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Principles of Chemistry: A Molecular Approach, 1st Ed. Nivaldo Tro Chapter 2 Atoms and Elements Roy Kennedy Massachusetts Bay Community College Wellesley Hills Hills, MA Tro, Principles of Chemistry: A Molecular Approach Laws of Matter Law off Conservation C off Mass (Antoine ( Lavoisier 1743–1794)) • In a chemical reaction, matter is neither created nor • destroyed destroyed. Total mass of the materials you have before the reaction must equal q the total mass of the materials yyou have at the end. total mass of reactants = total mass of products Law of Definite Proportions (Joseph Proust 1754–1826) 1754 1826) • All samples of a given compound, regardless of their source or how they were prepared, have the same proportions of their constituent elements. Law of Multiple p Proportions p (John Dalton 1766–1844)) • When two elements (call them A and B) form two different compounds, the masses of B that combine with 1 g of A can be expressed as a ratio of small whole numbers. 2 Tro, Principles of Chemistry: A Molecular Approach Law of Conservation of Mass Reaction of Sodium with Chlorine • The mass of sodium and chlorine used is determined by the number of atoms that combine. • Since only whole atoms combine and atoms are not changed or destroyed in the process, the mass of sodium chloride made must equal the total mass of sodium and chlorine atoms that combine t together. th 7.7 g Na Tro, Principles of Chemistry: A Molecular Approach + 11.9 g Cl2 3 19.6 g NaCl Law of Definite Proportions Proportions in Sodium Chloride Tro, Principles of Chemistry: A Molecular Approach 4 Law of Multiple Proportions Oxides of Carbon • Carbon combines with oxygen to form • • • two different compounds, carbon monoxide and carbon dioxide. Carbon monoxide contains 1.33 g of oxygen for every 1.00 g of carbon. Carbon dioxide dio ide contains 2 2.67 67 g of oxygen for every 1.00 g of carbon. Since there are twice as many oxygen atoms per carbon atom in carbon dioxide than in carbon monoxide, the oxygen mass ratio ti should h ld b be 2 2. Tro, Principles of Chemistry: A Molecular Approach 5 Dalton’s Atomic Theory y • 1)) 2)) 3) 4) Dalton proposed a theory of matter based on it having g ultimate,, indivisible p particles to explain p these laws. Each element is composed p of tiny, y, indestructible particles called atoms. All atoms of a g given element have the same mass and other properties that distinguish them from atoms of other elements. Atoms combine in simple, whole-number ratios to form molecules of compounds. In a chemical reaction, atoms of one element cannot change into atoms of another element. They simply rearrange the way they are attached. Tro, Principles of Chemistry: A Molecular Approach 6 Some Notes on Charge • • two kinds of charge g called + and – opposite charges g attract • like charges g repel p • + attracted to – + repels + – repels – To be neutral, something must have no charge or equal amounts of opposite charges. Tro, Principles of Chemistry: A Molecular Approach 7 Cathode Ray y Tubes • • glass tube containing metal electrodes from which almost all the air has been evacuated When connected to a high-voltage power supply, a glowing area is seen emanating from the cathode. Tro, Principles of Chemistry: A Molecular Approach 8 J JJ. Thomson J. • believed that the cathode rayy was composed p of • tiny particles with an electrical charge designed an experiment to demonstrate that these were particles by measuring the amount of force it takes to deflect their path a given amount like measuring the amount of force it takes to make a car turn Tro, Principles of Chemistry: A Molecular Approach 9 Thomson’s Experiment investigated the effect on a cathode ray of placing an electric field around tube (1) Charged matter is attracted to an electric field. (2) Light Light’s s path is not deflected by an electric field field. +++++++++++ cathode anode (+) ( ) (−) − −−−−−−− − + Power Supply Tro, Principles of Chemistry: A Molecular Approach 10 Tro, Principles of Chemistry: A Molecular Approach 11 Thomson’s Results • The cathode rays are made of tiny particles. • These particles have a negative charge. because the beam always deflected toward the + plate • The amount of deflection was related to two • • factors, the charge and mass of the particles. Every material tested contained these same particles. The charge:mass ratio of