GENERAL CHEMISTRY I
GENERAL CHEMISTRY I CHEM 121
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Date Created: 10/19/15
Atomic theory can be traced back to Democritus 460370 BC who believed that matter could be divided into indivisible particles atomsquotThe atomist theory was squashed by Aristotle and Plato and remained unpopular for almost 2000 years Newton Galileo and other luminaries embraced the idea of atoms in explaining phenomena lillte wind but failed to see atoms as chemical building blocks John Dalton devised a chemical atomic theory between 803 and l807 While his postulates would be proven incorrect in the coming hundred years the groundwork for an atomic theory of matter was set and the chemical age was born Atomic Theory of Matter Each element is composed of extremely small particles called atoms Atomic Theory of Matter Each element is composed of extremely small particles called atoms 2 All atoms of a given element are identical the atoms of different elements are different and have different properties including different masses Atomic Theory of Matter Each element is composed of extremely small particles called atoms 2 All atoms of a given element are identical the atoms of different elements are different and have different properties including different masses 3 Atoms of an element are not changed into different types of atoms by chemical reactions atoms are neither created nor destroyed in chemical reactions properties includin 3 Atoms of an element are not changed into different types of atoms by chemical reactions atoms are neither created nor destroyed in chemical reactions Atomic Theory of Matter Each element is composed of extremely small particles called atoms 2 All atoms of a given element are identical the atoms of different elements are different and have different properties including different masses 3 Atoms of an element are not changed into different types of atoms by chemical reactions atoms are neither created nor destroyed in chemical reactions 4 Compounds are formed when atoms of more than one element combine a given compound always has the same relative number and kind of atoms Recall we discussed the law of definite proportions when defining chemical compounds Water no matter where it is collected is chemically identical It is a compound By contrast sea water does not have a unique composition It is a mixture of water salt potassium chloride and many other compounds in smaller amounts Dalton s Law of Multiple Proportions Mumpie Prammans Dalton deduced the law of multiple proportions If two elementsA and B combine to from more than one compound the masses of B that can combine with a given mass ofA are in the ratio of small whole numbers H20 H202 co coz NO N02 N205 Sometimes ratios aren t whole numbers ll Crystal structure of La1XSrX2CuO4 single crystals which possess high temperature superconductivity Atomic Theory of Matter I Each element is composed of extremely small particles called atoms Probing the structure of the atom Atoms are not indivisible The discovery of subatomic particles has enabled a deep understanding of the structure of the atom Cathode Rays and Electrons Radioactivit Alpha Particles and the Nucleus Cathode Ray Tubes TVs Fhosphmezccnl background imp Egr l E7 Discovery of the electron 0 Nature of the rays is the same regardless of the identity of the cathode material 0 A metal plate exposed to the rays acquires a negative electrical charge 0 Deflected by electric or magnetic elds seem to carry an electrical charge The relative effects of these two elds showed that the particles had mass Cathode rays are streams of negatively charged particles with mass electrons Thomson s discovery of the electron Thomson measured the effect of electric and magnetic elds on the thin stream of electrons passing through the hole in the positively charged electrode He found that there were L76 x l0E Cg of the material Millikan Oil Drop Experiment Charge to Mass Ratio of an Electron mm on D up L u i b ennui M hkan determmes he exeemns mass Beltquere dwsmvered namequ Charge Man e eazron gtlt 04quot c The ummum ore puxhb ende spomneous y emns 1ng energy mason m eomd be observed wuzh Charge 0 mass mm 7s gtlt WE 0g photographm p ates Mass Man e eazron lt7 Ox 039 we and heme Cune worked 0 so ate he 2 M udmseme eomponems ohzhe mseen 2epted Va ue 5 lt7 0939x O39IEg Atomic Theory of Matter Eaeh e ement s eomposed o extreme y smaH parades aHed atoms A atoms 012 gwen e ementare denuahthe atoms 0 dw erent e emem are dw erent and have dmerent propemes mdudmg dwerenr masses oms Man e ememare not hanged mto dwerem types 012mm by hemwa mamonsat s e euzher created nor destroyed m herma reamons Thomson s model of the atom Types 0 Rad oamwty Small electron embedded in the atom like seed in 2 watermelon Rutneriord Bltperiment NueiearAtom Modernview oi tneAtom i9 i lt7 proton dismvered by Rutneriord i932 ChadWKk disltoVerSEhe neutron Mass oi atoms measured in atomie mass urmS or Daitonsi i amu i OSAx in s have diameters oi i gtlt Wm to s gtlt iU m TypKaiiy we useAngstoms i A gtlt L04 m Tne nueieus nas a diameter oi iU A in l in ii Aioie nxiviiquot no ii matinee on WWW vquot Isotopes Atomic and Mass Numbers AH atoms oian eie ment mve tne same number oi rotons intne nueieus They may mie diiienng number oineutronsiand onsequentiy a di ereru mass Tnese are eaiied isotopes Carbon is present in nature as one oiiour nueiides g ci lci gci gc Atomic weight Eariyslt d ientist eouid measure tne reiatwe masses oi indi ii La e ounds eiem nis Witnin enemieai eomb i a H was assigned a weignt oi i no urmSLO a weignt oi io ete Average Atomic Mass it is bossibie to get exam weignis oi nudidesi Witn vc being de ned as Ha iinga mass oi i 2amu intne periodimabieithe mass oi c is i2 oi i amu beeause tnere is aiso mtumiiy oeeurring EU 07 i3 ooaasamu i2oii 09893 i2 ooio7i3 00335 Mass Spectrometry M ma uuhkugvt no 2 mama mw sawmmngm