Experimental Physical Chemistry Experimental Physical Chemistry © seer snrion H DANIELS / WILLIAMS / BENDER / ALBERTY / CORNWELL McGRAW-HILL e 4 él ?INTERNATIONAL ATOMIC WEIGHTS, 1956-1957 ‘Journal of the American Chemical Society Saber QO AGH | Moment Symbol Ae 3o |) Mercury Hg for ne pnesron rocrrecic At cs Niobium Nb This book must be retumed on or before the date last stamped Beryllium Be 4 9.013 || Osmium Os TELE HORE Ey HESTON 9029188 kes lore Gioim Gk eaten” aes 3 me Dysprosium 66 162.51 Rubidium Rb 37 85.48 2 ne an oo xu eek ae eae, easy ee ae ee ee Boe ao fences, Het ies Peco ee aa suai 2 p ae | ee ee ee Pe eee ees eee eeealmee, ae Sh sae Li 36.040 || Xenon Xe st 131.30 | Me 12.24.32. || Yttrium: ¥ 33 ase | pee ladle es ‘Mase numbers for radioactive elements axe omitted except for naturally occurring uranium and thorium and for eartain other elements that are only very slightly radioactive. / * Because of natural variations in relative abundance of the sulfur isotopes, its atomic weight hhas a range of 0.003,Experimental | Physical Chemistry FARRINGTON DANIELS Professor Emeritus of Chemistry J. W. WILLIAMS Professor of Chemistry PAUL BENDER Professor of Chemistry ROBERT A. ALBERTY Professor of Chemistry 1962 C. D. CORNWELL New York Professor of Chemistry San Francisco Toronto University of Wisconsin Sixth Edition London McGRAW-HILL BOOK COMPANY, INC.EXPERIMENTAL PHYSICAL CHEMISTRY Copyright © 1956,1969) by the McGraw-Hill Book Company, Inc, Copyright, 1920, 1054, 1941, 1949, by the MoGraw-Hill Book Company, Inc. All Rights Reserved. Printed in the United States of America, ‘This book, or parts thereof, may not be reproduced in any form without permis- sion of the publishers. Library of Congress Catalog Card Number a 15336 jaca No. l SU\. O12 ExPPreface ‘To illustrate the principles of physical chemistry, to train in careful experimentation, to develop familiarity with apparatus, to encourage ability in research—these are the purposes of this book, as stated in the first edition a third of a century ago. In each of the five revised editions an attempt has been made to keep pace with the new developments in physical chemistry and to have the book representative of the teaching of the laboratory course in physical chemistry at the University of Wisconsin, ‘There are many more experiments in this book than can be performed by any one student. Selection will be made on the basis of the time and apparatus available and on the capacity and ultimate aims of the student. If an experiment is too short, the student will find interesting projects under Suggestions for Further Work; if itis too long, the instruc- tor may designate parts of the Procedure to be omitted. ‘The imperative is not used. Procedures are described, but orders are not given. The student studies the experiment first and then plans his ‘work—a method which develops both his power and his interest. ‘The high cost of laboratory apparatus restricts the choice of experi- ments, particularly where classes are small. Nevertheless, there has been no hesitation in introducing advanced apparatus and concepts. If stu- dents are not given an opportunity to become familiar with a variety of modern developments and new techniques, they will be handicapped in their later practice of chemistry. Space for additional material has been obtained by abbreviating parts of the last edition and omitting some of the older classical experiments which have found their way into first- and second-year chemistry courses. ‘All the experiments previously given have been reviewed, and changes have been made, based on continuing class experience, Some experi- ments have been deleted. New experiments include Knudsen vapor- pressure measurements, X-ray diffraction studies, dielectric constants of solids, dielectric constants of pure polar liquids, kinetics of the bromina- tion of acetone, azeotropic systems, determination of activity coefficientsvi PREFACE from liquid-vapor equilibria and from freezing-point equilibria, thermo- dynamic analysis of the mechanical properties of rubber, and spectro- photometric studies of chemical equilibrium. ‘A new practice is introduced in this edition, Students should have experience in making detailed calculations from exact data obtained with expensive apparatus such as high-resolution infrared spectrometers, nuclear-magnetic-resonance spectrometers, and microwave spectrom- eters. Such elaborate equipment is not generally available in the teach- ing laboratories of physical chemistry. Accordingly, an experiment has been introduced in which the student does no experimental laboratory work but is provided instead with raw data and charts obtained with these instruments, from which he ealeulates various molecular parameters, ‘The second part of the book describes apparatus and techniques, par ticularly for more advanced work. Tt is designed not only to encourage students to undertake special work, but to aid them in later years in the solution of their laboratory problems. No claim whatsoever is made for completeness. In their selection of material the authors have been guided by their own experience. ‘The difficulty of selection increases with each new edition because the literature on new apparatus and techniques is expanding at an explosive rate, and because commercial instrument manufacturers have developed so many new and improved products. ‘Many comprehensive