these particles was 1.76 76 × 108 C/g. C/g −1 The charge/mass of the hydrogen ion is +9.58 × 104 C/g. Tro, Principles of Chemistry: A Molecular Approach 12 Thomson’s Conclusions • If the particle has the same amount of charge as a hydrogen ion, then it must have a mass almost 2000× smaller than hydrogen atoms! Later experiments p by y Millikan showed that the p particle did have the same amount of charge as the hydrogen ion. • The Th only l way for f this thi tto b be ttrue iis if th these particles ti l were pieces of atoms. Apparently, Apparently the atom is not unbreakable. unbreakable • Thomson believed that these particles were, • therefore, the ultimate building blocks of matter therefore matter. These cathode ray particles became known as electrons electrons. Tro, Principles of Chemistry: A Molecular Approach 13 Millikan’s Millikan s Oil Drop Experiment Tro, Principles of Chemistry: A Molecular Approach 14 Electrons • • • • Electrons are particles found in all atoms. Cathode rays are streams of electrons. The electron has a charge g of −1.60 × 1019 C. The electron has a mass of 9.1 × 10−28 g. Tro, Principles of Chemistry: A Molecular Approach 15 A New Theory of the Atom • Since the atom is no longer indivisible, Thomson must propose a new model of the atom to replace the first statement in Dalton’s Atomic Theory. rest of Dalton’s theory still valid at this point • Thomson pproposes p that instead of being g a hard, marble-like unbreakable sphere, the way Dalton described it, that it actually has an inner structure. Tro, Principles of Chemistry: A Molecular Approach 16 Thomson’s Thomson s Plum Pudding Atom • The structure of the atom contains • many negatively charged electrons. These electrons are held in the atom by their attraction for a positively charged electric field within the atom. There had to be a source of positive charge because the atom is neutral. Thomson assumed there were no positively charged pieces because none showed up in the cathode ray experiment. Tro, Principles of Chemistry: A Molecular Approach 17 Predictions of the Plum Pudding Atom • The mass of the atom is due to the mass of the electrons within it. Electrons are the only particles in Plum Pudding atoms. • The atom is mostly empty space. cannot have a bunch of negatively charged particles near each other as theyy would repel p Tro, Principles of Chemistry: A Molecular Approach 18 Radioactivity • In the late 1800s, Henri Becquerel and • • Marie Curie discovered that certain elements l t would ld constantly t tl emit it small, ll energetic particles and rays. Th These energetic ti particles ti l could ld penetrate t t matter. E Ernest t Rutherford R th f d discovered di d th thatt th there were three different kinds of emissions. alpha, l h , particles ti l with ith a mass 4 4× H atom t and d + charge beta, beta , particles with a mass ~1/2000 1/2000 H atom and – charge gamma, , rays that are energy rays, not particles Tro, Principles of Chemistry: A Molecular Approach 19 Rutherford’s Experiment p • How can you prove something is empty? • Put something through it! Use large target atoms. Use very thin sheets of target so it will not absorb “bullet”. Use very small particle as bullet with very high energy. but not so small that electrons will affect it • bullet = alpha p p particles,, target g atoms = g gold foil particles have a mass of 4 amu and charge of +2 cu. Gold has a mass of 197 amu and is very malleable. Tro, Principles of Chemistry: A Molecular Approach 20 Tro, Principles of Chemistry: A Molecular Approach 21 Rutherford’ss Experiment Rutherford Alpha Particles Striking Screen Radioactive Sample Lead Box Fluorescent Screen Gold Foil Tro, Principles of Chemistry: A Molecular Approach 22 Rutherford’s Results and Conclusions Results • Over 98% of the particles went straight through through. • About 2% of the particles went through but were deflected by large angles. angles • About 0.005% of the particles bounced off the gold foil. foil Conclusions • An atom is mostly empty space. • An atom contains a dense pparticle that was small in volume compared to the atom but large in mass. • This dense pparticle was ppositivelyy charged. g Tro, Principles of Chemistry: A Molecular Approach 23 Plum Pudding Atom • • • • • • • • • • • • • • • • If an atom was like a plum pudding pudding, all the particles should go straight through. • • • • A few of the • • particles do not go through. Nuclear Atom . Almost all particles go straight through through. . . Tro, Principles of Chemistry: A Molecular Approach Some particles go through, but are deflected due to +:+ repulsion from the nucleus. 