Enthalpy, Entropy and Free Energy [PDF]

Internal Energy (ΔE) and Heat Flow. ▫ Refers to all of the energy contained within a chemical system. ▫ Heat flow b

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Advanced Placement

Chemistry Enthalpy, Entropy and Free Energy

2014

29 Cu 63.55

30 Zn 65.39

41 Nb 92.91

42 Mo 93.94

43 Tc (98)

†Actinide Series:

*Lanthanide Series:

105 Db (262)

106 Sg (263)

107 Bh (262)

33 As 74.92

34 Se 78.96

35 Br 79.90

109 Mt (266)

110 § (269)

111 § (272)

112 § (277)

§Not yet named

79 80 78 77 84 83 82 81 Au Hg Pt Ir Po Bi Pb Tl 192.2 195.08 196.97 200.59 204.38 207.2 208.98 (209)

85 At (210)

95 Am (243)

96 Cm (247)

97 Bk (247)

98 Cf (251)

99 Es (252)

100 Fm (257)

101 Md (258)

102 No (259)

103 Lr (260)

62 63 64 65 66 67 68 69 70 71 Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 150.4 151.97 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97

108 Hs (265)

91 92 93 94 90 Th Pa U Np Pu 232.04 231.04 238.03 237.05 (244)

59 60 61 58 Ce Pr Nd Pm 140.12 140.91 144.24 (145)

88 104 89 87 † Rf Ac Ra Fr (223) 226.02 227.03 (261)

32 Ge 72.59

36 Kr 83.80

17 16 15 14 18 Cl S P Si Ar 28.09 30.974 32.06 35.453 39.948

9 10 F Ne 19.00 20.179

2 He 4.0026

86 Rn (222)

48 46 47 45 44 53 52 51 50 49 54 Cd Pd Ag Rh Ru I Te Sb Sn In Xe 101.1 102.91 106.42 107.87 112.41 114.82 118.71 121.75 127.60 126.91 131.29

56 76 75 73 74 72 57 55 * Os Re Ta W Hf La Ba Cs 132.91 137.33 138.91 178.49 180.95 183.85 186.21 190.2

40 Zr 91.22

39 Y 88.91

28 Ni 58.69

38 Sr 87.62

27 Co 58.93

37 Rb 85.47

26 25 24 Fe Mn Cr 52.00 54.938 55.85 31 Ga 69.72

23 V 50.94

21 Sc 44.96

20 Ca 40.08

19 K 39.10

22 Ti 47.90

13 Al 26.98

12 Mg 24.30

11 Na 22.99

8 7 6 5 O N C B 10.811 12.011 14.007 16.00

4 Be 9.012

3 Li 6.941

1 H 1.0079

Periodic Table of the Elements

AP Chemistry Equations & Constants ADVANCEDPLACEMENT PLACEMENTCHEMISTRY CHEMISTRYEQUATIONS EQUATIONSAND ANDCONSTANTS CONSTANTS ADVANCED Throughoutthe thetest testthe thefollowing followingsymbols symbolshave havethe thedefinitions definitionsspecified specifiedunless unlessotherwise otherwisenoted. noted. Throughout L,mL mL L, gg nm nm atm atm

== == == ==

liter(s),milliliter(s) milliliter(s) liter(s), gram(s) gram(s) nanometer(s) nanometer(s) atmosphere(s) atmosphere(s)

ATOMICSTRUCTURE STRUCTURE ATOMIC EE == hhνν λν cc == λν

mmHg Hg mm kJ J,J,kJ VV mol mol

== == == ==

millimetersof ofmercury mercury millimeters joule(s),kilojoule(s) kilojoule(s) joule(s), volt(s) volt(s) mole(s) mole(s)

energy EE == energy frequency νν == frequency wavelength λλ == wavelength −34 Planck’sconstant, constant,hh == 6.626 6.626××10 10−34 Planck’s JJss −1 mss−1 Speedof oflight, light,cc == 2.998 2.998××10 1088m Speed −1 Avogadro’snumber number == 6.022 6.022××10 102323mol mol−1 Avogadro’s −19 Electroncharge, charge,ee == −1.602 −1.602××10 10−19 coulomb Electron coulomb

