Chem 106, Prof. J.T. Spencer CHE 106: General Chemistry CHAPTER TWO Copyright © James T. Spencer 1995 - 1999 All Rights Reserved 1 Chem 106, Prof. J.T. Spencer Chapter 2: Atoms, Molecules and Ions What 2 is Chemistry Logic Magic Chapt. 2.1 Chem 106, Prof. J.T. Spencer Atoms, Molecules and Ions Science: Atomic 3 Theory – “The strength of a science is that its conclusions are derived by logical arguments from facts that result from well-designed experiments. Science has produced a picture of the microscopic structure of the atom so detailed and subtle of something so far removed from our immediate experience that it is difficult to see how its many features were constructed. This is because so many experiments have contributed to our ideas about the atom.” B. Mahan from University Chemistry Chapt. 2.1 Chem 106, Prof. J.T. Spencer 4 “Seeing “Atoms STM image showing singleatom defect in iodine adsorbate lattice on platinum. Chem 106, Prof. J.T. Spencer 5 Atoms, Molecules and Ions Science: Atomic Theory – from a fundamental understanding of the macroscopic behavior of substances comes an understanding the microscopic behavior of atoms and molecules (Baseball rules from Baseball Game?) Macroscopic Substances Mixtures Physical Properties and Changes Microscopic Atomic theory Question: Can matter be infinitely divided? Most Greek Philosophers - Yes Democritus (460 BC) and John Dalton (1800s) - No (“atomos”means indivisible”) Chapt. 2.1 Chem 106, Prof. J.T. Spencer 6 Atoms, Molecules and Ions History of Atomic Theory and Scientific Inquiry – Aristotle - “metaphysics”, thought experiments and no experimental observations necessary to substantiate ideas. – Archimedes (287 - 212 BC) - Scientific Method, determined composition of the King of Syracuse’s crown by measuring density through water displacement. – Roger Bacon (1214 - 1294) - Experimental Science “ It is the credo of free men - the opportunity to try, the privilege to err, the courage to experiment anew. ...experiment, experiment, ever experiment”. Chapt. 2.1 Chem 106, Prof. J.T. Spencer Aristotle (384-322 BC) All of the sciences (epistêmai, literally "knowledges") can be divided into three branches: theoretical, practical, and productive. Whereas practical sciences, such as ethics and politics, are concerned with human action, and productive sciences with making things, theoretical sciences, such as theology, mathematics, and the natural sciences, aim at truth and are pursued for their own sake. 7 Chem 106, Prof. J.T. Spencer Archimedes (287-212BC) Archimedes 8 was a native of Syracuse (not NY). Stories from Plutarch, Livy, and others describe machines invented by Archimedes for the defence of Syracuse (These include the catapult, the compound pulley and a burning-mirror). Archimedes discovered fundamental theorems concerning the centre of gravity of plane figures and solids. His most famous theorem gives the weight of a body immersed in a liquid, called Archimedes' principal. His methods anticipated integral calculus 2,000 years before Newton and Leibniz. Chem 106, Prof. J.T. Spencer Archimedes (287-212BC) 9 Chem 106, Prof. J.T. Spencer Archimedes (287-212BC) 10 Suspecting that a goldsmith might have replaced some of the gold by silver in making a crown, Hiero II, the king of Syracuse, asked Archimedes to determine whether the wreath was pure gold. The wreath could not be harmed since it was a holy object. The solution which occurred when he stepped into his bath and caused it to overflow was to put a weight of gold equal to the crown, and known to be pure, into a bowl which was filled with water to the brim. Then the gold would be removed and the king's crown put in, in its place. An alloy of lighter silver would increase the bulk of the crown and cause the bowl to overflow. Pure Gold? Equal Weight of Gold Crown Displaced More Water Chem 106, Prof. J.T. Spencer 11 Greek Philosophers Fire Air Greek “Elements” Water Earth Democratus - First to say that all matter is NOT infinately divisible. [But the Greeks did not test their ideas] Alchemy - Pseudoscience by fakes and mystics devoted to turning base metals to gold BUT they did make (by accident) many ground breaking discoveries of nature (chemical reactions). Chem 106, Prof. J.T. Spencer Scientific Measurement 12 Robert Boyle - Robert Boyle (1627-1691) was born in Ireland. He became especially interested in experiments involving air and developed an air pump with which he produced evacuated cylinders. He used these cylinders to show that a feather and a lump of lead fall at the same rate in the absence of air resistance. In his book “The Sceptical Chemist” (1661), Boyle urged that the ancient view of elements as mystical substances should be abandoned and that an element should instead be defined as anything that cannot be