24 Rutherford’s Interpretation— th Nuclear the N l M Model d l 1) The atom contains a tiny dense center called the nucleus. The amount of space p taken by y the nucleus is only y about 1/10 trillionth the volume of the atom. 2) The nucleus has essentially the entire mass of the atom. The electrons weigh so little they give practically no mass to the atom atom. 3) The nucleus is positively charged. The amo amount nt of positi positive e charge balances the negati negative e charge of the electrons. 4) The electrons are dispersed in the empty space of the atom surrounding the nucleus. Tro, Principles of Chemistry: A Molecular Approach 25 Structure of the Atom • Rutherford proposed that the nucleus had a particle that had the same amount of charge as an electron but opposite sign. based on measurements of the nuclear charge of the elements • These particles are called protons. charge = +1.60 × 1019 C mass = 1.67262 × 10−24 g • Since protons and electrons have the same g , for the atom to be neutral amount of charge, there, must be equal numbers of protons and electrons. Tro, Principles of Chemistry: A Molecular Approach 26 Relative Mass and Charge g • It is sometimes easier to compare things to each other rather • • than to an outside standard. When you do this, the scale of comparison is called a relative scale. W generally We ll ttalk lk about b t th the size i off charge h on atoms t b by comparing it to the amount of charge on an electron, which we call −1 1 charge units. A proton has a charge of +1 cu. Protons and electrons have equal amounts of charge, but opposite signs. signs • We generally talk about the mass of atoms by comparing it to 1/12th the mass of a carbon atom with 6 p protons and 6 neutrons, which we call 1 atomic mass unit. Protons have a mass of 1 amu. Electrons have a mass of 0 0.00055 00055 amu, amu which is generally too small to be relevant. Tro, Principles of Chemistry: A Molecular Approach 27 Neutrons Problems • How could beryllium have 4 protons stuck together in the nucleus? • If a beryllium atom has 4 protons, then it should weigh 4 amu; but it actually weighs 9.01 amu! Neutrons • Rutherford and Chadwick proposed that there was another th particle ti l iin th the nucleus—it l it is i called ll d a neutron. t • Neutrons have no charge and a mass of 1 amu. mass = 1.67493 × 10−24 g slightly heavier than a proton no charge Tro, Principles of Chemistry: A Molecular Approach 28 Summary of Subatomic Particles Tro, Principles of Chemistry: A Molecular Approach 29 Elements • Each E h element l th has a unique i number b off protons t iin itits nucleus. • The Th number b off protons t in i the th nucleus l off an atom t is i called the atomic number. Th elements The l t are arranged d on th the P Periodic i di T Table bl in order of their atomic numbers. • Each E h element l th has a unique i name and d symbol. b l symbol either one or two letters one capital it l letter l tt or one capital it l letter l tt and d one lowercase • Some S symbols b l come ffrom th the element l t ‘‘s name, like C for carbon. Others come from the Latin name off the th element, l t like lik Au A for f gold ld (aurum) ( ) and d Cu C for f copper (cuprum) 30 Tro, Principles of Chemistry: A Molecular Approach Tro, Principles of Chemistry: A Molecular Approach 31 The Periodic Table of the Elements Tro, Principles of Chemistry: A Molecular Approach 32 Structure of the Nucleus • Soddy discovered that the same element could • have atoms with different masses, masses which he called isotopes. There are two isotopes of chlorine found in nature, one that has a mass of about 35 amu g about 37 amu. and another that weighs The observed mass is a weighted average of the g of all the naturally y occurring g atoms. weights The percentage of an element that is one isotope p is called the isotope’s p natural abundance. The atomic mass of chlorine is 35.45 amu. Tro, Principles of Chemistry: A Molecular Approach 33 Isotopes • All isotopes of an element are chemically identical. • • • • undergo d th the exactt same chemical h i l reactions ti All isotopes of an element have the same number of protons. Isotopes p of an element have different masses. Isotopes of an element have