mm Favhvgesrw essuzhx mama mawuuwugm an mm Wm m Wm mum rm mu mawuuwugm hesm uawwhn4Dimm D mung warm 01mm midwawa Fwsmi awmmumwmum wungerbemaxuvadmwwhnmnwmya pm mm mm mmwuummmumm a M mm m Namwwwmgmmgma wwngm Wands gmmmm WW I Mm mm mm gunman mygm mm m Wm m ahgarmdaanda mam m 7mm rmxw ma uuhkummdz wmangwmam mm Imdhnww ego m am mpth dmgmalzbahn m m mm hy mass spec Mass Spuzramuzrs 22 mm m mm and How does it work Massspznmmuus an in mm mmzhu unamnm Bmzuhna agy he mm aromzsmmda nhgnnudenude Hmnnauuum drug may nmbmalnm hemstryoharmatnknma drug membnrm drug mung datum hzsarrvk unammsugamnnas m m Invaduud mmth mmsauan sauru mm mmmm my I I mm mm m Eknmspmy amsauan ES m Lasu I m M amx A555 Dzsmpuan amsazmn MALD Enwmnmzmzl PAHPcsswmquam m4 nnmmmaunn maan m mmonwnn Spuzmmurwhu my in 52mmsz cardmgm 1m mass m hargl razms mmqumxy m umzra fhgm ror my Thtstpzmud mm 212 duznzd mdzhxsswgml sum adau sysum Wm m m mums m 5mm zaguhu Wm hw Mauv abundant I m 4 atoms 5 Nd Idl H Peaks 2 78 80 orrespond 0 I I I parent on wmh 350 MW 7E gmo H H H and parent On wmh 370 MW Bo gmo H Peaks 2 63 55 orrespond o I I the above wuzh one m ssmg methy S olids 1 Metallic and Ionic Solids a Crystal Lattices and Unit Cells of Metal Atoms b Structures and Formulas of Ionic Solids 2 Other Kinds of Solid Materials a Molecular Solids b Network Solids c Amorphous Solids 3 The Physical Properties of Solids ln solids the atoms do not moVe they may Vibrate and rotate but they remain in xed positions A regular repeating pattern of atoms or molecules within the structureilong range orderiis a characteristic of the solid state Crystal Lattices and Unit Cells What is a unit cell What does this have to do with stoichiometry How do we choose the right unit cell What are lattice points Nature uses seVen three dimensional unit cells We will only consider the cubic unit cells These cells have edges of equal length that meet at 90 ithing the cubic class there are three important cell symmetries simple bodyicentered and facekcentered E I To count the number of particles per unit cell remember than onekeighth of each corner particle is actually in a unit cell oneifourth of an edge atom is actually in the unit cell and onekhalf of a face atom is actually in a unit cell Example What is the simplest formula of a solid containing A B and C atoms in a cubic lattice in which the A atoms occupy the corners the B atoms the bodywentered position and the C atoms the faces of the units cells Example Calcium crystallizes in a facekcentered cubic structure How many atoms of Ca are there per unit cell What is the mass of the unit cell The density of calcium is 155 gcm3 what is the Volume of the unit cell Now determine the length of the unit cell and then calculate the radius of the Ca atom Example Iron has a density of 787400 gcmg7 and the radius of an iron atom is 126 pm What is the structure of this solid Structures and Formulas of Ionic Solids The lattice of many ionic compounds are built by taking a simple cubic or facekcentered cubic lattice of spherical ions of one type and plaicing ions of opposite charge in spaces between these ions holes within the lattice The packing of ions can be illustrated with LiCl Here7 the larger chloride ions form a facekcentered cubic lattice with the smaller lithium ions t into empty spaces between the chloride ions Example Lithium chloride crystallizes in a facewentered cubic structure The unit cell length is 514 gtlt10 8 cm The chloride ions are touching each other along the face of the diagonal of the unit cell The lithium ions t into the holes between the chloride ions 1 How many lithium ions are there in a unit cell 2 What is the mass of LiCl in a unit cell in grams 3 What is the density of lithium chloride Failures of the Bohr Model Why are certain spectral lines are brighter than othersThere is no mechanism for the calculation of transition probabilities 2The Bohr model of an electron as a miniature planet with de nite radius and momentum is in direct violation of the uncertaintyprinciple The Bohr model gives us a basic conceptual model of electrons orbits and energiesThe precise details of spectra and charge distribution must be left to quantum mechanical calculations Schrodinger Equation 0 Solutions to the Schrodinger equation called wavefunctions are chemically important 0 Only certain wavefunctions are allowed Each wavefunction corresponds to an allowed energy for the electron The energy of the electron is quantized Each wavefunction can only be interpreted in terms of probabilities 0 What are orbitals Why are the quantum number n l m Quantum Numbers 0 n principle quantum number l 2 3 O lzangular momentum QN20 l 5H 0 m3 magnetic QN 0 i l 2 i5 Quantum Numbers 0 nShell Contains 2n2 electrons 0 2 Subshell Contains 2052 l electrons 0 m3 Orbital Contains 2 electrons Quantum Numbers o wsneu Energyand m a number omodes SubsheHSMpe and energy a number otpxamrvsndm nodes m 0mm I lt2 mg 1 m Mammy e 29 2 E eumns 47KIEHS 1 a a m Fzmrg a Enthalpy is a state function the enthalpy change for a chemical or physical Change is independent of the pathway It depends only upon the initial and nal conditions An often tabulated quantity is the Standard Enthalpy of Formation standard state 0 standard enthalpy change 0 standard molar enthalpy of formation Example Vrite the equation for the standard molar enthalpy of the forma tion of forlnic acid HCOOH The enthalpy of this reaction is AH 74091 The standard enthalpies of formation of the elements in their standard states are zero Example f the species below the only one which has AH 0 is 0 7 CD A on V Most heats of fr111atiltn are negative because the proe of framing most compounds from these element is exothermic Could you have guessed thisquot Standard enthalpies of formation are very useful because the enthalpy of any reaction is AUG Z AU products 7 Z AU Tendons ra39n Example Evaluate AH m for the combustion of one mole of