CHAD’S ELEMENTARY PHYSICAL CHEMISTRY REVIEW

A Survey of Thermodynamics

Table of Contents
Chapter 1: Gases Page 1
Chapter 2: The 1st Law of Thermodynamics Page 4
Chapter 3: Enthalpy Page 6
Chapter 4: Entropy and the 2nd Law of Thermodynamics Page 9
Chapter 5: Gibb’s Free Energy Page 11
Chapter 6: Mixtures and Solutions Page 12
Chapter 7: Chemical Equilibrium Page 14
Chapter 8: Electrochemistry Page 17
Chapter 9: Kinetics Page 18

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 Chapter 1 - Gases
Pressure = Force / Area (P = F/A)
1atm = 760torr = 760mmHg = 1.01325bar = 101,325Pa = 101.325kPa

Gas Laws
Boyle’s Law pV = constant or p1V1 = p2V2 Gas Constant
R = 8.31447 J K-1 mol-1
V R = 8.31447 dm3 kPa K-1 mol-1
Charles’ Law  constant R = 0.0820574 dm3 atm K-1 mol-1
T
R = 62.364 dm3 torr K-1 mol-1
V
Avogadro’s Principle  constant
n

p 1V 1 p 2V 2
Combined Gas Law 
T1 T2

p 1V 1 p 2V 2
Better Combined Gas Law 
n 1T 1 n 2T 2

Dalton’s Law of Partial Pressures ptotal = pA + pB + pC + …

pA   A
p Total  A
= mole fraction A

1
Kinetic Model of Gases
Assumptions: 1) Gas molecules are in constant random motion.
2) Gas molecules don’t have volume (negligible volume anyway).
3) Gas molecules don’t experience any attractive forces between each other.
(All collisions are elastic.)

Perfect Gas Behavior

1) Gases behave more ‘perfectly’ at low pressures and high temperatures.
2) Gases with lower intermolecular forces tend to behave more ‘perfectly.’

Perfect Gas Equation of State pV = nRT

2
nMc
p  M = molar mass c = rms speed
3V

 3 RT  2
c   
 M 

Maxwell Distribution of Speeds

2
3/2 Ms
 M  
f  F (s) s F ( s )  4 
2

2 RT
s e
 2  RT 

Critical Temperature
Temperature above which a gas cannot be condensed
into a liquid by an increase in pressure.

2
Real Gases
Vm pV
Z  
m
Compression Factor: 0
Vm RT

nRT  
2
nB n C
Virial Equation of State: p  1    ... 
 2 
V  V V 
B C
derived from: Z 1  2
 ...
Vm Vm

2
nRT an
Van der Waals equation: p  
V  nb
2
V

 
2
an
 p   V  nb  nRT
 2 
 V 

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 Chapter 2 – The 1st Law of Thermodynamics
1st Law of Thermodynamics
“Conservation of Energy”

open system - energy and matter can be exchanged with the surroundings

closed system - energy but not matter can be exchanged with the surroundings

isolated system – neither energy nor matter can be exchanged with the surroundings

diathermic vs adiabatic
Isothermal (T = 0) (U = 0)
Adiabatic (q = 0)
Constant Volume (w = 0)

q
Heat Capacity C 
T

C
specific heat capacity C s

m

C
molar heat capacity Cm 
n

 U  U
CV    or CV  constant volume heat capacity U = CvT
 T V T

 H  H
CP    or C P
 constant pressure heat capacity H = CpT
 T  P T

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Internal Energy Work
U = q + w  U  C V dT or Always
w   p ex dV

w   p ex  V constant pex
V f
w   nRT ln Reversible, Isothermal
Vi

Heat
q  C V
dT Constant V
q  C P
dT Constant P
q  w Constant T

Enthalpy
H = U + pV  H  C P dT or

H = qp

CP – CV = nR (for a perfect gas)

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 Chapter 3 – Enthalpy
Enthalpy and the First Law of Thermodynamics
 U  U
CV    or CV  constant volume heat capacity U = CvT
 T V T

 H  H
CP    or C P
 constant pressure heat capacity H = CpT
 T  P T

Calculate the amount of heat needed to raise 90 grams of H2O from 10C to 75C at a constant pressure of 1bar
(Cp,m= 75.3JK-1mol-1).

54 grams of aluminum is transferred from boiling water (at 100C) to 100 grams of water at 25C causing the
temperature of the water to increase to 32.8C. What is the molar heat capacity of the metal? (Cp,m,water(l) =
75.3JK-1mol-1)

Phase Transitions
Calculate the amount of heat needed to completely melt 90 grams of ice at 0C and 1bar (ΔfusH = 6.01kJmol-1).

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ΔrH from Bond Enthalpies H = Dbroken - Dformed
Bond breaking is endothermic Bond making is exothermic

What is ΔrH for the following rxn? Mean Bond Enthalpies (kJ/mol)
C-H 413
C-Cl 328
Cl-Cl 242
H-Cl 431

Hess’s Law C2H4(g) + 6F2(g)  2CF4(g) + 4HF(g) ΔrH = ?

