Ideal gases

11. Ideal Gases Content 11.1 Equation of state 11.2 Kinetic theory of gases 11.3 Pressure of a gas 11.4 Kinetic energy of a molecule Learning Outcomes (a) recall and solve problems using the equation of state for an ideal gas expressed as pV = nRT. (n = number of moles) (b) infer from a Brownian motion experiment the evidence for the movement of molecules. (c) state the basic assumptions of the kinetic theory of gases. (d) explain how molecular movement causes the pressure exerted by a gas and hence deduce the relationship, p = Nm/V < c2 > . (N = number of molecules) [A rigorous derivation is not required.] (e) compare pV = Nm < c2 > with pV = NkT and hence deduce that the average translational kinetic energy of a molecule is proportional to T.
1

Microscopic model of a gas

Physics describes and explains the behaviour of various systems In some cases it is impossible to describe what happens to each component of a system e.g properties of a gas in terms of the motion of each of its molecules In such cases we describe the average conditions in the gas rather than describing the behaviour of each molecule i.e macroscopic instead of microscopic Kinetic theory of an ideal gas is one such example where we make simple assumptions to derive at a law relating kinetic energy to temperature

What is the evidence that gas molecules are moving around all the time?
1 cm3 of atmospheric air contains approx 3 x 1025 molecules 1827 biologist Robert Brown observed tiny pollen grains suspended in water with a microscope with a illuminating beam Although the water was completely still, the grains were always moving in a jerky, haphazard manner : we call this Brownian motion Hence the assumption that the water molecules are in rapid, random motion under the bombardment from all sides of the water molecules We can see the same movement of tiny soot particles in smoke A century later, Mr. Einstein did a theoretical analysis of Brownian motion and estimated the diameter of a typical atom in the order of 10-10 m It has been found that the average spacing of atoms of liquids is up to 2 times that of solids or still in the order of 10-10 m. For gases it is of the order of 10-9 m
3

The gas laws

Experiments in the 17th and 18th centuries showed that the volume, pressure and temperature of a given sample of gas are all related

Boyles Law

Robert Boyle 1627-91 Boyles Law states that the pressure of a given mass of gas at constant temperature is inversely proportional to its volume.

p 1/V or pV = constant
If p1,V1 are the initial pressure and volume of the gas, and p2,V2 are the final values after a change of pressure and volume carried out at constant temperature, then

p1 V 1 = p 2 V 2

Charles Law

Jacques Charles 1746-1823 Charles Law states that the volume of a given mass of any gas at constant pressure is directly proportional to its thermodynamic temperature T V T or V/T = constant If V1,T1 are the initial volume and temperature of the gas, and V2,T2 are the final values after a change of volume and temperature carried out at constant pressure, then V1/T1 = V2/T2

T K = (273 + ) degrees C

Pressure Law

Joseph Gay-Lussac 1778-1850 Pressure Law or Gay-Lussacs Law states that the pressure of a given mass of gas at constant volume is directly proportional to its absolute temperature. p T or p/T = constant If p1,T1 are the initial pressure and temperature of the gas, and p2,T2 are the final values after a change of pressure and temperature carried out at constant volume, then p1/T1 = p2/T2

Ideal Gas Equation

In practice, real gases obey the gas laws only at moderate pressures and at temperatures well above the temperature at which the gas would liquefy. An ideal gas is one which obeys the 3 gas laws and is given by: pV T or pV/T = constant i.e. p1V1/T1 = p2V2/T2 All the above laws relate to a fixed mass of gas It is also found by experiments that the volume of a gas is proportional to its mass giving a combined equation of pV mT or pV = AmT where m is the mass of the gas and A is a constant of proportionality As A is different for different gases we express the fixed mass of gas in terms of the number of moles of gas present
8

Avogadros Hypothesis

Avogadros hypothesis states that equal volume of all gases, at the same temperature and pressure, contain equal number of molecules.

As such, gases like O2, N2, CH4, CO2, CO, H2 etc all contain the equal number of molecules at the same temperature and pressure.

Mole (abbreviated as mol)

A mole is the number of elementary units (atoms or molecules) of any substance which is equal to the amount of atoms in 12 g of carbon-12.

