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PV = nRT
states : The pressure of a fixed mass of gas at constant temperature is inversely proportional to its volume.
P 1 V
if
T2 T1 T2 T1 V T2 T1
T = constant
OR
PV = constant
where
P 1V1 = P 2V2
0 c. P
d. PV
T2 T1
1 V
14.1.2
Charless law
states : The volume of a fixed mass of gas at constant pressure is directly proportional to its absolute temperature.
V T
If
P = constant
V1 V2 = T1 T2
V = constant T
where
T1 : initial absolute temperature T2 : final absolute temperature V1 : initial volume V2 : final volume
b. V
273.15
T(C)
T(K)
14.1.3
states : The pressure of a fixed mass of gas at constant volume is directly proportional to its absolute temperature. P T If V = constant
P = constant T
where
b. P
P P 1 = 2 T1 T2
T1 : initial absolute temperature T2 : final absolute temperature P 1 : initial pressure P2 : final pressure
273.15 0 T(C) 0 T(K)
10
P 1 V1 T1
12
1st stage
P2 V' T1
2nd stage
P2 V2 T2
Figure 14.1
In 1st stage, temperature is kept at T1 , Using Boyles law : PV P2V ' = P V '= 1 1 1V1 P2 In 2nd stage, pressure is kept constant at P2 , Using Charless law : V ' V2 VT = V '= 2 1 T1 T2 T2 Equating eqs. (1) and (2), thus
P1V1 P2V2 = T1 T2
Initial
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Consider 1 mole of gas at standard temperature and pressure (S.T.P.), T = 273.15 K, P = 101.3 kPa and Vm = 0.0224 m3 From equation (3),
(1)
R=
R = 8.31 J K 1 mol1
(2)
where R is called molar gas constant and its value is the same for all gases. Thus PV
m
OR
PV = constant T
T
(3)
=R
where
PVm = RT
For n mole of an ideal gas, the equation of state is written as
Final
PV = nRT
where n : the number of mole gas
n=
m M
where
Example 14.1 :
The volume of vessel A is three times of the volume vessel B. The vessels are filled with an ideal gas and are at a steady state. The temperature of vessel A and vessel B are at 300 K and 500 K respectively as shown in Figure 15.2.
OR
n=
A
(300 K) Figure 14.2
B
(500 K)
If the mass of the gas in the vessel A is m, obtain the mass of the gas in the vessel B in terms of m.
PV = NkT
16
Solution :
Solution :
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Example 14.2 :
connecting tap
Solution :
Figure 14.3
V0A = V1A = 3.00 m 3 ; T0A = T1A = 250 K; P0A = 5.00 104 Pa;V0B = V1B = 7.20 m 3 ; T0B = T1B = 400 K; P0B = 2.00 104 Pa
Refer to Figure 15.3. Initially A contains 3.00 m3 of an ideal gas at a temperature of 250 K and a pressure of 5.00 104 Pa, while B contains 7.20 m3 of the same gas at 400 K and 2.00 104 Pa. Calculate the pressure after the connecting tap has been opened and the system reached equilibrium, assuming that A is kept at 250 K and B is kept at 400 K.
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Learning Outcome:
Exercise 14.1 : Given R = 8.31 J mol1 K1 and NA = 6.0 1023 mol1
1. Estimate the number of molecules in a flask of volume 5.0 104 m3 which contains oxygen gas at a pressure of 2.0 105 Pa and temperature of 300 K. ANS. : 2.41 1022 molecules 2. A cylinder contains a hydrogen gas of volume 2.40 103 m3 at 17 C and 2.32 106 Pa. Calculate a. the number of molecules of hydrogen in the cylinder, b. the mass of the hydrogen, c. the density of hydrogen under these conditions. (Given the molar mass of hydrogen = 2 g mol1) ANS. : 1.39 1024 molecules molecules; ; 4.62 g; 1.93 kg m3
and pressure ,
P =
in related problems. Explain root mean square (rms) speed of gas molecules and use the equation,
kT m
14.2.2
Consider an ideal gas of N molecules are contained in a cubical container of side d as shown in Figure 15.4.
Wall B
Figure 14.4
Wall A
Let each molecule of the gas have the mass m and velocity v. The velocity, v of each molecule can be resolved into their components i.e. vx, vy and vz.
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Consider, initially a single molecule moving with a velocity vx towards wall A and after colliding elastically , it moves in the opposite direction with a velocity vx as shown in Figure 15.5.
