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An Introduction to Isotopic Calculations John M
An Introduction to Isotopic Calculations John M. Hayes ([email protected]) Woods Hole Oceanographic Institution, Woods Hole, MA 02543, USA, 30 September 2004 Abstract. These notes provide an introduction to: termed isotope effects. As a result of such effects, the • Methods for the expression of isotopic abundances, natural abundances of the stable isotopes of practically • Isotopic mass balances, and all elements involved in low-temperature geochemical • Isotope effects and their consequences in open and (< 200°C) and biological processes are not precisely con- closed systems. stant. Taking carbon as an example, the range of interest is roughly 0.00998 ≤ 13F ≤ 0.01121. Within that range, Notation. Absolute abundances of isotopes are com- differences as small as 0.00001 can provide information monly reported in terms of atom percent. For example, about the source of the carbon and about processes in 13 13 12 13 atom percent C = [ C/( C + C)]100 (1) which the carbon has participated. A closely related term is the fractional abundance The delta notation. Because the interesting isotopic 13 13 fractional abundance of C ≡ F differences between natural samples usually occur at and 13F = 13C/(12C + 13C) (2) beyond the third significant figure of the isotope ratio, it has become conventional to express isotopic abundances These variables deserve attention because they provide using a differential notation. To provide a concrete the only basis for perfectly accurate mass balances. example, it is far easier to say – and to remember – that Isotope ratios are also measures of the absolute abun- the isotope ratios of samples A and B differ by one part dance of isotopes; they are usually arranged so that the per thousand than to say that sample A has 0.3663 %15N more abundant isotope appears in the denominator and sample B has 0.3659 %15N. -
Mass Spectrometry: Quadrupole Mass Filter
Advanced Lab, Jan. 2008 Mass Spectrometry: Quadrupole Mass Filter The mass spectrometer is essentially an instrument which can be used to measure the mass, or more correctly the mass/charge ratio, of ionized atoms or other electrically charged particles. Mass spectrometers are now used in physics, geology, chemistry, biology and medicine to determine compositions, to measure isotopic ratios, for detecting leaks in vacuum systems, and in homeland security. Mass Spectrometer Designs The first mass spectrographs were invented almost 100 years ago, by A.J. Dempster, F.W. Aston and others, and have therefore been in continuous development over a very long period. However the principle of using electric and magnetic fields to accelerate and establish the trajectories of ions inside the spectrometer according to their mass/charge ratio is common to all the different designs. The following description of Dempster’s original mass spectrograph is a simple illustration of these physical principles: The magnetic sector spectrograph PUMP F DD S S3 1 r S2 Fig. 1: Dempster’s Mass Spectrograph (1918). Atoms/molecules are first ionized by electrons emitted from the hot filament (F) and then accelerated towards the entrance slit (S1). The ions then follow a semicircular trajectory established by the Lorentz force in a uniform magnetic field. The radius of the trajectory, r, is defined by three slits (S1, S2, and S3). Ions with this selected trajectory are then detected by the detector D. How the magnetic sector mass spectrograph works: Equating the Lorentz force with the centripetal force gives: qvB = mv2/r (1) where q is the charge on the ion (usually +e), B the magnetic field, m is the mass of the ion and r the radius of the ion trajectory. -
Determination of the Molar Mass of an Unknown Solid by Freezing Point Depression
