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Kinetic
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ofReal
RealGases
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Distribution
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GasMolecules
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The Ideal Gas
CONTENTS
• Real Gases
(A) gas expands to fill its container and its volume is readily
contracts when pressure is applied.
• P = 101.32 k Pa (1 atm)
Using Eq.1.2 we have that;
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We can calculate the gas pressure as follows
1.The pressure (P) is defined as the force (F) per unit area (A), viz.
F
P = (1.3)
A
2.The force exerted by gas molecule is defined as the rate of change of
momentum, that is
∆ (mu x )
F= (1.4)
∆t
We can calculate the gas pressure as follows
= 2 mux (1.5)
ux
•The number of collisions per second = (1.6)
2L
From Eqs. (1.1) – (1.5) we can find that the pressure on the wall A as
2
mu (1.7)
Px = 3
x
V
where V = L3 is the volume of the container.
•Now we can recognize that the pressure is the same for all walls of the
container. Thus we can discard the restriction “by side A”. We therefore
have 2
mu
P = 1
x
(1.8)
V
We can calculate the gas pressure as follows
2
If Nmu x
is written to indicate an average value, we have
2
Nmu
P = x
(1.9)
V
(2.9)
A relation between the pressure and the speeds of the
molecules, rather than a component of the speeds, is more
convenient.
•The velocity vector can be resolved into three orthogonal
components to give
u 2 = u x2 + u y2 + u z2
(2.10)
We can calculate the gas pressure as follows
u x2 = u y2 = u 2z and u 2 = 3u x2 (1.10)
Substitution of Eq. (1.10) in Eq. (1.9) gives the desired relation between P
and V
1 1
Nmu 2
or PV = Nmu 2
(1.11)
P = 3 3
V
We can calculate the gas pressure as follows
Example 1.1
∆(mu ) 2mu
F=N =N
∆t 1s
For 1 molecule
3 R 3
∈k = R = kt (1.13)
2 N A 2
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Equations of Real Gases
Contents:
• Compressibility Factor.
• Virial Equations
(2.1)
The density (ρ) of steam of 100.0oC and 1.01325 bar is 0.5974 kg m-3.
Calculate:
i. the compressibility factor.
ii. the deviation of the volume from the ideal behaviour
Solution
i- Submitting n = m/M and ρ = m/v into (2.1)
(m = mass of the gas)
PV PMV PM
Z = = = (2.2)
nRT mRT ρ RT
Example 2.1
PV PM
ii- Z = =
nRT ρ RT
⎛ RT ⎞
V real = ⎜ ⎟Z
⎝ P ⎠
V
real = V Ideal Z = 30618x0.9848 = 30152.6 L
V ideal − Vreal 30618 - 301526
Deviation = x100 = x 100 = 1 . 52 %
Videal 30618
Virial PV B C PV
= 1 + B ' P + C ' P + .....
= 1 + + 2 + .....and
nRT V V nRT
Berthelot ⎛ 2 ⎞
⎜ p + aT ⎟(V − nb) = nRT
n
⎜ V 2 ⎟⎠
⎝
Dieterici P x e [na/(RTV)] (V-nb) = nR
Redlich-Knowing ⎛ 2 ⎞
⎜ p + aT ⎟(V − nb) = nRT
n
⎜ V 2 ⎟
⎝ ⎠
Virial Equations
Virial Equations
PV B C
= 1 + + 2 + ..... (2.5)
nRT V V
PV
= 1 + B ' P + C ' P + .....
nRT (2.6)
RT is the first virial equation
B is the second virial coefficient.
C is the third virial coefficients.
They are temperature dependent.
Virial Equations
BP
Z = 1 + BV = 1 +
RT
(−0.417 L mol-1 )(400 bar)
= 1+ −2 -1 −1
= 0.9965
(8314 x10 L bar K mol )(573K )
molecules
Excluded Volume
If the total excluded volume for NA molecules (Avogadro’s
number) is b, then
⎡ 4 ⎛ d ⎞3 ⎤
b = 4 NA ⎢ π⎜ ⎟ ⎥
⎢⎣ 3 ⎝ 2 ⎠ ⎥⎦ (2.8)
Van der Waals made the correction for attractive forces as follows.
• Attraction occurs between pairs of molecules,
• Molecular attraction decreases the number of collisions on the walls of
the container ( n/V )
• Attraction forces increases as the number of molecules increases in
the container (n/V )
• Attraction forces should proportional with
the square of the concentration of molecules, (n/v)2.