methanol CHOH1 Example The thermochemical ecplatimi for the combustion of ethane Cj2H5g has a standard enthalpy of reaction of 156J J Usinggt the attached table calculate the standard enthalpy of formation of ethane TABLE 53 Standard Enthalpies of Formation AH at 298 K Substance Formula AH kJmol 1 Substance Formula AH kjmol Acetylene Calcium carbonate Calcium oxide Carbon dioxide Carbon monoxide Ethylene Glucose Hydrogen bromide Hydrogen chloride Hydrogen fluoride Hydrogen iodide Methane Methanol Propane Silver chloride Sodium bicarbonate Sodium carbonate Sodium chloride Sucrose Water Water vapor Helge ia ClS Ciz zzonis H200 H208 1 Determine gm for the combustion of the 100 2 Determine 1mm for the thermochemical eqnat ion g sznnple Example When a 100 g sample of naphthalene is burned in a bomb calorimeter with a heat capacity of 1324 kJK the temperature rises from W Hcr conlaincr Insulating Slcci humh 3 5 n 1 s lgmnnn t L7 39I hcrmnmclrr Bomb Calorimeter coffee cup solution calorimctors constant 12 There are two types of calorimeters bomb calorimeters constant V and Deter Ininl 39ng the enthalpies of react ion 1 alorirnetry Solution Calorimeter Reaction occurs in solution Temperature increases or decreases Insulatin cup traps heat or keeps out heat from the surroundins Example A student used a coffececup calorimeter to measure the increase in temperature for the reaction 2 H300 gt BaH2aq Hgg A sample of 2669 g of barium was added to 200 mL of water in a styrofoam cup The change in ternpru ature was 93 C The density of the solution was 101 gmL and the speci c heat of the solution was 417 JgK The heat capacity of the cup was 25 J K 1 Calculate the heat of reaction per gram of barium 2 Calculate AU per mole of barium For those experiments that you can t perfcu39m we can use Hess s Law If a reaction is carried out in a series of steps AH for the reaction will equal the sum of the enthalpy changes for the individual steps Example Calculate AU for the reaction NW8 0g 13902g given the following information Ng 03g N2g gg AH 719801 033 om AH 71423 k O g 2 0g AH 4950 kJ Understanding the heat 0139 111lLlStl 11 0f p1 ltgtpa nC Born Haber Cycle Lattice energy is a useful concept because it directly relates to the stability 3C graphite 4H2g 5025 f Elements l l D6C0mPOSitiOH FOFma O 0f 3C02 W39e want to know the the enthalpy associath with bringing in nitely sepa AHI 10385 k I l rated ions together into the lattice C3Hal 5023 7 l Reactants AHZ 1181 H We cmg a Name a Na ge Clg E a 3C02l8 41428 2023 5 153 m Formation of 41120 EC1 AH3 1143 k MNa 1ng CHE 3mm 411200 Products Nag Clg 310113 AHfWCMUJI o 1 l Nate 5le3 L AHFIWSH Nets Clzg DEN go A Eiaua 33mqu DEN go 31319 9314112 Aii NaCusm gt NaCls Chapter 5 Thermochemistry This chapter describes I classi cation of reactions as reactantifaVored or productifaVored reacn tions and examines the relation between these classi cations and energy transfers occuring during the reaction I basic thermal energy concepts and thermodynamic terminology I means of calculating heat ows that accompany both changes of temper ature and changes of physical state I First Law of Thermodynamics giving the relation between chane in in ternal energy heat7 and wor I use of Hess7s Law and the enthalpies of formation to calculate enthalpy changes for physical and chemical changes I using bomb calorimetry data constant V or coffee cup calorimetry data constant p to calculate heat ows7 changes in internal energy and enthalpy I available energy resources can we predict if a reaction will occur How Why doesn7t the heat in a room cause your cup of co ee to boil Why does the ocean remain liquid water when the air is below freezing U1 IO 00 11 Types of Chemical Reactions and Thermodynamics Energy transfer is a major factor in determining if reactions are reactant or product favored Energy Its Forms and Units Energy is the capacity to do work or supply heat temperature heat and the conservation of energy Speci c Heat Capacity and Thermal Energy Transfer The speci c heat is the amount of energy that must be transferred as heat to raise the temperature of exactly 1 gram of a substance by exactly 1 Kelvin 1 0 Energy and Changes of State When a solid melts and a liquid boils energy is required to enable the particles to overcome their attractions to one another This involves changes in potential energy so changes in state always occur at constant temperature Endothermic and exothermic changes fusion melting vaporization condensation Enthalpy system and surroundings internal energy rst law of thermodynamics reversible Enthalpy Changes for Chemical Reactions Hess s Law if a reaction is the sume of two or more other reactions the the change in enthalpy for the overall process must be the sum of the change in enthalpy for the consituent reactions State Functions All properties which are state functions are independent of the path that was used to take the system from the initial to the nal state Standard Enthalpies of Formation The enthalpies of many systems are de ned and tabulated at SATP 1 atm 293 K Determining Enthalpies of Reaction Calorimetry can be used to determine the change in internal energy or enthalpy of a system Applications of Thermodynamics Types of Chemical Reactions and Thermodynamics productifavored When reactions are favorable7 they often release heat The drian forces of the four major types of aqueous chemical reactions pushed the reactions in the forward direction I precipitation I acidbase I gas evolution I oxidation of metals reactantifavored When reactions are not favorable7 they require heat Any productifavored reaction written in the reverse direction would be reaci tant favored spontaneous I does not imply that the reaction occurs quickly Energy is a central idea when describing a reaction as productifaiored or reactantifaiored For this reason it is useful to know something about energy and its interactions with matter