Determination of the Molar Mass of an Unknown Solid by Freezing Point Depression GOAL AND OVERVIEW In the first part of the lab, a series of solutions will be made in order to determine the freezing point depression constant, Kf, for cyclohexane. The freezing points of these solutions, which will contain known amounts of p-dichlorobenzene dissolved in cyclohexane, will be measured. In the second part of the lab, the freezing point of a cyclohexane solution will be prepared that contains a known mass of an unknown organic solid. The measured freezing point change will be used to calculate the molar mass of the unknown solid. Objectives and Science Skills • Understand and explain colligative properties of solutions, including freezing point depression. • Measure the freezing point of a pure solvent and of a solution in that solvent containing an unknown solute. • Calculate the molar mass of the unknown solute and determine its probable identity from a set of choices. • Quantify the expected freezing point change in a solution of known molality. • Quantitatively and qualitatively compare experimental results with theoretical values. • Identify and discuss factors or effects that may contribute to the uncertainties in values determined from experimental data. SUGGESTED REVIEW AND EXTERNAL READING • Reference information on thermodynamics; data analysis; relevant textbook information BACKGROUND If a liquid is at a higher temperature than its surroundings, the liquid's temperature will fall as it gives up heat to the surroundings. When the liquid's temperature reaches its freezing point, the liquid's temperature will not fall as it continues to give up heat to the surroundings. -
Good Practice Guide for Isotope Ratio Mass Spectrometry, FIRMS (2011)
Good Practice Guide for Isotope Ratio Mass Spectrometry Good Practice Guide for Isotope Ratio Mass Spectrometry First Edition 2011 Editors Dr Jim Carter, UK Vicki Barwick, UK Contributors Dr Jim Carter, UK Dr Claire Lock, UK Acknowledgements Prof Wolfram Meier-Augenstein, UK This Guide has been produced by Dr Helen Kemp, UK members of the Steering Group of the Forensic Isotope Ratio Mass Dr Sabine Schneiders, Germany Spectrometry (FIRMS) Network. Dr Libby Stern, USA Acknowledgement of an individual does not indicate their agreement with Dr Gerard van der Peijl, Netherlands this Guide in its entirety. Production of this Guide was funded in part by the UK National Measurement System. This publication should be cited as: First edition 2011 J. F. Carter and V. J. Barwick (Eds), Good practice guide for isotope ratio mass spectrometry, FIRMS (2011). ISBN 978-0-948926-31-0 ISBN 978-0-948926-31-0 Copyright © 2011 Copyright of this document is vested in the members of the FIRMS Network. IRMS Guide 1st Ed. 2011 Preface A few decades ago, mass spectrometry (by which I mean organic MS) was considered a “black art”. Its complex and highly expensive instruments were maintained and operated by a few dedicated technicians and its output understood by only a few academics. Despite, or because, of this the data produced were amongst the “gold standard” of analytical science. In recent years a revolution occurred and MS became an affordable, easy to use and routine technique in many laboratories. Although many (rightly) applaud this popularisation, as a consequence the “black art” has been replaced by a “black box”: SAMPLES GO IN → → RESULTS COME OUT The user often has little comprehension of what goes on “under the hood” and, when “things go wrong”, the inexperienced operator can be unaware of why (or even that) the results that come out do not reflect the sample that goes in. -
Δtb = M × Kb, Δtf = M × Kf
8.1HW Colligative Properties.doc Colligative Properties of Solvents Use the Equations given in your notes to solve the Colligative Property Questions. ΔTb = m × Kb, ΔTf = m × Kf Freezing Boiling K K Solvent Formula Point f b Point (°C) (°C/m) (°C/m) (°C) Water H2O 0.000 100.000 1.858 0.521 Acetic acid HC2H3O2 16.60 118.5 3.59 3.08 Benzene C6H6 5.455 80.2 5.065 2.61 Camphor C10H16O 179.5 ... 40 ... Carbon disulfide CS2 ... 46.3 ... 2.40 Cyclohexane C6H12 6.55 80.74 20.0 2.79 Ethanol C2H5OH ... 78.3 ... 1.07 1. Which solvent’s freezing point is depressed the most by the addition of a solute? This is determined by the Freezing Point Depression constant, Kf. The substance with the highest value for Kf will be affected the most. This would be Camphor with a constant of 40. 