broken down into simpler substances. Chem 106, Prof. J.T. Spencer 13 Scientific Measurement Antoine Lavoisier (1743 - 1794) - Furthered measurement as basis for scientific reasoning. – “Je Veux Parler Des Faits” - Do Not Rely Upon Speculation But Build Upon Facts. More on Lavoisier on Next Slide Chem 106, Prof. J.T. Spencer Antoine Lavoisier 14 Antoine Lavoisier was born in Paris, and although Lavoisier's father wanted him to be a lawyer, Lavoisier was fascinated by science. From the beginning of his scientific career, Lavoisier recognized the importance of accurate measurements. He wrote the first modern chemistry (1789) textbook so that it is not surprising that Lavoisier is often called the father of modern chemistry. To help support his scientific work, Lavoisier invested in a private tax-collecting firm and married the daughter of one of the company executives. Guillotined for his tax work in 1794. Chem 106, Prof. J.T. Spencer 15 Atoms, Molecules and Ions Theory and Scientific Inquiry – Lavoisier (1743 - 1794) - founder of “modern chemistry”, not to rely on speculation but to build upon facts, ended the “time of alchemy”. Earth History Atomic pure water Alchemy Water evaporate out water from dust sealed container Law of Conservation of Mass Fire “earth” alchemists said that the water was “transmuted” to earth Lavoisier showed that the amount of “earth” found at the end of the experiment was equal to the weight the container lost, therefore, the water was not “transmuted” to earth. Chapt. 2.1 Chem 106, Prof. J.T. Spencer 16 Scientific Method Form and test hypothesis Patterns and Trends Theory Observations and Experiments Chapt. 2.1 Chem 106, Prof. J.T. Spencer John Dalton (1766-1844) 17 John Dalton (1766 -1844), an Englishman, began teaching school when he was 12. He was fascinated with meteorology (keeping daily weather records for 46 years), which led to an interest in gases and their components, atoms. He switched to chemistry when he saw applications in chemistry for his ideas about the atmosphere. He proposed the Atomic Theory in 1803. Dalton was a humble man with several apparent handicaps: he was poor; he was not articulate; he was not a skilled experimentalist, and he was color-blind (a terrible problem for a chemist). In spite of these disadvantages he did great things. Chem 106, Prof. J.T. Spencer 18 Atomic Theory John Dalton’s Atomic Theory –Designed a theory to account for a variety of experimental observations: –Each element is composed of extremely small particles (called atoms). –All atoms of a given element are identical (therefore, atoms of different elements are different and have different properties). Chapt. 2.1 Chem 106, Prof. J.T. Spencer 19 Atomic Theory (Continued) John Dalton’s Atomic Theory –Atoms of an element are not changed into different types of atoms by chemical reactions and atoms are neither created nor destroyed in chemical reactions. –Compounds are formed when atoms combine and a given compound always has the same relative number and kind of atoms. Chapt. 2.1 Chem 106, Prof. J.T. Spencer Atomic Theory 20 Dalton’s Atomic Theory –Atoms are the building blocks: –Elements are composed of only one kind of atom. –Compounds are made by mixing atoms in definite proportions –Mixtures do not involve the type of “small scale” (but strong) interactions found in Elements and Compounds Chapt. 2.1 Chem 106, Prof. J.T. Spencer 21 Atomic Theory; Dalton’s Theories Law of Constant Composition (or Definite Proportion, first proposed by Joseph Proust): – In any given compound, the relative number and kind of atoms are constant (same proportion of elements by mass). –implies that atoms interact in a specific way when they form a compound. –the elements making up a particular compound combine in the same proportions regardless of the manner in which the compound was prepared. Chapt. 2.1 Chem 106, Prof. J.T. Spencer 22 Atomic Theory; Dalton’s Theories Law of Constant Composition (or Definite Proportion): Copper Carbonate ALWAYS contains 5.3 parts Copper to 4 parts Oxygen and 1 part Carbon (by Weight). Carbon Dioxide ALWAYS contains 1.00 parts Carbon to 2.67 parts Oxygen Chapt. 2.1 Chem 106, Prof. J.T. Spencer Atomic Theory; Dalton’s Theories 23 Law of Conservation of Mass: – the total amount of material present after a chemical reaction is the same as the amount present before the reaction. Matter (elements, etc...) cannot be created nor destroyed during chemical reactions. Total Mass Before Chemical Reaction = Total Mass After Chemical Reaction Chapt. 2.1 Chem 106, Prof. J.T. Spencer Atomic Theory; Dalton’s Theories 24 Law of Multiple Proportions: –If two elements form more than one compound, then the ratios of the masses of a second element that combine with 1 g of the first elements can always be reduced to small whole numbers Mass of O Comb. w/ 1 g C I 1.33 g II 2.66 g III 3.99 g Chapt. 