• Attractive forces = a(n/V)2
Molecular Attraction
The result of both the van der Waals corrections is, therefore
Molecular Attraction
⎛ ⎛ n 2
⎞ ⎞
⎜ P + a⎜ ⎟⎟ ⎟ ( V − ab ) = nRT
⎜ ⎜ v 2 ⎟ (2.10)
⎝ ⎝ ⎠ ⎠
nRT an 2
or P = − (2.11)
v − nb v2
If n = 1, we have that
(P +
a
)(V − b) = RT (2.13)
2
V
The van der Waals Eqs. (2.10 and 2.11) represents the PVT
behavior of gases quite well when they deviate moderately
from ideality.
Example 2.3
Calculate the pressure needed to confine 1 mol of carbon
dioxide gas to a volume of 0.5 L at 298 K using van der
Waals equation. Estimate the radius of CO2 molecule.
a = 3.592 L2 atm mol-2 and b = 0.0427 L mol-1.
__________________________________________________
Pressure of CO2
nRT an 2
P= − 2
V − nb V
Since V =0.5 L and T = 298 K, then R = 0.082 L atm K-1 .mol-1
(0.082 L atm K -1mol −1 )(298K ) 3.592 L2 atm mol-2
Preal = −
0.5L mol − 0.0427 L mol
-1 -1
(0.5 L mol-1 ) 2
Example 2.3
Preal = 48.87 atm – 7.18 atm = 41.69 atm.
Pideal = nRT / V = 1 x 0.082 x 298 / 0.5 = 48.87 atm
The pressure is appreciably less 7 atm than that would be needed if carbon
dioxide behaved ideally.
Radius of CO2
⎡ 4 ⎛ d ⎞3 ⎤
Q b = 4 N A ⎢ π ⎜ ⎟ ⎥ = 4 N Aπr 3
⎢⎣ 3 ⎝ 2 ⎠ ⎥⎦
−3
b 0 . 0427 x10
∴ r3 = = =5.64x10-30 m3
4 N Aπ 4 x 6.02 x10 π
23
r = 2.15 x 10-10 m
The pressure is appreciably less than the 100 bar that would be needed if methane
behaved ideally.
Condensation of Gases
The constants of van der Waals equation can
be evaluated from critical-point data.
• The constants of van der waals equation can be evaluated from critical
point data. The van der Waals Equation is not exact, only a model.
Applying equation (2.13) to the point of inflction at the critical point, we
have that
a
(P + 2
)(V − b) = RT
V
(2.13) dP − RT 2a
=+ + 3 =0
dV (V − b) V
2 (2.14)
2
d P 2 RT 6a
and 2
= − 4 =0
dV (V − b) V
3
(2.15)
The constants of van der Waals equation can
be evaluated from critical-point data.
PC VC 3
Z= = (2.16)
RTC 8
The constants of van der Waals equation
can be evaluated from critical-point data.
The values of a and b are often chosen so that the van der
Waals PV isotherm with a horizontal point of inflection
occurs at PC and TC.
27 R 2TC2 RT C
a= and b=
64 PC 8 PC (2.17)
The constants of van der Waals equation
can be evaluated from critical-point data.
PC V C
Gas RT C
H2 0.33
He 0.32
CH4 0.29
NH3 0.24
N2 0.29
O2 0.29
Example 2.5
⎛ ⎞
⎜ PR + 3 ⎟⎛⎜ VR − 1 ⎞⎟ = 8 TR
⎜ 2 ⎟
R ⎠⎝
⎝ V 3⎠ 3 (2.18)
¾ In this form, van der Waals equation requires no
quantities that characterize a particular gas – other than
the critical-point data implicit in the reduced variables.
¾ Thus van der Waals equation is consistent with the law of
corresponding states.
Quiz 2
2.1. Why gases deviate from the ideal behavior ?
2.2. At what conditions gases can follow the ideal gas equation?
2.3. Define the terms;
(i) compressibility factor, (ii) excluded volume,
(iii) critical point and (iv)reduced variables.
2.4. Why the compressibility factor is important?
2.5. Give examples of real gas equations.
2.6. Show how van der Waals corrects the ideal gas equation for
real gases.