2. Which solvent’s freezing point is depressed the least by the addition of a solute? By the same logic as above, the substance with the lowest value for Kf will be affected the least. This is water. Certainly the case could be made that Carbon disulfide and Ethanol are affected the least as they do not have a constant. 3. Which solvent’s boiling point is elevated the least by the addition of a solute? Water 4. Which solvent’s boiling point is elevated the most by the addition of a solute? Acetic Acid 5. How does Kf relate to Kb? Kf > Kb (fill in the blank) The freezing point constant is always greater. -
2019 Redefinition of SI Base Units
2019 redefinition of SI base units A redefinition of SI base units is scheduled to come into force on 20 May 2019.[1][2] The kilogram, ampere, kelvin, and mole will then be defined by setting exact numerical values for the Planck constant (h), the elementary electric charge (e), the Boltzmann constant (k), and the Avogadro constant (NA), respectively. The metre and candela are already defined by physical constants, subject to correction to their present definitions. The new definitions aim to improve the SI without changing the size of any units, thus ensuring continuity with existing measurements.[3][4] In November 2018, the 26th General Conference on Weights and Measures (CGPM) unanimously approved these changes,[5][6] which the International Committee for Weights and Measures (CIPM) had proposed earlier that year.[7]:23 The previous major change of the metric system was in 1960 when the International System of Units (SI) was formally published. The SI is a coherent system structured around seven base units whose definitions are unconstrained by that of any other unit and another twenty-two named units derived from these base units. The metre was redefined in terms of the wavelength of a spectral line of a The SI system after the 2019 redefinition: krypton-86 radiation,[Note 1] making it derivable from universal natural Dependence of base unit definitions onphysical constants with fixed numerical values and on other phenomena, but the kilogram remained defined in terms of a physical prototype, base units. leaving it the only artefact upon which the SI unit definitions depend. The metric system was originally conceived as a system of measurement that was derivable from unchanging phenomena,[8] but practical limitations necessitated the use of artefacts (the prototype metre and prototype kilogram) when the metric system was first introduced in France in 1799. -
Electron Ionization
Chapter 6 Chapter 6 Electron Ionization I. Introduction ......................................................................................................317 II. Ionization Process............................................................................................317 III. Strategy for Data Interpretation......................................................................321 1. Assumptions 2. The Ionization Process IV. Types of Fragmentation Pathways.................................................................328 1. Sigma-Bond Cleavage 2. Homolytic or Radical-Site-Driven Cleavage 3. Heterolytic or Charge-Site-Driven Cleavage 4. Rearrangements A. Hydrogen-Shift Rearrangements B. Hydride-Shift Rearrangements V. Representative Fragmentations (Spectra) of Classes of Compounds.......... 344 1. Hydrocarbons A. Saturated Hydrocarbons 1) Straight-Chain Hydrocarbons 2) Branched Hydrocarbons 3) Cyclic Hydrocarbons B. Unsaturated C. Aromatic 2. Alkyl Halides 3. Oxygen-Containing Compounds A. Aliphatic Alcohols B. Aliphatic Ethers C. Aromatic Alcohols D. Cyclic Ethers E. Ketones and Aldehydes F. Aliphatic Acids and Esters G. Aromatic Acids and Esters 4. Nitrogen-Containing Compounds A. Aliphatic Amines B. Aromatic Compounds Containing Atoms of Nitrogen C. Heterocyclic Nitrogen-Containing Compounds D. Nitro Compounds E. Concluding Remarks on the Mass Spectra of Nitrogen-Containing Compounds 5. Multiple Heteroatoms or Heteroatoms and a Double Bond 6. Trimethylsilyl Derivative 7. Determining the Location of Double Bonds VI. Library -
