Pressure dZ

lim   = 0 at T = T B : Boyle temp

1 1
Vm →∞ d Vm
1 bar = 105 Pa
1 atm = 101.325 · 103 Pa Van der Waals Equation
1 T orr = 133.32 Pa PVm = RT (1 + B0 P + C 0 P2 + . . .)
B C
Number of Molecules = RT (1 + + + . . .)
Vm Vm2
N = nNA , NA = 6.022 · 1023
RT a
P= −
Gas Constant Vm − b Vm2
 RT  2  a  ab
R = 8.315 J K −1 mol−1 V 3m − b + Vm + − =0
P P P
= 8.315 · 10−2 L bar K −1 mol−1 3
b= NA π(2rmol )3
= 8.206 · 10−2 L atm K −1 mol−1 4
= 62.36 L T orr K −1 mol−1 Adiabatic Process

Boltzman Constant q= 0, ∆U = w = nC v ∆T
γ γ Cp
k= 1.381 · 10−23 J K −1 Pi Vi = P f V f , γ = , C p − Cv = nR
CV
Root Mean Square Speed Isothermal Process
r
3RT q = −w, ∆U = 0
Vrms = c =
M ! !
∂U ∂U
Average Speed dU = dT + dV
∂T V ∂V T
! 12 = C V dT + ΠT dV
8RT
Vavg = c̄ =
πM !
∂U
Most Probable Speed ΠT is internal pressure, ΠT =
∂P H
! 12
2RT Perfect Gas
c∗ =
M
ΠT = 0, ⇔ dU = CV ∆T
Related Speed
1
Isothermal Reversible Expansion
c̄rel = 2 2 c̄ Z !
! 12 Vf
8kT m1 m2 q= −w = − −Pex dV = nRT ln
= bases µ = Vi
πµ m1 + m 2
dH = C p dT = 0 ⇒ ∆H = 0
Collision Frequency
Joule-Thomson Coefficient
N
z = ρc̄rel , ρ = πd2 , d = collision diameter ∂H
!
V µ=
ρc̄rel P ∂P T
=
kT µ > 0 ⇒ cooling, µ > 0 ⇒ heating,
Mean Free Path µ = 0 ⇒ ideal gas
c̄
λ= Entropy
z
Compression Factor • definition

PVm dQ
Z= dS =
RT T
1
 • at constant pressure Arranged
!
Tf !
∆S sys = nC P.m. ln at p const ∂H
Ti = −µC p
∂P T
• at constant temperture !
∂S CV
Z
Vf
! =
∂T V T
q = −w = − −Pex dV = nRT ln !
Vi ∂S CP
Pi
! =
= nRT ln ∂T P T
Pf ∂H
!
= CP
∂H T
dQ
dS =
T !
Z Z Z
dQ dq Pi
∆S = = = nRT ln dT ΠT Question
T T Pf
!
Pi  
= nR ln probe ΠT = T ∂P
−P
Pf ∂T V

Carnot Engine
gain Tc ∂U
!
T dS − PdV
!
∂S
!
∂V
!
ε= =1− < 1 (2nd Law) ΠT = = =T −P
pay Th ∂V T ∂V ∂V T ∂V
T
dq
!
dS ≥ Clausius Inequality ∂S
T =T −P
dS ≥ 0 (2nd Law) ∂V T

1st, 2nd 3rd Law of Thermodynamics ΠT of real gas

1st Law U = Q+W nRT an2

P= − 2
2nd Law dS ≥ 0 V − nb
! V
∂P  nR 
3rd Law T → 0, ∆S → 0 ⇒ =
∂T V V − nb V
Math
! ! ! ! ! !
∂z ∂x ∂y ∂P ∂T dS − PdV ∂P
= −1 ΠT = = =T −P
∂y y ∂y z ∂z x ∂T T ∂T ∂T V
T
!
Z  nR  n2
n! =T −P= P+a 2 −P
xn e−ax dx = V − nb V V
an+1
a
Various Coefficient = 2
Vm
Maxwell Relation
Basics
! Basics
∂U Volume
= CV
∂T Heat Capacity →
!V z }| {
∂U internal d f = g dx −}h dy
= ΠT | {z
∂V T pressure !
←
!
1 ∂V
!
expansion ∂g ∂h
=α ⇒ =
V ∂T P coefficient ∂y x ∂x y
!
d2 f
!
∂V isothermal ∂g
= µT =
∂P T Joule-Thomson Coefficient ∂y x dydx
! !
∂T Joul-Thomson ∂h d2 f
=µ =
∂P H Coefficient ∂x y dxdy
2
Internal Energy

dU = T dS − PdV dG
slope =
! ! dT
∂T ∂P
⇒ =− =S ≤0
∂V S ∂S V

Enthalpy

dH = dU + d(PV)
= T dS − PdV + PdV + VdP
= T dS + VdP
! !
∂T ∂V
⇒ =
∂P S ∂S P

Gibbs Energy
dµ = Vm P − S m dT
dG = dH − d(T S ) ↑ P =↓ T
= T ds + VdP − T dS − S dT ⇒ easy to melt
= VdP − S dT
! !
∂V ∂S Surface Tensio0n
⇒ =−
∂T P ∂P T
dw = γdσ (σ is area)// = γ (ldh) = Fdh (∵ F = γl)

Helmholtz Energy Laplace Equation

dA = dU − d(T S )
= dU − S dT − T dS
= −PdV − S dT
! !
∂P ∂S
⇒ =
∂T V ∂V T

Gibbs-Helmholtz Equation

! ! !
∂ G  1 ∂G 1
= +G − 2
∂T T P T ∂T P T
! !
1 ∂G G
= −
T ∂T P T
H
= 2 2γ
T Pin − Pout =
r
!! 2γ 2γ cos θ
∂ ∆G ∆H h= h=
⇒ = 2 rρg rρg
∂T T P T
!
∆G f ∆Gi 1 1 Kelvin Equation for Vapor Pressure above Curved
⇒ − = ∆H −
Tf Ti T f Ti Surface
3
 ∆PVm
P = P∗ e RT for

2γVm
P = P∗ e RT for

−2γVm
P = P∗ e RT for
Binary Mixture
! !
∂V ∂V
dV = dnA + dnB
∂nA T,P,nB ∂nB T,P,nB
= VA dnA + VB dnB
V = nA VA + n B V B
G = VdP − S dT + µA dnA + µB dnB
!
∂G
µj =
∂n j T,P,n;

Eular Theorem
 P


 V = Vi n i


 P M
G = µi ni Vm =

 ρ
m = P M i n i



s-l

T − T ∗ ∆ f us H
P ≈ P∗ +
T ∗ ∆ f us V

l-g

(
∆vap H T1 − 1∗
T )
P ≈ P∗ e R