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1 INTRODUCTION

4.2 KINETIC MOLECULAR THEORY

4.3 GAS PRESSURE

4.4 THE IDEAL GAS LAW

4.5 GASES IN REACTION STOICHIOMETRY

4.6 DALTONS LAWOF PARTIAL PRESSURE

4.7 GRAHAMS LAW OF EFFUSION AND

DIFFUSION

4.8 REAL GASES

4.1 INTRODUCTION

Pressure is defined as the force exerted per unit

area of surface

Gas pressure are commonly measured in

atmospheres (atm) or in mmHg

The S.I unit in which pressure is the Pascal

(N/m

2

)

P = F

A

1 atm= 760 mmHg = 760 torr = 101 325 Pa (Nm

-2

) = 101.325 kPa

4.2 KINETIC MOLECULAR THEORY,KMT

The molecules are in constant random motion.

They can easily move when force is applied to

the gas

These molecules completely fill the container

The collisions between molecules are elastic,

there is no gain or loss of energy during

collisions

The molecules move faster as the temperature is

raised, temperature increases the average

kinetic energy

Gas pressure results from collisions of particles

with the walls of the container

4.3 GAS PRESSURE

Pressure is defined as force per unit area

The S.I unit of pressure is the newton (N) per square

metre. A pressure of 1 Nm

-2

is called a pascal (Pa)

1 kPa = 1000 Pa or 1000 Nm

-2

The atmospheric pressure is usually expressed in the

units of milimetres of mercury (mmHg)

Standard atmospheric pressure is 760 mmHg or 101 325

Pa or 101 325 Nm

-2

1 atm= 760 mmHg = 760 torr = 101 325 Pa (Nm

-2

) = 101.325 kPa

P = F (force) = N

A (area) = m

2

4.4 THE IDEAL GAS LAW

An ideal gas obeys the ideal gas law

P = pressure (usually atm)

V = volume (usually L)

n = moles

T = temperature (K)

R = ideal gas constant = 0.082058 L atmmol

-1

K

-1

Standard Temperature = 0

o

C or 273.15K

Standard Pressure = 1 atm

PV = nRT

Uses of the Ideal Gas Law:

(a) Combined Gas Law Problems:

(i) Boyles law

(ii) Charless law

(iii) Avogadros law

(b) Solving for one variables in PV = nRT

(c) Determination of molar mass, M

r

(d) Gas density problem

(a) Combined Gas Law

(i) Boyles law

- State that at constant temperature(T), the volume (V) of

a fixed mass of an ideal gas is inversely proportional

to its pressure(P)

- the mathematical expression of Boyles Law is shown below

v o 1/P (at constant temperature)

or PV = c (a constant)

or P

1

V

1

= P

2

V

2

P = pressure

V = volume

Boyles law

Charless law

Avogadros law

Example

A sample of chlorine gas occupied a volume of 0.50 dm

3

at

a pressure of 1 atm. What would be its volume if the

pressure is reduced to 0.4 atm at constant temperature?

Solution

P

1

V

1

= P

2

V

2

The volume at a pressure of 0.4 atm = 1.0 x 0.50

0.4

= 1.25 dm

3

(ii) Charless law

- State that at constant pressure(P), the volume(V) of a fixed mass of

an ideal gas is directly proportional to its absolute temperature(T)

- the mathematical expression of Charless Law is shown below

v o T

or V = c (a constant)

T

or V

1

/ T1 = V

2

/ T

2

T = temperature in K

V = volume

NOTE: if T in

o

C

need to change to K

Example

(a) A sample of gas occupies a volume of 125.0 cm

3

at 27

o

C.

Calculate its volume at 35

o

C, assuming the pressure

remains constant

(b) 100 cm

3

of a gas at a pressure of 100 kPa is compressed to

250 kPa at a constant temperature. What is the final

volume of the gas

Solution

(a) Charles Law

V

1

/T

1

= V

2

/T

2

(at constant pressure)

125 = V

2

V

2

= 128.3 cm

3

(27 + 273) (35 + 273)

(b) Boyles Law

p

1

V

1

= p

2

V

2

(at constant temperature)

100 x 100 = 250 x V

2

V

2

= 40 cm

3

(iii) Avogadros Law

- State that at a fixed temperature and pressure, the

volume of gas is directly proportional to the amount of

gas

- The molar volume ( 1 mol gas) of any gas at standard

temperature and pressure (s.t.p) is 22.4 dm

3

- The conditions of s.t.p are

Temperature : 0

o

C (273 K), Pressure : 101.3 kNm

-2

(1

atm)

V o n and V = cn

Molar volume of a gas is the volume of 1 mol gas under

certain condition. (1 mol of particles = 6.02 x 1023)

At the same temperature and athmospheric pressure,

all gases occupy the same amount of volume.

