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Kinetic Theory of Gases
Ideal Gas
The number of molecules is large
The average separation between
   molecules is large
Molecules moves randomly
Molecules obeys Newton’s Law
Molecules collide elastically with each
   other and with the wall
Consists of identical molecules
The Ideal Gas Law

     PV = nRT                             in K
n: the number of moles in the ideal gas
        N            total number
     n=
        NA           of molecules

             Avogadro’s number: the number of
             atoms, molecules, etc, in a mole of
             a substance: NA=6.02 x 1023/mol.

R: the Gas Constant: R = 8.31 J/mol · K
Pressure and Temperature
     Pressure: Results from collisions of molecules
     on the surface
                                   Force
                        F
     Pressure:       P=
                        A          Area

                        dp
     Force:          F=           Rate of momentum
                        dt        given to the surface

Momentum: momentum given by each collision
          times the number of collisions in time dt
Only molecules moving toward the surface hit
the surface. Assuming the surface is normal to
the x axis, half the molecules of speed vx move
toward the surface.
Only those close enough to the surface hit it
in time dt, those within the distance vxdt

The number of collisions hitting an area A in
time dt is    1  N
                     ⋅ A ⋅ vx ⋅ dt
              2V 
                                     Average density
The momentum given by each collision to
the surface 2mvx
Momentum in time dt:
                           1  N
             dp = (2mv x )⋅ ⋅     ⋅ A ⋅v x dt
                           2  V


Force:          dp           1  N
             F=    = (2mvx )⋅ ⋅      ⋅ A⋅ v x
                dt           2  V 


Pressure:       F N 2
             P = = mv x
                A V

Not all molecules have the same v x ⇒ average v2
                                               x

                 N 2
              P = mv x
                 V
2
            vx
                  1 2 1 2 2
                  3   3
                           (        2
                 = v = v x + v y + vz       )
             2    1 2 1 2
            vx   = v = vrms
                  3   3
 vrms is the root-mean-square speed
                                2      2      2
                               vx   + vy   + vz
            vrms = v 2 =
                                      3
              1N   2 2  N1      2
Pressure: P =    mv =           mv
              3V      3  V 2     

Average Translational Kinetic Energy:
              1 2 1 2
           K = mv = mvrms
              2        2
2 N
Pressure:                    P = ⋅ ⋅K
                                3 V

            2
From    PV = ⋅ N ⋅ K   and   PV = nRT
            3

                         3 nRT 3
Temperature:           K= ⋅   = ⋅ k BT
                         2 N   2
                          R              −23
Boltzmann constant: k B =    = 1.38 × 10     J/K
                          NA
1        2
From PV = ⋅ N ⋅ mvrms
         3

                 N
and   PV = nRT =    RT
                 NA
                         Avogadro’s number
                                N = nN A
                  3RT
         vrms   =
                   M         Molar mass
                               M = mN A
Internal Energy

For monatomic gas: the internal energy = sum
of the kinetic energy of all molecules:

                              3      3
       Eint   = N ⋅ K = nN A ⋅ k BT = nRT
                              2      2


                      3
              Eint   = nRT ∝ T
                      2
Mean Free Path

 Molecules collide elastically with other
 molecules

 Mean Free Path λ: average distance between
 two consecutive collisions
                     1
          λ=         2
                  2πd N / V
the bigger the molecules       the more molecules
   the more collisions         the more collisions
Q = cm ⋅ ∆T
      Molar Specific Heat        ∆Eint = Q − W
                                         3
                                   Eint = nRT
                                         2
Definition:

  For constant volume:     Q = nCV ∆T

  For constant pressure:   Q = nC p ∆T

The 1st Law of Thermodynamics:
               3
     ∆Eint    = nR∆T = Q − W   (Monatomic)
               2
3
                    nR∆T = Q − W
Constant Volume   2
                    (Monatomic)
                     Q = nCV ∆T
W = ∫ PdV = 0
                             3
                     Eint   = nRT
3                            2
  nR∆T = nCV ∆T
2
    3
CV = R
    2
Eint = nCV T
3
                            nR∆T = Q − W
                          2
      Constant Pressure     (Monatomic)
                             Q = nC p ∆T
W = P∆V = nR∆T
3
  nR∆T = nC p ∆T − nR∆T
2
                     5
CV = Cp − R     Cp = R
                     2
      Cp            5
γ =             γ =
      CV            3
1st Law
                              dEint = dQ − dW
        Adiabatic Process
                                 Ideal Gas Law
                                    pV = nRT
 (Q=0)                            Eint = nCV T
dEint = −dW = − pdV              C p = CV + R
       = nCV dT                                Cp
                                         γ =
                      pdV                    CV
pdV + Vdp = nRdT = nR −   
                      nCV 
Divide by pV:
dV dp     C p − CV  dV            dV
  +   = −              = (1 − γ )
V   p     CV  V                   V
dV dp            dV               Ideal Gas Law
  +   = (1 − γ )                    pV = nRT
V   p            V
dp    dV
   +γ    =0
 p    V
          γ            γ
ln p + ln V = ln( pV ) = const.
              γ
        pV = const.
  nRT γ
(    )V = const.
   V
              γ −1
        TV           = const.
Equipartition of Energy

The internal energy of non-monatomic
molecules includes also vibrational and
rotational energies besides the
translational energy.


