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# 4.

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
(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
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
- 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
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