The most common of these interactions is the transfer of energy as heat when chemical reactions occ39ar Thermodynamics is the science of the change in heat and work through chemical reactions It is also the science of energy conseriations recycling and the energy econorn39g Energy Its Forms and Units Energy is de ned as the capacity to do work Energ39g can be transferred between objects as either heat or work Energ39g comes in two forms kinetic and potential Energy is always conseried An object has kinetic energy because it is moving I thermal energy I mechanical energy I electric energy I sound energy An object has potential energy because of its position7 energy is stored in the object I Chemical potential energy I gravitational energy I electrostatic energy Energy can be converted between kinetic and potential energy I Water falls I Water turns turbine Temperature Heat and the Conservation of Energy Speci c Heat Capacity and Thermal Energy Tansfer The total energy of the universe is constant energy is conserved I Diving board Heat capacity is the amount of heat required to produce a given termpere ature change in some substance I A large object has a larger heat capacity than a small one I Water has an abnormally large heat capacity I Hot apple pie Heat or thermal energy is related to temperature but heat is not the same I speci c heat capacity is the heat required to procduce a given tempera ture change per gram of material as temperature Transferring energy by heating an objecet increases its temr perature and the temperature increase can be measured with a thermometer q mCAT Energy always transfers spontaneously from the hotter to the cooler object Why doesn t the heat in a room cause your cup of co 39ee to boil 39 in words I units I Directionality in heat transfer I Energy spreads over the greatest possible number of atoms or molecules I Thermal energy prefers to be spread evenly over the maximum number of molecules concentrating energy in only a few particles at the expense of many or even concentrating energy over a large number of particles If the heat capacity of glass is 084 JgK and the heat capacity of iron is at the Reuse Of 3 few 15 hlghly unhkdy and 15 never ObSHVEd on a 0451 JgK which one requires more heat to raise the temperature 1 Kelvin macroscopic scale I more on this next semester The greater the heat capacity and the larger the mass the more thermal energy a substance can hold Units A calorie cal was de ned as the quantity of energy required to raise one gram of water one degree Celsius Food is e ured in kilocalories kcal Cal In SI units energy is measured in Joules 4184 J 1 cal Example What is the speci c heat of benzene if 3450 J of heat is added to 150 g and its temperature increases from 225 C to 358 C Example How many k of heat is required to increase the temperature of Example A 35811 g piece of lead was heated in boiling water to 941 C 355 g of iron from 236 C to 434 C The speci c heat of iron is 0451 JgK It was removed from the water and placed into 100 mL of water in a styi rofoam cup The temperature of the water was initially 187 C The nal temperature of the lead and water was 261 C What is the speci c heat of lead I Energy is conserved the heat lost by the metal must be gained by the water I Signs of q When q is postive what does that mean 39 What 3 ATS When q is negative what does that mean In the calculation of AT does it matter if you use Kelvin of Celsius degrees Whenever you take the difference between two quantities in chemistry you should subtract the initial quantitiy form the nal quantity The algebraic sign of the result indicates an increase or decrease 7 in the quantity for the substance being studied The sign of q is just a signal to tell the direction of heat transfer Heat itself cannot be negative it is just a quantity of energy Think about your account Energy and Changes of State Energy is transferred when matter is transformed from one form to another in the course of a chemical or physical change Attractive forces must be oVercome in melting and boiling7 and this requires an input in energy As the energy is transferred7 there is no change in temperature We are trying to oVercome the potential energy of the molecular interactions7 not to change the kinetic energy of the particles heat of fusion7 vaporization Plot the quantity of heat absorbed and the consequent temperature change as 500 g of water is warmed from 7 50 C to 200 C Calculate the amount of heat inVolVed The speci c heat of ice 21 JgK7 water 42 JgK7 steam 20 JgK The heat of fusion of ice is 333 Jg7 the heat of vaporization of water is 2256 Jg Chapter 4 Reactions in Aqueous Soltuion Chapter Objectives a To understand the nature of innit substances when dissolved in Water I To be able to predict the water solubility of ionic compounds c To show that there are only a few general types of reactions that occur in aqueous solution c To learn how to handle quantitatch aspwts of reactions in aqueous solution Properties of Compounds in Aqueous Solutions homogeneous mixture Ions in Aqueous Solution Electrolytes 0 Why is water a good solvonl or dissolving ionic compounds 0 Thy is a salt solution called an electrolytequot o What are strong eleelrolytes 0 That are weak electrolytesquot o What are non electroly t 39 o How can We distinguish between electrolytes experimentally Solubility of Ionic Compounds in Water a Which cations usually form soluhlc salts 0 Which anions usually form soluble salts7 i liornical Formula Soluhlo in wa yes or no Narno Nl h Cl ammonium chloride potassium iodide P DSLM hagS silver chloride F0012 barium chloride Chemical Formula Soluble iu water yes or no Name Precipitation Reactions CuINO32 A precipitation reaction produces an insoluble procluctv Bat ng COO For the reaction AgNO aq l l39alaq a Agl5 l NaN3s V what are the seuble species and what is the insoluble salt magnesium perchlorate PliClO32 