterize it by repeating measurements, calculating the standard deviation, reporting it with the measurement and (if necessary) finding ways to reduce it if it is so large that it makes the results inconclusive.

Often the true value is not known and the mean (average) of multiple measurements is used instead.

12 SIGNIFICANT FIGURES

Numerical Uncertainty

To indicate the precision of a quantity, you must write its value with only one digit having an appreciable uncertainty. The uncertain digit and all digits to its left, except zeros to the left of all nonzero digits, are termed significant figures. Put another way, the significant figures of a value include all digits known with certainty and one known with appreciable uncertainty. This applies to both measurements and quantities calculated from measurements. It is from measurement that the uncertainty arises. (Counted quantities (there are 3 apples) and conversion factors have no uncertainty.) Since people recognize precision by the way a value is written, write only the significant digits, no more and no less. Digits are significant if they are: nonzero, zeros between nonzero digits, or zeros to the right of the decimal point and to the right of another significant figures. The value 80470 g indicates four, not five, significant figures. In order to indicate that the final zero is significant, the number would need to be written differently. Scientific notation, 8.0470 104 g, and different units, i.e. 0.080470 kg, both indicate five significant figures. (Neither zero to the left of the eight is significant.) When reading a value from an instrument (balance, pipet, grad cylinder, etc.) the uncertainty varies with the equipment used. When reading along a continuous scale, such as on a thermometer or grad cylinder, you are expected to estimate fractions, usually tenths, between the closest scale markings. The estimated digit is uncertain, and therefore the last one written. The estimation constitutes most of the appreciable uncertainty of the reading. (The rest is the uncertainty of the scale marking itself.) Digital displays like those on electronic balances typically have an uncertainty of one in the right-most digit. Though there is no estimation in the reading, there is still uncertainty. When there is only one mark, as with a pipet, the uncertainty can be obtained from the manufacturer (often printed as X with other label information) or can be measured using the standard deviation of a set of repeated measurements. When calculating a numeric value, that value should also have only one uncertain figure. Knowing which digit is the uncertain one depends on the type of calculation (addition, division, etc.) used. Apply one of the following three criteria (pretentiously called rules in many texts). In addition and subtraction, the number that ends first determines the end of the answer. When subtracting 22.50 from 24.283, the value 22.50 ends first at the hundredths place and therefore the answer should also end at the hundredths place. This is easily accomplished visually by lining up the decimal point as show here. 24.283 g flask and liquid 22.50 g flask uncertainty is in hundredths place 1.783 g 1.78 g round to the hundredths place In multiplication and division, the answer should have the same number of significant figures as the value being multiplied/divided with the fewest significant figures. When dividing 1.783 by 2.0 the answer should have two significant figures because 2.0 has fewer (two significant figures) than does 1.783. 1.783 g liquid 2.0 mL liquid = 0.8915 0.89 g/mL round to two significant figures

In logarithms (or antilogarithms), the number of significant figures in the value is the same as the number of significant figures in the mantissa of the logarithm (the part to the right of the decimal). The logarithm of 6.02214, should have six significant figures to the right of the decimal, corresponding to six significant figures in the original number. log (6.02214) = 23.779750848 23.779451 round to six significant decimal places

Numerical Uncertainty

13

Many calculations require more than just one of these types of mathematical operations (i.e. addition and multiplication). In these cases the larger calculation should be separated into parts containing only one operation and use the rule for the first operation on the first part then the rule for the second operation on the second part and so on until the entire calculation is complete. It is very important that you track where the last significant figure is but do not round intermediate answers, because rounding intermediate answers frequently results in an incorrect final answer. A very effective way to do this is to write the uncertain digits (two is enough) as subscripts. In the following example, it is clear that the intermediate answer 1.6739 from the subtraction has three significant figures (and we should round to the hundredths place if it were the final answer). This notation makes it easy to see that the final answer should be rounded to three significant figures. 24.17 g - 22.4961 g 1.6739 g = 2.000 mL = 0.837 g/mL round to three significant figures 2.000 mL Remember, if a calculation yields more digits than significant figures, round the final result (rather than truncating it - cutting it off) to the correct number of significant figures. Sometimes the final digits of a reading or calculated result are zeros and may or may not be significant. The final significant digits of a value must be written, zero or not, to properly indicate the uncertainty. Furthermore, calculators often do not display these zeros but they are still your responsibility. When Significant Figures Do Not Apply Counted quantities and conversion factors have no uncertainty. The rules of significant figures do not apply to these numbers. They are written with an appropriate number of digits but never limit the number of significant figures in the answer. Counted quantities and conversion factors can be recognized as such from the context in which they are used. 0.001 L 34.08 mL 1 mL = 0.03408 L conversion factor REPORTING UNCERTAINTY USING THE STANDARD DEVIATION Standard Deviation The standard deviation s from a mean (average) of n measurements is defined by, and calculated as indicated by, the equation
s= ( xi - x ) n -1
2

(3)

where x is the mean of the individual measurements x i and is the operation of adding the a series of values, in this case the squared difference between each value of x . (An example calculation of a standard deviation follows.) Standard deviation is often reported on its own, but may be written in parentheses following the mean value, e.g. 0.789 (0.0037) g/mL C2H5OH. Application of the significant figure rules to the addition/subtraction symbol of the standard deviation tells us that the mean and its standard deviation are always written to the same decimal place. Sometimes this results in rounding the mean more or less than what the significant figure rules would seem to otherwise indicate. For this laboratory, standard deviations should be reported to two figures (not more or less), one significant and one insignificant. (Keeping one insignificant figure is helpful because the standard deviation sometimes ends up being an intermediate answer.) DO NOT report standard deviations of zero; if you think your standard deviation is zero, go back and use more sig figs in your calculation.

14

Numerical Uncertainty

Example 1 Calculation of a Standard Deviation From repeated measurement of the density of ethanol at 25C, a student obtained the values: 0.788, 0.792 and 0.786. Determine the average and standard deviation of the density of the ethanol.

Plan
1. 2. 3. 4. 5. 6. Find the mean, find the difference between each density value and this mean, square the differences from step 2, add the squares from step 3, divide the sum from step 4 by one less that the number of values averaged, take the square root of the quotient from step 5.

Solve
Find the mean (0.788 + 0.792 + 0.786)/3 = 0.78867 g/mL Find the standard deviation value difference 0.788 0.788 - 0.78867 = 0.00067 0.792 0.792 - 0.78867 = +0.00333 0.786 0.786 - 0.78867 = 0.00267 Sum = difference squared 0.000 000 45 0.000 011 09 0.000 007 13 0.000 018 67

Sum/(n-1) = (.000 018 67)/2 = 0.000 009 34 Square root {Sum/(n-1)} = s = 0.003 056 0.0031 g/mL

Report
The density of ethanol is 0.7887 0.0031 g/mL.

Properties of an Aqueous Sample

15

Project B Properties of an Aqueous Sample


OBJECTIVE Compare two methods of volume measurement in determination of density. Compare determinations of density and concentration on an aqueous solution. SKILLS REHEARSED 1. Coming prepared to laboratory sessions 2. Use of a laboratory notebook - setting up a data table 3. Application of safe laboratory practices 4. Significant figures in a measurement and result 5. Use of an electronic milligram balance 6. Use of a pipet 7. Use of a Bunsen burner 8. Observation of a solid BACKGROUND In Project A the observations you made were qualitative or semi-quantitative and your sample was a pure solid. In this project you will make quantitative measurements of density and concentration of brine, a solution of salt in water. Density is the mass per unit volume of matter. The IUPAC symbol for density is . (The symbol for relative density, d, is often used for density by English-speakers.) The densities of solids and liquids are conveniently reported in grams per cubic centimeter, or the equivalent grams per milliliter, because values are near 1 with these units. mass sample density = volume sample (1)

Density is a useful physical property of pure substances and solutions. At a specified temperature, the density of a pure liquid or solid is fixed and so can be used to identify a substance as you will do in Project C. (The density of gases, but not liquids or solids, varies with pressure.) The density of solutions indirectly indicates their concentration. Density can be measured directly (e.g. by floatation), but is commonly obtained by dividing a sample mass by its volume at a given temperature. In this project you measure volumes with a graduated cylinder and a pipet. To determine mass you weigh a stoppered flask to the nearest milligram, add the measured volume of water, restopper, and reweigh. (The stopper minimizes change of mass due to evaporation.) Concentration is the quantity of one component, divided by the total quantity of a mixture. masssolute msolute concentration = volume ;c=V solution solution (2)

This appears the same as density unless you write it out completely - a good practice. Compare equations 1 and 2. Concentration is a ratio of a part over the whole (solute over solution), while the density ratio is the whole over the whole (sample over sample). Because solutions range from concentrated to extremely dilute, several units are widely used. The concentration unit used here is gram of solute per milliliter of solution. To measure the mass of solute in a solution, one has to apply a physical property. Using a difference in boiling point for example, one evaporates all the solvent and then stops heating before the solute evaporates or decomposes. Data Tables should be used whenever you anticipate taking replicate readings set up a data table before coming to lab but even when work is not repeated, such as the single determination of

16

Properties of an Aqueous Sample

density in this project, preparing a table for the data still helps organize all the information needed (and may help you get a better grade). Be sure to include table headings, label each quantity and give the units of measurement. Data tables should be double spaced, to allow easy insertion of corrections and instructor comments. Figure 3 is an example of a complete table for the type of density data collected in this project. Adjust the headings appropriately; for example in place of CH2Cl2, identify your brine. For this project, come to class having prepared in your lab notebook one table for density using a graduate cylinder and a second for density using a pipet. Regardless of the order in which you do the lab work, place the graduated cylinder data table first in your notebook. It can reliably be set up with room for just three trials. When you may need to take optional data, such as additional pipetted samples, allow room to expand your data table. The orientation of the table above would be good since trials can be easily added to the bottom; just leave several open lines in your notebook. If your pipetting goes well and you do not need the room, you can leave the space blank. Density of 25.0-mL samples measured with a 100-mL graduated cylinder -------------------------- Data ----------------------------------- Results -------Trial Mass flask Mass flask, stopper Temp Mass Density & stopper (g) & sample (g) (C) sample (g) (g/mL) 30 1 35.678 68.843 23.8 33.165 1.327 2 35.814 69.064 23.8 33.250 1.330
Figure 3 Sample data table

Significant figures note The data table shown in Figure 3 illustrates a problem with the simple, significant figure rules. The results were identical when rounded by the rules and subsequently the variation inherent in the measurement was lost. In this case, the rules have led us to round too far and the results should be show with another digit to the right. (If you have two identical measurements, take a third reading. Unless you are biased or not reading closely enough to obtain the uncertain digit this reading will differ from the first two.) Sample Calculation The table above includes experimental data (solution masses) and calculated results (density values). While this is a good way to report a series of parallel results, you must still show a sample calculation, Figure 4, for 33.165 g CH2Cl2 one of the calculated values. Use real data with = 1.3266 g/mL 1.33 g/mL 25.0 mL proper significant figures and clear units. Weighing Balances are designed to weigh any mass within its (maximum) capacity, and give excellent precision for the cost. Balance precision is generally 1 in the last marked digit, an appreciable uncertainty. Balances are referred to by their capacities (300-g balance) or their precisions (milligram balance). Laboratory balances display mass values in grams (with a comma instead of a decimal if the balance was made in Europe). Use the balance assigned to you according to your laboratory drawer number. The assignments are posted on the door to the weighing room (electronic balances) or on the back of the shelves holding the balances (mechanical). For proper operation, any balance must be clean and dry. Take your notebook into the balance room so that you can record data directly and immediately. TECHNIQUES Measurement of mass with an electronic 0.001 g balance To use the same balance for repeated measurements of the same object, write down the balance number even if it is the one assigned to you. Empty and clean the pan. Close the doors of the draft shield. Press TARE if the empty pan reading is not zero. Place the object (dry, room temperature and nonmagnetic) on the pan
Figure 4 Sample Calculation of Density

Properties of an Aqueous Sample

17

and close the doors again. When the reading becomes stable, record it in your notebook. If readings jump or drift in one direction for more than 15 seconds, report the problem to your instructor. Gas burner A Tirrill burner, Figure 5, and tubing are part of your standard drawer equipment. The needle valve at the bottom adjusts the gas flow. The gas mixes with air, which enters through holes at the bottom of the barrel. The barrel and air holes are features introduced by Bunsen, which leads to the malpractice of calling all laboratory burners Bunsen burners. Check the tubing for cracks and have your lab instructor check it if it needs to be trimmed or replaced. Connect the tubing to a gas jet above the sink; the stopcocks have a blue cap. Gas flow is OFF with the gas valve handle to either side and ON with the handle in line with the jet. Regulate gas flow and flame height with the needle valve. The gas valve should either fully open or closed. Leave the gas off for now. Prepare to light the burner by turning the barrel of the burner down so that the gap for air between the barrel and base is about as thick as the spacing in the adjacent threading. Figure 5 Tirrill Burner Close the needle valve at the bottom of the base, then open it revolution. Closing is a clockwise motion viewed from the bottom, counter-clockwise viewed down the barrel. Have matches ready. Open the stopcock fully. Promptly light the burner by holding a lighted match to the side of the barrel just below the top. The best (and safest) flame is smooth with a pale blue inner flame cone and a blue-violet outer cone. It should crackle slightly and NOT wobble. Regulate flame profile/appearance by turning the barrel, to allow more or less air. Never use so little air (or so much gas) that the flame is luminous - yellow - and never use so little gas (or so much air) that the flame roars; both are dangerous. For more heat, open the needle valve. For higher temperature, turn the barrel counterclockwise to admit more air. Pipetting Volume measurement to high precision is relatively easy only for fixed volumes. A volumetric pipet, Figure 6, is a calibrated tube with a carefully designed delivery tip, a bulb, and an upper stem with a single, fixed volume marking. Pipets come in a variety of sizes from over 100 mL to less than 1 mL. The pipet is designed to deliver the labeled volume of liquid. The bit of liquid left in the tip is there by design and must not be blown or shaken out. A pipet delivers the labeled volume with high precision only if chemically clean, unchipped, and properly used. When a pipet is clean, liquid will drain smoothly off its inside walls. If drops are left on the inside of your pipet below the volume mark, return it to your instructor and get another. If you believe your pipet is chipped at the top or bottom, ask your instructor to inspect it.

Figure 6 Pipet

18

Properties of an Aqueous Sample

Drawing air into the pipet tip often splashes liquid into the rubber bulb. To remove this liquid, remove the white adapter from the blue bulb, quickly squeeze the bulb or pound its open end onto paper towel on the bench to expel most of the liquid, then reassemble. Rinsing a pipet Unless the pipet is known to be clean and dry, the first step in its use is to rinse it three times with the liquid to be dispensed. Avoid contaminating the bulk sample. Place a small volume of liquid sample in a large test tube or small beaker. Use a rubber bulb to take liquid into the pipet up to where the lower stem widens. Quickly stopper the pipet at the top with a finger. Turn the pipet horizontal and rotate it to wet the bulb and upper stem with solution. Drain the pipet through the tip to a sink or waste container. Repeat all steps twice more. Delivering a set volume from a pipet, Figure 7 Wet your index finger with a drop of water and wipe, leaving your finger just damp. Use a bulb to fill the pipet above the mark on the stem (keeping the tip off the bottom of the beaker, as shown in diagram a. Place your damp finger over the end. Lift the pipet out of the liquid. Dab all drops from the outside of the pipet with a paper towel. (See b.) With the pipet nearly vertical and the tip touching the edge of the beaker (See c.), let the meniscus drop slowly until it just grazes the top of the mark. (See d.) Separate the tip from the beaker wall and stop flow with your finger. Do not bounce or wipe the pipet. Transfer the tip to the receiver. Release your finger and let the pipet drain. While the final portion of liquid drains, keep the pipet tip against the wall of the receiver above any liquid. (See e.) This will prevent beading of the final fraction of a drop, and give extremely consistent delivery.

Figure 7 Using a pipet

Holding a Bottle or Flask Stopper The prevent contamination from or to a stopper, hold the top of it between your fingers with the tip facing the back of your hand. If you need to set the stopper on a counter, rest it on its top, so nothing touches the wet bottom.

Properties of an Aqueous Sample SAFETY This project involves the dangers related to working with glassware and heating with a burner. Avoid touching anything heated until it has cooled to a comfortable temperature. PRELAB

19

Before the pre-lab meeting, do the following. Write the appropriate heading information at the top of the page in your notebook. (See Project A and the Notebook Interpolation. Set up the data table for determination of density using three trials with a graduated cylinder, part 2. (See Figure B.1.) In place of CH2Cl2, leave space to enter the identification code of your brine sample. Read directions below to get the appropriate volumes for the table heading. Set up a data table for part 3. Leave room to expand beyond three trials, as many people require some practice to obtain good consistency. If not done previously, assemble matches, towel, sponge, soap and goggles to bring to lab. INSTRUCTIONS 1. Determine the concentration of total solids Obtain a thermometer, 50 mL Erlenmeyer flask, rubber stopper, 10 mL volumetric pipet, and rubber bulb. Pick up a ring stand from the coat room. Pick up a small iron ring from a box on the counter in the lab. In a 100 mL graduated cylinder, collect 75 to 80 mL of brine (saltwater) from the bottle in the laboratory. Record the volume to the nearest 0.1 mL. Record the identification code of this sample in your notebook. Set up a ring stand and burner as shown in Figure 8. Place the Bunsen burner on the ringstand. Attach the small ring to the ringstand about 2-3 inches above the Bunsen burner. Place a watchglass over the evaporating dish. Weigh the evaporating dish and watch glass to the nearest milligram. Transfer about 25 mL of brine from the graduated cylinder to the evaporating dish and place the watch glass back on the evaporating dish. Record the new graduated cylinder liquid level to the nearest 0.1 mL. This way the delivered volume is measured by difference. Replace the watchglass on top of the evaporating dish. Light the burner and set it to a low, nonluminous flame, (with an inner blue cone 3 cm high, an outer cone about the same height, and no more noise than a light crackle). Record the time you place the burner under the evaporating dish. Figure 8 Set up for Brine Do parts 2 and 3 while the solvent evaporates. Record any Evaporation observations you make during evaporation. Use lower heat if you need to reduce splattering. Heat the evaporating dish until the residue is just dry. Turn off the gas and record the time. Describe the product. Let the evaporating dish cool to room temperature. (Hint: use this time to clean up or calculate standard deviations for the two density determinations.) Weigh the evaporating dish, watch glass and remaining residue to the nearest milligram, 0.001 g.

20

Properties of an Aqueous Sample

2. Weigh a 10.00-mL solution sample from a graduated cylinder Weigh a clean, stoppered, 50 mL flask - dry on the outside - on a milligram balance. Measure the temperature of the brine to the nearest 0.1C. Remove the thermometer. Use an eyedropper to get exactly 10.00 mL saltwater in a 10 mL graduated cylinder. Remove the stopper from the 50 mL Erlenmeyer. (see TECHNIQUE for Holding a Stopper) Transfer the sample from the graduated cylinder to the Erlenmeyer flask without spilling or splashing. Restopper the flask. Weigh the flask with the saltwater sample in it. Pour the sample back to a beaker or graduated cylinder. Repeat this step in its entirety twice more. 3. Weigh a 10.00 mL solution sample from a 10 mL pipet (see TECHNIQUES for Rinsing a Pipet and Delivering a Set Volume from a Pipet.) Weigh a clean, stoppered, 50 mL flask - dry on the outside - to the nearest milligram. Measure the temperature of the unknown solution. Use a rinsed, 10 mL volumetric pipet to transfer 10.00 mL of the solution into the 50 mL Erlenmeyer flask. Restopper the flask. Weigh the 50 mL flask with the saltwater in it. Pour the sample back into the beaker from which it was pipetted. Determine the mass of saltwater by difference. sample mass = (mass of sample & flask) (mass of the flask) Repeat this step in its entirety twice more. 4. Arrange by size the three sample masses from step 3. Find the range by subtracting the lowest from the highest. If the range is 0.021 g or greater, repeat part 3 again. Then repeat part 4 using the last three measurements. Continue replacing the oldest run until the range of the last three consecutive runs is less than 0.021 g. If you have trouble with this, check first that your pipet drains completely. If that is not the problem, ask the instructor or other students to help you with your technique. CLEAN-UP Use the wash bottle to rinse the pipet by flushing distilled water into the stem. Return the equipment checked out (thermometer, Erlenmeyer flask, stopper, pipet and bulb) to the stockroom before the end of the scheduled period and cross your name off the checkout list. Wash the residue from the evaporating dish. Discard any remaining water sample to the sink. Rinse the flask, evaporating dish, and graduated cylinder with distilled water. They may be returned to your drawer without drying. CALCULATIONS 5. Density Show one determination of density as a sample calculation. (Refer to BACKGROUND.) Report the densities from the repetitions of part 2. Calculate the mean, and the standard deviation of these. (Dont do any rounding until you have calculated the mean and standard deviation.) Report the densities from the trials of part 3, and the mean and standard deviation of the last three. 6. Concentration By difference calculate the actual volume of sample taken for determination of concentration, Vsample = Vbefore sample removed Vafter sample removed and the mass of evaporation residue. Show calculation of the concentration of solids as a single sample calculation with units.

