CHEMISTRY 3X

General Information and Experiments

CALIFORNIA INSTITUTE OF TECHNOLOGY

PASADENA, CALIFORNIA

TABLE OF CONTENTS
INTRODUCTION ................................................................................................................i Collaboration Policy ......................................................................................................ii Chemistry 3X Experiments ..........................................................................................iii General Notes for Chem 3X .........................................................................................iv EXPERIMENT 1 .................................................................................................................1 Absorption of Light by Matter 1st Weekly Assignment (10 points).......................................................................18 Report Grading Scheme (50 Points Possible) .......................................................19 EXPERIMENT 2 ...............................................................................................................23 Luminescence of [Ru(bpy)3]2+ 2nd Weekly Assignment (10 points) .....................................................................36 Computer Programming: MATLAB 3rd Weekly Assignment (10 points) ......................................................................66 Report Grading Scheme (100 Points Possible) .....................................................67 EXPERIMENT 3 ...............................................................................................................69 Electrochemistry of Water and [Ru(bpy)3]Cl2 4th Weekly Assignment (10 points) ......................................................................88 Photochemical Hydrogen Production Using Ru(bpy)3Cl2 5th Weekly Assignment (10 points) ......................................................................96 Report Grading Scheme (150 Points Possible) .....................................................97 EXPERIMENT 4 ...............................................................................................................99 Semiconductor Metal Oxide Synthesis and Processing 6th Weekly Assignment (10 points) ....................................................................110 Photoelectrochemical Water Oxidation 7th Weekly Assignment (10 points) ....................................................................123 Dye-Sensitized Solar Cells 8th Weekly Assignment (10 points) ....................................................................133 Report Grading Scheme (200 Points Possible) ...................................................134 APPENDIX I....................................................................................................................137 Some General Comments About Electromagnetic Radiation

INTRODUCTION
The aim of this quarter's experiments is threefold: (1) to apply chemical principles to immediate experimental situations and thus better understand the relationship between theory and empirical observations (2) to provide experience in a variety of chemical operations and laboratory techniques; and (3) to develop the spirit of experimental inquiry and critical evaluation necessary for creative research. The concepts stressed this quarter are redox chemistry, coordination chemistry, chemical kinetics and reaction mechanisms, and the application of chemical principles to solar power. In the course of demonstrating and acquiring a practical understanding of these subjects, you will become familiar with a variety of synthetic and analytical techniques, e.g., UV-Vis spectroscopy, potentiometery, electrochemical titration, synthesis using catalysis, and vacuum filtration. All of these techniques are fundamental to research in chemistry.

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Collaboration Policy
Although students taking Chemistry 3X are most definitely encouraged to discuss the problems and challenges they encounter in this course with each other, the actual notebook and reports submitted, should be undertaken and accomplished on an individual basis. If you feel you need assistance in completing a notebook, report, or other assignment, you should consult with the instructor or teaching assistants in this course -- not with your fellow students or students who have taken the course in the past. In the same vein, do not refer to graded notebooks or reports from previous terms. To help you learn to correctly interpret your observations and results, as well as to obtain optimal data, is one of the goals of this class. You can acquire this ability more expeditiously if you confront any problems on your own, not by having someone else consistently do the analyses for you. Furthermore, as the course progresses, your experiments will be assayed on your own individual products, which will have their own unique contaminants. In this respect, your rationalization of a <100% yield and a less than ideal melting range reflect your own accomplishments of the synthetic and product-isolation procedures and hence cannot, and should not, be generalized. If you have any questions regarding this policy, please see Dr. Mendez. He will be glad to consider and discuss any problems you have "honoring" it.

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Chemistry 3X Experiments
Experiment Time 3 hrs Points 100

Beers Project Understanding Beers Law The Laser Project Kinetics and Mechanism of Ru(bpy)32+ The Hydrogen Project Electrochemistry and Production of H2 The Semiconductor Project Synthesis of nano-particles of TiO2 Understanding Semiconductors Website

6 hrs

200

6 hrs

300

9 hrs

400

This lab manual, lecture notes, and TA contact information can be found on the Chem 3X website :http://chemlabs.caltech.edu/wiki/ch3x:home

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General Notes for Chem 3X

Lecture: One hour per week is provided for a lecture period (Friday at 9 AM in 151 Crellin). These lectures are a required part of the curriculum and will include discussion of the techniques of synthesis and characterization encountered. Preparation and Pre-Lab Prior to the first laboratory period, you should purchase a laboratory notebook. The most critical guarantee of performance in the laboratory is careful preparation before beginning any experimental work. In general, such pre-labs should include the following: 1. An outline of the procedures you plan to undertake and a proposed timetable for such work. Keep in mind that the laboratory period is only three hours long. It is important that ALL EXPERIMENTATION and clean-up be completed BEFORE the end of the lab period. 2. Answer "pre-lab questions". 3. Construct a table of all chemicals used in the lab listing important physical data (molecular mass, density, melting and boiling points), and safe handling information from the Material Safety Data Sheets. Such data can be found in the MSDS folder located in the Ch3 lab or accessed on the internet at: http://www.chemfinder.com/ or http://www.sigma-aldrich.com/ All computers in the instrument room are connected to the internet and hence can be used for this purpose. All pre-lab write-ups must be initialed by your T.A. before you are permitted to begin any experimental work. It is strongly recommended that you preview the report format for the experiments to make sure that all necessary data is being collected and observations are being made during the lab period.

