Syllabus Chemistry 102 Spring 2009 Sec. 501, 503 (MWF 9:10-10:00, 12:40-1:30) RM 100 HELD Professor: Dr. Earle G. Stone Office: Room 123E Heldenfels (HELD)

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 845-2356

email: [email protected] (put CHEM 101-Sec. # + subject in subject line of

your email)Office Hours: HELD 408: Wed. 8:00-10:50 AM

I.A. Esther OcolaS.I. Leader: Analise Castellano

mailto:[email protected]

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

AllCollege 493 100%BIMS 149 30% 2012 260Science 118 24% 2011 193GEST 57 12% 2010 33Ag BICH, NUSC, GENE 35 7% whoop 2009 9Engineering 55 11% RIP 2008 0Education 18 4% 495Geosciences 20 4%Liberal Arts 10 2% 73% pre-somethingAgriculture other 25 5% 27% widely diverging

Architecture 0 0% academic foci

Business 5 1%501 503

College 242 100% BIMS 82 33%BIMS 67 28% Science 56 22%Science 62 26% GEST 28 11%Ag BICH, NUSC, GENE 22 13% Ag BICH, NUSC, GENE 13 5%GEST 31 9% Engineering 28 11%Engineering 27 11% Education 9 4%Education 9 4% Geosciences 14 6%Geosciences 6 2% Liberal Arts 9 4%Liberal Arts 5 2% Agriculture other 9 4%Agriculture other 10 4% Architecture 0 0%Architecture 0 0% Business 2 1%Business 3 1% BIMS 82 33%

Week Date ChapterEnd of Chapter Questions 6th

1 21-Jan Syllabus

23-Jan

Chapter 19 1,5,29,39,49,592

26-Jan

28-Jan

30-Jan

3

2-FebChapter 14Sect 14.1-14.4

1,2,11,21,31,35,49, 51,93

4-Feb

6-Feb

4

9-Feb

11-Feb Exam #1 Chapters 14, 19

13-Feb

Chapter 151,3,7,9,11,17,23,27,41,43,47,53,55,87,89

5

16-Feb

18-Feb

20-Feb

6

23-Feb

25-Feb

Chapter 161,5,9,19,23,25,33, 49,63

27-Feb

7

2-Mar

4-Mar

6-Mar

8

9-Mar Exam #2 Chapters 15, 16

11-MarChapter 17 7,11,15,23,27,35

13-Mar

Week Date ChapterEnd of Chapter Questions 6th

9 14-Mar through 22-Mar Spring Break

10

23-MarChapter 17

61,71,93,107,109 25-Mar

27-Mar

11

30-Mar

Chapter 181,3,9,15,19,33,35,37,43,53,69,75,85, 99

1-Apr

3-Apr

12

6-Apr

8-Apr

10-Apr Reading Day

13

13-Apr Chapter 18

15-Apr Exam # 3 Chapters 17, 18

17-Apr

Chapter 201,3,5,13,25,31,45

14

20-Apr

22-Apr

24-Apr

15

27-Apr

29-Apr Exam # 4 Chapter 20

1-May Reading Day

16 4-7 May Reading Days

17 11-MayFinal Sect 501 8-10 a.m. Final Sect 503 10:30 a.m.-12:30 p.m

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.

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 Rank

ABCD,F,Q,W

A is > average + 1B is > average but less than average + 1 C = > average - 1 but less than average

What you are used toWhat you are used toThe way the real world worksThe way the real world works

60%60%

72%72%

8484%%

96%96%48%48%

100%100%

9090%%

80%80%

70%70%

6060%% A

BC

D

++3%3%

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

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

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

Solution - Something worked out to explain, resolve, or Solution - Something worked out to explain, resolve, or provide a method for dealing with and settling a provide a method for dealing with and settling a problem.problem.

The mere formulation of a problem is far more The mere formulation of a problem is far more often essential than its solution, which may be often essential than its solution, which may be merely a matter of mathematical or experimental merely a matter of mathematical or experimental skill. To raise new questions, new possibilities, to skill. To raise new questions, new possibilities, to regard old problems from a new angle requires regard old problems from a new angle requires creative imagination and marks real advances in creative imagination and marks real advances in science. science.