Properties of an Aqueous Sample

21

REPORT Considering a graduated cylinder and a pipet, state one advantage to each in measuring volume of liquid. (The advantage of greater precision would go to whichever had the smaller standard deviation.) Submit your laboratory report before the end of the period. EVALUATION You must have data tables prepared before the pre-lab. You may not improve your grade on this item once submitted. For full credit, pipetting must be repeated until reproducible to 0.02 g or better. Requested observations and data must be consistent with that expected for the sample. You may modify these items only by repeating the entire project or convincingly identifying the systematic error responsible. Data must be properly labeled, and correctly written (i.e. significant figures). Sample calculations, other calculations, and conclusions are required. Since this is your first quantitative lab of this course, your instructor will try to make helpful suggestions during the lab on these items. You should ask if you have particular questions

Properties of a Liquid Substance

23

Project C Properties of a Liquid Substance


OBJECTIVE Measure quantitative properties of a liquid and compare them to literature values to identify a substance. SKILLS REHEARSED 1. Application of safe laboratory practices. 2. Significant figures in a measurement and result. 3. Measurement of boiling point. 4. Use of an electronic milligram balance. 5. Use of a pipet. 6. Use of a refractometer. 7. Effective mixing in a test tube. 8. Use of a laboratory notebook - setting up a data table. BACKGROUND Quantitative Properties Handbooks are reference volumes found on the desks of most scientists. Handbooks help those seeking to identify or understand the behavior of samples, as dictionaries help those seeking to identify or understand the proper use of words. Quantitative properties, which can be reported as numbers, tend to be more reliable (reproducible), and useful than qualitative (descriptive) properties. Thus handbooks report mostly quantitative properties. This project proposes to use quantitative properties to identify a material from a list of possibilities such as might be found in a handbook. Boiling Point The boiling point of a liquid is the temperature at which further heating of a liquid does not increase its temperature but instead results in conversion of some of the liquid into its vapor/gas. When heat is added to a liquid at its boiling point, the tendency to form vapor becomes so great that bubbles form below the liquid surface. It boils. Boiling points decrease at lower atmospheric pressure because less pressure is required to form bubbles. (Much smaller bubbles may also form well below the boiling point as dissolved gases come out of solution; not boiling.) Refractive Index Refractive index is the ratio of the speed of light in vacuum to its speed through a sample. It is responsible for the redirection (refraction) of light as it passes from one medium to another. Most values are between one and two, though some are nearly three. Refractive indices decrease with temperature increase, about 0.00045 per degree. Because it is a ratio of speeds, it has no units. It is measured with a refractometer. Solubility of Liquids in Water When two liquids are mixed, they dissolve in each other. If the amounts combined are in the range of mutual solubility, then only one phase (layer) exists, and the liquids are termed miscible (able to mix). The same word is used to describe two liquids which are miscible in all proportions. Starting with a few drops of sample, at first youre testing the solubility of water in the sample liquid by counting the number of drops of water added before there are two phases. It may be hard to see if two liquids have combined in one phase or remain separated in two. The first drop of water, if it does not dissolve, may cling to the tube wall where it can be missed. With more water, look for cloudiness or small beads of the other liquid floating or not fusing immediately when touched with water. With each drop of water added, mix well and observe changes. If you have two phases after addition of ten drops water, you will continue counting and adding water until a single phase returns or until more than 40 drops have been added and complete dissolution doesnt seem close. This point indicates the solubility of the sample in water. As in Project A, you are only estimating solubility, so measuring quantities simply by counting drops is acceptable. One drop of water has a volume of 0.05 mL. One drop of the other

24

Properties of a Liquid Substance

liquids has a volume closer to 0.04 mL. To convert to the concentration units most common in handbooks use these volumes as conversion factors. For example, using a students measurement on 2-butanol, and extending the result to two significant figures:
4 drop 2 - butanol 37 drop water 0.04 mL 2 - butanol 1drop water 0.086 mL 2 - butanol 1 drop 2 - butanol 0.05 mL water = 1 mL water

or using density to get mass solute per volume solution units:


4 drops 2 - but 0.04 mL 2 - but 0.81 g 2 - but 1 drop water 0.070 g 2 - butanol 37 drops water 1 drop 2 - but 1 mL 2 - but 0.05 mL water = 1mL water 7.0 g 2 - butanol 0.070 g 2 - butanol/0.070 1 g 2 - butanol also shown as or = 100 mL water 1 mL water/0.070 14 mL water

Identification by Comparison with Reference Data You are to identify your sample by comparing the values you measured with those listed on the table. There will probably be some ambiguity. A common strategy scientists use is to simplify the problem. Eliminate from further consideration those substances which have one property so different from your measurement that they cannot be your unknown. For this, you need to consider how reliable each measurement is, to know what difference would allow you to eliminate a substance. The solubility data are semi-quantitative at best. Use this to eliminate possibilities, not to make subtle distinctions. Boiling points are sensitive to atmospheric pressure and impurities. Both tend to lower boiling points noticeably, so you can eliminate compounds which boil at temperatures lower than what you measure. Densities and refractive indices vary with temperature, but any effect on your data is small because room temperature is close to standard temperature. Refractive indices vary in four significant figures, densities in only three, so you can expect refractive index to be more reliable. With a small list of substances, find the best match between listed properties and your measurements. Consider significant figures when considering the possibilities. If one measurement seems inconsistent, take a new reading. TECHNIQUES Measuring Boiling Point Use about 2-mL liquid in a clean, dry 18 x 150 mm test tube. Add a capillary tube (open end down) to foster smooth boiling. Insert a stopper containing a reflux tube and a thermometer with a range appropriate to the expected boiling point as in Figure 9. Clamp the tube to a ring stand. Cautiously and smoothly heat the liquid. If boiling becomes too vigorous, lift the tube higher in the sand; if boiling is slow, pile sand up around the tube; if boiling occurs in violent bursts, agitate the tube or lift it from the sand and carefully add a piece of broken glass capillary.
Figure 9 Boiling Point Apparatus

Properties of a Liquid Substance

25

When the level of liquid condensing on the inside walls reaches the bottom of the thermometer, liquid will start to drip off the bulb of the thermometer and the temperature will rise quickly. When the temperature becomes steady again, record the value to the nearest 0.1C. Otherwise, describe whatever temperature variations you find and record the best value you can. Measurement of Refractive Index Refer to Figure 10. The upper prism case is hinged on the left; lift it by the clip on the right. Use a lens tissue to wipe the upper and lower prism faces. Apply about three drops of your liquid sample directly to the lower prism with a dropper, but do not use the dropper to spread the liquid, the prism faces should never touch metal or glass. Turn the power/lamp selector switch on the left side panel to the center position, applying light to the prism in contact with the sample.

Figure 10 Refractometer

Through the eyepiece you may see a marked horizon, dark below and light above. If not, turn the handwheel on the right to bring the horizon into view: if the view appears generally dark, turn the handwheel clockwise (top away from you); if the view appears bright, turn the wheel counterclockwise (top toward you). Adjust the prism lamp at the front of the instrument for best visibility of the borderline. Turn the compensator dial (above the prisms) to minimize the appearance of any color and to maximize the sharpness of the horizon. Rotate the handwheel to set the horizon precisely at the cross hair intersection seen through the eyepiece. Depress the power/lamp selector switch then read the refractive index through the same eyepiece. Values differing by 0.01 are labeled. Lines of intermediate height correspond to each 0.001; the shortest lines correspond to 0.0005 in refractive index, so the scale can be read to 0.0001 by reading fifths of the way between the smallest graduations, see Figure 11.

1.340

1.350

Figure 11 Appearance of refractometer scale, read as 1.3464

26 SAFETY

Properties of a Liquid Substance

CAUTION Some samples are flammable. Avoid vapor buildup in the lab by keeping the tubes capped when not removing sample, supported so they do not spill and by allowing the liquid to cool before removing boiling point samples from the fumehood. Recall proper technique for determining odor. If the odor of your sample is particularly strong or unpleasant, you should move it to a hood and transfer sample there. Keep the liquids off your skin. If any liquid gets on your skin, flush it with copious water without delay. If your doctor has advised you that you are particularly sensitive to some chemicals, notify the instructor before the start of the pre-lab discussion or earlier. Before coming to lab, set up a data table for the density data. It is not important that the notebook match the order in which you take experimental measurements.

PRE-LABORATORY WORK

INSTRUCTIONS Obtain a 2.000 mL volumetric pipet, pipet bulb, 25 mL Erlenmeyer flask with stopper and a tube containing your sample from the instructor. Record the identification code from the tube and a description of your sample. This is your first nonaqueous liquid sample, so extra attention should be given to its description. Possible samples are listed in the table of properties on the last page of this project. As the necessary equipment becomes available, measure the following in any order. Save liquid from density and boiling point determinations for other measurements. boiling point of your sample density of your sample refractive index of your sample solubility in water of your sample 1. Boiling point - to be done in the hood (see TECHNIQUES Measuring Boiling Point) Transfer roughly 2 mL of liquid sample (You dont need to measure it.) to a clean, dry 18 x 150 mm test tube. Add a capillary - closed end up - obtained from the hood. Place the tube in the clamp of the apparatus in the hood, and insert the thermometer/stopper assembly. The thermometer bulb must be at least 1 cm above the surface of the liquid and 1 cm below the level of the clamp on the tube. Ask your instructor to adjust your thermometer up or down in the stopper if this is necessary. Turn the hotplate control no higher than four. Lower the tube into the hot sand and adjust the level of the tube in response to the rapidity of boiling obtained. When the level of vapor condensing on the tube walls reaches the thermometer bulb, start taking readings. Readings should stabilize with liquid dripping slowly from the thermometer. Read the stable or highest value to 0.1 C. If the reading slowly increases, lower the tube in the sand or increase heating, and continue observation to find a temperature maximum. Read the barometric pressure or obtain the value from your instructor. 2. Density Dry and weigh a 25-mL Erlenmeyer flask and stopper to the nearest milligram. Start with a clean, dry, 2-mL pipet or rinse a 2-mL pipet with small portions of your sample from a test tube. (TECHNIQUES-B. The appended letter indicates the project to look back to. Collect the rinse liquid in a tube for disposal in the mixed-organics container in the hood.) You may use sample left from boiling point measurement, even if mildly discolored; do not use sample left from the solubility test. Use the pipet to dispense 2.000 mL liquid into the 25-mL flask. (TECHNIQUES-B) Immediately restopper the flask. Weigh the stoppered flask and contents to 0.001 g.

Properties of a Liquid Substance Dispense another 2.000-mL portion of liquid sample into the 25-mL flask, restopper and reweigh. The flask need not be empty. If it is emptied, it must be reweighed before adding new sample. For each 2-mL addition, calculate the sample mass by difference. If the samples are more than 0.010 g different, repeat until two successive trials are this close. To cleanup, use the propanone (acetone) washbottle in the hood to rinse the inside of the pipet with three brief squirts. Allow each to drain to a mixed-organic container before adding the next. Use a paper towel and the pipet bulb to remove the last liquid. Always replace the lid on the bottle when you are finished with it. Show a sample calculation of density. Report the density from each trial. Report the mean and range of the two consecutive, consistent results. 3. Refractive Index (see TECHNIQUE Measurement of Refractive Index) Use a dropper to place three drops of liquid near the center of the lower prism. Close the upper prism and swing the prism lamp up to the window in the upper prism. Record the refractive index of the liquid. Record the temperature from the refractometer. Wipe both sides of the prism with lens tissue provided, then place the tissue in the trash.

27

4. Solubility with Water (see BACKGROUND Solubility in Water) Place six drops of sample in a 10 x 75 mm tube. Add a drop of water. Mix thoroughly. (TECHNIQUES-A) Note whether there are two phases (a cloudy mixture or globules of two liquids) or a homogeneous mixture (a single, clear liquid after mixing). If two phases are present: Continue adding water dropwise with mixing to determine the volume of water required to dissolve the sample. If one phase is present: Add ten more drops of water, mixing and making observations between each drop to see if two phases reappear. If the mixture appears as one phase throughout the addition of the eleven drops of water, stop adding water and report the sample as miscible. The point at which two phases appear (if two phases appear) indicates the solubility of water in the unknown liquid. Note the number of drops of water added at this point, then continue adding water drop wise, mixing after each drop until there is only one phase again (up to 40). This point indicates the solubility of the unknown liquid in water. For comparison with the table of properties, convert the number of drops of sample and water to an approximate sample-in-water solubility in milliliters sample per milliliter water. CLEAN-UP Discard your solubility test to the sink and flush with water. Discard remaining sample to the mixed-organic container in the hoods. Leave the sample tube and cap in the designated receptacle in the hood. Return stockroom equipment (propanone-rinsed pipet, bulb, 25-mL flask and stopper) by the end of the scheduled period. REPORT Identify your sample by comparing the properties measured with those listed in Table 1. You are encouraged to narrate your reasoning, or make appropriate comments about any measurement. Put your identification in your notebook and report it to your instructor, who will say if it is correct. If it is not, you are encouraged to check your reasoning with the instructor to find how it was flawed.

28 EVALUATION

Properties of a Liquid Substance

Density determinations must be repeated until reproducible. Data must be: sensible, properly labeled, and reported and calculated to the correct number of significant figures. To obtain higher than 65 out of 80, you must correctly identify a sample. Compound Name acetonitrile 2,3-butanedione 2-butanol 2-butanone n-butyl acetate sec-butyl acetate cyclohexane dichloromethane 3,3-dimethyl-2-butanone (pinacolone) ethanol, 95% ethyl acetate ethylbenzene methyl butyrate methylcyclohexane octane 2,4-pentanedione (acetylacetone) 1-propanol 2-propanol (iso-propyl alcohol) propanone (acetone) toluene water
Table 1

Density in g/mL 0.786 @ 25 0.990 @ 15 0.808 @ 20 0.805 @ 20 0.882 @ 20 0.865 @ 25 0.778 @ 20 1.33 @ 25 0.725 @ 25 0.801 @ 20 0.810 @ 25 0.902 @ 20 0.898 @ 25 0.866 @ 25 0.898 @ 20 0.770 @ 20 0.702 @ 20 0.972 @ 25 0.805 @ 20 0.785 @ 20 0.781 @ 25 0.788 @ 25 0.866 @ 20 0.997 @ 25

Boiling Point in C 81.6 88 99.5 80 124-6 112 80.7 40 106 78 77 136 102 101 125 140 97.2 82.5 56.5 111 100

Refractive Index 1.3393 @ 30 1.3950 @ 20 1.3949 @ 25 1.3788 @ 20 1.3941 @ 20 1.3840 @ 25 1.4262 @ 20 1.4222 @ 20 1.3939 @ 25 1.3640 @ 20 1.3719 @ 20 1.4932 @ 25 1.3879 @ 20 1.4231 @ 20 1.3975 @ 20 1.4512 @ 20 1.3862 @ 20 1.3772 @ 20 1.3749 @ 25 1.3591 @ 20 1.4967 1.3330 @ 20

Solubility in water miscible 0.25 mL/mL 0.10 mL/mL 0.31 mL/mL sparingly 0.0083mL/mL sparingly 0.0072mL/mL insoluble sparingly 0.020 mL/mL sparingly 0.033 mL/mL miscible 0.10 ml/mL insoluble sparingly 0.017 mL/mL insoluble insoluble 0.13 mL/mL miscible miscible miscible v slight NA

Properties of selected solvents

Inorganic Forms of Copper

29

Project D Inorganic Forms of Copper


Their Interconversion and Separation1
OBJECTIVE To witness a series of chemical reactions that exemplify the variety of different forms in which most individual elements exist. TECHNIQUES PRACTICED AND CONCEPTS APPLIED 1. Using electronic and mechanical balances 2. Vacuum filtration 3. Measuring liquid volumes using a graduated cylinder 4. Chemical nomenclature 5. Separation of mixtures INTRODUCTION Copper is an element common in our lives in its metallic form. It is used for plumbing, coins, roofing material and electrical wiring among other things. Copper in other chemical forms is less familiar to us but is also not difficult to find, such as when a penny or roofing material gets that aqua colored stuff on it. That aqua colored stuff still contains copper, but it is now in the form of a compound. Compounds are materials that contain more than one element, where those elements are chemically bonded to each other and always occur in the same definite proportions. Compounds have chemical and physical properties that are independent of the properties of the elements that make them up. This experiment describes how to convert solid copper metal into a number of other copper containing compounds and then back into solid copper metal. Throughout these transformations of form and color, the copper atoms are always present and never cease to be anything but copper. In these compounds the copper atoms are only chemically bonded to other atoms. Copper forms metallic bonds with other copper atoms and ionic bonds with several ions in this experiment. Copper also forms complexes in this experiment by coordinating with ligands, in this case NH3 (ammonia) and H2O (water). A metal and its ligands in a complex are written in square brackets, i.e. tetraaquacopper (II) chloride [Cu(H2O)4]Cl2. During the experiment a copper compound is separated from two other compounds, water and nitrate, using the physical process of filtration. Separation of a single compound into individual elements requires a chemical process, such as the last reaction in this experiment which separates the copper from CuCl2. The reactions in this experiment also serve as good examples of several important and common categories of reactions (some reactions serve as examples of more than one reaction type). There are three acid-base reactions, three redox reactions, one decomposition reaction, three precipitation reactions and four double displacement reactions (also known as metathesis reactions). Vacuum filtration is much faster than gravity filtration and is suitable when the solid particles to be filtered are sufficiently large so as not to pass through or around the filter paper. Place a piece of filter paper flat in the Bchner funnel, Figure 12, and moisten it with a small volume of the wash liquid. Attach the vacuum tube to your filter flask and a water aspirator. Apply a mild vacuum by turning the water on and then decant the mother liquor onto the center of the filter paper. The filtration will proceed much faster if the mother liquor is delivered prior the majority of

Based on an article by Condike, George F., Near 100% Student Yields with the Cycle of Copper Reactions Experiment, J. Chem. Ed., 1975, 52 (9), 615.

30

Inorganic Forms of Copper

the solids, Figure 13. Use a small amounts of wash liquid (typically the same liquid that makes up the mother liquor) to rinse out any solid remaining in the original beaker/flask. Typically the filtered solids need to be washed with small amounts of additional wash liquid. This removes excess solutes that were present in the mother liquor that would otherwise adversely affect the quality and perceived quantity of the filtered solid.

Figure 12 Bchner funnel setup

Figure 13 Vacuum filtration

Triple beam, centigram balances are stored at numbered locations on shelves in the laboratory. The balances are assigned to pairs of students according to desk number. See the sign at the shelves to learn which balance you are to use. Carry the balance to your desk area for use, holding the red post with one hand and supporting the pan with the other. Before using the balance, it must be properly zeroed. Place all poises in their zero positions. With nothing on the pan, rotate the knurled compensator knob at the left end of the beam until the pointer on the right lines up with the zero mark. The balance frame, pan, and pan support must all have the same serial number. The pan and pan support may be removed to clean and dry them. If reassembling these, the pan support must be suspended from the upper notch of the end loop assembly. When not in use, set all poises to their zero positions. Before leaving lab, return your balance to its proper location.

Inorganic Forms of Copper SAFETY

31

There are two acids (HNO3 and HCl) and two bases (NH4OH and NaOH) used in this experiment, each is quite concentrated and should be used with the utmost care. If you suspect that any of these has come into contact with your skin flush with copious amounts of water. Three gasses are produced or otherwise present in this experiment: NO2 is brown, toxic and a component of smog; NH3 is colorless, caustic and can have an overwhelming odor; and H2 is colorless, highly flammable and explosive. (Ever heard of the Hindenburg? That was H2) On the page following your procedural summary, find/determine the correct name for each chemical formula in the safety and procedure of this experiment, you may stop at 20 substances, though there are a few more depending on how you count them. Some are ions, so be sure to say ____ ion as in Cu2+ is the copper ion which, incidentally, is NOT the same as Cu which is copper metal.

PRE-LABORATORY WORK

PROCEDURE 1. Dissolution of Copper Metal 3 Cu(s) + 8 HNO3(aq) 3 Cu(NO3)2(aq) + 2 NO(g) + 4 H2O(l) (redox) 2 NO(g) + O2(g) 2 NO2(g) (redox) Obtain a piece of copper wire and measure its mass to the nearest 0.001 g on an electronic balance. Bend the wire into a coil so that it lays flat on the bottom of a 250 mL beaker and label your beaker. Label your beaker, take it to a fume hood and add 3.50.5 mL of concentrated HNO3 (nitric acid). While this reaction proceeds, obtain 0.400.1 g of magnesium turnings (using a mechanical balance) for use at the end of the experiment. Be patient. Continue with part 2 only after all of the copper wire has dissolved. 2. Precipitation of Cu(OH)2 First NaOH(aq) + HNO3(aq) NaNO3(aq) + H2O(l) (acid-base) Second Cu2+(aq) + 2NaOH(aq) Cu(OH)2(s) + 2Na+(aq) (metathesis/ precipitation) Use your graduated cylinder to obtain 100.5 mL of 4 M NaOH (sodium hydroxide) and very slowly add this to your copper nitrate solution, stirring between additions, to form the light blue precipitate of Cu(OH)2 (copper II hydroxide). Never pour excess chemical back into the stock container. If you have too much of a chemical, offer instead the excess to someone else in lab who still needs some. Otherwise consult your lab instructor. Add distilled water to your beaker of Cu(OH)2 (copper II hydroxide) to dilute it to a total volume of approximately 100 mL. Use your stirring rod to place a drop of the solution onto a piece of litmus paper. For the reaction to be complete, the solution needs to be basic to litmus paper. If it is not, add 10 more drops of NaOH (sodium hydroxide)and repeat litmus paper test. 3. Decomposition of Cu(OH)2 to CuO Cu(OH)2(s) CuO(s) + H2O(l) (decomposition) Prepare to boil your Cu(OH)2 (copper II hydroxide) mixture by setting up a Bunsen burner, ringstand, one large ring, one small ring according to Figure 14. Place the Bunsen burner on the ringstand, attach the small ring 2-3 inches above the Bunsen burner and place the wire

32

Inorganic Forms of Copper gauze on that ring. Attach the large ring about 2 inches above that so that your beaker will fit in the large ring and rest on the wire gauze. This way the beaker will not easily be knocked off. Stir the mixture continuously while gently heating it to a slow boil. Stop heating the mixture when all of the light blue precipitate has been converted to muddy brown CuO (copper II oxide). See your instructor if your mixture is not muddy brown after 5 minutes of heating, you may need a drop or two of base.

4. Separation of the CuO Prepare to vacuum filter your CuO (copper II oxide) by setting up your vacuum filter flask and Bchner funnel as described previously in TECHNIQUES. Turn on the water to provide the vacuum for filtration and then empty your CuO (copper II oxide) mixture into the Bchner funnel. Dont worry if some of the copper oxide remains in the beaker, the goal is simply to remove the NO 3 (nitrate) containing solution. When filtration is complete, turn off the suction and discard the liquid in the designated container in the hood. 5. Dissolution of CuO
Figure 14 Beaker setup

CuO(s) + 2HCl(aq) CuCl2(aq) + H2O(l) (metathesis) Using your forceps and/or microspatula, place the filter paper with CuO back into the beaker that contained the CuO (copper II oxide). Rinse your 10 mL graduated cylinder twice, discarding the rinses down the drain, and use it to obtain 50.5 mL of 6 M HCl (hydrochloric acid). Add the HCl to the CuO (copper II oxide) in the beaker. Swirl the solution in the beaker to help dissolve the CuO (dont break up the filter paper it needs to be removed). Use your dropper to collect some of the solution and squirt it on any CuO (copper II oxide) remaining in the Buchner funnel or on the wall of the beaker to dislodge it and help it to dissolve. Once all of the CuO has dissolved, use your forceps to remove the filter paper and use your wash bottle to rinse it and the funnel into the beaker using as little water as possible. 6. Formation of a Copper-Ammonia Complex Ion First HCl(aq) + NH4OH(aq) H2O(l) + NH4Cl(aq) (acid-base) Second CuCl2(aq) + 2NH4OH(aq) Cu(OH)2(s) + 2NH4Cl(aq) (metathesis/precipitation) Third Cu(OH)2(s) + 2NH4OH(aq) [Cu(NH3)4](OH)2 aq) + 2H2O(l) (methathesis) Rinse your graduated cylinder, discarding the rinses down the drain. Take your copper solution and your 10 mL graduated cylinder to a fume hood. Obtain 100.5 mL of 6 M NH4OH (ammonium hydroxide) and slowly add this to your CuCl2 (copper II chloride) solution with constant stirring. Addition of the NH4OH first re-forms the light blue Cu(OH)2 precipitate and then converts it to a dark blue Cu(NH 3 )4
2+

(tetraaminecopper II) solution. See your instructor if your mixture doesnt turn a deep, royal blue.

