Heat, Thermodynamics:

Temperature and Heat: L

R=
 Temperature Scales: k
- Fahrenheit: o Heat Current in Radiation:
9 H= Aeσ T 4
T F = T C + 32o
5
- Celsius:  Radiation and
5 Absorption:
T C = (T F −32)
9 H net = Aeσ ( T 4 −T 4S )
- Kelvin: Thermal Properties of Matter:
T K =T C +253.15
 Total Mass:
- Rankine: m total=nM
 Thermal Expansion: - Molar Mass:
- Linear Expansion: M =N A m
ΔL=α L0 ΔT
 Expansivity:
- Volume Expansion:
1 ∂v
ΔV =β V 0 ΔT β=3 α
- Thermal Stress:
β=
v ∂T p ( )
F  Isothermal Compressibility:
=−YαΔT −1 ∂ v
A
 Heat:
κ= ( )
v ∂P T
dQ=mc dT  Equations of State:
dQ=nC dT - Critical Points:
- Specific Heat: ∂p ∂2 p
c=
1 dQ ( ) ( )
∂v
=0
∂ v2
=0
m dT - Ideal Gas Equation:
- Molar Heat Capacity: pV =nRT
1 dQ pV =n N A kT
C= =Mc
n dT o Combined Gas Law:
∂q ∂q
CV= ( )∂T V ( )
Cp=
∂T p
p1V 1 p2V 2
T1
=
T2
- Phase Change:
o Density of a Gas:
Q=± mL
pM
 Heat Transfer: ρ=
RT
- Heat Current
- Van der Waals Equation:
dQ
H= a n2
dt
o Conduction:
( )
p+ 2 ( V −nb )=nRT
V
dT a
H=kA
dx ( )
p+ 2 ( v −b )=RT
v
 Temperature Gradient: o Critical Values:
dT T H −T C 8a a
= v c =3 b T c = pc=
dx L 27 Rb 27 b2
 Thermal Resistance:
 o Expansivity: - Root-Mean-Square Speed of a Gas
1 Molecule:
β=
T 3 kT 3 RT
o Compressibility:
1
√ √
v rms= √( v 2 )av =
m
- Collision Between Molecules
=
M
κ=
P o Number of Collisions per
- Berthelot Equation: unit Time:
RT a dN 4 π r 2 vN
p= − 2 =
v−b T v dt V
o Mean Free Time:
o Critical Values: V
t mean=
8a 1 2 aR 4 π √ 2r 2 vN
v c =3 b T c =
√
- Dieterici Equation:
27 Rb
pc =
√
12 b 3 b o Mean Free Path:
V
RT a/ RTv λ=v t mean=
p= e 4 π √2 r 2 N
v−b  Equipartition Theory:
o Critical Values: f f
U =Nϵ= NkT = nRT
a a 2 2
v c =2b T c =
√ 4 Rb
pc = 2 2
- Approximate Equation of State for
4e b U f
u= = RT
n 2
Solids and Liquids:  Heat Capacities:
V =V 0 ( 1+ βΔT −κΔp ) f
C V= F
Kinetic Theory of Gasses: 2
 Molecular Properties of Matter: - Ideal Gas:
- Lennard-Jones Potential: o Mayer’s Equation:
R 0 12 R0 6 C P =CV + R
U ( r )=U 0
[( ) ( ) ]
r
−2
r C p= ( )f +2
2
R
o Force
o Ratio of Heat Capacities:
U 0 R 0 13 R0 7
[( ) ( ) ]
F r=12
R r
−
r γ= P
C
CV
 Kinetic-Molecular Model of an Ideal f +2
Gas: γ=
2
- Average Translational Kinetic o Monoatomic Gas ( f =3):
Energy of n Moles of an Ideal Gas: 3 5
3 C V = R C P= R
K T = nRT 2 2
2 o Diatomic Gas ( f =5):
- Average Translational Kinetic 5 7
Energy of a Gas Molecule: C V = R C P= R
2 2
1 3
m ( v 2 )av = kT - Ideal Solids:
2 2 o Ideal Monoatomic Solid:
C V =3 R
 Molecular Speeds: - Gay-Lussac – Joule Experiment
∞
(for an Ideal Gas):
v av=∫ v f ( v ) dv ∂U
n
0
∞
n
( )
∂V T
=0
( v )av =∫ v f ( v ) dv o Gay-Lussac – Joule
0
Coefficient:
∞
v rms= √( v )av =

-
2

Molecular Flux:
√ ∫ v 2 f ( v ) dv
0
η=
∂T
( ) 1
= ( p− )
∂ v u Cp
Tβ
κ
- Molar Heat Capacity at Constant
1N Volume (Reversible Process):
Φ= v
4 V av ∂u
- Translational Kinetic Energy:
CV= ( )
∂T v
1
ϵ = m v2 - Internal Energy of an Ideal Gas:
2 T

- Maxwell-Boltzmann Distribution: u−u0=∫ C V dT

m 32 2 −m v /2 kT T0

( )
2

f ( v )=4 π v e  Enthalpy:
2 πkT
H=H ( p ,T )
8π m 32 −ϵ / kT
f ( ϵ )=
m 2 πkT ( ϵe ) H=U + pV
- Differential:
o Peak: dH =dQ+V dp
ϵ =kT ∂H ∂H
o Most Probable Speed:
2 kT
dH = ( ) ( )
∂p T
dp+
∂T p
dT

v mp=
m √
o Average Speed:
- Joule – Thomson Experiment (for
an Ideal Gas):
∂H
8 kT ( ) =0
v av=
πm √
o Root-Mean-Square Speed:
∂p T
o Joule – Thomson
Coefficient:
3 kT

