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1 Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. proceeds Equilibrium How far a rxn proceeds towards completion Thermodynamics Study of energy relationships & changes which occur during chemical & physical processes

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Page 1: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Chapter 19Chemical Thermodynamics

Kinetics

How fast a rxn. proceeds

Equilibrium

How far a rxn proceedstowards completion

Thermodynamics

Study of energy relationships &changes which occur duringchemical & physical processes

Page 2: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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A) First Law of Thermodynamics

Law of Conservation of Energy :

Energy can be neither created nor destroyed but may be converted fromone form to another.

Energy lost = Energy gained

by system by surroundings

1) Internal Energy, E

E = total energy of the system

Actual value of E cannot be determined

Only )E

Page 3: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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2) Relating )E to Heat & Work

2 types of energy exchanges occurbetween system & surroundings

Heat & Work

+ q : heat absorbed, endothermic

! q : heat evolved, exothermic

+ w : work done on the system

! w : work done by the system

a) First Law

)E = q + w

Page 4: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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3) System and Surroundings

System = portion we single out for study

- focus attention on changes which occur w/in definite boundaries

Surroundings = everything else

System : Contents of rx. flask

Surround. : Flask & everything outside it

Agueous soln. rx :

System : dissolved ions & moleculesSurround : H2O that forms the soln.

Page 5: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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B) Thermodynamic State & State Functions

Thermodynamic State of a System

defined by completely specifyingALL properites of the system

- P, V, T, composition, physical st.

1) State Function

prop. of a system determinedby specifying its state.

depends only on its presentconditions & NOT how it got there

)E = Efinal ! Einitial

independent of path takento carry out the change

- Also is an extensive prop.

Page 6: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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C) Enthalpy

In ordinary chem. rx., work generallyarises as a result of pressure-volumechanges

Inc. vol. & system does work againstpressure of the atmosphere

Constant Pressure

w = ! P )V

Negative because work done by system

Page 7: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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)E = q ! P )V

1) )E at Constant Volume

)E = qv

2) )E at Constant Pressure :

)E = qp ! P )V

qp = )E + P)V

Page 8: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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3) Enthalpy, H

H = E + PV

Change in enthalpy at constant P is:

)H = )E + P )V

&

)H = qp

Can think of as heat content

state fnc. & is extensive

Page 9: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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D) Enthalpies of Reaction

)Hrxn = Hproducts ! Hreactants

2 H2(g) + O2(g) 6 2 H2O(R) )H = !572 kJ

Thermochemical eqn.

Physical states are given and energyassociated w. rx. written to right

- MUST give physical states

If product is H2O(g), )H = !484kJ

)H corresponds to molar quantities given in eqn. as written

H2(g) + ½ O2(g) 6 H2O(R) )H = !286 kJ

Page 10: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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1) Guidelines

a) Enthalpy is extensive

Multiply a rxn by some factor the)H is multiplied by that factor

b) )Hreverse = ! )Hforward

c) Enthalpy is a state function

)H depends on the states ofreactants and products.

Page 11: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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E) Hess’s Law

)H is a state fnc.

Same whether the process occurs asa single step or as a series of steps

The )Hrxn is the sum of the )H’sfor the individual steps.

)Hrx = G )Hsteps Steps

* Add chem. eqn’s for stepsto get overall rxn.

* Add )Hsteps | )Hrxn

Page 12: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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1) Note:

In using Hess’s Law:

a) If an eqn. is multiplied by afactor, )H is multiplied bythe same factor.

b) If an eqn. is reversed,sign of )H changes

c) All substances NOT appearing indesired eqn. MUST cancel

Page 13: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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F) Enthalpy of Formation

Enthalpy change for the formationof a compound from its elements

)Hf

1) Standard enthalpy change

Enthalpy change when all reactants and and products are in their standard states

)H°

Page 14: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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2) Standard State

Most stable state of a substance in itspure form under standard pressure(1 atm) & some specified temp. ofinterest (usually 25 °C)

3) Thermochemical Standard States

A) solid or liquid

Pure substance at 1 atm

b) gas

pressure of 1 atm

c) species in solution

Conc. of 1 M

Page 15: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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4) Standard Enthalpy of Formation

)H for the rxn in which 1 mole of acmpd. is formed from its elementswith ALL substances in theirstandard states (in kJ/mol)

)Hf°

Note: )Hf° = 0 for an element inits standard state

)Hf°

1/2 N2(g) + 3/2 H2(g) 6 NH3(g) ! 46.2

Na(s) + 1/2 Cl2(g) 6 NaCl(s) ! 411.0

C(graphite) 6 C(diamond) + 1.897

Page 16: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Page 17: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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C) Determine )Hrxn° from )Hf°

)Hrxn° = 3 n )Hf° ! 3 m )Hf°prod. react.

n = coef. in bal. eqn. for each product

m = coef. in bal. eqn. for each reactant

Page 18: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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I) Spontaneous Processes

Spontaneous Process

Process which proceeds on ownwithout outside assistance

- occurs in one direction only

NONspontaneous Process

Can NOT proceed w/o outside assistance

- reverse of spont. process

Processes which are spont. inone direction are nonspont. inthe reverse direction.