H2(g) + F2(g)  2HF(g) ΔrH = -537kJ

C(s) + 2F2(g)  CF4(g) ΔrH = -680kJ
2C(s) + 2H2(g)  C2H4(g) ΔrH = +52.3kJ

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Enthalpies of Formation
ΔrH = fHproducts -  ΔfHreactants
Given the following standard enthalpy of formation values, calculate the Hrxn of the following reaction:
PCl3(g) + 3HCl(g)  3Cl2(g) + PH3(g)
Compound  f H (kJ/mol)
PCl3(g) 288.07
HCl(g) 92.30
PH3(g) 5.40

Kirchoff’s Law
ΔrH(T’) = ΔrH(T) + ΔrCp(T’–T)

What is the enthalpy of vaporization of H2O at 110C given vapH(373.15K) = 40.65kJmol-1, Cp,m(H2O(l)) =
75.3JK-1mol-1 and Cp,m(H2O(g)) = 33.58JK-1mol-1?

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 Chapter 4 – Entropy and the 2nd Law of Thermodynamics
Three laws of thermodynamics
1) Conservation of energy (Energy can’t be created or destroyed).
2) For a spontaneous process, the entropy of the universe increases.
3) A perfectly ordered crystal at 0K has zero entropy.

Entropy
q rev
S 
T

V f Pi
 S  nR ln  S  nR ln (Entropy Change during Expansion/Compression)
Vi Pf

T f
 S  C ln (Entropy Change during heating; constant heat capacity)
Ti

Calculate the entropy change when 0.5 mol of a perfect gas expands from 12L to 24L and is simultaneously
cooled from 298K to 200K. (Cv,m = 12.5 JK-1mol-1)

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  Hrs
 S trs  (Entropy Change of a Phase Transition)
Trs

 H 1 1
(Trouton’s Rule)
vap
 vap
S   85 JK mol
Tb

q
 S sur  
T

1
C p ,m
 aT
3
and Sm  C p ,m
(Debye T3-law; at Temps close to 0K)
3

 
 r S     S m ( products )
   S m ( reac tan ts )

S = k lnW (Boltzmann’s Expression; k = 1.381x10-23JK-1)

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 Chapter 5 – Gibb’s Free Energy
Gibb’s Free Energy
G = H - TS G < 0 Spontaneous
G > 0 Nonspontaneous
G = 0 At equilibrium

dG = VdP - SdT

Gm = Vmp (dependence on pressure changes for solids/liquids)

p
 G m  RT ln (dependence on pressure changes for a perfect gas)
f

pi

Gm = -SmT (dependence on temperature changes)

p  trs H
 (Clayperon Equation)
T T  trs V

 (ln p )  vap
H  vap
H  1 1 
 and ln p '  ln p     (Clausius-Clayperon for a Perfect Gas)
T
2
RT R T T '

What is the boiling temperature of water at a pressure of 0.80atm? (vapH(373.15K) = 40.65kJmol-1)

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 Physical Chemistry Chapter 6 – Mixtures and Solutions
Properties of Mixtures
V  n AV A  n B V B (Volume of a mixture using partial molar volumes)
G  nA A  nB B (Gibbs Free Energy using partial molar chemical potentials)

Gases
p
G m ( p )  G m  RT ln
0
0
p

 J   J  RT ln p J
0
(chemical potential of a gas)
 mix G  nRT (  A
ln  A
  B ln  B )
 mix S   nR (  A
ln  A
  B ln  B )

Solutions
 mix G  nRT (  A
ln  A
  B ln  B )
 mix S   nR (  A
ln  A
  B ln  B )

Solvents
pJ   J
*
pJ PJ
*
= vapor pressure of pure J (Raoult’s Law—for a solvent in an ideal solution)
 A   A  RT ln 
*
A
(chemical potential of a solvent)

Solutes
pB   B K H
(Henry’s Law—for a solute in ideal-dilute solutions)
 B   B  RT ln  B
*

 B   B  RT ln[ B ]
0

Real Solutions
 J   J  RT ln a J aA    a B   B [B]
0
A A
for solvents for solutes

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Colligative Properties
mol solute
molality=
kg solvent

van’t Hoff factor (i) – number of ions a compound dissociates into per formula unit

Freezing Pt. Depression T f

 K f bB b = molality  T F   iK F
m

Boiling Pt. Elevation  Tb  K b b B b = molality  T B  iK B

m

Osmotic Pressure   [ B ] RT   iMRT

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 Chapter 7 – Chemical Equilibrium
Chemical Equilibrium
rG = rG + RTlnQ (Free energy under non-standard conditions) G < 0 Spontaneous
G > 0 Nonspontaneous
G = 0 At equilibrium

rG = -RTlnK G < 0 Keq > 1 Exergonic

G > 0 Keq < 1 Endergonic
G = 0 Keq = 1

rG  =   f Gproducts -   f Greactants

rG = rHo - TrSo rHo rSo -TrSo

- + - Spontaneous at all temperatures
+ - + Non-spontaneous at all temperatures
- - + Spontaneous at low temperatures
+ + - Spontaneous at high temperatures

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Equilibrium constants
2C(s) + O2(g)  2CO(g)
What is the equilibrium constant expression for the reaction above?

