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General Chemistry II Exam III Review: Chapter 20 CHAPTER 20 Nuclear Chemistry 1. Radioactivity i.

Alpha rays bend away from positive plate toward a negative plate 1. Positive charge ii. Beta rays bend towards positive plate 1. Negative charge iii. Gamma rays are unaffected by magnetic and electric fields 1. Similar to X-rays, but shorter wavelength b. Nuclear Equations 1. Symbolic representation of a nuclear reaction ii. Positron mass = electron mass, but with opposite charge (+) iii. Total charge and total # of nucleons is conserved 1. The sum of subscripts of reactants equals sum of subscripts of products 2. The sum of superscripts of reactants equals sum of superscripts of products c. Nuclear Stability i. Nuclear force strong attraction between nucleons 1. Only effective at distances of 10-15cm 2. Protons farther apart will repel each other because of their electric charges; inside the nucleus, the protons are close enough for the nuclear force to keep them together a. stable nucleus ii. Shell Model of the Nucleus 1. A nuclear model in which protons and neutrons exist in levels, or shells, analogous to the shell structure for electrons 2. Magic number a number of nuclear particles that make a nucleus very stable a. A magic number is the number of nuclear particles in a completed shell of protons or neutrons b. For protons: 2, 8, 20, 28, 50, 82, 114 c. For neutrons: 2, 8, 20, 28, 50, 82, 126 3. Evidence for shell model: a. Helium nuclei (seen in alpha particle emission) are especially stable, and they contain 2 protons and 2 neutrons (both are magic numbers) b. Uranium-238 decays to the final product 206/82Pb c. Other radioactive decays series end at 208/82N d. Isotopes of all elements tend to favor arrangements with even numbers of neutrons and protons 1

4. Band of Stability a. For nuclides up to Z = 20, the ratio of protons to neutrons is about 1.1:1.0 b. As Z increases, the ratio increases to 1.5:1.0 i. Larger numbers of protons increasingly repulse each other in the nucleus, so more neutrons are required to give attractive nuclear forces to offset repulsions c. No stable nuclei exist above Z = 83 d. All elements with Z less than or equal to 83 have at least one stable nuclide, except technetium (Z = 43) and promethium (Z = 61) d. Types of Radioactive Decay i. Alpha emission 1. Emission of a helium nucleus from an unstable nucleus 2. The product has an atomic number that is two less, and a mass number that is four less, than original nucleus ii. Beta emission 1. Emission equivalent to the conversion of a neutron to a proton 2. The product has a number that is one more than that of the original nuclear, and the mass number remains the same 3. Emission of a high-speed electron from an unstable nucleus iii. Positron emission 1. Positron is a particle identical to an electron in mass, but has a positive charge instead of a negative charge 2. Equivalent to the conversion of a proton to a neutron 3. The product nucleus has an atomic number that is one less than that of the original nucleus, and the mass number remains the same iv. Electron capture 1. The decay of a unstable nucleus by capturing/picking up an electron from an inner orbital of an atom 2. In effect, a proton is change to a neutron, as in positron emission 3. The product nucleus has an atomic number one less than the original nucleus, and the mass number remains the same 4. When another orbital electron fills the vacancy in the innershell orbital created by electron capture, an x-ray photon is emitted 5. Same effect as positron emission a. Rather than emitting a positron, it captures an electron, but both effectively reduce atomic number by 1 without changing the mass number v. Gamma emission 1. Emission from an excited nucleus of a gamma photon, corresponding to radiation with a wavelength 10-12 2

2. Decayed product nucleus are often unstable, so they undergo gamma ray emission to get to a lower-energy state 3. Often occurs very quickly after radioactive decay 4. Metastable nucleus a nucleus in an excited state with a lifetime of at least one nanosecond (10-9) a. In time, metastable nucleus decays by gamma emission b. There is no change in atomic number vi. Spontaneous fission 1. The spontaneous decay of an unstable nucleus in which a heavy nucleus of mass number greater than 89 splits into lighter nuclei and energy is released e. Predicting which type of radioactive decay i. Nuclides to the left of the band of stability have a higher neutron:proton ratio than needed for stability 1. These nuclides decay by beta emission 2. In beta emission, a neutron becomes a proton ii. Nuclides to the right of the band have a lower neutron:proton ratio than needed for stability 1. These nuclides decay by positron emission or electron capture 2. Both these processes convert a proton to a neutron iii. For example: 1. 11C 11B + 0 e 6 5 1 a. Positron emission b. Neutron:proton ratio increases when Carbon-11 decays to boron-11 14 C 14 N + 0 e 2. 6 7 1 a. Beta emission b. Neutron:proton ratio decreases 3. Phosphorous-31 has atomic mass of 31.0amu; you can expect that Phorphorous-31 is a stable isotope. Phorphorous-30 should be expected to undergo positron emission or electron capture (positron emission is observed) iv. Positron emission and electron capture are competitive decay processes 1. Rate of electron capture increases with atomic number of the nuclide, so it is more important in heavier elements 2. Positron emission typically seen in lighter elements (like phosphorous-30) v. In very heavy elements (Z 83) alpha emission is common form of decay (uranium-238) 2. Radioactive decay series i. All nuclides with Z > 83 are radioactive b. Radioactive decay series a sequence in which one radioactive nucleus decays to a second, followed by a third, fourth, and so on i. Eventually, a stable nucleus, which is an isotope of lead, is reached

ii. There are three radioactive decay series found in nature: 1. 238U 206Pb 92 82 2. 238U 207Pb 92 82 3. 232Th 208Pb 90 82