Inorganic Forms of Copper 7. Precipitation of Solid Copper Metal First [Cu(NH3)4](OH)2 aq) + HCl(aq) CuCl2(aq) + 4NH4+(aq) 2H2O(l) (acid-base) Second CuCl2(aq) + Mg(s) Cu(s) + MgCl2(aq) (redox/precipitation) Also Mg(s) + 2HCl(aq) H2(g) + MgCl2(aq) (redox)

33

Leave your dark blue Cu(NH 3 )4 (tetraaminecopper II) solution in the hood and rinse your
2+

graduated cylinder, discarding the rinses down the drain. Back in the hood, add 120.5 mL of 6 M HCl (hydrochloric acid) very slowly to your dark blue Cu(NH 3 )4 solution and stir. Addition of 6 M HCl to the very basic Cu(NH3 )2+ 4
2+

solution is VERY exothermic and will become very hot. Handle with care! Take your solution and graduated cylinder back to your bench top. Slowly add 0.400.1 g of magnesium turnings (measured earlier) to your copper solution. ----------------------------------------------------------TIME OUT-----------------------------------------------------------Just let your mixture react for a bit while you think about these questions. The goal here is to precipitate all of the copper out of the solution AND dissolve all of the magnesium. (The reaction will stop prematurely if there was not enough magnesium or acid.)
Question! The reaction works best in an acidic solution. What are two ways to tell if the solution is acidic? Hint One way is a tool the other is based on the solution appearance. Question! How will you know if all of the solid copper has formed and is no longer in solution? Hint Think about the color of the various solutions that you have had/used today, magnesium chloride forms a colorless solution. Record your answer Question! How will you know if all of the magnesium has been consumed? Hint Look back at your beaker what else is happening besides precipitation of copper? Record your answer ------------------------------------------------------------------------------------------------------------------------------------Dont add any more magnesium or HCl (hydrochloric acid) until what youve already added has almost completely reacted. If then it appears that you need more of one or the other or both, add small portion(s) (~0.1 g of magnesium, ~2 mL of HCl) and allow those to react. (Remember all of the magnesium needs to have been consumed, so while adding a lot will form the solid copper quickly, you will be waiting longer for the excess magnesium to be consumed.) After you are confident that all of the copper has precipitated, measure the mass of a new piece of filter paper and a small watch glass on the electronic balance. Using that new filter paper, vacuum filter your solid copper and rinse it thoroughly. After filtration, remove the top of the funnel and flip it over onto the watch glass so that the copper and filter paper are left on the watch glass. Place the watch glass in your drawer to allow it to dry until next week. Describe your product. Empty the filtrate down the drain with excess water. 8. The Following Week Measure the mass of the watch glass with your copper and filter paper. Subtract the original mass of the watch glass and filter paper from the new mass and report the mass of your recovered copper to your instructor. Describe your product, particularly any changes from the week prior. Calculate the percent recovery by dividing your final copper mass by its initial mass and multiplying by 100%.

34
POST LAB QUESTIONS

Inorganic Forms of Copper

1.

The copper atoms remain copper throughout the experiment (they never are converted to a different element). Which subatomic particle is gained and lost by the copper atoms in these reactions? If there was a shortage of HCl and how would using HNO3 in part 7 instead affect the final product? How would it be possible to have greater than 100% recovery of copper in this experiment?

2. 3.

EVALUATION Most of the points for this experiment are based on the quality of your observations.

Analysis of Lead in Soil

35

Project E Analysis of Lead in Soil


OBJECTIVE To determine the lead content of a soil sample in collaboration with other chemistry and geology/geography students as part of a larger research objective to study origin of lead in contaminated soil from within and around an EPA Superfund site in the city of Omaha. TECHNIQUES PRACTICED AND CONCEPTS APPLIED 1. Use of an electronic milligram balance 2. Use of a pipet 3. Atomic structure specifically isotopes 4. Gravity filtration 5. Mass spectrometry BACKGROUND

Lead is a toxic heavy metal with an average concentration of about 12 ppm1 in the Earths crust.2 Higher concentrations of lead may be the result of contamination from sources of lead mining, refinement or use. Lead is used in paint, batteries, solder, weights (for fishing, curtains, etc.), and pottery glazes to name a few. Lead contamination of soil in Omaha is well documented and is a significant problem.3 Almost 14 square miles (8840 acres) have been contaminated as a result of more than 100 years of air emissions from lead smelting operations. The area is home to over 65,000 residents, and includes 20 public schools. Remediation is taking place on child care properties and at residences where children have blood lead concentrations greater than 10g/dL and the soil lead concentration is greater than 400 g/kg.4 Although the Asarco lead smelting plant is now closed, the source of the lead pollution is still in some dispute, in part because lead contamination also comes from other sources. Another possible source is lead from house paint sold prior to the 1970s. Since 1998, students in the sophomore level Quantitative Analysis course have collected soil samples and analyzed them for lead by atomic absorption spectroscopy (a related undergraduate research project created a preliminary map of the soil lead concentrations in Omaha). Cumulative data from these analyses indicate the need for isotope detection capability for lead and higher sensitivity for lead, bismuth and other elements to differentiate between lead from paint and lead the local smelter. The Inductively Coupled Plasma Mass Spectrometer (ICPMS) instrument is uniquely suited to this source discrimination because of its sensitivity and ability to distinguish between different isotopes of the same element. Lead has four stable isotopes whose distribution varies with the source of the lead ore,5 providing one possible means of discrimination between lead from paint and lead from the smelter.

2 3 4 5

ppm stands for parts per million and is a counted quantity. That counted quantity might be grams, liters or people depending on the situation. For example, if 100 librarians lived in a city with population one million, the concentration of librarians would be 100 ppm. Krauskopf, K.B. Introduction to Geochemistry, 1967, McGraw Hill. http://www.epa.gov/superfund/sites/npl/p020226.htm http://www.epa.gov/superfund/sites/npl/nar1660.htm a) Yaffe, Y., et al., Identification of Lead Sources in California Children Using the Stable Isotope Ratio Technique, Archives of Environmental Health, 1983. 38(4): p. 237-245. b) Sutherland, R.A., J.P. Day, and J.O. Bussen, Lead Concentrations, Isotope Ratios, and Source Apportionment in Road Deposited Sediments, Honolulu, Oahu, Hawaii, Water, Air, and Soil Pollution, 2003. 142(1-4): p. 165-186. c) Viczian, M., A. Lasztity, and R.M. Barnes, Identification of Potential Environmental Sources of Childhood Lead Poisoning by Inductively

Analysis of Lead in Soil

36

The ICP-MS instrument, Figure 15, uses plasma (superheated, ionized gas like that on the surface of the sun the fourth state of matter) at about 10,000C to break any/all chemical bonds reducing a sample to individual atoms. Those atoms are then sorted by the mass analyzer according to their mass and ultimately passed on to a detector one mass at a time. It is capable of measuring concentrations of 1 ppt (part per trillion) and better. More on mass spectrometry can be found on page 48 in your text book, Brown, LeMay and Bursten, 10th edition. In this project, you will work with geology/geography students to test the hypothesis that the origin of the lead contamination was the Asarco lead smelter. To test the hypothesis, soils should be sampled regionally for 5 to 10 miles around the former smelter. Local experiments will be needed to discriminate the effect of any contribution from lead in paint. Statistical testing will need to be applied to demonstrate that a relationship does or does not exist. The ICP-MS can also detect additional elements, such as arsenic, antimony, zinc and bismuth, which could be used as additional evidence of the lead source(s). This research could encompass 100 square miles and easily generate 1000s of soil samples, requiring computer based manipulation and graphical display. Geology students will also be responsible for this effort. Clearly this project will be ongoing for several years.
SAFETY

Figure 15 Varian ICP-MS instrument

Concentrated nitric acid, HNO3, should be used with the utmost care. If you suspect that any has come into contact with your skin flush immediately with copious amounts of water. Nitrogen dioxide, NO2, is a brown, toxic gas and a component of smog.

PROCEDURE

Soil samples will be provided by geology students via your lab instructor. There will be 12 total field samples, 8 small and 4 large. The eight small samples will be used as is and the four large samples will be each split into quarters resulting in a total of 24 instrument samples.
1. Soil Sample Preparation Obtain a soil sample and mortar & pestle. Be sure that you mortar and pestle appear clean. If they do not, return them for clean ones. Transfer your soil sample to your mortar and grind it to a fine powder. If you are working with a small sample, go to step 2. o Transfer your soil sample into one neat, symmetrical pile on a sheet of butcher paper. Use a ruler to divide the soil evenly into two new piles, and then divide each of those piles in two for a total of 4 piles. o With scissors, cut the paper into fourths, one for each pile, so that each of student may take their soil sample. o Each of these four new samples will have the same ID as the original followed by a letter a, b, c or d.

Coupled Plasma Mass Spectrometry, Verification and Case Studies, Journal of Analytical Atomic Spectrometry, 1990. 5(4): p. 293-300.

Analysis of Lead in Soil 2. Soil Digestion Label a clean Erlenmeyer flask (in pencil) with your sample number. Transfer between 0.991.01 grams of your soil sample to a weighing boat and record the mass to the nearest mg. a. It is very important that you transfer this exact mass. (Normally, this would be weighed differently but other requirements take precedence here.) b. For comparison, a full stick of chalk weighs 10 grams. Quantitatively transfer the soil to your labeled Erlenmeyer flask using small squirts of water from your wash bottle. Add 10 mL of distilled water and 10 mL of concentrated nitric acid to your flask. Cover with a Tuttle cap, place on a hotplate in the fume hood and heat to just under boiling for 1 hour, swirling occasionally. Prepare to filter your sample in the following step and then study for your upcoming lab exam. This time may also be used to introduce you to the ICP-MS instrument. Remove the Tuttle cap momentarily to allow any remaining nitrogen dioxide to escape the flask before removing it from the fume hood. Allow to cool and then add 25 mL distilled water. 3. Filter and dilute your sample Fold a piece of Whatman #1 filter paper in half and then in half again so that it is the shape of a quarter circle. Open the filter paper such that three layers of paper are on one side and one layer is on the other, this will make it the shape of a cone. Place the filter paper in a longstem glass funnel supported by a ringstand and filter your solution into a clean 100 mL volumetric flask. Leave as much of the soil in the Erlenmeyer flask as possible to reduce filtering time. Wash the soil left in the flask and on the filter paper with small portions of distilled water. Dilute to the mark on the neck of the flask. o Caution: Do not let the liquid level go over the mark on the volumetric flask. While holding onto the cap so it doesnt fall off, invert your volumetric flask 10x to ensure that it is completely mixed. Pipet 1.00 mL of this solution to a clean 25 mL volumetric flask and dilute to the mark. While holding onto the cap so it doesnt fall off, invert this volumetric flask 10x as you did before. Obtain a instrument sample label and complete it with the rest of your sample ID. o If you split a single soil sample with 3 other students, be sure to add the letter a, b, c or d to your sample ID. Fill a sample tube for the ICP-MS instrument full. Apply the instrument sample label and place your sample in the sample rack. Empty all remaining solutions into the designated used materials container. Clean your mortar and pestle with water only, rinse with distilled water and dry completely. Clean all other glassware with soap and water and return to their appropriate location. 4. Analysis of soil sample solution by ICP-MS

37

The laboratory instructor will introduce you to the ICP-MS instrument where your sample will be analyzed. The results will be made available during the next week.
CLEAN-UP

Discard remaining solution into the designated used materials container. Wrap your filter paper and filtered soil in a paper towel and place in the trash can. Use water and a brush to clean and rinse the vacuum filtration apparatus and return it.

Analysis of Lead in Soil

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NEXT PERIOD

You will receive a printout with the analysis data from the ICP-MS instrument. Record the identity and quantity of the elements/isotopes in your notebook.
CALCULATIONS

Accounting for dilution, calculate the average and standard deviation of the lead concentration in your soil sample. Report this in the format average standard deviation. (Recall the use of appropriate significant figures as presented earlier in this manual.)
EVALUATION

Evaluation will focus on the quality of your observations.

Molecular and Electronic Geometry

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Interpolation 4 Molecular and Electronic Geometry


A = # of central atoms X = # of attached atoms E = # of lone pairs on central atom
Is the example molecule polar?

Electronic Geometry

Shape
A

Ideal Angles

AXE AX2 AX3 AX2E AX4 AX3E AX2 E2 AX5 AX4E AX3 E2 AX2 E3 AX6

Molecular Geometry

Example

Linear

180

Linear Trigonal Planar Bent Tetrahedral Trigonal Pyramidal Bent Trigonal Bipyrmidal Seesaw T-shaped Linear Octahedral Square Pyramidal Square Planar

BeCl2 BF3 SO2 CH4 NH3 H2O PF5 SF4 ClF3 XeF2 SF6 ClF5 XeF4

No No Yes No Yes Yes No Yes Yes No No Yes No

Trigonal Planar

120

Tetrahedral

109.5

Trigonal Bipyrmidal

120 between equatorial and 90 between equatorial and axial

Octahedral

90

AX5E AX4 E2

Adapted from Ronald Gellespie and Ronald Nyholm

Molecular Modeling I

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Project F Molecular Modeling I


The Basics of Molecular Bonding and Geometry
OBJECTIVE

To draw Lewis structures and to use them to build ball and stick molecular models for the purpose of: (a) predicting electronic and molecular geometries (b) predicting molecular polarity (c) predicting the stability of possible resonance structures and (d) drawing VESPR models.
CONCEPTS USED IN THIS PROJECT

1. Lewis structures a. octet structures and non-octet structures b. formal charge c. resonance structures 2. Electronegativity and polar covalent bonds 3. VSEPR theory a. electron group shapes for central atoms with 2, 3, 4, 5, and 6 electron groups b. molecular shapes c. molecular polarity
SPECIAL INSTRUCTIONS

Unlike the other projects thus far, the required data for THIS project should be recorded in this manual on the following pages, which will be turned in for grading. These forms will provide space for your Lewis structures, your VSEPR drawings and space to answer questions about each substance. Since you may need to correct some of your Lewis structures or VSEPR drawings, you should use a pencil in place of the usual ballpoint pen. For this project, you will be assigned a partner. You will work as a team but each individual will be responsible for his/her own completed report.
BACKGROUND

Chemistry is the study of matter and the changes that matter undergoes. In the beginning, the study of chemistry was undertaken only at the macroscopic level. Early chemists could only interpret their observations in terms of what they could see or measure. Their observations included such things as color changes, formation of a precipitate, mass changes or temperature changes. The development of atomic and molecular theories of matter allow modern chemists to explain and even predict macroscopic behavior of matter in terms of the microscopic particles we call atoms, molecules and ions. The development of your ability to visualize and to be comfortable with the microscopic side of matter is a very important part of your general chemistry knowledge. This is especially true if your academic program requires you to take additional chemistry courses beyond General Chemistry I. Over the years, chemists have used a wide variety of models (props) to help students develop a microscopic view of matter. Most likely you have been exposed to a number of different models in previous science courses. In high school you may have used Styrofoam balls and wooden sticks to build models of water or other small molecules. Models help you see matter not simply as a glass of water (macroscopic view) but also as a very large collection of H2O molecules (microscopic view). To become comfortable with the microscopic view of matter requires practice and the ability to consolidate the topics of Lewis structures (including formal charge and resonance structures), electronegativity and VSEPR theory. The next two molecular modeling projects are designed to help you accomplish this goal.

Molecular Modeling I

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Most molecular modeling experiments begin with the Lewis formula of the substance to be modeled. In this project you will be drawing Lewis formulas for several different substances. Once you have the correct Lewis formula, you will construct ball and stick models of each substance. Based on your Lewis formula and your ball and stick model, you will be asked to draw the VSEPR model of the substance and make predictions concerning some of the geometric properties of each substance.
VSEPR DRAWINGS

Lewis structures provide only a 2-dimensional picture of chemical substances. It is not the purpose of Lewis structures to show the geometry of a substance, it is the purpose of Lewis structures to show what is bonded to what and show the location of the bonding and non-bonding electrons. At the molecular level, chemical substances have a 3-dimensional geometry. It is the purpose of VSEPR drawings to convert the 2-dimensional information of a Lewis structure into a 3-dimensional illustration of the substance. You will use a technique, commonly referred as the wedge and slash method, to give your VSEPR drawings a 3-dimensional appearance. Consider the VSEPR drawing in Figure 16 for a central atom in the trigonal bipyramid electronic geometry. The central atom (X) is always located in the plane of the paper. Solid lines () represent electron groups also located in the plane of the paper. Solid wedges represent electron groups located in front of the plane of the paper. Slash wedges represent electron groups located behind the plane of the paper. With a little practice you should become comfortable with this style of 3-dimensional representation. You will also construct a ball and stick model of the compound. The ball and stick model will give you a better feeling for the 3-dimensional nature of molecules and you can use it to help you draw the VSEPR model. Your VSEPR model will be most useful if you draw an orientation where all electron domains and bonded atoms are visible. For example, draw trigonal bipyramid systems similar to the one illustrated above and not like the one in Figure 17 where the back electron group is hidden by the central atom. Your lab instructor will take a few minutes at the beginning of the lab to discuss the use of the ball and stick modeling sets. Good luck and enjoy the project.
Figure 17 incorrect trigonal bipyramid molecular geometry slash

Figure 16 trigonal bipyramid molecular geometry

PRE-LAB PREPARATION No procedural summary is required for this project. Be able to name the 5 possible electron group arrangements used by the VSEPR theory. Be able to match the following molecular geometries with their correct electron group geometry. a) bent b) square planar c) trigonal pyramidal d) seesaw e) square pyramidal f) t-shape

Molecular Modeling I

43

H2O
1. 2. 3. 4. Draw the Lewis structure. Build the ball and stick model. Draw the VSEPR model. Answer the questions. Lewis structure VSEPR model

Electronic geometry of the oxygen atom = Molecular geometry = ____________________ Ideal HOH bond angle = Polar molecule = Yes No Polar bonds = Yes No

H2O2

(HOOH)

1. Draw the Lewis structure for which all atoms have a formal charge of zero. 2. Build the ball and stick model. 3. Answer the questions.

Lewis structure

Electronic geometry of the oxygen atoms = ______________________ Ideal HOO bond angle = _______

Molecular Modeling I

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N2H4

(NN)

1. Draw the Lewis structure for which all atoms have a formal charge of zero. 2. Build the ball and stick model. 3. Answer the questions.

Lewis structure Electronic geometry of the nitrogen atoms = ______________________ Ideal HNN bond angle = _______ Ideal HNH bond angle = _______

N2H2

(NN)

1. Draw the Lewis structure for which all the atoms have a formal charge of zero. 2. Build the ball and stick model. 3. Answer the questions.

Lewis structure

Electronic geometry of the nitrogen atoms = ______________________ Ideal HNN bond angle = _________

Molecular Modeling I

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N2
1. Draw the Lewis structure. 2. Build the ball and stick model. 3. Answer the questions. Electronic geometry of the nitrogen atoms = _____________________ Polar bonds = Yes Polar molecule = Yes No No

Lewis structure

Of the last three molecules which will have the longest NN bond? N2H4, N2H2 or N2 Briefly explain your choice:

O3

(OOO)

1. Draw the two possible resonance structures for ozone. 2. Calculate the formal charges for all atoms in both forms. 3. Answer the questions. Lewis structure 1 Lewis structure 2

What is the formal charge on central oxygen of form 1 = _____ What is the formal charge central oxygen of form 2 = _____ Which form is most stable? 1 2 or both are equally stable equal different

The bonds lengths in ozone will be:

Molecular Modeling I

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N2O (NNO)
1. Draw the three possible resonance structures for dinitrogen monoxide. 2. Calculate the formal charges for all atoms in all three forms. 3. Answer the questions. Lewis structure 1 Lewis structure 2 Lewis structure 3

Formal charge on central atom of form 1 = Which form is most stable?

Formal charge on central atom of form 2 = 1 2 3

Formal charge on central atom of form 3 =

All are equally stable different

Bonds lengths in the resonance hybrid are expected to be: equal Briefly explain your answer on bond lengths.

CO
1. Draw the Lewis structure of carbon monoxide. 2. Build the ball and stick model. 3. Answer the questions Lewis structure Electronic geometry of the carbon atom = ______________ Electronic geometry of the oxygen atom = ______ Polar bonds = Polar molecule = Yes Yes No No

Molecular Modeling I

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CO2
1. Draw the Lewis structure of carbon dioxide which has a formal charge of zero on all atoms. 2. Answer the questions. Lewis structure Electronic geometry of the carbon atom = _____________ Electronic geometry of the oxygen atoms = _____________ Polar bonds = Yes Polar molecule = Yes No No

CF4
1. 2. 3. 4. Draw the Lewis structure for carbon tetrafluoride. Build the ball and stick model. Draw the VSEPR model. Answer the questions.

Lewis structure

Electronic geometry of carbon atom = __________________ Molecular geometry = __________________ Ideal FCF bond angle = ________ Polar bonds = Yes Polar molecule = Yes No No

VSEPR model

Consider the compound CF3Br, where carbon is still the central atom. State the one property, based on molecular geometry, which would be different between CF4 and CF3Br.

Molecular Modeling I

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SF4
1. 2. 3. 4. Draw the Lewis Structure for sulfur tetrafluoride. Build the ball and stick model. Draw the VSEPR model. Answer the questions.

Lewis structure

Electronic geometry of sulfur atom = ________________ Molecular geometry = ________________ Ideal FSF bond angles = Polar bonds: Yes No No and and _______ VSEPR model

Polar molecule: Yes

PF5
1. 2. 3. 4. Draw the Lewis structure for phosphorus pentafluoride. Build the ball and stick model. Draw the VSEPR model. Answer the questions.

Lewis structure

Electronic geometry of phosphorus atom = ________________ Molecular geometry = ________________ Ideal FPF bond angles = Polar bonds: Yes No No and _______ and _______ VSEPR model

Polar molecule: Yes

Molecular Modeling I

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XeF4
1. 2. 3. 4. Draw the Lewis structure for xenon tetrafluoride. Build the ball and stick model. Draw the VSEPR model. Answer the questions.

Lewis structure

Electronic geometry of xenon atom = ________________ Molecular geometry = ________________ Ideal FXeF bond angles = Polar bonds: Yes No No and _______ VSEPR model

Polar molecule: Yes

BrF5
1. 2. 3. 4. Draw the Lewis structure for bromine pentafluoride. Build the ball and stick model. Draw the VSEPR model. Answer the questions.

Lewis structure

Electronic geometry of bromine atom = ________________ Molecular geometry = ________________ Ideal FBrF bond angles = Polar bonds: Yes No No and _______ VSEPR model

Polar molecule: Yes

Molecular Modeling I

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Ball and Stick Models of Large Molecules


Build ball and stick models for each of the following large molecules. Although there is no single central atom in these molecules, one can still identify the electronic geometry of the non-hydrogen atoms and predict ideal values for the many bond angles which exist in the these type of molecules.

Butane
H H C H H C H H C H H

1. 2. 3. 4. 5. 6. 7.

Consider the Lewis structure of butane given at the right. Build the carbon skeleton model (no hydrogens) of butane.

C H

Is the carbon skeleton straight as suggested by the Lewis structure? Add the hydrogen atoms. What is the electronic geometry of the carbon atoms? ________________ What is the ideal CCC bond angle? ______ What is the ideal HCH bond angle? ______

Cyclohexane
1. 2. 3. 4. 5. 6. 7. 8. Consider the Lewis structure of hexane given at the right. Using only the short bonds, build the carbon skeleton model of hexane. The carbon skeleton planar (flat) as suggested by the Lewis structure? True or False Add the hydrogen atoms. What is the electronic geometry of the carbon atoms? ________________ What is the ideal CCC bond angle? ______ What is the ideal HCH bond angle? ______ What is the ideal CCH bond angle? ______
H H C C H C H H H H C C C H H H

Molecular Modeling I

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Benzene
1. 2. 3. 4. 5. 6. 7. Consider the Lewis structure of benzene given at the right. Build the carbon skeleton model of benzene (no hydrogen atoms). Is the carbon skeleton planar (flat) as suggested by the Lewis structure? True or False Add the hydrogen atoms. What is the electronic geometry of the carbon atoms? _________________ What is the ideal CCC bond angle? _______ What is the ideal CCH bond angle? _______
H H H H H H

Aspirin (acetylsalicylic acid)

1. 2. 3. 4. 5. 6. 7. 8.