Page 19: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Mix 2 ideal gases

Open stopcock

Spontaneously mix

Reverse process is NOT spont.

Page 20: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Will all spont. rxns. beexothermic or vice versa?

Will all nonspont. rxns. beendothermic or vice versa?

NO!

Spontaneity can dependon temp. & pressure

T > 0 °C : melting spont.

T < 0 °C : freezing spont.

T = 0 °C : equilibrium and neitherconversion occurs spont.

Page 21: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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A) Reversible & IRreversible Processes

1) Reversible Process

Change made in a way that system &surroundings can be restored to theiroriginal states by exactly reversing chg

NO net chg. to system or its surr.

2) IRreversible Process

Can NOT simply be reversed torestore system & surroundingsto their original states

A reversible change produces the max.amt. of work which can be done by asystem on its surroundings.

Page 22: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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3) Isothermal Expansion of a Gas

Expansion of ideal gas atconstant temperature.

Remove partition - gas spont. expandsto fill the whole cylinder. No work isdone by the system.

Compressing the gas back to theoriginal state requires surroundingsto do work on the system.

Process is IRreversible

Page 23: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Can be done reversibly by doing theexpansion and compression infinitelyslowly so the external and internalpressures are always in equilibrium.

- can not actually bedone in real processes

- ALL real processes areIRreversible

4) Conclusions

a) A spont. process is anIRreversible process

b) Driving force is tendency to goto a less ordered state or stateof higher probability.

Page 24: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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II) Entropy, S & 2nd Law of Thermodynamics

Measure of randomness ordisorder in a system

or

Extent to which energy is distributedamong the various motions of themolecules in the system.

State Fnc: )S = Sfinal ! Sinitial

)S > 0 Sf > Si inc. in disorder

)S < 0 Sf < Si dec. in disorder

Page 25: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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A) Isothermal Process

Constant temp. process

qrev)S = ------

T

qrev = heat which would betransferred if processwere reversible

S is a state function

- Thus this eqn. can be used to calc. )S for any isothermalprocess (whether reversibleor irreversible).

Page 26: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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1) )S and Phase Changes

Phase changes occur at constant T

qrev = )Hphase change

)Hphase change)Sphase change = ---------------

T

a) Ex: boiling water at 100 °C

)Hvap = 44.01 kJ/mol

)Hvap 44.01 kJ/mol )Svap = --------- = -----------------

T 373.15 K

= 0.1178 kJ/molCK

= + 117.8 J/molCK

Page 27: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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B) 2nd Law of Thermodynamics and S

Irreversible Process

Results in inc. in Stotal ()S > 0)

Reversible Process

Results in no change in Stotal ()S = 0)

2nd Law of Thermodynamics

Total entropy of a system &its surroundings always inc.for a spont. process

Irreversible (Spont.) Process

)Suniv = )Ssys + )Ssurr > 0

Reversible Process

)Suniv = )Ssys + )Ssurr = 0

Page 28: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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1) Ex: 1 mole of Liquid water is leftoutside where it’s -10.0 °C and itfreezes. Calc. )Ssys & )Ssurr.Will it spontaneously freeze?

)Hfus = + 6.01 kJ/mol

)Hfreezing = ! )Hfus = ! 6.01 kJ/mol

)Hfrz (1 mol)(- 6.01 kJ/mol) )Ssys = -------- = -----------------------------

T 273 K

= ! 22.0 J/mol

)Hsurr (1 mol)(+ 6.01 kJ/mol) )Ssurr = --------- = -----------------------------

T 263 K

= + 22.9 J/mol

)Suniv = )Ssys + )Ssurr

= (! 22.0 J/mol) + (+ 22.9 J/mol)

= + 0.9 J/mol Spont.

Page 29: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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This shows that even though the entropyof the system DEC. the process was stillspont. because the entropy of thesurroundings increased more.

)Suniv > 0

Spont. processes occur w.an overall INC. in )Suniv

Practically speaking we can’talways easily determine )Suniv.

Want to focus on the system.Will see how to determinespontaneity based on )Ssys.

Simplify notation and referto )Ssys simply as )S

Page 30: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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III) Molecular Inerpretation of Entropy

A) Expansion of Gas at Molecular Level

Have the following system:

Open stopcock:

We know gas expands spont.

Why?

Look at possible arrangementsof the particles

Page 31: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Probability that blue molecule is in leftflask is ½. Same for the red particle.

Probability that both moleculesremain in the left flask is:

(1/2)2 = 1/4

For 3 particles it would be

(1/2)3 = 1/8

Page 32: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Consider a mole of gas:

Prob. all the molecules are in theleft flask at the same time is:

(1/2)N where N = 6.02 x 1023

Infinitesimally small!!!

Essentially ZERO prob.of all molecules in leftflask at same time.

- Gas SPONT. expandsto fill both flasks

- Does NOT spont. goback to left flask

Page 33: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Most probable arrangements arethose with essentially equal numbersof particles in both flasks.

