Syllabus Chemistry 102 Spring 2009Sec. 501, 503 (MWF 9:10-10:00, 12:40-1:30) RM 100 HELD

Professor: Dr. Earle G. Stone Office: Room 123E Heldenfels (HELD) Telephone: 845-3010 (no voice mail) or leave message at 845-2356email: stone@mail.chem.tamu.edu (put CHEM 101-Sec. # + subject in subject line of your email)Office Hours: HELD 408: Wed. 8:00-10:50 AMI.A. Esther OcolaS.I. Leader: Analise Castellano

Suggested Course Materials:Chemistry and Chemical Reactivity, Any Edition, by KotzHelpful1. Dictionary of Chemistry Or online dictionary2. Mastering the Fundamental Skills General Chemistry I as a Second Language

Useful LaterAs A Second Language Organic Chemistry I by Klein, There is a O-chem II and a Physics as a Second Language (Algebra based or Calculus based) for those who will have to take those classes.Ebook includesOnline tutorialSolution manual$45 per semester

Hardbound ~$160Solution Manual ~$40Online Tutor ~$45

AllCollege493100%BIMS14930%2012260Science11824%2011193GEST5712%201033Ag BICH, NUSC, GENE357%whoop20099Engineering5511%RIP20080Education184%495Geosciences204%Liberal Arts102%73% pre-somethingAgriculture other255%27% widely divergingArchitecture00% academic fociBusiness51%501503College242100%BIMS8233%BIMS6728%Science5622%Science6226%GEST2811%Ag BICH, NUSC, GENE2213%Ag BICH, NUSC, GENE135%GEST319%Engineering2811%Engineering2711%Education94%Education94%Geosciences146%Geosciences62%Liberal Arts94%Liberal Arts52%Agriculture other94%Agriculture other104%Architecture00%Architecture00%Business21%Business31%BIMS8233%

May 11, Monday 8-10 a.m. MWF 9:10-10 a.m. May 11, Monday 10:30 a.m.-12:30 p.m. MWF 12:40-1:30 p.m.

WeekDateChapterEnd of Chapter Questions 6th1 21-JanSyllabus 23-JanChapter 19 1,5,29,39,49,592 26-Jan 28-Jan30-Jan3 2-FebChapter 14Sect 14.1-14.41,2,11,21,31,35,49, 51,93 4-Feb 6-Feb4 9-Feb 11-FebExam #1 Chapters 14, 1913-FebChapter 151,3,7,9,11,17,23,27,41,43,47,53,55,87,895 16-Feb 18-Feb 20-Feb6 23-Feb 25-FebChapter 161,5,9,19,23,25,33, 49,63 27-Feb7 2-Mar 4-Mar 6-Mar8 9-MarExam #2 Chapters 15, 16 11-MarChapter 177,11,15,23,27,35 13-Mar

WeekDateChapterEnd of Chapter Questions 6th9 14-Mar through 22-Mar Spring Break10 23-MarChapter 1761,71,93,107,109 25-Mar 27-Mar11 30-MarChapter 181,3,9,15,19,33,35,37,43,53,69,75,85, 991-Apr 3-Apr12 6-Apr 8-Apr 10-AprReading Day13 13-AprChapter 1815-AprExam # 3 Chapters 17, 18 17-AprChapter 201,3,5,13,25,31,45

14 20-Apr 22-Apr 24-Apr15 27-Apr 29-AprExam # 4 Chapter 201-MayReading Day16 4-7 MayReading Days1711-MayFinal Sect 501 8-10 a.m. Final Sect 503 10:30 a.m.-12:30 p.m

Grading:

Your grade will be based on Four one-hour examinations (each worth 200 points) A final examination (400 points)

Major Examination Schedule Spring 2009:Wed.Feb. 11 Major Exam No.1Mon.Mar. 9 Major Exam No.2Wed.Apr. 15 Major Exam No.3Wed.Apr. 29 Major Exam No.4

Final ExamsSection 501Mon. May 11 8:00 to 10:00Section 503Mon. May 11 10:30 to 12:30

2% 16% 50% 84% 98% Percentile RankABCD,F,Q,WA is > average + 1 sB is > average but less than average + 1 sC = > average - 1 s but less than average What you are used toThe way the real world works+3%

Problem - A situation that presents difficulty, uncertainty, or perplexity:

Question - A request for data: inquiry, interrogation, query.

Answer - A spoken or written reply, as to a question.

Solution - Something worked out to explain, resolve, or provide a method for dealing with and settling a problem.The mere formulation of a problem is far more often essential than its solution, which may be merely a matter of mathematical or experimental skill. To raise new questions, new possibilities, to regard old problems from a new angle requires creative imagination and marks real advances in science. Albert Einstein

Numbers Significant Figures, Rounding Rules, Accuracy, Precision, Statistical Treatment of the Data

Units 5 of the 7Time seconds Length Meters Density?Mass grams Molecular Weight (Mass)Amount Moles Mole Ratio, Molarity, molalityTemperature Kelvins Vocabulary Approximately 100 new terms or words and applying new or more rigid definitions to words you may already own.