Modern Mass Spectrometry
Modern Mass Spectrometry MacMillan Group Meeting 2005 Sandra Lee Key References: E. Uggerud, S. Petrie, D. K. Bohme, F. Turecek, D. Schröder, H. Schwarz, D. Plattner, T. Wyttenbach, M. T. Bowers, P. B. Armentrout, S. A. Truger, T. Junker, G. Suizdak, Mark Brönstrup. Topics in Current Chemistry: Modern Mass Spectroscopy, pp. 1-302, 225. Springer-Verlag, Berlin, 2003. Current Topics in Organic Chemistry 2003, 15, 1503-1624 1 The Basics of Mass Spectroscopy ! Purpose Mass spectrometers use the difference in mass-to-charge ratio (m/z) of ionized atoms or molecules to separate them. Therefore, mass spectroscopy allows quantitation of atoms or molecules and provides structural information by the identification of distinctive fragmentation patterns. The general operation of a mass spectrometer is: "1. " create gas-phase ions "2. " separate the ions in space or time based on their mass-to-charge ratio "3. " measure the quantity of ions of each mass-to-charge ratio Ionization sources ! Instrumentation Chemical Ionisation (CI) Atmospheric Pressure CI!(APCI) Electron Impact!(EI) Electrospray Ionization!(ESI) SORTING DETECTION IONIZATION OF IONS OF IONS Fast Atom Bombardment (FAB) Field Desorption/Field Ionisation (FD/FI) Matrix Assisted Laser Desorption gaseous mass ion Ionisation!(MALDI) ion source analyzer transducer Thermospray Ionisation (TI) Analyzers quadrupoles vacuum signal Time-of-Flight (TOF) pump processor magnetic sectors 10-5– 10-8 torr Fourier transform and quadrupole ion traps inlet Detectors mass electron multiplier spectrum Faraday cup Ionization Sources: Classical Methods ! Electron Impact Ionization A beam of electrons passes through a gas-phase sample and collides with neutral analyte molcules (M) to produce a positively charged ion or a fragment ion. -
Find the Molar Mass of Sodium Carbonate, Na 2CO3. Na 2 X
Moles and Molar Mass The mole is the "counting unit" used by chemists to indicate the number of atoms, ions, molecules, or formula units present in a particular chemical sample. The mole is similar to other counting units that you've used before....pair (2), dozen (12), and gross (144). One mole of a compound contains Avogadro's number (6.022 x 1023) of molecules (molecular compound) or formula units (ionic compound). The molar mass of a compound tells you the mass of 1 mole of that substance. In other words, it tells you the number of grams per mole of a compound. The units for molar mass are, therefore, grams/mole. To find the molar mass of a compound: 1. Use the chemical formula to determine the number of each type of atom present in the compound. 2. Multiply the atomic weight (from the periodic table) of each element by the number of atoms of that element present in the compound. 3. Add it all together and put units of grams/mole after the number. Example: Find the molar mass of sodium carbonate, Na2CO3. Na 2 x 23.0 = 46.0 C 1 x 12.0 = 12.0 O 3 x 16.0 = 48.0 molar = 106.0 g/mole mass For many (but not all) problems, you can simply round the atomic weights and the molar mass to the nearest 0.1 g/mole. HOWEVER, make sure that you use at least as many significant figures in your molar mass as the measurement with the fewest significant figures. -
Arxiv:0801.0028V1 [Physics.Atom-Ph] 29 Dec 2007 § ‡ † (People’S China Metrology, Of) of Lic Institute Canada National Council, Zhang, Research Z
CODATA Recommended Values of the Fundamental Physical Constants: 2006∗ Peter J. Mohr†, Barry N. Taylor‡, and David B. Newell§, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-8420, USA (Dated: March 29, 2012) This paper gives the 2006 self-consistent set of values of the basic constants and conversion factors of physics and chemistry recommended by the Committee on Data for Science and Technology (CODATA) for international use. Further, it describes in detail the adjustment of the values of the constants, including the selection of the final set of input data based on the results of least-squares analyses. The 2006 adjustment takes into account the data considered in the 2002 adjustment as well as the data