Gas spreads out and the arrangementof gas particles is more disorderedthan when confined to one flask

Greater entropy

Just seen disorder onthe molecular level

Page 34: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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B) Boltzmann’s Eqn. & Microstates

Statistical Thermodynamics

Uses statistics and probability to linkmicroscopic & macroscopic worlds.

Microstate

Single possible arrangement ofthe positions and kinetic energiesof the molecules - snapshot

Exceptionally LARGE # microstates

Can use probability and statisticsto determine total # microstatesfor a thermodynamic state

Page 35: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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W = # microstates

Very Large # for a mole of particles

Related to Entropy

Boltzmann Eqn.

S = k C ln W

k = Boltzmann’s constant

= 1.38 x 10!23 J/K

S is a measure of # microstatesassociated w. a particularmacroscopic state

Page 36: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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)S = k C ln Wfinal ! k C ln Winitial

Wf = k C ln ------

Wi

When Wf > Wi )S > 0

Entropy inc. w. # microstates

Ex: Inc volume of a gas

greater vol - greater # of positionsavailable to the particles andgreater # microstates

ˆ Entropy inc. as vol. inc.

Page 37: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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C) Molecular Motions and Energy

Ideal gas particles are idealizedpoints w. no vol. and no bonds

- translational motion only

Real molecules

- translational motion

- rotational motions

spin about an axis

Linear: 2 axes of spin

Nonlinear: 3 axes of spin

Page 38: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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- vibrational motions

Atoms periodically move toward& away from each other

Linear: 3N - 5Nonlinear: 3N - 6

N = # atoms in molecule (N > 2)

# microstates inc. as complexityof molecule inc.

- there are many more vibrational motions

Page 39: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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D) Predicting Sign of )S

1) Phase changes

Solid ----> Liquid ----> Gas

)S > 0 )S > 0

2) Number of Molecules Inc.

F2(g) ----> 2 F(g)

)S > 0

3) Inc. # Atoms in a Molecule

Inc. degrees of freedom

)S > 0

Page 40: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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4) Mixing of Substances

Generally, )Ssoln > 0

5) Temp. Changes

Inc. Temp., KE inc.

- molecules move faster

- broadens distribution of speeds

)S > 0

6) Vol. Inc.

Vol. inc. - greater # positionsavailable to atoms

)S > 0

Page 41: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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E) Ex: The )Hf° of liquid acetone is- 247.6 kJ/mol at 25 °C. The )Hf° forthe vapor is -216.6 kJ/mol at 25 °C.What is the entropy change when1.00 mol of liquid acetone vaporizesat 25 °C?

Page 42: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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F) Ex: A sample of 2.00 mol of an idealgas expands from a vol. of 1.0 L to10.0 L at constant temperature. Whatis the entropy change, )S? Is the signof )S consistent w. your expectations?

Page 43: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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IV) Third Law & Standard Entropy

A) 3rd Law

A perfectly crystalline substanceat 0 K has entropy of zero

Can measure Absolute entropy,also called standard entropy, So

- entropy value for standard state of species

Standard State

Pure substance: 1 atm pressure

Species in Soln: 1 M

Page 44: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Can calculate from heat capacities

T Cp(T) dTST° = m0 -------------

T

1) Values for compounds doNOT correspond to formationfrom the elements

2) Absolute entropy of an elementin its solid state … 0

3) Values on order of 10's of joules(not kJ like enthalpy)

Page 45: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution
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B) Entropy Change for a Rxn.

)Srxn° = 3 n S° ! 3 m S°prod. react.

n = coef. in bal. eqn. for each product

m = coef. in bal. eqn. for each reactant

Page 47: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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1) Ex: Calculate the entropy changefor the formation of H2O from itselements at 25 °C.

So(H2) = 130.58 J/molCK

So(O2) = 205.0 J/molCK

So(H2O, liq) = 69.91 J/molCK

2 H2 (g) + O2 (g) W 2 H2O (R)

)Srxn° = 2 So(H2O, liq) ! [2 So

(H2) + So(O2)]

= (2 mol) (69.91 J/molCK) ! [(2 mol) (130.58 J/molCK) + (1 mol)(205.0 J/molCK)]

= ! 326.3 J/molCK

Page 48: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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V) Gibbs Free Energy & Spontaneity

G = H ! TS

State Fnc: )G = Gfinal ! Ginitial

At constant T & P

)G = )H ! T )S

Under standard state conditions,

)Go = )Ho ! T )So

How does this relate to spontaneity?

Page 49: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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! qsys ! )Hsys)Ssurr = --------- = -----------

T T

)Suniv = )Ssys + )Ssurr

! )Hsys

= )Ssys + ------------ T

Rearrange:

! T )Suniv = )Hsys ! T )Ssys

)G = ! T )Suniv

Page 50: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution

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Now have an eqn. whichrelates spont. to the system.

At constant T & P

)G = )H ! T )S

)G < 0 spont.

)G > 0 NONspont.

)G = 0 equilibrium

Page 51: Chapter 19 Chemical Thermodynamics · Chapter 19 Chemical Thermodynamics Kinetics How fast a rxn. ... 5 B) Thermodynamic State ... species in solution
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