Nuclear bombardment reactions 3. Transmutation the change of one element to another by bombarding the nucleus of the element with nuclear particles or nuclei a. Ernest Rutherford found that when alpha particles emitted from a radioactive element collided with a stable nitrogen nuclei, a protons were ejected in the process of forming an oxygen nucleus b. Bombardment of beryllium with alpha particles led to the discovery of the neutron in 1932, as the radiation from the beryllium atom was found to be without charge c. Abbreviated form for bombardment notation 4 1 i. 14 N + 2 He 17O + 1 H 7 8 ii. 14 N (, p) 17O 7 8 Particle Abbreviation n Neutron Proton p Deuteron d Alpha d. Very heavy elements cant be transmutated by natural alpha emissions e. Particle accelerator necessary to shoot charged particles into heavy nuclei i. Device used to accelerate electrons, protons, alpha particles, and other ions to very high speeds ii. Kinetic energy of these particles is measured in electron volts (eV) 1. An electron volt is the quantity of energy that would have to be imparted to an electron to accelerate it by on volt potential 2. Particle accelerators typically give particles energies of millions of electron volts iii. Cyclotron 1. Type of particle accelerator with two hollow, semicircular metal electrodes called dees, in which charged particles accelerate by stages to higher kinetic energies 4. Transuranium elements i. Elements with atomic numbers great than that of uranium (Z = 92) ii. Prepared in a laboratory by firing various particles at uranium isotopes 1. Plutonium-239 is prepared in large quantities in nuclear reactors, and is used for nuclear weapons 2. Plutonium was first produced by accelerating a deuteron at a uranium atom to yield neptunium-238, which decayed to plutonium-238 (beta decay)

iii. Glenn Seaborg proposed that the next elements to be discovered beyond actinium (Z=89), called actinides, should be placed at the bottom of the periodic table under the lanthanides 5. Radiation Counters a. Geiger counter ionization counter used to count particles emitted by radioactive nuclei, consisting of a metal tube filled with gas, like argon i. Radiation enters through thin glass or plastic window ii. A wire runs from tube center, from which wire is insulated iii. The tube and wire are connected to high-voltage source so that the tube becomes negative electrode, and the wire becomes positive electrode iv. Normally, gas in tube is insulator and no current flows, but when radiation, like an alpha particle, passes through the window of the tube and into the gas, atoms are ionized v. Free electrons accelerate towards positively charged wire vi. These electrons collide with more atoms to set additional electrons free vii. This process gives a pulse of current, amplified as a click viii. Alpha and beta particles can be detected by a Geiger counter 1. Neutrons can be detected only with boron trifluoride is added to the gas in the tube 2. Neutrons react with boron-10 nuclei to produce alpha particles, which can then be detected b. Scintillation counter i. A device that detects nuclear radiation from flashes of light generated in material by the radiation ii. A phosphor is a substance that emits a flash of let when radiation strikes it iii. The activity of a radioactive source is the number of nuclear disintegrations per unit time occurring in a radioactive material 1. A curie (Ci) a unit of activity is equal to 3.7 x 1010 Rate of Radioactive Decay 6. Rate of decay and half-life a. Rate = kNt i. k = radioactive decay constant (different for each nuclide) ii. Nt = number of radioactive nuclei at time t b. The decay constant comes from the number of nuclear disintegrations over a period of time c. Given activity in curies (Ci), you can calculate rate: i. Rate = (activity in Ci) x [(3.7 x 1010 nuclei/s)/(1.0 Ci)] ii. k = rate/Nt d. Half-life i. The time it takes for one half of the nuclei in a sample to decay ii. Related to radioactive decay: 1. t1/2 = 0.693/k 5

2. k = decay constant iii. With decay constant, you can calculate the fraction of the radioactive nuclei that remain after any given time 1. ln(Nt/N0) = -kt 2. If given half life, time elapsed, but no k: a. Plug in (-0.693t/t1/2) for k b. Solve for the ratio of Nt/N0 7. Radioactive dating a. Carbon dating i. Carbon-14 has half life of about 5700 years ii. Present in atmosphere because of cosmic rays iii. A nitrogen-14 atom collides with a neutron from space, yielding a proton and a carbon-14 atom iv. By measuring the level of beta emissions in a dead object (or, the conversion of carbon-14 back into nitrogen-14) you can determine how long it has been dead Mass-Energy Calculations 8. Mass-energy equivalence a. When objects lose energy, they lose an equivalent amount of mass b. E = mc2 c. c = 3.00 x 108 m/s2 d. Miniscule amount of mass lost as energy is lost in chemical reactions e. Nuclear reactions involve 1,000,000 times bigger mass changes per mole of reactant than chemical reactions 9. Nuclear binding energy a. Binding energy the energy needed to break a nucleus into its individual protons and neutrons b. Mass defect the nucleon mass minus the atomic mass i. A larger positive difference indicates a more stable atom, as more energy is released when the nucleus forms ii. Larger mass defect = more stable nucleus c. Nuclear fission a nuclear reaction in which a heavy nucleus splits into lighter nuclei and energy is released d. Nuclear fusion a nuclear reaction in which light nuclei combine to give a more stable, heavier nucleus plus possible several neutrons, and energy is released Nuclear Fission and Fusion e. Both processes are ways for atoms of extreme size to attain a size closer to the intermediate range (mass number = 50) 10. Nuclear fission and nuclear reactors a. When uranium-235 nucleus splits, about two or three neutrons are released, which are then absorbed by other uranium-235 nuclei, which then split and release more neutrons