Net Ionic Equations Czin The net ionic equation includes only fhr spears That particzpatr in the reaction For the reaction above calcium sulfate 81804 BdSOt iet ionic equations have atom balance aurl Charge balance Acids and Bases Acid Formal de nition An acid is any substance that when dissolved in pure wa ter increases the concentration of hydrogen ions in the water Examples Base Formal de nition A base is any substance that when dissolved in pure water increases the concentration of hydroaiide ions in the water Examples What is the cause of acid rain Oxides of Nonmetals and lVIetals Noriiiictal oxides can roact with water to produce 11 ions I l39letzi oxides can react with water to produce OH ions Reactions of Acids and Bases Acids react With bases in aqueous solution to produce a salt and water What is the net ionic equation for the reaction between a strong acid and a strong basegt What is a neutralization rcaction39 What is the not ionic equation for the reaction of hydrobroniic acid with KOII397 What are the spectator ions in the reaction of silver nitrate and hydrochloric acid Write the balanced overall equation and the net ionic equation for the reaciton of hariuni hydroxide with sulfuric acid Gas Forming Reactions OxidationiReduction Reactions What is the general equation for the reaction of metal carbonates and bicarbonates With l t V r v acids How about baking soda and Vinegar 0X1lt a 100 0 reduction oxidizing agent 0 reducing agent Organizing Reactions in Aqueous Solutions Oxidation Numbers What is an Change reactionI l lhe oxidation number of an atom in an element is 2 The oxidalion number of an elemenl in a monalomic ion is 3 ln uorine containing compounds uorine has an oxidation number of Prempltation Reaction g 4 Cl Br and 1 when not in compounds with 0 F have oxidation number 0 And Rase Reaction in most compounds ll and O are 0 ms Forming Reaction I I I 6 The algebraic sum ol39 the oxidation numbers is equal to the net Charge on the speries o Oxidation Reduction Reaction Chemical Formula Oxidation Vinnbeis Name What are the driving forces of these exehange reactions A120 lVIore on Net Ionic Equations sodium chloride S trong acids strong bases and soluble salts arbonntu ion ha i I 7 I rr39eallt acids insoluble and weal bases and insoluble salts potassium permanganate sodium hydroxide abetie acid Clues Change in oxidation number397 Heaetion involves an elemen 7 Reaction involves a common oxidizing or reducing agent nitrous dCHl lithium liydi39oxule Maieriai Science 0 Why do siiyer mirrors re eoi iighi ihai pmes ihrough a sheei of glm 0 Why oioes ihe meiai body of a car left in ihe Sun feel so much hoiier ihah ihe gym 0 Why does glm shaccergt but not the spoon you used to stir its contents 0 Why do meiais conduct heal and eieoirioiiy but hoi ceramics Bonding in Solids The bonding oeiweeh aiorhs in a solid is oieierrhiheoi by Metallic solids Ionic solids Molecular solids Network covalent solids Carbon 0 diamond o graphite a s s 0 99 9 g s o Charcoal carbon black coke 39 C60 Metals Semiconductors and Insulators Electrical conductivity 0 Cu and Ag 0 Si and Ge 0 Diamond and Quartz Materials have a 1024fold range in conductivity Metals become better conductors when they are cooled lmpurities have little effect on the conductivity large concentrations of impurity may decrease the conductivity by about a factor of 10 Semiconductors become better conductors when heated As little as 001 impurity can change the conductivity of a semiconductor by 6 orders of magnitude Consider Li Consider Ll2 Consider Li metal The valence electrons are no longer con ned to the region between pairs of lithium nuclei In the metal7 the energy states of each atom are slightly altered The is orbitals on the various metal atoms interact to form a band or obritals whose energy galls within a range from slightly below the energy of the isolated 1s orbital to slightly above The same thing happens to the 2s orbitals Each orbital in the band can hold electrons The is band is The 2s band is It takes little7 if any7 energy to excite one of the electrons in the 2s band from one orbital to another in the band The energy gap between orbitals is about 10 45 J By moving from orbital to orbital within the 2s band7 electrons can move from one end of the crystal to the other This band or or bitals is therefore called a conduction band7 it enables Li to conduct electricity The model is frequently considered an electron sea77 Typical band theory diagrams for a conductor7 an insulator7 and a semiconductor Why do metals conduct better at cold temperatures Why do semiconductors conduct better at high temperatures What do impurities do in a semiconductor Molecular and Ionic Compounds I Representation molecules Hi H mm im u I structural formula I perspective drawing y lt9 I ball and stick model I space lling model 39 c H60 2 CCAI39 COC l1 I39lIV OH I Iiv H ethanol dimethyl ether Ions and Ionic Com pounds I Nuclei are unchanged by chemical processes atoms can readily gain and lose electron to form ions 39 cation Periodic Table of the Elements I anion I Na atom I CI atom I Metal atoms tend to lose electrons to form cations whereas nonmetal atoms tend to gain electrons to form anionst I In addition to simple ions such as Na and Cl39 there are polyatomic ions such as nitrate NO339 and sulfate 0421 These ions consist of atoms joined as in a molecule but they have a net positive of negative charge I The chemical properties of ions are very different from those of the atoms from which they are derived Predicting Ionic Charge I Ions frequently try to achieve a noble gas electron count Why I Noble gases are quite nonreactive so we can deduce that they are stable Predict the charge on Aluminum s most common ion Periodic Table of the Elements 0 Chemical activity frequently involves the transfer of electrons between substances to form ionic compounds 0 Generally ionic compounds are