Each degree of freedom has associated with
                1
it an energy of k BT per molecules.
                2
Eint = nCV T
       Monatomic Gases


3 translational degrees of freedom:
                 3           3
         Eint   = kBT ⋅nN A = nRT
                 2           2
             1 dEint 3
         CV = ⋅     = R
             n dT    2
Eint = nCV T

            Diatomic Gases
3 translational degrees of freedom
2 rotational degrees of freedom
2 vibrational degrees of freedom

HOWEVER, different DOFs require different
temperatures to excite. At room temperature,
only the first two kinds are excited:

                 5              5
         Eint   = nRT       CV = R
                 2              2

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Kinetic theory of gases

  • 2. Ideal Gas The number of molecules is large The average separation between molecules is large Molecules moves randomly Molecules obeys Newton’s Law Molecules collide elastically with each other and with the wall Consists of identical molecules
  • 3. The Ideal Gas Law PV = nRT in K n: the number of moles in the ideal gas N total number n= NA of molecules Avogadro’s number: the number of atoms, molecules, etc, in a mole of a substance: NA=6.02 x 1023/mol. R: the Gas Constant: R = 8.31 J/mol · K
  • 4. Pressure and Temperature Pressure: Results from collisions of molecules on the surface Force F Pressure: P= A Area dp Force: F= Rate of momentum dt given to the surface Momentum: momentum given by each collision times the number of collisions in time dt
  • 5. Only molecules moving toward the surface hit the surface. Assuming the surface is normal to the x axis, half the molecules of speed vx move toward the surface. Only those close enough to the surface hit it in time dt, those within the distance vxdt The number of collisions hitting an area A in time dt is 1  N ⋅ A ⋅ vx ⋅ dt 2V  Average density The momentum given by each collision to the surface 2mvx
  • 6. Momentum in time dt: 1  N dp = (2mv x )⋅ ⋅ ⋅ A ⋅v x dt 2  V Force: dp 1  N F= = (2mvx )⋅ ⋅ ⋅ A⋅ v x dt 2 V  Pressure: F N 2 P = = mv x A V Not all molecules have the same v x ⇒ average v2 x N 2 P = mv x V
  • 7. 2 vx 1 2 1 2 2 3 3 ( 2 = v = v x + v y + vz ) 2 1 2 1 2 vx = v = vrms 3 3 vrms is the root-mean-square speed 2 2 2 vx + vy + vz vrms = v 2 = 3 1N 2 2  N1 2 Pressure: P = mv = mv 3V 3  V 2  Average Translational Kinetic Energy: 1 2 1 2 K = mv = mvrms 2 2
  • 8. 2 N Pressure: P = ⋅ ⋅K 3 V 2 From PV = ⋅ N ⋅ K and PV = nRT 3 3 nRT 3 Temperature: K= ⋅ = ⋅ k BT 2 N 2 R −23 Boltzmann constant: k B = = 1.38 × 10 J/K NA
  • 9. 1 2 From PV = ⋅ N ⋅ mvrms 3 N and PV = nRT = RT NA Avogadro’s number N = nN A 3RT vrms = M Molar mass M = mN A
  • 10. Internal Energy For monatomic gas: the internal energy = sum of the kinetic energy of all molecules: 3 3 Eint = N ⋅ K = nN A ⋅ k BT = nRT 2 2 3 Eint = nRT ∝ T 2
  • 11. Mean Free Path Molecules collide elastically with other molecules Mean Free Path λ: average distance between two consecutive collisions 1 λ= 2 2πd N / V the bigger the molecules the more molecules the more collisions the more collisions
  • 12. Q = cm ⋅ ∆T Molar Specific Heat ∆Eint = Q − W 3 Eint = nRT 2 Definition: For constant volume: Q = nCV ∆T For constant pressure: Q = nC p ∆T The 1st Law of Thermodynamics: 3 ∆Eint = nR∆T = Q − W (Monatomic) 2
  • 13. 3 nR∆T = Q − W Constant Volume 2 (Monatomic) Q = nCV ∆T W = ∫ PdV = 0 3 Eint = nRT 3 2 nR∆T = nCV ∆T 2 3 CV = R 2 Eint = nCV T
  • 14. 3 nR∆T = Q − W 2 Constant Pressure (Monatomic) Q = nC p ∆T W = P∆V = nR∆T 3 nR∆T = nC p ∆T − nR∆T 2 5 CV = Cp − R Cp = R 2 Cp 5 γ = γ = CV 3
  • 15. 1st Law dEint = dQ − dW Adiabatic Process Ideal Gas Law pV = nRT (Q=0) Eint = nCV T dEint = −dW = − pdV C p = CV + R = nCV dT Cp γ =  pdV  CV pdV + Vdp = nRdT = nR −   nCV  Divide by pV: dV dp  C p − CV  dV dV + = −  = (1 − γ ) V p  CV  V V
  • 16. dV dp dV Ideal Gas Law + = (1 − γ ) pV = nRT V p V dp dV +γ =0 p V γ γ ln p + ln V = ln( pV ) = const. γ pV = const. nRT γ ( )V = const. V γ −1 TV = const.
  • 17. Equipartition of Energy The internal energy of non-monatomic molecules includes also vibrational and rotational energies besides the translational energy. Each degree of freedom has associated with 1 it an energy of k BT per molecules. 2
  • 18. Eint = nCV T Monatomic Gases 3 translational degrees of freedom: 3 3 Eint = kBT ⋅nN A = nRT 2 2 1 dEint 3 CV = ⋅ = R n dT 2
  • 19. Eint = nCV T Diatomic Gases 3 translational degrees of freedom 2 rotational degrees of freedom 2 vibrational degrees of freedom HOWEVER, different DOFs require different temperatures to excite. At room temperature, only the first two kinds are excited: 5 5 Eint = nRT CV = R 2 2