Consider the Lewis structure of aspirin given at the right. Build the carbon skeleton model of aspirin. Add the hydrogen atoms and non-bonded electrons. What is the ideal CCC bond angle? ______ What is the ideal HCH bond angle? ______ What is the ideal CCO bond angle? ______ What is the ideal COH bond angle? ______ What is the ideal COC bond angle? ______
H H C C C H H O H C C O C C C H O C O H H

EVALUATION There is not a report to be turned in for this project. Your score will be based on the responses youve recorded in your lab manual.

PC Spartan Pro

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Interpolation 5 PC Spartan Pro


This preliminary exercise is intended to help familiarize you with PC Spartan Pro software which will be used in a second molecular modeling lab. You must complete this exercise before you will be allowed to begin Project G. (It will also be most helpful to you to complete the exercise prior to taking the pre-lab quiz.) The exercise should take you less than 30 minutes and requires you to use the PC Spartan Pro software which is only provided in DSC rooms 107 and 370. (NOTE: DSC 370 will be unavailable during times when other lab sections meet there for Project G.)
GETTING STARTED

To begin your modeling exercise, double click on the PC Spartan icon located on the computers desktop or find it under through the start menu under programs. 1. Once Spartan is open, left click (LC) on File then New. This will open the builder window, Figure 18, which will appear on the right side of your screen. LC on Expert. This will give you the builder that you will use to build all the substances used in your computer modeling assignments. 2. The builder view shown at the right shows a nitrogen atom in tetrahedral electronic geometry. 3. Notice that several different electronic geometries are available below the periodic table in Figure 18. To start building a molecule, choose the central atom and the correct electronic geometry of the central atom. You can transfer your selection from the builder to the main screen by placing the pointer on the main screen and LC. 4. You may have to rotate the image to get a view that you will recognize. To rotate the model, LC on the model and move the mouse. 5. To delete a model, go to FILE and then delete. 6. Practice this with different atoms and different electronic geometries. Can you name the geometries?
BUILDING AN AMMONIA MOLECULE

Figure 18 PC Spartan Pro builder window

Figure 19 tetrahedral nitrogen

In this preliminary exercise, you will build ammonia and measure its bond angles, bond lengths and dipole moment. 1. The correct Lewis structure for ammonia has nitrogen as the central atom with tetrahedral electronic geometry. LC on nitrogen and then LC on the tetrahedral geometry. 2. Place the pointer in the middle of the screen and LC. You may have to rotate the atom to get the view shown. It should look like Figure 19. 3. LC on the hydrogen atom in the builder. Select the monovalent bonding shape, Figure 20.
Figure 20 builder window, monovalent hydrogen selected

PC Spartan Pro

54

4. Place the pointer at the end of a nitrogen bond and LC once. Repeat on two additional nitrogen bonds.
MANIPULATING MOLECULES

1. If you have more than one molecule on the screen at the same time, you can select the one you want by a LC on the molecule. 2. The selected molecule can be moved around on the screen by holding the right mouse button down and dragging the molecule. 3. Rotation of a selected molecule is accomplished by holding the left button down and moving the mouse. 4. Rotation of a selected molecule in a plane is accomplished by holding both the shift key and the left button down and moving the mouse. 5. Practice these movements on the nitrogen atom
MAKING CALCULATIONS ON AN AMMONIA MOLECULE

1. As far as we are concerned, the ammonia molecule is now built. However Spartan has been programmed to assume that every unused bond must have a hydrogen attached to it. So if you leave the extra bond on the nitrogen, Spartan will assume you want to do a calculation on NH4! To prevent this, the unused bond must be deleted. This is done by first a LC on the delete button on the tool bar and then a LC on each unused bond. Your molecule should now look like the one in Figure 21. 2. Spartan does not show non-bonded electrons. It will be up to you to remember whether they are part of the molecule or not. 3. At this point the bond lengths and bond angles have ideal values. To get more realistic values, the molecule needs to be minimized. The process of minimization uses the mathematics of quantum mechanics to find the bond lengths and bond angles which will give the molecule its lowest energy. Spartan can do this at several levels of sophistication. We will work at a level which will give reasonable results in fairly short time.
MENU AND TOOLBAR

Figure 21 Ammonia molecule

Before you minimize the ammonia molecule you just built, you need to become familiar with some of the other menu and toolbar, Figure 22, options that you will use in this exercise.

Closes builder Recall builder erase atom or bond

measure bond angles measure bond lengths preliminary minimization

Figure 22 PC Spartan Pro menu and toolbar

PC Spartan Pro

55

1. You must close the builder to do any measurements or calculations on a molecule. 2. Clicking on the delete button and then clicking on an atom or unwanted empty bond in your molecule allows you to erase one or more unwanted atoms or bonds. 3. Recalling the builder, Figure 22, allows you to add atoms to your molecule. 4. Clicking on the bond length icon and then clicking on a bond will give the bond length. The calculated bond length will be displayed in the lower right hand corner 5. Clicking on the bond angle icon and then clicking on the three atoms in the angle to be measured will give the value of the angle. The center atom of the angle must be the second atom selected. 6. On the menu bar, LC on Model (the builder must be closed, Figure 22). 7. The first 5 items allow you to change the way your molecule is portrayed on your monitor. Try each one. 8. The only other item you will use from this menu is Dipole. The use of the Dipole function will be discussed later.
IMPORTANT: If you have more than one molecule displayed on your monitor, only one can be active at a time. You activate a molecule with a LC on the molecule. MINIMIZATION

1. LC on the preliminary energy minimization icon on the toolbar, see Figure 22. This step usually takes only a few seconds. A completed scroll bar at the bottom of the screen indicates this step is done. 2. LC on Setup then LC on Calculation. 3. Change your calculation choices to match those given in Figure 23, then LC on OK. 4. You may think you have started the calculation but you have not. You need to again LC on Setup and then LC on Submit. This will start the actual minimization calculation. 5. Spartan will ask you if you want to save the molecule. LC on Save if you are working in DSC 370 or Save/my documents if you are in DSC 107.

Figure 23 Calculation window

6. Spartan will notify you the calculation has started. LC on OK. 7. Spartan will also notify you when the calculation is finished. Again LC on OK. 8. You will have to repeat this set of 7 steps every time you perform a new minimization. There does not appear to be any way to change the default choices in this version of Spartan. Remember a molecule must be minimized twice (preliminary and calculation) before any measurements are made. 9. If you have not already done so, do both minimization steps for your model of ammonia. Once the second calculation is complete, measure the bond lengths and bond angles. You should get a value of 1.001A (100.1 pm) for all NH bond lengths and a value of 107.60 for all the HNH bond angles. Record the bond angle and bond length you measured.

PC Spartan Pro

56

10. If you did not get these values you will need to redo your calculations. Before redoing the calculations, please go to the next section of this interpolation to see a table of common errors and the values obtained when these errors are made.
MOLECULAR POLARITY

One of the other properties that Spartan calculates is molecular polarity, also called the molecular dipole moment or sometimes it is just called the dipole. To display the dipole value of ammonia, LC the View icon, see Figure 22, then LC Display (on the Menu bar) and then LC on properties. For ammonia you should get a value of 1.837 debye. Record this value in your notebook. If the calculated dipole value is greater than 0.1 debye, it is considered polar and you will want to also display the molecular polarity arrow. To display the arrow, LC on Model, LC on ball and wire, LC on model again and then LC on dipole. If the dipole value is less than 0.1 debye, the molecule is not considered to be polar and there is no need to display the molecular polarity arrow. Since the dipole of ammonia is greater than 0.1 debye, we consider it to be polar and after displaying the polarity arrow your ammonia molecule should look like Figure 24. It is always best to check the numerical value of the polarity before displaying the polarity arrow. Spartan does not scale the polarity arrow. It displays the same size arrow for all non zero values of the dipole moment. That means the arrow for a dipole of .001 debye looks the same as the arrow for a dipole value of 10.00 debye!
CHECKING YOUR CALCULATIONS

Figure 24 ammonia with dipole

At this point you should have values for the bond lengths, the bond angles and the dipole moment for ammonia recorded in your lab notebook. If you did not get the values given, you probably forgot one of the minimization steps. Start with a new model and repeat the entire exercise being very careful to do both minimization steps. The most common error is to forget to submit the second minimization calculation after you set it up. See the box below for typical error values and the correct values. 1. Values if only a preliminary calculation was performed. This would be the result if you did not do any part of the second minimization step or if you forgot to submit the calculation set up. 2. Values if no preliminary minimization was done and only the second minimization was performed. 3. Expected values if all steps are correctly done. NH bond length = 1.019 A HNH bond angle = 106.0 Dipole moment = nothing calculated NH bond length = 1.001 A HNH bond angle = 107.57 Dipole moment = 1.842 debye NH bond length = 1.001 A HNH bond angle = 107.60 Dipole moment = 1.837 debye

CONGRATULATIONS! You should now have the basic knowledge needed to do Project G. Dont forget, to do the preparation questions on page 58 and take the pre-lab quiz before coming to lab for Project G.

Do Not Begin Project G Before Your Assigned Lab Class Time!

Molecular Modeling II

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Project G Molecular Modeling II


A Closer Look
OBJECTIVE

To use a molecular modeling software package to investigate the effects that molecular geometry, atom size, bond type and resonance has on bond lengths, bond angles and molecular polarity. Most of the compounds you will model in this project will be the same ones you modeled in Project L. In Project L you gained mostly a qualitative appreciation for covalent molecules. In this project you will gain a much more quantitative feeling for bond lengths, bond angles and molecular polarity.
CONCEPTS APPLIED 1. Periodic trends in atomic/covalent radii (Brown, LeMay & Bursten, p266, Fig 7.6) 2. Lewis structures (Brown, LeMay & Bursten, pages 310-328) a. octet structures and non-octet structures b. formal charge c. resonance structures d. bond order 3. Electronegativity and polar covalent bonds (Brown, LeMay & Bursten, page 312-317) 4. VSEPR theory (Brown, LeMay & Bursten, Chapter 9) a. electron group shapes for central atoms with 2, 3, 4, 5, and six electron groups b. molecular shapes c. molecular polarity d. effect of atom size and bond types on ideal bond angles and bond lengths MOLECULAR MODELING

Today, the term modeling no longer implies Styrofoam balls, glue and sticks. With the development of computers, modeling often refers to the process of describing a system (a bridge, the weather, a water molecule) with one or more mathematical equations. Frequently many equations are needed to produce reasonable results. Most modeling projects are very complex and require thousands of calculations to produce a single result. The advent of computers removed the problem of multiple calculations but still left the individual scientist with the chore of writing the software to perform the required calculations. Today we have fast, inexpensive computers and software packages that perform all the calculations. All areas of science have benefited from these developments. There is modeling software available for engineering, weather forecasting, prescription drug design and, of course, chemistry just to name a few. Modeling software has become so friendly, in very little time you can be doing the same experiments as the experts. The system of mathematical equations used in molecular modeling has been known for many years. In theory, with a big enough computer and unlimited computing time these equations can produce results which agree almost exactly with experimental results. Very few of us have unlimited computing capacity and unlimited time so we have to make some compromises. The time needed for a calculation increases dramatically as the required accuracy is increased. Do we want our results in two or three minutes or in two or three days? For this reason most molecular modeling software packages have several calculation levels you can choose from depending on the accuracy wanted, time limitations and the number of electrons involved. It is easier to get good results for HF ( 10 electrons) than it is for HBr (54 electrons). Because of these limitations, you will change calculation levels a few times during the course of this project.

Molecular Modeling II

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You will be using a software package called PC Spartan Pro. It was developed by Wavefunction, Inc., Irvine, California. PC Spartan Pro is easy to use. It provides several levels of calculation which will allow you to get reasonable accuracy in minimum time. In this experiment you will build several molecules and calculate their bond lengths, bond angles and molecular dipole moments. Your ability to build the molecules and understand the results will require you to use the concepts contained in the topics of Lewis structures, electronegativity, periodic table trends in atomic size, molecular polarity and VSEPR theory.
PRE-LAB PREPARATION 1) The preliminary exercise in Interpolation 5 must be done before you will be allowed to begin this project. (It will be most helpful to you if you complete that exercise prior to taking the pre-lab quiz.) It should take you less than 30 minutes and requires you to use the PC Spartan Pro software which is provided in DSC rooms 107 and 370. (NOTE: DSC 370 will be unavailable during times when other lab sections meet there during this week.) 2) Be able to calculate the formal charge on any ion or neutral molecule. 3) Know why the AsCl bond is longer than the AsH or AsF bond lengths. 4) Know why the CC bond length in the compound CHCH will be shorter than the CC bond length in either CH2CH2 or CH3CH3. List (in your notebook) two factors which cause bond angles to deviate from ideal values. Give an example of a compound that has polar bonds but is not a polar molecule. SPECIAL INSTRUCTIONS

Correct any incorrect Lewis structures or other responses from 0. Verify all corrections with your lab instructor before proceeding with this project. You may be assigned to work individually or in pairs depending on availability of computers in the lab. Each student or student pair will have access to a computer with PC Spartan Pro. The data collected during this project will be used to answer the set of post lab questions that follow. Your answers to the post lab questions should also be recorded in your laboratory notebook. Each student will turn in a complete lab report. The final report will consist of your laboratory notes and the completed post laboratory questionnaire.

COVALENT /ATOMIC RADII 1. Build and minimize H2O2 (File/New and then Expert) using the same minimization steps used for NH3, Figure 23. Determine and record the O O bond length. Calculate and record the covalent radius of oxygen. Do not delete this molecule, it will be used again. 2. Build and minimize N2H4 Determine and record the NN bond length Calculate and record the covalent radius of nitrogen Do not delete this molecule, it will be used again. 3. Build and minimize H2S2 Determine the SS bond length Determine the covalent radius of S. EFFECT OF BOND ORDER ON BOND LENGTHS

Up to now you have been working with compounds containing only single bonds. Some of the remaining molecules will contain double or triple bonds. Initially the builder uses only single

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bonds. If you need a double or triple bond, simply click on the bond type needed and then double click on the bond in your molecule which you want to change. You may need to change the orientation of your molecule to see that the bond has been changed. Bond order is defined as the number of electron pairs shared between two covalently bonded atoms. A single bond, which consists of one pair of bonding electrons, has a bond order of 1. Similarly a double bond, which requires two bonding pairs, has a bond order of 2. A triple bond has a bond order of 3. In general as the bond order between two bonding atoms increase, the length of the bond decreases. Bond CO C=O CO Bond order 1 2 3 Bond length 1.43 A 1.23 A 1.13 A

In this section you will use data from previously modeled molecules of N2H4 and H2O2 and new models of N2H2, N2 and O2 to determine the effect of bond order on bond lengths.
4. Build and minimize N2H2, N2 and O2 Measure their bond lengths. Do not delete N2 it will be used again. RESONANCE STRUCTURES

We can often write more than one Lewis structure, with the same connectivity of the atoms but different placement of electrons, for a molecule or ion. Such structures are called resonance structures. Resonance structures are not real representations of the actual bonding in the substance but result from the inability of static Lewis structures to accurately depict the location of highly mobile electrons in many molecules and ions. Resonance structures are classified as low energy structures or as high energy structures. High energy forms are generally not considered to be significant. Once the high energy forms have been identified, the bonding in the actual molecule, sometimes called the resonance hybrid, is generally pictured as an average of the remaining lower energy forms. The concepts of formal charge are frequently used to classify the resonance structures as low or high energy structures. Consider the possible resonance structures and formal charges (written above each atom) for the cyanate (CNO1) ion.

Structure C is a high energy form (do you know why?) and will not make a significant contribution to the resonance hybrid. Structures A and B have low formal charges but A is much more important than B. (Do you know why?) This means the bonding in the resonance hybrid will be more like structure A than either structures B or C. What does this have to do with molecular modeling? Since we expect the true version of the hybrid to have bonding very similar to structure A, the minimized model of the cyanate ion should have one long bond (the single bond between carbon and oxygen) and one significantly shorter bond ( the triple bond between nitrogen and carbon).

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When multiple resonance structures are possible, it does not matter to Spartan which structure you build to submit for minimization you will get the same results. The minimization calculations are based on which elements are present, the number of atoms of each element and the total number of electrons in the system. For example, CO2 may be built with two carbon oxygen double bonds or one carbonoxygen triple bond and one carbonoxygen single bond. Either model will give the same results for all calculated properties such as bond lengths, bond angles and molecular polarity. However, Spartan is not smart enough to change the model you submitted. If you submitted the triple bonded form, you will continue to see the triple bonded form on your screen no matter what changes the minimization calculation may make. The most stable resonance form or forms will become clear only by looking at formal charges and the calculated values for bond lengths.
5. Build and minimize O3 (ozone) Consult the Lewis structures you drew for ozone in 0. Measure and record both OO bond lengths. How do the bond lengths support your conclusions based on formal charges? 6. Build and minimize N2O Consult the Lewis structures you drew for N2O in 0. Measure the NO and NN bond lengths. MOLECULAR POLARITY

Covalent bonds are said to be polar if the bond joins two atoms with different electronegativities. The polarity is caused by an unequal sharing of the bonding electrons. The bonding electrons will be drawn more toward the higher electronegative atom making that end of the bond somewhat negative in charge. The other end of the bond will, conversely, contain less of the bonding electrons and acquire a somewhat positive charge. This condition is frequently indicated with an arrow () over the bond pointing toward the negative end of the bond. In diatomic molecules there is only one bond. In these simple compounds a polar bond causes the molecule to also be polar. In molecules containing more than two atoms, molecular polarity is determined by both bond polarity and molecular shape. Once you have done a minimization on any molecule, the molecular polarity of the molecule can be displayed. As mentioned earlier, the fact that Spartan displays a polarity arrow does not always mean the molecule is polar. The best judge of polarity is found under properties in the Display menu. To display the molecular polarity arrow for any molecule you have built and minimized, go to model and LC on dipole. Just remember an arrow is no guarantee of actual molecular polarity. If only a plus (+) sign is displayed the molecule is non-polar.
7. Display the molecular polarity of N2 (nitrogen gas) Activate the nitrogen molecule and display its molecular polarity. Draw the VSEPR model for N2. Sketch in the molecular polarity arrow if the molecule is polar. Record the value of the dipole. 8. Build and minimize CO (carbon monoxide) Draw the VSEPR model for carbon monoxide. Sketch in the molecular polarity arrow if the molecule is polar. Record the value of the dipole. 9. Build and minimize CO2 (carbon dioxide) Draw the VSEPR model for carbon dioxide. Sketch in the molecular polarity arrow if the molecule is polar. Record the value of the dipole.

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VSEPR theory tells us that molecules with their central atom in the trigonal planar arrangement will have bond angles close to the ideal angle of 120. Tetrahedral systems will be close to the ideal angles of 109.5. The ideal angles predicted by VSEPR theory are seldom realized because bond angles are greatly influenced by the presence of one or more bulky groups attached to the central atom. The major groups that cause these deviations are nonbonded electrons, double or triple bonds and very large atoms. The following exercises are intended to illustrate the effect of these bulky groups on bond angles and to give you additional experience with molecular polarity.
10. Build and minimize CF4 (carbon tetrafluoride) Measure and record the bond angles in carbon tetrafluoride. Measure the dipole value. Display the molecular polarity of carbon tetrafluoride. Draw the VSEPR model for carbon tetrafluoride. Sketch in the molecular polarity arrow, if the molecule is polar. 11. Build and minimize NF3 (nitrogen trifluoride) Measure and record the bond angles in nitrogen trifluoride. Measure the dipole value. Draw the VSEPR model for nitrogen trifluoride. Sketch in the molecular polarity arrow on the VSEPR model if the molecule is polar. 12. Build and minimize CH2O (formaldehyde) carbon is the central atom Measure and record the bond angles in formaldehyde. Measure the dipole value. Draw the VSEPR model for formaldehyde. Sketch in the molecular polarity arrow on the VSEPR model if the molecule is polar. MOLECULES WITH A HYPERVALENT CENTRAL ATOM NOTE: Some of the following calculations will take a few minutes 13. Build and minimize SF4 (sulfur tetrafluoride) Draw the VSEPR model of sulfur tetrafluoride Measure the bond angles on your VSEPR model. Measure bond lengths on your VSEPR model. Measure the dipole value. Sketch in the molecular polarity arrow on the VSEPR model if the molecule is polar. 14. Build and minimize phosphorus pentafluoride. Draw the VSEPR model of phosphorus pentafluoride. Measure the bond angles on the VSEPR model. Measure the bond lengths on the VSEPR model.. Sketch in the molecular polarity arrow on the VSEPR model if the molecule is polar. 15. Build and minimize xenon tetrafluoride. Remember, in octahedral systems, to place bonding atoms across from each other to the extent possible. Use the 3-21G* level for this calculation Draw the VSEPR model of xenon tetrafluoride. Measure the bond angles on the VSEPR model. Measure the bond lengths on the VSEPR model. Measure the dipole value. Sketch in the molecular polarity arrow on the VSEPR model if the molecule is polar.

Molecular Modeling II 16. Build and minimize bromine pentafluoride. Use the 3-21G* level for this calculation Draw the VSEPR model of bromine pentafluoride. Measure the bond angles on the VSEPR model. Measure the bond lengths on the VSEPR model. Measure the dipole value. Sketch in the molecular polarity arrow on the VSEPR model if the molecule is polar. MODELING LARGE MOLECULES

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17. Butane H H H H Consider the Lewis structure of butane in . Build the model of butane. Minimize your model using only the energy minimization H C C C C H icon on the tool bar. Rotate the molecule so you have an end on view. Notice H H H H that the hydrogens are staggered for maximum separation. Get a pair of stereo glasses from your instructor. To view a molecule in stereo, strike the number 3 on the keyboard (the number pad does not work for this). The atoms should all have faint red and blue halos. Put on the stereo glasses and view the molecule as you rotate it. When you are finished viewing in stereo, strike the 3 key again to turn off the stereo effect 18. Cyclohexane Consider the Lewis structure of hexane given at the right. Build the model of cyclohexane (use the rings tool near the bottom of the builder window, Figure 18). Minimize your model using only the minimization icon on the tool bar. Is cyclohexane planar (flat) as suggested by the Lewis structure? View the molecule in stereo.
H H H H C C H C H H H C C C H H H

19. Benzene Consider the Lewis structure of benzene given at the right. Build the model of benzene. Minimize your model using only the minimization icon on the tool bar. Is benzene planar (flat) as suggested by the Lewis structure? View the molecule in stereo.
H

H
H C C O O C C C C H H O H H

H H

20.

Aspirin (acetylsalicylic acid)


Consider the Lewis structure of aspirin given at the right. Build the model of aspirin. Minimize your model using only the minimization icon on the tool bar. View the molecule in stereo.
H

C C C

Molecular Modeling II

63 NAME _________________________

EVALUATION

Your lab report should consist of the notes you took during the modeling exercise and the answers to the following questions. Remember, even if you worked with a partner on this project, you both need to turn in your own work separately. This worksheet is to be completed INDIVIDUALLY. Write your answers here and tear these pages out when you submit your lab report. 1. Using your understanding of VSEPR theory, briefly explain why the measured bond angle in ammonia is smaller than the ideal angle expected for a tetrahedral central atom.

2. The bond angle between two hydrogen atoms is larger in ammonia than in water. Explain why this is so, using your understanding of VSEPR theory.

3. Record your calculated values for the atomic radii for oxygen, nitrogen and sulfur. Oxygen _____________ Nitrogen _____________ Sulfur _____________ Yes or No

a. Do these agree with the trends predicted by the periodic table? b. Briefly explain this trend.

4. Based on your calculated values of the nitrogen and oxygen atomic radii, predict the NO bond length. Be sure to include the unit. NO bond length __________________ 5. Record your calculated values for the NN, N=N and NN bond lengths. NN _____________ N=N _____________ NN _____________ Yes or No

a. Do these agree with the trends predicted by the periodic table? b. Briefly explain this trend.

