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St Andrews Junior College JC1 H2 Chemistry 2011

St. Andrews Junior College H2 Chemistry 2011 Lecture Notes 5 States of Matter
Assessment Objectives: Candidates should be able to: a) state the basic assumptions of the kinetic theory as applied to an ideal gas b) explain qualitatively in terms of intermolecular forces and molecular size: (i) the conditions necessary for a gas to approach ideal behaviour (ii) the limitations of ideality at very high pressures and very low temperatures c) state and use the general gas equation pV = nRT in calculations, including the determination of Mr Lecture Outline 1. Kinetic Theory of Matter 2. 2.1 2.2 3. 3.1 3.2 3.3 3.4 4. 4.1 4.2 4.3 5. 5.1 5.2 Real and Ideal Gases Features of a Real Gas Features of an Ideal Gas The Gas Laws Avogadros Law Boyle's Law Charles' Law The Ideal Gas Equation / The General Gas Law Mixture of Gases Partial Pressure Dalton's Law of Partial Pressure Mole Fraction, Partial Pressure and Total Pressure Deviation from Ideal Gas Behaviours Negative Deviation Positive Deviation

Recommended Materials: 1) Cann, Peter and Hughes, Peter, Chapter 4, Chemistry for advanced level, 2002 Web Animations: 1. Kinetic Theory of Matter Animation

http://www.harcourtschool.com/activity/states_of_matter/
2. Boyles Law

http://www.grc.nasa.gov/WWW/K-12/airplane/aboyle.html
3. Ideal Gas Law

http://www.phy.ntnu.edu.tw/java/idealGas/idealGas.html 1.
Introduction: Kinetic Theory of Matter

St Andrews Junior College JC1 H2 Chemistry 2011

The Kinetic Theory describes the particles in solids, liquids and gases and the movement of these particles. Some of the characteristics that distinguish these three states of matters are: Property Volume Shape Forces between particles Arrangement of particles Packing of particles Density Compressibility Boiling / Melting point Movement of particles Energy Solids Fixed Fixed Strong Orderly manner Close High; packed closely, the volume is very small Nil High Vibrate and rotate about fixed position Little Liquids Fixed Fills or partially fills the container Less strong Not in orderly manner Close but not as close as solids High Almost Nil Moderate to high Vibrate, rotate and move anywhere but at a lower speed as compared to gases More than solids but less than gases Depends on the depth of the liquid Gases Takes the volume of the container Fills the container fully Weak Random arrangement Far apart Low; far apart, high volume High Low Vibrate, rotate and move anywhere within the container High Yes due to particles bouncing off the walls of the container

Pressure

Negligible

Changes of States sublimation melting Solid freezing vaporisation condensation Gas

Liquid

Vapour pressure of a liquid is the pressure exerted by those molecules that deposition escape from the liquid to form a separate vapour phase above the liquid.

St Andrews Junior College JC1 H2 Chemistry 2011

Saturated vapour pressure is the maximum vapour pressure that is exerted by a vapour when it is in dynamic equilibrium with its liquid (in a closed container).

Boiling: A liquid boils when its saturated vapour pressure equals the external pressure. When external pressure decreases, the boiling point also decreases. E.g. H2O boils at 100C at 1 atm (101kPa) but boils at 93C at 80 kPa.

2.

Real and Ideal Gases

Candidates should be able to: a) state the basic assumptions of the kinetic theory as applied to an ideal gas. 2.1 Features of a Real Gas

The particles have a certain volume, i.e., the volume of particles is not
completely negligible in comparison to the total volume of the gas.

There are forces of attraction between particles, though they are usually
very weak.

When the particles collide, the collision is not elastic, i.e., there is loss of
kinetic energy and the molecules stick together after collision. 2.2 Features of an Ideal Gas (Assumptions of the Kinetic Theory applied to Ideal Gases)

The particles have negligible volume as compared to the volume occupied by the gas. There are negligible forces of attraction between particles. When the particles collide, the collision is perfectly elastic, i.e., the particles bounce apart after they collide with no loss of kinetic energy and molecules do not stick together after collision.

The gas particles are in constant random motion. The average kinetic energy of the particles is proportional to the absolute temperature.

3.