The number of molecules per mole for all substances is the same and is called the Avogadros constant or number NA
NA is 6.02 x 1023/mol

10

Relative atomic mass & atomic mass unit

The relative atomic mass Ar is the ratio of the mass of an atom to one-twelfth of the mass of an atom of carbon-12 The relative atomic mass is numerically equal to the mass in grams of a mole of atoms The relative molecular mass Mr is the ratio of the mass of a molecule to one-twelfth of the mass of an atom of carbon-12, and is numerically equal to the mass in grams of a mole of molecules The atomic mass unit u is one-twelfth of the mass of an atom of carbon-12, and has the value 1.66 x 10-27 kg (also called the unified atomic mass constant) Simple way to find the mass of 1 mole of an element is to take its nucleon number expressed in grams e.g nucleon number of argon 40Ar is 40. Therefore, 1 mole of argon then has a mass of 40 g
11

Gas laws in terms of moles & molar gas constant

Hence in terms of moles, pV nT and putting in a new constant of proportionality R, pV = nRT R is called the molar gas constant (or sometimes universal gas constant as it has the same value for all gases) R has a value of 8.3 J K-1mol-1 The above equation is expressed in the form pVm = RT where Vm is the volume occupied by 1 mole of the gas Another version is pV = NkT where N is the number of molecules in the gas and k is a constant called the Boltzmann constant which has a value of 1.38 x 10-23 J K-1 The molar gas constant R and the Boltzmann constant k are connected through the Avogadro constant NA 12 R = kNA

Experiment has confirmed that one mole of all gases at s.t.p. ( 0 degrees C and 760mm Hg or 1.01 x 105 Pa ) occupies 22.4 litres (1 litre is 1000 cm3).

From pV/T = k , substituting the above values, the constant for one mole R, called the molar gas constant, is therefore the same for all gases and has a value of 8.31 J/K/mol

13

Equation of state
The precise relation between volume, pressure, temperature and the mass of the given gas in a sample is called the equation of state of the gas An ideal gas is one which obeys the equation of state: pV = nRT For approximate calculations the ideal gas equation can be used with real gases

14

Example
Find the volume occupied by 1 mole of air at stp (273K and 1.01 x 105 Pa), taking R as 8.3 J K-1 mol-1 for air.
Solution: pV = nRT,

so V = nRT/p = 2.24 x 10-2 m3

15

Example
Find the number of molecules per cubic metre of air at stp.
Solution: from above example, 1 mole of air at stp is 2.24 x 10-2 m3 but 1 mole of air contains NA molecules where NA is the Avogadro constant. thus the number of molecules per cubic metre of air is 6.02 x 1023/2.24 x 10-2 = 2.69 x 1025 m-3

16

Example
A syringe contains 25 x 10-6 m3 of helium gas at a temperature of 20 C and a pressure of 5.0 x 104 Pa. The temperature is increased to 400 C and the pressure on the syringe is increased to 2.4 x 105 Pa. Find the new volume of gas in the syringe.
Solution: Using

p1V1/T1 = p2V2/T2 with T1 = 293 K & T2 = 673 K V2 = 12 x 10-6 m3

17

Example

Oxygen gas contained in a cylinder of volume 1 x 10-2 m3 has a temperature of 300 K and a pressure 2.5 x 105 Pa. Calculate the mass of the oxygen used when the oxygen pressure has fallen to 1.3 x 105 Pa.

Solution Let the initial and final number of moles of oxygen be n1 and n2 respectively. n1 = p1V/(RT), n2 = p2V/(RT) no. of moles used = n1 n2 = (p1 p2)V/(RT) = [(2.5 1.3) x 105 x 10-2]/(8.31 x 300) = 0.48 moles = 0.48 x 32 x 10-3 kg = 0.015 kg.

