THE GASEOUS STATE (H2 ONLY)

E-learning website: http://prezi.com/ljik54dzcxcv/gas-laws/

1. Modern Physical Chemistry, G.F.Liptrot, J.J. Thompson, G.R.Walker 2. Chemistry in Context, Hill and Holman 3. Chemistry in Action, Michael Freemantle 4. Understanding Advanced Physical Inorganic Chemistry, Jeanne Tan and Kim Seng Chan

Content Ideal gas behaviour and deviations from it pV= nRT and its use in determining a value for Mr.

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. Outline 1. Kinetic Theory of Matter 2. The Gas Laws 2.1 2.2 2.3 Boyles Law Charles Law Avogadros Law

3. Daltons Law of Partial Pressures 4. Ideal Gas Equation 4.1 4.2 4.3 4.4 To determine relative molecular mass from ideal gas equation Deviation from ideal gas equation Negative deviation Positive deviation

1. KINETIC THEORY OF MATTER The kinetic theory of matter describes the arrangement of the particles in solids, liquids and gases and the movement of these particles. Basic Assumptions of the Kinetic Theory (as applied to an ideal gas) 1. 2. 3. 4. The particles are in continuous random motion. 5. The average kinetic energy of the particles is directly proportional to the absolute temperature (in Kelvins). The concept of completely independent gas particles applies to what are called ideal gases. Ideal gases do not actually exist. 2. THE GAS LAWS 2.1 BOYLES LAW Boyles Law states that at a ______________________________________________ _____________________________________________________________________.

It follows that under different conditions (but at constant temperature),

P1: Initial pressure V1: Initial volume P2: Final pressure V2: Final volume At a constant temperature, PV = constant from Boyles Law. P1 x V1 = k P2 x V2 = k where k = constant Since the two ks are identical, P 1 x V1 = P2 x V2

PV = k where k = constant. A plot of PV against P or reciprocal of volume 1/V is a straight line of zero slope (since PV is a constant) for a gas that obeys Boyle's Law.

Practice 1: A student places some marshmallows in a flask. The flask is then evacuated, i.e. the air is withdrawn from the flask using a vacuum pump. What would happen to the marshmallows? Solution: Since temperature is constant, we can apply Boyle's Law to predict the outcome. According to Boyle's Law, P1V1 = P2V2 = constant P1: Initial pressure V1: Initial volume of air in marshmallows P2: Final pressure V2: Final volume of air in marshmallows _______________________________________________________.In view of the fact that P2 decreases, V2 must increase since ______________________. Therefore, the marshmallows expanded. Problem 1: Suppose you fill a balloon, made of a perfectly elastic substance, to a volume of exactly 1 dm3 at sea level. Now, keeping its temperature constant, you carry it up the side of a mountain to an altitude of some 900 m, where the atmospheric pressure is exactly 90% of its value at sea level. What would the new volume of the balloon be? Solution:

Food for thought: Do you know that the working of Boyles Law is happening right inside our body? (Refer to Applications of Gas Laws)

2.2 CHARLES LAW Charles Law states that at ______________________________________________ _____________________________________________________________________.

V = kT or V/T = k where k = constant and T = temperature in Kelvins It follows that at different conditions (but at constant pressure),

At constant pressure,

V1 =k T1

V = constant from Charles Law. T V and 2 =k where k = constant T2

T1: Initial temperature (expressed in Kelvins) V1: Initial volume T2: Final temperature (expressed in Kelvins) V2: Final volume

Since the two ks are identical,

V1 V2 = T1 T2

Can a gas shrink to nothing at all? Theoretically, a gas can reach zero volume when the temperature is -273.15 oC or 0 K (i.e. absolute zero). Absolute zero is the lowest possible temperature. In practice, however, gases will not actually reach zero volume as they will liquefy well above that temperature!

Problem 2: Suppose you inflate a balloon with helium to a volume of 1 dm3 at 30 oC and then place it in a refrigerator kept at 7 oC. What will be the volume of the balloon when the gas in it cools to the refrigerators temperature? Solution: Let the volume of the balloon at 7 oC be V2 dm3. Original Conditions: T1 = (30 + 273) = 303 K V1 = 1 dm3 Final Conditions: T2 = (7 + 273) = 280 K V2 = ?