Gas Laws

St Andrews Junior College JC1 H2 Chemistry 2011

Candidates should be able to: c) state and use the general gas equation pV = nRT in calculations, including the determination of Mr 3.1 Avogadros Law At a constant temperature and constant pressure, the volume of a gas, V, is directly proportional to the number of moles of the gas, n.

V n
V1 V2 = n1 n2

3.2

Boyles Law At a constant temperature, the volume of a given mass of gas, V, is inversely proportional to the pressure, p.

1 V

pV = Constant p1V1 = p2V2

St Andrews Junior College JC1 H2 Chemistry 2011

Do you know?
A diver's body can be affected by Boyle's law. As the diver goes deeper into the sea, water pressure increases and this causes the volume of the compressible body areas (which contain air spaces such as, air canals, lungs, sinuses nasal passages and hollow organs) to decrease. As a result, the diver would suffer the consequences as explained by Boyle's law in them. This way, it is very important that divers foresee the problems which their bodies might have to face. 3.3 Charles Law At a constant pressure, the volume of a given mass of gas, V, is directly proportional to its absolute temperature, T.

V T
V1 V2 = T1 T2

St Andrews Junior College JC1 H2 Chemistry 2011

3.4

The Ideal Gas Equation / The General Gas Law From Avogadros Law, V n From Boyles Law, p
1 V

From Charles Law, V T Combining Avogadros Law, Boyles Law and Charles Law, V
n T p

For 1 mole of gas, constant R is designated as molar gas constant, R. R is also known as universal gas constant.
pV = constant = R nT

These expressions can be combined to form one single equation for the behaviour of gases: The Ideal Gas Equation. It gives the relationship between the volume of a given mass of gas and the prevailing conditions (temperature, pressure and the number of moles). Ideal Gas equation / General Gas Equation

pV = nRT

Where R: Universal Gas Constant (Molar gas constant) Value of R depends on units of P, V, n and T P V n T R Pressure Volume No. of moles Temperature Universal Gas Constant Pa or Nm-2 m3 mol K 8.31 J K-1 mol-1 (S.I. units) atm dm3 mol K 3 atm dm mol-1 K-1 0.0821

Determination of molar gas constant, R

St Andrews Junior College JC1 H2 Chemistry 2011

Useful conversions:

1 atm = 760 mmHg = 101325 Pa 1 dm3 = 1000 cm3 = 10-3 m3 1 cm3 = 10-6 m3

1 mol of gas occupies 22.4 dm3 at s.t.p, i.e., 0oC and 101325 Pa or Nm-2 V = 22.4 dm3 = 0.0224 m3 pV = nRT R= =
pV nT
(101325 0.0224) (1 273)

= 8.31 Nm K-1 mol-1 = 8.31 J K-1 mol-1 The ideal gas equation can also be used to find the relative molecular mass (Mr) or the density ( ) of the gas. Given that n =
m m and = , Mr V

pV = nRT

pV =
Mr =

m RT Mr mRT RT
pV = p

Mrp RT

Exercise 1

St Andrews Junior College JC1 H2 Chemistry 2011

1. Calculate the pressure exerted by 0.05 mol of gas at 25oC and having a volume of
500 cm3. Solution:
pV = nRT p 500 10 6 = 0.05 8.31 298 p= 0.05 8.31 298 500 10 6 = 247638 Pa = 2.48 10 5 Pa

2. A sample of a gas exerts a pressure of 82.5 kPa in a 300 cm3 container at 25oC. What pressure would the same gas sample exert in a 500 cm3 container at 50oC? Solution:
p1V 1 p2 V 2 = T1 T2 82 .5 300 p2 500 = 298 ( 273 + 50 ) 82 .5 300 323 p2 = = 53 .7 kPa 298 500

3. 0.574 g of a gas occupies 548 cm3 at 22oC and 740 mmHg pressure. Calculate the relative molecular mass, Mr, of the gas. Solution:
pV = nRT m pV = RT Mr 740 0.574 101325 548 10 6 = 8.31 ( 273 + 22 ) 760 Mr 0.574 8.31 295 Mr = = 26 .0 740 101325 548 10 6 760

4. Which of the following diagrams correctly describes the behaviour of a fixed mass of an ideal gas? Give reasons for your choice. [T is measured in K] J86 & N91 A B C D E

St Andrews Junior College JC1 H2 Chemistry 2011

P
Ans: E

constant T
5. Which graph is correct for a given mass of an ideal gas at constant pressure? Give reasons for your choice. J2000 A B C D