b. Chain reaction a self-sustaining series of nuclear fissions cause by the absorption of neutrons released form previous nuclear fissions c. Critical mass the smallest mass of fissionable material in which a chain reaction can be sustained i. If mass is too small, the neutrons released when a nucleus splits will be lost too quickly for the chain reaction to be sustained ii. Supercritical mass a mass much larger than the critical mass which results in huge numbers of rapidly splitting nuclei 1. Atomic bombs contain two subcritical masses of uranium that, when pushed together with explosives, form a supercritical mass d. Nuclear fission reactor i. A device that permits a controlled chain reaction of nuclear fissions ii. Fuel rods cylinders that contain fissionable material iii. Control rods cylinders composed of substance that absorb neutrons, like boron and cadmium, to slow the cahin reaction iv. Moderator a substance that slows down neutrons, required if uranium-235 is the fuel 1. Slows down nuclei released by uranium-235 so that they arent absorbed by uranium-238, but by other uranium-235 atoms 2. Heavy water, light water, and graphite e. Nuclear fusion i. Energy can be obtained by combining light nuclei into a heavy nucleus, because of the bonding energy of the nucleus ii. To get two light nuclei to fuse, one nucleus must bombard enough with enough kinetic energy to overcome the repulsion of electric charges iii. Cold fusion of deuterium atoms is best power source, but it unlikely iv. Much more feasible is hot fusion 1. Tritium and deuterium are heated to 1 million degrees Celsius, at which point they form a plasma 2. Plasma an electrically neutral gas of ions and electrons 3. At this temperature, the plasma is essentially separate nuclei and electrons 4. Hydrogen bombs work by first using a fission reaction to create the extreme temperatures needed for fusion components in the bomb to react v. Plasma quickly loses heat when it touches any material 1. Magnetic or laser fusion reactors would solve this problem CHAPTER 21 1. General Observations About the Main-Group Elements a. Elements on the left side- largely metallic b. Right side- largely nonmetallic 7

c. Metallic elements: i. Low ionization energies and low electronegativities ii. Tend to lose their valence elections to form cations iii. Oxides of metals are usually basic iv. Oxides of most reactive metals react with water to give basic solutions v. Generally have oxidation states equal to the group number 1. Some in fifth and sixth periods have ox states equal to the group number minus 2 d. Nonmetallic elements: i. Form monoatomic anions and oxoanions ii. Oxides are acidic iii. Have a variety of oxidation states ranging from the group number (most positive value) to the group number minus eight (most negative value) e. Metallic characteristics of the main group elements in the periodic table generally decrease in going across a period from left to right f. Metallic characteristics of the main group elements in the periodic table become more important going down any column (group) g. Second period element is often rather different from the remaining elements in its group i. Has a small atom that tends to hold electrons strongly high electronegativity ii. Bonding only includes s and p orbitals, other elements may use d orbitals 2. Metals: Characteristics and Production a. Metal- lustrous, high electrical and heat conductivities, and is malleable and ductile b. Alloy- material with metallic properties that is either a compound or a mixture (can be homo- or heterogeneous) c. Sources of metals i. Mineral- naturally occurring inorganic solid substance or solid solution with a definite crystalline structure ii. Ore- a rock or mineral from which a metal or nonmetal can be economically produced d. Metallurgy- scientific study of the production of metals from their ores and the making of alloys having various useful properties i. Steps in the production of metal from its ore: preliminary treatment, reduction, refining e. Preliminary Treatment i. Separate mineral from ore f. Reduction i. If a metal isnt already free, must be obtained from one of its compounds by reduction (using electrolysis or chemical reduction) 1. Electrolysis: uses an electric current to reduce a metal compound to the metal (lithium from lithium chloride)

g. Refining i. Metal contains impurities and needs to be purified (refined) various techniques are used 3. Bonding in Metals a. Special properties of metals result from delocalized bonding (bonding electrons are spread over a number of atoms) b. Electron-sea model: array of positive ions surrounded by a sea of valence elections free to move over the entire metal crystal i. When metal is connected to electric current, electrons easily move away from negative side of electric source and toward positive side ELECTRIC CURRENT ii. Metal is conductor because of mobility of valence electrons iii. Good heat conductor because mobile electrons can carry additional kinetic energy across the metal c. Molecular orbital theory of metals i. Molecular orbitals- form between two atoms when atomic orbitals on the atoms overlap ii. Some cases, atomic orbitals on three or more atoms overlap to form molecular orbitals that encompass all atoms (these molecular orbitals are delocalized) iii. Number of molecular orbitals that form by overlap of atomic orbitals = number of atomic orbitals iv. Metal: outer orbitals of an enormous number of metal atoms overlap to form an enormous number of molecular orbitals that are delocalized over the metals a large number of energy levels are crowded together into bands band theory v. Band theory (sodium): [Ne]3s1 1. When two Na atoms approach each other their 3s orbitals overlap to form two molecular orbitals when N atoms approach each other there is N molecular orbitals overlapping and encompassing the whole crystal 2. At each stage the number of energy levels grows eventually the energy levels effectively merge into a band of continuous energies (called the 3s band for sodium metal) 3. 3s band formed of N atoms will have N orbitals that hold a max of 2N electrons 4. Sodium has one valence electron, N atoms will supply N 3s electrons and will half-fill the 3s band 5. Conductivitybecause electrons become free to move throughout a crystal when they are excted to unoccupied orbitals of a band requires very little energy in sodium (because of half filled 3s band, unoccupied orbitals lie just above the occupied orbitals of highest energy)