Albert EinsteinAlbert Einstein

http://www.youtube.com/watch?v=kO8x8eoU3L4

(m)c (ms-1)

E =

[C]c[D]d

[A]a[D]b

1.1. Numbers – Significant Figures, Rounding Rules, Accuracy, Numbers – Significant Figures, Rounding Rules, Accuracy, Precision, Statistical Treatment of the DataPrecision, Statistical Treatment of the Data

2.2. Units – 5 of the 7Units – 5 of the 71.1. Time – seconds Time – seconds 2.2. Length – Meters Density?Length – Meters Density?3.3. Mass – grams Mass – grams Molecular Weight Molecular Weight

(Mass)(Mass)4.4. Amount – Moles Amount – Moles Mole Ratio, Mole Ratio,

Molarity, molalityMolarity, molality5.5. Temperature – Kelvins Temperature – Kelvins

3.3. Vocabulary – Approximately 100 new terms or words and Vocabulary – Approximately 100 new terms or words and applying new or more rigid definitions to words you may applying new or more rigid definitions to words you may already own.already own.

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

ccpp = q/m = q/mTT rate = k[A]rate = k[A]mm[B][B]nn ∆E ∆E = q + w= q + wG = G = H – TH – TSS EEoo

cellcell = E = Ecathodecathode = E = Eanodeanode

PV = nRTPV = nRT %yield = actual/theoretical * 100%%yield = actual/theoretical * 100% K K ==T = KT = Kmimi

Chemistry Review

The prediction of Chemical Reaction in general relies on

1. The Law of Conservation of Mass – this leads to• Stoichiometry that allows us to compare apples and

oranges• Equilibrium predictions of reversible reactions which

leads to• Kinetics allowing us to determine how fast the

reaction will occur

2. The Law of Conservation of Energy – this leads to Thermodynamics which is stated in 3 laws1. First Law – the energy of the Universe is

constant

Some Thermodynamic Terms

ThermodynamicsThermodynamics - The study of the relationship between heat, work, and other forms of energy.

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

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

1.There are 3 scales for measuring temperature •FahrenheitFahrenheit - relative

•32 F is the normal freezing point temperature of water; 212 F is the normal boiling point temperature of water.

•CelsiusCelsius (centigrade) - relative •0 C is the normal freezing point temperature of water; 100 C is the normal boiling point temperature of water.

•KelvinKelvin - absolute •0 K is the temperature at which the volume and pressure of an ideal gas extrapolate to zero.



Caloric Theory of HeatCaloric 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

1. Divides the universe into two parts:

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

B. SurroundingsSurroundings - Everything not included in the system, i.e. the rest of the universe.

2.A BOUNDARYBOUNDARY separates the system and the surroundings from each other and can be tangible or imaginary.

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

B. Heat is NOT conserved.

Some Thermodynamic TheoriesKinetic Theory of HeatKinetic Theory of Heat

• The set of conditions that specify all of the properties of the

system is called the thermodynamic state of a thermodynamic state of a systemsystem.

• 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 Changes

1.1. Thermochemical standard state conditionsThermochemical standard state conditions• The thermochemical standard T = 298.15 K.• The thermochemical standard P = 1.0000 atm.

– Be careful not to confuse these values with STP.

2.2. Thermochemical standard states of matterThermochemical standard states of matter• For 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.


1. State 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)

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

There are two basic ideas of importance for thermodynamic systems.

1. Chemical systems tend toward a state of minimum minimum potential energy.potential energy.

2. Chemical systems tend toward a state of maximum maximum disorderdisorder.

The Three Laws of Thermodynamics

The First Law of Thermodynamics

• The first law is also known as the Law of Conservation of Law of Conservation of

Energy.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

1. KE – kinetic energy: translational, rotational, vibrational

2. PE – energy stored in bonds (Bond energy)


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 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:

1. Heat can increase the temperature of a system. This is sensible heat. 2. Heat that does ONLY WORK on a system is latent heat.