2.1 Chem 106, Prof. J.T. Spencer Atomic Theory; Dalton’s Theories 25 Law of Multiple Proportions: –If two elements form more than one compound, then the ratios of the masses of a second element that combine with 1 g of the first elements can always be reduced to small whole numbers C I II III O C O 1:1 O C O 2:1 O C O 3:1 Mass of O Comb. w/ 1 g C I 1.33 g II 2.66 g III 3.99 g Chapt. 2.1 Chem 106, Prof. J.T. Spencer Atomic Theory; Dalton’s Theories Law 26 of Multiple Proportion: Another Example Oxygen combines with hydrogen to form 2 compounds Compound 1 8 grams of oxygen combines with 1 gram of hydrogen [H2O] Compound 2 16 grams of oxygen combines with 1 gram of hydrogen [H2O2] Chapt. 2.1 Chem 106, Prof. J.T. Spencer 27 Atomic Theory; Dalton’s Theories Law of Multiple Proportion: Yet Another Example Chlorine combined with oxygen to form four binary compounds [A, B, C, D]. Compound A B C D Mass of O combined with 1.0000 g Cl 0.22564 g 0.90255 g 1.3539 g 1.5795 g Div. by 0.22564 1.00 4.00 6.00 7.00 Allowed Dalton to prepare the first atomic mass table Chapt. 2.1 Chem 106, Prof. J.T. Spencer 28 Guy-Lussac Joseph Guy-Lussac (1778 - 1850) found that (at the same temperatures and pressures): 2 volumes of hydrogen reacts with 1 volume of oxygen to yield 1 volume of water vapor O + H = Water Amedeo Avogadro (1776 - 1856) proposed that (at the same temperatures and pressures), equal volumes of different gases contain the same number of particles: 2 molecules of H + 1 molecule of O yield 1 molecule of water Chem 106, Prof. J.T. Spencer Experiments in Atomic Theory 29 Dalton’s Laws Set Groundwork for Atomic Theory but Important Experiments Lead to Our Modern Understanding Faraday - Electrodeposition Millikan - Oil Drop Experiment Roetgen - Radioactivity Curie - Radioactive Particles Rutherford - Gold Foil Experiment Chem 106, Prof. J.T. Spencer Michael Faraday (1791-1867) 30 Experiments in electromagnetism, electrical power conversion, etc... Humble scientist rose from very poor background to become one of the most influential of his age. Believed that careful observations were most important. “Try desperately to succeed and do not hope for success” Chem 106, Prof. J.T. Spencer 31 Atomic Structure Electrical Nature –Michael Faraday (1833) (first ideas about the nature of electricity –The weight of a material deposited at an electrode by a given amount of electricity is always the same. –The weights of various materials deposited by fixed amounts of electricity are proportional to their equivalent weights. [remember equivalent weights] Electrodeposition Cell electrodes - + deposition electrolyte Chapt. 2.1 Chem 106, Prof. J.T. Spencer Sir J. J. Thomson 32 British physicist who worked with electrical currents and fields. Appointed Prof. of Physics at Cambridge when he was 27 and Received the Nobel Proze in 1906 for his characterization of the electron. Chem 106, Prof. J.T. Spencer 33 Atomic Structure J. J. Thomson: Cathode Ray Tube (CRT) Experiment – Set up a large electrical potential between a pair of electrodes in a glass tube and an electrical current will flow between the elctrodes. –The current will flow even when all the air is pumped out of the tube. The invisible charge carriers were called “cathode rays”. –Cathode rays travel in straight lines and form a luminious spot when they hit a glass tube. (-) (+) Cathode Ray Tube [evacuated glass tube] Chapt. 2.1 Chem 106, Prof. J.T. Spencer 34 Atomic Structure: CRT The cathode rays are deflected by an electric field. (-) (+) Electric Field The cathode rays are deflected by an magnetic field. (-) The same effect was observed regardless of what gas was used in the discharge tube. Therefore, electricity must be a universal fragment. (+) Magnetic Field Chapt. 2.1 Chem 106, Prof. J.T. Spencer Electricity: Thomson’s charge to mass (-) CRT (+) (-) Magnetic Field 35 1 2 3 (+) Electric Field Spot mag field 1 3 2 On Off Off On elec. field Off On Off On Chapt. 2.1 Chem 106, Prof. J.T. Spencer Thomson’s charge to mass 36 Ee = Electrical Field He = Magnetic Field [where e = electric charge (unk) and = velocity] Set up experiment such that; Electrical Field = Magnetic Field Ee = He or E / H Now, turn off the mag. field and measure deflection of beam () Using Newton’s 2nd Law can calculate e/m CRT (-) (-) Magnetic Field (+) (+) 1 2 3 Chem 106, Prof. J.T. Spencer Thomson’s charge to mass 37 calculated charge to mass ratio (e/m) for electron = 1.76 x 108 coulombs/g found; (1) e/m was 1000x greater than for any known ion (2) e/m of independent of gas in tube [Universal Fragment] (3) Not electrified atoms but fragments (called electrons) Chem 106, Prof. J.T. Spencer Robert Millikan (1868-1953) 38 Nobel Prize, 1923; for