1 mol of any gas occupies 242.4 dm3 at standard

temperature and pressure (s.t.p). This volume is

known as= molar volume of gas.

Molar volume of gas at s.t.p= 22.4 dm3/ mol

Molar volume of gas at room condition = 24 dm3/ mol

No of moles = Volume (dm3)

Molar volume (dm

3

/mol)

Example

Calculate the volume at s.t.p of

(a) 0.20 moles of carbon dioxide gas

(b) 6.0 g of chlorine gas

Solution

(a) Volume of 0.20 mol of CO

2

at s.t.p

= 0.2 x 22.4 = 4.48 dm

3

(b) 6.0 g of chlorine gas (CI

2

) = 6.0 = 0.0845 mol

Volume = 0.0845 mol x 22.4 dm

3

mol

-1

= 1.89 dm

3

35.5 x 2

Example

The density of a gas at s.t.p is found to be 1.960 g dm

-3

.

What is the relative molecular mass of the gas?

Solution

Density = Mass

Volume

Mass of 1 dm

-3

of gas = 1.960 g

Mass of 1 mol (22.4 dm

-3

) of gas = 1.960 x 22.4 = 43.9 g

Relative molecular mass of the gas = 43.9

(iii) Gay Lussacs Law

- At constant volume and moles, The pressure exerted

by a gas at constant volume is directly proportional to its

absolute temperature

P o T (at constant volume )

or P = c T(c is constant)

or P1= P

2

T1 T2

P = pressure

T= temperature

P o T

(a) Combined Gas Law

(i) Boyles law - describes the effect of pressure V o 1/P

(ii) Charless law - describes the effect of temperature V o T

(iii) Avogadros law - describes the effect of the amount of gas V o n

Combination of (i)Boyles law and (ii)Charless law formGeneral gas Law.

Boyles law

Charless law

Avogadros law

V T

P

V = c T

P

PV = c

T

General Gas Law

P1V1 = P2V2

T1 T2

We can combine these 3 laws (i), (ii) and (iii) into a single

equation the ideal gas equation that includes

all four gas variables volume, pressure, temperature and

amount of gas

Fromthe 3 simple gas laws, it seems reasonable that

the V of gas should be:

- directly proportional to the amount of gas, n

- directly proportional to the Kelvin temperature, T

- inversely proportional to pressure, P

- That is

- Which R = gas constant

V o nT and V = RnT , PV = nRT

P P

The numerical value of R can be derived using

Avogadros law, which states that one mole of any gas at

STP will occupy 22.4 liters.

PV = nRT R = PV

nT

R = ( 1 atm) (22.4 L) = 0.08205 atm L mol

-1

K

-1

(1 mol) (273 K)

Or

R = (101325 Nm

-2

) (22.4 L)

(1 mol) (273K) = 8.31 Nm mol

-1

K

-1

= 8.31 Pa L mol

-1

K

-1

= 8.31 J mol

-1

K

-1

THE IDEAL GAS LAW

An ideal gas obeys the ideal gas law

P = pressure (usually atm)

V = volume (usually L)

n = moles

T = temperature (K)

R = ideal gas constant = 0.082058 L atmmol

-1

K

-1

Standard Temperature = 0

o

C or 273.15K

Standard Pressure = 1 atm

PV = nRT

(b) Determination of Molar Mass, M

- one application of the ideal gas equation is the determination

of the molar mass of a gas or a volatile liquid

- the ideal gas equation can be rearranged as follows

PV = nRT = m x R x T m= mass of gas

M=molar mass of gas

M= mx R x T

P V

From above equation, the molar mass) of any gas can be determined if the

values of m, p, V and T for the gas are known. Notice that m/V represents the

density (p) of a gas. Thus equation can be written as

M = pRT p = density of a gas

P

M

Example 5

Calculate the relative molecular mass of a gas from the following data

Mass of empty flask = 25.385 g

Mass of flask fully filled with gas = 26.017 g

Mass of fully filled with water = 231.985 g

Temperature of the experiment = 32

o

C

Atmospheric pressure = 101 kNm

-2

Solution

Mass of gas = (26.017 25.385) = 0.632 g

Volume of the flask = (231.985 25.385) = 206.6 x 10

-6

m

3

Temperature = (273 + 32) = 302 K

Pressure = 101 kNm

-2

= 101 x 10

3

Nm

-2

M

r

= m x RT = 0.632 x 8.31 x 305

pV 101 x 10

3

x 206.6 x 10

-6

= 76.8

Exercise 1 and 2:

1. At 750 torr and 27 C, 0.60 g of certain gas occupies

o.50 L. Calculate it molecular weight?

