CHEM 1110 NOTES, SUMMER 2012

Chapter 1 Matter- Stuff - anything that occupies space Substance- matter that has a defined, fixed composition Mass- the quantity of substance Weight- mass x gravity (force) Three common states of matter: 1. Gas (no set volume or shape) 2. Liquid (set volume but not set shape) 3. Solid ((set volume and shape). Physical properties and changes: Properties are those shown by the substance itself, without changing into or interacting with another substance. (e.g., color, mp, density, conductivity). Changes occur when the substance alters its physical form, not its composition. Chemical properties and changes: Properties are those that a substance shows as it changes into or interacts with another substance (e.g., flammability, corrosiveness, reactivity with acids). Changes (i.e., reactions) occur when a substance is converted into a different substance Extensive properties are those dependent on the amount of substance, i.e., mass, volume. Intensive properties are those independent on amount of substance, i.e., m.p., color. Energy: Potential energy is stored energy. Kinetic energy is energy of motion. Heat: The energy that flows between objects of different temperatures- extensive property, e.g., the energy depends on the mass of the objects. Temperature: The intensive factor of heat- the heat energy flows from the higher temperature to the lower temperature- intensive property, e.g., boiling water does not change temperature no matter how much water there is. Electrostatic forces: opposite charges attract each other, like charges repel. Magnets fit this definition, but so do charged particles, e.g., ions. Energy is neither created nor destroyed; 1st Law of Thermodynamics. Note that all reactions involve relative amounts of energy- energy of reactants equals energy of products. 1

Scientific Method: 1. Observations 2. Hypotheses (Theory) (See page 9 for excellent example)

3. Experiment 4. Model

Metric System: Measured quantities require units as well as number. SI Units: Seven fundamental units: Mass- kilogram (kg) Length-meter (m) Time- seconds (s) Temperature- Kelvin (k) Electric current- ampere (A) Amount of substance mole (mol) Luminosity- candela (cd) Conversions- kilo 1000, centi one hundredth, milli one thousandth (do a few conversions) Temperature: Fahrenheit, Celsius and Kelvin. Show conversions Dimensional analysis- show several examples, emphasizing cancelling units. Measured numbers- using measuring device; inherent possibilities of error. Exact numbers- defined numbers, e.g, 12 in = 1 ft Significant figures and scientific notation- show a number of examples. Precision- how close results are to one another. Accuracy- how close the figure is to the true figure. Systematic error- values always higher or lower than real figure- part of the experimental system, e.g., faulty measuring device. Random error- values that are higher or lower than real figure, always present in experimental work. Density- mass/unit volume- intensive property. Make several calculations showing units. Chapter 2 Substance- matter whose composition is fixed. Element- consists of one type of atomeach element is unique because its atoms are unique. Molecules- two or more atoms bound together. Compound- consists of fixed numbers of different elements Also mention mixtures. Law of Definite Proportions- no matter what its source, a particular compound is composed of the same elements in the same parts by mass. The fraction by mass is 2

that part of the compounds mass that each element contributes. The % by mass is the fraction expressed as %. For instance, 20 grams of CaCO3 has the following composition: Analysis by mass Mass fraction percent by mass 8.0 g calcium 0.40 calcium 40% calcium 2.4 g carbon 0.12 carbon 12% carbon 9.6 g oxygen 0.48 oxygen 48% oxygen 20.0 g 1.00 part by mass 100% by mass Mass of element = mass of compound (Do a sample computation using CaCO3) Daltons Atomic Theory 1. All matter consists of atoms, tiny invisible particles of an element that cannot be created or destroyed. 2. Atoms of one element cannot be converted into atoms of another element. 3. Atoms of an element are identical in mass and other properties and are different from atoms of any other element. 4. Compounds result from the chemical combination of a specific ratio of atoms of different elements. Daltons postulates explain the mass laws: Mass conservation- atoms cannot be created or destroyed (postulate 1) or converted into other types of atoms (postukate 3) Definite composition- a compound is a combination of a specific ratio of different atoms (postulate 4), each of which has a particular mass (postulate 3). Multiple proportions- atoms of an element has the same mass (postulate 3) and are indivisible (postulate 1). X Part by mass of elemnt one part by mass of compound

Rutherfords Experiment: The particle is a radioactive particle. Rutherford aimed the particle from radium at a thin gold foil, expecting the small dense particles to pass right through the gold atom (plum-pudding model). Instead about 1-in-20000 particles were reflected back. From these data, Rutherford concluded that the atom is mostly space occupied by 3

electrons, but in the center of that space is a tiny region (the nucleus) that contains all the positive particle and nearly all the mass. The positive particles were called protons. The building blocks of atoms: Nucleus- protons (mass 1, charge +) and neutrons (mass 1, charge 0). Electrons (mass ~0, charge -) surrounding the nucleus. Charge Name Relative Absolute Coulomb Proton (p+) +1 1.602 x 10-19 Neutron (n0) 0 0 Electron (e ) -1 -1.602 x 10-19 Mass Relative, Amu 1.00727 1.00866 0.00055

Absolute, g 1.67 x 10-24 1.67 x 10-24 9.11 x 10-28

Location Nucleus Nucleus outside

Atomic Number (Z)- number of protons Mass Number (A)- protons + neutrons Atomic mass- weighted average of isotopes Isotopes- same number of proton, different number of neutrons Symbols:
mass number atomic number
A Z

Example
37 17

Cl

In 1871, the Russian chemist Dmitri Mendeleev arranged the elements in a table of increasing atomic weights in which elements with similar chemical characteristics fell in the same column. Now the elements are in order of atomic numbers rather than weights. Identify metals, metalloids and non-metals, d-transition elements in the Periodic Chart. Valence electrons are the electrons in the outer shell and are the ones involved in chemical reactions.

Chemical bonding

In the A elements, the most stable valence electron configuration is 8 electrons, except for those with less where the most stable valence electron configuration is 2. Metals lose electrons to form positive ions (charged particles); cations, non-metals take electrons to form negative ions- anions. Give list of about 50 ions. Ionic bonds- transfer electrons, bonds are attraction of opposite charges. Covalent bonds- share electrons, bond are shared electrons. Covalent compounds consist of molecules. Ionic compounds consist of arrays of ions. Some ions consist of a number of atoms with covalent bonds, i.e., CO3-2 . Show simple dash structures of covalent compounds. Empirical formula- ratio of various atoms Molecular formula- actual ratio of atoms Structural formula- the relative placement and connections of atoms. Show use of subscripts and parentheses in writing formulae. Name simple and ionic and covalent compounds. Hydrate- association of a specific number of waters with a compound, e.g., Na2SO4 .10H2O Name some simple acids. Mixtures- heterogenous, one or more boundaries so that it composition is not uniform. Homogeneous, no visible boundaries so composition is uniform. CHAPTER 3 Mole- simply the molecular mass expressed in grams. It is defined as exactly the same number of atoms as in exactly 12 grams as carbon-12. It amounts to 6.022 x 1012 atoms- which is named Avagadros Number after the Italian physicist Amedeo Avagardro. THIS MEANS THAT A MOLE OF ANY ELEMENT OR COMPOUND CONTAINS 6.022 x 1023 ATOMS. A mole is a fixed number of atoms and so has a fixed mass. The mass of one atom of iron is 55.85 atomic mass units (amu). The mass of one mole of iron is 55.85 g. One molecule of water has a mass of 18.02 amu, and one mole of water has a mass of 18.02 g. 5

Calculations based on mass, molar mass and number of moles. The fundamental definition is: number of moles = grams/molecular weight

Mass percent: Mass % of element X = moles of X in formula x molar mass of X (g/mol) x 100 mass (g) of 1 mol of compound

Example: what is mass percent of each element in C6H12O6 (mol wt = 180.16)? 6 moles in C6H12O6 x 12.01 g/mol = 0.4000 180.16 g Similarly mass fraction of H = 0.06714 and mass fraction of O = 0.5329. The corresponding mass %s are 40.00% C, 6.714% H and 53.29% O. Mass fraction of C = The mass of C in 16.55 g glucose = 16.55 g x 0.4000 = 6.620 g C. or more simply: Mass of C = 16.55 g glucose x 72.06 g C = 6.620 g C 180.16 g glucose Calculations based on analytical data: Analysis of an unknown compound shows 0.21 mol Zn, 0.14 mol P and 0.56 mol O. Since these data are the fractions of elements, the formula can be written: Zn0.21P0.14 O0.56 . Next divide the subscripts by the smallest one, 0.14, to give Zn1.5P1.0O4.0. Then multiply through by the smallest integer that will turn the subscripts into integers to give Zn3.0P2.0O8.0 or more simply Zn3P2O8. Isomers have the same molecular formula but different structures. For instance:

