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Thermal physics equations

1. Ideal Gas Law:

P = Pressure of the Gas (SI: Pa = M/m2; 1 atm =101.3 kPa)


V = Volume of the Gas (SI: m3; 1 liter = 10-3 m3 = 1000 cm3)
T = Temperature of the Gas (SI: K; oC = K - 273.15)
N = Number of molecules in the Gas
k = Boltzmann's Constant (SI: k = 1.38x10 -23 J/K)
n = number of gram moles in the Gas
R = Universal Gas Constant ( R = 8.314 J/mole/K)
NA = 6.022x1023 molecules/mole (Avogadro's Number)
M = Molecular Weight of the Gas in grams per mole
m = mass of the Gas (SI: kg; 1 g = 10-3 kg)
Useful Relations

2. Kinetic Theory of Gases

• The Temperature of a gas is a measure of the Average Kinetic Energy of the


molecules that make up the gas.

• This relation is only valid for a monatomic molecule like Helium.

PHAS1228 – Thermal Physics 1


Equipartition-of-Energy Theorem for an Ideal Gas

• For each mode (degree of freedom) in which a molecule can store energy, the
average internal energy per mode is 1/2 kT

Monatomic Molecule Rigid Diatomic Molecule Vibrating Diatomic Molecule

Molecular Velocities:

= Normal average or mean speed. Half the molecules have speed greater than vav
vav and half are slower.
= The square root of the average of the square of the velocity of the molecules in
vrms the gas.
vp = The speed at which the largest number of molecules move.

Maxwell - Boltzmann velocity distribution:

dNv(v)/N ~ v2 exp(-KE/kT)dv

Boltzmann distribution law: n(E) = n0 × exp( -E/kBT)

Energy states: Ni/Nj = exp×{-(Ei – Ej)/kBT}

3. Interactions between atoms

Lennard-Jones potential:
σ σ
U(r) = 4εε [( )12 − ( )6
r r

ε is the binding energy.

PHAS1228 – Thermal Physics 2


4. van der Waals equation

(P + an2/V2)(V - nb) = nRT

The constant "a" is a correction term for intermolecular force and "b" is a correction for
the real volume of the gas molecules.

The observed pressure is less than the pressure would be without the intermolecular
forces, i.e. in ideal gas:
nRT an 2
P= − 2
V − nb V
a and b are empirical constants obtained for each gas so that vdW equation gives a
good fit to the experimental PVT data.

Parameter “b” in vdW equation can be viewed as “excluded” volume in a gas sample
due to the presence of molecules.

1 4 3 1 4 4
Excluded volume per molecule = ( πd ) = [ (2r )3 ] = 4( πr 3 ) .
2 3 2 3 3

5. Thermal expansion
Average coefficient of linear expansion, α
If the initial length of the object was Li and the temperature change ∆T, then the length
will increase by the amount ∆L = αLi∆T
The change in volume at constant pressure is proportional to initial volume Vi and to the
change in temperature according to similar relation: ∆V = βVi∆T
β is the average coefficient of volume expansion, β = 3 α

6. Thermal conduction

= Heat Flow (SI: J/s = W)

k = Thermal Conductivity of the Substance (SI: W/m oC)


(The bigger the value of k, the larger the heat flow)
A = Cross-sectional Area of Surface Perpendicular to the
heat flow (SI: m 2)
L = Distance in the medium through which the heat flows
(SI: m)

PHAS1228 – Thermal Physics 3


Th = Temperature of the hotter end/surface of the substance
(SI: oC)
Tc = Temperature of the cooler end/surface of the substance
(SI: oC)
R= L/k = Thermal Resistance or Insulation's R-value. The bigger
the R-value, the smaller the heat flow. (SI: (W/m 2 o C)-1)
Building Materials' R-value is measured in units of
(BTU/hr ft 2 oC)-1.

Heat Flow Through Compound Layers:

7. First Law

Q = ∆U + W

U – internal energy of the system

W - Work done by (or on) one system on another system

OUT: W>0 System Does External Work Sys --> Work

INTO: W<0 Work Done on the System Work --> Sys

Work done by a Gas


:

Q - Microscopic Energy flow into (or out of) the System

INTO: Q > 0 System Absorbs Heat Heat --> Sys


OUT: Q < 0 System Releases Heat Sys --> Heat

For a system insulated from surroundings:


mAcA∆TA + mBcB∆TB + mCcC∆TA + … = 0

PHAS1228 – Thermal Physics 4


8. Efficiencies of heat engines & heat pumps

9. Entropy

Adiabatic and Reversible : (Isentropic Process)

Isothermal: (Phases Changes)

(For Solids and Liquids,


Constant Pressure :
C is approximately constant)

Ideal Gas
for any type of
Quasi-Equilibrium Processes:

PHAS1228 – Thermal Physics 5


THERMODYNAMIC PROCESSES FOR AN IDEAL GAS

PVn = Constant
Process Isobaric Isochoric Isothermal Adiabatic
Variable => Pressure Volume Temperature. No Heat
Flow
Quantity ∆P = 0 ∆V = 0 ∆T = 0 Q=0
Constant =>
n 0 1 γ = Cp/Cv
First Law ∆U = Q - W ∆U = Q ∆U = 0 ∆U = -W
W=0 Q=W Q=0
Work

Heat Flow

Q 0
Heat 0
Capacity
Internal
Energy
0
Entropy

0*

Ideal Gas
Relations

* For Adiabatic Reversible Processes


n cp = m C p n cv = m C v cp - c v = R nR=Nk

γ = Cp/Cv = c p/cv = Ratio of Specific Heats

Cp = Constant Pressure Specific Heat Capacity (J/kg/ oC)


Cv = Constant Volume Specific Heat Capacity (J/kg/ oC)
cp = Molar Constant Pressure Heat Capacity (J/mole/oC)
cv = Molar Constant Volume Heat Capacity (J/mole/oC)

PHAS1228 – Thermal Physics 6

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