2. Reduction: cheapest chemical reducing agent is some form of carbon such as hard coal or coke.

6. When voltage applied, electrons are excited into the unoccupied orbitals and move towards positive pole of voltage source CURRENT vi. Band theory (magnesium): [Ne]3s2 1. Forms a 3s band like sodium 2. Both sodium and magnesium have an unoccupied 3p band formed from the unoccupied 3p orbitals 3. Presence of this band in sodium = no effect 4. Magnesium- orbitals of individual atoms interact forming the metals, the energy levels spread so that bottom of 3p band merges with top of 3s band 5. When electrons reach energy where two bands have merged, electrons begin to fill orbitals in both bands 3s and 3p bands of magnesium metal are only partially filled by the time you have accounted for all 2N valence electrons 6. Voltage highest energy electrons are easily excited to unoccupied orbitals, CONDUCTOR vii. IN GENERAL: solid that has a partially filled band will be an electrical conductor; solid that has only completely filled bands (without a nearby unfilled band) will be a nonconductor (insulator) 4. Group IA: The Alkali Metals a. Except hydrogen, are all soft silvery metals b. Most reactive of all metals (react readily with air and water) c. Ns1: usually form +1 ions (most compounds of these ions are soluble in water) d. Never occur as free metals in nature e. Lithium i. Chemically reactive ii. Relatively soft, hardest of all Group 1A iii. Many of ionic compounds are less soluble than similar compounds of other alkali metals iv. Metallurgy: source = the ore spodumene v. Reactions: 1. Reacts readily with water and with moisture in air to produce lithium hydroxide and hydrogen gas (not as vigorous as mixture of sodium and water) 2. Burns in air to produce lithium oxide 3. Reacts with nitrogen gas to form lithium nitride vi. Lithium compounds: 1. Lithium carbonate: Li2CO3 primary source of all other lithium compounds 2. Lithium hydroxide: LiOH strong base produced by reaction of lithium carbonate with calcium hydroxide in a precipitation reaction a. Li2CO3 + Ca(OH)2 2LiOH + CaCO3 f. Sodium and Potassium 10

i. Sodium metal = more reactive than potassium metal ii. As you move down column of alkali metals, metals become more chemically reactive (forming the +1 ions) 1. Partly because of decrease in ionization energy 2. Atomic size increases going from top to bottom, valence electrons held less strongly iii. Group 1A metals also increase in softness going from top to bottom 1. Result of increasing atomic size, which results in decreasing strength of bonding by valence s shell electrons iv. Sodium metallurgy: obtained by electrolysis of molten sodium chloride 1. Strong reducing agent v. Reactions of Sodium Metal: 1. Reacts with water (greater vigor than lithium) 2. Burns in air, producing some sodium oxide but mainly sodium peroxide a. Peroxide ion = oxidizing agent vi. Sodium compounds: 1. NaOH one of top ten industrial chemicals; strong base 2. Sodium carbonate= important (Na2CO3) consumed with sand and lime in making glass vii. Potassium and potassium compounds 1. Principal source of potassium and potassium compounds is KCl 2. Almost all of potassium metal produced is used in prep of potassium superoxide KO2 for self-contained breathing apparatus 5. Group IIA: The Alkaline Earth Metals a. Less reactive and harder than Alkali metals b. Occur in nature as silicate rocks/ carbonates/ sulfates c. Magnesium i. Metallurgy: 1. Important as a structural metal a. Low density and relative strength of alloys 2. Pure magnesium is relatively reactive (alloys add strength and corrosive resistance) 3. Magnesium metal used as a reducing agent in the manufacture of titanium and zirconium from their tetrachlorides ii. Reactions of magnesium metal 1. Burns in air vigorously to form the oxide 2. Burns in carbon dioxide, producing magnesium oxide and soot, or carbon 3. Pure metal reacts slowly with water but reacts readily with steam iii. Magnesium compounds 1. When magnesite, a magnesium carbonate mineral, is heated above 350, it decomposes to the oxide, a white solid 11