that became available between 31 December 2002, the closing date of that adjustment, and 31 December 2006, the closing date of the new adjustment. The new data have led to a significant reduction in the uncertainties of many recommended values. The 2006 set replaces the previously recommended 2002 CODATA set and may also be found on the World Wide Web at physics.nist.gov/constants. Contents 3. Cyclotron resonance measurement of the electron relative atomic mass Ar(e) 8 Glossary 2 4. Atomic transition frequencies 8 1. Introduction 4 1. Hydrogen and deuterium transition frequencies, the 1. Background 4 Rydberg constant R∞, and the proton and deuteron charge radii R , R 8 2. Time variation of the constants 5 p d 1. Theory relevant to the Rydberg constant 9 3. Outline of paper 5 2. Experiments on hydrogen and deuterium 16 3. -
AP Chemistry Summer Assignment #6 1. What Is the Molecular Mass Of
AP Chemistry Summer Assignment #6 1. What is the molecular mass of crotonaldehyde C 4H6O? 2. A substance contains 23.0 g sodium, 27.0 g aluminum, and 114 g fluorine. How many grams of sodium are there in a 120.-g sample of the substance? 3. NaHCO 3 is the active ingredient in baking soda. How many grams of oxygen are in 0.35 g of NaHCO 3? 4. A sample of copper weighing 6.93 g contains how many moles of copper atoms? 5. Roundup, a herbicide manufactured by Monsanto, has the formula C 3H8NO 5P How many moles of molecules are there in a 500.-g sample of Roundup? 6. What is the molecular weight of ammonium chloride? 7. What is the percent by mass of bromine in ammonium perbromate? (The perbromate ion is BrO 4-.) 8. A chloride of rhenium contains 63.6% rhenium. What is the formula of this compound? 9. The mass percent of carbon in a compound containing only oxygen and carbon is 27.29%. Calculate the empirical formula. 10. A 2.00-g sample of an oxide of bromine is converted to 2.936g of AgBr. Calculate the empirical formula of the oxide. (Mol. mass. for AgBr = 187.78) 11. Phenol is a compound which contains 76.57% carbon, 6.43% hydrogen, and 17.0% oxygen. The empirical formula of phenol is __ 12. The empirical formula of a group of compounds is CHCl. Lindane, a powerful insecticide, is a member of this group. The molecular weight of lindane is 290.8. -
Atomic Weights and Isotopic Abundances*
Pure&App/. Chem., Vol. 64, No. 10, pp. 1535-1543, 1992. Printed in Great Britain. @ 1992 IUPAC INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY INORGANIC CHEMISTRY DIVISION COMMISSION ON ATOMIC WEIGHTS AND ISOTOPIC ABUNDANCES* 'ATOMIC WEIGHT' -THE NAME, ITS HISTORY, DEFINITION, AND UNITS Prepared for publication by P. DE BIEVRE' and H. S. PEISER2 'Central Bureau for Nuclear Measurements (CBNM), Commission of the European Communities-JRC, B-2440 Geel, Belgium 2638 Blossom Drive, Rockville, MD 20850, USA *Membership of the Commission for the period 1989-1991 was as follows: J. R. De Laeter (Australia, Chairman); K. G. Heumann (FRG, Secretary); R. C. Barber (Canada, Associate); J. CCsario (France, Titular); T. B. Coplen (USA, Titular); H. J. Dietze (FRG, Associate); J. W. Gramlich (USA, Associate); H. S. Hertz (USA, Associate); H. R. Krouse (Canada, Titular); A. Lamberty (Belgium, Associate); T. J. Murphy (USA, Associate); K. J. R. Rosman (Australia, Titular); M. P. Seyfried (FRG, Associate); M. Shima (Japan, Titular); K. Wade (UK, Associate); P. De Bi&vre(Belgium, National Representative); N. N. Greenwood (UK, National Representative); H. S. Peiser (USA, National Representative); N. K. Rao (India, National Representative). Republication of this report is permitted without the need for formal IUPAC permission on condition that an acknowledgement, with full reference together with IUPAC copyright symbol (01992 IUPAC), is printed. Publication of a translation into another language is subject to the additional condition of prior approval from the relevant IUPAC National Adhering Organization. ’Atomic weight‘: The name, its history, definition, and units Abstract-The widely used term “atomic weight” and its acceptance within the international system for measurements has been the subject of debate.