different numbers of neutrons. Isotopes are identified by their mass numbers. protons + neutrons Tro, Principles of Chemistry: A Molecular Approach 34 Isotopes p • Atomic Number Number of protons Z • Mass Number Protons + Neutrons Whole number A • Abundance = relative amount found in a sample Tro, Principles of Chemistry: A Molecular Approach 35 Neon Symbol Number of Number of A, Mass Protons Neutrons Number Percent Natural Abundance Ne-20 or 20 10 Ne 10 10 20 90.48% 21Ne Ne-21 or 10 10 11 21 0.27% 22 Ne Ne-22 or 10 10 12 22 9.25% Tro, Principles of Chemistry: A Molecular Approach 36 Charged Atoms:Ions and Compounds • When atoms gain or lose electrons, they acquire a • • • charge. Charged particles are called ions. When atoms gain electrons, electrons they become negatively charged ions, called anions. When atoms lose electrons, electrons they become positively charged ions, called cations. Note: N t • Ions behave much differently than the neutral atom. • Since materials like table salt are neutral, there must be equal amounts of charge from cations and anions i iin th them. Tro, Principles of Chemistry: A Molecular Approach 37 Atomic Structures of Ions Anions • Nonmetals form anions. anions • For each negative charge, the ion has 1 more electron than the neutral atom atom. • Anions are named by changing the ending of the name to -ide. ide Cations • Metals form f cations. • For each positive charge, the ion has 1 less electron than the neutral atom atom. • Cations are named the same as the metal. Tro, Principles of Chemistry: A Molecular Approach 38 Mendeleev • ordered elements byy atomic mass • saw a repeating pattern of properties • Periodic Law—When Law When the elements are arranged • • • in order of increasing atomic mass, certain sets of properties recur periodically. put elements with similar properties in the same column used pattern to predict properties of undiscovered elements Where atomic mass order did not fit other properties, he reordered by other properties. Te & I Tro, Principles of Chemistry: A Molecular Approach 39 Periodic Pattern Tro, Principles of Chemistry: A Molecular Approach 40 Periodic Patterns NM H2O a/b H 10 1.0 H2 M Li 6.9 Li2O b M LiH 9.0 Be Na2O M b M Na 23.0 NaH 24.3 M K2O b K 39.1 KH BeO NM a/b B BeH2 10.8 MgO b M MgH2 27.0 CaO b C BH3 12.0 M Mg B2O3 NM a Al Al2O3 a/b M/NM AlH3 28.1 Si CO2 NM a N N2O5 NM a CH4 14.0 NH3 16.0 NM P4O10 NM a SiO2 a SiH4 31.0 P PH3 32.1 O2 NM O F H2O 19.0 S SO3 a HF NM H2S 35.5 Cl Cl2O7 a HCl Ca 40.1 CaH2 M = metal metal, NM = nonmetal, nonmetal M/NM = metalloid a = acidic oxide, b = basic oxide, a/b = amphoteric oxide Tro, Principles of Chemistry: A Molecular Approach 41 Mendeleev’s Predictions for Ekasilicon (Germanium) Tro, Principles of Chemistry: A Molecular Approach 42 Tro, Principles of Chemistry: A Molecular Approach 43 Metals • solids at room temperature, except Hg • reflective surface shiny • conduct heat • conduct electricity • malleable can be shaped • ductile drawn or pulled into wires • lose electrons and form cations in reactions • lower left on the table Tro, Principles of Chemistry: A Molecular Approach 44 Nonmetals • • • • • • ffound d in i allll th three states t t poor conductors of heat poor conductors of electricity Solids are brittle. gain electrons in reactions to become anions upper right on the table except H Tro, Principles of Chemistry: A Molecular Approach 45 Sulfur, S(s) Bromine Br2(l) Bromine, Chlorine, Cl2(g) Metalloids • show h some • properties of metals and d some off nonmetals also known as semiconductors Tro, Principles of Chemistry: A Molecular Approach Properties p of Silicon shiny conducts electricity d does nott conduct d t heat h t wellll brittle 46 Patterns in Metallic Character = Metal = Metalloid = Nonmetal Tro, Principles of Chemistry: A Molecular Approach 47 The Modern Periodic Table • Elements with similar chemical and physical • properties are in the same column. Columns are called Groups or Families. designated by a number and letter at top • Rows are called Periods. • Main Group = Representative Elements = “A” groups • Transition Elements = “B” groups all metals • Bottom Rows = Inner Transition Elements = Rare Earth Elements metals really belong in Periods 6 & 7 Tro, Principles of Chemistry: A Molecular Approach 48 Tro, Principles of Chemistry: A Molecular Approach 49 = Alkali Metals = Halogens g = Alkali Earth Metals = Lanthanides = Noble N bl G