C2H6O
H 3C H2 C OH H3 C O CH 3

Ethanolb. p. = 78.5 0C density = 0.789 g/mol @ 200 C

Dimethyl Etherb. p. = -25 0C density = 0.00195 g/mol @ 200 C

Writing and balancing equations: BALANCING BY INSPECTION. IT INVOLVES:

1. COUNT THE NUMBER OF MOLES OF ATOMS OF EACH ELEMENT ON BOTH PRODUCT AND REACTANT SIDE. 2. DETERMINE WHICH ELEMENTS ARE NOT BALANCED. 3. BALANCE ONE ELEMENT AT A TIME USING COEFFICIENTS. 4. CHECK TO BE SURE THE NUMBER OF MOLES OF ATOMS OF EACH ELEMENT ON BOTH PRODUCT AND REACTANT SIDE ARE THE SAME. EXAMPLES ARE: C3H8 + O2 CO2 + H2O

REACTANTS MOLES H MOLES C MOLES O 8 3 2

PRODUCTS 2 1 3

INSERT 3 BEFORE CO2 ON THE PRODUCT SIDE. C3H8 + O2 3 CO2 + H2O

REACTANTS

PRODUCTS 7

MOLES H MOLES C MOLES O

8 3 2

2 3 7

MULTIPLY H2O ON PRODUCT SIDE BY 4. C3H8 + O2 3 CO2 + 4 H2O PRODUCTS 8 3 10

REACTANTS MOLES H MOLES C MOLES O 8 3 2

MULTIPLY O2 ON REACTANT SIDE BY 5. C3H8 + 5 O2 REACTANTS MOLES H MOLES C MOLES O 8 3 10 3 CO2 + 4 H2O PRODUCTS 8 3 10

THE EQUATION IS NOW BALANCED. Stoichiometry- equivalence. In the equation shown above, 1 mol of C3H8 is equivalent to 5 mol of O2, 3 mol CO2 and 4 mol H2O. Calculations using stoichiometry. CALCULATE THE NUMBER OF GRAMS OF O2 THAT WILL REACT 1.00 MOLES OF C3H8:
C3H8 + 5 O2 1.00 mol C3H8 x 1 3 CO2 + 4 H O 2 5 moles O2 x 1 mol C3H8 32.0 g O2 = 160g O2 = 1.60 x 102 g O2 mol O2

Limiting Reagent:

If there is only 0.80 mol of C5H8 involved in the equation shown above, then quite obviously less than 5 moles of O2 will react and less than 3 moles of CO2 and 4 moles of H2O will be formed. The C5H8 is the LIMITING REAGENT and only 4/5 of the other reagents will be involved. In the reaction shown above, only 4/5 x 1.60 x 102 g of O2 or 1.28 x 102 grams of O2 will be used up. If everything went perfectly, in the original equation, then exactly 1 mole of C3H8, 44.0 g, would give 3 x mol weight of CO2 = 3 x 44.0 g/mol = 132 g CO2. This is the THEORETICAL YIELD. It is rare for chemical reactions to go perfectly, so the ACTUAL yield might be, e.g., 120 g. The % yield the % the actual yield is of the theoretical yield. In this case the % yield is 120 g/132g x 100 = 90.9 % It is assumed in the discussion shown above, the reagents are all 100% pure. Such is generally not the case. If, for instance, the CO2 were to be only 90.0% pure, then the % yield would be only 81.8% of 100% product. molarity = M = number of moles of solute number of liters of solution or M = moles solute L of solution

moles solute = M x L of solution = MV In dilution the moles solute does not change, so Mconc x Vconc = Mdil x Vdil or M1 V1 = M2 V2 Given 3 of the amounts, the 4th can be calculated easily. For instance: Prepare 0.80 L of 0.15 M NaCl from 6.0 M NaCl. What volume of 6.0 M NaCl is needed? M1V1 = M2V2 V1 = M2V2 = 0.15 M x 0.80 L M1 6.0 M = 0.020 L

m solute oles m olality = m = kg of solvent The same manipulations can be made with m as with M. Calculations in involving converting m and D to M: What is the M of a 0.25 m NaCl, D = 1.25 g/mL, m solution? Assume a solution with 1000 g solvent. Then:

0.250 m= So: Total w eight =1015 g,

0.25m x 58.5 g/m oles ol 1000 g H2O

= 14.6 g NaCl 1000 g H2O = 0.0144 = 1.44%

therefore % of m = 14.6 g NaCl ass 1015 g H2O

1 .25g/m = L

1 015g V =

1 V = 10 5g 1 25g/m L 0 .25m ol 0 2L .81 =0.301M

= 8 12m =0.81 L 2L

oles M = noofm V

CHAPTER 4 Polar covalent bond- see page 297 When atoms of different negativities form a covalent bond, the electrons in that bond are unequally distributed. The more negative end is denoted by - and the more positive end by +.
+ H F

A polar covalent molecule has more than one polar covalent bond.
O H3C C

OH

The water molecule is a polar covalent molecule.

O +
H H

O H H

Based on polarity, water will separate ions by replacing the attraction between ions with attraction between the ions and water. The negative end of the water molecule is attracted to the positive ion (cation) and the positive end with the negative ion (anion). This is called solvation the general term, or hydration when water is the solvent. When the attraction between ions is greater than salvation, then the compound is insoluble. For instance, NaCl is 36.5% while AgCl is only 0.009% soluble in water. 10

The convention for showing the state of a compound or ion is as follows: Gas (g) Liquid (l) Solid (s) Aqueous (i.e., solvated) (aq) When a substance is dissolved in water to give ions, the solution will allow electric current to flow, i.e., it becomes conductive (see pp 115, 116). Those ionic compounds that are very soluble ionize to give many ions and so are strong electrolytes. Those that ionize very little are weak electrolytes. Those that are soluble but dont ionize are nonelectrolytes. The number of ions depends on the ratio of the elements in the ionic compound: KBr ((s) CuBr2(s)
H2O H2O

K+(aq)

Br- (aq)
+ 2 Br (aq)

Cu+2(aq)

Solubility refers to the amount of substance dissolved. In precipitation, the soluble ions react to produce an insoluble compound. When does an insoluble compound form? See Table 4.1, page 121. Basically, all common Group 1 and ammonium compounds are soluble. All common nitrates, acetates and most perchlorates are soluble. All common chlorides are soluble with the exception of those of Ag+, Pb+2, Cu+ and Hg2+2.. All common fluorides are soluble with the exception of those of Pb+2 and Group 2A. All common sulfates are soluble with the exception of those of Ca+2, Sr+2, Ba+2, Ag+ and Pb+2.. All common metal hydroxides are insoluble except for those of Group 1A and the larger members of Group 2A, beginning with Ca+2. All common carbonates and phosphates are insoluble except for those Group 1A and NH4+. All common sulfates are insoluble except for those of Group 1A, 2A and NH4+. Equations can be written three ways: a. Molecular equation- all species are shown as molecules: 2 KF(aq) + Sr(NO3)2 (aq) SrF2 (s) + 2 KNO3 (aq) b. Total ionic equation:
2K (aq) + 2F (aq) + Sr (aq) + 2 NO3 (aq)
+ +2 -

2K+(aq) + 2 NO3-(aq)

+ SrF2(s)

c. Net ionic equation, i.e., removing the ions that appear on both sides: Sr+2(aq) + 2F-(aq) 11 SrF2(s)

Arrhenius acid: forms H3O+ in water. Arrhenius base: forms OH- in water. H3O+ (hydronium ion) is formed by reaction of H+ with H2O. This always occurs when H+ is dissolved I H2O. Strong acids and bases dissociate 100% in water and are strong electrolytes. Weak acids and bases dissociate very little in water and are weak electrolytes. Soluble bases are can be either strong bases (NaOH) or weak bases (NH4OH). Insoluble bases (Mg(OH)2) are weak bases since very few OH- ions are produced. An Arrhenius acid-base reaction is: HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) Note that the acid forms H+ and the base forms OH- in aqueous solution. Also note that H2O is formed from these ions in the acid-base reaction. Consider the following reaction: HCl(aq) + NH3(aq) NH4Cl(aq) The acid certainly forms H3O+ in solution, but where is the OH- in the NH3? This introduces another and more general definition of acids and bases, the BrnstedLowery definition. An acid is a proton donor and a base is a proton acceptor. In chemical equilibria, the rate of the reaction going to the right is equal to the rate of the reaction going to the left, so that although the reactions are continually occurring, there is no net concentration change. Consider the reaction of the weak base NH3 with water: NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) Note that the NH3 accepts an H+, so it is a Brnsted-Lowery base while the water donates a proton, and so is a Brnsted-Lowery acid. This is a chemical equilibrium. Chemical equilibria are not limited to acid-base reactions, as you will find out further down the line. An acid-base reaction in molecular, ionic and net-ionic form is: Molecular: HCl(aq) + NaOH(aq) Ionic: NaCl(aq) + H2O(l)

12

H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) Net ionic: H+(aq) + OH-(aq) H2O(l)