d. Calcium i. Metallurgy: obtained by reduction of calcium oxide with aluminum 1. Mainly used in some alloys ii. Reactions of calcium metal 1. Soft reactive metal 2. Reacts with water like the alkali metals to produce the metal hydroxide and hydrogen, the reactions are much less vigorous 3. Calcium burns in air to produce the oxide CaO, and with chlorine to produce calcium chloride calcium reacts directly with hydrogen to give the hydride iii. Calcium compounds 1. Limestone, dolomite, anhydrite, gypsum 2. Calcium oxide= in top ten industrial chemicals 6. Group IIIA and Group IVA Metals a. Group IIIA- increasing metallic character in going down the column i. Boron- metalloid- chemistry is typical of nonmetal 1. B(OH)3 is actually acidic ii. Rest of the elements are metals, but their hydroxides change from amphoteric for aluminum and gallium to basic for indium and thallium iii. Bonding to Boron is covalent, atom shares its 2s2sp1 valence electrons to give +3 oxidation state iv. Aluminum has many covalent compounds, but also has definitely ionic ones (AlF3) 1. Al+3 is present in aq solutions of aluminum salts v. Gallium, indium, and thallium also have ionic compounds and give cations in aq solutions vi. Aluminum: only +3 important vii. Gallium and indium: +1 compounds viii. Thallium: +3 and +1 are important ix. Group IVA show trend of greater metallic character in going down column 1. Last two in column, tin and lead, well known metals a. Exist in +2 and +4 states b. Tin: both are common c. Lead: mostly +2 b. Aluminum i. Metallurgy: soft and chemically reactive; very good conductor of electricity ii. Reactions of aluminum 1. Much less reactive than alkali and alkaline earth 2. Does not react at an appreciable rate with water at room temp 12

a. Careful heating at low temp results in a powdery form of the oxide that is relatively reactive reacts slowly with water to produce magnesium hydroxide but reacts readily with acids to yield the corresponding salts

3. Reacts readily with oxygen, but oxide coating that forms makes it corrosion resistant iii. Aluminum compounds 1. Most important= aluminum oxide (alumina) Al2O3 a. Most used to make aluminum metals, some used as a carrier (support) for many heterogeneous catalysts required in chemical processes c. Tin and Lead i. Tin- two different forms (allotropes) one is metal and the other is nonmetal 1. Nonmetal called gray tin (gray powder) 2. Metallic- white tin (at low temp white tin transitions to gray tin) ii. Reactions of Tin and Lead 1. Much less reactive than other metals of group IA IIA and IIIA 2. Aluminum reacts vigorously with dilute hydrochloric and sulfuric acids, tin reacts only slowly with these acids 3. Tin reacts more rapidly with the concentrated acids 4. Lead metal reacts with these acids, but the products are insoluble and adhere to the metal so the reaction soon stops iii. Tin and Lead compounds 1. Tin(II) Chloride, SnCl2, used as a reducing agent 2. Lead exists in compounds in the +2 and +4 states but Lead (II) more common

Chemistry of Non-metals Hydrogen 1. Properties and preparation of hydrogen a. Easily produced on a small scale: i. 2HCl(g) + Zn(s) ZnCl2(aq) + H2(g) b. Colorless, odorless gas, less dense than air c. Not much in common with Group IA elements i. Much less likely to form a cation ii. Forms covalent compounds with nonmetallic elements 1. CH4, H2S, PH3 d. Three isotopes i. Protium, deuterium, and tritium 1. Deuterium has boiling point of 101.42 degrees Celsius 2. Tritium is radioactive ii. Often used as a marker in experiments e. Hydrogen is generally prepared industrially by steam-reforming process

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i. Steam with hydrocarbons from natural gas or petroleum react at high temperature and pressure in the presence of a catalyst to form carbon monoxide and hydrogen ii. Water-gas reaction steam is passed over red-hot coal, producing carbon monoxide and hydrogen gas iii. To remove carbon monoxide, it is reacted with steam in the presence of a catalyst to give CO2 and more hydrogen gas iv. The CO2 is then removed by passing the mixture of gases through a basic aqueous solution 2. Hydrogen reactions and compounds a. Mostly used to prepare ammonia b. Also used in petrochemical industry c. Food industry i. Hydrogenation converts liquid fats to solid fats by saturating carboncarbon double bonds with H2 gas d. Synthesis gas reaction i. Cobalt-catalyzed reaction with carbon monoxide to produce methanol e. Reduction of metal oxides to extract pure metals f. Binary hydride i. A compound that contains hydrogen and one other element ii. Ionic hydrides 1. Contain hydride ion (H-) 2. Can be directly forms via reaction of an alkali metal or large Group IIA metals (Ca, Sr, and Ba) with H2 gas near 400 degrees Celsius a. 2Li(s) + H2(g) 2LiH(s) b. Ba(s) + H2(g) BaH2(g) 3. White crystalline compounds 4. H has oxidation state of -1 5. Can undergo oxidation-reduction reaction with water to produce hydrogen and a basic solution a. LiH(s) + H2O(l) H2(g) + LiOH(aq) iii. Covalent hydrides 1. Molecular compounds in which hydrogen is covalently bonded to another element a. NH3, H2O, H2O2 2. Some formed by direct reaction of the elements 3. If the nonmetal reacting with hydrogen is reactive, the reaction will readily occur without high temp. or a catalayst a. F2(g) + H2 (g) 2HF(g) 4. Other reactions will require temp. or catalyst a. 2H2(g) + O2(g) 2H2O(g) [exothermic, rapid] 5. Clean fuel source, most efficient heat per gram of any fuel iv. Metallic hydrides 1. Compounds containing transition metal and hydrogen 2. MHx, where x is often not an integer 14