Format of the Chem 3X Lab Notebook An ancient Chinese proverb states the faintest ink is more powerful than the strongest memory. Since human memory is fallible, every scientist should keep a written record of all experiments, ideas, and hypotheses. Such a notebook preserves this information for him or herself and others. An important objective of this course is to develop good practices in keeping permanent notes of experimental work. A laboratory notebook should be a fundamental record of actual laboratory operations and observations. It should provide an account of what was done, how it was done, and what happened. It must be possible for someone else, using your notebook, to repeat the experiment and obtain the same results. requirements which will help you achieve these goals are as follows:
1. The notebook must be a permanent record. a. Use a bound book with a hard cover. b. Use it only for experimental work. c. Use ink! If an error occurs, draw a single line through the incorrect entry. It is important that the original, incorrect entry remain legible. 2. The information must be accurate. It is not possible to reconstruct a record from isolated numbers on scraps of paper or from memory. On the other hand, your data cannot be recorded before they exist. It is necessary to record observations, operations and measurements as they are done or made. 3. The notebook must be complete. Record not just measurements, but what apparatus was used, significant time intervals, experimental conditions (e.g., temperature, solvent used), changes in appearance (color, precipitate formation, gas evolution), and all other relevant data. 4. The notebook should be legible. It may seem impossible to meet the first three conditions and still maintain an intelligible notebook, without transcribing it. However, if you plan your experiment including how you will record your data, etc., you can produce a quite acceptable notebook. For example, each experiment should be dated and placed on a separate page or pages.

Certain

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Lab Report Format You must submit your work in two forms: 1) weekly submission of data tables, graphs, and other processed data, 2) a report which describes and discusses your efforts and results following the completion of each experiment. The format for these assessments varies considerably from one week to another and one experiment to the next, guidelines are given at the end of each experiment, and most importantly, in the lecture. In general, you should strive to make your reports complete, concise, and coherent. It is important to take care in the write-up of your laboratory work, for learning the difficult art of communicating your laboratory experiences to others is part of your education. Please note the posted report due dates. A penalty -10% (of total points earned on your report) per day will be imposed for lateness. Laboratory Rules and Regulations 1. Each student must be prepared to show written evidence in the notebook of preparation for the laboratory. 2. Safety glasses or goggles, a lab coat or apron, and closed shoes must be worn at all times. Violations will result is removal from the lab. 3. The working space, desk drawers, cabinets, and instruments must be kept neat and clean following each experiment. 4. Attendance in the assigned section of the course is compulsory, and attendance records will be kept. In cases where it appears necessary to attend another section, permission from the instructor is required. 5. Work is not permitted in the laboratory except during the regularly assigned periods when teaching assistants are present. 6. The performance of unauthorized experiments is absolutely not allowed. 7. Common sense and consideration for fellow workers must be exercised rigorously and constantly. 8. Handle chemicals with care. Avoid contact with skin and clothing. Wipe up spills immediately, especially near balances and reagent storage areas. Replace caps on bottles as soon as possible.

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9. Drinking, eating, or smoking in the laboratory is not allowed. 10.Proper disposal of chemicals must be respected. All waste has specific and special waste bottles, read the waste label before disposing of any waste. Finally, solid samples (e.g. drying agents) are to be disposed of in the "SOLID WASTE" container. The penalty for noncompliance with Rules 1 and 2 will be removal from the laboratory until the deficiency is remedied. Violation of Rule 5 & 6 may, at the discretion of the instructor, call for expulsion from the course. Grading To pass Ch 3X: all reports must be submitted and earn a minimum of 50%, the total points amassed must add up to at least 60% of the total possible. numerical grade will be assessed as follows:
Assignment Beers Project 1 Pre-Lab In-Lab 10 10 10 Assignments Quizzes 10 10 50 100 Laser Project 2 20 30 20 20 10 100 200 H2 Project 2 20 70 30 20 10 150 300 Project
Semiconductor

This

Points

Percentage

Lab Periods Notebook Technique Weekly Reports Total

3 30 90 40 30 10 200 400 80 200 100 80 40 500 1000 8% 20% 10% 8% 4% 50% 100%

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References
"Ch 3X Topics" in Oxtoby Gillis and Campion: Principles of Modern Chemistry, 7th edition Electrochemistry
Electrochemical Cells: pp 764-769 Cell Potentials and Gibbs Free Energy: pp 770-779 Molecular Interpretation of Electrochemical Processes: pp 780 Concentration Effects and the Nerst Equation pp 781-786 Molecular Electrochemistry pp 787-799

Bonding in Transition Metal Compounds and Coordination Complexes

Chemistry of the Transition Metals: pp 348-354 Introduction to Coordination Chemistry: pp 355-360 Structures of Coordination Complexes: pp 361-366 Crystal Field Theory: Optical and Magnetic Properties: pp 367-373 Optical Properties and SPectrochemical Series: pp 374-375 Bonding in Coordination Complexes: pp 376-385

Rates of Chemical and Physical Processes

Rates of Chemical Reactions: pp 836-838 Rate Laws: pp 839-846

Molecular Spectroscopy and Photochemistry

Introduction to Molecular Spectroscopy: pp 942-946 Experimental Methods in Molecular Spectroscopy: pp 947 Electronic Spectroscopy and Excited State Relaxation Processes: pp 973-991