his work on the elementary charge of electricity and on the photoelectric effect. Robert Millikan was one of the first American scientists to be recognized in Europe. In 1909 he performed the first of a series of experiments to measure the fundamental charge of an electron, the Millikan Oil Drop Experiment. The value determined by this experiment was used in Bohr's formula for the energy of the Hydrogen line spectrum as a first confirmation of the quantized atom. He named and studied "cosmic rays" as well. Chem 106, Prof. J.T. Spencer Electricity: Millikan’s electron mass 39 Oil Drop Experiment (1909) atomizer - high voltage + viewer Ionization by radiation causes the oil to pick up “extra” electrons Goal: to measure the electrical charge on each oil droplet Procedure: measure the velocity of the falling oil drop both with and without the high voltage plates urned on Found: charges were always multiples of 1.60 x 10-19 C Postulate: charge of one electron was 1.60 x 10-19 C Chapt. 2.1 Chem 106, Prof. J.T. Spencer 40 Electricity: electron mass Thomson Millikan charge = mass e = m charge = e 1.76 x 108 coul g-1 = 1.60 x 10-19 coul Combine and Solve mass = charge = 1.60 x 10-19 C = 9.10 x 10-28 g 1.76 x 108 coul g-1 1.76 x 108 C g-1 mass of the electron was 2000x smaller than the lightest atom (hydrogen) Chapt. 2.1 Chem 106, Prof. J.T. Spencer Wilhelm Conrad Roentgen Wilhelm Conrad Roentgen 41 Wilhelm Conrad Roentgen was born in Lennep, Germany, on 27 March 1845. He obtained a degree in mechanical engineering and, in 1869, was awarded a degree in physics. While working as a professor of physics at Wurzburg University, he made his famous discovery. He called the unknown radiation "X rays," since "X" frequently stands for an unknown quantity in mathematics. His unique discovery truly changed the world and immediately became a useful tool for medical science. Chem 106, Prof. J.T. Spencer Radioactivity: 42 Wilhelm Roetgen and Henri Becquerel metal target CRT e beam invisible radiation (X-rays) U X-rays - not affected by magnetic fields - passed thru many materials -produced images on film (ionized Ag emulsions) glowed in dark (phosphorescence) emitted high energy radiation in the dark (radioactivity) Chapt. 2.1 Chem 106, Prof. J.T. Spencer 1903 Nobel Prize for Radioactivity Pierre and Marie Curie Henri Becquerel 43 Chem 106, Prof. J.T. Spencer Marie Sklodawaska Curie 44 The most famous of all women scientists, Marie Sklodowska-Curie is notable for many firsts. In 1903, she became the first woman to win a Nobel Prize for Physics (Pierre Curie and Henri Becquerel, for the discovery of radioactivity. She was also a professor at the Sorbonne University in Paris (1906). In 1911, she won an unprecedented second Nobel Prize (in chemistry for her discovery radium. She was the first person ever to receive two Nobel Prizes.) Marie Sklodowska-Curie She was the first mother of a Nobel Prize In 1934, Maria Curie died of leukemia Laureate; daughter- Nobel Prize 1932. Chem 106, Prof. J.T. Spencer 45 Radioactivity: Marie Curie and Ernest Rutheford Marie Curie (1867 - 1934) - separated the pure radioactive material (Uranium) which was spontaneously radioactive (from the mineral pitchblende) Ernest Rutheford (1871 - 1937) - found radiation from uranium was of three types (, , and ) U + - heavy particles with +2 charge, combines with electrons to form helium, 4He - electrons with -1 charge Chapt. 2.1 - high energy electromagnetic radiation slits Chem 106, Prof. J.T. Spencer 46 Nuclear Atom: Thomson’s Model (ca. 1900) Since the electron made up only a small amount of an atom’s mass it was proposed that it must similarly make up a small amount of the atoms volume. “Plum-pudding” model positive charge spread over sphere = electron Chem 106, Prof. J.T. Spencer Ernest Rutherford 47 Ernest Rutherford (1871-1937) was born on a farm in New Zealand. In 1895 he placed second in a scholarship competition to attend Cambridge University, but was awarded the scholarship when the winner decided to stay home and get married. As a scientist in England, Rutherford did much of the early work on characterizing radioactivity. He also invented the name proton for the nucleus of the hydrogen atom. He received the Nobel Prize in chemistry in 1908. Chem 106, Prof. J.T. Spencer Nuclear Atom: Rutheford and the Gold Foil 4He particles slits thin gold foil 48 experiment - fired heavy particles at a thin gold foil and looked for deflections detector found - most particles passed straight through foil, some had deflections thru small angles BUT some had VERY large deflections ( = 180°) “...as if you fired a 15-inch cannon shell at a piece of tissue paper and it came back and hit you...” Chem 106, Prof. J.T. Spencer Nuclear Atom: Rutheford and the Gold Foil A:C around 13,000:1 Beam