EQUILIBRIUM EQUILIBRIUM [C]cc [D]dd [A] [B] [B] [A]

EquilibriumConstants Constants Equilibrium

((PPCC))cc((PPDD))dd

(molarconcentrations) concentrations) KKcc (molar (gaspressures) pressures) KKpp (gas

[C] [D] R ccCC++ddD where aaAA++bbBB R D ,,where KKcc == aa bb

KKpp ==

((PPAA))aa((PPBB))bb

[H++ ][A-- ] KKaa == [H ][A ] [HA] [HA]

KKbb ==

[OH--][HB ][HB++]] [OH [B] [B]

(weakacid) acid) KKaa (weak (weakbase) base) KKbb (weak (water) KKww (water)

−14 [H++][OH ][OH−−]] == 1.0 1.0 ××10 10−14 25°C atat25°C KKww == [H

== KKaa××KKbb pOH==−log[OH −log[OH−−]] pH == −log[H −log[H++]],, pOH pH 14 == pH pH++pOH pOH 14 [A--]] pH == pK pKaa++log log[A pH

[HA] [HA]

pKaa==−logK −logKaa,, pK pKbb ==−logK −logKbb pK KINETICS KINETICS ln[A]t t−−ln[A] ln[A]00 == −−ktkt ln[A]

11 -- 11

[[AA]]t t [[AA]]00

== ktkt

0.693 0.693 tt½ ½ == kk

rateconstant constant kk == rate time tt ==time tt½ half-life ½ == half-life

GASES, LIQUIDS, AND SOLUTIONS PV = nRT PA = Ptotal × XA, where XA =

moles A total moles

Ptotal = PA + PB + PC + . . . n= m

M

K = °C + 273 D= m V

KE per molecule = 1 mv 2 2

Molarity, M = moles of solute per liter of solution A = abc

THERMOCHEMISTRY/ ELECTROCHEMISTRY

q = mcDT = DSD Â SD products - Â SD reactants = DH D Â DHfD products - Â DH fD reactants = DGD Â DGfD products - Â DGfD reactants G D DH D - T D S D D= = - RT ln K = - n F ED I

 

q t

P V T n m M D KE Ã A a b c

= = = = = = = = = = = = =

pressure volume temperature number of moles mass molar mass density kinetic energy velocity absorbance molar absorptivity path length concentration

Gas constant, R = 8.314 J mol -1 K -1 = 0.08206 L atm mol -1 K -1 = 62.36 L torr mol -1 K -1 1 atm = 760 mm Hg = 760 torr STP = 0.00 D C and 1.000 atm

q m c T SD

= = = =

heat mass specific heat capacity temperature

= standard entropy D H = standard enthalpy GD = standard free energy n = number of moles E D = standard reduction potential I = current (amperes) q = charge (coulombs) t = time (seconds)

Faraday’s constant, F = 96,485 coulombs per mole of electrons 1 joule 1volt = 1 coulomb

THERMODYNAMICS Enthalpy, Entropy, Free Energy, & Equilibrium What I Absolutely Have to Know to Survive the AP Exam The following might indicate the question deals with thermochemistry and thermodynamics: calorimeter; enthalpy (ΔH); specific heat (Cp); endothermic; exothermic; heat (q); heat capacity (C); heat transfer; bond energy; entropy (ΔS); Gibb’s free energy (ΔG); spontaneous; state function

Zeroth Law: First Law: Second Law: Third Law:

Laws of Thermodynamics Heat flows from hot to cold Energy and matter are conserved Matter tends towards chaos Entropy of a pure crystal at 0K is zero

Thermodynamic Terms What does each term tell us? Enthalpy (ΔH)

Energy content

+ endothermic

− exothermic

Entropy (ΔS)

Disorder

+ increase in the dispersal of matter

− decrease in the dispersal of matter

Free energy (ΔG)

Thermodynamically favored or not favored

+ not thermodynamically favored

− thermodynamically favored

Equilibrium (K )

Extent of reaction

>1 reaction favors products

1, products favored

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