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Instructor: J. Blandino

Worcester Polytechnic Institute, Fall 2015

Introductory Concepts

Real Gas:

- intermolecular forces important

Cp = f (T, p), h = h(T, p)

- may or may not be chemically reacting

- Real Gas Equation of State: Van der Waals is one

example:

(P +

a

)(v

v2

− b) = RT

**- appropriate for high pressure, low temperature (near
**

condensed state)

**Thermally Perfect Gas:
**

Cp = f (T ), h = h(T )

- vibrational and electronic energy excitation

- high temperature, low pressure

1

**Notes are based on material from the course text, Ref. 1: Introduction to Physical Gas
**

Dynamics, Vincenti, W. and Kruger, C., Krieger Pub., Copyright 1965. Any figures used from

Ref.1 are so noted and copyrighted by Krieger Publishing Co.

1

Some texts refer instead to “high temperature effects.) The term “real gas effects” was used even for thermally perfect gases or chemically reacting mixtures of perfect gases.” Microscopic Description of Gases kinetic theory: atomic/molecular interactions (collisions) 2 .g.ionization . vibration.Perfect Gas Equation of State applies: pv = RT Calorically Perfect Gas: Cp = const.excitation (e.may be chemically reacting (each species obeys equation of state) In aerodynamic literature (beginning in the 1950s). dh = Cp dT γ= Cp Cv . etc.perfect gas equation of state .dissociation .. “real gas effects” was a term used to denote effects at high temperature: .

all parts of a system at the same temperature. and composition are macroscopic observable quanti3 .no unbalanced forces. If no body forces. temperature.system has no tendency to undergo a spontaneous change in chemical composition If all three of these conditions are satisfied → “Thermodynamic Equilibrium” Note: pressure. which is the same temperature as surroundings Chemical Equilibrium .distribution function: describes probability of an atom or molecule at a particular point in space having a particular velocity Boltzmann Equation: PDE which can (in principle) be solved to determine the distribution function statistical mechanics: describes how energy is partitioned in collections of atoms and molecules Macroscopic Description of Gases Conservation equations for a fluid : these are moments of the Boltzmann equation constitutive equation: equation relating stress and strain in the fluid (or other properties) equation of state: constitutive equation relating thermodynamic state functions for a fluid Equibilibrium of a Thermodynamic System Mechanical Equilibrium . then p = const Thermal Equilibrium .

Local Thermodynamic Equilibrium (LTE) .Local Chemical Equilibrium (LCE) implies local chemical composition corresponds to equilibrium at local temperature and pressure .implies some subsystem is in local equilibrium internally. though not necessarily with surroundings. this is the approach taken in gas dynamics .e. These are related to average values of microscopic qantities. we speak of local equilibrium: . Molecular Transport: mass → diffusion momentum→ viscosity energy→ heat conduction 4 .in cases of chemical nonequlibrium.the subsystem can be a fluid element→ often. In a flow. Pressure and Temperature are related to the distribution of energy at a molecular level. we often still assume local thermal equilibrium so that temperature can be defined for analysis of reactions Equilibrium also has implications at a molecular level.ties. i.

statistical.Kinetic Theory: . interact through collisions . description of a gas .particle model in contrast to a continuum fluid model Simple Force Models The Rigid Sphere (or Billiard Ball ) and Sutherland law are simplified models to describe the force between particles (atoms and molecules): Figure 1: Models of intermolecular force [1] Rigid Sphere Model → adequate to explain much behavior derived from collisional processes (e.molecules are in constant motion.microscopic. pressure. transport) 5 .g.

C3 and C 2 = C12 + C22 + C32 . for every collision deflecting a molecule from its original velocity Ci . there will on average. be another molecule undergoing a collision resulting in a velocity Ci . C2 . say the wall perpendicular to the x1 axis: 6 .motion with velocity components C1 . for a small region about a given point.velocity components assumed constant (neglect intermolecular collisions) The pressure on a wall of this box will be due to force from colliding molecules: F = d (momentum) dt We assume the gas molecule collisions are specular Note: for a gas in equilibrium. Consider molcules colliding with one of the walls. rotational) Kinetic Theory: Introduction Begin with a simple picture to interpret pressure of a gas: Consider a cubical box of length l on a side: .molecules in the box are in constant motion . ⇒ So the gas (in equilibrium) behaves as if the assumption of constant velocity and specular reflection were true.Internal molecular structure → determines distribution ofenergy in molecule (vibrational.

each with a different mass.two traverses between each collision with wall.and the pressure (force/area) is given by: mC12 1 mC12 mC12 · 2 = 3 = p= l l l V If there are many molecules..change in momentum per collision: 2m|C1 | . the pressure on the wall will be due to the momentum contributions from all: p= 1 X mz Cz21 V z 7 . so number of collisions per unit time: |C1 | 2l .time to traverse distance l between walls l |C1 | .the total change in momentum per unit time: 2m|C1 | · |C1 | mC12 = 2l l .

Comparing the equation of state to the previous expression for pV 3 Etr = N <T 2 ⇒ temperature is a measure of translational kinetic energy 8 .314Jmol−1 K −1 ). ideal gas equation of state can be expressed as pV = N <T where N is the number of moles in the system and < is the universal gas constant (< = 8. These can be combined: 2 pV = Etr 3 Recall that the empirical.There will be pressure exerted on the walls perpendicular to x2 and x3 as well p= 1 X 1 X mz (Cz21 + Cz22 + Cz23 ) = mz Cz2 3V z 3V z We can also write the translational kinetic energy for the entire system Etr as Etr = 1X mz Cz2 2 z The summation of particle mass times the speed squared is common to both the pressure and energy.

Note that the Boltzmann constant is related to the universal gas constant and Avogadro’s Number: k= < NA and Avogadros Number relates the number of molecules and moles in the system NA = Nm N so we can write e˜tr = Etr 3 = kT Nm 2 So e˜tr represents the average kinetic energy per molecule. On a per unit mass basis etr = e˜tr 3 kT NA = · mi 2 mi NA 9 .on a per molecule basis e˜tr = Etr Nm where Nm is the number of molecules in the system.

subscript not shown). Note that M With these simple results. ˆ = NA mi .The internal energy per unit mass can also be written as etr = 3 <T 3 = RT ˆ 2M 2 ˆ is the molecular weight of species i and R is where M the gas constant for species i on a mass basis (for clarity. we can also find an expression for the specific heats: Cv = Cp = ∂e ∂T ∂h ∂T = v p 3 detr = R dT 2 5 = R + Cv = R 2 and the ratio of specific heats γ is γ= Cp 5 = Cv 3 This value agrees well with the experimental value for monatomic gases and confirms validity of simple model which includes only translational kinetic energy. 10 .where mi is the mass of a single molecule of species i.

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