descriptions of experimental methods may be found in Weissberger’s “Technique of Organic Chemistry.” This edition, like its predecessors, owes much to many people—col- leagues at the University of Wisconsin, students, laboratory assistants, and teachers in other universities and colleges—who, over the years, have offered thoughtful criticisms and provided many worthwhile sug- gestions for improvements. The authors greatly appreciate this help and weleome further suggestions for future editions. ‘They are indebted to Professors John D. Ferry, Lawrence F. Dahl, Edward 0. Stejskal, ‘Monroe V. Evans, John L. Margrave and other staff members for critical reading of parts of the manuseript. ‘They wish to acknowledge the help of Lawrence Barlow, Lee Thompson, and others connected with the teach- ing of physical chemistry in this laboratory. They are indebted to Harry A. Schopler for many of the drawings retained from earlier editions, and to Mrs. Irene Frey for careful typing and preparation of the manuscript. Farrington Daniels John Warren Williams Paul Bender Robert A. Alberty C. Daniel CornwellContents Preface fee Symbols PART I, LABORATORY EXPERIMENTS Chapter 1. Gases 1. Gas Density 2. Vapor Density Chapter 2. Thermochemistry 3. Heat of Combustion: Bomb Calorimeter 4. Hest of Solution 5. Heat of Reaction in Solution: Constant-pressure Calorimeter Chapter 3. Vapor Pressures of Pure Substances 6. Vapor Pressure of a Pure Liquid 7. Knudsen Sublimation-pressure ‘Measurement Chapter 4. Solutions . 8. Liguid-Vapor Equilibrium in Binery Syatema_9. Fractional Distillation 10. Variation of Azeotrope Composition with Presure 11. Elevation of the Boiling Point 12. Activities from Froeaing-point Depression Data 13. Partial Molal Properties of Solutions Chapter 5. Homogeneous Equilibria 14, Equilibrium in Solution 15. Dissociation of Nitrogen Tetroxide 16. Speetrophotometrio Determination of an Equilibrium Constant 17. Dissociation Constant of Methyl Red Chapter 6. Heterogeneous Equilibria 18, Distribution of a Solute between Immiscible Solvents 19. Phase Dia gram of a Binary Solid-Liquid System 20, Three-component Systems 21, Solubility as a Funetion of Temperature Chapter 7. Chemical Kinetics 22, Hydrolysis of Methyl Acetate 23. Reaction of Ethyl Acetate with Hydroxyl Ion 24. Inversion of Sucrose 25. Bromination of Acetone xii as 5 93 10 129viii contents Chapter 8. Irreversible Processes in Solution 26. Viscosity of Liquids 27. Conductance Behavior of Weak and Strong Electrolytes 28. Transference Number of the Rydrogen Ton by the Mov- ing-boundary Method 29. Transference Number of the Silver Ton by the Hittorf Method 80. The Dropping-mercury Electrode Chapter 9. Electromotive Force 1. Single-lectrode Potentials 32. The Hydrogen Electrode 33. The Glass Electrode 34, Free Energy and the Equilibrium Constant 35. ‘Thermodynamics of Hlectrochemical Cells Chapter 10. Dielectric and Optical Properties of Matter 36, Dipole Moment from Dieleetrio-constant, Measurements on Solutions; Heterodyne-beat Method 37. Diclectrie Constants of Polar Liquids; Resonance Method 8, Dielectric Constant of a Solid ae a Function of Temperature 39. Optical Rotatory Dispersion Chapter 11. Spectroscopy . 40. Spectrometry and Spectrography 41. Raman Spectrum 42. Spee- troscopic Methods for the Study of Molecular Structure Chapter 12. Diffraction 43, X-ray Diffraction of Crystals Chapter 13. Macromolecular Chemistry 44, Viseosity of High-polymer Solutions 45. Determination of the Os- ‘otic Pressure of a Solution of High Polymer 46. Ton-exchange Chroma- tography 47. Sedimentation Rate and Particle Size Distribution 48. ‘Thermodynamic Analysis of Rubberlike Elasticity Chapter 14. Surface Chemistry 19. Surface Tension 50. Adsorption trom Solution §1- Adsoption of Gases Chapter 15. Photochemistry 52. Photohydrolysis of Monochloroacetic Acid Chapter 16. Radioactive Isotopes and Tracers 53, Determination of Range and Energy 54. The Srilard-Chalmers Proo- and the Halflife of Radioiodine 55. Exchange Reactions with Deu- terium Oxide Chapter 17. General Experimental Techniques 56, Glassblowing 57. High Vacuum £8. Electronics PART II, APPARATUS AND METHODS Chapter 18. Treatment of Experimental Data ‘Errors of Measurement. Estimation of Experimental Errore—Influence of Experimental Errors ut 183 a2 m3 32 339 343 361 393, 393CONTENTS oon the Final Reault—Addition and Subtraction—Multiplication or Divi- sion—Propagation of Probable Errors—Random Errors Significant Figures . Representation of Data ‘Tabular Representation—Representation of Data by Graphs—Represen- tation of Data by Equations Error Problems Chapter 19. Opticochemical Measurements Refractometry. ‘Refractometers Measuring Critical Angle—Differential Instruments— Schlieren Techniques—Interferometrie Methods Light Scattering Microscopy. - Light Mirosoope—Bleetron Mierncope Polarimetry Chapter 20, Thermal Measurements ‘Thermometry . The International Temperature Seale—Mereury Thermometers—Other Liquid Thermometers—Bimetallie Thermometers—Gas Thermometers— Resistance Thermometers—Thermocouples—Optical Pyrometers Calorimetry. Chapter 21. Physical Properties of Fluids Physical Properties of Gases ‘Volume by Displacement—Flowmeters—Manometers—Bourdon Gauge Deadweight Gauge—Pumpe Determination of the Boiling Point . ‘Superheating—Ebulliometors ‘Measurement of Vapor Pressure. Dynamic Method—Static Method—Gas-saturation