3. Non-stoichiometric amounts of hydrogen enter a crystalline structure under different conditions, e.g. pressure a. MH0.4, MH0.7 Group IVA the Carbon Family 3. Carbon a. Catenation the covalent bonding of two or more atoms of the same element to one another i. Carbon is by far the most prevalent b. Allotropes of carbon i. Diamond 1. Each carbon tetrahedrally (sp3) bonded to four other carbon atoms 2. Among hardest substances known ii. Graphite 1. Black substance 2. Layer structure a. Each layer consists of carbon atoms bonded to three other carbon atoms to give hexagonal pattern of carbon atoms arranged in a plan b. Layers easily slide over one another, making it soft 3. Bonding involved sp2 hybridization of the carbon atoms with delocalized pi electrons 4. Good conductor, because of delocalized bonding within layers iii. Buckminsterfullerene 1. Stable soccer ball form c. Carbon black i. Composed of extremely small crystals of carbon with imperfect graphite structure ii. Used in tires, printer ink d. Oxides of carbon i. Carbon and organic compounds burn in an excess of O2 to give CO2 ii. Equilibrium among carbon, carbon dioxide, and carbon monoxide favors CO above 700 degrees Celsius 1. CO2(g) + C(s) 2CO(g) 2. CO is almost always a product of combustion iii. CO is produced industrially from CH4 with steam or partial oxidation 1. CH4(g) + H2O(g) CO(g) + 3H2(g) iv. Methanol production requires CO 1. CO(g) + 2H2(g) CH3OH v. CO2 is colorless, odorless vi. CO2 is produced whenever carbon or organic materials are burned e. Carbonates i. CO2 dissolves in water to form aqueous solution of carbonic acid 1. CO2(g) + H2O(l) H2CO3(aq)

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4. Silicon a. Basic material in semiconductor devices in most electronics b. Silicates compounds of silicon and oxygen with one or more metallic compounds c. Elemental silicon is obtained by reducing quartz san (SiO2) with coke (C) at 3000 degrees Celsius i. SiO2(l) + 2C(s) Si(l) + 2CO(g) d. Diamond-like structure e. Must be exceptionally pure for industrial use i. Si(s) + 2Cl2(g) SiCl4(l) ii. SiCl4(g) + 2H2(g) SiCl4(l) 1. Pure silicon crystallizes on surface of pure silicon rod f. Silica (silicon dioxide) i. SiO2 ii. A covalent network solid in which each silicon atom is covalently bonded in tetrahedral directions to four oxygen atom, and each oxygen atom is in turn bonded to another silicon atom iii. Quartz crystals 1. Piezoelectric effect a. In a piezoelectric crystal, like quartz, compression of the crystal in a particular direction causes an electric voltage to develop across it b. This effect allows quartz crystals to be used in sound systems, as they are sensitive to sound vibrations and can convert them to electrical currents g. Silicates i. A compound of silicon and oxygen with one or more metals that may be formally regarded as a derivative of silicic acid, H4SiO4 or Si(OH)4 ii. Not isolated, but silicate ions are present in liquid silica 1. Via condensation reactions, two molecules of silicate are chemically joined by the elimination of H2O 2. All silicate minerals have long chain structure h. Silicones i. A polymer containing chains of silicon-oxygen bonds, with hydrocarbon groups such as CH3 attached to silicon atoms ii. Preparation: 1. Reaction of silicon with methyl chloride at high temp with copper catalyst a. Si(s) + 2CH3Cl(g) (CH3)SiCl2 2. The product is reacted with water 16

ii. Carbonic acid is diprotic (two acidic H atoms), and dissociates to form carbonate ion iii. Carbonate ion then dissociates to form hydrogen carbonate and carbonate ions iv. CO2 reacts very readily to form salts 1. CO2(g)+ Ca(OH)2(aq) CaCO3(s) + H2O(l)

a. (CH3)2SiCl2(l) + 2H2O(l) (CH3)2Si(OH)2 + 2HCl(g) 3. Then the product undergoes a condensation reaction to form a silicone oil Group VA Nitrogen and Phosphorous Family 5. Nitrogen a. N2 makes up 78.1% of the atmosphere i. Relatively unreactive b. Exists in important compounds with oxidation states between -3 and +5 c. Properties and uses i. Stable triple bond ii. Some very reactive metals do react with N2 1. Magnesium metal burns in air, forming nitride as well as oxide a. 3Mg(s) + N2(g) Mg3N2(s) 3- is very strong base, reacting with water to produce 2. N ammonia a. N3-(aq) + 3H2O(l) NH3(g) + 3OH-(aq) iii. Good blanketing gas, which is used as the atmosphere for protecting a material from oxygen in the air during storage d. Nitrogen compounds i. Ammonia (NH3) 1. Colorless gas 2. Prepared from N2 and H2 by Haber process 3. Can be prepared in the lab with ammonium salt and a strong base a. NH4Cl(aq) + NaOH(aq) NH3(g) + H2O(l) + NaCl(aq) 4. Liquid used as fertilizer ii. Nitrous oxide (N2O) 1. Prepared by careful heating of molten ammonium nitrate a. NH4NO3(s) N2O(g) + 2H2O(g) iii. Nitrogen monoxide (NO) aka nitric oxide 1. In preparation, ammonia is oxidized in the presence of platinum catalyst a. 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) iv. Nitric acid (HNO3) 1. Produced by Ostwald process a. Ammonia is burned in the presence of platinum catalyst to give NO b. NO reacts with oxygen to form NO2 c. NO2 is dissolved in water, where it reacts to form nitric acid and NO 2. Strong oxidizing agent a. 3Cu(s) + 8H3O+(aq) + 2NO3- 3Cu2+(aq) + 2NO(g) + 12H2O(l) v. When certain nitrates are heated, they decompose to the nitrites 1. 2NaNO3(s) 2NaNO2(s) + O2(g) 17