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6. Consider the two resonance forms of ozone you drew. Based on their formal charges, do you expect both resonances forms of ozone to contribute equally to the resonance hybrid, yes or no? Briefly explain your answer using the measured bond lengths as evidence.

7. Both resonance structures for ozone have one single bond (bond order = 1) and one double bond (bond order = 2). Based on the measured bond lengths for ozone, what bond order would you assign to the bonds in the resonance hybrid of ozone? Briefly explain.

8. Consider the three resonance forms for N2O which you drew. Based on formal charges, do you expect all three resonances forms of N2O to contribute equally to the resonance hybrid, yes or no? Briefly explain your answer using the measured bond lengths as evidence.

9. Draw the Lewis structure for CBr4. a. What value would you expect for the BrCBr bond angle? _____________ b. Do you expect CBr4 to be polar or non-polar, yes or no? (circle one) 10. Consider your data for PF5 a. Are all the bond lengths the same, yes or no? (circle one) b. If not, which bond lengths are longer?

CBr4 Lewis Structure

COS Lewis Structure

11. Draw the Lewis structure for COS using carbon as the central atom. a. Predict the molecular geometry of COS. ________________________ b. Do you expect COS to be polar or non-polar? (circle one) c. Draw its VSEPR model of COS including the polarity arrow if you predicted it to be polar. Draw the polarity arrow just as Spartan would draw it. Remember you are indicating the polarity of the molecule and not the polarity of a bond. COS VSEPR Structure

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12. What is the ideal HCH bond angle in formaldehyde? ______________ Briefly explain why your measured HCH angle is different than the ideal angle.

For the following questions use an X for the central atom and As for the attached atoms

13. Is it possible for any covalent molecule containing only one central atom and having one nonbonded electron pair on the central atom to still be non-polar? If your answer is yes, draw the VSEPR model for one such molecule.

14. Is it possible for any covalent molecule containing only one central atom and having two nonbonded electron pairs on the central atom to still be non-polar? If your answer is yes, draw the VSEPR model for one such molecule.

15. Is it possible for any covalent molecule containing only one central atom and having three non-bonded electron pairs on the central atom to still be non-polar? If your answer is yes, draw the VSEPR model for one such molecule.

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Project H Introduction to Chromatography


Quantitative analysis of the prevalent ions in drinking water
OBJECTIVE Separate pigments in black ink, separate the ions in a water sample and determine the total ion content and water hardness of that water sample. CONCEPTS APPLIED 1. Chromatography one of the most important and powerful separation techniques currently available. 2. Charge balance of aqueous solutions INTRODUCTION

Chromatography is a technique that separates1 components of a mixture based on differences in their relative affinities (intermolecular forces) for two different materials. The word chromatography comes from Greek words meaning color and to write. The analyte sample is dissolved in a solvent, called the eluent or mobile phase. The eluent flows over/through a solid material that is called the stationary phase. The stationary phase is commonly made of cellulose (paper), silica or alumina; all of which can be and frequently are chemically modified to have a particular effect on the separation. Depending on the type of chromatography, the solvent can be a liquid or gas and the stationary phase can be in the form of a thin sheet or column. The column can either be packed or coated on its inner surface with the stationary phase material. In general, each component of the mixture does not stay permanently in either the mobile or stationary phases, but instead is exchanged back and forth repeatedly during the separation forming an equilibrium between the two phases. The different affinities (attraction) of each component for the mobile and stationary phases reflect their equilibrium concentrations. A component with greater affinity for the mobile phase will have a higher mobile phase equilibrium concentration, spend more time in the mobile phase over the course of the separation and as a result will move through/over the stationary phase rapidly. The two types of chromatography used in this project are paper chromatography and a form of high performance liquid chromatography (HPLC) called ion chromatography (IC). Paper chromatography is a very simple and inexpensive separation technique that uses paper as the stationary phase. The eluent (a liquid) is allowed to slowly soak up the surface of the paper stationary phase. As it does, the sample components move and separate based on their different affinities for the eluent and paper. The movement of each component is quantified by the ratio of distance traveled by the substance to the distance traveled by the solvent and this ratio is called the retention factor, Rf. This measurement is a primary means of qualitatively identifying compounds separated by paper chromatography. In ion chromatography, the stationary phase is a column typically packed with a synthetic, organic polymer. The eluent is generally an aqueous solution containing small amounts of specific acids or bases, such as nitric acid or sodium bicarbonate, and possibly some small amounts of organic solvents such as acetone or methanol. Completely controlled by a computer, the modern IC instrument consists of a sample injector, pump, column and detector. The most important applications of IC today center on the routine analysis of aqueous systems:

For a review of basic separation techniques see pages 12-13 in the 10th ed. of Brown, LeMay and Bursten, Chemistry: The Central Science, Prentice Hall, 2006.

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drinking water, environmental water systems (ponds, rivers, aquifers, etc.) and industrial processes that require ultra pure water such as that found in nuclear power plants and semiconductor manufacturing.2
Pigments in Ink Ink markers are available in a variety of colors and forms: permanent, dry erase, washable, etc. Many of these markers, especially the black ones, use more than one pigment to achieve their color. For instance, the ink in a black marker may actually contain green, purple, orange and pink pigments. As a point of reference, if enough different colors of paint are mixed together, the mixture eventually turns a gray or blackish color. Permanent markers are not supposed to run or smear, but being permanent really only applies to water as the solvent. The ink in these markers is much less permanent when a different solvent is used, such as ethanol or acetone. Ions in Water Water generally contains appreciable amounts of dissolved salts dissolved from soil and rock. Among the most important salts are the chlorides, sulfates and hydrogen carbonates of calcium, magnesium and sodium. Calcium and magnesium are the most prevalent ions that contribute to water hardness, which is actually a measure of the total concentration of all divalent cations. Water hardness is normally expressed as the equivalent number of milligrams of CaCO3 per liter, Example 1. Water containing less than an equivalent of 60 mg CaCO3 per liter is considered soft and water with more than 270 mg/L is considered hard.3 (Another common unit used to express small concentrations is parts per million (ppm) which is a measure of mg of solute per kg of solution.) Hard water is a problem for some household and industrial uses. For instance, the hard water ions react with soap to form a precipitate. This results in the need for additional soap to achieve the same cleaning effectiveness.

Another important ion in drinking water is fluoride, which helps to prevent tooth decay. Naturally occurring amounts of fluoride are supplemented to achieve a total fluoride concentration of approximately 1 ppm.4 Unfortunately, certain types of home treatment devices will remove 85 to more than 95% of all the minerals in water, including fluoride. These are reverse osmosis, distillation units and deionization units. Water softeners, however, do not remove appreciable amounts of fluoride. Other common ions present in water are sodium, chloride, nitrate, sulfate and bicarbonate. The presence of these ions in drinking water is generally not a health concern, except nitrate, but do affect its taste. Although the common ions in drinking water are colorless, they can be separated based on the same fundamental principles as the separation of pigments in the ink pens. Different stationary and mobile phases are required and the instrument detects the separated ions based on changes in conductivity of the mobile phase. In paper chromatography, it is more difficult to quantify the amount of a separated substance; however, with the ion chromatography instrument and computer, the area under the peak is quickly measured and is directly proportional to the quantity of substance present.

3 4

Eith, C.; Kolb, M.; Seubert, A. Practical Ion Chromatography; Metrohm Ltd.: Herisau, Switzerland, 2001-02. Harris, D. C. Quantitative Chemical Analysis, 5th ed.; Freeman, 2001. Metropolitan Utilities District; City of Omaha, NE: http://www.mudomaha.com/water/faq.html, 2002.

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Example 1 Calculate the hardness of water containing 4.62 ppm Mg2+ and 3.74 ppm Ca2+. (Assume that the density of the solution is 1 kg/L.) Plan

Step 1. Convert ppm to molarity assuming the density of water is 1 g/mL. 1 mg solute 1 mg solute 1 ppm = 1 kg solution 1 L solution Step 2. Add Ca2+ and Mg2+ molarities (retain units of M Ca2+) Step 3. Convert equivalent M Ca2+ to equivalent mg CaCO3 per liter of solution.

Solution Step 1 Calculation

4.62 mg Mg2+ 1 g Mg2+ 1 mol Mg2+ 1 kg solution = 1.90 x 104 M Mg2+ 1 kg solution 1000 mg Mg2+24.30 g Mg2+ 1 L solution 3.74 mg Ca2+ 1 g Ca2+ 1 mol Ca2+ 1 kg solution = 9.33 x 105 M Ca2+ 1 kg solution1000 mg Ca2+40.08 g Ca2+ 1 L solution

1.90 x 104 M Mg2+ + 9.33 x 105 M Ca2+ 2.83 x 104 equivalent M Ca2+

g CaCO3 1 mol CaCO3 100.0 g CaCO3 2.83 x 104 eq. M Ca2+ 1 mol Ca2+ 1 mol CaCO = 2.83 x 102 L solution 3 g CaCO3 1000 mg CaCO3 1 L solution eq. mg CaCO3 2.83 x 102 L solution 1 g CaCO 1 kg solution = 28.3 1 kg solution

28.3 < 60; therefore, this water is soft.

SAFETY

Isopropyl alcohol is flammable and may cause eye, respiratory tract and skin irritation 5% acetic acid solution (commonly available as vinegar) does not pose any serious health or safety hazards. Information for glacial (~pure) acetic acid is not relevant. Carbonic, nitric, sulfuric and dipicolinic acids as used in the ion chromatographs, all are sufficiently dilute so as not to pose any serious health or safety hazards. These solutions, after being used, are collected and disposed of by a department professional.

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POSSIBLE ADVANCE PREPARATION ONLY IF INSTRUCTED IN LAB

During the lab meeting prior to the day that this experiment will be done, acquire an approved, properly labeled bottle from your laboratory instructor to use to collect your drinking water sample. Determine who will acquire the water sample and from where. (You will only need one water sample between you and your partner.) Record the date, time and any other identifying information about the sample including water system (i.e. private well, MUD, etc.) and address for tap water or brand, place purchased, and manufacturers id code for bottled water.

PROCEDURE

This experiment is intended to be collaborative. You will be working in pairs throughout these experiments but will be evaluated based on your individual notebook/report.
1. Paper Chromatography Separation of Dyes

Step 1. Step 2.

Obtain two pieces of chromatography paper. Using a pencil, draw a straight line 1 cm from the bottom of each piece of paper. On the line, make 4 marks 2 cm from each other and at least 2 cm from either vertical edge of the paper. Label them A thru D. With each piece of paper, make a small spot 1-2 mm in diameter with one of the markers at mark A. Repeat, using a different marker on each remaining mark. Be sure to record which spot corresponds to which marker. Form a cylinder and staple as shown so that the line and spots are at the bottom, making sure that the two stapled edges must not touch, Figure 25.

Step 3.

Step 4.

Figure 25

Step 5.

Collect approximately 20 mL of 70% isopropyl alcohol solution in a 400 mL beaker and 20 ml of vinegar in another 400 mL beaker. Make sure that the spots are not submerged in the vinegar/alcohol. Gently place one piece of chromatography paper in each beaker and cover with a watch glass. Be sure that the paper does not touch the sides of the beaker. The eluent will move up the paper by capillary action. After the chromatograms have developed for 15-20 minutes or when separation of the individual ink pigments has occurred, remove the chromatograms from the beakers. (Do not allow the solvent front to get all the way to the top edge of the paper.) Carefully remove the staples and lay flat to dry. Quickly (before the eluent evaporates) draw a line in pencil across the paper at the solvent front. Remaining 70% isopropyl alcohol must be collected in the unwanted materials container. Discard remaining vinegar into the sink with a 5-fold excess water. Keep your chromatograms and submit them with your lab report (one per student).

Step 6.

Step 7.

Step 8. Step 9.

Step 10. Create a table for each marker and eluent, record the colors separated, their order, their Rf values and any other pertinent information. The Rf value is the principle means of quantifying the behavior of the substances being separated.
Rf = distance from the base line to the center of each color distance from the base line to the solvent front

Introduction to Chromatography 2. Ion Chromatography of a Water Sample You will analyze your water sample twice: once for anions and once for cations. The procedure is the same for each, only the way that the instruments have been setup is different. (Three instruments will be setup for cation determination and three for anion.)

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Step 1. Step 2.

Take your water sample to the undergraduate chromatography lab (DSC 323). The 792 Basic IC program should be open on the computer and the system window, Figure 26, should be visible. (Check with your lab instructor if this is not to be the case.) The instrument is completely computer controlled.The 792 Basic IC instrument, Figure 27, should be on and ready for your sample when you get there.

Syringe and aspirator tubing

Figure 26 the 792 Basic IC system window

Figure 27 the 792 Basic IC

Step 3. Step 4. Step 5.

Click the start button, Figure 26, and enter your sample id information. Leave the other fields unchanged then click OK. Make sure that the fill button in the system window is depressed, as in Figure 26. Use a Kimwipe to wipe clean the last 3-4 inches of the inlet tube, then place it in your water sample and the syringe in the coupling on the other tube. (These are the only two tubes that stick out of the instrument when the door is closed, Figure 27.) Draw approximately 1 ml into the syringe, then click the inject button, Figure 26, to begin the separation and analysis of your water sample. Detach the syringe and empty it into the unwanted materials container at the back of the instrument. Return the syringe to the syringe tubing coupler. Remove the inlet tube from your water sample and replace the lid on the sample bottle. After the separation is complete, the chromatogram window will disappear. Click the open file button, , select your file and click OK. Print the chromatogram and record the file name, retention times and peak areas in a table in your notebook. Repeat steps 3-8 for determination of the other ions being sure to use an instrument set up for those ions. START FILL LOAD INJECT

Step 6. Step 7.

Step 8.

Step 9.

Step 10. Record the concentration for each ion on your instructors report sheet/website. Step 11. Submit a copy of each chromatogram report with your lab report. Step 12. Return your sample to your laboratory instructor.

Introduction to Chromatography DATA PROCESSING 1. Record these concentrations on the data collection website before you leave the laboratory. 2. Convert the concentrations to units of molarity and record these to your data tables. (Step 1 in the example) 3. Check the charge balance of your sample. Just as an ionic solid must maintain electrical neutrality (CaF is not a stable ionic substance but CaF2 is) so do solutions with dissolved ions. After multiplying the molarity of each ion by the absolute value of its charge, the sum of those values of the cations should equal the sum of those values of the anions. For example, if H+, K+, Ca2+, OH, HPO 2 and PO3 are the only ions present 4 4 then the following must be true. (Remember [X] refers to the molarity of species X.)
2 [H+ ] + [K + ] + 2[Ca2+ ] = [OH ] + 2[HPO4 ] + 3[PO3 ] 4

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(sum of the cations = sum of the anions) 4. The ions detected in your water sample probably do not achieve a charge balance because one anion, bicarbonate, was not detected by the chromatograph and is therefore not included in your chromatograms. It is not detected because it is also part of the eluent. (Any bicarbonate in your sample is indistinguishable from the bicarbonate in the eluent.) Assuming that your separations went well, bicarbonate constitutes the remaining ions needed to achieve charge balance. Report the difference in your charge balance as the concentration of bicarbonate. 5. Add this ion and its calculated concentration to your data table.
POST LAB QUESTIONS 1. Pigments with the smallest Rf values have the greatest affinity for which phase, the mobile or stationary phase? 2. Were there any unidentified ions in your water sample that showed up on your chromatogram? If yes, suggest some other possible ions that might be acceptably found in drinking water, i.e. not CN (cyanide). (Disregard peaks or dips that appear on your chromatograms prior to sodium or fluoride.) 3. What is the hardness of your water sample in equivalent mg of CaCO3 per liter? (see the example) 4. Does your water appear to be fluorinated? Cite evidence to support your conclusion. EVALUATION Credit is based on your recorded observations/data, calculations and responses to the pre and post lab questions.

Your notebook should include a discussion of the results and data quality but not a conclusion for this project. The conclusions will be determined and shared during the presentations to follow.

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Project I Chemical Equations


OBJECTIVE

Conduct chemical reactions, observe evidence of reaction, and correlate observations with an appropriate chemical equation.
SKILLS REHEARSED 1. Using reagent solutions in molar concentration. 2. Collection of a gas over water. 3. Describing chemical reactions. 4. Writing molecular equations consistent with observations. 5. Use of an indicator to characterize solution acidity. BACKGROUND Chemical Properties In Projects A and C, substances were identified by physical properties. These are important in recognizing materials previously investigated, and useful because they are generally non-destructive; the same portion of sample can be measured for more than one property.

This project introduces chemical reactions, by which substances are consumed and made. Chemical reactivity is usually noted descriptively, for example: a sample doesnt react, reacts slowly and incompletely, or reacts quickly and completely to give specified products under stated conditions. Yet the variety of ways a substance can react with other reagents is so varied, chemical properties taken together can identify a substance as specifically as quantitative physical properties. The materials consumed in a chemical reaction are termed reactants or reagents. The first term refers to pure substances, the second to pure substances or mixtures. The materials produced are products (by-products if they are not of direct interest).
Reagent Solutions Chemical reactions involve bringing things together or taking things apart. Just as with quilting or car repair, this is easier to do while the pieces are supported. When the pieces are molecules and ions, the support comes from working in a solution. Most reactions are done with solutions of pure substances in a solvent such as water.

To specify how much reacting substance is dissolved in a given volume of water, chemists find the concentration unit of molarity most useful. Molarity is the concentration expressed as amount of solute per volume solution in the units mole per liter, or an equivalence such as mmol/mL. The abbreviation for molarity is M. In taking reagent solutions, check both for the substance and the concentration to see that it matches the instructions.
Chemical Equations A chemical equation is a shorthand representation of a chemical reaction. By convention, reactants are placed on the left and products to the right of an arrow. Formulas are separated by addition signs (+). Coefficients are written before formulas to balance an equation, equalize the number of product and reactant atoms of each element. If two reactions occurring together give different products, then two separate equations should be shown. If no reaction occurs, then NR - standing for no reaction - should replace the products.

This is chemistry boys, this is chemistry where you learn to translate what you see into the magnificent hieroglyphics of the chemical equation.
Edward L. Haenisch, to students at a mens college

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Chemical Equations

Though an equation only needs to list reactant and product formulas, it is helpful to indicate phases and conditions - what you see - as part of the equation. Phase is shown by an abbreviation in parentheses following each formula. Solid, liquid and gaseous phases are (s), (l) and (g) respectively. Solutes in water solution are indicated by (aq), for aqueous. For example, 3 Cu(s) + 8 HNO3(aq) 3 Cu(NO3)2(aq) + 2 NO(g) + 4 H2O(l)
Predicting Reaction Products Equations take only a limited set of forms, differentiated by the number of reactants and products. Complex usually over two reactants or products Replacement two reactants, two products Combination two reactants, one product Decomposition one reactant, two products Rearrangement one reactant, one product

Replacement, the most common equation form, has two categories: substitution and metathesis. If part of a compound is replaced by another reactant, this is a substitution reaction. Active metals (aluminum, zinc, alkaline earth and alkali metals) replace others metals and hydrogen from their compounds. 2 Al(s) + Fe2O3(s) 2 Fe(l) + Al2O3(s) Nonmetals tend to replace other nonmetals in compounds. Cl2(aq) + 2 KBr(aq) Br2(aq) + 2 KCl(aq) If parts of two compounds switch, then the form of reaction is a metathesis or double replacement. CaCl2(aq) + Na2CO3(aq) CaCO3(s) + 2 NaCl(aq) The reaction type with one product and two reactants is termed addition, combination, or synthesis. CH2=CH2 + Br2 CH2BrCH2Br The reverse of a combination reaction is decomposition, which is the type of reaction done in Project D. Another classic example is: 2 HgO(s) 2 Hg(l) + O2(g) Reactions with one reactant and one product, will not be demonstrated in this project. If the reactant and product have the same molecular formula, the process is a rearrangement. CH3NC(l) CH3CN(l) If the product is a multiple or fraction of the reactant, the process is polymerization or depolymerization. x CH2=CH2 (CH2CH2)x
Evidence of a Chemical Reaction Though reactions in colorless solutions may occur with almost no apparent change, an observer can usually find one or more indications of reaction such as: Consumption 1. Gradual consumption of a solid, or immiscible liquid; 2. Decrease of gas volume or pressure in a closed container; Formation 3. Bubbling or fizzing (but not boiling); 4. Precipitation of an insoluble solid from solution (formation of cloudiness);

Chemical Equations

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Appearance 5. Color change, including emission of light; 6. Change in crystal appearance, or formation on the surface of a solid reactant of a new solid; Non-visual Senses 7. Release or consumption of heat (which may cause solvent evaporation, as well as simply warming or cooling the surroundings); 8. Change in odor during reaction; 9. Noise may come from strain in a solid or escape of a gas; Test 10. A liquid or gas can be tested for change of condition such as conductivity or acidity, for example moist red litmus test paper held in ammonia turns blue. SAFETY

Flames If you are about to light your Bunsen burner and someone near you is finishing off work on Project C, warn them so that they can move to a hood or separate counter. Nitric acid, HNO3, is a strong, oxidizing acid. At low concentrations it produces brownyellow patches of dead skin which peel off after several days. At high concentrations this is dangerously reactive. Flush skin or clothing immediately with water to dilute and rinse out the acid. Nitrogen oxide gases (NOx) are reactive and steps 1 and 2 must be done in the hood. Diphosphorus pentaoxide, P2O5, is a solid that reacts with water to generate considerable heat. Do not breath the dust. Flush any solid off your skin immediately with copious water. Calcium is a moderately active metal which can produce considerable heat and caustic products. Sodium carbonate, Na2CO3, is caustic. Flush from the skin with copious water.

PROCEDURE

Students are encouraged to start at different parts the project at different items. As you do each, place descriptions of reactants and products, and evidence of reaction in your notebook. You may work with one other student only on items 1 and 2.
1. A complex reaction Roll a few strands of copper shavings into a loose ball slightly larger than the mouth of an 18 x 155 mm test tube. Label a 150-mL beaker with your drawer number. Using hot tap water, nearly fill the beaker and completely fill an empty 18 x 155 mm test tube. Squeeze the ball of copper into the mouth in the tube without pushing it down the tube at all. With your thumb or a finger over the end, invert the tube and put it into the beaker until its mouth is entirely beneath the water surface, then remove your finger. Pour as much water as possible from the beaker without admitting air to the tube. (Tiny bubbles are no problem, but one filling the rounded portion of the tube is too big. Repeat this step if you get one.) Label the beaker uniquely with pencil, or note labeling marks already on it. When space is free, go to the hoods with your gas-collection setup and a 10 mL graduated cylinder. Add 10 mL concentrated nitric acid (17 M HNO3) to the beaker near the mouth of the tube. Observe the reaction carefully. Try to keep the copper at the mouth of the tube, where it makes contact with the nitric acid. Allow this reaction to continue until the tube is about half full of gas. Once you have made initial observations, you may leave the reaction in the hood and come back to it after sufficient reaction time. The reaction may be hastened by occasionally swirling the tube in

76

Chemical Equations the beaker, but keep the copper at the mouth of the tube, and the mouth below the liquid surface. If the reaction continues very slowly, you may add up to 10 mL more nitric acid. Describe the gas which collects in the tube (Note, it cannot be very soluble in water!). Save the whole set up for Part B. The chemical equation for this reaction is 3 Cu(s) + 8 HNO3(aq) 3 Cu(NO3)2(aq) + 2 NO(g) + 4 H2O(l)

2. Combination reaction I Using the setup left from part A and being sure not to allow the gas in the test tube to escape or air from the room to enter the test tube, remove any remaining copper from the mouth of the test tube, you may need to use your tongs. Lift the inverted test tube out of the water long enough to allow a volume of air equal to the volume of gas collected to flow into the tube. (If the tube was more than half full of gas produced in item 1, just let all water drain out of the tube.) The first reaction can be observed immediately. As soon as you put the mouth of the tube back under the surface of the water, note the water level in the tube. The second reaction happens as the product of the first reaction makes contact with the water along the walls of the tube. Note any changes in the gas in the tube. When finished, lift the test tube out of the reaction beaker. Hold the tube upside down over the plastic beaker and flush its outside surface with water to wash away all the acid solution. Invert the tube and fill it with water from the fume hood faucet. Place the contents of the reaction beaker including any remaining copper into the appropriate used materials container in the hood. Take your glassware to your sink to finish rinsing it. Air is principally N2 and O2. The first reaction involves one of these combining with the NO collected earlier. The product is gaseous nitrogen dioxide. The equation for the second reaction is complex; it has two reactants and two products, but cannot be understood as a replacement. (It is a redox reaction.)