Method—Teopiestic ‘Method ‘Fractional Distillation. ‘High-vacuum Distillation Density ‘Pycnometers—Buoyaney Methods—Flonting auibrium—Faling Drop Viscometry Surface Tension Diffusion. Free Dffsion—ResiriotedDiffusion—Stendy-etate Dion ‘Osmotic Pressure Chapter 22. Electrical Measurements Galvanometers. ‘Measurement of Eleetromotive Force Potentiometers—Recording Potentiometers—Standard Cells—Standard Electrodes Measurement of Electrolytic Conductance. ix 404 405 au 418 418 422 424 428 428 437 439 439 45 ar 40 458, 457 458 460 468 amX CONTENTS Alvernating-current, Wheatstone Bridge—Conduetivity Cells—Conduet- lance of Potassium Chloride Solutions—Conduetance Water Measurement of Current and Quantity of Electricity. Measurement of Electrical Energy in Calorimetry... Measurement of Transference Numbers and Ionie Mobilities ‘Measurement of Dielectric Constant, ‘Measurements at Very High Frequencies Chapter 23. Nuclear and Rav Availability of Teotopes Analysis for Stable Tsotopes Mase Spectrometry Analysis for Radioactive Isotopes oo Tonization Chambers—Proportional Countere—Geiger-Mller Counters Scintillation Counters—Solid-state Detectors—Neutron Counters— Miscellaneous Methods Radiation Chemistry ‘Radiation Safety ial Chapter 24. Purification of Mat os 5 Methods—Crystallisation—Fractional Distillation—Azeotropie Distills tion—-Adsorption—Drying—Zone Refining—Criteria of Purity—Water —Mercury—Benzeno—-Hydrocarbons-—Sodium Chloride—Sodium Hy- droxide Chapter 25. Photochemistry Sources of Light ‘Tungsten Filament—Mercury Arc—Other Ares ‘Techniques for Produoing Atoms and Radicals Optical Filters Fi Glass Filtors—Solutions—Golatin Filters—Interference Filters ‘Monochromators 5 Thermopiles Calibration Bolometers| Photoelectric Colle, Ronetion Cells Photography Chapter 26. Spectroscopy Resolution—Sensitivity—Bandwidth and Response ‘Time—Saturation Effect—Absorption and Dispersion Radiofrequeney Spectrometer Microwave Spectrometer Infrared Spectrometer. Chapter 27. Electron Alternating-current Circuit Theory Basic Circuit Elements—Properties of Sinusoidal Waveforms ance—Impedence of a Network Parallel Resonant Circuit. 476 477 479 480 438 484 485, 486 493 495 508 su on 518 514 519CONTENTS Active Circuit Klements—Thévenin's Theorem—Impedance Matehing— ‘Magnetic Coupling—Response to Nonsinusoidal [xcitation—Amplitude Modulation and Detestion—Frequeney Modulation—Mixing—Harmonie Generation—Bandwidth and Response Time ‘Vacuum Tubes. ‘The Diode and Rectification—The ‘Triode and Amplifcation—Graphical Analysis of Triode Amplifier—Dynumie Characteristies of Triodes—Gain of a Triode Amplifier—Lauivalent Circuit—Practical Triode-amplifier Cireuit—The Pentode Semiconductor Devioes ‘Semiconductors—Thermistors—Diodes-—’Transistors Noise Noise as the Ultimate Limit to Sensitivity Frequency Distribution of Noise—Johnson Noise—Shot-offect, Noiso—Flieker-effect_ Noise—Cur- rent Noise—Noise in Transistors—Noise Figure—Noise Calculations Measurements and ‘Test Equipment, Multimeters—Vacuum-tube Voltmeters—Potentiometrio Instruments— —The Cathode-ray Oscilloseope-—Measurement of Resistance, Capaci- tance, and Inductance—Measurement of Frequency—Time and Fre- quency Standards Miscellaneous Electronic Circuits Full-wave-rectifier Power Supply—Alternating-current Voltage Regula- tors—Direct-current Voltage Regulator—Constant, Current Supply- Vacuum-tube Relay—Cathode Follower—Amplifier with Peedback— Amplifiers with Negative Feedback—Narrow-band (Frequency-selective) ‘Audio Amplificr—Vacuum-tube Oscillator—Kecles-Jordan Trigger Cir- suit—Puleecounting, or Sting, Cireut—Phate-wniive Detector Safety Precautions, APPENDIX Algebra of Complex Numbers Physical-Chemical Constants ‘Values of the Defined Constants. Values of the Basie Constants Values of the Derived Constants. Values of Certain Auxiliary Relations Reduction of Barometer Readings on a Brass Seale to O° ‘Vapor Pressure of Water Density of Wator in Grams per Milliliter Concentration Seales Golor-code Conventions for Electronio-cireuit Components ‘Schematic Symbols for Electronic-cireuit Components ‘Common Abbreviations of Electronics Index. International Atomic Weights, 1956-1957 (nowt pup raren) ‘Table of Logarithms (eAck EXD PAPER) xi 550 570 817 581 610 610 on 611 Bi Bil 612 613 614 615 817 618 a9UR AN AACR SaRRVEZED p Symbols reciprocal moment of inertia, absorbancy angstrom rotational constant, reciprocal moment of inertia heat capacity, capacitance diffusion coefficient potential difference, voltage, electric field ‘Arrhenius activation energy faradey Gibbs free energy enthalpy, magnetic field strength ionic strength, moment of inertia, intensity of light, current, angular momentum (nuclear spin) angular momentum (generalized), spin-spin coupling constant, rotational quantum number equilibrium constant Kelvin scale boiling-point elevation constant freezing-point depression constant angular momentum (orbital) molecular weight molar seale Avogadro’s number pressure, polarization, angular momentum (molecular rotation) gas constant, Rydberg constant entropy absolute temperature, Kelvin seale transference number internal energy, potential energy function for diatonic molecule volume encrey mole fraction compressibility factor electrical conductance Hamiltonian, Hamiltonian operator molar polarization molar refractivityxiv symnos a activity, lattice constant a absorbaney index e concentration in moles per