Principles (Theories and Laws) Stoichiometry, Quantum Theory, Bonding, Chemical Periodicity, Solutions, Thermodynamics, Intermolecular Forces, Gas Laws, Collogative Properties, Kinetics, Equilibrium, Electrochemistry

cp = q/mDTrate = k[A]m[B]nE = q + wDG = DH TDSEocell = Ecathode = EanodePV = nRT%yield = actual/theoretical * 100%K =DT = Kmi

Chemistry ReviewThe prediction of Chemical Reaction in general relies on

The Law of Conservation of Mass this leads toStoichiometry that allows us to compare apples and orangesEquilibrium predictions of reversible reactions which leads toKinetics allowing us to determine how fast the reaction will occur

The Law of Conservation of Energy this leads to Thermodynamics which is stated in 3 lawsFirst Law the energy of the Universe is constant

Some Thermodynamic TermsThermodynamics - The study of the relationship between heat, work, and other forms of energy.

Thermochemistry - A branch of thermodynamics which focuses on the study of heat given off or absorbed in a chemical reaction.

Temperature - An intensive property of matter; a quantitative measurement of the degree to which an object is either "hot" or "cold".

There are 3 scales for measuring temperature Fahrenheit - relative 32 F is the normal freezing point temperature of water; 212 F is the normal boiling point temperature of water. Celsius (centigrade) - relative 0 C is the normal freezing point temperature of water; 100 C is the normal boiling point temperature of water. Kelvin - absolute 0 K is the temperature at which the volume and pressure of an ideal gas extrapolate to zero.

Some Thermodynamic Terms

Some Thermodynamic Terms

Caloric Theory of Heat

Served as the basis of thermodynamics. Is now known to be obsolete Based on the following assumptions Heat is a fluid that flows from hot to cold substances. Heat has a strong attraction to matter which can hold a lot of heat. Heat is conserved. Sensible heat causes an increase in the temperature of an object when it flows into the object. Latent heat combines with particles in matter (causing substances to melt or boil) Heat is weightless.

The only valid part of the caloric theory is that heat is weightless.

Heat is NOT a fluid, and it is NOT conserved. Some Thermodynamic Theories

Divides the universe into two parts:

System. - The substances involved in the chemical and physical changes under investigation: In chemistry lab, the system is the REACTANTS inside the beaker.

Surroundings - Everything not included in the system, i.e. the rest of the universe. A BOUNDARY separates the system and the surroundings from each other and can be tangible or imaginary.

Heat is something that is transferred back and forth across boundary between a system and its surroundings

Heat is NOT conserved. Some Thermodynamic TheoriesKinetic Theory of Heat

The set of conditions that specify all of the properties of the system is called the thermodynamic state of a system. For example the thermodynamic state could include:The number of moles and identity of each substance.The physical states of each substance.The temperature of the system.The pressure of the system.Some Thermodynamic Theories The kinetic theory of heat is based upon the last postulate in the kinetic molecular theory which states that the average kinetic energy of a collection of gas particles is dependent only upon the temperature of the gas.

where R is the ideal gas constant (0.08206 L-atm/mol-K) and T is temperature (Kelvin) The kinetic theory of heat can be summarized as follows:

When heat enters a system, it causes an increase in the speed at which the particles in the system move.

Standard States and Standard Enthalpy ChangesThermochemical standard state conditionsThe thermochemical standard T = 298.15 K.The thermochemical standard P = 1.0000 atm.Be careful not to confuse these values with STP.Thermochemical standard states of matterFor pure substances in their liquid or solid phase the standard state is the pure liquid or solid.For gases the standard state is the gas at 1.00 atm of pressure.For gaseous mixtures the partial pressure must be 1.00 atm.For aqueous solutions the standard state is 1.00 M concentration.

Some Thermodynamic TermsState Functions are independent of pathway:T (temperature), P (pressure), V (volume), E (change in energy), H (change in enthalpy the transfer of heat), and S (entropy)

Examples of non-state functions are:n (moles), q (heat), w (work)

There are two basic ideas of importance for thermodynamic systems.Chemical systems tend toward a state of minimum potential energy.Chemical systems tend toward a state of maximum disorder.The Three Laws of Thermodynamics

The First Law of ThermodynamicsThe first law is also known as the Law of Conservation of Energy.

Energy is neither created nor destroyed in chemical reactions and physical changes.

The energy of the universe does not change. The energy in a system may change, but it must be complemented by a change in the energy of its surroundings to balance the change in energy.