A A C B B A A Gold Foil 49 Chem 106, Prof. J.T. Spencer Rutheford’s Atom Based on gold foil experiment and previous work with electrical and nuclear particles, proposed a nuclear theory; (1) atoms are mostly empty space with very dense (pos. charged) nuclear core (<10-12 cm dia.) (2) atoms are highly “non-uniform” (3 ) atomic nucleus must contain large electrical forces of considerable mass (since small electron cannot be responsible for such large deflections) 50 Chem 106, Prof. J.T. Spencer Nature’s Basic Forces 51 Electromagnetic - force between charged or magnetic particles (electrical and magnetic forces + - are very closely related). DRIVES MOST OF CHEMICAL BEHAVIOR (Coulomb’s Law; F = kQ1Q2/d2) Gravitational - force between objects proportional m m to their masses. Strong Nuclear - force keeping like charged nucleons (such as protons) together + + + (very strong but very short range). + Weak Nuclear - nuclear force observed in some radioactive behavior (weaker than electromagnetic but stronger than gravitational). Strong Nucl. > Electromagnetic > Weak Nucl. > Gravitational Chem 106, Prof. J.T. Spencer 52 Modern Atomic Structure dimensions; nucleus 10-4 Å and atom 1 - 2 Å (1 Å = 10-10 m) “... if a nucleus were 2 cm (ca. 1 in.) then the atom would be 200 m (ca. 200 yds)” atom composed of many “subatomic” particles but only three of these are important to chemists atomic mass (1 amu = 4 x 10-22 g), charge (1 esc = 1.60 x 10-19 coul), density (1014 g/cm3) atom = dense nucleus with mostly empty space; electrons of most chemical import. (matchbox of nucl. = 2.5 billion tons) atomic particle proton neutron electron charge (esu) +1 0 -1 mass (amu) 1.0073 1.0087 5.486 x 10-4 Chem 106, Prof. J.T. Spencer Modern Atomic Structure Sample exercise: The diameter of a carbon atom is 1.5 angstroms. A) express this diameter in picometers 53 Chem 106, Prof. J.T. Spencer Modern Atomic Structure Sample exercise: The diameter of a carbon atom is 1.5 angstroms. A) express this diameter in picometers 1.5 angstroms 54 Chem 106, Prof. J.T. Spencer Modern Atomic Structure Sample exercise: The diameter of a carbon atom is 1.5 angstroms. A) express this diameter in picometers 1.5 angstroms 10-10 meters 1 angstrom 55 Chem 106, Prof. J.T. Spencer 56 Modern Atomic Structure Sample exercise: The diameter of a carbon atom is 1.5 angstroms. A) express this diameter in picometers 1.5 angstroms 10-10 meters 1 angstrom 1012 pm 1 meter Chem 106, Prof. J.T. Spencer 57 Modern Atomic Structure Sample exercise: The diameter of a carbon atom is 1.5 angstroms. A) express this diameter in picometers 1.5 angstroms 10-10 meters 1 angstrom 1012 pm 1 meter 150 pm Chem 106, Prof. J.T. Spencer Modern Atomic Structure 58 Sample exercise: The diameter of a carbon atom is 1.5 angstroms. B) How many carbon atoms could be aligned side by side in a straight line across the width of a pencil line that is 0.10 mm wide? 0.10 mm 1 meter 103 mm 1010 angstrom 1 carbon 1 meter 1.5 angs. Chem 106, Prof. J.T. Spencer Modern Atomic Structure 59 Sample exercise: The diameter of a carbon atom is 1.5 angstroms. B) How many carbon atoms could be aligned side by side in a straight line across the width of a pencil line that is 0.10 mm wide? 0.10 mm Chem 106, Prof. J.T. Spencer Modern Atomic Structure 60 Sample exercise: The diameter of a carbon atom is 1.5 angstroms. B) How many carbon atoms could be aligned side by side in a straight line across the width of a pencil line that is 0.10 mm wide? 0.10 mm 1 meter 103 mm Chem 106, Prof. J.T. Spencer Modern Atomic Structure 61 Sample exercise: The diameter of a carbon atom is 1.5 angstroms. B) How many carbon atoms could be aligned side by side in a straight line across the width of a pencil line that is 0.10 mm wide? 0.10 mm 1 meter 103 mm 1010 angstrom 1 meter Chem 106, Prof. J.T. Spencer Modern Atomic Structure 62 Sample exercise: The diameter of a carbon atom is 1.5 angstroms. B) How many carbon atoms could be aligned side by side in a straight line across the width of a pencil line that is 0.10 mm wide? 0.10 mm 1 meter 103 mm 1010 angstrom 1 carbon 1 meter 1.5 angs. Chem 106, Prof. J.T. Spencer Modern Atomic Structure 63 Sample exercise: The diameter of a carbon atom is 1.5 angstroms. B) How many carbon atoms could be aligned side by side in a straight line across the width of a pencil line that is 0.10 mm wide? 0.10 mm 1 meter 103 mm 1010 angstrom 1 atom 1 meter 1.5 angs. = 6.7 x 105 atoms Chem 106, Prof. J.T. Spencer 64 Atomic Theory: Isotopes differences/similarities between atoms of an element; all atoms of an given element have the same number of protons (and therefore the same number of electrons to balance charge) atoms of an element may have different numbers of neutrons - called isotopes AE Z 11C 6 12C 6 13C 6 14C 6 atomic number (Z) - number of protons mass number (A) - number of protons + number of neutrons nuclide - atoms of a specific elemental isotope Chem 106, Prof. J.T. Spencer 65 Atomic Theory: Isotopes 14N 7 electrons, 7 protons, 7 neutrons 17O 8 electrons, 8 protons, 9 neutrons 35Cl 17 electrons, 17 protons, 18 neutrons 238U 92 electrons, 92 protons, 146 neutrons 7 8 17 92 Chem 106, Prof. J.T. Spencer 66 Atomic Theory: Isotopes Sample exercise:How many protons, neutrons, and electrons are in a 39K atom? Chem 106, Prof. J.T. Spencer 67 Atomic Theory: Isotopes Sample exercise:How many protons, neutrons, and electrons are in a 39K atom? Atomic# = 19 Chem 106, Prof. J.T. Spencer 68 Atomic Theory: Isotopes Sample exercise:How many protons, neutrons, and electrons are in a 39K atom? Atomic# = 19 # of protons = 19 # of electrons = 19 Chem 106, Prof. J.T. Spencer 69 Atomic Theory: Isotopes Sample exercise:How many protons, neutrons, and electrons are in a 39K atom? Atomic# = 19 Mass # = 39 # of protons = 19 # of electrons = 19 Chem 106, Prof. J.T. Spencer 70 Atomic Theory: Isotopes Sample exercise:How many protons, neutrons, and electrons are in a 39K atom? Atomic# = 19 # of protons = 19 # of electrons = 19 Mass # = 39 39 - 19 = 20 neutrons Chem 106, Prof. J.T. Spencer 71 Atomic Theory: Isotopes Sample exercise:Give the complete chemical symbol for the nuclide that contains 18 protons, 18 electrons, and 22 neutrons. Chem 106, Prof. J.T. Spencer 72 Atomic Theory: Isotopes Sample exercise:Give the complete chemical symbol for the nuclide that contains 18 protons, 18 electrons, and 22 neutrons. Atomic # = 18 , element is Argon Chem 106, Prof. J.T. Spencer 73 Atomic Theory: Isotopes Sample exercise:Give the complete chemical symbol for the nuclide that contains 18 protons, 18 electrons, and 22 neutrons. Atomic # = 18 , element is Argon 40Ar 18 Chem 106, Prof. J.T. Spencer 74 Atomic Theory: Isotopes Allotropes - Different chemical forms of the same element existing in the same physical state. Fullerene Graphite Diamond Chem 106, Prof. J.T. Spencer 75 Periodic Table; Dmitri Mendeleev (1869) Displays chemical reactivity trends and relationships and constructed to account for (and predict) chemical reactivity of the elements. For example: Li, Na, K soft metals, v. reactive w/ water He, Ne, Ar gases and not reactive F, Cl, Br reactive with many other elements in a similar fashion Cu, Ag, Au Metal w/ similar reactivity Chem 106, Prof. J.T. Spencer Periodic Table; Dmitri Mendeleev 76 Chem 106, Prof. J.T. Spencer 77 Periodic Table 1 2 16 17 18 Group or Family 1 2 3 4 5 6 Alkali metals Alkaline earth metals Chalcogens (chalk formers) Halogens (salt formers) Noble Gases (inert gases) 7 8 9 10 11 12 13 14 15 Li, Na, K,... Be, Mg, Ca,... O, S, Se,... F, Cl, Br,... He, Ne, Ar,... 16 17 1H Row 18 2 He 3 Li 4 Be 5B 6C 7N 8O 9F 10 Ne 11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar 19 K 20 Ca 21 Sc 22 Ti 23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 30 Zn 31 Ga 32 Ge 33 As 34 Se 35 Br 36 Kr 37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 P d 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe 55 Cs 56 Ba 57 La 72 Hf 73 Ta 74 W 75 Re 76 Os 77 Ir 78 P t 79 Au 80 Hg 81 Tl 82 P b 83 Bi 84 P o 85 At 86 Rn 87 Fr 88 Ra 89 Ac 104 Un q 105 Un p 106 Un h 107 Ns 108 Hs 109 Mt 58 Ce 59 P r 60 Nd 61 P m 62 Sm 63 Eu 64 Gd 65 Tb 66 Dy 67 Ho 68 Er 69 Tm 70 Yb 71 Lu 90 Th 91 P a 92 U 93 Np 94 P u 95 Am 96 Cm 97 Bk 98 Cf 99 Es 100 Fm 101 Md 102 No 103 Lr Chem 106, Prof. J.T. Spencer 78 Periodic Table alkali metals alkaline earth metals 1 2 3 4 5 1H 6 7 8 9 10 non-metals noble gases metalloids 11 13 14 15 16 17 18 2 He metals 5B 6C 7N 8O 9F 10 Ne 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar 30 Zn 31 Ga 32 Ge 33 As 34 Se 35 Br 36 Kr 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe 78 P t 79 Au 80 Hg 81 Tl 82 P b 83 Bi 84 P o 85 At 86 Rn 69 Tm 70 Yb 71 Lu 3 Li 4 Be 11 Na 12 Mg 19 K 20 Ca 21 Sc 22 Ti 23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 P d 55 Cs 56 Ba 57 La 72 Hf 73 Ta 74 W 75 Re 76 Os 77 Ir 87 Fr 88 Ra 89 Ac 104 Un q 105 Un p 106 Un h 107 Ns 108 Hs 109 Mt rare earth metals 12 58 Ce 59 P r 60 Nd 61 P m 62 Sm 63 Eu 64 Gd 65 Tb 66 Dy 67 Ho 68 Er 90 Th 91 P a 92 U 93 Np 94 P u 95 Am 96 Cm 97 Bk 98 Cf 99 Es 100 Fm 101 Md 102 No 103 Lr Chem 106, Prof. J.T. Spencer 79 Periodic Table (1869) metals non-metals conductors shiny high thermal conductivity solids at RT ductile insulators dull thermal insulators freq. non-solids at RT brittle Metalloids (along line in table) have properties between metals and non-metals Chem 106, Prof. J.T. Spencer Molecules and Ions - “assembly” of two or more atoms (with properties different from constituent types of atoms (see “Law of Multiple Proportions”). i.e., H2O, H2O2, CaCO3, HNO3, H2SO4,... some