Na+(aq) + Cl-(aq) + H2O(l)

A neutral solution is one that has no excess H3O+ or OH-. A neutralization reaction is one where an acid is added to a base, or vice-versa, until there is no excess H3O+ or OH-. A titration is a reaction is one solution of a known concentration is used to determine the concentration of another solution through a monitored reaction. The monitoring is often done by using an acid-base indicator where there is a color change at the neutral point. Of course, other monitoring methods can be used. Consider adding a solution of NaOH from a buret to a solution of HCl. An equivalence point in the titration occurs when all the moles of H3O+ present in the original solution have reacted with the equivalent moles of OH- added from the buret. The end point occurs when a tiny excess of OH- turns the indicator permanently to its color in base. In this case the amount of base needed to reach the endpoint is the same as the amount needed to reach the equivalence point. Oxidation-reduction (redox) reactions involve the transfer of electrons. The applicable nmomic is LEO the lion goes GER. LEO- Loss of Electron is Oxidation; GER- Gain of Electrons is Reduction. Consider the reaction: Zn+2(aq) + Cu0(aq) Zn0(aq) + Cu+2(aq) Zn+2 gains 2 electrons to give Zn0, and so is reduced. Cu0 loses two electrons to give Cu+2, and so is oxidized. The gain of 2 electrons by Zn+2 results in the oxidation of Cu0, so Zn+2 the oxidizing agent. The loss of 2 electrons by Cu0 results in the reduction of Zn+2, so Cu0 the reducing agent. So that which is oxidized is the reducing agent and that which is oxidized is the reducing agent. The charges on these ions are oxidation numbers. Rules of thumb is that elements are always 0 oxidation number, O in a compound is always -2 and H in a compound is +1. Group 1 is always +1, Group 2 is +2, Group 7 (with certain exceptions) is always -1. For instance, consider the oxidation of N in NO3-. The 3 Os are 3 x -2 = -6. The overall charge is -1. So the oxidation number of N must be +5. The oxidation number of Mn in KMnO4 is: K is +1, 4 Os are 4 x -2 = -8. +1 plus -8 = +7, so this is the oxidation of Mn in this compound. 13

Obviously some reduction agents are stronger than others. They are arranged with strongest reducing agent at the top of the series with the rest in order of descending reducing power. See page 136. (Discuss this) Balancing redox reactions can be done by the half-reaction method. (See page 706709). This is carried out by dividing the reaction into a reduction reaction and an oxidizing reaction. Consider the following redox reaction: I -(aq) + H+(aq) + Cr2O7-2(aq) The reduction half-reaction is: Cr2O7-2 2 Cr+3 I 2(s) + H2O(l) + Cr +3(aq)

The O needs to be balanced by adding H2O to the right side of the reaction. Cr 2O 7-2 Cr 2O 7-2 + 14H+ 2 Cr +3 + 7H2O

The H's on the right need to be added to the left. 2 Cr +3 + 7H2O

The charges on both sides need to be balanced by adding 6 electrons to the left side. 6 e- + Cr 2O7-2 + 14H + The oxidation half-reaction is: 2II2 2 Cr+3 + 7H2O

No H's or O's are needed to balance the half-reaction, but the charges on both sides need to be balanced by adding 2 electrons to the right side. 2I I2 + 2e-

Note that there are 2 electrons on the right and 6 on the left. Multiplying the oxidation half-reaction by 3 gives the same number electrons in both half-reactions. 6 e- + Cr2O7-2 + 14H+ 6I 3 I2 + 6e2 Cr +3 + 7H2O

Cancelling the electrons by adding the two half-reactions gives: 6 I- (aq)+ Cr 2O 7-2(aq) + 14H+(aq) 3 I2(s) + 7 H2O(l) + 2 Cr+3(aq) 14

Note that this is a net ionic equation, the easiest way to balance redox equations. CHAPTER 5 Gases have no definite volume or shape, as contrasted with liquids (definite volume, no definite shape) and solids (definite volume and shape). Gas volume changes greatly with pressure and/or temperature. Gases have relatively low viscosity and density. Gases are totally miscible with each other. An ideal gas is one in which individual molecule do not affect each other, a condition is essentially present in simple gases at normal temperature and pressure. Pressure is defines as force exerted per unit area, e.g., psi: P = force area The molecules of a gas are moving rapidly in every direction and are bouncing off the walls of the container, which is pressure. (Point out that a balloon bursts if there is more pressure on the inside than the outside.) Pressure is measure by a barometer. (Note: bar means pressure.) If a tube closed at one end is filled with Hg, and the open end is placed in a dish filled with Hg, gravity will pull the Hg down while atmospheric pressure will push it up. At sea level at 00C, the average height of the column of Hg in the tube is 760 mm (1 atm, one atmosphere). (See page 148 for a diagram of a barometer.) The units used are mmHg (usually just mm), atm and torr. The torr equals mmHg and is named in honor of the Italian physicist Torricelli. The SI unit for pressure is the pascal, the force of one newton per square meter. We will not use these units. One atm, 760 mm and 760 torr are defined quantities and so have an infinite number of significant figures. There are three fundamental gas laws correlating pressure, volume and temperature. Boyles Law: At constant temperature, the volume of a given moles of gas is inversely proportional to the pressure. 1 V = k PV = k V P P If the volume of a given amount of gas at constant temperature is changed, then: P1V1 = P2V2 Where 1 is initial P and V and 2 is the final P and V Charles Law: At constant pressure, the volume of a given moles of gas is directly proportional to the absolute temperature. 15

V =k T If the volume of a given amount of gas at constant pressure is changed, then: V T V = kT V1 V = 2 T1 T2 Where 1 is initial T and V and 2 is the final T and V

Combined Gas Law: This is a simple combination of Boyles and Charles Laws: T PV = k V =k V T T P P Avagadros Law: At constant pressure and temperature, the volume of a gas is directly proportional to the number of moles, n. V =k V = nk V n n The combination of Boyles, Charles and Avagadros Laws gives the Ideal Gas Law:
V n V = nk V n =k

R is the universal gas constant and is a combination of the constants of the three gas laws. Its value when pressure is expressed in atm, temperature in K, volume in L and amount in moles is: atm-L 0.0821 mol-K You should memorize this number. A calculation using the Ideal Gas Law: What is the volume of 2.5 moles of gas at 3.0 atm and 27 0C (300 K)? V = 2.5 x 0.0821 x 300 = 20.5 L V = nRT 3.0 P Note that units are not shown. The n, T and P units are cancelled out by the units of R, leaving L for the volume. PV = nRT Standard conditions for gas temperature and pressure are referred to as STP. The standard temperature is 00C and the standard pressure is one atm. The standard molar volume, that is the molar volume of ANY ideal gas at STP, is 22.4L. The molar volume can be calculated by using the Ideal Gas Law:

16

PV = nRT

V = nRT P

V = 1.00 x 0.0821 x 273 = 22.4 L 1.00

Daltons Law of Partial Pressures state that the total pressure is equation to the sum of the partial pressures of the constituent gases: Ptotal = p1 + p2 + p3 + . . . Each component in a mixture contributes a fraction of the total number of moles in the mixture, which is the mol fraction (X) of that component. Consider a mixture of hydrogen and nitrogen (pp 163, 164). The text shows how the ideal Gas Law can be used to define mol fraction, but it is easier to see that the equation can be written as: Ptotal = pH2 + pN2 = (XH2 x Ptotal) + (XN2 x Ptotal) = (XH2 + XN2)Ptotal = 1 x Ptotal What is the pressure of oxygen a gas mixture at a pressure of 0.75 atm where the mole fraction is 0.040. pO2 = XO2 x Ptotal = 0.040 x 0.75 = 0.030 atm

Stoichiometric amounts of gases are shown in a balanced equation. Consider the reaction: Cu(s) + H2O(g) CuO(s) + H2(g) What is the volume of H2 at 765 torr and 225 0C is needed to 35.5 g of CuO. Calculate the nH2: The molar ratio of CuO and H2 is 1:1, so the same number of moles of CuO and H2 are needed. nH2 = 35.5 g CuO x 1 mol CuO x 1 mol H2 = 0.446 mol H2 79.77 g CuO 1 mol CuO P(atm) = 765torr/760torr/atm = 1.01 atm, V = nRT P 225 0C = (225 + 273) = 498K

V = 0.446 x 0.0821 x 498 = 18.1 L 1.01

Kinetic Molecular Theory:

17

Questions concerning gas behavior: a. Pressure is the force that a gas exerts on a surface. How do individual gas particles cause this force? b. Gas pressure is inversely proportional to the volume (Boyles Law). What happens to the particles when pressure is applied? Why are solids and liquids not compressible? c. The pressure of a gas mixture is the sum of the partial pressures (Daltons Law). Why does each gas contribute to the total pressure in proportion to its mole fraction? d. Volume changes in direct proportion to the absolute temperature (Charles Law). What causes the effect of temperature on volume (and pressure)? What does temperature measure of the molecular scale. e. Gas volume depends on the number of moles, not on the nature of the gas (Avagadros Law). Why shouldnt 1 mol of a larger molecule occupy more volume than a smaller molecule? To answer these questions, the Kinetic-Molecular Theory postulates: 1. Particle Volume: The volume of a gas molecule is extremely small in relation to the volume of the container. 2. Particle motion: The individual molecule is in constant straight-line motion, except when it collides with the vessel wall or another molecule. 3. Particle collision: Collisions are elastic- they exchange energy but do not lose overall energy. In answer to the questions posed above: a. Pressure is the force that a gas exerts on a surface. How do individual gas particles cause this force? Postulate 2: The particle collisions cause the pressure. b. Gas pressure is inversely proportional to the volume (Boyles Law). What happens to the particles when pressure is applied? Why are solids and liquids not compressible? Postulate 1: There is a great deal of vacant space. As the volume decreases, the molecules get closer together and so collisions are more frequent, with a consequence of pressure increase. c. The pressure of a gas mixture is the sum of the partial pressures (Daltons Law). Why does each gas contribute to the total pressure in proportion to its mole fraction? Postulate 2: Adding a given amount of gas causes a corresponding increase in the number of collisions with the walls so that each gas exerts its mole fraction on the total. d. Volume changes in direct proportion to the absolute temperature (Charles Law). What causes the effect of temperature on volume (and pressure)? What does 18

temperature measure of the molecular scale. Postulate 3: As the temperature increases, the average kinetic energy increases, the collisions increase and the internal pressure increases, which causes the volume to increase. Temperature measures the average kinetic energy of the system. e. Gas volume depends on the number of moles, not on the nature of the gas (Avagadros Law). Why shouldnt 1 mol of a larger molecule occupy more volume than a smaller molecule? Adding more molecules increases the total of collisions, increasing the internal pressure. The volume increases until the number of collisions per unit of wall area is the same as it was before the addition. It can be shown (page 171) that the root mean square speed (urms) of gas molecules can be calculated by the following equation. The urms is basically the average speed. 3RT Where M = molar mass M R needs to be used in units that will give u in m/s and so must be in joules which equals 8.314J/molK. urms = For instance, the urms of O2 (M = 3.200 x 10-2/mole) at 200C (293 K) is: urms = 3RT M = 3 x 8.314 x 293 3.200 x 10-2 = 478 m/s

Effusion is the process by which a gas escapes from its container through a tiny hole into an evacuated space. Grahams Law of Effusion states that the effusion rate is inversely proportional to the square root of its molecular mass: 1 Rate of effusion M The ratio of effusion rates of Gas A and Gas B is: Rate A = Rate B MA MB

This means that gases can be separated in an effusion process based on their molecular mass. This is the way that isotopes of uranium, as the hexafluoride, were separated for the atomic bomb in WW2. Diffusion, the movement of one gas through another, can also be treated by Grahams Law. For two gases at equal pressure, the comparative diffusion rates are:

19

Rate A = Rate B

MA MB

which is the same rate relation as with effusion. Real gases deviate from ideality because they are treated as point masses, but are not in reality. There can also be attraction between gas molecules, which means they can deviate from ideality. For instance, high pressure can force molecules close enough to exert influence on each other. Temperature can be lowered so that the velocity of the molecules is so slow that attractive forces can come into play. Special variations of the Ideal gas Law have been developed to address such conditions.

CHAPTER 6 Thermodynamics is concerned with heat and its transformation to and from other forms of energy. Thermochemistry deals with the heat involved in chemical and physical changes. The surroundings include everything that is relevant to the change being investigated. The 1st Law of Thermodynamics is the Law of Conservation of Energy. One statement of the law is energy transfers between system and surroundings but the energy of the system plus the energy of the surroundings remains the same. Mathematically this is: Euniverse = Esystem + Esurroundings = 0 In chemical reactions, the energy of the reactants is not the same as the energy of the products. In order to obey the 1st Law of Thermodynamics, heat is evolved or absorbed. 2 H2 + O2 2H2O + 572J The SI unit of energy is the joule (J). The calorie is the more familiar unit. The relation between calorie and J is: 1 cal = 4.184 J 1 J = 0.2390 cal A property dependent only on the state of the system (composition, volume, pressure and temperature) not on the path taken to get to that state is called a state function. E is a state function. The changes in state functions are E, P, V. No matter what path the reaction takes, the energy change is dependent only the initial and final states. Energy change involves both work, w, PV work, and heat, q. Work (w) done on the surroundings is negative, w done on the system is positive; q evolved is negative, q absorbed is negative. E=q+w w = -PV 20

For reactions at constant pressure, a thermodynamic variable called enthalpy (H) eliminates the need to consider PV separately. H = E + PV The change in enthalpy at constant pressure is: H = E + PV Since most chemical reactions occur at constant pressure, H is the relevant state function to measure.

If heat is evolved, the reaction is exothermic and the sign of the heat is negative. If heat is absorbed, the reaction is endothermic and the sign of the heat is positive. So no matter what pathway of reactions is used, the same heat is evolved or absorbed. Thermodynamics involves only the initial and final states. THIS IS HESSS LAW. Heat capacity is the constant in the following equation. q =constant q =constant x T q T T Specific heat, c, is the amount of heat necessary to raise the temperature of one gram of a substance 1 K. The text refers to specific heat as specific heat capacity. q = c x mass x T A calorimeter is used to measure heat released or absorbed in a physical or chemical process. A coffee-cup calorimeter is a constant-pressure calorimeter. (See p. 196). A solid is weighed, heated to a known temperature and added to the cup containing water at a known temperature and mass. The final temperature of the water, which is also the temperature of the solid, is measured. -qsolid = qwater csolid x masssolid x Tsolid = cH2O x massH20 x TH2O cH2O x m H2O x TH2O ass m solid x Tsolid ass

csolid =

Since cH2O = 4.184 J/gK and the massH20, TH2O, masssolid and Tsolid are measured, the csolid can be calculated. Heat of reaction can also be calculated. qsoln = csoln x masssoln x Tsoln qsoln = -qrxn q is in J. Consider an acid base reaction where the heat of reaction is due to formation of water. The heat of reaction can be calculated: 21

Hrxn =

qrxn m H2O ol

1 kJ 1000 J

The thermochemical equation is a balanced equation that includes the Hrxn. Keep in mind that Hrxn refers to the moles of substance and their states of matter in that specific equation. 1. The sign depends on whether the reaction is exothermic (-) or endothermic (+) Decomposition of 2 moles of water into its elements is endothermic. 2 H2O(l) 2H2 + O2 2H2 + O2 Hrxn = 572 kJ Hrxn = -572 kJ Formation of 2 moles of water from its elements is exothermic. 2 H2O(l)

2. The magnitude of the Hrxn is proportional to the amount of the substance reacting. Formation of 1 mole of water from its elements (half the amount in the preceding equation) is exothermic. H2 +
1 2

O2

H2O(l)

Hrxn = -286 kJ

Note that fractional coefficients are often used in thermochemical equations. Many reactions are difficult, or even impossible, to carry out separately. It is often possible to break up the reaction in a series of steps for which the enthalpy is known. Hesss Law involves heat of summation: the enthalpy change in the overall process is the sum of the enthalpy changes of the individual steps. An example is reaction of S and O2 to give SO3: Equation 1: S(s) + O2(g) Equation 2: 2 SO2(g) + O2(g) Equation 3: S(s) +
3 2

SO2(g) 2SO3(g) SO3(g)

H = -296.8 kJ H = -198.4kJ H = ?

O2(g)

Divide Equation 2 by 2, and the equations can be added together to give Equation 3, including the addition of the Hs.

22

Equation 1: S(s) + O2(g) 1 Equation 2: SO (g) + 1 O (g) 2 2 2 2 Equation 3: S(s) +

3 2

SO2(g) SO3(g) SO3(g)

H = -296.8 kJ H = -99.2kJ H = -396.0

O2(g)

This emphasizes that since H is a state function, so the overall H depends only on the initial and final enthalpies.

The standard states of matter are as follows: For a gas, the standard state is one atm, with the gas behaving ideally. For a substance in solution, the standard state is 1 M concentration. For a pure substance (element or compound) the standard state is the most stable form of the substance at 1 atm and 25 0C (298 K).

A superscript degree sign ( 0 ) is used to denote the standard state.

0 The standard heat of formation, H f , is the enthalpy changes for the formation equation when when all substances are in their standard states, in this case the elements in their most stable form. For instance, the formation for the equation for the formation for methane is:

C(graphite) + 2H2

CH4(g)

H 0 = -74.9 kJ f

See page 203 for a table of standard heats of formation. Note: the text does not show that the standard heats of formation are often determined using Hesss Law.
0 0 The standard heat of reaction, H rxn, can be determined from the H f .