2. What volume will 1.216 g of SO

2

gas occupy at 18 C

and 755 torr.

Daltons Law of Partial Pressures: the sum of all the

pressures of all the different gases in a mixture equals the

total pressure of the mixture.

4.6 DALTONS LAW OF PARTIAL PRESSURE

.... 3

2

1 + + + = P P P P

tot

- In a mixture of gases which do not interact with one another, each

gas in the mixture will exert its own pressure independent of the

other gases.

- This pressure is known as the partial pressure of that particular gas

in the mixture.

- Dalton`s law of partial pressure state in a mixture

of gases which do not interact with one another, the

total pressure of the mixture is the sum of the

partial pressure of the constituent gases.

- Daltons Law of partial pressures can be

P

total

= P

1

+ P

2

+ P

3

+.... = n

1

RT/V + n

2

RT/V + n

3

RT/V

= (n

total

)RT/V

P

1

, P

2

, P

3

.are the partial pressures of different gases

in the mixture

n

total

= n

1

+ n

2

+ n

3

+.

MOLE FRACTION(;)

- definition: amount of one substance / total amount

- The composition of a gaseous mixture can be expressed in

terms of a mole fraction or percentage (%)

- The mole fraction of gas A in a mixture of gas A and gas B

is

Mole fractionof a gas A(;

A

) = number of moles of gas A______________

number of moles of gas A + number of moles of gas B

= n

A

= n

A

n

A

+ n

B

n

T

Partial pressure, P = mole fraction x total pressure

P = ; x P

T

If the mixture is made up of two components A and B, then ;

A

+ ;

B

= 1

The partial pressure of a component of a gas mixture is equal to the mole

fraction of the gas times the total pressure of the mixture

P

A

= ;

A

x P

T

where P

T

= total pressure, P

A

= partial pressure of gas A

and ;

A

= mole fraction of gas A

Example

A gases mixture contains 0.274 mol methane, 0.072 mol of ethane and

0.011 mol of propane. The mixture exerts a pressure of 1.60 atm. Calculate

the partial pressure of each component in the mixture

Partial pressure, P = mole fraction x total pressure

n

t

= 0.274 + 0.072 + 0.011 = 0.357 mol

P

methane

= 0.274 x 1.60 = 1.22 atm

0.357

P

ethane

= 0.072 x 1.60 = 0.32 atm

0.357

P

propanee

= 0.011 x 1.60 = 0.049 atm

0.357

Example

A mixture of 20% nitrogen, 35% oxygen and 45% carbon dioxide has a

pressure of 9.5 x 10

4

Nm

-2

. What is the partial pressure of nitrogen in

this mixture

Solution

Partial pressure of nitrogen = 9.5 x 10

4

x 20/100

= 1.90 x 10

4

Nm

-2

Example

0.60 g of oxygen and 1.30 g of carbon dioxide are introduced into a

Container. If the total pressure of the gaseous mixture is 52.0 Nm

-2

,

what are the partial pressures of oxygen and carbon dioxide?

Solution

Number of moles of oxygen = 0.60/32 = 0.0188 mol

Number of moles of carbon dioxide = 1.3/44 = 0.0295 mol

Mole fraction of oxygen = 0.0188 = 0.39

0.0188 + 0.0295

Partial pressure of oxygen = 52.0 x 0.39 = 20.28 Nm

-2

Partial pressure of carbon dioxide = 52.0 20.28 (Daltons Law)

= 31.72 Nm

-2

4.7 GRAHAMS LAW OF EFFUSION AND

DIFFUSION

- Effusion refers to the passage of a substance

through a small hole a container or through

a small orifice

- The faster the speed of a molecule, the faster it will effuse. Let's

compare two gases at the same temperature and pressure. Which gas

will effuse faster?