Gases = Actinides A ti id = Transition Metals Tro, Principles of Chemistry: A Molecular Approach 50 Important Groups—Hydrogen • nonmetal • colorless, diatomic gas very low melting point and density • reacts with nonmetals to form molecular compounds HCl is acidic gas H2O is a liquid q • reacts with metals to form hydrides metal hydrides react with water to form H2 • HX dissolves in water to form acids Tro, Principles of Chemistry: A Molecular Approach 51 Important Groups—Alkali Metals • Group 1A = Alkali Metals • hydrogen usually placed here, though it doesn’t doesn t • • • • • really belong soft, low melting points, low density flame tests Li = red, Na = yellow, K = violet very reactive, never find uncombined in nature t d to tend t form f water-soluble t l bl compounds, d th therefore f salt is crystallized from seawater then molten salt is electrolyzed colorless solutions react with water to form basic (alkaline) solutions and H2 2 Na + 2 H2O 2 NaOH + H2 releases a lot of heat Tro, Principles of Chemistry: A Molecular Approach 52 Important Groups—Alkali Earth Metals • Group 2A = Alkali Earth Metals • harder, h d hi higher h melting, lti and dd denser th than alkali lk li metals t l • • • • • Mg alloys used as structural materials flame tests Ca = red, Sr = red, Ba = yellow-green reactive, but less than corresponding alkali metal form stable, insoluble oxides from which they are normally extracted oxides are basic = alkaline earth reactivity with water to form H2 Be = none; Mg = steam; Ca, Sr, Ba = cold water Tro, Principles of Chemistry: A Molecular Approach 53 Important Groups—Halogens • • • • • • • • Group 7A = Halogens nonmetals F2 and Cl2 gases; Br2 liquid; I2 solid allll di diatomic t i very reactive Cl2, Br2 react slowly with water Br2 + H2O HBr + HOBr react with metals to form ionic compounds HX a all ac acids ds HF weak < HCl < HBr < HI Tro, Principles of Chemistry: A Molecular Approach 54 Important Groups — Noble Gases • Group 8A = Noble Gases • all gases at room temperature • • very low melting and boiling points very unreactive, practically inert very hard h d tto remove electron l t ffrom or give i an electron to Tro, Principles of Chemistry: A Molecular Approach 55 Ion Charge and the Periodic Table • The charge on an ion can often be determined • • • • ffrom an element’s l t position iti on the th Periodic P i di Table. T bl Metals always form positively charged cations. For many main group metals, the charge = the group g p number. Nonmetals form negatively charged anions. For nonmetals, nonmetals the charge = the group number −8. Tro, Principles of Chemistry: A Molecular Approach 56 Predictable Ion Charges Tro, Principles of Chemistry: A Molecular Approach 57 Atomic Mass • We previously learned that not all atoms of an element have the same mass. isotopes • We generally use the average mass of all an element’s atoms found in a sample in calculations. However, the average must take into account the abundance of each isotope p in the sample. p • We call the average mass the atomic mass. Tro, Principles of Chemistry: A Molecular Approach 58 Counting g Atoms by y Moles • If we can find fi d the th mass off a particular number of atoms, we can use this information to convert the mass of an element sample into the number of atoms in the sample sample. • The number of atoms we will use is 6.022 x 1023 and we call this a mole. 1 mole = 6.022 × 1023 things like 1 dozen = 12 things Tro, Principles of Chemistry: A Molecular Approach 59 Chemical Packages—Moles g • • mole = number of particles equal to the number off atoms t in i 12 g off C-12 C 12 1 atom of C-12 weighs exactly 12 amu. 1 mole of C-12 weighs exactly 12 g. The number of particles in 1 mole is called Avogadro’s Number = 6.0221421 × 1023. 1 mole of C atoms weighs 12 12.01 01 g and has 6.022 × 1023 atoms. The Th average mass off a C atom t is i 12.01 12 01 amu. Tro, Principles of Chemistry: A Molecular Approach 60 Relationship between M l and Moles dM Mass • • • • The mass of one mole of atoms is called the molar mass. The molar mass of an element, in grams, is numerically equal to the element’s atomic mass, in i amu. The lighter the atom, the less a mole weighs. The lighter the atom, the more atoms there are in 1 g. Tro, Principles of Chemistry: A Molecular Approach 61 Mole and Mass Relationships 1 mole carbon 12.01 g Tro, Principles of Chemistry: A Molecular Approach 1 mole sulfur 32.06 g 62