liter, number of components in phase rule, velocity of light a distance e electronic charge, electron, voltage (time-dependent part) ev electron volts j fugacity, frequency a acceleration of gravity h Planck's constant i current (time-dependent part) i Boltzmann constant, reaction-rate constant cell constant 1 mean free path, ionic conductance m ‘mass, molal concentration n molal scale n number of moles, refractive index partial pressure, number of phases in phase rule, linear mo- mentum PH measure of hydrogen-ion activity q quantity of heat absorbed r internuclear distance, particle radius t centigrade temperature, time » velocity, variance w work done y activity coefficient on molar scale a degree of dissociation, angle of optical rotation, alpha particle 8 beta particle 7 activity coefficient on the molal scale, gamma ray, surface tension, gyromagnetic ratio dielectric constant, energy of a radiation quantum, viscosity freezing-point depression, boiling-point elevation fugacity coefficient specific conductance wavelength equivalent conductance dipole moment, chemical pot frequeney wave number density torque summation ial, micron, reduced mass Mave re eaceoseSYMBOLS xv * quantum yield ® angular velocity ‘A superscript zero on a symbol for a thermodynamic quantity means that the value given corresponds to standard-state conditions, ‘A symbol 4, as in AM, indicates the increment in the thermodynamic quantity accompanying the change from the initial to the final state. A bar over the symbol for a thermodynamic quantity designates the partial molal ‘quantity (which for a pure substance is equal to the molar value of the quantity). The notation used for vectors (quantities having magnitude and direction) is lus trated by the following example: A = veotor quantity A = magnitude of A As, yy de = components of A along axes x, y, 2, respectively.PARTI Laboratory ExperimentsCHAPTER 1 Gases 1. GAS DENSITY This experiment illustrates the simplest and most direct method for determining the molecular weight of a gas. ‘The density of a gas is determined also by means of a density balance. ‘Theory. According to the ideal-gas law, 2RT @ T = absolute temperature (!°C + 273.15°) 9 = weight of gas of molecular weight M For the evaluation of the ideal-gas constant R, measurements with a substance of known molecular weight are required. ‘The chemical scale of atomic and molecular weights is defined by taking the molecular weight of atmospheric oxygen as 32 g mole~!, Careful experiments have shown that the pressure-volume product for 32 g of oxygen at 0°C approaches 22.414 liter-atm as the pressure approaches zero, leading to the value of 0.08205 liter-atm mole-* deg-! for R. From measurements of P and V for a known weight g of gas at a known absolute temperature 7’, a value of an unknown molecular weight M may be calculated. For permanent gases and pressures of the order of atmospheric pressure, this value of I is reasonably accurate, but, strictly speaking, Eq. (1) is obeyed exactly only as the pressure approaches zero. In the second part of the experiment the density of a gas is determined by means of a density balance. The principle of Archimedes is used, according to which the upward force is equal to the weight of the gas displaced. A large glass bulb on a balance beam is counterpoised { By international agreement this definition of the chemical atomie-weight scale hhas recently been replaced by one in which the atomic weight of the isotope Cis ‘akcen as 12.000000. This lowers atomie weights by 43 ppm relative to the old chemi= cal scale, but this change is not significant for most purposes. 34 LARORATORY EXPERIMENTS fexe. 1 with a weight, A reference gas such as oxygen is admitted, and its pressure adjusted. ‘The density at this pressure P, of the reference gas of molecular weight M; may be written as 0) _ Pils (#), RT @ If the apparatus is evacuated and another gas admitted, the pressure has to be adjusted to a different value in order to obtain a zero reading on the balance. At this new pressure the density of the gas of molecular weight ‘Mzis the same as that given by Eq. (2). If the temperature is constant PMs = PMs 3) ‘Thus, for gases which obey the ideal-gas law, this equation offers a con- venient method for determining the molecular weight of an unknown gas. Apparatus, A 200-ml thin-walled bulb with « small espillary stopcock; counter- poise of eame volume; analytical balaneo; vacuum-pump and manometer assembly; gae-density belance; barometer; carbon dioxide; other gases. Procedure. Gases are weighed in the glass bulb of the type shown in Fig. 1. The bulb is first weighed evacuated, and it is then weighed after filling to a known pressure with a gas the molecular weight of which is to be determined. In weighing large glass vessels it is necessary to maintain uniform conditions. ‘The bulb is wiped with a clean damp cloth and allowed to stand in the balance for 5 or 10 min to come to constant weight. A counterpoise, consisting of a closed glass bulb of practically the same volume, is used on the opposite balance pan to minimize errors due to adsorption of moisture and changes in buoyancy of the air due to baro- metric fluctuations. ‘The assembled apparatus is shown in Fig, 1, ‘The pressure is read to a fraction of a millimeter on a closed-end manometer. ‘The pressure inside tho glass bulb B, in millimeters of mercury, is equal to the difference in height of the mercury menisci in the two limbs of the manometer. ‘The tube at the base of the manometer has a small bore to prevent splashing the mercury when the pressure is raised or lowered suddenly. ‘The bulb is first evacuated to 1 mm or less with a motor-driven oil pump that is properly protected by use of a suitable trap. In order to obtain a steady pressure, it is important that the system be free of leaks, as proved by evacuating the bulb and observing that the mereury levels in the manometer remain constant when the connection to the pump is closed. Leaks at the rubber connections may be stopped by substituting new gum rubber which fits tightly over the glass tubes andExe. 