Wall Wall
The molecule has to travel a distance 2d (from A to B and back to A) before its next collision with wall A. The time taken for this movement is 2d
t = vx
B
Figure 14.5 Wall Wall
If Fx1 is the magnitude of the average force exerted by a molecule on the wall in the time t, thus by applying Newtons second law of motion gives P 2mvx m 2 Fx1 = x = Fx1 = v x t 2d d
m 2 m 2 m 2 Fx = v x1 + v x 2 + ....... + v xN d d d For N molecules of the ideal gas,
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B Therefore the change in the linear momentum of the molecule is given by P = mv (mv )
x x x
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v x
Px = 2mvx
Fx =
m 2 2 2 vx1 + v x 2 + ....... + v xN d
where vx1 is the x component of velocity of molecule 1, vx2 is the x component of velocity of molecule 2 and so on. The mean (average ) value of the square of the velocity in the x direction for N molecules is
Thus, the x component for the total force exerted on the wall of the cubical container is
Fx = m 2 N < vx > d
2 2 2
then
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Since the velocities of the molecules in the ideal gas are completely random, there is no preference to one direction or another. Hence 2 2 2 < vx >=< v y >=< vz > 2 < v 2 >= 3 < v x > < v2 > 2 < v x >= 3 The total force exerted on the wall in all direction, F is given by m 2 m < v2 > F = N < vx > F = N d d 3 2 N m<v > F= 3 d
where
A = d2
and
F=
N m<v > 3 d
1 P = < v2 > 3
(14.1) where
(14.3)
PV =
where
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1 Nm < v 2 > 3
(14.2)
where vrms
Since
vrms =
3P
vrms
31
3kT = m
OR
vrms
3RT = M
32
therefore the equation of root mean square velocity of the gas molecules also can be written as
Example 14.3 :
Eight gas molecules chosen at random are found to have speeds of 1,1,2,2,2,3,4 and 5 m s1. Determine a. the mean speed of the molecules, b. the mean square speed of the molecules, c. the root mean square speed of the molecules. Solution : N = 8 a. The mean speed of the molecules is given by
Solution :
N =8
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Example 14.4 :
A cylinder of volume 0.08 m3 contains oxygen gas at a temperature of 280 K and pressure of 90 kPa. Determine a. the mass of oxygen in the cylinder, b. the number of oxygen molecules in the cylinder, c. the root mean square speed of the oxygen molecules in the cylinder. (Given R = 8.31 J mol1 K1, k = 1.38 1023 J K1, molar mass of oxygen, M = 32 g mol1, NA = 6.02 1023 mol1) V = 0.08 m3 ; T = 280 K; P = 90 103 Pa Solution : a. By using the equation of state, thus
Solution : a.
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Learning Outcome:
14.3 Molecular kinetic energy and internal energy
At the end of this chapter, students should be able to: Explain and use translational kinetic energy of gases,
K tr = 3 R 3 T = 2 kT N 2 A
State the principle of equipartition of energy. Define degree of freedom. State the number of degree of freedom for monoatomic, diatomic and polyatomic gas molecules. Explain internal energy of gas Relate the internal energy to the number of degree of freedom, and use the equation
U =
38
1 fNkT 2
P=
2 N 1 2 m < v > 3 V 2
N increases V
K tr =
where
3 3 R kT = 2 2 NA
2 1 N m < v2 > 3 2
and
PV = NkT
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K tr : average translati onal kinetic energy of a molecule T : absolute temperature k : Boltzmann constant R : molar gas constant N A : Avogadro constant
For N molecules of an ideal gas in the cubical container, the total average (mean) translational kinetic energy, E is given by
E = NK tr 3 E = N kT 2 3 E = NkT 2
OR
States : the mean (average) kinetic energy of 1 every degrees of freedom of a molecule is kT .
2
Therefore
< K >=
OR
f kT 2 f RT 2
E=
41
3 nRT 2
42
< K >=
where
f : degrees of freedom
T : absolute temperatu re
Degree of freedom ( f )
is defined as a number of independent ways in which an atom or molecule can absorb or release or store the energy. Monoatomic gas (e.g. He, Ne, Ar) The number of degrees of freedom is 3 i.e. three direction of translational motion where contribute translational kinetic energy as shown y in Figure 15.6.
Diatomic gas (e.g. H2, O2, N2) The number of degrees of freedom is
y
H Figure 14.7
vy
vz
3 2 5
vx
vy
He
43
vz
vx
44
Polyatomic gas (e.g. H2O, CO2, NH3) The number of degrees of freedom is Translational kinetic energy 3 Rotational kinetic energy 3
y
Figure 14.8
vy
O
Figure 15.6
vz
vx
Degrees of freedom depend on the absolute temperature of the gases. For example : Diatomic gas (H2)
H H vibration Figure 15.9
0
2 kT 2 3 kT 2
3 kT 2 5 kT 2 6 kT 2
Diatomic
H2 H2O
Polyatomic
Table 14.1
Hydrogen gas have the vibrational kinetic energy (as shown in Figure 15.9) where contribute 2 degrees of freedom which correspond to the kinetic energy and the potential energy associated with vibrations along the bond between the atoms. when the temperature, f =3 At 250 K f =5 At 250 750 K f =7 At >750 K
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Example 14.5 :
A vessel contains hydrogen gas of 2.20 1018 molecules per unit volume and the mean square speed of the molecules is 4.50 km s1 at a temperature of 50 C. Determine a. the average translational kinetic energy of a molecule for hydrogen gas, b. the pressure of hydrogen gas. (Given the molar mass of hydrogen gas = 2 g mol1, NA= 6.02 1023 mol1 and k = 1.38 1023 J K1) N Solution : = 2.20 1018 ; < v 2 >= 4.50 103 m s 1 ; T = 323.15 K a. The average translational kinetic energy of a molecule is
Solution :
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U=
f NkT 2
and
k=
R NA
OR
U=
f nRT 2
3 U = NkT 2
49
OR
U=
3 nRT 2
50
where
THE END
Next Chapter
CHAPTER 15 : Thermodynamics
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