TiCl4(l) + 2H2O(g)

TiO 2(s) + 4HCl(g)

The equation can be broken down to a series of equations, and the equation can be added together using Hesss Law. TiCl4(l) 2H2O(g) Ti(s) + O2(g) 2H2(g) + 2Cl2(g) TiCl4(l) + 2H2O(g) Ti(s) + 2Cl2(g) -H 0 [TiCl4(l)] f 0 2H2(g) + O 2(g) -2H H2O(g) f TiO 2(s) 4HCl(g) H 0 [TiO2(s)] f
0 4H [HCl(g)] f

TiO 2(s) + 4HCl(g)

And H 0 is the sum of the individual H 0 's. rxn f 23

The Greenhouse effect is caused by the following: The earth receives its energy as visible light from the sun. This energy is used to, among other things, produce heat energy. The heat energy is radiated from the earth as infrared emission. When a steady state condition is reached, then the heat on the earth remains constant. However if something keeps the infrared from radiating as much as the steady state amount, the excess heat will cause the temperature on earth to rise. Natural events can cause this- for instance, volcanic eruptions spew particles into the atmosphere that deflect the infrared emission, but also they reflect the sunlight, which reduces the energy reaching the earth which makes everything more complicated. Carbon dioxide has a greenhouse effect. It is transparent to the light energy coming in but reflects the infrared, leaving a net gain of heat. Plant life utilizes CO2 and so the amount of CO2 originally present in the atmosphere has decreased to 0.028% by volume. The use of fossil fuels in the last 200 years has increased this to 0.036%. Based on current trends, the concentration will rise to between 0.049% and 0.126% by 2100. This greenhouse effect has increased the average temperature by 0.6+/-0.2 0C since the late 19th century, of which 0.2-0.3 0C has occurred in the last 25 years. This temperature rise may seem small, but based on the size of the earth the amount of heat is actually tremendous. This heat has affected rainfall, has melted ice has the affected ocean currents, etc. The sea level has risen 4-8 inches over the last century, and flooding and other extreme event have occurred. Low-lying areas such as Bangladesh could easily disappear. We must cut CO2 emissions by using less fossil fuel and turning to alternate energy sources such as wind and tidal power and by sequestering CO2. Nuclear power is also a viable option, but disposal of radioactive waste is a problem.

CHAPTER 7 Classical physics cannot describe what happens at the atomic level. For instance, why doesnt a negative electron spin into the positive nucleus? Classical physics would say that the orbiting electron would continually lose energy so that fall into the nucleus. New explanations are needed, and atomic physics provides the rationale. An involved explanation is beyond these lectures, but see 213-221 for details. Briefly, light energy has two natures- particle and wave.

24

A wave has two attributes- wave length, , the distance between the crests (or troughs) and frequency, , the number of cycles the wave undergoes. For the electromagnetic spectrum: x = c(the speed of light) The electromagnetic spectrum covers the wave length from meter , such as radio and TV waves, to 10-10 meters, X- and waves. The shorter the , the higher the energy. The amplitude is is the height of the crest or trough of the wave. Waves have certain attributes that are not shared with particles. For instance wave are refracted. When a wave hits a boundary between air and water at an angle other than 900, the change in speed causes a change in direction, refraction. When a wave strikes an object, it bends around in a phenomenon called diffraction. When a wave passes through a slit about as wide as the wavelength, diffraction causes a semicircular wave on the other side. When there are two slits side by side, the two semicircular waves interfere with one another to cause interference. If the crests of the waves coincide (in phase), they interfere constructively and the amplitude is increased. If the crests coincide with the troughs, they interfere destructively and the amplitudes disappear. A single photon (see below) may be refracted by a lens or exhibit wave interference with itself, but also act as a particle giving a definite result when quantitative momentum is measured. So light energy also has the attribute of a particle and has wavelength. When a solid is heated it begins to emit visible light at about 10000C. As the temperature is increased, the light becomes brighter and brighter. This is blackbody radiation, light given off by a hot blackbody, an idealized body that absorbs all radiation hitting it. Max Plank proposed that a hot, glowing object can only emit (or absorb) only certain quantities of energy. E= nh, where n is a positive integer, is frequency and h is Planks constant. The photoelectric effect, the flow of current when monochromatic light of sufficient frequency shines on a metal plate. Wave theory associates light energy with amplitude (intensity) not frequency (color), so wave theory predicts that electrons would break free if sufficient energy of any frequency is used, but frequency is the defining attribute. Also wave theory predicts that there would be a time lag in initial current flow until enough energy is built up to break electrons free. But there is no time lag if the correct frequency is used. Einstein proposed that light itself is particulate- quantized into small packers of energy called photons. These photons have wavelength as well as particle attributes. Energy depends on frequency, so a photon with the correct frequency would 25

break an electron free- and would break it free immediately. Thus, Einsteins concept of photons explains both the wave and particle nature of light. The spectrum formed from white light contains all colors, or frequencies, and is known as a continuous spectrum. Light emitted when an element is vaporized and then thermally or electrically excited and passed through a prism gives a line spectrum, a series of fine lines separated by colorless (black) spaces. The wavelength of these lines is characteristic of the element. Niels Bohr, a young Danish physicist working in Rutherfords Cambridge laboratory in 1913, proposed a model to explain the hydrogen line spectrum, using Planks and Einsteins ideas about quantized energy. He made three postulates: 1. The H atom has only certain allowable energy levels, which Bohr called stationary states. Each of these states is associated with a fixed circular orbit of the electron around the nucleus. 2. The atom does not radiate energy while in one of these stationary states. The atom does not change energy while moving in this orbit, thus violating the ideas of classical physics. 3. The atom changes to another stationary state, i.e., the electron moves to another orbit, by either emitting or absorbing a photon whose energy equals the difference in energy between the two states. Therefore Bohrs model explains that an atomic spectrum is not continuous because the atoms energy has only discrete levels, or states. Bohrs theory involved fitting the theory to data, but his conclusions had no basis in physical theory. In the early 1920s, a young French physicist Louis de Broglie proposed that if energy is particle like, the perhaps matter is wavelike. He reasoned that if electrons have wavelike motion and are restricted to orbits of fixed radii, they would have only certain possible frequencies. He developed the following equation: h where h = Plank's constant, m = mass and u = speed = mu This means that any object- baseball or electron- has a wavelength. See page 229 for the wavelengths of some objects from electrons to the earth. The German physicist Werner Heisenberg postulated the uncertainty principle, which states that it is impossible to know the exact position and momentum (mass times speed) at the same time. 26

h 4 x = uncertainty in position and u is the uncertainty in speed So increasing the accuracy for the speed change will decrease the accuracy in position and vice-versa. This means that we cannot assign fixed paths for electrons, such as the circular orbits of the Bohr atoms. The most one can ever hope for is the probability of finding an electron in a given region of space. > x . mu _ Acceptance of the dual nature of matter and energy and of the uncertainty principle culminated in the field of quantum mechanics. In 1926, Erwin Schrdinger derived the equation that is the basis for the quantum-mechanical model of the hydrogen atom, which has certain allowed quantities of energy due to the allowed frequencies of an electron whose behavior is wavelike and whose exact location is impossible to know. This complex equation is quit complex, but is represented by: H = E H is the Hamiltonian Operator, E is the Energy and is the wave function.

Solution of this complex equation (see the bottom of page 232) gives an atomic orbtal (not to be confused with Bohrs orbit- the obital is strictly a mathematical function with no physical meaning. 2 is the probability function from which an electron density can be drawn (see Figure 7.17, page 233). The atomic orbital defined by is specified by three quantum numbers: 1. The principal quantum number (n) is a positive integer (1,2,3,) that indicates the relative size of the orbit and therefore the distance from the nucleus in the radial probability plot. The higher the n value, the higher the energy level. 2. The angular momentum quantum number (l) is a positive integer from 0 to n-1. For instance, for n = 3, l is 0,1,2. The number of possible ls is the same as n. 3. The magnetic quantum number (ml) is an integer from l to 0 to +l. See Table 7.2, page 234, for the hierarchy of quantum numbers in atomic orbitals. The total number of orbitals for n is n2. A 4th quantum number is discussed in the next chapter. Atomic orbitals have shapes. For an orbital with l = 0, the shape is spherical and is called the s orbital. Each n will have an s orbital.