Theory of Gases
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Distribution of Velocities of Gas Molecules in One
Direction (Boltzmann Distribution)
dN − (1 / 2 ) mu x2 / kT dN − (1 / 2 ) mu x2 / kT
αe du x ∴ = Ae du x (3.1)
N N
This constant can be evaluated by recognizing that integration of the
right side of Eq. (3.1) over all possible values of ux, that is, from ux = -∞ to
ux = +∞, must account for all the velocity points. Thus we can write
+∞
A∫ e − (1 / 2 ) mu x2 / kT
du x = 1 (3.2)
−∞
Gas Molecules Simulation
m (3.4)
A=
2π kT
Gas Molecules Simulation
Finally, the equation for the distribution over the velocities
along the x direction for a sample of N molecules can be written
as
1/ 2
dN / N ⎛ M ⎞ ⎛ mux2 ⎞
f (u x ) = =⎜ ⎟ exp⎜⎜ − ⎟⎟ (3.5)
dU X ⎝ 2πRT ⎠ ⎝ 2 RT ⎠
u 2 = u 2x + u 2y + u 2z (3.6)
It is given analytically ;
f(ux, uy, uz) duxduy,duz = dN
N
3/ 2
(3.7)
∴
dN ⎛ m ⎞
=⎜ ⎟
⎡ m 2
exp ⎢− (
u x + u y2 + u z2 )
⎤
⎥ du x du y du z
N ⎝ 2πkT ⎠ ⎣ 2kT ⎦
3/ 2
2⎛ m ⎞ ⎛ mu 2 ⎞
F (u )du = 4πu ⎜ ⎟ exp⎜⎜ ⎟⎟du (3.8)
⎝ 2πkT ⎠ ⎝ 2kT ⎠
Maxwell – Boltzmann Distribution
(in three dimensions)
3/ 2
⎛ m ⎞ ⎛ mu 2 ⎞
F(u) = 4πu2 ⎜ ⎟ exp⎜⎜ ⎟
⎟ (3.9)
⎝ 2πkT ⎠ ⎝ 2 kT ⎠
dN / N A
= 5.79 x10 − 4 sm −1
du
Example 3.2
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Speeds of Gas Molecules
3/ 2
dF (u ) ⎛ m ⎞ − mu 2 / 2 kT ⎡ 2⎛ mu ⎞⎤
=⎜ ⎟ e ⎢8πu + 4πu ⎜ − ⎟⎥ = 0
du ⎝ 2πkT ⎠ ⎣ ⎝ kT ⎠⎦
1/ 2 1/ 2
⎛ 2kT ⎞ ⎛ 2 RT ⎞
∴u p = ⎜ ⎟ =⎜ ⎟ (4.1)
⎝ m ⎠ ⎝ M ⎠
Speeds of Gas Molecules
Mean speed (u):
It is calculated as the average of (u) using the probability distribution F(u):
∞
u = ∫0
uF ( u ) du
1/ 2 1/ 2
⎛ 8 kT ⎞ ⎛ 8 RT ⎞
∴u = ⎜ ⎟ =⎜ ⎟
⎝ πm ⎠ ⎝ πM ⎠ (4.2)
Speeds of Gas Molecules
Root-mean square speed (urms):
2
Which is defined as the square root of u
1/ 2
⎡∞
⎤
urms = (u 2 )1/ 2
⎢∫
= ⎢ u 2 F (u )du ⎥
⎣0
⎥
⎦
Substituting Eq. 3.9 and using tables again, we find
1/ 2 1/ 2
⎛ 3 kT ⎞ ⎛ 3 RT ⎞
u rms =⎜ ⎟ =⎜ ⎟
⎝ m ⎠ ⎝ M ⎠ (4.3)
Speeds of Gas Molecules
1/ 2 1/ 2
⎛ 8 RT ⎞ ⎡ ( 8 )( 8 . 314 Jk − 1 mol −1
)( 273 k ) ⎤
u =⎜ ⎟ = ⎢ ⎥ = 1.69 x 103 m s-1
⎝ π M ⎠ ⎣ ( 3 . 146 )( 2 . 016 x10
−3
kg mol -1 ⎦
Example 4.1
1/ 2
⎛ 3RT ⎞ ⎡ 3(8.314Jk−1mol−1 )(273.15k )1/ 2 ⎤
urms = ⎜ ⎟ =⎢ −3 -1 ⎥= 1.84 x 103 m s-1
⎝ M ⎠ ⎣ 2.06x10 kg mol ⎦
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COLLISION PROPERTIES
OF GAS MOLECULES
Molecular Collision
Two Gases
COLLISION
Collision
Frequency
Collision
Density
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Volume = π d
2
AB u A
1/ 2
or ⎛ 8RT ⎞ (5.5)
Z A( B ) = πd ⎜⎜
2
⎟⎟ ρ B
⎝ πµ ⎠
AB
Z A( A) = πd A2 u A ρ A (5.6)
1/ 2
⎛ 8RT ⎞
Or Z A( B ) = πd ⎜⎜
2
⎟⎟ ρ B (5.7)
⎝ πµ ⎠
AB
Collision Frequency of Identical Molecules
⎛ 8kT ⎞⎛ 1 1 ⎞
(u 12 ) = ⎜
2
⎜
⎟⎜ + ⎟⎟ = (u 1 ) 2 + (u 2 ) 2
⎝ π ⎠⎝ m1 m2 ⎠
1/ 2
⎛ 8 kT ⎞
z1( 2 ) = ρ 2π d u 12
2
= ρ 2π d ⎜⎜
2
⎟⎟
⎝ πµ
12 12
⎠
Molecular Collision
2 2
u 11 = 2u 1 d2 z1(1) = 21/2
d2 = 21/2
u 12 = 2u 1 = 2 u
1/ 2
⎛ 8kT⎞
u = ⎜ ⎟
⎝ πµ ⎠
Molecular Collision
32 . 00 x 10 − 3 kg mol -1 − 26
m2 = 23 -1
= 5 . 314 x 10 kg
6 . 022 x 10 mol
Note that the mean relative speed is closer to the mean speed
of molecular hydrogen (1920 ms-1) than to that of molecular
oxygen (482 ms-1) .