The term internal energy is often used synonymously with the energy of a system. It is the sum of the kinetic and potential energies of the particles that form the system. The last postulate in the kinetic molecular theory states that the average kinetic energy of a collection of gas particles is dependent only upon the temperature of the gas.

Esys = KEsys + PEsys

KE kinetic energy: translational, rotational, vibrationalPE energy stored in bonds (Bond energy)The First Law of Thermodynamics

If a system is more complex than an ideal gas, then the internal energy must be measured indirectly by observing any changes in the temperature of the system. The change in the internal energy of a system is equal to the difference between the final and initial energies of the system:

The equation for the first law of thermodynamics can be rearranged to show the energy of a system in terms of the energy of its surroundings. This equation indicates that the energy lost by one must equal the energy gained by the other:

The First Law of Thermodynamics

The energy of a system can change by the transfer of work and or heat between the system and its surroundings. Any heat that is taken, given off, or lost must be complemented by an input of work to make up for the loss of heat. Conversely, a system can be used to do any amount of work as long as there is an input of heat to make up for the work done. This equation can be used to explain the two types of heat that can be added to a system: Heat can increase the temperature of a system. This is sensible heat. Heat that does ONLY WORK on a system is latent heat. The First Law of Thermodynamics

Exchange of heat (q) Endothermic and exothermicWork is performed (w)DE = q + wSolids, Liquids, SolutionsChanges in volume are negligibleTherefore w is effectively zero

DE = q + 0 = DH

DH is change in enthalpy which is the transfer of heat and is measuredexperimentally by determining changesin temperature.GasesWhy only gases? Because changes in volume results in workw = FdF = Pressure x Area d = DhW = P (A Dh) = DVThe First Law of Thermodynamics

By convention except for some engineers whose frame of reference is the work done on the surroundings.A(hf-hi)0 DVw = -PDVDE =DH + w = DH PDV = DH D(PV)

DE = DH D(PV) Constant Volumew = -PDVDV = 0DE = DHCheck the temperature change Constant PressureApply some stoichiometry And the Ideal Gas LawPV=nRTD(PV)=D(nRT)Hold Temperature constant k1D(PV)=D(nRk1)Combine constants and multiply through by -1-D(PV) = -R1Dnw = -PDV = -R1DnDE = DH + w = DH - R1Dn

DEDHDnDE = DH exothermicNo changeDE = DH endothermicNo changeDE > DH exothermicincreaseDE > DH endothermicdecreaseDE < DH exothermicdecreaseDE < DH endothermicincrease

Thermochemical EquationsThermochemical equations are a balanced chemical reaction plus the H value for the reaction. For example, this is a thermochemical equation.The stoichiometric coefficients in thermochemical equations must be interpreted as numbers of moles.

1 mol of C5H12 reacts with 8 mol of O2 to produce 5 mol of CO2, 6 mol of H2O, and releasing 3523 kJ is referred to as one mole of reactions.

Thermochemical EquationsWrite the thermochemical equation for CuSO4(aq) + 2NaOH(aq) Cu(OH)2(s) + Na2SO4(aq)

50.0mL of 0.400 M CuSO4 at 23.35 oC 50.0mL of 0.600 M NaOH at 23.35 oC Tfinal 25.23oC CH2O = 4.184 J/goCDensity final solution = 1.02 g/mL

The Second Law of ThermodynamicsThe second law of thermodynamics states, In spontaneous changes the universe tends towards a state of greater disorder.Spontaneous processes have two requirements:The free energy change of the system must be negative.The entropy of universe must increase.Fundamentally, the system must be capable of doing useful work on surroundings for a spontaneous process to occur.Changes in S are usually quite small compared to E and H. Notice that S has units of only a fraction of a kJ while E and H values are much larger numbers of kJ.

Entropy (S) - A measure of the disorder in a system. Entropy is a state function.

where k is a proportionality constant equal to the ideal gas constant (R) divided by Avogadro's number (6.022 x 10-23)

and lnW is the natural log of W, the number of equivalent ways of describing the state of a system.

In this reaction, the number of ways of describing a system is directly proportional to the entropy of the system.

The Second Law of Thermodynamics

Number of Equivalent Combinations for Various Types of Poker HandsThe Second Law of Thermodynamics

HandWln WRoyal flush (AKQJ10 in one suit)41.39Straight flush (five cards in sequence in one suit)36 3.58Four of a kind624 6.44Full house (three of a kind plus a pair)3,7448.23Flush (five cards in the same suit)5,1088.54Straight (five cards in sequence)10,200 9.23Three of a kind54,912 10.91Two pairs123,552 11.72One pair 1,098,24013.91No pairs1,302,540 14.08Total2,598,960

Entropy of Reaction (DS) The difference between the sum of the entropies of the products and the sum of the entropies of the reactants:

In the above reaction, n and m are the coefficients of the products and the reactants in the balanced equation.As with H, entropies have been measured and tabulated in Appendix L as So298. When:S > 0 disorder increases (which favors spontaneity).S < 0 disorder decreases (does not favor spontaneity).The Second Law of Thermodynamics

Natural processes that occur in an isolated system are spontaneous when they lead to an increase in the disorder, or entropy, of the system.