27

For orbitals with l = 1, there are 2 regions (lobes) on either side of the nucleus and is called the p orbital. Since the maximum value of l is n-1, only levels with n = 2 will have a p orbital. Since for every l = 1, there are three m orbitals,(-1,0,+1) which are lobes lying on the x, y and z axes. For orbitals with l = 2, there are 5 possible m orbitals (-2 -1,0,+1,+2). These are the d orbitals and have complex shapes. See page 239 for the diagrams. Orbitals with l = 3, there are 7 m orbitals. These are the f orbitals and are extremely complex. See page 239 for one of the possible 7 f orbitals. Note that lower the principal quantum number, the smaller the diameter of the atom. Since the hydrogen atom has only one electron. When that electron jumps from n = 1 to n = 2 or 3 or 4, etc, the s, p, d and f orbitals will have the same value because there is only one electron. Other atoms have >1 electron, so this does not hold for any atom except H. CHAPTER 8 The three quantum numbers- n, l and ml- describe the energy, shape and orientation of the atomic orbitals. Another quantum number is needed to describe a property of the electron itself, called spin. This becomes important when more than one electron is present. A single electron can have two possible values of spin, each of which develops a tiny magnetic field. Like charge, spin is an intrinsic property of the electron, and the spin quantum number, ms, has values of either +1/2 or -1/2. Thus each electron is described completely by a set of four quantum numbers- the 1s t three describe its orbital and the fourth describes its spin. See Table 8.1, page 247, for a summary of these quantum numbers. We can write a set of four quantum numbers for any electron in the ground state of any atom. For example, the set of quantum numbers for the lone electron is n = 1, l = 0, ml = 0 and ms = +1/2 (+1/2 for the 1st electron by convention). The Pauli Exclusion Principal states that no two electrons in the same atom can have the same four quantum numbers. Because the spin quantum number can have only two values, the major consequence of the exclusion principle is that an atomic orbital can hold only two electrons, and those electrons have opposite spins. According to the Aufbau Principle, electrons fill orbitals starting at the lowest available (possible) energy states before filling higher states (e.g. 1s before 2s). The number of 28

electrons that can occupy each orbital is limited by the Pauli Exclusion Principle. If multiple orbitals of the same energy are available, Hund's rule says that unoccupied orbitals will be filled before occupied orbitals are reused (by electrons having different spins). See pages 251-255 for atomic orbital energy diagrams. These show graphically how electronic configurations are built up. The electrons in a complete shell form a perfectly symmetrical shield of electron density, effectively shielding the outer shell electrons from that same number of protons. An electron in an s orbital has a finite probability of being found right at the nucleus. An electron in a p orbital on the other hand has a node in its density distribution at the nucleus. Thus an s electron penetrates the inner shell density more effectively than does a p electron and is consequently more tightly bound to the atom. In a hydrogen atom, there are no inner electrons and both a 2s and 2p electron always experience the full nuclear charge and have the same energy. The crux of this penetration effect on the energy is that the inner shell electron density does possess a finite extension in space. Thus an outer electron can penetrate inner shell density and the screening effect is reduced. If the inner shell density was contracted right onto the nucleus, then no matter how close the outer electron came to the lithium nucleus, it would always experience only a charge of +1. This dependence of the orbital energies on their l value is aptly called the penetration effect. The electron notations for an atom can be best seen by example. For instance, that for sodium, 11 electrons, is: 1s22s22p63s1. The notation is: n = integer; s, p, d and f = orbital; and superscript = number of electrons. The notation is built up based on aufbau and exclusion principles. Chlorine- 17 electrons is: 1s2,2s2,2p6,3s2,3p5. This works well until the element 21. The filling order can be seen by the following diagram:

29

1s 2s 3s 4s 5s 6s 7s 2p 3p 4p 5p 6p 7p 3d 4d 5d 6d 4f 5f

Thus, Zn, 30 electrons: Zn 1s22s22p63s23p64s23d10 Examination of the Periodic Table shows that Groups 1A and 2A have s valence electrons, Groups 3A, 4A, 5A, 6A, 7A and 8A have p valence electrons. The dtransition elements, 3B, 4B, 5B, 6B, 7B, 8B, 1B and 2B, have d valence electrons. The f-transition elements, Lanthanides and Actinides, have f valence electrons. Categories of electrons: 1. Inner (core) electrons fill all the lower energy levels. 2. Outer electrons are those in the highest energy levels. 3. Valence electrons are outer electrons that take part in chemical reactions. As the principal quantum number increases, i.e., the outer shell moves farther from the nucleus, the atomic size increases. CHAPTER 9 The transfer of electrons between atoms is easiest when there is largest difference in electronegativities, i.e., their tendencies to gain or lose electrons. Basically this means that non-metals take electrons away from metals, i.e., form ionic bonds. Non-metals with small differences in electronegativities share electrons, i.e., form covalent bonds.

30

Metals with metals- In general metal atoms are relatively large, and their few outer electrons are well shielded by filled inner shells. They neither gain nor lose electrons and they dont share them as with covalent compounds. In short, they pool their electrons in an evenly distributed sea of electrons that flows around the metal-ion cores. Unlike the localized electrons in covalent bonds, the delocalized electrons move freely through the piece of metal. Lewis structures show the valence electrons as dots. For instance: 1A Li Na 2A Be Mg 3A B Al 4A C Si 5A N P 6A O S 7A F Cl 8A Ne Ar

The Born-Haber Cycles are simply energy/enthalpy cycles that show how ionic compounds are formed from their constituent elements. They are useful because they allow lattice energies to be calculated theoretically from observations and data collected from experiments. For instance, for NaCl: Na(s) + 1/2 Cl2(g) NaCl (s) The cycle would include atomizing Na and then ionizing it to give Na+(g), and atomizing 1/2Cl2 and then ionizing it to give Cl- (g), with the energies of each step determined. The Hf0 of NaCl can be determined as shown above. The lattice energy is the sum of the atominzation and ionization of the ions minus the Hf0. The lattice energy to break the lattice will be positive because it takes energy to break the lattice (endothermic). The energy to form the lattice will be negative (exothermic) to form the lattice fron its constituent gaseous ions. Coulombs Law states that the electrostatic energy between two charges (A and B) is directly proportional to their masses and inversely proportional to the distance separating them: Charge A x Charge B Electrostatic Energy distance For the lattice, the ions lie as close together as they can, so the distance is the sum of the radii of the cation and the anion. Cation Charge x Anion Charge Electrostatic Energy Cation Radius + Anion Radius

31

As one moves down the Periodic Chart, the atomic radius increases so the lattice energy will also decrease. The cation charge increases as one move to the right in the Periodic Table and the anion charge increases as one move to the left. As the product of these charges increase, the lattice energy will increase. For instance, the lattice energy of LiF = 1050 kcal/mol while that of MgO = 3923 kcal/mol. The covalent bond formation is different. As the atoms approach each other, each nucleus attracts the others electron(s). As they come closer together, repulsions begin between the electrons and nuclei of the atoms. The result is that there is a point where there is a minimum energy that is a balance between the two effects (see Figure 9-10, page 287). Bond Order is the number of electrons pairs being shared by a pair of bonded atoms. A single bond has an order of 1, a double bond an order of 2, a triple bond an order of 3 and a free radical, an unpaired electron, a n order of 0. The bond length of the single bond is longer than that of the double bond that is in turn longer than that of a triple bond. The bond strength is the reverse- the strength of a triple bond is greater than that of a double bond that is stronger than that of a single bond. See Table 9.3, page 290, for data. Covalent bonds within a molecule are very strong, as can be seen from the data in Table 9.3. There are also interactions between molecules, e.g., it takes energy to melt or boil a covalent compound. These intermolecular bonds are MUCH weaker than the intramolecular covalent bonds. In general, covalent bonds occur with an individual molecule. However there are a few covalent compounds where the covalent bonds extend in three dimensions throughout the sample. These are network solids. Examples are diamond (covalently connected carbon atoms) and silicon dioxide (Si-O bonds that extend throughout the sample). These compounds are high melting, similar to ionic compounds, but which are nonconducting, similar to covalent compounds. Reactions involve making an breaking bonds. The difference in the sum of the bond energies of the products and the sum of the bond energies of the reactants is the enthalpy of reaction. For instance:

32

NOTE: Bonds broken are endothermic, bonds formed are exothermic

H H C H H H

3 Cl

Cl

Cl

C Cl

Cl

+ 3 H

Cl

Bond Energy

C-H 1652 kJ

Cl-Cl -243 kJ

C-Cl C-H -339 kJ -413 kJ

H-Cl -1281 kJ

4 x C-H + 3 Cl-Cl 4(1642) + 3(243) = 2381 kJ

3 C-Cl + 1 x C-H + 5 H-Cl 3(-339) + 1(-413) + 3(-1281) = -2711 kJ

0 0 0 Hrxn = Hbonds broken + Hbonds formed = 2381 kJ + (-2711kJ) = -330 kJ

Polar covalent bonds occur when the electronegativity of the atom connected are different. F is more electronegative than H, so the electrons on the bonds are pulled closer to the F, giving a partial negative on the F and a partial positive on the H.
H

F H F

The polar bond can be represented by an arrow, with the longest part on the side of the electronegative atom

An electronegativity scale (EN) was developed by Linus Pauling. The greater the EN difference, the more energy it takes to break that bond. The elctronegativity of atoms increase as one moves to the right and up in the Periodic Chart, and decrease as one moves down and to the left. This means that F is the most electronegative atom. The relative bond polarities show which atom is + and which is Based on the discussion shown above, it is obvious that one can think of polar covalent bonds having partial ionic character that is related to the electronegativity difference (EN). The greater the EN, the greater the partial ionic character. An ionic bond has complete ionic character, while in a covalent bond, the partial ionic character becomes less and less until where the two atoms of a covalent bond are the same, the bond becomes wholly covalent with zero ionic character. This change is a continuum from large EN to zero EN. See Figure 9.22, page 300, for illustrations of this continuum.