Note: Dont forget to convert the units of oC to K when performing the calculations which involve adding 273 to the temperature expressed in oC. There is no need to convert the units of dm3 to m3 since these conversions involve simply by multiplying the volume in dm3 by a factor of 10-3. The factor 10-3 will be cancelled out in the ratio.

Substituting in the values for V1, T1 and T2, we have

V1 V2 = T1 T2 V 1 = 2 303 280

V2 = 0.924 dm3

Food for thought: Do you know that the working of hot-air balloons is related to Charles Laws? (Refer to Applications of Gas Laws)

2.3 AVOGADROS LAW Under conditions of constant temperature and pressure, equal volumes of gas contain equal number of molecules.

V: volume of gas

n: number of moles of gas

Problem 3: Methane burns in oxygen to give CO2 and H2O according to the following equation: CH4(g) + 2O2(g) CO2(g) + 2H2O(g) 22.4 dm3 of gaseous CH4 is burned. Assuming that the volume of all gases were measured at the same temperature and pressure, calculate the a) volume of O2 required for complete combustion; b) volumes of CO2 and H2O produced.

Solution (for Problem 3): a) Since mole ratio of CH4 to O2 the volume of O2 required b) Since mole ratio of CO2 to H2O Volume of CO2 produced Volume of H2O produced

= 1 : 2, = 2 x 22.4 = 44.8 dm3 = 1 : 2, = 22.4 dm3 = 2 x 22.4

= 44.8 dm3

Food for thought: When one tries to inflate a balloon, is there any application of gas laws?

DALTONS LAW OF PARTIAL PRESSURES

The ___________________________ exerted by a mixture of gases which do not react is equal to the ____________________________________ of the constituent gases at the same temperature. PT = P1 + P2 + P3 + ........ Pi = total pressure of gas mixture Where Pi = partial pressure of gas i in the mixture

e.g. in air, the total pressure is the sum of the partial pressures of oxygen, nitrogen, carbon dioxide, the rare gases such as argon. Ptotal = PO2 + PN2 + PCO2 + PAr ......

In general, the total pressure, PT, exerted by a mixture of gases, 1, 2,......n, is PT PT = P1 + P2 + P3 + P4 + . + Pn = Pi i.e. summation of partial pressure of gases 1 to n.

Each gas in the mixture _______________________________ as when it _____________________________________________________________________. Another expression relating partial pressure to total pressure PT = P1 + P2 + P3 + ........ = = = n1RT/V + n2RT/V + n3RT/V + ...... ( n1 + n2 + n3 ) RT/V nT RT/V

Note: PV = nRT (Ideal gas equation, p9)

Therefore,

nA is the mole fraction of gas A in the gaseous mixture. nT nA can also be expressed as A. nT
From Avogadro's law, Vn

nA VA = nT VT
Problem 4: 50.0 cm3 of carbon dioxide at 100 kPa was mixed with 150 cm3 of hydrogen at the same pressure. If the total pressure of the mixture is 100 kPa, what is the partial pressure of carbon dioxide? Solution:

Problem 5: A mixture of gases at pressure of 1.01 x 105 Nm-2 has the molar composition of 30% CO, 50% O2 and 20% CO2. (a) What is the partial pressure of each gas? (b) If the carbon dioxide is removed by sodium hydroxide, what will be the partial pressures of oxygen and carbon monoxide? Solution: (a)

PCO2

= 2.02 x 104 Nm-2

20 1.01 10 5 100

PO2

= 5.05 x 104 Nm-2

50 1.01 10 5 100

PCO

= 3.03 x 104 Nm-2

30 1.01 10 5 100

(b) No change. __________________________________________________________ ____________________________________________________________________ ____________________________________________________________________. Neither Boyles Law nor Charles Law depends on the identity of the gas being studied. These laws describe the behaviour of any gaseous substance, regardless of its identity. 4. IDEAL GAS EQUATION Putting Boyles Law, Charles Law V 1/P Therefore, V nT/P The Ideal Gas Equation is obtained: VT and Avogadros Law together, Vn

P: V: T: n: R:

pressure of gas in ______________________ volume of gas in ____________ absolute temperature in ____________ number of moles of gas Universal gas constant (8.314 J K-1 mol-1)