elements found in nature as molecules (i.e., O2, N2, etc... [diatomic]) Formulas Molecular - actual numbers and types of atoms in a molecule Empirical - smallest whole number ratio of constituentStructural - “picture” showing how the atoms are attached to one another Molecule 80 Chem 106, Prof. J.T. Spencer 81 Molecules Molecular Formula Empirical Formula Structural Formula O H2O (water) H2O2 C2H4 (hydr. peroxide) H H2O HO H H O O H H (ethylene) CH2 H C C H H CH2 OH C6H12O6 (glucose) CH2O H O H OH H H OH OH H OH Chem 106, Prof. J.T. Spencer Formulas Ethylene is a gas at room temperature and is the starting material for for many plastics. Its molecular formula is C2H4. – What is its empirical formula? – What other molecular formulas are possible for this same empirical formula? 82 Chem 106, Prof. J.T. Spencer 83 Formulas Ethylene is a gas at room temperature and is the starting material for for many plastics. Its molecular formula is C2H4. – What is its empirical formula? CH2 – What other molecular formulas are possible for this same empirical formula? C2H4 , C3H6 , C4H8 , C5H10 , ... Chem 106, Prof. J.T. Spencer Formulas Cucurbituril is a compound with cage-like molecules big enough to surround and loosely trap smaller molecules. It has the molecular formula C36H36N24O12. – What is its empirical formula? 84 Chem 106, Prof. J.T. Spencer 85 Formulas Cucurbituril is a compound with cage-like molecules big enough to surround and loosely trap smaller molecules. It has the molecular formula C36H36N24O12. – What is its empirical formula? C3H3N2O Chem 106, Prof. J.T. Spencer Formulas Sample exercise: Give the empirical formula for the substance whose molecular formula is Si2H6. 86 Chem 106, Prof. J.T. Spencer 87 Formulas Sample exercise: Give the empirical formula for the substance whose molecular formula is Si2H6. SiH3 Chem 106, Prof. J.T. Spencer 88 Ions atoms can gain or lose electrons to become charged (called ions) positive ion = cation negative ion = anion Na (neutral has 11 electrons) can easily lose 1 electron to become a cation (Na+1) Chem 106, Prof. J.T. Spencer 89 Ions Polyatomic ions; molecules with charges. i.e., NO3-1, SO4-2, PO4-3, etc... chemical properties of ions may be VERY different from similar neutral species Predicting charges on ions - use periodic table (gain or lose electrons to end up with the same number as the nearest noble gas) Chem 106, Prof. J.T. Spencer 90 3 Ions 4 5 6 7 8 9 10 11 12 13 +1 +2 14 15 16 17 -3 -2 -1 e Mg 5B 6C 7N 8O 9F 13Al 14Si 15P 16S 17C Ca 21Sc 22Ti 23V 24Cr 25Mn 26Fe 27Co 28Ni 29Cu 30Zn 31Ga 32Ge 33As 34Se 35B Sr 39Y 40Zr 41Nb 42Mo 43Tc 44Ru 45Rh 46Pd 47Ag 48Cd 49In 50Sn 51Sb 52Te 53I Ba 57La 72Hf 73Ta 74W 75Re 76Os 77Ir 78Pt 79Au 80Hg 81Tl 82Pb 83Bi 84Po 85A Ra 89Ac 104Unq 105Unp 106Unh 107Ns 108Hs 109Mt 58Ce 59Pr 60Nd 61Pm 62Sm 63Eu 64Gd 65Tb 66Dy 67Ho 68Er 69Tm 70Yb 71L Chem 106, Prof. J.T. Spencer 91 Ions Sample exercise: How many protons and electrons does the Se2- ion possess? Chem 106, Prof. J.T. Spencer 92 Ions Sample exercise: How many protons and electrons does the Se2- ion possess? Se atomic number = 34 Chem 106, Prof. J.T. Spencer 93 Ions Sample exercise: How many protons and electrons does the Se2- ion possess? Se atomic number = 34 # of protons = 34 # of electrons = 34 + 2 = 36 Chem 106, Prof. J.T. Spencer 94 Ionic Compounds transfer of electrons between atoms, Na + Cl = [Na]+[Cl] ionic compounds contain anions and cations, typically combinations of metals and non-metals (molecular compounds, in which electrons are shared, are usually result from the combination of non-metals only); FeS, LiBr, CuSO4, TiO4, etc... total charge is neutral; total (+) = total (-) ionic compounds are arranged in a 3D array (packing of ping-pong balls) usually only empirical formulas can be written for ionic compounds (because no real molecular unit in solid phase but “extended” lattice) usually solids but soluble in water insol. in organic sols. Chem 106, Prof. J.T. Spencer 95 Ionic Compounds total charge is neutral; total (+) = total (-) Cation Anion Charges sodium (Na) chlorine (Cl) Na+1 + Cl-1 NaCl magnesium(Mg) nitrogen (N) aluminum (Al) bromine (Br) Mg+2 + N-3 Al+3 + Br-1 Mg3N2 AlBr3 barium (Ba) lithium (Li) nickel (Ni) Ba+2 + SO4-2 Li+1 + CO3-2 Ni+2 + Cl-1 Ni+3 + Cl-1 BaSO4 Li2CO3 NiCl2 NiCl3 sulfate (SO4) carbonate (CO3) chloride (Cl) Empirical Formula Chem 106, Prof. J.T. Spencer 96 Ionic Compounds + - + + + - - + - - + + - - + + + - + - + - + - + - + - - - + Unit Cell + - Cell Face Chem 106, Prof. J.T. Spencer 97 Ionic Compounds Sample exercise: Which of the following compounds are molecular? CI4 FeS P4O6 PbF2 Chem 106, Prof. J.T. Spencer 98 Ionic Compounds Sample exercise: Which of the following compounds are molecular? CI4 FeS P4O6 PbF2 Chem 106, Prof. J.T. Spencer 99 Ionic