3 NO2(g) + H2O(l) 2 HNO3(aq) + NO(g)


3. Combination reaction II Place 5 to 6 grams magnesium sulfate (dried Epsom salt) in a small beaker. This is about 5 cm on a large spatula, or enough to fill a 10x75 mm test tube. (Do not actually fill a test tube, just use it as a guide.) Add enough distilled water to wet the solid thoroughly, but not cover it, the product is also a solid not a solution. You may mix with a stirring rod. You may see a mixture of very small, translucent crystals of the heptahydrate, MgSO47H2O, or whiter, opaque solid of intermediate hydration. When you are finished with this part, place the product in the trash in a piece of paper towel or rinse down the drain with much water. 4. Combination reaction III Because diphosphorus pentaoxide is a dust, take a small, dry beaker and a dry stirring rod to the designated hood to conduct this reaction. Place roughly 2 grams diphosphorus pentaoxide in a beaker. (Refer to item 3 for a guide. It is okay if some gummy material comes with the powdery diphosphorus pentaoxide. You do not need to observe this separately as a reactant.) Add small portions of distilled water from an eyedropper or wash bottle, stirring after each addition. (The mist you may see is not a reaction product. It is some of the water you added, which has evaporated and recondensed. Since these are not chemical changes, this water is not shown in the chemical equation.) Continue until the solid has entirely dissolved. Test the solution with red and blue litmus paper. Discard the solution to the sink with tap water.

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77

5. Single replacement reaction I Add about 20 mL cold, distilled water to a 50-mL beaker. Place a small calcium turning in the water. Allow it to stand for observation as you start other items. If nothing happens, break the calcium with your spatula. Test the water with litmus or other pH indicator paper. When finished, pour the water down the sink, and place any remaining calcium in unwanted materials container in the hood. 6. Single replacement reaction II Obtain a 5-cm piece of magnesium ribbon. Scrape it with a microspatula to remove any dullgray or black film, leaving a shiny surface. Cut the piece into quarters. Use these in items 6 through 8. Support a 250 mL beaker half filled with distilled water using two iron rings as you did earlier in the semester, one beneath the wire gauze and one surrounding the beaker. Place the circular test tube rack in the beaker and heat the water to boiling. (This may be shared with other students in lab.) In three clean small test tubes, add about 1 mL of distilled water and 2 drops of indicator to each. (The solution color needs to be the same in all three. If it isnt, clean your test tubes again.) Place a piece of magnesium into two of them. Place the one without any magnesium and one with magnesium in the hot water bath leaving the third at room temperature for comparison. Compare the color of the two solutions after 5 minutes. Compare the reaction of magnesium with that of calcium (item 5). Discard the solutions. Retain remaining magnesium for item 8. 7. Single replacement reaction III To a small beaker, add enough 3 M hydrochloric acid to cover a piece of magnesium lying flat. To another beaker, add the same volume of 3 M acetic acid (HC2H3O2). Place a piece of magnesium ribbon in each of the two beakers. Compare reaction in the two acids. Which acid would you term strong? Write an equation for each acid. Flush product solutions down the sink with tap water; place any remaining metal in the appropriate used materials container in the hood. 8. Single replacement reaction IV Half-fill an 18 x 155 mm test tube with 0.1 M magnesium chloride (MgCl2). Add a small piece of zinc metal. Half-fill another 18 x 155 mm test tube with 0.1 M zinc chloride (ZnCl2). Add a piece of magnesium metal. After about 5 minutes, use your forceps to remove each piece of metal and wipe them with a paper towel. Write an equation for each part. Some samples of zinc chloride contain HCl as an impurity. In item 7 you saw evidence that HCl reacts with magnesium ribbon and wrote that equation. Do not repeat that here, look for evidence of a different reaction. Flush solutions left from part 8 into the sink; place any remaining metal in the appropriate container in the hood. 9. A metathesis reaction Combine equal volumes of 0.1 M magnesium chloride and 0.1 M sodium carbonate solutions in a 10 x 75 mm test tube. Mix well. You may flush the product mixture to the sink with tap water.

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Chemical Equations

If you are uncertain about any observation, or feel you missed something, you should repeat that item. If uncertain about a particular formula, ask nearby students or the lab instructor. Try to complete and balance equations before asking for assistance. EVALUATION To facilitate grading, you must prepare an additional notebook page on which you: write a balanced chemical equation for each reaction in the order of the manual. The phases of all reactants and products should be consistent with your observations. (If there is no evidence of reaction, write NR on the product side of the equation.); indicate evidence for each reaction using just the appropriate underlined words beginning on page 74; (If you use color, note the color change; if you use test, note the test and result.)

Original observations will be spot checked and graded. They are especially important when the evidence for reaction seems ambiguous or wrong. Without prompting you should have briefly described the solid reactants (calcium, copper, magnesium, diphosphorus pentaoxide, and magnesium sulfate) to support your evidence of reaction. This reaction summary page will be returned to you with missing or erroneous equations marked. You may return it to the instructor without changes; or you may add or rewrite the marked equations and resubmit the corrected summary page(s) with the marked originals. Your grade for the revised equations will replace the original grade without penalty. The summary page will not be returned a second time. Loss of credit for missing or erroneous observations cant be recovered.

Introduction to Titrimetry

79

Project K Introduction to Titrimetry


OBJECTIVE Prepare and standardize an aqueous solution of sodium hydroxide of approximately 0.l M. SKILLS REHEARSED AND CONCEPTS TESTED 1. Titration technique and buret use 2. Weighing by difference 3. Solution preparation from solid reagents 4. Solution standardization 5. Reporting a measured value with its uncertainty; Interpolation 3 TOPICS TO REVIEW 1. Titrimetry 2. Stoichiometry 3. Accuracy and precision 4. Uncertainty 5. Statistics; Interpolation 3 BACKGROUND Titrimetry is a laboratory technique used to determine the concentration of one solution (the analyte) based on its reaction with another solution having known concentration (the standard). The molar quantities of both solutions must be accurately known and are calculated from measured quantities of mass or volume depending on if the substances involved are solids or liquids respectively. Frequently both are liquids, in which case the analyte is normally measured with a pipet (see project B) and the standard is delivered from a buret (explained below).

During a titration, the titrant (the solution delivered from the buret) is added to the other solution until there is a rapid change in the solutions appearance, most commonly a color change, called the endpoint. If the titration is correctly set up, the endpoint will closely approximate the equivalence point, which is the point at which both reactants (analyte and standard) are limiting; i.e. neither is in excess. Only at this point in the reaction are the molar equivalents of both reactants the same; thus, in the following example, 1 mole of oxalic acid is equivalent to 2 moles of sodium hydroxide. Then the unknown concentration can be determined using this molar ratio, the measured volumes, and the one known concentration, see the example below. Titrations are frequently categorized based on their purpose as one of two types: standardization or analysis. Solutions of some substances, such as potassium hydrogen phthalate (KHP), can be prepared with a high degree of accuracy in their concentration. Those solutions can be used without standardization to analyze or standardize another substance/solution. Solutions of other substances, such as NaOH, cannot be easily prepared with an accurately known concentration and thus must be standardized against something that can, such as KHP, before they are used in a titration. Information obtained from titrations is not very valuable if there is a large amount of uncertainty in the concentration of the standard. A titration is normally carried out using a buret; a long, narrow tube with volume markings along most of its length. It is a very good tool for measuring varied volumes with a high degree of accuracy and precision. The volume markings begin with 0 at the top and increase down its length. Double check your buret volume readings until you get used to the larger readings being lower on the buret. The volume in any piece of glassware (including a buret) should always be read at the bottom of the meniscus, the curved surface an aqueous solution. Always read the buret with your eye at the same level as the meniscus, Figure 28, otherwise the reading will be inaccurate, increasing the uncertainty in your results. The mark closest to the meniscus should look like a line; those further above or below the meniscus will appear as ovals. Read the buret volume to

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Introduction to Titrimetry

Example What is the concentration of a NaOH solution if 43.61 mL of that solution was required to titrate 2.1537 g of oxalic acid to a phenolphthalein endpoint? Plan Step 1. Make sure you understand the stoichiometry of the chemical reaction. Step 2. Determine the number of moles of oxalic acid used. Step 3. Use the mole-to-mole ratio to find the equivalent moles of the analyte, sodium hydroxide. Step 4. Determine the concentration of the analyte solution. Solution Step 1 2 Calculation

H2C2O4(aq) + 2NaOH(aq) 2NaC2O4(aq) + 2H2O(l)


1 mole H 2C 2 O 4 2.1537 g H 2C 2 O 4 90.035 g H C O 2 2 4 = 0.02392 moles H 2C 2 O 4 = 0.04784 moles NaOH

2 moles NaOH 0.02392 moles H 2C 2 O 4 1 mole H C O 2 2 4


0.04784 moles NaOH = 1.097 M NaOH 0.04361 L NaOH

the nearest 1/10th of a mark (0.01 mL) by interpolating between the smallest marks on the buret, Figure 29. This requires a good eye and benefits from the use of a buret reading card. Place the card so the upper edge of the dark stripe just touches the bottom of the meniscus. It will help guide your eye to the marks on the buret and help you accurately interpolate the distance between the two closest marks.

Practically speaking, for an efficient titration you must control the stopcock (the valve at the bottom of the buret) and swirl the flask at the same time. This is accomplished most effectively by using your dominant hand to swirl the flask and your other hand to operate the stopcock. This will probably seem awkward at first (many new things are) but with a little practice, this method will work well. Any drops remaining on the tip of the buret or on the inside wall of the flask must be rinsed into the solution in the flask. Failure to do so will increase the uncertainty in your calculations.
5

0 1 2 3 4

Figure 28 Proper eye position when reading a buret

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81

Figure 29 Appearance of each 1/100th mL buret volume

The data and observations collected from titrations should be recorded in a table similar to the example in Figure 30. It is a good idea to leave space following the table so that it can be expanded if more than the expected number of titrations become necessary.
Titration type: acid/base, redox, etc.

Analyte

Standard

The indicator: phenolphthalein, methyl red etc

titration of Run # 1 2 3 4 KHP mass (g) 0.792 0.673 0.725 Final Buret Reading (mL) 29.06 30.02 Initial Buret Reading (mL) 0.77 1.38

with Volume of NaOH Delivered (mL) 28.29 29.64

to a

endpoint.

Notes 1 drop HCl to reverse color 4 drops HCl to reverse color, over shot!

Result

Calculated analyte concentration with appropriate units: %, molarity, ppm, etc.

Figure 30 Example titration data table

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Introduction to Titrimetry

Standard Preparation of a Buret Pour out the water (if any) left in the buret during storage. Rinse the buret 3 times with ~5 mL portions of the titrant. o Each time, turn the buret nearly horizontal and rotate it to rinse the inside entirely. o Collect the rinses if necessary for proper disposal. Return the buret to the buret clamp. o Be sure it is seated properly in the buret clamp so that it is secure and vertical. Fill the buret to near the 0 mark with titrant. Open the stopcock wide open for 1-2 seconds to remove any air from the buret tip. o If an air bubble leaves the tip of the buret during a titration, that individual titration must be discarded. Refill the buret if necessary so that the volume is between 0 and 2 mL. o Do not attempt to fill the buret to a specific volume such as 0.00 mL it will increase the uncertainty in your results. Just fill it to between 0 and 2 mL and then read what the buret volume is. Weighing by difference can be done one of two ways: additively or subtractively. When weighing by difference in the additive manor, a container is first weighed empty and then weighed a second time after the material of interest has been added. The difference between the two masses is the mass of the material of interest (used in projects D and E). When weighing by difference in the subtractive sense, a container and its contents are weighed together, then a portion of the contents are removed and then the container and remaining contents are reweighed. The difference in these two masses is the mass delivered. Advantages to weighing by difference include (particularly for this experiment): better precision because the weighing flask is much lighter than the Erlenmeyer flask less bias and better precision because the weighing bottle is reliably dry, while the Erlenmeyer flasks are frequently damp and subject to variation in mass due to evaporation of water less risk of contamination of the balance fewer overall weighings when multiple sample portions are needed because the final mass for the first portion is the initial mass for portion two and so on an internal check on all but the first mass readings because any mistake will produce an error in the results of two consecutive sample portions Potassium hydrogen phthalate (KHP) is a potassium salt of the diprotic acid phthalic 2 acid. The P in KHP stand for phthalate, C8H4O4 , which dominates the product side of the equation show below. In KHP, one of the two acidic protons from phthalic acid has been replaced by a potassium ion, leaving just one acidic proton. Since KHP still has one acidic proton, it will still react with bases such as NaOH. This reaction results in the formation of a salt, KNaP, and water according to the following equation. The sodium and potassium ions are bystander ions.
H H C C H C H C C C C
(aq)

O C O OH K H C

H C C C C H

O C O O C O Na
(aq)

aci

NaOH(aq)
dic pro t
H

H2O(l)

on

Introduction to Titrimetry

83

SAFETY

Solid sodium hydroxide is extremely caustic, avoid contact with skin. In event of skin contact, rinse with water immediately until the skin no longer feels slick. Aqueous sodium hydroxide is also caustic. Skin contact should also be avoided and rinsed with water immediately until the skin no longer feels slick. The phenolphthalein solution is flammable because it contains alcohol.

PROCEDURE 1. Preparation of a ~0.1 M aqueous NaOH solution Here you will prepare your NaOH solution from solid NaOH and distilled water. Ideally the solution concentration will be between 0.12 and 0.10 M. Obtain one 500 mL plastic bottle from the stockroom. It needs a proper label because it will be filled with your NaOH solution outside of the time you are using it in lab. Using labeling tape, label it with its contents 0.1 M aqueous sodium hydroxide, pertinent safety information caustic, the date and your name. Labeling the contents as 0.1 M NaOH is not acceptable. Using a mechanical balance, TECHNIQUE Project D, measure out enough solid NaOH into a disposable weighing boat necessary to prepare 500 mL of an approximately 0.1 M solution of NaOH. (Calculate this mass prior to coming to lab and record the calculation and result in your one page project summary). Transfer this NaOH to your 500 mL bottle and add about 50 mL of distilled water. Swirl the water briefly then hold your hand on the bottom of the bottle. It may feel slightly warm. The dissolution of sufficient quantities of some chemicals, such as NaOH, are noticeably exothermic (heat releasing). Finish filling the bottle with distilled water until the solution level reaches the top of the side of the bottle. Dont fill the curved upper portion of the bottle or its neck. Place the lid on the bottle and invert it 5-7 times to aid in the complete dissolution of the solid NaOH. 2. Prepare to standardize your NaOH(aq) solution The concentration of your NaOH, as prepared, is only approximately 0.1 M. Its concentration needs to be known with much greater accuracy so that it can be used effectively when titrating a weak acid sample in Project N at the end of the semester. Obtain two additional 250 mL Erlenmeyer flasks (you have one in your drawer) and one small bottle of KHP from the stockroom. Label your three 250 mL Erlenmeyer flasks 1, 2 and 3. Using an electronic balance, weigh by difference 0.6-0.8 grams of KHP to the nearest 0.001 grams into each flask. The mass of KHP delivered to each of the 3 flasks does not need to be the same; they just need to each be between 0.6 and 0.8 grams. (Remember to take your notebook with you to the balance.) Add approximately 75 mL of distilled water to each flask to dissolve the KHP and 3 drops of the phenolphthalein indicator solution. (For measurement of the water volume, the marks on the side of the Erlenmeyer flasks are sufficient because the water is not a reactant). Using the approximate molarity of your NaOH, calculate the volume of NaOH solution that will be needed to titrate the amount of KHP in your first flask. This is the approximate ( ~5 mL) volume your titration should require. Check to see that all of the solid NaOH in your 500 mL bottle has dissolved and invert the bottle several times again to ensure that the solution is homogeneous (evenly mixed). Prepare your buret. (see the background information on page 81)

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3. Begin titrating Record the initial buret volume and begin titrating: first rapidly add about 90% of the titrant volume just calculated for this flask and then slow to a drop-wise addition until the faint-pink phenolphthalein endpoint is reached and persists after 30 seconds of swirling. Record the final buret volume. Check your endpoint by drop-wise addition of 0.1 M HCl. The endpoint is good only if the solution becomes colorless again after the addition of 1 or 2 drops. If more than 2 drops of 0.1 M HCl are needed then you have overshot the endpoint. Record the number of drops of HCl needed and, if more than 2, overshot in the results column of your titration data table. (The titration is only a success if the endpoint is good. Data from unsuccessful titrations should not be used.) Calculate the molarity of your NaOH solution based on the result of your titration (not the theoretical volumes), it should be between 0.08 and 0.12 M. If not, check with your instructor. Repeat the titration process until you have 3 successful titrations. (If you wish to calculate the volume of titrant needed for these subsequent titration, use your new molarity value from the first titration.) Check the quality of your titrations by comparing the NaOH molarities calculated from each titration. You may do additional titrations as time permits. (You will need to weigh out additional portions of KHP. An Erlenmeyer flask needs to be rinsed but not dry before reusing it. DONT USE MORE THAN HALF OF YOUR NaOH SOLUTION, YOULL NEED HALF FOR THE LAST PROJECT THIS SEMESTER.) 4. Clean up If youve not done so already, calculate the NaOH molarity for each titration, then calculate the average and standard deviation of the NaOH molarity based on all your successful titrations. (See page 13 in your lab manual for a review of how to calculate and report a standard deviation.) Modify the label on your NaOH bottle to show this new, more accurate NaOH molarity. Store it in the location designated by your lab instructor. When you are satisfied with the results of your titrations, drain your buret, rinse it three times with distilled water and place it upside down back in the buret stand to dry. Rinse your Erlenmeyer flasks and other glassware before returning them to the stockroom or your lab drawer respectively. These solutions are OK to be sewer disposed. Return your KHP bottle and any unused KHP to the stockroom. POST LAB QUESTIONS 1. What is the balanced, net ionic equation for the reaction between KHP and NaOH? 2. Indicate if the calculated NaOH molarity will increase, decrease or be unaffected by each of the following observations. a. An air bubble left the tip of your buret during the titration. b. When dispensing some KHP into an Erlenmeyer flask, you didnt see that a small portion of it fell outside the flask. c. After you reached the endpoint, you forgot to rinse the drop off the tip of your buret into the Erlenmeyer flask. d. There were some water droplets inside the Erlenmeyer flask to which you added your KHP. 3. How would reading the buret to only one decimal place affect the accuracy of your results? the precision? EVALUATION Credit is based on your recorded observations, calculations and the precision of your NaOH molarity. The quality of your work here will also affect your grade on the last project this semester.

Nomenclature

85

Interpolation 6 Nomenclature
Elements A periodic table is handy only if you know the symbol-name correspondences for the common elements, and know roughly where to look on the table for each element. A reasonable goal is to know the elements with atomic numbers 1 through 36, plus: 42(Mo), 47(Ag), 48(Cd), 50(Sn), 53(I), 54(Xe), 55(Cs), 56(Ba), 78(Pt), 79(Au), 80(Hg), 82(Pb), and 92(U). These are listed inside the cover of virtually every general chemistry text.

A step line on the periodic table running between boron and aluminum, aluminum and silicon, and so on, is a recognized boundary between metals - to the left and below the line - and nonmetals above and to the right. In compounds metal atoms tend occur as positive ions, called cations; nonmetal atoms occur in groups of one to several atoms as negative ions, anions.
Salts Salts are ionic compounds composed of cationic (metal or ammonium ion) and anionic parts, with zero total charge. In writing formulas for compounds, or giving names in English, cation are listed before anions. In formulas ion charges are generally omitted, since their values are implied by the formula.

The numbers of cations and anions in an ionic formula are those which produce the lowest common multiple of cation charge and anion charge. Because of this, ionic compounds are fully identified from just the names of their cation and anion. the lowest common multiple of 1 and 2 is 2; the formula of cesium sulfate, the compound of Cs+ and SO2 , is Cs2SO4. 4 the lowest common multiple of 2 and 2 is 2; the formula of zinc sulfate, the compound of Zn2+ and SO2 , is ZnSO4. 4 the lowest common multiple of 2 and 3 is 6; the formula of chromium(III) sulfate, the compound of Cr3+ and SO2 , is Cr2(SO4)3. 4
Cations If there is no ambiguity, the names of metal cations are simply the names of the elements. You need to know the important cations with consistent charge. Ammonium (NH4+), silver (Ag+), and the metals of group 1 (IA; especially Li+, Na+, K+, Cs+) have an ion charge of 1+. Zinc (Zn2+) and the metals of group 2 (IIA; especially Mg2+, Ca2+, and Ba2+) have an ion charge of 2+. The aluminum cation (Al3+), has a charge of 3+.

Other metals occur in different charge states. Their ion names must include the charge, shown as a Roman numeral written after the element name without a space. For example, Ti3+ is the titanium(III) cation, and TiO2 is titanium(IV) oxide. (Cation names ending in -ous and -ic, e.g. titanous, are no longer accepted, but may still be seen. You are not responsible for these.)
Anions Anions of one nonmetal atom (monoatomic anions) are named with the stem of the element and an -ide ending, e.g. iodide. The ion charge is the new group number minus 18, or the old group number minus 8. For iodide, this is 1718= 1. CsI is named cesium iodide. Oxoanions, anions in which a central element is surrounded by oxygen, are named with the stem of the element, followed by an -ate or -ite suffix, which indirectly indicates the number of oxygens in the formula. For BO3 CO2 NO3 3 3 an -ate anion, the number of oxygen atoms is three for elements in the second period and halogen family, and SiO4 PO3 SO2 ClO3 4 4 4 four for the rest of the nonmetals.