6. Phosphorous a. Exists in important compounds with oxidation states of +3 to +5 b. Allotropes of phosphorous i. White phosphorous (P4) 1. Waxy, white solid 2. Highly unstable and reactive 3. Molecular solid a. A solid held together by van der Waals forces b. Low melting point 4. Forms tetrahedral pyramid with high-energy 60-degree bond angles a. Seeks to replace bonds with more stable ones a. Gases are cooled by water to condense phosphorous vapor to the liquid ii. Red phosphorous 1. Made by heating white phosphorous to 400 degrees C 2. Relatively safe, amorphous c. Phosphorous oxides i. Tetraphosphorus hexoxide (P4O6) 1. Tetrahedron of phosphorous atoms with oxygen atoms between each pair of P atoms 2. Low-melting solid (23 degrees C) ii. Tetraphosphorus decoxide (P4O10) 1. Structure similar to P4O6, except each P has an additional O bonded to it 2. Preparation by burning white phosphorous in air a. P4(s) + 5O2(g) P4O10 d. Phosphorous oxoacids i. Phosphoric acid 1. H3PO4 2. Salts: NaH2PO4, Na2HPO4, Na3PO4 3. Obtained from tetraphosphorus decoxide or from rock a. Ca3(PO4)2 + 3H2SO4(aq) 3CaSO4(s) + 2H3PO4(aq) 4. Undergoes condensation reactions to form other phosphoric acids (diphosphoric acid, triphosphoric acid, et cetera) a. Hn+2PnO3n+1 ii. Metaphosphoric acids 1. Acids with the general formula (HPO3)n a. When n is very large, the acid is called polymetaphosphoric acid iii. Cause eutrophication of aquatic ecosystems Group VIA Oxygen and sulfur family 1. Oxygen

2. The corresponding acid, nitrous acid (2HNO2), is unstable

5. 2Ca3(PO4)2(s) + 6SiO2(s) + 10C(s) 6CaSiO3(l) + 10CO(g) + P4(g)

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a. Exists mainly in -2 oxidation state i. Other Group VIA elements exist mostly in +4 to +6 state b. Very electronegative c. Bonding involves on the s and p orbitals i. For other elements in Group VIA, d orbitals are a factor in bonding d. Most oxygen on earth is present as oxide or oxoanion minerals i. Only 20% of Earths oxygen exists as O2 in the air e. Properties and preparation of oxygen i. Common form is O2 ii. Very low-melting and low-boiling iii. Can be prepared in small quantities by decomposing certain oxygencontaining compounds 1. Heating mercury oxide a. 2HgO(s) 2Hg(l) + O2(g) 2. Heating KClO3 with pure manganese(IV) oxide catalyst a. 2KClO3(s) 2KCl(s) + 3O2(g) f. Reactions of oxygen i. Molecular oxygen is very reactive ii. Oxide binary compound with oxygen in the -2 oxidation state 1. Most metals react readily with oxygen to form oxides, especially metals in a form with large surface area 2. 2Mg(s) + O2(g) 2MgO(s) 3. 3Fe(s) + 2O2 Fe3O4(s) iii. Metal oxides are basic oxides 1. Metals in a high oxidation state may be acids a. Cr2O3 is a base b. CrO3 is an acid iv. Alkali metal oxides 1. When burned, yield peroxides a. A compound with oxygen in the -1 oxidation state b. 2Na(s) + O2(g) Na2O2(s) 2. When burned, yield superoxides a. Binary compound with oxygen in the -1/2 oxidation state b. K(s) + O2 KO2(s) v. Nonmetals react with oxygen to form covalent oxides, which are mostly all acidic 1. C burns in excess O2 to form CO2 2. S8(s) + 8O2(g) 8SO2(g) vi. Compounds with at least one element in a reduced state are oxidized by oxygen, giving compounds that would be expected to form when the individual elements are burned in oxygen 1. C8H18 burns in oxygen to give CO2 and water a. 2C8H18(l) + 25O2(g) 16CO2(g) + 18H2O(g) 2. 2H2S(g) + 3O2(g) 2H2O(g) + 2SO2(g) 2. Sulfur 19

a. Free sulfur formed by volcanic gas reactions i. 16H2S(g) + 8SO2(g) 16H2O(l) + 3S8(s) b. Allotropes of sulfur i. Rhombic sulfur most stable allotrope of sulfur under normal conditions 1. Yellow, crystalline lattice of crown-shaped S8 molecules ii. Monoclinic sulfur same structure as rhombic sulfur, except for the way the molecules are packed to form crystals iii. Unstable below 96 degrees C, reverts back to rhombic sulfur c. Production of sulfur i. Mined from deep underground deposits by Frash process ii. Hydrogen sulfide, H2S, recovered from natural gas and petroleum 1. Also a source of free sulfur 2. Free sulfur obtained from H2S by Claus process a. 8H2S(g) + 4O2(g) S8(s) + 8H2O(g) b. 2H2S(g) + 3O2(g) 2SO2(g) + 2H2O(g) c. 16H2S(g) + 8SO2(g) 3S8(s) + 16H2O(g) d. Sulfur oxides and oxoacids i. SO2 1. Suffocating odor 2. Present in polluted air 3. Very soluble in water, producing acidic solutions a. H2O(l) + SO2(g) H2SO3(aq) b. H2SO3(aq) + H2O(l) H3O+(aq) + HSO3 c. HSO3(aq) + H2O(l) H3O+(aq) + SO32(aq) 4. With appropriate amount of base, the corresponding hydrogen sulfite salt or sulfite salt is obtained b. Na2CO3(aq) + SO2(aq) Na2SO3(aq) + CO2(g) 5. When treated with acids, sulfites and hydrogen sulfites decompose to produce SO2 a. NaHSO3 + HCl(aq) NaCl(aq) + H2O(l) + SO2(g) 6. Burning S8 produces SO2
a. Na2CO3(aq) + 2SO2(aq) + H2O(l) 2NaHSO3(aq) + CO2(g)