1] cases 5 by winding wire around the connection, which is then painted with a solution of Glyptal resin. ‘The bulb is removed from the rubber connecting tube, wiped with a clean, damp (not wet), lintless cloth, and allowed to hang in the balance Fro. 1, Manometer and vacuum system for gae-density measurements, for 5 or 10 min to come to constant weight. The counterpoise, wiped in the same way, is used on the opposite pan. ‘The bulb is replaced in the apparatus and subjected to a second evacua- tion, after which it is weighed again. If the two weights do not check, the process is repeated until they do check. The evacuated bulb is now filled with carbon dioxide or other gas from stank. A diaphragm regulator connected to the tank is used to regulate6 LABORATORY EXPERIMENTS [exp. 1 the pressure, The bulb is returned to the vacuum system which has previously been evacuated. With the two-way stopcock closed, the stopcock on the bulb is opened and the pressure measured. ‘The tem- perature of the air in the vicinity of the bulb is recorded. After wiping with a damp cloth and waiting for equilibrium in the balance case, the bulb of gas is weighed. After weighing, the bulb is again evacuated and filled cautiously with earbon dioxide, the measured temperature and pressure are recorded, and the bulb is weighed, ‘The weight of carbon dioxide is determined in the same manner at about 2 and again at about } atm pressure, It is essential in this work that there be no leaks. The density of air or city gas or of some unknown gas or mixture of gases may be determined, introducing the gas through the drying tube 7’. The volume V of the bulb in eubie centimeters is obtained by weighing it empty and filled with distilled water. ‘The bulb is filled by evacuating it, closing the stopcock, immersing the end of the tube in a beaker of distilled water, and then opening it to permit the bulb to fill. A hypo- dermic syringe may be used to complete the filling of the bulb. ‘The bulb is then emptied by use of a water aspirator and placed in a drying oven. It is evacuated several times while hot to remove the last traces of moisture. In the second part of the experiment, the gas-density balance is used to determine the average molecular weight of dry air. A balance developed by Edwardst is illustrated in Fig. 2. ‘The case of the balance is connected to a closed-end manometer and has connections for attaching a vacuum pump or tank of purified gas. ‘The window at the end of the balance containing the counterpoise is marked so that the position of the pointer may be determined. Several readings are made on gas of known molecular weight such as ‘oxygen. The pressure necessary to bring the pointer to the zero point is determined. The pressure required for a zero balance with air, which has been passed through a tower of soda lime to remove water vapor, is determined next. In order to fill the gas balance with a new gas, it is evacuated, filled with gas, evacuated, and refilled with gas to sweep out the last traces of the first gas. A second density reading is then taken after further sweeping out with the new gas. If the two readings do not agree, the sweeping process is continued until two successive readings agree closely. Calculations. If the counterpoise has practically the same volume as the bulb, it is unnecessary to make a correction for the buoyancy of the air (see Appendix). ‘The weight g of the gas is obtained by subtracting the weight of the dry evacuated bulb from that of the bulb when filled with the gas.uxp. 1] cases 7 Tf a closed-end manometer is used, the observed pressure in millimeters of mercury is corrected to 0° by use of the equation ppt 5 Blt ~ 4) where Po, P = corrected and observed pressures t= centigrade temperature of manometer t, = temperature at which scale was calibrated, normally 20°C @ = mean cubical coefficient of expansion of mercury between 0 and 35° 8 = linear coefficient of expansion of scale material ‘The value of is 181.8 X 10-, and the value of 8 is 18.4 X 10-® for brass. If a wooden scale is used, taking the value of @ equal to zero introduces a negligible error, since 6 for wood is about 5 X 10-*, ino i Fic. 2. Gas-density balance, Hf an open-end manometer is used, the pressure in the bulb is equal to the difference between the corrected barometer pressure (see Appendix) and the manometer pressure corrected by use of Eq. (4)8 LABORATORY EXPERIMENTS [exr. 1 ‘The molecular weight of carbon dioxide is calculated at each pressure. If carbon dioxide were a perfect gas, the calculated molecular weight would be the same at all pressures. In determining the true molecular weight of a gas, it is necessary to plot the molecular weight obtained at different pressures and extrapolate to zero pressure. If the precision of the data warrants, a more accurate value of the molecular weight of carbon dioxide may be obtained in this way. ‘The mean molecular weight of air is calculated from measurements with the gas-density balance by using Eq. (3) and compared with the average molecular weight obtained from the known composition of air. Practical Applications. The formula of a chemical compound may be caleuleted from the molecular weight, together with the atomic weights, and the percentage ‘composition found by chemical analysis, In the most accurate work, globes of 8 to 20 litera have been used and corrections were made for the loss of buoyancy of the globe when it contracted on evacuation.’ The determination of the density of ammonia gas by Dietrichson and coworkers illustrates the experimental techniques ‘used in accurate work. Birge and Jenkins havo discussed the methods for extrap- olating to the limiting gas density and the errors involved. The work of Cady and Rarick? indicates the high precision with which molecular weights may be determined with a gas-density balance. ‘The chemical equilibrium between different gases may often be calculated from the density of the equilibrium mixture of gases. ‘Suggestions for Further Work. The accurate determination of the molecular weight of hydrogen gas by this method constitutes a real test of a student's care and kill ‘The molecular weights of other gases may be determined. Small tanks of methane, ethylene, nitrous oxide, Freon, and other gases can be purchased. ‘The peroentage composition of a mixture of two gases such as oxygen and carbon dioxide may be determined from the density of the mixture. ‘More exact values of the molecular woights may be calculated with equations of state such as those of Berthelot, van der Waals, or Beattic and Bridgman. How- ever, the use of these equations requires a knowledge of certain constants characteristic of the gas which will not be available for an unknown gas ‘The gas-density balance is well adapted to measuring the density of « mixture of gases, "For example, the carbon dioxide content of the exhaled breath may be deter- mined by blowing the breath through a calcium chloride drying tube and a cotton packing into the balanc In the analysis of a mixture of gases, the density in grams per liter is determined with the balanee, and the density of each pure gas at the same pressure is known. ‘A formula is derived that will give the percentage composition corresponding to the observed density at the observed pressure. It is assumed that any interaction among the diferent gases leading to density changes is negligible in the experiments described hero. References 1, Baxter and Starkwesther, Proc. Natl. Acad. Sci. U.8., 12, 699 (1926). 2. Binge and Jenkins, J. Chem. Phye., 2, 167 (1034). 3. Cady and Rarick, J. Am. Chem, Soe, 63, 1357 (1941).Exp. 2] Gases 9 4. Dietrichson, Bircher, and O'Brien, J. Am. Chem. Soe., 50, 1-21 (1983). 5. Edwards, Ind. Eng. Chem., 9, 790 (1917), 2. VAPOR DENSITY This experiment illustrates a practical method for determining the molecular weight of a volatile material. It provides excellent practice in the use of physical-chemical apparatus, which demands some skill in manipulation. Theory. ‘The density of a vapor is more easily determined than the density of a gas because the substance may be weighed accurately when condensed to a liquid at room temperature. Very accurate vapor- density results can be obtained in this way. When only moderate accuracy is required, the Victor Meyer** method is one of the simplest, and it is still frequently used. A known weight of liquid is vaporised in a chamber maintained at an appropriate and constant high temperature. The air displaced from the chamber is cooled to room temperature, and its volume carefully meas- ured. Substitution of air for the actual vapor thus provides a means of determining the volume the known weight of vapor would occupy at room temperature if it could be cooled without condensation, It should be noted that it is not necessary that the temperature of the vaporization chamber be known, but it must be constant. Apparatus, Modified Vietor Meyer apparatus; gas burette and leveling bulb; ¥° thermometer; barometer; glass bulblets; carbon tetrachloride, benzene, acetone, or chloroform; water aspirator; large and small test tube. Procedure. A modified form of the Victor Meyer apparatus is assembled as shown in Fig. 3. It consists essentially of four parts: (a) 9 small bulblet containing a weighed amount of a volatile liquid, (6) a vaporizer tube which contains the vapor after the bulblet is broken, (©) s gas burette for measuring the volume of air displaced by the forma- tion of the vapor, and (d) a steam generator connected to a heating jacket surrounding the vaporizer tube. ‘The bulblets for containing the weighed samples of liquid are made by drawing out 4 mm soft glass as shown in Fig. 4. ‘The tubing is rotated evenly during the heating operation. The micro flame shown is formed by a jet of gas issuing from a capillary section drawn at the end of a Pyrex tube. After drawing, bending, and sealing the right-angled tail, the bulblet is weighed on an anslytical balance. About 0.1 ml of the liquid to be used is placed in a miniature test tube (§ by 2 in.), and the latter is then placed in a large test tube (1 by 6 