combinations of metals and nonmetals 0 Molecular compounds are generally composed of nonmetals only b c l d 2 e 3 Molecular or Ionic A B 39 PFs phosphorous pentafluoride 0 Nal sodium iodide o SCI2 sulfur dichloride o CaN032 calcium nitrate o FeCl3 ironlll or ferric chloride 0 CoCO3 cobaltl or cobalnous carbonate Predict the correct formula for the ionic compound composed of aluminum and chlorine a AICI b AI3C cAICI3 d AICI2 e AIZCI Predict the correct formula for the ionic compound composed of sodium and sulfur 3 N35 b N335 c NaS3 d NaS2 e NaZS Naming Inorganic Compounds Cations Many cations formed from metal atoms have the same name as the metal Na Al3 Mg2 silver Naming Inorganic Compounds Cations Many cations formed from metal atoms have the same name as the meta Na Sodium Al 3 Aluminum Mg 2 Magnesium silver Ag Naming Inorganic Compounds Cations I Cations formed from metals which can form cations with differing charges are given by a Roman numeral in parentheses following the name of the metal Fe 2 Fe 3 Naming Inorganic Compounds Cations I Cations formed from metals which can form cations with differing charges are given by a Roman numeral in parentheses following the name of the metal Fe 2 Fe 3 Iron I I Iron I II Naming Inorganic Compounds Cations I In the olden days we used the Iatin root or the elements name along with an ous or and ic LO OUS HI IC I ferrousferric FeII and FeIII stannousstannic Sn I and SnIV mercurousmercuric Hg2l and HgII Naming Inorganic Compounds Cations I In the olden days we used the Iatin root ofthe elements name along with an ous or and ic LO OUS HI IC I ferrousfern39 c stan nousstannic mercurousmercuric Choose the correct name Fe203 a iron II oxide b iron III oxide Choose the correct formula mercurous chloride a HgCI b HgCl2 c ngCl2 d Hg2C Naming Inorganic Compounds Cations O Cations formed from nonmetal atoms have names that end in ium NH4 H3O Naming Inorganic Compounds Cations O Cations formed from nonmetal atoms have names that end in ium NH4 ammonium H3O hydronium Charge nnnnna Nam anmlla Name H n Hydrogen inn NH Ammomum un Lx Lnnnnn mn Cu Coppenn m upmus Ion Nn39 Klium imv K39 Potassium mu CM u m an en rr inn Commquot 0 almlimvs ion Cappex l or nipr inn Izomll 0 Emmi inn mnngnmrnn 0r umngdnuus Ion mun m manunnb inn many in or mm xiiimu uriilckelmia nm Land ll m plumbous mu mun in ilmmous ion Nlngnrsmm ion Cnluum nm lmnlium mu Hdmmi nm Znn um n admmm mn um ion Cluomium m m lumnic 10 A1 Aluminum an Inmllll m rnr m Naming Inorganic Compounds Anions 0 Monatomic anions ide 8239 N339 H 0 Nonmetal polyatomic anions hydroxide cyani e peroxide azide Naming Inorganic Compounds Anions 0 Monatomic anions ide 8239 sul de N339 nlmde H39 hydride 0 Nonmetal polyatomic anions hydroxide 39 e Naming Inorganic Compounds Anions o b Poi atomm anions ontainin ogtlt en have names endin in rate and ne 7 g Vg g nitratenitrite squatesuI te perchIorate hIorate hIorite hypochIorite hromate dichromate permanganate acetate carbonate Naming Inorganic Compounds An i o n s b Ponatomic anions containing oxygen have names ending In rate and ne nitratenitrite squatesuI te perchIorate hIorate hIorite hypochIorite alt arb onate Naming Inorganic Compounds Anions 0 Adding an H to an oxyanion adds hydrogen or dihydrogen as appropriate bicarbonate OOPS HCO hydrogen carbonate 3 O potassium dihydrogen phosphate Choose the correct name for KZSO3 a potassium sul te b potassium bisul te c potassium sulfate d potassium sul de Choose the correct name for calcium sul de a CaS b CaS2 c CaSO4 d CaSO3 e CaZS TABLE 25 Common Anions Charge l39mnlula Name Formula Name in H y e inn cz gon Ac F FIunndc mu 10 Merck um Cl CIvIoride Ion C10 I el chlovaLe ion BE 13 nuuumun No itmtuluu I Indl e in MM 4 I39ermnngnnal Inn CI Cyanideum OH Hydrmide ion 2 0k Oxide ion to 51 Carbonate ion 022 I emxidelun Crof Chi um ion 5quot 5mm iun ego Daduomam ion so 4 SulfaIeion an x NitndLwn POE Pimapimewn Naming Ionic Compounds cation followed by anion calcium chloride chromium Ill oxide lead nitrate Naming Acids O ide becomes hydro ic hydrocyanic 0 ate and ite become ic and ous perchloric acid sulfuric acid sulfurous acid Choose the correct formula for hydrobromic acid a HBrO3 b HOBr c HBr d HzBrO4 e HBr2 Choose the correct name for HCIO2 a chloric acid b perchloric acid c hydrochloric acid d chlorous acid e hypochlorous acid What s periodic aicd Binary Molecular Com pound s 0 Less electronegative atom goes rst 0 Second element gets and ide 0 Greek pre xes indicate numbers SiBr4 S2C2 Binary Molecular Compounds 0 Less electronegative atom goes rst 0 Second element gets and ide 0 Greek pre xes indicate numbers SiBr4 339 S2C2 3n tetra I31 amide V uliui39 dichloride Naming Simple Organics 0 alkanes H H O methane CuH o ethane Hmwi H O propane H X H 0 butane HcccH Humquot quot39ImH O pentane H H TABLE 26 Prefixes Used in Naming Binary Compounds Formed Between Nonmetals Prefix Meaning 4 b n m I gtomummummia Alchohols o Ketones one quot Carboxylic acids oic acid N quotvquot N P X Triple bond yne N 39 h Double bond ene I Functional groups 0 Alchohols o lbutanol 0 Ketones one NquotN methanone 0 Carboxylic acids oic acid HN ethanoic acid 0 Double bond ene 2butene OTriple bond yne N rquot 2butyne h a b C e il cCC Hum quot39IIIIH H H dimethyl methanone 2propanol 2ethanone 2propanone methyl ethanoate m 539 Q ethanoic acid acetic acid vinegar CH3COOH C2H402 0 ii H c mvc OH The ability to make fairly strong7 directional bonds by accepting electron pairs from neigh boring molecules or ions is characteristic of the transitionimetal elements Coordination occupies a middle place energetically between the weak intermolecular attractions in solids and liquids and the stronger covalent and ionic bonding characteristic enthalpies Coordination complexes often involve transition metal ions or atoms bonded with at least partial covalent character to a small number usually 2 to 6 of ions of neutral