Collision Density
ρ ( 1 bar)(6.022 x10 23
)( 10 3 Lm − 3 ) − 3
= N / V = PN / RT = = 2 . 43 x 10 25
m
mol − 1 )( 298 K )
A
( 0 . 083145 L bar K -1
Example 3.2
u 1
λ = = 1/ 2
z 1 (1) 2 ρπ d 2
Mean Free Path
Assuming that the collision diameter d is independent to
temperature,
the temperature and pressure dependence of the mean free
path may be obtained by substituting the ideal gas law in the
form ρ = P/kT:
1
λ =
21 / 2
πd 2
1
λ =
2 1 / 2 ρπ d 2
( 0 . 2 Pa )( 6 . 022 x 10 23 m − 1 )
(b) ρ =
PN
RT
A
=
( 8 . 314 J K -1 mol − 1 )( 298 K )
= 2 . 43 x 10 19
m − 3
= 0.071 m = 7.1 cm
At pressure so low that the mean free path becomes
comparable with the dimensions of the containing vessel,
the flow properties of the gas become markedly different
from those at higher pressures.
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TRANSPORT PHENOMENA IN GASES
Transport
Properties
Thermal
Diffusion Viscosity
Conduction
TRANSPORT PHENOMENA IN GASES
DIFFUSION
Transport of (labelled)
particles
PROPERTIES
Transport of thermal
energy
OF GASES
VISCOSITY
Transport of momentum in
one direction through a gas
in another direction
TRANSPORT PHENOMENA IN GASES
In each case,
¾ Rate of flow ∞ Rate of change of some property with
distance, a so-called gradient
¾ All have same mathematical form:
Flow of____(per unit area, unit time) = (___x gradient___)
Diffusion: Fick’s Law
1 dn dc i
J N J= -D
iz A dt dz
dci (6.1)
J iz = − D
dz
Diffusion: Fick’s Law
Heavy
Thermal Conduction: Fourier’s Law
Planes constructed at
distance ±λ (the mean free
path) from the origin. The
concentration gradient is in
the z direction.
⎡ ⎛ dπ ⎞⎤ u
J+ = ⎢ρ0 + λ⎜ ⎟⎥
⎣ ⎝ dz ⎠ ⎦ 4
Diffusion Coefficient
1/ 2 1/ 2
3π ⎛ kT ⎞ 1 3 ⎛ RT ⎞ 1
D= ⎜ ⎟ = ⎜ ⎟
⎝ πm ⎠ ρπ d 8 ⎝ πM ⎠ ρd
2 2
8
Example 6.1
Predict D(O2,N2) of an equimolar mixture of O2 and N2 gases
at 1.00 atm and 00C using dO2 = 0.353 nm and dN2 = 0.373
nm.
____________________________________________________________________________________________________________________________________
1
x −10 2 −3 -1
= 1.59x10−5 m2 s −1
(3.63x10 m) (2.64x10 kg mol )
Example 6.1
25.26 JK-1mol−1
x 23 −10 2
= 0.027 Jm-1s−1K−1
(6.022x10 mol)(5.0x10 m)
Example 6.2
1/2
3 ⎛ kT ⎞ m
η = ⎜ ⎟
32 2 ⎝ πm ⎠ d2
Example 2
Note that this does not imply that real molecules are hard
spheres; in fact, we are forcing a model on the
experiment. Nevertheless, the results in Table 6.1 show
that a consistent set of molecular diameters result from
this analysis of the data.
Example 6.3
32 . 00 x 10 − 3 kg mol -1
m =
6 . 022 x 10 23 mol − 1
− 26
= 5 . 314 x 10 kg
1/ 2
5π ⎛ kT ⎞ m
η= ⎜ ⎟
16 ⎝ πm ⎠ πd 2
Example 3
1/ 2
5π ⎡ (1.380x10− 23 JK−1(273.2K) ⎤ 5.314x10− 26 kg
= ⎢ ⎥
16 ⎣ π(5.314x10− 26 kg) ⎦ π(0.360x10−9 m)2