ii. SO3 1. Exists in liquid form at room temp in equilibrium with S3O9 2. Vapor-phase is is SO3, planar triangular geometry 3. SO2 reacts slowly with oxygen in air to form SO3 a. Reaction is much faster with catalyst, e.g. platinum b. 2SO2(g) + O2(g) 2SO3(g) 4. SO3 reacts vigorously and exothermically with water to produce sulfuric acid a. SO3(g) + H2O(l) H2SO4(aq) iii. Contact process 1. Industrial method for synthesis of sulfuric acid

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2. Reaction of sulfur dioxide with oxygen to form sulfur trioxide using vanadium oxide catalyst, followed by reaction of sulfur trioxide with water iv. SO3 in the atmosphere dissolves in rain, producing H2SO3, and falling as acid rain v. Hot, concentrated sulfuric acid can oxidize metals not normal dissolved by acids, like copper Group VIIA the Halogens e. Fluorides differ somewhat from the rest of the group i. Not soluble in water, whereas CaCl, CaBr, and Iodide are very soluble in water ii. All, including fluorides, form stable compounds in which the halogen is in a -1 oxidation state 1. In fluorine compounds, this is the only oxidation state 2. In Cl, Br, and I, compounds can form in which the halogen is in a positive oxidation state (+1, +3, +5, +7) 3. Higher positive oxidation states are due to d orbitals in bonding 3. Chlorine a. Discovered in 1774 by heating HCl with manganese oxide i. 4HCl(aq) + MnO2(s) MnCl2(aq) + Cl2(g) + 2H2O(l) b. Most commercially important halogen c. Very reactive oxidizing agent, similar to oxygen i. Oxidizing power decreases among halogens down the group ii. Chlorine is stronger oxidizing agent than bromine or iodide 1. Cl2(g) + 2KBr(aq) 2KCl(aq) + Br2(aq) 2. Cl2(g) + 2KI(aq) 2KCl(aq) + I2(aq) d. Chlorine reacts with water by being both oxidized and reduced i. Cl2(g) + H2O(l) HClO(aq) + HCl(aq) e. Hydrogen chloride i. Very soluble in water 1. HCl(g) + H2O(l) H3O+(aq) + Cl(aq) ii. HCl can be produced by heating NaCl with concentrated sulfuric acid 1. NaCl(s) + H2SO4(l) NaHSO4(s) + HCl(g) iii. Heated more strongly, sodium hydrogen sulfate reacts with sodium chloride to produce additional hydrogen chlorida 1. NaCl(s) + NaHSO4(s) Na2SO4(s) + HCl(g) 2. Hydrogen bromide and hydrogen iodide can prepared by analogous reactions replacement reaction with their salts a. Phosphoric acid used instead of HCl because sulfuric acid will oxidize bromide and iodide ions b. 2Br(aq) + HCl(aq) Br2(g) 3. HCl prepared as byproduct of chlorinate hydrocarbon a. CH4(g) + Cl2(g) CH3Cl(g) + HCl(g) f. Oxoacids of chlorine 21

i. More acidic with more oxygen atoms bonded to halogen atom 1. (weakest) HClO, HClO2, HClO3, HClO4 (strongest) ii. Hypochlorous acid 1. Cl2(g) + 2OH(aq) Cl(aq) + ClO(aq) + H2O(l) 2. Hypochlorite ion is unstable, and decomposes a. 3ClO(aq) ClO3(aq) + 2Cl(aq) 3. The reaction is fast with heat and a base 4. Production of percholate and potassium percholate a. ClO3(aq) + 3H2O(l) ClO4(aq) + 2H3O+(aq) + 2e b. KClO4(s) + H2SO4(l) KHSO4(s) + HClO4(l) Group VIIIA the Noble Gases 4. Helium and the other Noble Gases a. All except helium and radon are obtained by distillation of liquid air b. Helium has lowest boiling point (-268.9 degrees Celsius) of any substance c. All noble gases are used in gas discharge tubes d. Argon is mixed with nitrogen to fill incandescent lightbulbs e. Neon used in signs because of highly visible red-orange emission f. Xenon reacts directly with fluorine at 400 degrees Celsius to give tetrafluoride i. Xe(g) + 2F2(g) XeF4(s) ii. Reaction at room temperature when exposed to sunlight
a. 3Cl2(g) + 6NaOH(aq) NaClO3(aq) + 5NaCl(aq) + 3H2O(l)

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