Ch 3

δ𝑄 δ𝑄
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑑𝑊' | 𝑇
= 𝑑𝑆 | 𝐶 = 𝑑𝑇
| γ = 𝐶𝑝/𝐶𝑣
Adiabatic Relations:
γ (1−γ) (γ) (γ−1)
𝑃𝑉 = 𝑘, 𝑃 𝑇 = 𝑐𝑜𝑛𝑠𝑡, 𝑇𝑉 = 𝑐𝑜𝑛𝑠𝑡, 𝑊 = (1/(1 − γ))(𝑃2𝑉2 − 𝑃1𝑉1)
Ideal Gas: PV=nRT, U=U(T), CP=(5/2)R, CV=(3/2)R (monoatomic, diatomic add R)
(T2/T1)=(V1/V2)^(nR/Cv) | α = (1/𝑇), β = (1/𝑃)

Terms: Isobaric: constant P, W= -PdV easy.

Isothermal: Constant T, for ideal gas dU=0, δ𝑄 ≠ 0
Adiabatic: δ𝑄 = 0, does not mean that T is constant. Look at Adiabatic relations.
Isochoric: constant volume -> dW=0 ya?

𝐶𝑃
dV=(𝑉α)𝑑𝑡 − (𝑉β)𝑑𝑃 | dS=( 𝑇
)dT− (𝑉α)𝑑𝑃
U=Q+W = dU=TdS-PdV+dW’ = dU=(𝐶𝑝 − 𝑃𝑉α)𝑑𝑇 + 𝑉(𝑃β − 𝑇α)𝑑𝑃
H=U+PV, dH=dU+PdV+VdP | 𝑑𝐻 = 𝐶𝑝𝑑𝑇 + 𝑉(1 − 𝑇α)𝑑𝑃
F=U-TS, dF=dU-TdS-SdT| dF=− (𝑆 + 𝑃𝑉α)𝑑𝑇 + 𝑃𝑉β𝑑𝑃
G=H-TS = U+PV-TS, dG=− (𝑆)𝑑𝑇 − (𝑃)𝑑𝑉 + 𝑑𝑊'
1 ∂𝑉 1 ∂𝑉
α= 𝑉
( ∂𝑇 )𝑝, β =− 𝑉
( ∂𝑃 )𝑇
𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑑𝑆𝑟𝑒𝑣 + 𝑑𝑆𝑖𝑟𝑟𝑒𝑣

η = (𝑇𝑏 − 𝑇𝑎)/𝑇𝑏

Chemical potential µ
𝑎 𝑎
1 𝑎 𝑝 𝑎 µ 𝑎
dS’a= 𝑎 𝑑𝑈' + 𝑎 𝑑𝑉' − 𝑎 𝑑𝑛 , µ= molar value of Gibb’s Free Energy
𝑇 𝑇 𝑇
Ch 5: Conditions for Eq: Ta=TB, Pa=PB, µa=µB
Systematic approach to solving for differential equations that cannot easily be solved.
1. write diff eq for change in entropy that system may experience when taken through an
arbitrary process, explicitly including terms for all possible variations in the state of the system.
2. Write diffy expression that describes the constraints that apply to the system because it is
isolated (dV=0, dU=0, dn=0)
3. use isolation constraints to eliminate dependent variables in the description of the change in
entropy of the system.
Set coefficients of each of the differentials in the new expression for dS equal to 0, this will find
you the extrema, so make sure it's a maxima.
𝑁0! 𝑟 𝑛
Ω= 𝑛 !𝑛 !...𝑛 !
, S=kbln(Ω) ln(x!)=~ xln(x)-x, θE=hv/kB , dS= -kb ∑ 𝑙𝑛( 𝑁𝑖 )𝑑𝑛𝑖
1 2 𝑟 𝑖=1 0

U=kbTln(W), b=-1/T

# of microstates: (# of energy levels)^(# of particles)

dSsys = dSa + dSb = (1/Ta)dUa+(Pa/Ta)dVa-(µa/Ta)dna+(1/Tb)dUb+(Pb/Tb)dVb-(µb/Tb)dnb

dUsys = dUa + dUb = = TadSa – PadVa + µadna + TbdSb - PbdVb + µbdnb