- Grahams Law of Effusion states that the effusion of a gas through a

small hole a container is inversely proportional to its density

or since the density of a gas is proportional to its molar mass or

molecular weight, M

w

Effusion rate o 1/ \M

w

where M

w

= molecular weight /molar mass

Effusion rate o 1/ \d where d = density

- Equivalently, the relative rates of effusion of two gases at the

same pressure and temperature are given by the inverse square

roots of their densities or molecular weight

Rate A = \M

B

Rate B \M

A

`

t

A

= \M

A

t

B

\M

B

- Diffusion refers to the passage of one substance through another.

An example for gases would be the passage of an aroma, such as a

perfume through still air.

- Comparing two gases at the same pressure and temperature, lower

molecular mass molecules diffuse faster than higher molecular

mass molecules.

- Grahams Law of Diffusion states that the rate of diffusion of a

gas is inversely proportional to the square root of its density

or since the density of a gas is proportional to its molecular weight,

M

w

Diffusion rate o 1/ \d where d = density

Diffusion rate o 1/ \M

w

where M

w

= molecular weight

Eg; An unknown gas effuses through a small hole in

94.0 s. Under the same quantity of neon gas effuses in

54.0 s. Calculate the molar mass of the unknown gas.

(Molar mass Ne = 20.0 g/mol)

t

unknown

= \M

unknown

t

Ne

\M

Ne

\M

unknown

= \M

neon

x t

unknown

t

neon

= \20.0 x 94.0

54.0

\M

unknown

= 7.78

M

unknown

= 7.78

2

= 60.61 g/mol

4.8 REAL GASES

- We know that all of the assumptions of the kinetic-molecular

theory (KMT) cannot be exactly true:

(i) if there were no forces of attraction between molecules,

then molecules would not stay together in liquids or

solids

(ii) If molecules truly have no volume, then liquids and

solids would have no volume either

- The Van Der Waals equation takes account of both of these

objections

The Van Der Waals equation takes account of both of these

objections:

(i)

(ii)

(iii) This gives the Van der Waals equation:

V

correction

= V - nb

b = the volume occupied by the

molecules

P

correction

= P + an

2

V

2

a = the attractives forces between

gas molecules

P + an

2

(V nb) = nRT

V

2

P V= nRT

the ideal gas law

the real gas law

P V

- Scientists have attempted to discover an equation which is more

closely related to the behaviour of real gases than the ideal gas

equation. The most well-known is the Van der Waals equation

P + an

2

( V nb) = nRT

V

2

- where a and b are constants for each gas

- The terms an

2

/V

2

is added to the pressure, p, to take into

account the intermolecular attractions

- So, corrected pressure = P + an

2

V

2

- The volume available for the molecules to move about in the

container is always less than the observed volume because of the

space occupied by the molecules themselves. This tends to make pV

greater than RT, and causes over-perfect behaviour. The Van der

Waals equation takes into account to co-volume effect of gas by

substracting a correcting term, b, fromthe observed volume

- Corrected volume = V nb

- where b (co-volume of the gas) is a constant, depending on

the nature of the gas

- If the ideal gas equation is modified by introducing the correct

pressure and the corrected volume in the place of p and V, the

results is Van der Waals equation

P + an

2

( V nb) = nRT

V

2

This equation is obeyed by all gases, with reasonable

accuracy, up to quite high pressures

SUMMARY

1 Boyles Law states that, at constant temperature, the volume

occupied by a given mass of ideal gas is inversely proportional to

the applied pressure

2 Charless Law states that, at constant pressure, the volume of a

given mass of ideal gas is proportional to its temperature expressed

in kelvin

3 Avogadros Law states that, under the same conditions of

temperature and pressure, equal volumes of all ideal gases contain

the same number of molecules

4 Daltons Law of partial pressures states that, in a mixture of ideal

gases, the total pressure is equal to the sum of the partial pressures

of all the gases making up the mixture

5 The partial pressure of a gas is the pressure that the gas would

exert if it alone occupied the total volume of the vessel at the same

temperature.

6 An ideal gas or perfect gas is a gas that obeys the gas laws or the

ideal gas equation exactly

7 A real gas is a gas that does not obey the gas laws or the ideal gas

equation exactly

8 The molar volume (that is, the volume occupied by one mole) of

any gas at s.t.p is 22.4 dm

3

9 The kinetic theory of gases states that

(a) a gas is composed of tiny molecules, the molecules are in

rapid and randommotion, moving in straight lines

(b) the molecules have negligible volume

(c) there are no intermolecular forces, that is the particles exert

no attraction on one another

(d) the molecules will frequently collide with each other and with

the walls of the container

(e) the average kinetic energy of gas particles is directly

proportional to the absolute temperature, and remains

constant at any one temperature

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