1. Exchange of heat (q) Endothermic and exothermic

2. Work is performed (w)E = q + w

Solids, Liquids, SolutionsChanges in volume are negligibleTherefore w is effectively zero

E = q + 0 = H

H 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 work

w = FdF = Pressure x Area d = h

W = P (A h) = V

h


heat transfer outheat transfer out(exothermic), -q(exothermic), -q

heat transfer inheat transfer in(endothermic), +q(endothermic), +q

SYSTEMSYSTEM∆E = q + w

w transfer inw transfer in(+w)(+w)Compression of systemCompression of system

w transfer outw transfer out(-w)(-w)Expansion of systemExpansion of system

By convention except for some engineers whose frame of reference is the work done on the surroundings.hi hf

A(hf-hi)<0 V

hihf

A(hf-hi)>0 V

w = -PVE =H + w = H – PV = H – PV)

E = H – PV)

Constant Volumew = -PVV = 0

E = HCheck the temperature change

Constant PressureApply some stoichiometry

And the Ideal Gas LawPV=nRT

(PV)=(nRT)Hold Temperature constant k1

(PV)=(nRk1)Combine constants and multiply through by -1

(PV) = -R1nw = -PV = -R1n

E = H + w = H - R1n

E H n

E = H exothermic No change

E = H endothermic

No change

E > H exothermic increase

E > H endothermic

decrease

E < H exothermic decrease

E < H endothermic

increase

Thermochemical Equations• 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.

moles 6 moles 5 moles 8 mole 1

kJ 3523 OH 6 CO 5O 8 HC )(22(g)2(g))12(5

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/goC

Density final solution = 1.02 g/mL

The Second Law of Thermodynamics• The second law of thermodynamics

states, “In spontaneous changes In spontaneous changes the universe tends towards a the universe tends towards a state of greater disorderstate of greater disorder..”

• Spontaneous processes have two requirements:1. The free energy change of the system

must be negative.2. 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

Hand W ln WRoyal flush (AKQJ10 in one suit)

4 1.39

Straight flush (five cards in sequence in one suit)

36 3.58

Four of a kind 624 6.44Full house (three of a kind plus a pair)

3,744 8.23

Flush (five cards in the same suit)

5,108 8.54

Straight (five cards in sequence)

10,200 9.23

Three of a kind 54,912 10.91Two pairs 123,552 11.72One pair 1,098,240 13.91No pairs 1,302,540 14.08

Total 2,598,960

Number of Equivalent Combinations for Various Types of Poker Hands


Entropy of Reaction (S) •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 So

298. When:

S > 0 disorder increases (which favors spontaneity).S < 0 disorder decreases (does not favor spontaneity).


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 Ssys > 0, the system becomes more disordered through the course of the reaction

If Ssys < 0, the system becomes less disordered (or more ordered) through the course of the reaction.


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 > Ssolid


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.


Entropy, S• The 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, S

BEC

Entropy and Temperature

S increases slightly with T

S increases a large amount with phase changes

Entropy, S• Entropy 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.

oreactants

n

oproducts

n

o298 SnSnS

Entropy, S• Calculate the entropy change for the following

reaction at 25oC. Use Appendix L.

Entropy, S• Calculate So

298 for the reaction below. Use Appendix L.

Free Energy Change, G, and Spontaneity

• In the mid 1800’s 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.

G = H-TS at constant T and P


• The 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 nonspontaneous G = 0 system is at equilibrium G < 0 reaction is spontaneous


• Changes in free energy obey the same type of relationship we have described for enthalpy, H, and entropy, S, changes.

0reactants

n

0products

n

0298 GnGnG


• Calculate Go298 for the reaction in Example 15-8.

Use Appendix L.

The Temperature Dependence of Spontaneity

• Free 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 T’s.< 0 < 0 T dependent at low T’s.> 0 > 0 T dependent at high T’s.> 0 < 0 > 0

Nonspontaneous at all T’s.

G H S

Low T

High T

G = 0 EquilibriumG < 0 SpontaneousG > 0 Non Spontaneous

). .

). .

). .

). .). .

). . ). . ). .

). .

). .

Spontaneity is favored whenH < 0 S > 0

G = H -TS

The Temperature Dependence of Spontaneity

• Calculate 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.

Documents

Syllabus Chemistry 102 Spring 2009 Sec. 501, 503 (MWF 9:10-10:00, 12:40-1:30) RM 100 HELD Professor: Dr. Earle G. Stone Office: Room 123E Heldenfels (HELD)