in.) with the open capillary of the bulblet dipping into the liquid. A stopper with outlet tube is10 LABORATORY EXPERIMENTS (exe. 2 fitted to the test tube and attached by vacuum tubing to a water aspira- tor. The tube is evacuated, and some of the air contained in the bulblet bubbles out. ‘The vacuum is then broken by suddenly removing the connecting tube, and the liquid is driven into the bulblet. ‘The bulblet is then removed and inverted to drain the capillary, and the capillary is Fro, 8, Modified Vietor Meyer apparatus sealed off with a small flame from a wing-top bunsen burner or a Pyrex capillary, about an inch from the end, care being taken that no liquid is present in the immediate area of heating and that the flame does not strike the open end of the eapillary, where it can deposit condensed water. The sealed bulblet with its liquid and the remaining sealed-off end are then weighed again to obtain the weight of the liquid. Any liquid remaining in the open capillary tip which has been sealed off must be removed before weighing. Because leaking bulblets are the main cause of difficulty in this experiment, the quality of the seal should be tested. ‘The bulblet, inaExp. 2] oases 11 dry miniature test tube, is returned to the filling apparatus, which is then evacuated as far as possible with the water aspirator. Any serious deficiency in the seals will become obvious by leakage. The assembled apparatus is shown in Fig. 3, The inner vaporizer tube B, 40 cm in length and 2 or 3 em in diameter, is provided with a J Pie eer fh io aspirator Wire for removal of sample 0.1 mi. sample Fio, 4, Preparation and filling of Vietor Meyer bulblet, rubber stopper through which passes a brass tube C. At the bottom of the tube C a hole is bored through both walls to hold the bent tail of the bulblet D. Three or four metal disks, spaced along the brass tube C and somewhat smaller in diameter than the vaporizer tube, reduce the rate of upward progress of the vapor when the bulblet is broken and thus reduce the chanee of condensing vapor. ‘They are cut from thin metal and provided with a central hole so that they can be slipped along the tube and soldered in position. A loosely fitting cylinder I of suitable plastic or hard rubber is placed at the top of the tube to reduce the dead air space and hasten the attainment of thermal equilibrium.12 LABORATORY EXPERIMENTS (exp. 2 A loosely fitting brass rod F passes through the tube C and ends just, above the holes drilled in it for holding the bulblet. It is securely held at its upper end by a rubber tube @ which passes around both the brass tube and the brass rod, thus providing a vertically adjustable but gas-tight joint. The rod is pushed down at the appropriate time to break the bent tail of the bulblet. A side arm at the top of the vaporizer tube B leads through a rubber tube to a gas burette and leveling bulb, which is filled with water. ‘The vaporizer tube is surrounded by an outer jacket A of Pyrex which is about 40 cm long and 5 cm in diameter. It is centered in a ring stopper and is connected through a sidearm to a steam generator with a safety tube. The bottom of the jacket is provided with an outlet and rubber tube through which condensed water and excess steam pass to a sink. ‘When the bulblets have been filled and weighed and the steam jacket is operating, the vaporizer is swept out with a current of air to remove any condensible vapor from previous determinations. The rubber stopper containing the brass tube is loosened to provide air entrance, and the aspirator draws air through the vaporizer and the rubber tube @. ‘The apparatus is assembled with the sealed bulblet in an inverted position as shown in Fig. 3. After steam has passed through the jacket for at least 10 min, the stoppers are tightened and the screw clamp His closed. ‘The vaporizer is tested for leaks and thermal equilibrium by lowering the leveling bulb to create a pressure less than that of the atmosphere. If the water in the burette does not continue to fall when the leveling bulb is maintained at this lower level, the apparatus is air- tight and in thermal equilibrium. ‘The apparatus is then in condition for the start of the experiment. ‘The reading of the gas burette is taken with the leveling bulb adjusted to make the liquid level the same in the bulb and in the burette. The pressure inside the system is then equal to atmospheriepressure. The brass rod is now pushed down sufficiently to break off the lower capillary tip of the bulblet, whereupon the heated liquid is rapidly vaporized. As the vaporization takes place, the leveling tube is lowered so as to maintain nearly equal pressure inside and outside the apparatus, to minimizo leakage. When the hot air displaced into the gas burette cools, a slight contraction may be noted. When the level of the liquid in the burette ceases to change position, the levels of the liquid are carefully adjusted to exactly the same height, and the final reading of the volume is made. After the apparatus has stood for a longer time, the volume of the meas- ured air may decrease, because of diffusion of the vapor from the vaporizer into the cooler parts of the apparatus where it condenses. The final reading is taken before such condensation occurs, just as soon as the level becomes constant. ‘The temperature is taken from a thermometer hang-Exp. 2] cases 13 ing close to the burette. For