Isolated system - System in which neither heat nor work can be transferred between it and its surroundings. This makes it possible to ignore whether a reaction is exothermic or endothermic. If DSsys > 0, the system becomes more disordered through the course of the reaction If DSsys < 0, the system becomes less disordered (or more ordered) through the course of the reaction.

The Second Law of Thermodynamics

There are a few basic principles that should be remembered to help determine whether a system is increasing or decreasing in entropy. Liquids are more disordered than solids. WHY? - Solids have a more regular structure than liquids. Gases are more disordered than their respective liquids. WHY? - Gases particles are in a state of constant random motion. Any process in which the number of particles in the system increases consequently results in an increase in disorder. In general for a substance in its three states of matter:Sgas > Sliquid > SsolidThe Second Law of Thermodynamics

Does the entropy increase or decrease for the following reactions?

Answers: INCREASES - The number of particles in the system increases, i.e. one particle decomposes into two. In addition, one of the products formed is a gas which is much more disordered than the original solid. DECREASES - The number of particles in the system decreases, i.e. there are four moles of gas reactants and only 2 moles of gas products. INCREASES - The number of particles in the system increases, i.e. the single reactant dissociates into two ion particles. In addition, the ions in the ionic solid are organized in a rigid lattice structure whereas the ions in aqueous solution are free to move randomly through the solvent. DECREASES - The reactant changes from a gas to a liquid, and gases are more disordered than their respective liquids. The Second Law of Thermodynamics

Entropy, SThe Third Law of Thermodynamics states, The entropy of a pure, perfect, crystalline solid at 0 K is zero.This law permits us to measure the absolute values of the entropy for substances.To get the actual value of S, cool a substance to 0 K, or as close as possible, then measure the entropy increase as the substance heats from 0 to higher temperatures.The coldest place in nature is the depths of outer space. There it is 3 degrees above Absolute Zero. Notice that Appendix L has values of S not S.Bose-Einstein Condensation in a gas: a new form of matter at the coldest temperatures in the universe...

A. Einstein S. Bose Predicted 1924... ...Created 1995 Cornell and Wieman cooled a small sample of atoms down to only a few billionths (0.000,000,001) of a degree above Absolute Zero

Entropy, SBEC

Entropy and TemperatureS increases a large amount with phase changes

Entropy, SEntropy changes for reactions can be determined similarly to H for reactions.This is only true, i.e. conserved, for the system. This is not included for the surroundings.

Entropy, SCalculate the entropy change for the following reaction at 25oC. Use Appendix L.

Entropy, SCalculate So298 for the reaction below. Use Appendix L.

Free Energy Change, G, and SpontaneityIn the mid 1800s J. Willard Gibbs determined the relationship of enthalpy, H, and entropy, S, that best describes the maximum useful energy obtainable in the form of work from a process at constant temperature and pressure.The relationship also describes the spontaneity of a system.The relationship is a new state function, G, the Gibbs Free Energy.DG = DH-TDS at constant T and P

Free Energy Change, G, and SpontaneityThe change in the Gibbs Free Energy, G, is a reliable indicator of spontaneity of a physical process or chemical reaction.G does not tell us how quickly the process occurs.Chemical kinetics, the subject of Chapter 16, indicates the rate of a reaction.Sign conventions for G.G > 0 reaction is nonspontaneousG = 0 system is at equilibriumG < 0 reaction is spontaneous

Free Energy Change, G, and SpontaneityChanges in free energy obey the same type of relationship we have described for enthalpy, H, and entropy, S, changes.

Free Energy Change, G, and SpontaneityCalculate Go298 for the reaction in Example 15-8. Use Appendix L.

The Temperature Dependence of SpontaneityFree energy has the relationship G = H -TS.Because 0 H 0 and 0 S 0, there are four possibilities for G.

Forward reaction H S G spontaneity< 0 > 0 < 0 at all Ts.< 0 < 0 T dependent at low Ts.> 0 > 0 T dependent at high Ts.> 0 < 0 > 0 Nonspontaneous at all Ts.

DG = 0 EquilibriumDG < 0 SpontaneousDG > 0 Non SpontaneousSpontaneity is favored whenDH < 0 DS > 0G = H -TS

DGDHDS

Low THigh T

The Temperature Dependence of SpontaneityCalculate So298 for the following reaction C3H8(g) + 5 O2(g) ) 3 CO2(g) + 4 H2O(g)We know that Ho298= -2219.9 kJ, and that Go298= -2108.5 kJ.