Except for oxoanions with a central atom from the top row of Figure 31 (the first full period), the oxoanion charges are the new group number minus 18, the same as the monoatomic anion charges of the same element. The charges of oxoanions of the

AsO3 4

SeO2 4

BrO3

TeO3 4

IO3 3

Figure 31 Formulas for oxoanions named as -ates

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Nomenclature

second-period elements are the new group number minus 16. The charge on sulfate predicted by this pattern is 1618 = 2. Examples of sulfate salts are named above.
Other Oxoanions The anions in Table 4-1 are important because most occur commonly, and they are a basis for naming related ions. Early transition metals, especially those of group 6, have oxoanions analogous to those of the group ten higher; chromate and molybdate are CrO2 and 4 MoO2 respectively, analogous to sulfate. 4

Anions with the same nonmetal and charge as those in Figure 4.1, but having one less oxygen, use an -ite ending on the element stem. Thus nitrite is NO2 . Anions with two less oxygens than an -ate anion add a hypo- prefix as well as the -ite suffix, e.g. hypochlorite, ClO. Halogens, Group 17, (and the manganese group, Group 7) add a per- prefix to the -ate names to indicate the monoanion with four oxygens. Periodate is IO4 .
Acids The neutral compounds of these anions with hydrogen are molecular. Naming them in the pattern of ionic compounds, e.g. hydrogen sulfide for H2S and hydrogen phosphate for H3PO4, works fine except that such names cannot be used for their water solutions! The compounds of oxoanions with hydrogen are all acidic in water, and must be named as "acids," replacing -ate with an -ic ending, and -ite with -ous. The name of H2SO4, sulfuric acid, is irregular because -ur- is added to the anion stem. Examples of the pattern are: HClO4, perchloric acid; H3BO3, boric acid; HNO2, nitrous acid; and HIO, hypoiodous acid.

Other than carbonic acid and carbonate, carbon based acids and salts have a separate naming pattern. The most common organic acid is acetic acid (ethanoic acid), HC2H3O2. The most common (and smallest) organic diacid is oxalic acid (ethanedioic acid), H2C2O4. You must know the corresponding anions: acetate, C2H3O2 , and oxalate, C2O2 . 4
Binary Nonmetal Hydrogen Compounds The hydrides of group 16 and 17 elements are acidic in water. Their names in solution are formed by adding a hydro- prefix and -ic suffix to the stem of the element name. HBr is hydrobromic acid and H2Se is hydroselenic acid, for example. The compounds of hydrogen with elements of groups 13, 14, and 15 are neutral or basic; their naming is different again. The two substances you must know are methane, CH4, and ammonia, NH3. A water solution of ammonia is basic; it is named and written either as aqueous ammonia, NH3, or as ammonium hydroxide, NH4OH. Acid Salts Acids with two or three hydrogens can form compounds - acid salts - by replacing only one or two hydrogens with a cation. Order in the name is cation, hydrogen, then anion. Americans often put a space between hydrogen and the anion name; the rest of the world does not. NaHCO3 is sodium hydrogencarbonate or sodium hydrogen carbonate. Archaic names abound as well. Only "bicarbonate" for HCO3 is common enough that you should recognize it; the safety bottle in lab for acid spills contains NaHCO3. Irregular Anions You must know hydroxide, OH (hydrogenoxide is never used). The name for another ion you will use, SCN, thiocyanate, is derived from the irregular name cyanide, CN, by substituting an -ate ending suggesting oxygen (cyanate is OCN) and adding a thio- prefix to indicate that sulfur has replaced the oxygen. PRACTICE PROBLEMS Name. Co Answers
cobalt

P3-

Hg2+ 2
mercury(I) cation

HC2H3O2
acetic acid

BaCO3
barium carbonate

phosphide anion

Give the formula. arsenic calcium ion Answers As

hydrochloric acid sodium phosphate iron(III) hydroxide


Ca2+ HCl(aq) NaPO4 Fe(OH)3

Ionic Equations

87

Interpolation 7 Ionic Equations


Metathesis The most common, and most easily predictable, form of reaction in water is metathesis, also called double replacement or double displacement. It requires that both reactants be compounds which split into positive and negative fragments.

FeCl3(aq) + 3 NaOH(aq) Fe(OH)3(s) + 3 NaCl(aq) Fe3+(aq) + 3 Cl(aq) + 3 Na+(aq) + 3 OH(aq) Fe(OH)3(s) + 3 Na+(aq) + 3 Cl(aq) Fe3+(aq) +3 OH(aq) Fe(OH)3(s) The cations iron and sodium in this example replace each other, becoming paired with the other anion. There is an exchange of cations (or anions). Once the possibility of a reaction of this form is recognized, it leads directly to prediction of potential products. Such products will not actually form unless there is some driving tendency favoring them.

(1) (2) (3)

Driving Tendencies for Metathesis Prediction of metathesis reactions involves two steps. First you predict the formulas of the potential products of double replacement of cations and anions. Second you look for a tendency for the reaction to occur as written, to form these products. A reaction is expected if ions are brought together more in the products than in the reactants. The two common ways to come together are to form: (1) insoluble salts (precipitates), and (2) weak electrolytes. The weak electrolytes you need to recognize are water, weak acids and weak bases. ("The reaction of an acid with a base produces a salt and water." is a part of this.) Some weak electrolytes come out of solution as gases, increasing the tendency to produce this product. After studying the solubility rules, weak electrolytes, and gases sections below, you should recognize examples of reactions with each driving tendency. The more information you recall from these sections, the more reasonable reaction chemistry will seem. Ionic Equations Salts, strong acids, and strong bases dissociate into separate ions as they dissolve in water. The electrical conductivity of such solutions (suggested by the term electrolyte) demonstrates the presence of ions. In an ionic equation such ions are shown separately. Net ionic equations (e.g. 3 above) include only those species which associate or dissociate during reaction, which change their surroundings. Complete ionic equations show all ions, including "spectator ions," counterions to those reacting. The driving tendencies for metathesis can be seen as effects which bring ions together in a new pairing. Ionic equations, such as 2 and 3 above, and

Ag+(aq) + C2H3O2 (aq) + H+(aq) + Br(aq) AgBr(s) + HC2H3O2(aq),

suggest the effects clearly by showing insoluble salts and weak electrolytes as neutral compounds, and soluble salts and strong electrolytes as separate ions.
Solubility Rules If a precipitate forms from a solution in which the concentrations of solute ions are each 0.05 M, the solid is said to be "insoluble". Expect ionic substances to be insoluble if the charges of both the cation and anion are two or greater. Some exceptions to this pattern are quite important to chemical analysis, and worth memorizing. Many other solubilities can be looked up quickly and qualitatively, as in the solubility matrix at the end of this interpolation. Quantitative solubilities can be found in the literature if required for particular application.

Acids (with H+) and salts of ammonium (NH4+) or any ion of group 1A (Li+, Na+, K+, Rb+ and Cs+) are soluble. These are termed monocations because their charge is 1+. The only other common monocation is Ag+. Its insolubility with halides and related species (Cl, Br, I and SCN) is particularly useful in identifying the presence of these colorless ions in a solution. Monoanions (charge 1) which are soluble with virtually all cations include: acetate (C2H3O ), 2 chlorate (ClO ), nitrate (NO ), nitrite (NO ), and perchlorate (ClO ). Salts of hydroxide (OH) are 3 3 2 4 insoluble, except those with the Group 1 metals, barium, strontium, calcium (borderline), and

88

Ionic Equations

ammonium. (In its solubility, hydroxide behaves as if it were oxide. Consistent with this, some metal hydroxides cannot be isolated since they decompose to metal oxide and water readily.) Sulfate is another important exception to the pattern; most of its compounds are soluble. The insoluble sulfates are salts with barium, strontium and lead ions. Sulfate salts with borderline solubility include calcium sulfate and silver sulfate.
Weak Electrolytes Weaker acids and bases are formed from stronger ones. Thus "strong" acids will react with any base; "strong" bases will react with any acid. The important strong acids and bases are listed in Table 2. Weak acids or bases react if the product is water. Common Strong Acids HCl HClO4 HClO3 HBr HI H2SO4 HNO3
Table 2

Common Strong Bases LiOH NaOH KOH Sr(OH)2 SrO CsOH Ba(OH)2 BaO

Strong acids and bases

Gases The tendency to form a weak acid or weak base is increased if the product decomposes to a gas. The gas is most apparent if a strong acid is added to a solid containing one of these anions. The most important examples are: 2 H+(aq) + CO2 (aq) H2CO3 H2O(l) + CO2(g) 3 2 2 H+(aq) + SO3 (aq) H2SO3 H2O(l) + SO2(g) 3 H+(aq) + 3 NO (aq) 3 HNO2 H2O(l) + H+(aq) +NO (g) + 2 NO(g) 2 3 NH4+(aq) + OH(aq) NH4OH H2O(l) + NH3(g) Dangerous examples, because the gases are highly poisonous, are: 2 H+(aq) + S2(aq) H2S(g) and H+(aq) + CN(aq) HCN(g). Ba2+ BrCO2 3 ClCrO2 4 FOHI2 C2O4 SO
2 4

Ca2+ S A S S I B S A B S A S

Co2+ S A S A S A S A S I A S

Cu2+ S A* S A* S A

Fe2+ S A S

Pb2+ B A B A A A I A I A A I

Mg2+ S A S S I A S A S A B S

Hg2+ 2 I A I A d A I I A I I

Ni2+ S A S A S A S A S I A S

Ag+ I A I A S A I A B A A I

Zn2+ S A S A S A S A S A B S

S A S A B S S A I S A S

A S I A

A A S A S A A S

S SO2 3

2-

SCN-

S=soluble, B=borderline soluble, A=insoluble in water but soluble in acidic solution, I=insoluble in water or acid, d=decomposes in water to an insoluble product.
*

The solid is a double salt containing CuO. The solid is an oxide rather than the matrix salt. The salt cannot be made because the cation and anion react with one another.

+ Note that salts of the ions Na+, K+, Cs+, NH4 , acetate, chlorate, nitrate, nitrite, and perchlorate are all expected to be soluble and so are not listed in the table.

Table 3

Solubilitys of Salts in Water near Room Temperature

Qualitative Anion Analysis

89

Project L Qualitative Anion Analysis


OBJECTIVE

Use reactions of some anions to identify the anion in unknown salts, and represent the reactions as ionic equations.
SKILLS REHEARSED 1. Conversion of chemical formulas to names and vice versa. 2. Practice with solubility rules. 3. Mixing in a test tube. 4. Writing ionic equations to match reaction observations. 5. Identifying a substance from a set of chemical tests. 6. Use of knowns to increase (qualitative) analytical accuracy. 7. Use of a water bath. NOMENCLATURE PROFICIENCY AND IONIC EQUATION PREPARATION

In this project you investigate characteristic solution reactions of ionic substances. You need to be able to name simple ionic substances, so that you can reliably find reagents, and interpret test results. Study nomenclature in your text and in Interpolation 6. There will be a pre-lab test of basic inorganic nomenclature. You will be asked the formula or name of 20 substances or ions, given the name or formula. The test will concentrate on formulas from this project. For safety the lab instructor will exclude you from lab work on this project until you can demonstrate at least 70% proficiency on this test. Study Interpolation 7 and your text before lab to prepare yourself for writing ionic equations for each reaction of this project (listed at the end).
BACKGROUND

The chemical properties of a substance are the reactions which produce and consume (or, if inert, dont consume) the substance. As noted in Project C, chemical properties show such variety that, taken together, they identify a substance. You will identify which anions are present on the basis of these chemical properties.
Anion Analysis You will get four tubes, each containing a single, solid salt. There are few anions for which a single test serves as an unambiguous identification. Even if there were such test, testing each salt for each of the many common anions would be too tedious. It is better to use a preliminary reaction to classify anions into groups, then do tests to differentiate anions in each group. By the scheme of Figure 3, anions are classified as: insoluble with silver ions insoluble with barium ions or generally soluble.

Because of the nature of the work, you will NOT follow the laboratory instructions linearly, from step 1 to step 2 and so on. (You cannot set up a data/observation table before lab!) Each salt will be tested first for its group, then identified. Tube A contains a silver precipitator: chloride, iodide, or thiocyanate. Tube B has a barium precipitator: carbonate, oxalate, phosphate, or sulfate. Tubes C and D contain any one of these anions or acetate. You are to identify each anion, starting from the top of the following Anion Analysis Scheme.

90

Qualitative Anion Analysis

Soluble ions (in solution) C2H3O2

Insoluble ions (precipitate) SCN SO4


2

CO3

C2O4

Cl I PO4

Part 1 silver precipitator ions

Add AgNO3 C2H3O2

SO4

CO3 Add HNO3

C2O4

Cl I PO4

SCN

C2H3O2

CO3

C2O4

PO4

SO4

Cl I SCN ion specific tests for silver precipitator ions

A fresh portion of solution C2H3O2

Part 2 barium precipitator ions

CO3

C2O4

Cl I PO4

SCN SO4

Add BaCl2 C2H3O


2

CO3

C2O4

PO4

SO4

Cl I SCN Ion specific tests for barium precipitator ions

Part 3 - on specific test for acetate


Figure 32 Anion Analysis Scheme

Colors of Silver Precipitates The color of the precipitate formed upon addition of silver ions to an anion solution gives some indication of the anion. A brown precipitate of silver oxide may form in a strongly basic solution, such as that of carbonate, especially if heated. Silver iodide and silver phosphate are yellow. The other anions do not precipitate or give white precipitates with silver (AgCl, AgSCN, Ag2C2O4, Ag2SO3, Ag2SO4) if they form. Avoiding Contamination Before analysis, clean all test tubes with a brush and soapy water. Rinse the tubes with tap water until no soap is apparent (up to seven times), then three times with distilled water. Tubes need not be dry. Avoid contaminating your solutions or solids by cleaning your spatula or dropper just before transferring it to each new solid or solution. Knowns You are strongly advised to test known samples of anions for comparison with your results. On the counter in the lab there are reagent bottles with salts of each anion. You are responsible for confirming your analysis with these knowns. This approach is critical to analytical quality control. International and U.S. consumers are increasingly demanding better quality control in manufacture and analysis. Quality control in drug and environmental analyses is essential to the legal and ethical application of the results. No analytical procedure or set of instructions can be free from potential misinterpretation. While improvements in these are constantly sought, the responsibility for the result is the analysts.

Qualitative Anion Analysis


SAFETY

91

Concentrated sulfuric acid is extremely dangerous. It is an acid, dehydrating agent, and oxidizing agent. It must not contact skin. If it does, flush immediately with copious tap water. Clean up all drips carefully with bicarbonate, water, and paper towel before they have a chance to cause burns. Nitric acid is a strong acid and strong oxidizing agent. If contact occurs, flush the skin immediately with copious tap water. Treat spills with bicarbonate and then wipe up. Hydrogen peroxide is a strong oxidizing agent, and will chemically burn the skin rather rapidly. Flush immediately with copious tap water. Anions may be caustic, causing skin to feel slippery. Flush skin with copious tap water. To protect your hands and glassware, wipe contamination from glass surfaces with a wet towel. Silver ion binds to components in skin and is converted to silver by light, producing temporary black patches of skin. Record the identification code on the set of four anion sample tubes you received from your instructor. Each tube should have the same number and a different letter, A through D. Assume the cation is sodium for all these salts. To set up a hot water bath, place a 250-mL beaker containing about 175 mL distilled water on a wire gauze supported on a ring stand above your burner. Warm the water to about 60C, that is until the beaker is almost too hot to hold for an extended period. Place the circular test tube rack from your drawer into the beaker. (If it does not fit, use your 400-mL beaker and more water.) Label four 10 x 75 mm test tubes with A through D. In each, prepare a dilute solution of the corresponding salt by dissolving two centigrams (2 cg; 0.02 g) of salt in one mL of distilled water. (Two cg is a volume roughly equivalent to a large drop of water; it should not be weighed. One milliliter is about 20 drops water and does not need to be measured in a graduated cylinder.) If your solid has not completely dissolved, do the following in order: Make sure the solution in the small test tube has been well mixed (see Project A mixing in a testtube). Up to five minutes is not unreasonable. Add a few more drops water and mix to complete dissolution. Discard the mixture, clean your glassware with soap and rinse, and check that the water used is distilled.

PROCEDURE

Notes on Progressing Through Parts 1 through 3


Do all appropriate tests on one salt before starting another. Start testing a salt solution by adding silver nitrate and nitric acid (part 1). Anions from the silver precipitator group form precipitates which remain insoluble after mixing with nitric acid. If you have one, conduct the specific ion tests (parts 1a, 1b, and 1c) in any order until you get a positive identification. Only if the anion is not in the silver precipitator group should you add barium chloride solution to a fresh portion of your salt solution. Precipitation (part 2) indicates an ion of the barium precipitator group. Identify which anion in this group from specific ion tests for the group (parts 2a, 2b, 2c, and 2d), which can be one in any order until you get a positive test for one anion. Only if the anion is in neither silver- nor barium-precipitator groups should you do part 3, the confirmation test for acetate. People unfamiliar with the tests occasionally misinterpret the results, especially if mixing technique is poor. If you finish your four identifications before the end of the period, or if you feel unsure about a particular test, you should run the same tests on the known sodium salts supplied in

92

Qualitative Anion Analysis

the lab. Alternatively, you may try other specific tests on your salt, though this helps little if your group identification is wrong.
1. Testing for an anion of the silver precipitator group. Place two drops of dilute salt solution in a small test tube. Add 10 drops water and one drop 0.1 M silver nitrate. If there is precipitation, observe the color, then add two to four drops 3 M nitric acid, with vigorous mixing after each drop. If the precipitate mostly/completely dissolves, discard the sample and go to part 2. If most of the precipitate remains, one of the silver precipitator anions is indicated; save the mixture and go to part 1a. 1a. Chloride Test To the precipitate formed in step 1, add 7.5 M aqueous ammonia (ammonium hydroxide) dropwise with vigorous mixing after each drop. The first drops react with nitric acid.

NH3(aq) + H+(aq) NH4

(aq).

Carefully observe the quantity of precipitate. If chloride is present, the precipitate should dissolve easily, in two to four drops. The equation for the dissolution involves dissociation of silver and chloride ions and combination of silver ion with ammonia: AgCl(s) + 2 NH3(aq) Ag(NH3)2
+

(aq)

+ Cl (aq)

Other insoluble silver salts may also dissolve, but remain cloudy or require more aqueous ammonia. (If the nitric acid addition of Item 4 were omitted, most silver precipitates would dissolve upon adding ammonia.)
1b. Thiocyanate Test To one drop of a fresh portion of salt solution add five drops water, one drop 3 M hydrochloric acid, and one drop of 0.5 M iron(III) chloride. An extremely intense, blood-red color, due to Fe(SCN)2+(aq), indicates thiocyanate. (Iodide may give a red-orange color, but it is much less intense; use knowns for comparison.) 1c. Iodide Test To three drops of a fresh portion of salt solution add a drop of 3 M hydrochloric acid, then a drop or two of dilute bleach (sodium hypochlorite, 0.1 M NaClO). Mix thoroughly. The redbrown solution color of triiodide, formed by the reaction

3 I(aq) + H+(aq) + HClO(aq) I3

(aq)

+ H2O(l) + Cl (aq)

or the presence of solid, black iodine, I2, indicates iodide. If a brown color forms, but is rapidly consumed, repeat with more anion or less bleach. Fading happens if excess NaClO converts the iodine to colorless iodate. If the color is faint, you can add a drop of starch solution. Starch and triiodide make a complex (which has no definite formula) which has an intense blue-black color.
2. Testing for an anion of the barium precipitator group. Place four drops of dilute salt solution in a small test tube. Add two drops of 0.2 M barium chloride. Mix well, observe and save any precipitate for part 2a. If there is no precipitate, go to part 3. Otherwise do specific anion tests 2a through 2d as necessary to identify the anion present in the salt. 2a. Sulfate Test To the mixture saved from part 2, add five drops each of water and 3 M hydrochloric acid. Mix well. The sulfate is the only barium salt which remains insoluble in strongly acidic solution. Lack of dissolving confirms sulfate.

Qualitative Anion Analysis


2b. Phosphate Test To five drops of fresh salt solution add five drops of 3 M nitric acid and four drops acidified ammonium molybdate solution, (NH4)2MoO4 (0.3 M in molybdate), then mix thoroughly. Place the tube in a hot water bath for two to five minutes. Formation of a yellow molybdophosphate precipitate of (NH4)3PO4(MoO3)12 indicates phosphate. The net ionic equation for the precipitation is

93

3NH4

(aq)

+ H3PO4(aq) + 12 MoO4 (aq) + 21 H+(aq) (NH4)3 PO4(MoO3)12(s) + 12 H2O(l)

2c. Oxalate Test To two drops of a fresh portion of salt solution add one drop 6 M acetic acid and one drop 0.2 M calcium chloride. (If oxalate is present, a precipitate will form, but this is not the confirmation test. Acetic acid is omitted from the equation; it does not react; it just prevents misleading reaction of other ions.) Add five drops of 3 M sulfuric acid. An ionic equation for the reaction is

CaC2O4(s) + H+(aq) + HSO4 (aq) H2C2O4(aq) + CaSO4(s) Since a precipitate may be produced as another is consumed, the change is hard to observe. This reaction has two driving tendencies: formation of borderline insoluble calcium sulfate and formation of a weak acid, oxalic acid, from a strong acid, sulfuric acid. Add one drop of 0.02 M potassium permanganate, KMnO4. The intense purple color is due to permanganate. This is consumed by oxalate, but the reaction may take a couple minutes to start. The combination of initial precipitation and decoloration confirms the presence of oxalate. 5 H2C2O4(aq) + 6 H+ + 2 MnO4

(aq)

10 CO2(g) + 8 H2O + 2 Mn2+

2d. Carbonate Test To a portion of solid the size of a capital letter O in a small, dry test tube, add 3 M hydrochloric acid dropwise, and look for immediate fizzing. While the mixture is still bubbling, place part of a drop of barium hydroxide solution on the dry, upper walls of the tube. (You may actually want to place the drop of barium hydroxide on the inside wall of the test tube before carefully adding the hydrochloric acid, so as not to disturb the drop of barium hydroxide.) Carbon dioxide gas from decomposition of carbonic acid produces a barium carbonate precipitate in the drop. The bubbling and precipitation confirm carbonate. 3. Acetate Test Any salt must have some anion. The most likely reasons for absence of precipitate in parts 1 and 2 are: (i) presence of a soluble anion (such as acetate), (ii) contamination of solutions with acid or (iii) poor precipitation of barium oxalate. The first can be checked with an acetate confirmation test as follows. The third can be checked by doing step 2c. Place 5 mg solid (see Project A estimation of a small mass) in a small test tube. Add one drop of concentrated sulfuric acid [CAUTION]. A strong vinegar odor confirms acetate. You may also add two drops of ethanol (C2H5OH) to the tube, mix and warm briefly in a hot water bath. Waft vapor from the tube toward your nose and note the fruity vapor of ethyl acetate (C2H5C2H3O2), which confirms acetate. Because there is virtually no water in the test tube, the sulfuric acid appears as a solvent, analogous to (aq), and as a reactant in the first equation.