more precise work, the measuring tube may be jacketed with a coneentric tube containing water and a thermometer. Carbon tetrachloride, benzene, or any low-boiling liquid may be used. ‘The material must be pure. Two or more determinations are made until satisfactory checks are obtained. After each determination the vapor is removed before a second experiment is started, for an excessive volume of vapor leads to condensation in the connecting tube. The apparatus should not be dismantled until the calculations have been made and the results compared. Calculations. The pressure is read from the barometer and cor- rected to 0°C, using tables or calculations (Appendix). ‘The correction amounts to 2 or 3 mm. Another correction should be made for water vapor in the measured air volume. The partial pressure of water in the gas burette is equal to 78,0, the vapor pressure of water at the prevailing temperature. The air introduced from the vaporization tube has a partial pressure of water vapor, r7%,0, determined by the relative humid- ity r of the laboratory air. The latter may be determined with a sling psychrometer or, more conveniently, a hair hygrometer reading directly in relative humidity. The difference in partial pressure of water between saturated air and the unsaturated laboratory air is subtracted from the total pressure P in the burette, which is equal to the atmospheric pressure as recorded by the barometer. This correction assumes that no diffusion of water vapor into the vaporization tube occurs during the preliminary phases of the experiment, and it becomes less accurate if the experiment requires an extended period of time. The molecular weight Mf of the vapor is calculated from the familiar equation 9 ov = Rr where p = partial pressure, in burette, of air displaced by vapor P — Proll — 1) V = volume of displaced air, mi ibsolute temperature at which volume is measured weight of liquid taken gas constant Better results are obtained by using van der Waals’ equation or Berthelot’s equation. A convenient form of the latter is Rr 9 PT, r w= o5p[1 + 5 (i-6 | 7 where P. = critical pressure of compound used T. = critical temperature of compound used T, = temperature of steam jacket14 LABORATORY EXPERIMENTS exe. 2 Such an equation is obviously of no use in the case of an unknown com- pound, since the critical temperature and pressure will not be known. Tt is used, however, for testing the reliability of the apparatus on known substances. Practical Applications. The determination of the molecular weight is useful in identifying » chemical compound and in establishing its formula. ‘When gases dissociate on heating, the equilibrium may be studied quantitatively through measurements of the gas densities. Suggestions for Further Work. The densities of several organic or inorganic vapors may be measured. For substances having boiling points above 80°, somo liquid boiling higher than water must. he used to generate vapor for the jacket,* or a furnace may be used for extremely high temperatures.* ‘The jacket should be at a temperature at least 20° above the boiling point of the substance whose vapor density is being determined, because of the failure of the gas laws to apply to vapors that are ‘near the condensation point. References . Evans, J. Am. Chem. Soc, 35, 958 (1913). , Harris and Meyer, Ber., 27, 1482 (1894), and earlier papers. . Kretschmer and Wiebe, J. Am. Chem. Soe, 76, 2579 (1954). | Meyer, Ber., 11, 1867 (1878). 5. Meyer and Meyer, Ber., 12, 1112 (1879).CHAPTER 2 Thermochemistry 8, HEAT OF COMBUSTION: BOMB CALORIMETER ‘The enthalpy of combustion is determined in this experiment by means of a bomb calorimeter. Theory.™** The standard enthalpy of combustion for a substance is defined as the enthalpy change, AH, which accompanies a process in which the given substance undergoes reaction with oxygen gas to form specified combustion produets [such as COx(g), H:0(), Nu(g), $Ox(9)], all reactants and products being in their respective standard states at the given temperature 7. Thus the standard enthalpy of combustion of benzoic acid at 298.15°K is AHsys.1e for the process CsHsCO:H(s) + 4#0:() = 7CO.(9) + 3H:0() @ with reactants and products in their standard states for this temperature. As will be shown below, the enthalpy of combustion can be caleulated from the temperature rise which results when the combustion reaction oceurs under adiabatic conditions in a calorimeter. Tt is important that ‘the reaction in the calorimeter take place rapidly and completely. ‘To this end, the material is burned in a steel bomb with oxygen under a pressure of about 25 atm. A special acid-resistant alloy is used for the construction of the bomb because water and acids are produced in the reaction, In the adiabatic-jacket bomb calorimeter (Fig. 5) the bomb is immersed in a can of water, fitted with a precise thermometer. ‘This assembly is placed within an outer water-filled jacket. Both before and after the combustion occurs, the jacket temperature is maintained (by external means) at the same value as that of the water in the can. If the tem- peratures are matched with sufficient accuracy, the can and contents do not gain or lose energy by radiation or conduction, and the process is therefore adiabatic. This method affords convenience in work of moderate accuracy, but there is inevitably some error due to time lag in adjustment of the outer- 15