Compounds Sample exercise: Write the empirical formulas for the compounds formed by the following ions: a) Na+ and PO43- Chem 106, Prof. J.T. Spencer 100 Ionic Compounds Sample exercise: Write the empirical formulas for the compounds formed by the following ions: a) Na+ and PO43Na3PO4 Chem 106, Prof. J.T. Spencer 101 Ionic Compounds Sample exercise: Write the empirical formulas for the compounds formed by the following ions: b) Zn2+ and SO42- Chem 106, Prof. J.T. Spencer 102 Ionic Compounds Sample exercise: Write the empirical formulas for the compounds formed by the following ions: b) Zn2+ and SO42- ZnSO4 Chem 106, Prof. J.T. Spencer 103 Ionic Compounds Sample exercise: Write the empirical formulas for the compounds formed by the following ions: c) Fe3+ and CO32- Chem 106, Prof. J.T. Spencer 104 Ionic Compounds Sample exercise: Write the empirical formulas for the compounds formed by the following ions: c) Fe3+ and CO32- Fe2(CO3)3 Chem 106, Prof. J.T. Spencer 105 Nomenclature: naming inorganic compounds Method for unambiguously referring to the a. 15 million known molecules) Organic compounds - containing C combined typically with H, O, N, and S (originally associated with living organisms but no longer relevant definition) Inorganic compounds - all other compounds Chem 106, Prof. J.T. Spencer 106 Nomenclature: naming inorganic compounds Traditional names for compounds long known (ammonia [NH3], water [H2O], Zeise’s salt [Pt(C2H4)Cl3]-1], Muriatic Acid [HCl], etc...) common names (somewhat systematic, ferrous chloride, cupric chloride, etc...) International Union of Pure and Applied Chemistry rules (IUPAC) Chem 106, Prof. J.T. Spencer 107 Nomenclature: naming ionic compounds Ionic compounds are names based upon the component ions. Positive ion (cation) named and written first Negative ion (anion) named and written last Solve ambiguity in charge by using Roman numerals Cation Anion Compound Na+ Al+3 Fe+2 ClO-2 O-2 NaCl Al2O3 FeO Name sodium chloride aluminum oxide iron(II) oxide (ferrous oxide) Fe+3 O-2 Fe2O3 iron(III) oxide (ferric oxide) Chem 106, Prof. J.T. Spencer 108 Nomenclature: naming cations Monoatomic - take the name from the element » Li+1 lithium ion » Ca+2 calcium ion Polyatomic Sr+3 strontium ion - only one common polyatomic cation » NH4+1 ammonium ion Multiple Cationic Charge Possible - specify charge with Roman numerals to be unambiguous » Fe+2 iron(II) ion » Cr+6 chromium(VI) ion Fe+3 Cr+5 iron(III) ion chromium(V) ion For metals, older method used to distinguish between ions differing by one charge unit by adding suffix (-ous for lower charge, -ic for higher charge) » Fe+2 ferrous ion » Co+2 cobaltous ion Fe+3 Co+3 ferric ion cobaltic ion Chem 106, Prof. J.T. Spencer 109 Nomenclature: naming anions Monoatomic » F-1 » O-2 Polyatomic - add -ide suffix fluoride ion oxide ion P-3 B-5 phosphide ion boride ion - some common use -ide suffix » OH-1 hydroxide ion » N3-1 azide ion CN-1 O2-2 cyanide ion peroxide ion Oxyanions - (1) when only two, the one with less oxygen ends in -ite and the one with more oxygen ends with -ate » NO2-1 nitrite ion » SO3-2 sulfite ion Oxyanions- NO3-1 SO4-2 nitrate ion sulfate ion for species with more than two members use prefixes (hypo- less oxygen and per- more oxygen) ClO-1 ClO2-1 ClO3-1 ClO4-1 hypochlorite chlorite chlorate perchlorate Chem 106, Prof. J.T. Spencer 110 Nomenclature: acids - compound which yields H+ when dissolved in water write hydrogen first; HCl, H2SO4, H3PO4, etc... anions which end in -ide use hydro- as prefix and -ic as suffix Anion Acid Cl- (chloride) HCl (hydrochloric acid) F- (fluoride) HF (hydrofluoric acid) oxyacids - replace -ate suffix of anion with -ic, replace -ite suffix of anion with -ous (leave prefixes!) Anion Acid ClO2- (chlorite) HClO2 (chlorous acid) ClO3- (chlorate) HClO3 (chloric acid) ClO4-1 (perchloric) HClO4 (perchloric acid) Acid Chem 106, Prof. J.T. Spencer 111 Nomenclature: molecular compounds Similar to ionic compounds – More positive element (left and down on periodic table) named first (first in Prefix Number formula also) Mono1 – Second element name ends with -ide Di2 Tri3 – Use numbering prefixes if necessary Formula N2O5 IF7 XeO3 SiCl4 H2Se P4O6 Name (text prob. 2.45) dinitrogen pentoxide iodine heptafluoride xeon trioxide silicon tetrachloride dihydrogen selenide tetraphosphorus hexoxide TetraPentaHexaHeptaOctaNonaDeca- 4 5 6 7 8 9 10 Chem 106, Prof. J.T. Spencer 112 Nomenclature: examples Formula ZnCl2 (NH4)2SO4 FeF3 HBr HBrO4 SF6 HCN Name zinc(II) chloride ammonium sulfate iron(III) fluoride hydrobromic acid perbromic acid sulfur hexafluoride hydrogen cyanide Chem 106, Prof. J.T. Spencer End Chapter 2 Atomic Theory Experiments leading to the discovery of atomic structure The Periodic Table Molecules and Ions Nomenclature 113