18

The kinetic theory

Robert Boyle in 17th century developed an explanation of how a gas exerts pressure Daniel Bernoulli in 18th century explained it in greater detail The basic idea was that gases consist of atoms or molecules moving about at great speed (later visualised by Robert Brown) and that the gas exerts a pressure on the walls of its container because of the continued impacts of the molecules with the walls Its value is the total rate of the momentum change of the molecules per unit area of the wall. The assumptions of the kinetic theory of an ideal gas are:
All molecules behave as identical, hard, perfectly elastic spheres The volume of the molecules is negligible compared with the volume of the containing vessel There are no forces of attraction or repulsion between molecules There are many molecules, all moving randomly so that average behaviour can be considered 19

Derivation of pressure of gas

Assume a gas of N molecules each of mass m are contained in a cube of side l. Let the velocity of one molecule be c at any instant where its component along the x, y and z axis are u, v and w respectively. Therefore resultant c2 = u2 + v2 + w2. Consider the force F exerted on the face X of the cube due to u for 1 molecule momentum change on impact = mu - (- mu) = 2mu time of travel before next collision for one impact = 2l/u number of collisions per second = 1/(2l/u) = u/(2l) momentum change per second = [u/(2l)] x 2mu = mu2/l force on X, F = mu2/l pressure, p on X due to one molecule = F/A = F/l2 = mu2/l3
20

 For N molecules, mean square speed of all molecules is u2 where u2 = (u12+u22+u32+ .+uN2)/N p = (Nmu2)/l3 = (Nmu2)/V also u2 = v2 = w2 u2 = < c2> hence p = (N/V)(m<c2 >) giving pV = Nm<c2> = nRT = NkT p = <c2> where is density <c2> = 3p/ c2 = (3p/) where c2 is root mean square(rms)

or or

In deriving the above, we have made use of p = F/A, Newtons 2nd law F = rate of change of momentum and Newtons third law
21

Example
The speed of 7 molecules in a gas are numerically equal to 2,4,6,8,10,12 and 14 units. Find the numerical values of (a) the mean speed <c> (b) the mean speed squared <c>2 (c) the mean square speed <c2> (d) the rms speed.
a) <c> = (2+4+6+8+10+12+14)/7 = 8 units b) <c>2 = 82 = 64 units2 c) <c2> = (4+16+36+64+100+144+196)/7 = 80 units2 d) rms speed = 80 = 8.94 units

22

Worked Example
Calculate the rms speed of hydrogen gas at s.t.p. where its density is 0.09 kg m-3. Solution At s.t.p., p = 1.013 x 105 Pa Using p = c2 c2 = (3 x 1.013 x 105)/0.09 = 3.37 x 106 ms-2 c2 = (3.37 x 106) = 1840 m/s

23

Mean Energy of Molecules

The kinetic energy of a molecule moving at an instant with a speed v is mv2 The average kinetic energy <Ek> of translation of the random motion of the molecule of a gas is therefore m<c2>. Since pV = Nm<c2> substituting for <Ek> we arrive at a link between our kinetic theory equation, energy and temperature pV = N( m<c2>) = N <Ek> = NkT i.e <Ek> = m<c2> = 3/2 kT <c2> = (3kT/m)

24

Conclusion
The r.m.s. speed or velocity of the molecules of a gas T. The r.m.s. speed of the molecules of different gases at the same temperature 1/M, so gases of higher molecular mass have smaller r.m.s. speeds Hence the rms speed is proportional to the square root of the thermodynamic temperature of the gas, and inversely proportional to the square root of the mass of the molecule. Thus at a given temperature, less massive molecules move faster, on average, than more massive molecules i.e the higher the temperature, the faster the molecules move. The molecules of air at normal temperatures and pressures have an average velocity of the order of 480 m/s

25

Example
The r.m.s. speed of hydrogen gas at s.t.p. is 1840 m/s. Calculate its new r.m.s. speed at 1000 C and the same pressure. What is the r.m.s. speed of oxygen at s.t.p.? Let cr = r.m.s. speed of hydrogen at 1000 C cs = r.m.s. speed of oxygen at s.t.p.
cr/1840 = (373/273) cr = 1840 x (373/273) = 2150 m/s cs/1840 = (2/32) (H2 is 2, O2 is 32) cs = 1840 x (2/32) = 460 m/s
26

Example
Find the total kinetic energy of the molecules in one mole of an ideal gas at standard temperature.
Solution: Average kinetic enrgy of 1 molecule = 3/2 kT The energy for 1 mole Ek i.e for NA molecules is Ek = 3/2 NAkT or 3/2 RT = 3400 J mol-1

27

Example
Find the rms speed of the molecules in nitrogen gas at 27 C. The mass of a nitrogen molecule is 4.6 x 10-26 kg.
Solution: crms = (3kT/m) = 520 ms-1 where k is the Boltzmann constant

28