molecules that have lone pairs of electrons characteristic equation Brackets are used in the chemical formulas to group together the symbols of the central atom and the coordinated ligands Three di erent compounds are known with the some empirical formula CrC39lg 6H20 When epposed to a dehydrating agent compound I which is dark green loses two moles of water per mole of compound compound II light green loses one mole of water and compound II violet loses no water Coordination modi es the chemical and physical properties of both central atom and ligands Consider the chemistry of aqueous cyanide and ironll Reaction between the two gives which undergoes neither reaction When PtlV and ammonia complex to form a sixicoordinate species7 the ammine ligands can act as an acid Aside from simple ligands like uoride F 7 cyanideCN 7 thiocyanide SCN and even isothiocyanide NSC 7 there are polydentate ligands like oxalate and carbonate Show how the glycinate ion HgNiCHgiCOO can act as a bidentate ligand Draw a Lewis structure if necessary Which atoms in the glycinate ion will bind to a metal ion We should be able to name any transition metal complex7 to determine the oxidation state of any metal from a chemical formula7 and to determine a chemical formula from a name Give the systematic name 07quot ehemiealformula of each of the following chemical compounds z 39 Man 2 tiiaquabromoplatinum l ehloiide 3 NH40rNH32NSO4 4 KMn0N5 Ligand substitution reactions are common Changing colors allows an easy way to follow the progress Nickelll sulfate is a yellow crystalline solid lf exposed to moist air it takes up six water molecules per formula unit This forms a brightigreen complex Heating the green hexaaquanickelll sulfate drives of the water and regenerates the yellow solid When the yellow compound is exposed to colorless ammonia vapor7 a blueiviolet complex is formed Heating the blueiviolet complex also regenerates a yellow solid Can we then rationalize what occurs when a green solution of nickelll is mixed with ammonia to form a blueiviolet solution When there are several different ligands it is possible to have isomers of the complex which may behave quite different chemically Draw the structures of all possible isomers for the following complemes Indicate which iso mers are mirrorimage pairs ehahtiomers 1 diammihebromochloroplatihum l square planar 2 diaquachlorotricyahocolbaltate U octahedral 3 triomalatovahadate HI octahedral What is the nature of bonding in coordination complexes Why does PtIV form only octahedral complexes While PtII forms square planar ones A simple but quite useful model for bonding in coordination compounds is crystal eld theory Which starts from an ionic description of the metaliligand bonds Crystal led theory considers the response of the metal s diorbitals coming into contact With lone pairs of ligands El El 112 le 2 1 IA IV EDD CID D D D d 11 Ix v All are de D 1172 ate de 1 orbllal energies Average energy a d orbitals b d orbitals c d orhimls in quotfreequot metal of d rals in in tetrahedral in octahedral in square atom or ion the presence of complex complex planar ligands complex eriments can measure not only whether a compound is paramagnetic but also the number of unpaired electrons It is found that the octahedral complex ion FeCN5 has few une paired electrons than the octahedral complex ion Fe H20 iv How many unpaired electrons are present in each species Give the dielectron con guration of each species Lawrield splitting 000f0 Higl field splitting 900039 0 Med 5 The two cases of crystal field spllmngfor the octahedral geometry Will the coordination compound CoNH35Cl2 be diamagnetic or paramagnetic Among the most striking properties of the complexes of transition metals are their colors A single transition element can form complexes that range in color across the rainbow de pending on the ligands Cobalt for example I hexaamminecobaltlll is orange I tetraamminedichlorocobaltlll is green or Violet I pentaammineaquacobaltlll is red Colors arise when complexes absorb light in the Visible The color perceived in a sample is the color complementary to that which is most strongly absorbed The red compound aboVe as an absorption maximum in the green region of the spectrum Many of the colors of octahedral transition metal compounds arise from excitation of an electron from an occupied t2g leVel to an empty eg leVel The frequency of light that is capable of inducing such a transition is related to the crystali led splitting energy The larger AD the higher the frequency of light absorbed most strongly and the lower bluer its Wavelength The ligands can tune the crystal eld splitting according to the spectrochemical series Field strength g Weak CN gt N05 gt an gt NH3 gt H20 gt OH gt F gt Cl gt Br gt I dLeve splining A Small The chromlarnUH lon ln aqueous solatlon has a blaerololet color I What ls the color complementary to blaerm olet 2 Estlrnate the wavelength of mazlrnarn absorptlon for UNA03k solatlon 3 Wlll the wavelength of mazlrnarn absorptlon lncrease or decrease lf cyano llgands are sabstltateal for the coordlnated water Ezplaln Schrodinger s Model of the Hydrogen Atom and Wave 1 D 00 4 0 Ch Functions Only certain wavefunctions are allowed Each wavefunction lJ corresponds to an allowed energy for the electron The energy of the electron is quantized Each wavefunction lJ can only be interpreted in terms of the idea of probability What are orbitals There are three spatial quantum numbers 717 l7 and ml What do we know a priori about W What is a node What does IJ look like What does IJ2 represent What does 47rr2IJ2 represent What is the shape of an 5 orbital What is the difference between 5 orbitals of different 71 values What is a radial node What does lJ look like What does lJ2 represent What does 47rr2lJ2 represent What is the shape of a p orbital What does ngp look like What does the electron density look like What does