Mechanical equilibrium!

Chapter 1: Properties of gases!

The perfect gas!
Gas laws, perfect gas equation!

Partial pressures! Barometric formula! Real gases!

The van der Waals equation!

Thermal equilibrium!

Temperature scales: Thermometry! Fahrenheit scale: three reference points:! a. lowest temperature: 0 degrees (brine: a mixture ice, water and ammonium chloride)! b. ice melts at 32 degrees (he did not use this in his original scale)! c. 96 degrees: the temperature in the mouth or armpit of his wife (or a living man in good health)! Later on it was adjusted between the freezing (32 F) and boiling points of water and (212 F). ! In the original Celsius (Swedish astronomer) scale water boils at 0 degrees and ice melts at 100 degrees. This was reversed later.! TF = 32 + 1.8 TC! Thermal equilibrium:! Illustration of zeroth law! Of thermodynamics!

Boyle s law:! ! pV=constant at constant n, T!

Boyle s law:! p1/V! at constant n, T!

Charle s law:! VT, at constant n, and p!

Charle s law:! pT, at constant n, and V!

Barometric formula!

Partial pressures!
Dalton s law: pressure exerted by a mixture of gases is equal to sum of their partial pressures!

p=p0 exp(-h/H)! H7.4 km!

p=JpJ! pJ=nJRT/V (perfect gas)!

Example problems

!
When & why is the ideal gas equation valid?!
T= 260 K and p= 10 atm!
Compound! Molar volume (liter/mol)! 6.86! 2.04! 1.99! 2.13!

1. Use the barometric formula to calculate the altitude at which the pressure is 1/10th of that at sea level.!

T=400 K and p= 1 atm!

Compound! C2H6! N2! CH4! NH3! Ideal gas law! Molar volume (liter/mol)! 32.73! 32.83! 32.81! 32.73! 32.8!

C2H6! N2! CH4! Ideal gas law!

Real gases!
Do not obey perfect gas equation exactly! Characterized by intermolecular interaction! ! repulsive at short distances! ! attractive at intermediate separations!

Real gases!
Compression factor! Z=Vm/V0m! For a perfect gas, Z=1! Z >1: repulsive interaction! Z <1: attractive interaction!

Critical temperature, Tc! Temperature above which ! the gas cannot be liqueed!

Boyle temperature!
Temperature at which properties of real gases coincide with that of the perfect gas!

van der Waals isotherms!

Surface of possible states allowed by the van der Waals equation!

Critical compression factor: Zc=pcVc/RTc=3/8=0.375!

Reduced variables!
pr=p/pc! Vr=Vm/Vc! Tr=T/Tc! Reduced van der Waals equation of state!

pr=8Tr/(3Vr-1)-3/Vr2!

Ethane at 350 K!
Vexp! 28.588! 5.6119! 2.7387! 0.13720! 0.09840! 0.0868! 0.07160! 0.07089! 0.07022! pexp (atm)! Pideal (atm)! 1! 5! 10! 100! 150! 200! 450! 475! 500! 1.004! 5.114! 10.470! 209.184! 291.667! 330.645! 400.838! 404.853! 408.715! pvdW (atm)! 0.9994! 4.999! 9.998! 99.373! 262.513! 519.193! 2608.65! 2955.56! 3357.07! pBB (atm)! pBWR (atm)! 1.0004! 4.10! 9.99! 102.903! 160.709! 209.143! 348.118! 358.492! 368.752! 1.000! 4.998! 9.989! 99.073! 147.070! 200.201! 450.277! 474.984! 500.237!

vdW: van der Waals equation! BWR: Benedict-Webb-Rubin equation! BB: Beattie-Bridgeman equation!

Summary!

Benedict - Webb - Rubin Equation (BWR) p = RT + ( BRT A C0T ) + (bRT a) + a 6 + cT 2 3 (1 + 2) exp( 2 ) where A, B, C0 , a, b, c, , are constants Beattie - Bridgeman equation (BB) & & c )& bB ) a) 2 pVm = RT(1 V + B + A(1 + 3 +( m Vm * ' Vm T *' ' Vm * where A, B, a, b, c are constants
2 2 3

Ideal gas equation: pV=nRT!

No intermolecular interaction between gas molecules!

Dalton s law of partial pressures: pJ=xJp; xJ=nJ/n; JpJ=p!

Valid for both perfect gases and real gases!

Barometric formula: p=p0exp(-h/H); H=RT/Mg! Real gases: ideal gas equation not valid due to intermolecular forces! Compressibility factor, Z=Vm/Vm0; Vm0=RT/p; Z=1 for ideal gas! Virial equation of state: PVm=RT(1+B#p+C#p2+)!
! PVm=RT(1+B/Vm+C/Vm2+)!

Boyle temperature: Temperature at which real gases exhibit ideal gas behavior! van der Waals equation: p=RT/(Vm-b)-a/Vm2! Critical constants: Vc=3b; pc=a/27b2; Tc=8a/27Rb! Reduced variables: pr=p/pc; Vr=V/Vc; Tr=T/Tc! Reduced van der Waals equation of state: pr=8Tr/(3Vr-1)-3/Vr2!