V
Ans: C

St Andrews Junior College JC1 H2 Chemistry 2011

For each of the questions below, one or more of the three numbered statements 1 to 3 may be correct. The responses A to D should be selected on the basis of A 1, 2 and 3 are B 1 and 2 only are C 2 and 3 only are D 1 only is correct

correct correct correct 6. Which of the following equations apply to an ideal gas? (p = pressure, V = volume, m = mass, M = molar mass, = density, c = concentration, R = gas constant, T = temperature) 1 p= J91 3 pV =
cRT M

RT
M

pV = MRT

Ans: D

7. Which statements correctly represent the behaviour of an ideal gas? (p denotes pressure, Vm molar gas volume, M molar mass, c concentration, d density and T temperature) 1 pVm T 2 pM dT 3 p cT Ans: A J96

8. The Gas Laws can be summarised in the ideal gas equation, pV = nRT, where each symbol has its usual meaning. Which of the following statements are correct? N92 1 2 3 One mole of any ideal gas occupies the same volume under the same conditions of temperature and pressure. The density of an ideal gas at constant pressure is inversely proportional to temperature. The volume of a given mass of an ideal gas is doubled if its temperature is raised from 250C to 50OC at constant pressure. Ans: B

4. 4.1

Mixture of Gases Partial Pressure

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St Andrews Junior College JC1 H2 Chemistry 2011

The pressure of gas is due to the particles bouncing off the walls of the container after hitting onto them. For a mixture of gases which do not react with each other, each gas exerts its own pressure (independent of the other gases) - known as its partial pressure. The partial pressure of each gas is the pressure it would exert if it alone occupied the same volume. 4.2 Dalton's Law of Partial Pressure At constant temperature, for gases which do not react chemically, the total pressure of a mixture of gases in a given volume is equal to the sum of the partial pressures of the constituent gases.

pT = pA + pB + pC + .
4.3 Mole Fraction, Partial Pressure and Total Pressure Assuming a mixture of gas A and gas B contained in a volume, V, at temperature, T kelvin, Partial pressure of gas A: Partial pressure of gas B: pA = pB =

n A RT V
n B RT V

Total pressure,

pT

= = =

pA + pB

n A RT n RT + B V V
(n A + n B ) RT V

pA / pT = =

n A RT (n A + n B ) RT / V V
V n A RT x (n A + n B ) RT V

= nA / (nA + nB) Hence partial pressure of a particular gas is the product of the mole fraction of the gas and the total pressure of the mixture.

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St Andrews Junior College JC1 H2 Chemistry 2011

pA = ApT
Where nA / (nA + nB) = A

Exercise 2 9. A 2.0 dm3 flask contained 0.2 mol of nitrogen and 0.4 mol of oxygen at 400K. Calculate: (a) the partial pressure of nitrogen (b) the partial pressure of oxygen (c) the total pressure in the flask. Solution: PV = nRT a) pN2 = (0.2 x 8.31 x 400) / 2 x 10-3 = 332400 Pa b) pO2 = (0.4 x 8.31 x 400) / 2 x 10-3 = 664800 Pa c) pT = pN2 + pO2 = 332400 + 664800 = 997200 Pa = 9.97 X 105 Pa

10. A gas mixture consists of 0.4 mol of N2, 0.6 mol of O2 and 0.2 mol of Ar at a total pressure of 300 kPa. Calculate the partial pressure of each gas in the mixture. Solution: pN2 = N2pT = 0.4 / (0.4 + 0.6 + 0.2) x 300 = 100 kPa pO2 = 0.6 / 1.2 x 300 = 150 kPa pAr = 0.2 / 1.2 x 300 = 50 kPa

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St Andrews Junior College JC1 H2 Chemistry 2011

11. A 2 dm3 flask containing a gas N at a pressure of 7 atm was connected to another flask containing a gas M with a volume of 3 dm3 at a pressure of 4 atm. What is the final pressure, assuming that the 2 gases do not react and temperature was constant throughout? Solution: For gas N, pbeforeVbefore = pafterVafter 7 x 2 = pN (5) pN = 2.8 atm pT = pN + pM = 2.8 + 2.4 = 5.2 atm For gas M, pbeforeVbefore = pafterVafter 4 x 3 = PM (5) pM = 2.4 atm

5.