the radial electron density look like What is an angular node What does ngp look like What does the electron density look like What does the radial electron density look like What is the shape of a d orbital There is a fourth quantum number m5 A statement of the Pauli exclusion principle is that no two elec trons in an atom can have the same set of A consequence of the exclusion principle is that N 0 atomic or bital can contain more than The four quantum number of the two electrons in the He atom are Experimental Evidence for Electron Con guration What is ionization energy Why is the second ionization energy greater than the rst Why is the second ionization energy for Li7 Na7 and K much greater than that for the removal of the second electron from Be7 Mg7 and Ca Which of the following has the highest ionization energy for the re moval of the third electron 1 Mg 2 Al 3 Si 4 Cl 5 Ar Order of Subshell Energies and Assignments What is the n l rule How can the periodic table be used to predict the electron con gu ration of an atom E ective Nuclear Charge Z5k What is the effective nuclear charge Why does the third electron in lithium occupy the 25 subshell rather than the 2p subshell What do the radial probability functions of 25 and 2p look like Electron Con gurations of the Main Group Elements What is the spectroscopic notation for the lithium atom What is the orbital box diagram for the boron atom What is Hundls rule What is the orbital box diagram for the oxygen atom What is the spectroscopic notation of the potassium atom What is the noble gas notation for potassium Give the electron con guration of chlorine using the spectroscopic7 noble gas7 and orbital box notations What quantum number de scribe an electron in the outermost shell Electron Con gurations for the Transition Elements Elements Whose atoms are lling the d subshell are called What is the electron con guration of Zn Sometimes there are minor difference between the predicted and ac tual con gurations Cr Electron Con gurations of Ions When main group atoms form ions7 electrons are removed from the electron shell of highest n If there is a choice of subshell Within the nth shell7 the electron or electrons of maximum l are removed Al When transition metal atoms form positive ions7 the outer 5 electrons are lost rst Mn Atomic Properties and Periodic Trends Atomic Size Ionization Potential Electron A initg What is the covalent radius For example For the main group elements atomic radii increase going down a group in the periodic table Why For the main group elements atomic radii decrease going across a period Why The periodic trend in the atomic radii of the transition metal atoms is somewhat different than for main group elements Why The elements in Which of the following sequences have most nearly the same atomic radius 1 Mg Al Si P 2 F Cl Br I 3 Li Na K Rb 4 O S Cl Ar 5 Mo Tc Ru Rh The correct order for decreasing atomic radius of the ve atoms Cs Ba Cl Br l is Ionization energy is the energy to Removing each subsequent electron requires more and more energy Why For main group elements rst ionization energies increase across a period and decrease down a group Why Why does a dip to lower ionization energy occur on passing from Group 5A to Group 6A A measure of the electron a inity of an atom is the Electron a inity and ionization energy are similar in that they rep resent the energy required to Compare the three elements Al7 C7 and Si 1 Place the three elements in order of increasing atoniic radius 2 Rank the elements in order of increasing ionization energy 3 Which elernent7 Al or Si7 is expected to have the more positive electron a inity value Fundamental Concepts of Matter Scienti c Measurement Matter anything that has mass and occupies space The properties of mat ter relate not only to the kinds of atoms it contains elemental composition but also the arrangements of these atoms structure Macroscopic vs Microscopic Liquid Solid Pure substances Elements 0 Hydrargyrum Compounds 0 Law of De nite Proportions Elemental compostion of a pure com pound is always the same 0 Why buy Vitamin C from Whole Foods instead of ascorbic acid or Oyster shell calcium77 Mixtures o heterogeneous o homogeneous solution Homogeneous Mixture Pure Substance Heterogeneous Element Properties of Matter Characteristics that allow us to recognize and distinguish substances Physical Properties 0 extensive o intensive The Box Revisited Chemical Properties Physical Changes Chemical Change Separation of Miwt39ares Because each component of a mixture retains its own properties they can be separated by taking advantage of differences in their properties 0 ltration o distillation o chromatography Units of Measurement Dimension Unit Name Abbreviation mass length time temperature amount Derived Units Volume Density Pre x Power of 10 Giga Mega Kilo Deci Centi Milli Micro Nano Pico Fe Int 0 Uncertainty in Measurement Measurements are always inewact Conversion factors are frequently ewact Precision Accuracy Signi cant Figures Typically the last digit of a measured quantity contains the uncertainty Weight of a dime on an analytical balance 22405 l 00001 g All digits including the uncertain one are signi cant gures Mass in grams Representative Uncertainty 22 22405 Precision or Accuracy77 Everything is easy eaccept for the zeros Mass in grams Sig Figs Representative Uncertainty 1234 1000 10000 In calculations Rounding Adding amp Subtracting Multiplying amp Dividing How many atoms are in 12 g of H2504 sulfuric acid The atomic weight of Hydrogen is 10079 gmol Sulfur is 32065 gmol and Oxygen is 159994 gmol There are 6 022 x 1023 objects in one mole Dimensional Analysis Conversion Factor A fraction7 equal to 17 which can convert from one set of units to another Ewample WWW M WWVWWW N WWWquot Weiwet HiriiiW OH HHH H HHHHHH H H W Hydrocavbnnlike chain cavhnxyl gmup
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