33

CHAPTER 10 Determining the number of valence electrons in a covalent structure is relatively simple using the Octet Rule. For instance, the Lewis structure of CCl4 is easily assigned as follows: C has 4 valence electrons and each Cl has 7. Thus the total valence electrons are 32. There are 4 covalent bonds, which consume 8 electrons, leaving 24 as free pairs around the four Cls, or 6 per Cl. The result is as follows. Note that each atom has 8 electron, which satisfies the Octet Rule.

Cl Cl C Cl Cl

Similarly a polyatomic ion such as CO3-2 works out to be:

O C O O

Remember that: H atoms form one bond C atoms form four bonds N atoms form 3 bonds forms two bonds Halogens for one bond when they are surrounding atoms Note that the number of bonds shown above satisfies the Octet Rule. (Studentsconvince yourselves of this.) Also note that the least electronegative atom is the central atom in a polyatomic ion. The CO3-2 structure has 3 Os- one with a double bond and two with single bonds (see structure shown above.) One can write three structures for CO3-2: 34

O C O O O

O C O O

O C O

You will note that the motion of electrons can give these three structures:

O C O O O

O C O O

O C O

(The double headed arrow is used only with electron pair motion.) However CO3-2 has only one structure, so one electron pair is floating and is shared by all three Os, which can be depicted as:
O C O O -2

This is a resonance hybrid which has both attributes of single and double bonds, but which is neither. A mule is a hybrid- the offspring of a mare and a donkey, and it has attributes of each of its parents, but is neither. The three structures shown above are resonance forms that only represent extreme structures, not the real structure, which is represented by the hybrid. (Show the benzene resonance structures and hybrid.) There are three exceptions to the Octet Rule: 1. Group 3A metals are stable with only 6 valence electrons. Examples are BF3 and AlCl3.
F B F F

35

2. Free radicals are molecules with a single unpaired electron. This will give an odd number of valence electrons, so there is no way that there can be the even number of valence electrons required by the Octet Rule. An example is NO2. lone electron
N O O O N O

3. SF6 and PCl5 are perfectly stable compounds. Note that this will require that there will be 12 valence electrons for SF6 and 10 valence electrons for PCl5.
F F S F F F Cl Cl F Cl Cl P Cl

P and S can expand their valence shells to 10 and 12. The formal charges of an atom is its total number of valence electrons minus all of its unshared electrons and half of its shared electrons. For NCO-1:
-2 N 0 C +1 O -1 N 0 C 0 O 0 N 0 C -1 O

2 3 1 o Smaller formal charges are preferable to larger formal charges o Having the same non-zero charges on adjacent atom is not preferred o A more negative formal charge should reside on the more electronegative atom.. Based on these criteria, (2) and (3) are preferred (smaller formal charges). (3) is preferred to (2) since O is more electronegative than N Electronic structures include all electrons, both shared and unshared pairs. Molecular geometry includes only the shared electrons. See pages 316-323 for examples.

36

Valence-Shell Electron-Pair Repulsion (VSEPR) theory states that areas of high electron density repel each other. This explains both the molecular and electronic structures. To determine the molecular shape: 1. Write the Lewis structure from the molecular formula to see the relative placement of atoms and the number of electron groups. 2. Assign an electron-group arrangement by counting all electron groups around the central atom, bonding plus non-bonding. 3. Predict the ideal bond angle from the electron group arrangement and the direction of any deviation caused by lone pairs or double bonds. 4. Draw and name the molecular shape by counting bonding groups and nonbonding groups separately. Again see pages 322-324. See linear and trigonal planar (page 317), tetrahedral (page 3i8), trigonal bipyamidal (page 320) and octahedral (page 321). Dipole moment () is the orientation of a molecule in an electric field with the + pointing to the negative plate and the - pointing to the positive plate. The orientation of the atoms in a molecule results in the polarity of the molecule based on the relationship of polar bonds. Consider H2O and CO2 Both have polar bonds, but H2O is a polar molecule while CO2 is non-polar:
O H

Vector addition of the partial charges in H2O result in the center of charge being below the O and between the Hs to give a polar molecule, but vector addition of partial charges on CO2 results is cancellation of charges to give a non-polar molecule.

CHAPTER 11 Consider the valence electrons of carbon. The distribution is 2s2 2p2 so that the bonding electrons are either s or p so that covalent bonds formed with H, for instance, should be different. In fact, they are all four the same- they are hybridized. The original 2s2 2p2 become all the same and are sp3, i.e., the four electrons are spread out through hybridized orbitals: 37

2p

2p

2p

mix 2s sp3 sp3 sp3 sp3

hybridized C atom Isolated carbon atom The four identical orbitals can form four identical bonds with, e.g., four H atoms. The hybridized orbitals overlap the orbitals of the H atoms to form a valence bonds. This is the valence bond (VB) theory of bonding. The hybridization of one s and three p orbitals is called sp3 hybridization. The molecular geometry is tetrahedral but is shown here as planar for convenience. See Figure 11.4, page 326, for a three dimensional representation. H
1s sp3

H 1s

sp3C sp3 1s H sp3 1s

H For boron there are only three valence electrons, 2s2 2p1. These three electrons are hybridized to give three hybrid orbitals, or sp2. These hybrid bonds are areas of high electron density. These areas occupy space and they are negative electrons. They repel each other to give the least hindered shape. This is Valence Shell Electron Pair Repulsion, VSEPR. See page 36 of these notes. Multiple bonds have two types of bonds.

38

C C

The single bonds between of C are bonds that are all the same. The other bonds that make up the 2nd or 3rd bonds are different and are bonds. The hybridized bonds overlap end-to-end. The unhybridized bonds overlap on the sides.

These representations are rather cluttered. See figures 11.10 and 11.11, page 341, for much better representations. Note that the overlap in bonds is end-to-end while the bond overlap is side-to-side. The end-to-end bond is much stronger than the side-toside, so the electrons are much more reactive than the electrons, which explains the reactivity of double and triple bonds. The side-to-side overlap also pulls the atoms together so that a double bond is shorter than a single bond and a triple bond is shorter than a double bond. Rotation around a single bond is uninhibited, but the side-to-side interaction of the electrons in multiple bonds means that these bonds are rigid. The VB theory explains shape very well, but does not explain magnetic and spectral properties and underestimates the importance of electron delocalization. In order to deal with these phenomena, chemists use molecular orbital (MO) theory. In VB theory, a molecule is pictured as a group of atoms bound together through localized overlap of valence shell atomic orbitals. In MO theory, a molecule is pictured as a collection of nuclei with the electron orbitals delocalized over the entire molecule. The molecule has molecular orbitals with given energy and shape that are occupied by the molecules electrons. However MOs are much harder to visualize than with VBVSEPR representations. The student must use the text to follow the discussion given below, starting on page 344.

See Figure 11.13. Atomic wave functions can either add together to reinforce each other to give a bonding MO or cancel each other out to give an anti-bonding MO. Thus there are two nodes, one bonding and the other anti-bonding (Figure 11.14). The MO 39

diagram is shown in Figure 11.5 for H2. This is for s electrons. The MO diagram for p electrons is shown in Figure 11.18. Note that orbitals lying along a single line give endto-end overlap to give a bonding MO bond with high electron density, i.e., bond. . Orbitals perpendicular to the interrnuclear axis undergo side-to-side overlap to form two bonds, one above and one below the plane of the bond. MO theory redefines bond order. MO Bond order = [(number of e- in bonding MO) (number of e- in anti-bonding MO)] A bond order of zero shows no net stability, and so the species will not form. Bond order >0 shows that the molecular species is stable relative to the separate atoms, and the higher the bond order, the stronger the bond. See Figure 11.16 for illustration as to why He2+ exists but He2 does not. Orbital occupancy corresponds with magnetic properties. If the electrons are unpaired, the substance is attracted to an external magnetic field- paramagnetic. If the electrons are paired, the substance is unaffected by the magnetic field- diamagnetic. Consider the B2 molecule. (See Figure 11.20, page 349) The molecule has 6 outer electrons to place in its MOs. Four fill the 2 and 2* MOs, and the remaining two electrons occupy the two 2p, one in each orbital. (Hunds Rule- the electronic configuration of lowest energy has the maximum number of electrons with parallel spins.) The bond order of B2 is (4-2) = 1. As expected from the unpaired electrons, it is paramagnetic. CHAPTER 12 Whether a substance is a gas, liquid or solid depends on the interplay of intermolecular attractions, which tend to draw the molecules together, and the kinetic energy of the molecules, which tends to disperse them. In a gas, the energy of attraction is small relative to the energy of motions, so the molecules are relatively far apart. A gas moves randomly throughout the container and fills it. Gases are highly compressible, and they flow together and diffuse easily into one another. In a liquid, the attractions are stronger because the particles are virtually in contact. But their kinetic energy still allows them to tumble randomly over and around each other. Therefore liquids conform to the shape of the container, but are essentially non-compressible.