K = Kc (RT)  = change in moles gas

Equilibrium constants are CONSTANTS. The constant will only change with a change in temperature.
rH
0
 1 1 
ln K '  ln K    
R T T '

N2O4(g)  2NO2(g) If N2O4 is 20% dissociated at equilibrium at 298K and standard pressure, then what is the
value of K?

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Proton Transfer Equilibria (Acid/Base Equilibria)
pH = -log a H O = -log[H3O+] 
3

pOH = -log a OH  = -log[OH-]

.
Kw = a
H 3O
 a
OH
 = [H3O+][OH-] = 1.0x10-14

pH + pOH = 14 and pKa + pKb = 14

a  a  [ H 3O
 
][ A ]
Acid dissociation in water: HA + H2O  H3O+ + A-
H 3O A
K a
 
a HA [ HA ]

a  a HA [ OH

][ HA ]
Base dissociation in water: A- + H2O  HA + OH-


 
OH
K b 
a  [A ]
A

KaKb = Kw = 1x10-14 (If you know Ka, you know Kb and vice versa)
The stronger the acid, the weaker the conjugate base and vice versa.

1
Amphiprotic Species: [ H 3O

] K a1
K a2
pH   pK a1
 pK a2

2

Solubility Equilibria
AgCl(s)  Ag+(aq) + Cl-(aq) Ksp = 1.8x10-10 = a
Ag
 a
Cl
  [ Ag

][ Cl

]

Mg(OH)2(s)  Mg2+(aq) + 2OH-(aq) Ksp = 1.6x10-12 = 2 

2
a  [ Mg
2
a 2  ][ OH ]
Mg OH

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 Chapter 8 – Electrochemistry
Electrochemistry
Standard Cell Potentials
E = ER - EL E = Ecat - Ean E = Ered + Eox

Remember that the standard hydrogen electrode (SHE) has a potential of 0.00V
Al3+ + 3e-  Al -1.66V
2H+(aq) + 2e-  H2(g) Ered = 0
Mn2+ + 2e-  Mn -1.18V
Zn2+ + 2e-  Zn -0.76V
Cr3+ + 3e-  Cr -0.74V
Zn2+(aq) + Co(s)  Zn(s) + Co2+(aq) Calculate E. Fe2+ + 2e-  Fe -0.44V
Co2+ + 2e-  Co -0.28V
Ni2+ + 2e-  Ni -0.25V
Cu2+ + 2e-  Cu +0.34V
Ag+ 1e-  Ag +0.80V
Br2 + 2e-  2Br- +1.07V

2Fe2+(aq) + Au3+(aq)  Au+(aq) + 2Fe3+(aq) Calculate E. Au3+ + 3e-  Au 1.40V

Au+ 1e-  Au 1.69V
Fe3+ + e-  Fe2+ 0.77V

Non-standard Cell Potentials (Nernst Equation)

RT 0 . 0592 0 . 0257
E  E  ln Q E  E  log Q E  E  ln Q
F  

Calculate the cell potential for the Zn/Co cell above with [Zn2+] = 0.001M and [Co2+] = 0.1M.

Relationship between E, rG˚, and K

rGo = -FEo  = # moles electrons transferred

0 . 0592
E  log K


2Cr3+ + 3Cu  2Cr + 3Cu2+ Calculate E, rG˚, and K.

17
 Chapter 9 – Kinetics
Kinetics
Rate Expressions
 [H 2O ] [H 2 ]  [O 2 ]
2H2O(g)  2H2(g) + O2(g) = =
2t 2t t

Rate Laws
rate = kr[A]x[B]y

Elementary Reactions and Molecularity

Integrated Rate Laws

Zero Order [A] = [A]0 – krt

[ A]  krt
1st Order ln[A] = ln[A]0 - krt or ln  krt or [ A]  [ A]0 e
[ A]0

2nd Order 1/[A] = 1/[A]0 + krt

Half-Life
ln 2
1st order t1 
2
kr

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Reaction Coordinate Diagrams

Arrhenius Equation
The rate constant (kr) increases with increasing temperature and decreasing activation energy (by adding a
catalyst).
kr = Ae-Ea/RT
Ea  1 
ln k r      ln A
R T 

k r1 Ea  1 1 
ln    
 
k r2 R  T2 T1 

Collision Theory (Requirements for a chemical reaction)

1) Collision
2) Proper orientation of reactant molecules
3) Sufficient energy for a reaction to occur
-An increase in temperature increases collision frequency and the percentage of high energy collisions.

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