Deviation from Ideal Gas Behaviours

Candidates should be able to: b) explain qualitatively in terms of intermolecular forces and molecular size: (i) the conditions necessary for a gas to approach ideal behaviour (ii) the limitations of ideality at very high pressures and very low temperatures. An ideal gas (one which obeys the ideal gas equation) is hypothetical in nature. All real gases do not obey the ideal gas equation. Deviations from the ideal gas behaviour can be observed by plotting
pV versus p. An ideal gas will have a nRT

constant value of 1 since pV = nRT = constant.

NOTE: z=
pV is known as the compressibility factor of a gas. nRT

z = 1 if the gas is ideal. If z < 1 (negative deviation), the gas is more compressible than an ideal gas. If z > 1 (positive deviation), the gas is less compressible than an ideal gas.

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St Andrews Junior College JC1 H2 Chemistry 2011

Deviation from ideality is due to: attractive forces between gas molecules & significant volume occupied by the gas molecules. Factors affecting the extent and type of deviation are namely nature of gas pressure temperature A real gas behaves like an ideal gas under low pressure and high temperature (at least ten times greater than the boiling point of gas) conditions:

At low pressure, the particles are so far apart that (i) (ii) the attractive forces between them are negligible. the volume of particles is negligible as compared to the volume occupied by the gas.

At high temperature, the particles possess high kinetic energy and move about quickly. The particles can thus overcome the forces of attraction between them and do not stick together after collision. The collision is hence elastic.

A real gas shows deviation from ideal gas behaviour especially at high pressure and low temperature (not far from the boiling point).

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St Andrews Junior College JC1 H2 Chemistry 2011

Fig 1: Graph of pV/RT vs p (atm) for 1 mol of nitrogen gas at 3 different temperatures

Fig 2: Graph of pV/RT vs p (atm) for 1mol of several gases at 300K. The data for CO2 is perched at 313K as CO2 liquefies under high pressure at 300K. 5.1 Negative Deviation Real gases tend to exhibit negative deviation when the temperature is low (not far from boiling point of gas). At low temperature, the gas molecules are moving slowly and thus are not able to overcome attractive forces between them. As such, the intermolecular forces of attraction become significant and that the basic assumptions of the Kinetic Theory are violated. In the presence of intermolecular forces of attraction, the force with which a gas molecule strikes the wall of container is reduced. Thus, the measured pressure (due to the impact of the molecules with the wall of container) of the gas will be lower. As such, the product of pV will be lower than expected as calculated based on the ideal gas equation. Pressure of real gas < Pressure of ideal gas
pV pV of real gas < of ideal gas nRT nRT pV of real gas < 1 (Negative Deviation) nRT

From fig 1, as the temperature gets higher, the extent of deviation gets lesser and the gas tends to ideality. The stronger the intermolecular attraction, the
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St Andrews Junior College JC1 H2 Chemistry 2011

greater will be the extent of negative deviation. From fig 2, the extent of negative deviation for CO2 is greater than that for N2 as the induced dipole-induced dipole interaction for CO2 is stronger than that for N2 (to be covered in lecture of chemical bonding) 5.2 Positive Deviation Real gases show positive deviation at high pressure. This is because at high pressure, the gas molecules are closer, causing the collective volume of the particles to be significant with respect to the volume that they occupy (i.e the volume of the container). The gas thus becomes less compressible and the volume of the gas will be larger than expected. As a result, the product pV is larger than expected as calculated based on the ideal gas equation. For gases with the same type of intermolecular attraction, the larger the size of the gas, the greater the positive deviation. From fig 2, N2 shows greater positive deviation from ideal behaviour than H2 because of its larger molecular size. Volume of real gas > Volume of ideal gas
pV pV of real gas > of ideal gas nRT nRT pV of real gas > 1 (Positive Deviation) nRT

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St Andrews Junior College JC1 H2 Chemistry 2011

Exercise 3 12. The value of pV is plotted against p for two gases, an ideal gas and a non-ideal gas, where p is the pressure and V is the volume of the gas. N94, J98

pV

Ideal gas Non - ideal gas

0 A Ammonia C

Which of the following gases shows the greatest deviation from ideality? Methane Ans: A N96 B Ethene D Nitrogen 13. Which gas is likely to deviate most from ideal gas behaviour? A HCl B He C D CH4 N2 Ans: A

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