Since R is a constant, the ideal gas equation can also be written in the form: P1: V1: T1: n1: Initial pressure Initial volume Initial temperature Initial no. of moles P2: V2: T2: n2: Final pressure Final volume Final temperature Final no. of moles

4.1 To determine relative molecular mass from Ideal Gas Equation PV = nRT where Therefore, n = no. of moles of gas = m / Mr (m = mass of gas)
PV mRT Mr

On rearranging, gives: Since density of a gas, = m / V

Mr

mRT PV

Problem 6: A 4.8 g sample of SO2 gas exerts a pressure of 1.2 x 105 Pa when held in a 2 x 10-4 m3 container at a temperature of 27 oC. What is the pressure the SO2 will exert if it is transferred to a 1.5 x 10-4 m3 container which is maintained at a temperature of 77 oC? Solution: Initial state P1 = 1.2 x 10 Pa V1 = 2 x 10-4 m3 T1 = (27 + 273) = 300 K
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Final state P2 = ? V2 = 1.5 x 10-4 m T2 = (77+ 273) = 350 K

P1 V 1 T1

P V 2 2 T2

P V T P 2 1 1 2 1.87x10 5 Pa V 2 T1
Problem 7: If 0.574 g of a gas occupies a volume of 549 cm3 at 22 oC and a pressure of 740 mmHg, calculate the relative molecular mass of the gas. Solution: PV = nRT where n = mass / Mr

740 mmHg 549 cm3 22 oC

= = =

Problem 8: Helium-filled balloons are used to carry scientific instruments high into the atmosphere. Suppose that a balloon is launched when the temperature is 22.5 oC and the barometric pressure is 754 mmHg. If the balloons volume is 4.19 103 dm3 (and no helium escapes from the balloon), what will the volume be at a height of 50 km, where the pressure is 76.0 mmHg and the temperature is 33.0 oC? [760 mmHg = 1 atm = 101 325 Pa] Solution: Let V2 = new volume of the weather balloon. Initial Conditions: Final Conditions:

P1 = 754 mmHg V1 = 4.19 x 103 dm3 T1 = (22.5 + 273) = 295.5 K Re-arranging we have

P2 = 76.0 mmHg V2 = ? T2 = (-33 + 273) = 240 K

P1 V 1 T1

P V 2 2 , T2

P V T V2 1 1 2 T1P 2

754 x 4.19 x 10 3 240 3.38 x 10 4 l 295.5 76.0

Note: As the pressure decreases by almost a factor of 10, this should lead to about a 10-fold volume increase. This increase is partly offset by a drop in temperature that leads to a volume decrease. On balance, the volume increases because the pressure has dropped so substantially.

Problem 9: Labels on spray cans warn not to dispose of the empty can in an incinerator since it might explode. Why would the can explode? Solution: Even though the can is "empty", a small amount of gas remains inside, at a pressure equal to atmospheric pressure. Since the can is sealed, the volume of this remaining gas remains constant, i.e. V1 = V2 and P T. Thus the general gas law becomes

P1 T1

P2 T2

When the "empty" can is placed in an incinerator, as the temperature of the gas in the sealed can rises, so does the pressure. At some high temperature, the pressure of the sealed gas would become great enough to rupture the can and produce an explosion!

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Problem 10: A 5 dm3 flask containing a gas A at a pressure of 8 atm is connected to another flask containing a gas B at a pressure of 2 atm and having a volume of 10 dm3. What is the final pressure in the flasks if the valve between the two flasks is opened and the pressures allowed to equilibrate, assuming the two gases do not react and there is no change in temperature? Solution:

P1 = 8 atm V1 = 5 dm3 n1 = no. of moles of gas A

P2 = 2 atm V2 = 10 dm3 n2 = no. of moles of gas B

After the valve is opened, the gases will equilibrate and the total volume will be 15 dm3.

4.2. DEVIATION FROM IDEAL GAS BEHAVIOUR

An ideal gas (which obeys the ideal gas equation) does not exist in reality. Real gases do not obey the ideal gas equation. Deviation from ideal gas behaviour can be shown by plotting PV/nRT against P. For an ideal gas under all conditions, _____________________________. PV should be independent of the individual values of P and V and a plot of PV/nRT against P should be a horizontal line.