NaC2H3O2(s) + H2SO4(l) NaHSO4(H2SO4) + HC2H3O2(g) The role of sulfuric acid in the second equation is to speed the reaction and tie up the water product. C2H5OH(l) + HC2H3O2(H2SO4) C2H5C2H3O2(g) + H2O(H2SO4)

94
CLEAN-UP

Qualitative Anion Analysis

If not done previously, tightly stopper the four tubes containing the unused portion of your samples. Wrap a rubber band around the set, and return them as directed. If you believe you contaminated a sample, wrap only the uncontaminated tubes with a rubber band, and give all four to your instructor. The quantities of reagent and product are so small, product mixtures may be flushed to a sink unless you are specifically instructed otherwise. Use the small test tube brush in your drawer to clean your testtubes; rinse them with distilled water and store.
REPORT AND EVALUATION

In your notebook briefly record each step as completed. These notes receive only general credit, but can be very helpful as you sort out your results. Identify each anion. When you have completed all four anion analyses, submit your identifications to your instructor. The analyses count for about half of the project credit. Your instructor will tell you the correct identity of any anion you didnt identify correctly. To obtain full credit for mistaken analyses you must (1) clear up the problem of your misidentification, and (2) identify the anion of another sample. For (1), differentiate what you had from what you identified by comparing them in parallel tests using knowns; this will be graded from your notebook carbons. For (2), obtain a new tube from the instructor and proceed as before. You will receive credit both are done correctly. Below the experimental section in your notebook, write a NET ionic equation for every reaction of the project listed below. If you work on these in the laboratory, your instructor may be able to suggest corrections. You are encouraged to discuss equations with other students and finish this work during your scheduled laboratory period. Equations for the starred reactions are given as part of instructions, or related to equations in the Ionic Equations Interpolation. This counts for about one third of the project credit. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. Precipitation of the chloride ion with silver ion Precipitation of the thiocyanate ion with silver ion Precipitation of the iodide ion with silver ion Temporary precipitation of the oxalate ion with silver ion Dissolution of silver oxalate with nitric acid Dissolution of silver chloride with aqueous ammonia * Complexation of the iron(III) ion by thiocyanate ion Oxidation of the iodide ion by hypochlorite solution * Precipitation of the carbonate ion with barium ion Precipitation of the oxalate ion with barium ion Precipitation of the phosphate ion with barium ion Precipitation of the sulfate ion with barium ion Lack of reaction of barium sulfate with hydrochloric acid Dissolution of barium phosphate with hydrochloric acid Reaction of sodium phosphate solution with hydrochloric acid Reaction of phosphoric acid with ammonium molybdate solution * Precipitation of the oxalate ion with calcium ion Reaction of calcium oxalate with sulfuric acid * Reaction of oxalic acid with acidic permanganate solution * Production of carbon dioxide from solid sodium carbonate and hydrochloric acid Reaction of carbon dioxide with barium hydroxide solution (1 or 2 steps) Production of acetic acid OR ethyl acetate in sulfuric acid *

Graphing

95

Interpolation 8 Graphing
A graph is a convenient way to display a large amount of data and indicate relationships. The most common scientific graphs plot two-variable data on a rectangular grid. Linear relationships are most easily appreciated and most reliably determined. (Non-linear data is often transformed is case where the data can be made linear by taking the logarithm or reciprocal of each measurement for example, if this makes the relationship linear.) The independent variable is determined by the experimentor and dependent variable is then observed in the experiment while any other variables are held constant. The independent variable is plotted on the x-axis (horizontal) and the dependent variable is plotted along the y-axis (vertical).
SOME STEPWISE GUIDELINES TO GRAPHING

Use fine grid graph paper, with squares no bigger than 0.1 inch, to allow reading values to three significant figures. Count the number of major scale increments in each direction. (Unless the paper has these margins, allow 2 cm on all sides of the graph for title, scale labels, and key. For each variable, decide the minimum range of data to be plotted (largest value minus smallest). You need not plot zero or outlying (strikingly high or low) points unless there is justification for including them. Plot the data with higher relative precision data (more significant figures or larger range of values) along the longer axis. Turn the graph to make the measurements independent variable the horizontal scale. For each variable, divide the minimum data range by the number of major scale increments. The next larger value from the list: 1, 2, (2.5, 4) or 5 (or any of these times a power of ten, i.e. 0.002, 0.02, or 0.2 in place of 2), is the best interval per increment. For each variable, select a round value smaller than the smallest measurement in the data set. Make the (x,y) point the lower left hand corner of the graph. Use a ruler to mark scale lines, the graph boundaries. At major scale increments (at least four) along each axis, add tick marks and label the value of the variable at each mark. For each axis, label the variable plotted; include units in parentheses. By convention labels belong to the left and below the graph. Plot each datum as a small point. If required for visibility, surround each point with a plotting symbol (circle, diamond, triangle). Use a data label, placed in the data region or as a key in the border region, to identify data sets with different plotting symbols. Draw one smooth line, a trend line, on the graph for each relationship represented. The trend line may be curved, but NOT discontinuous (point-to-point connection). Use a line which represents (comes closest to) all valid data, rather than one which goes through two particular points. Ignore outliers when evaluating the best-fit line. Use an informative title, one which describes the relationship or experiment graphed. It is wrong title the graph using the variables, which are already indicated as scale labels.

Introduction to Calorimetry

97

Introduction to Calorimetry

98

Introduction to Calorimetry

99

Project M Introduction to Calorimetry


The Enthalpy of Decomposition of Hydrogen Peroxide1
OBJECTIVE

Determine the enthalpy of decomposition and formation of hydrogen peroxide.


CONCEPTS APPLIED 1. Calorimetry the laboratory measurement of heats of reaction 2. Titration the laboratory determination of the concentration of one solution based on its reaction with another solution having known concentration 3. Hesss law of heat summation 4. Graphing and extrapolation TOPICS TO REVIEW

1. 2. 3. 4.

Thermochemistry Titration Redox chemistry Reporting a measured value with its uncertainty; Project B

BACKGROUND

Chemical reactions transform chemical potential energy into heat and work, or vice versa. The food we eat allows our bodies to do work and keep us warm. The energy in food is stored in substances such as sugars produced by plants as a net result of photosynthesis the process by which energy in light is converted into chemical energy. It is comparatively much easer to measure the energy change in a system than to measure a systems actual energy at any particular point in time. Energy is generally transferred from a system to its surroundings and visa versa in the form of heat and/or work. The symbol for heat is q. When heat is absorbed q is positive and when heat is released q is negative. However, helping to simplify matters is the fact that many reactions involve very little (if any) work, thus the change in energy is closely approximated by the change in heat. The heat transferred at constant pressure is called the change in enthalpy, H. In this experiment, you will measure H for the decomposition of household hydrogen peroxide, H2O2, the solution that bubbles when used to clean wounds. The same net reaction that forms those bubbles is the one that occurs in this experiment.

H2O2(aq) H2O(l) + O2(g)


The molar enthalpy of decomposition of H2O2 is determined in this experiment by dividing the heat released, q, by the moles of H2O2 that were decomposed. The heat (energy) released by the reaction is calculated from the solutions mass, specific heat and change in temperature. The decomposition of H2O2 normally occurs very slowly, so a catalyst is used here to speed up the reaction. A catalyst is a substance that speeds up a reaction but is not consumed by the reaction. This makes it relatively easy to determine the heat (energy) released by the reaction because the solution temperature increases rapidly. Catalysts come in a variety of forms. Enzymes in your body, finely powdered metals, even something as simple as potassium iodide are all catalysts.

Based on an article by Marzzacco, Charles J., The Enthalpy of Decomposition of Hydrogen Peroxide, J. Chem. Ed., 1999, 76 (11), 1517-1518.

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Titrations Remember to use good technique when preparing and using your buret. You are expected to record your titration data and observations in an appropriate data table. Refer back to Project I to remind yourself of these details. Hesss Law In this experiment, Hesss Law is applied to calculate the enthalpies of formation and decomposition of H2O2. Hesss law takes advantage of the fact that H is a state function (it depends only in the initial and final states) and allows the H of a multi-step reaction to be determined by adding together the H of each individual step. An example is shown here and further explanation can be found in your textbook with the discussion of Hesss Law. Example In Project J, nitric acid was formed from a reaction between nitrogen dioxide and water vapor. Determine the enthalpy of the reaction based on the standard enthalpies of formation of NO2(g), H2O(l), HNO3(aq) and NO(g). Plan Step 1. Identify the target equation, noting the number of moles of each reactant and product. Step 2. Manipulate the equations with known enthalpies so that the target number of moles of reactants and products are on the correct sides of the equations. Remember to change the sign of H when you reverse an equation. When increasing the number of moles in a reaction, increase H by the same factor. Step 3. Add the manipulated equations to obtain the target equation. Add the H values to obtain the unknown H. Solution Step 1 2 Calculation

3NO2(g) + H2O(l) 2HNO3(aq) + NO(g)

Hrxn = ???
These reactions are the reverse of the formation so the sign of their H is switched

2 ( 1/2H2(g) + 3/2O2(g) + 1/2N2(g) HNO3(aq) ) 2 Hf = 206.57 kJ/mol 3 ( NO2(g) 1/2N2(g) + O2(g) ) H2O(l) H2(g) + 1/2O2(g) 1/2N2(g) + 1/2O2(g) NO(g) 3 Hf = 33.2 kJ/mol Hf = 285.84 kJ/mol Hf = 90.29 kJ/mol

3NO2(g) + H2O(l) 2HNO3(aq) + NO(g)

Hrxn = 136.61 kJ/mol

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Hydrogen peroxide is a strong oxidizing agent but is not particularly hazardous at the concentrations used in this experiment. 4 M H2SO4 is a strongly acidic solution and should be used with caution. Rinse thoroughly with water if it comes in contact with skin. KMnO4 is a strong oxidizing agent and should be used with caution. In your pre-lab summary, calculate (if necessary) and record the following information. They will be needed for this experiment. - The volume of 0.0200 M KMnO4 needed to titrate 1.0 mL of 3% H2O2. Hydrogen peroxide available at the grocery/drug store is 3% and this concentration is equivalent to 0.882 moles/L. (This is your expected titration volume for this experiment.) - The standard heat of formation, H f , values (found in the appendix of your textbook) and the associated chemical reactions for H2O(l). You will also need the standard heat of formation for H2O2(aq) which is -191.2 kJ/mole. The value for the molar enthalpy of decomposition of H2O2(aq) calculated using Hesss Law and the standard heats of formation of H2O2(aq) and H2O(l). Prepare a data table for the temperature vs. time calorimetry data. Prepare a data table for the other calorimetry data. Prepare a graph, on graph paper, that Decomposition of Hydrogen Peroxide you will use to plot your calorimetry data as it is collected, using the graph shown 50.0 here as an example. Label the vertical 45.0 axis Temperature in C (the dependent Tf variable) with a scale from 20 to 50C. 40.0 Label the horizontal axis Time in minutes (the independent variable) 35.0 with a scale from 0 to 25 minutes. You should also include an appropriate title 30.0 on your graph. (For graphing guidelines 25.0 see the graphing interpolation in your lab Ti manual on page 95. Use graph paper 20.0 with a minimum of 10 divisions per 0 5 10 15 20 25 inch.) Tim e (m inutes) Prepare a data table for your titration data following the example in Project I.
Figure 33 example graph for decomposition of hydrogen peroxide
Temperature C

ADVANCE PREPARATION

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PROCEDURE This experiment is intended to be collaborative. You will be working in pairs while collecting the calorimetry data. Titration of the H2O2 with KMnO4 will be done individually. 1. Determination of the enthalpy of decomposition of H2O2

While you are conducting this experiment be sure to record your observations, especially before the catalyst is added, immediately after the catalyst is added and at the end of the experiment. For this portion of the experiment you will need to obtain a magnetic stir plate, a magnetic stir bar, a thermometer and 2 coffee cups (stacked one inside the other, from here on referred to as the calorimeter). Measure the mass of the calorimeter with the magnetic stir bar to the nearest 0.1 gram using a mechanical balance. Obtain about 50 mL of the 3% H2O2 solution using a graduated cylinder and transfer it to the calorimeter, record the volume that you actually use to the nearest 0.1 mL. Place the magnetic stir bar in the calorimeter and the calorimeter on the magnetic stir plate. Turn the stir plate on to a speed that thoroughly mixes the solution but does not splash any out. Using a 10 mL graduated cylinder, obtain about 10 mL of the catalyst assigned to you either 0.75 M FeCl3 or 500 ppm catalase and record the volume that you actually use to the nearest 0.01 mL. This solution will be added to the H2O2 solution at the 5-minute mark. Measure the temperature of the H2O2 solution to the nearest 0.1 degree and continue to measure the temperature every minute. (The first reading is the zero minute reading.) One student of the pair should be reading the thermometer while the other records the data in a notebook and plots it on their graph. At the 5-minute mark, add the catalyst but do not measure the temperature. Closely monitor the appearance of the reaction mixture immediately after adding the catalyst, during the reaction and after the reaction is complete. At the 6-minute mark, measure and record the temperature. Continue measuring and recording the temperature every minute until the 20 minute mark is reached. Remember to record your observations. Measure the mass of the calorimeter, magnetic stir bar and the reaction solution. Discard the reaction mixture in the sink and rinse the calorimeter with water. Dont let the magnet go down the drain! Return the calorimeter, thermometer, stir bar and stir plate. On your graph draw a vertical line at the point of mixing (the 5 minute mark). Extrapolate the first five data points by drawing a best fit line through them and continuing just past the point of mixing (the five minute mark). Record the temperature at the intersection of these two lines; this is the temperature at the point of mixing, the initial temperature Ti. The last 5-10 data points collected should be fairly linear. Extrapolate these data points by drawing a best fit line through them and continuing just before the point of mixing. Record the temperature at the intersection of these two lines as Tf. Calculate T = Tf Ti, record it in your notebook and report it to your lab instructor.
2. Determination of the concentration of H2O2 (To be done individually) Normally, the volume in a buret is read from the bottom of the meniscus, however, in this experiment the meniscus is very difficult or impossible to see because of the intense dark color of the permanganate solution. In this case you should read the top of the meniscus. The buret volume should still be read to the nearest 0.01 mL by interpolating of the distance between the smallest marks on the buret.

Obtain a 1 mL pipet and about 10 ml of 3% H2O2 in a small, labeled beaker.

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Obtain about 150 mL of the standardized KMnO4 solution in a beaker. Record its concentration in your notebook. Fill your buret with the KMnO4 solution and prepare to titrate the H2O2 applying what you read about in the background information. Pipet 1.000 mL of the H2O2 solution into a clean 250 mL Erlenmeyer flask (it does not need to be dry). Add 5 mL of 4.0 M H2SO4 and enough water to bring the level of the solution to the 75 mL mark. Titrate the H2O2 solution to the faint but persistent pink color of a slight excess of KMnO4. The titration goes according to the following equation. 2 MnO4 (aq) + 5H2O2(aq) + 6H+(aq) 2Mn2+(aq) + 5O2(g) + 8H2O(l) Check the endpoint of your titration by drop wise addition of dilute H2O2 prepared by diluting 1 mL of 3% H2O2 with distilled water to 50 mL using your pipet and graduated cylinder respectively. Record how many drops are needed turn the solution colorless again. Two drops or less is good, three is OK, but the titration data should be discarded if more than three drops are needed. Empty only the solution in the flask down the drain. Repeat steps 2-7 until you have three good titrations. The range of your three titration volumes must be less than 0.30 mL to receive full credit here. You may do additional titrations as time permits, check with your lab instructor. Drain your buret into the beaker with your remaining KMnO4. Empty your excess KMnO4 solution into the designated unwanted materials container. Rinse your buret until no pink color remains only these rinses can go down the drain.
BEFORE LEAVING THE LAB

Submit your values of T and average [H2O2] to your lab instructor. Record the average values for T for both catalysts as determined by your lab instructor.
DATA PROCESSING

1. Calculate the [H2O2] for each titration (remember, the brackets around H2O2 mean concentration). Note that there are three reactants in this reaction, the H+ is from the sulfuric acid and is in excess. 2. Calculate the average and standard deviation of the [H2O2] with units of molarity. (See page 14 in your lab manual for a review of how to calculate a standard deviation.) 3. In your notebook, record your [H2O2] as the average the standard deviation with the appropriate number of significant figures. Recall what you learned from the density measurements in Project C. 4. Calculate qsol, the heat absorbed by the reaction mixture using your value of T. Assume that the specific heat capacity of the solution is not significantly different from that of pure water, 4.18 J/gC. (This assumption is reasonable based on the similar specific heat capacities of water and H2O2 and relatively low concentrations of the H2O2 and catalyst.) Remember, the symbol for heat is q. When heat is absorbed q is positive (endothermic) and when heat is released q is negative (exothermic).
qsol = (specific heat of the solution ) (solution mass ) T

5. Calculate the qcal, the heat absorbed by the coffee cup calorimeter, using your value of T. Use a value of 5.00 J/C for the calorimeter constant, it has already been determined and accounts for heat transferred to the calorimeter itself.
q cal = ( calorimeter constant ) T

6. Calculate qtotal, the total heat released by the decomposition reaction. (Note that the sign of q changes because the heat gained by the system is lost in the reaction.)

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qtotal = (q sol + q cal )

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7. Using the average H2O2 molarity from part B and volume of H2O2 used in part A, calculate the moles of H2O2 that were decomposed by the catalyst in part A. 8. Calculate H for this reaction in kJ/mol; the heat change (qtotal) divided by the number of moles of H2O2 decomposed in part A. (You just calculated these two quantities). Be sure your sign of H is correct. 9. Compare your experimental heat of decomposition of H2O2 with the theoretical value you determined in the prelab question. (Are your units the same?) Calculate your % error in the enthalpy of decomposition of H2O2(aq).
% error =

(measured - theoretical )
theoretical

POST LAB QUESTIONS

1.

If a different catalyst concentration or entirely different catalyst were used, the speed of the reaction could definitely change but does the nature of the catalyst have any effect on the amount of heat released per mole of H2O2 decomposed? Base your answer on the class average T values for the two catalysts from this experiment. Keep in mind that the error in the average T values could be as much as 0.3C or more. Formation of a gas during a chemical reaction (like the one observed here) is a common sign of what type of reaction? Write the balanced chemical equation for one other redox reaction that you have observed in chemistry lab this semester.

2. 3.

EVALUATION Credit is based on your recorded observations, your graph, your enthalpy calculations, the accuracy and precision of your calculated [H2O2], the accuracy of your enthalpy results and your responses to the pre and post-lab questions.

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Project N Identification of an Unknown Acid


Titration of a Weak Acid with Standard Base
OBJECTIVE Determine the molar mass and ultimately the identity of a weak acid. CONCEPTS APPLIED 1. Titration the laboratory determination of the concentration of one solution based on its reaction with another solution having known concentration 2. Weighing by difference TOPICS TO REVIEW 1. Reporting a measured value with its uncertainty; Project C 2. Titrimetry; 3. Uncertainty BACKGROUND

As the title indicates, in this experiment you are asked to determine the identity of an unknown weak acid according to its molar mass which will be determined experimentally by titration with your standardized sodium hydroxide solution (from Project I). All of the possible acids in this experiment are diprotic, meaning they have two acidic protons. Both protons will react with the strong base, sodium hydroxide, used in this experiment and the titration endpoint (phenolphthalein) will occur only after both have reacted. Titrations are very useful, in part, because they allow us to experimentally measure equal molar amounts of reactants in a chemical reaction. Dividing the mass of unknown acid used in the titration by the moles of unknown acid determined by the titration provides the molar mass of the unknown acid. If the identity of the weak acid was truly unknown, this would only be part of the information necessary to identify it. In this experiment however, you only need to identify your weak acid from a relatively small list of possibilities and knowing only its molar mass will allow you to make that determination. This experiment is intended to test your titration skills and practical laboratory knowledge that were introduced earlier this semester, particularly in Projects C, I and L. Subsequently, less specific guidance is provided for this experiment. Remember to use good technique when preparing and using your buret. You are expected to record your titration data and observations in an appropriate data table. Refer back to Project I to review either of these topics.
ADVANCE PREPARATION

Prepare a data table for your titration data following the example in Project I. If you know nothing about the identity of a weak acid, you should treat it as though it were toxic and an irritant. In reality, the identity of your weak acid is known (to your lab instructor) and as such you can safely handle it with the same precautions as the KHP (another weak acid) used in Project I. Aqueous sodium hydroxide is caustic. Skin contact should be avoided. In the event of skin contact, rinse with water immediately until the skin no longer feels slick. The phenolphthalein solution is flammable because it contains alcohol.

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The procedure for identifying your unknown weak acid by titrimetry amounts to doing one quick titration to get a rough idea of its molar mass followed by three or more titrations using a mass of weak acid that will lead to more accurate and precise results. Obtain a sample of solid, unknown weak acid and two additional 250 mL Erlenmeyer flasks (you should have one in your drawer) from your lab instructor or the stockroom. Using an electronic balance, accurately weigh by difference 0.2 0.02 grams of your weak acid into one flask. Add approximately 75 mL of distilled water and 3 drops of the phenolphthalein indicator solution. Invert your bottle of sodium hydroxide several times to ensure that the solution is homogeneous and prepare your buret. Titrate this sample of your weak acid. ----------------------------------------------------------TIME OUT-----------------------------------------------------------Based on the amount of titrant used, you may be better off using a larger or smaller mass of your weak acid for your remaining titrations. Ideally titrations with a 50 mL buret should use about 40 mL of titrant. The mass needed to react with 40 mL can be easily calculated using data from the titration you just did. For example, if your first titration used 27.12 mL of titrant and you want to use about 40 mL for future titrations, that is an increase of basically 40/27 or 148%, so you would multiply the mass you used in that first titration by 1.48 to get the mass that will react with about 40 mL of titrant. ----------------------------------------------------------TIME IN-----------------------------------------------------------Empty and rinse the flask you used for the first titration. Prepare to do additional titrations until you have at least 3 good titrations. When you are satisfied with the results of your titrations, drain your buret, rinse it three times with distilled water and place it upside down back in the buret stand to dry. Rinse your Erlenmeyer flasks and other glassware before returning them to the stockroom or your lab drawer respectively. These solutions are OK to be sewer disposed. Empty any remaining standard sodium hydroxide solution into a designated container in the lab, then rinse and return the bottle. Also return any unused weak acid.

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DATA PROCESSING

1.

Calculate the molar mass of your unknown acid for each titration except the quick titration. Record these values to 4 significant figures (even though there will be only 3 in the mass of the acid and perhaps also your NaOH concentration). The extra significant figures in this intermediate answer prevents rounding errors in your average and standard deviation. Calculate the average and standard deviation of these molar masses. (Remember, report your standard deviation to 2 significant figures. Report your average with the same number of decimal places as your standard deviation, i.e. where ever your standard deviation starts, is where your average ends. For example, if the average is 125.738 g/mol and the standard deviation is 1.7 g/mol then round the average to 126 g/mol.) Using your calculated molar mass, determine the identity of your unknown acid from the following list of possibilities.
Possible unknown weak acids Molar mass Molecular formula H2CO3 H2SO3 H2C2O4 H2C3H2O4 H2C4H2O4 H2C4H4O5 H2C4H4O6 H2C8H4O4 H2(C7H7O)PO3 H2C8ClH3O4

2.

3.

Carbonic Sulfurous Oxalic Malonic Maleic Malic Tartaric Phthalic Phenoxymethyl phosphonic Chlorophthalic
POST LAB QUESTIONS

62 82 90 104 116 134 150 166 188 200.5

1. 2.

Write the balanced molecular and net ionic equations for the reaction of YOUR acid with sodium hydroxide. Carbon dioxide gas readily dissolves in basic solutions, neutralizing some of the base. How would this affect the experimental molar mass of your unknown weak acid?

EVALUATION Credit is based on your recorded observations, the accuracy and precision of your data, your identification of the acid and your responses to post-lab questions.

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Index
accuracy, 11, 85 analyte, 85 average. See mean bias, 11 Boiling Point, 23 buret, 85 Concentration, 15 Data Tables, 16 Density, 15 deviation, 11 endpoint, 85 equivalence point, 85 Extrapolate, 106 interpolating, 86 interpolation, 106 mean, 11 meniscus, 85 Pipetting, 17 precision, 11 qualitative, 5 Quantitative Properties, 23 random error, 11 Sample Calculation, 16 Significant Figures, 12 Solubility, 23 standard, 85 standard deviation, 11 Standard Deviation, 14 systematic error. See bias titrant, 85 titration, 85 Titrimetry, 85 uncertainty, 11, 86 Weighing, 16 Weighing by difference, 88