 Effusion:
v rms=
m √ μ=
∂T
( ) v
= (Tβ−1)
∂ p h Cp
- Molar Heat Capacity at Constant
3 2 πkT
v e, av =
√
4 m
First Law of Thermodynamics:
Volume (Reversible Process):
C p=
∂h
( )
∂T p
dU =dQ−dW - Enthalpy of an Ideal Gas:
 Work Done in a Volume Change: T

dW = p dV h−h0=∫ C p dT
 Internal Energy: T0

U =U (V , T )  Latent Heat of Transformation:

L=H 2 −H 1
- Differential:
∂U ∂U Second Law of Thermodynamics:
dU = ( )
∂V T
dV +
∂T ( ) T
dT  Heat Engines:
- Work:
 W =QH +QC =|QH|−¿ QC ∨¿  Combined First Law and Second Law:
- Thermal Efficiency: dU =T dS− p dV
W Q Q  Thermodynamic Processes:
e=
QH
=1+ C =1− C
QH | |
QH - Isobaric Process:
W =pΔV
 Refrigerators (W , Q H < 0): dT
−Q H =Qc −W dS=C p
T
|Q H|=QC +¿ W ∨¿ - Isochoric Process:
- Coefficient of Performance: dW =0
K=¿Q C ∨ ¿ ¿ dU =dQ
¿W ∨¿=¿ QC ∨ ¿ ¿¿ dT
|QH|−¿ QC ∨¿ ¿ dS=C V
T
 Otto Cycle:
- Isothermal Process:
1 V1
e=1− γ−1 r= Qr
r V2 ΔS =
T
 Joule Cycle: o Ideal Gas:
p1 (γ −1)/γ dU =0
e=1−
( )p2 dQ=dW
 Carnot Cycle: V P
W =nRT ln 2 =nRT ln 1
T T −T C V1 P2
e Carnot =1− C = H
TH TH o Isothermal and Isobaric
TC Phase Change:
K Carnot = l
T H −T C ΔS =
 Entropy: T
dQ - Adiabatic Process:
dS ≥ dQ=0
T
- Clausius Inequality: dU =−dW
dQ dS=0
∮ T ≤0
o Reversible Cyclic Process: CV 1
W =n CV ( T 1−T 2 )= ( p1 V 1 −p 2 V 2 ) = ( p V −p 2 V 2 )
dQ R γ −1 1 1
∮ T =0
o Irreversible Cyclic Process: T V γ−1=constant
dQ p V γ =constant
∮ T <0 T
1
=constant
- Entropy of the Universe: 1−
γ
d S sys +d S sur =d Suniv p
- Ideal Gas:
T2 V2
ΔS =CV ln + R ln
T1 ( ) V1
- Microscopic State:
S=k ln w

 TdS Equations:
 
TdS=CV dT +T ( ∂∂ PT ) dV
V
Enthalpy:
U ( S ,V ) → H (S , p)
Tβ H=U + pV
¿ C V dT + dV
κ dH =T dS +V dp
- Reciprocity Relations:
∂H ∂H
TdS=C p dT −T ( ∂∂TV ) dp
p
( )∂S p ( )
=T
∂p S
=V
¿ C p dT +TVβ dP - Maxwell Relations:
∂T ∂V ∂2 H
∂T ∂T ( ) ( ) =
∂ P S ∂S p ∂ p∂S
=
TdS=C P ( )
∂V p
dV +CV ( )
∂P V
dP
 Helmholtz Function:
Cp CV κ U ( S ,V ) → F (T ,V )
¿ dV + dP F=U −ST
βv β
- Difference in Molar Heat dF=− p dV −S dT
Capacities: - Reciprocity Relations:
Tv β 2 ∂F ∂F
C p−C V =
κ ( )
∂V T
=− p ( ) ∂T V
=−S
- Adiabatic Compressibility: - Maxwell Relations:
−1 ∂ v κ ∂S ∂p −∂2 F
κS= ( )
v ∂p S γ
=
( ) ( ) = =
∂ V T ∂ T V ∂ V ∂T
o Difference in Isothermal - Isothermal Reversible Process:
and Adiabatic W ≤− ΔF (no change ∈T )
Compressibilities: - Equilibrium Condition at Constant
Tv β 2 Volume:
κ−κ s =
Cp dF=0
 Entropy Change for the Free  Gibbs Function:
Expansion of an Ideal Gas: U ( S ,V ) → G(T , p)
V G=U −ST + PV
ΔS =R ln 1 dG=−S dT +V dp
V0
 Entropy Change for a Liquid or Solid: - - Reciprocity Relations:
T ∂G ∂G
Δs=C P ln −v 0 β (p− p0 )
T0
( )
∂T p
=−S ( ) ∂p T
=V

Thermodynamic Potentials: - Maxwell Relations:

 Internal Energy: ∂S ∂V −∂2 G
U (S,V ) ( ) ( )
∂p T
=− =
∂T p ∂ p∂T
dU =T dS− p dV - Isothermal and Isobaric Process:
- Reciprocity Relations: dG=0
∂U ∂U - Nonmechanical Forces Acting on
( )∂S V
=T ( ) ∂V S
=− p the System:
W nm ≤− ΔG ( no change∈T ∨ p )
- Maxwell Relations:
∂T ∂p ∂2 U - Clausius-Clapeyron Equation:
( ) ( )
∂V S
=− =
∂ S V ∂V ∂ S
( ) dp
=
l 12
dT 12 T ( v 2−v 1 )
 Conditions for Stable Equilibrium:
1. SUU <0
−1
SUU =
CV T 2
2
2. D=S UU SVV −( S UV ) >0
1
D=
CV κ T 2V