__________________ and is called the ____________________________ of a gas.

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If the gas is ______________, z___1. (i.e. obeys PV = nRT ) If z ___ 1 (negative deviation), the gas is ______________________ than an ideal gas. If z ___ 1 (positive deviation), the gas is _______________________ than an ideal gas.

Plotting PV/RT for various gases as a function of pressure

Deviation from ideal gas behaviour can be attributed to the significant volume occupied by gas molecules the attractive forces between the gas molecules The extent and nature of deviation depends on pressure temperature nature of the gas Real gases only tend towards ideal gas behaviour when ____________________________________________. ____________________________________________.

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4.3 NEGATIVE DEVIATION

Real

gases

tend

to

exhibit

_________________________

when

the

_________________________. At low temperature, the gas molecules are moving very slowly and hence not able to overcome attractive forces between them. Intermolecular forces of attraction become significant and the force with which a gas molecule strikes the wall is reduced. Hence, the measured pressure of the gas (arising from molecular impact with the wall) will also be lower. As a result the product of PV _____________ than we expect on the basis of the ideal gas equation and PV / nRT of real gas < 1 (__________________ Deviation).

Therefore in summary,

Pressure of real gas ______ pressure of ideal gas PV/nRT of real gas ______PV/nRT of ideal gas PV/nRT of real gas ______ 1 (______ Deviation)

The deviation from ideal behaviour of nitrogen gas at different temperatures:

Notice that negative deviation is ___________________________________________. Therefore, at low temperature the basic assumptions of the Kinetic Theory are not entirely true because attractive forces operate between the gas particles at low temperatures.

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Question: When is the temperature considered low?

When the experimental temperature (temperature at which experiment is carried out) is near the boiling point of the gas (which depends on the nature of the gas). Gas NH3 N2 H2 BP/K 240 77.4 20.5 Experimental Temp = 273K Low Fairly high High

Plot of PV/nRT against P for one mole of gas at 273K

Relative boiling point: NH3 > N2 > H2

At low pressure, NH3 shows the greatest negative deviation (Note: boiling point of NH3 is higher than the other three gases, so 273K is relatively a lower temperature than for the other gases).
Reason: This is due to the relative stronger intermolecular forces of attraction (hydrogen bond) between NH3 molecules. ____________________________________________

_____________________________________________________________________.

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4.4 POSITIVE DEVIATION

Real gases tend to exhibit ___________________ when the ___________________. At high pressure, the basic assumptions of the Kinetic Theory are not entirely true because gas particles do not have negligible volume compared to the volume of the container at high pressures.

When the pressure is high, gas molecules are closer, _______________________________________________________________ and gas molecules take up space (incompressible). Hence the _____________________________________________ than expected. As a result the product ______________________________________ and PV / nRT of real gas > 1 (__________________ Deviation).

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1) Boyles Law applied in our body: Action of the diaphragm of our body This is a muscle that is located just below the lungs. When we inhale the diaphragm moves down ward allowing the lungs an increased volume. This decreases the pressure inside the lungs so that the pressure is less than the outer pressure. This results in forcing air into the lungs (Air flows from a region of high pressure to low pressure). When we exhale the diaphragm moves upward and decreases the volume of the lungs. This increases the pressure inside the lungs above the pressure on the outside of the lungs so that gases are forced out of the lungs. Of course, all of this is totally automatic and we take this important cycle which is performed hundreds of times a day for granted. This is also the reason why when a person chokes, we would perform abdominal thrusts. Reason being as we exert pressure onto the diaphragm, we are decreasing the volume inside the lungs and thus increase the pressure inside the lungs. This then forces out the foreign object blocking the airway.

2) Charles Law How does a hot-air balloon works? A hot-air balloon, for instance, floats because the air inside it is not as dense than the air outside. By itself, this fact does not depend on any of the gas laws, but rather reflects the concept of buoyancy. However, the way in which the density of the air in the balloon is reduced is the working of Charles Law. As the air inside the balloon is heated, its volume increases. The density of the air then decreases (=mass/volume) as the air inside the balloon is heated. The difference in density between the air inside and outside the balloon makes the hot-air balloon rise.

3) Avogadros Law Inflating a balloon As the balloon is being inflated, the size (volume) of the balloon increases because more gaseous particles (air) are being pumped into the balloon at a constant temperature.

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