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In a solid, the attractions dominate the motions so much that the particles remain in a position relative to one another, jiggling in place. With the particles fixed, the solid has a particular shape and are non-compressible.

When the forward and reverse rates in a phase change or a reaction, etc, are the same, the condition is called a dynamic equilibrium. For instance: Liquid Solid

Solid-liquid (melting), liquid-gas (vaporization) and solid-gas (sublimation) are examples of dynamic equilibria. These phenomena can be seen in terms of the kinetic molecular theory. The higher the energy of a system, the more liquid will form (melting) and the more gas will form (vaporization and sublimation) because the molecular motion will increase, causing the phase change. Within a phase, the temperature rises because the temperature is a measure of the average kinetic energy. The more the kinetic energy, the faster the movement of particles and so in the liquid phase the vapor pressure increases. The standard heat of fusion, Hfus0, is the standard enthalpy per mole measured at one atmosphere and the temperature of change. Fusion is the temperature at which a liquid turns to solid, and numerically it is equal to the temperature at which a solid turns into a liquid. Similarly, the standard heat of vaporization, Hvap0, is the standard enthalpy per mole measured at one atmosphere and the temperature of change when a substance boils and the standard heat of sublimation, Hsub0, is the standard enthalpy per mole measured at one atmosphere and the temperature of change when a solid turns into a gas. Particle-particle attractive forces affect heat changes within a phase and within phase changes. The higher the attraction, the more heat is required to raise the temperature within a phase, and the more heat is required to give the particles enough kinetic energy to melt a solid or vaporize a liquid. Vapor pressure is the pressure exerted by a liquid at equilibrium with the vapor above the liquid. The definition of a boiling point is that temperature at which the vapor pressure equals the external pressure. Thus, as external pressure is increased, the boiling point is raised. Phase diagrams are shown in Figure 12.8, page 367. The plot is pressure vs temperature and shows the relationship between the three phases. The concept of melting, boiling and subliming is shown graphically.

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Both bonding (intramolecular) forces and intermolecular forces arise from electrostatic attractions between opposite charges. Ion-ion- the very strong attraction between full positive and negative charges is the strongest bond. Non-bonding particle- intermolecular forces are relatively weak because they involve smaller charges that are farther apart. They include dipole-ion or dipole-dipole attraction. The H-bond is not as strong as ion-ion but is much stronger than non-bonding particles. H-bonds occur when hydrogen attached to a highly electronegative atom (O, N or F) is attracted to another highly electronegative atom (O, N or F). The bond is shown by a dotted line. For instance:
O O H H O H H H N H H H CH3 H H N H H H N H

The ease with which the electron cloud of can be distorted is called its polarizability. Smaller atoms (or ions) are less polarizable than larger ones because their electrons are closer to the nucleus and therefore are held more tightly. Polarizability affects all intermolecular forces. Dispersion (London) forces are caused by momentary oscillations of electron charge (think of it as electrons piling up on one side of the particle) and are therefore present in all particles- atoms, ions and molecules. This is called an instantaneous dipole. When an instantaneous dipole is close to another particle, it induces a dipole in the second particle. The result is a synchronized motion of the electrons in the two atoms, which causes an attraction between them. This process occurs with other nearby atoms and thus throughout the sample. The dispersion forces are instantaneous-induced dipole forces. London forces exist between all particles and contribute to the overall attraction of all substances. Calculation show that 85% of the total energy of attraction between HCl is due to London forces and only 15% to dipole-dipole forces. Even for water, estimates show that dispersion forces account for 25% of the total energy of attraction, with 75% from H-bonding. Since 42

polarizability depends on the number of electrons, the larger the atom, the greater the polarizabilty Surface tension occurs because the attractive forces in a liquid operate in all direction in the bulk of the liquid, but only down into the liquid at the surface. Therefore a liquid surface tends to have the smallest surface area and behaves like a taut skin covering the liquid interior. Capillary action occurs when there is competition between intermolectular forces and adhesive forces between the liquid and a capillary tube. Because the cohesive forces (H-bonds) within the liquid, typically water, are lower than the adhesive between the liquid and tube walls, a thin film of water pulls up the wall. The surface tension within the liquid pulls the liquid surface down, giving rise to the familiar meniscus. The meniscus climbs up the tube until gravity pulling down balances the capillary action. Viscosity is resistance to flow by the liquid. The more the intermolecular forces, the more difficult it is for the molecules to slide by each other, which gives rise to resistance to flow, i.e., viscosity. Water has several unique properties that are accounted for by the two bonding pairs and two lone pairs of electrons around the oxygen and the large electronegative difference between oxygen and hydrogen. Water dissolves ionic compounds through ion-dipole interactions that separate the ions and dissolves non-ionic polar compounds, such as ethanol, through Hbonding. Water has a high heat capacity (the measure of heat absorbed by a substance to raise the temperature) and a high heat of vaporization and of fusion (melting) because of H-bonding. Water has high surface tension and capillarity because of H-bonding. Water has unique solid properties, again because of H-bonding. Ice can be liquefies by pressure because of the H-bonding breakdown. The large spaces between water molecules in ice due to H-bonding makes the density less, so ice will float in water at 00C. When ice melts, the tetrahedral arrangement breaks down and the molecules pack closer together in the liquid.

Solids are either crystalline with molecules and atom in an orderly arrangement throughout or amorphous where particles lack long range ordering throughout the sample. 43

The regular pattern throughout a crystal is called the lattice, which consists of all points with identical surroundings. The smallest portion of the lattice that, if repeated in all directions, give the crystal lattice is called the unit cell. The coordination number is the number of of particles that a given particle touches. There are 7 crystal systems and 14 types of unit cells, but only the cubic system will be discussed in this course. There are three types of cubic unit cells: Simple cubic cell- (see Figure 12.24A, page 381). Centers of 8 particles define the corners of the cube. Attractions pull the particles together so that they touch along the edges of the cube, but do not touch diagonally. The coordination number is of each particle is 6- 4 in its own layer and one in the layer above and one in the layer below. Body centered cubic- (see Figure 12.24B, page 381). Particles lie at each corner and in the center of the cube. Those at the corner do not touch each other but do touch the one in the center, so coordination number of each particle is 8 , 4 particles above and 4 below. Face centered cube-- (see Figure 12.24C, page 381). Particles lie at each corner and in the center of the face. The particles at the corner touch those in the faces but not each other. The coordination number is 12. There are several types of crystalline solids. See pages 384-387 for illustrations. Atomic solids are held together only by dispersion forces. Noble gases are the only examples, and their melting points are very low. Molecular solids are molecules held together by dipole-dipole, dispersion forces and H-bonding- either singly or in combination. Their melting points are much higher than those of atomic solids, but are less than ionic solids. Ionic solids held together by whole or partial charged particles. These ionic bonds are much stronger than the van der Waals forces of atom or molecular solids. Cations are surrounded by as many anions as possible and vice-versa. Thus the unit cell has the same ratio cation/anion ratio as the empirical formula. Metallic solids are bound together by powerful metallic forces. The electrons are delocalized, which gives rise to the high electrical and thermal conductivity. Metals have varying melting points based on how tightly the atoms are packed together. Another view of metallic bonds is the MO model. See Figure 12-34, page 389, for an illustration of the MO model. Network covalent solids do not have separate particles; strong covalent bonds bind atoms together in a network. Diamond is the most obvious example, but by far the most important network solids are the silicates, e.g., quartz.

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The MO model can be applied to explain conductors, semiconductors and insulators. See Figure 12.35, page 390, for illustrations. In the MO model, there are two bandsthe valence band, where the valence electrons lie, and the conduction bands, MOs formed by the combination of the metal atoms in the lattice. When the conduction and valence bands no gap between them, the electrons are free to move in both bands so conduction is facile. NOTE: When temperature rises, random motion of the atoms increases so that the electron movement is hindered, and the conductivity decreases. When there is a relatively small gap between the conduction and valence bands, the result is semiconductivity where thermally excited electrons can jump the gap. In this case, conductivity increases with temperature. When there is a large gap between the conduction and valence bands, the gap is too large for the electrons can jump the gap so the result is insulation.

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