Engineering Chemistry 2

(AAECH2A)

www.vut.ac.za

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Engineering Chemistry 2 (AAECH2A)
Dr. M. PHIRI
Dept. of Biotechnology & Chemistry
Vaal University of Technology, Vanderbijlpark Campus

Office: J201E
Email: [email protected]
Telephone: 016 950 9089

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 Learning unit 3 Gases: their properties and
behavior
Outlook
➢ Gases and gas pressure

➢ The gas laws

➢ The Ideal gas law

➢ Stoichiometric relationships with gases

➢ Partial pressure and Daltons law

➢ The Kinetic-molecular theory of gases

➢ Grahams law: Diffusion and effusion of gases

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 Gases and gas pressure
➢ Everything around us is made up of matter. Matter is any thing that has mass and
occupy space.
➢ A quick look around tells us that matter takes many forms (solid, liquid or gas)
Solids: substances whose constituent
atoms, molecules or ions are held rigidly
together in a definite way. They have
definite volume and shape

Liquids: substances whose constituent

atoms or molecules are held less strongly.
Giving liquids a definite volume but
changeable and indefinite shape.
Gases: substances whose constituent atoms or molecules have little attraction for one
another and are therefore free to move about in whatever volume is available.
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Gases and gas pressure

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 Gases and gas pressure
➢Gases have a number of properties that are very different from liquids and solids:
1) Gas mixtures are homogeneous, i.e, they are uniform in composition.

2) Gases are compressible

3) Gases exert measurable pressure on the walls of their container

4) Gas pressure depends on the amount of confined gas

5) Gases fill their container

6) Gases mix freely with each other

7) Gas pressure increases with temperature

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 Gases and gas pressure
Molecular view of a gas

The pressure is a force per unit area

force m  a
pressure = =
area A
Where acceleration (a) = 9.81m/s2 and SI units
for force is newton (N), where 1 N = 1(kg.m)/s2
and of pressure is pascal (Pa), where 1Pa = 1
N/m2 = 1 kg/(m.s2)

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 Gases and gas pressure
➢ The pressure is a force per unit area
force m  a
pressure = =
area A
➢The earth exerts a gravitational force on everything with mass near it
➢What we call weight is the gravitational force acting on an object
➢The pressure due to air molecules colliding with an object is called the atmospheric
pressure

➢As is frequently the case with SI units, which must serve many disciplines, the pascal is
an inconvenient size for most chemical measurements.

➢Thus, the alternative pressure units millimeter of mercury (mm Hg), atmosphere
(atm), and bar are more often used.
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Gases and gas pressure
➢ Atmospheric pressure is measured with a barometer.
➢ The height of the mercury column varies with altitude
➢ The average pressure at sea level or the standard
atmosphere (atm) was defined as the pressure needed
to support a column of mercury 760 mm high
measures at 0 oC
➢ The SI unit of pressure is the pascal (Pa)

1N −2
1 Pa = = 1 N m
1 m2
1 atm = 760 mm Hg = 101,325 Pa
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 Gases and gas pressure
➢ You may encounter a number of pressure units
➢The standard atmosphere 1 atm is given by;
760 mm Hg (measured at 0o C)
760 torr
101,325 Pa = 101.325 kPa
1.013 bar = 1013 mb
14.7 lb in − 2
➢Another conversion to consider is as follows
1 bar = 100000 Pa = 100KPa = 0.986923 atm
➢Chemical reactions often involve gases

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 Gases and gas pressure
➢A manometer is used to measure the pressure inside closed containers

➢The difference between the pressure of the gas in the container and the pressure of the
atmosphere is equal to the difference between the heights of the mercury level in the two
arms of the U-tube.
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Example
If the atmospheric pressure is 760 mm Hg, what is the pressure of the gas in a monometer?

(a) If the mercury column is 60 mm higher on the atmospheric side.

(b) If the mercury column is 50 mm lower on the atmospheric side.

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 Gases and gas pressure
• Study worked examples 10.1 and 10.2 thoroughly and make sure you understand
them

• Lets look at Practice 10.1 and 10.3

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 The gas laws
➢Unlike solids and liquids, different gases show similar physical behavior regardless of
their chemical make-up.

➢There are four variables that affect the properties of a gas: pressure, volume,
temperature, and the amount of the gas.

➢The specific relationship amongst these variables are called gas laws

➢A gas whose behavior follows the laws exactly is called an ideal gas.

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 The gas laws
➢Boyle’s Law: The relationship between gas Volume and Pressure

➢Charles’ Law: The relationship between gas Volume and Temperature

➢Avogadros’s law: The relationship between volume and amount

➢Gay-Lussac’s Law: The relationship between pressure and temperature

➢Combined Gas Law
➢Ideal Gas Law
➢Dalton’s Law of Partial Pressure
➢Graham’s Law

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 The gas laws
BOYLE’S LAW
➢ The relationship between volume and pressure is called Boyle’s law or the pressure-
volume law
The volume of a given amount of gas held at constant temperature varies inversely
with the applied pressure. 1
V
P
➢ The proportionality can be removed by introducing a proportionally constant, C
1
V =  C or PV = C (constant amount and temperature)
P

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 The gas laws
BOYLE’S LAW

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 The gas laws
BOYLE’S LAW

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 The gas laws
charle’s law
➢The relationship between volume and temperature is called charle’s law or the
temperature-volume law

➢The volume of a fixed amount of gas is directly proportional to its temperature at

constant pressure
VaT
➢The proportionality can be removed by introducing a proportionally constant, C
V = constant x T
➢Temperature must be in Kelvin (K)
T (K) = t (0C) + 273.15

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 The gas laws
charle’s law

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 The gas laws
charle’s law

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 The gas laws
Avogadros’s law
➢The relationship between volume and amount is called Avogadros’s law

The volume of a gas is directly proportional to its number of moles, n

➢Thus, the volume of one mole of any gas at standard temperature and pressure (STP)
or 0 oC and 1 atm is 22.4 L (a constant for all ideal gases)

➢This is called the standard molar volume of a gas

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 The gas laws
Avogadros’s law

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 The gas laws
➢The relationship between pressure and temperature is called Gay-Lussac’s law or
the temperature-pressure law

➢The pressure of a fixed amount of gas is directly proportional to its temperature at

constant volume

P  T or P = C"T (constant amount and volume)

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 Ideal gas Law
➢The gas law can be combined into single statement called Ideal gas law
➢The ideal gas law is PV = nRT
R = universal gas constant
atm L
= 0.0821
mol K
➢R = 8.3145J/K.mol (When P is in pascal and V is in cubic meter (m3 ).
➢It describe how volume of a gas is affected by changes in P, T and n.
(PV)intial = (PV)final = nRT

➢Standard temperature and pressure (STP ) for gases T= 0 ℃= 273.15 K, P= 1 atm

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 Ideal gas Law
Example
How many moles of gas (air) are in the lungs of an average adult with a lung capacity
of 3.8 L? Assume that the lungs are at 1.00 atm pressure and a normal body
temperature of 37 ℃.

PV=nRT
PV/RT=n
n= (1 atm)(3.8 L)/(0.08206 L.atm/K.mol)(37+273 K)
n= 0.15 mol

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 Ideal gas Law
Example
In a typical automobile engine, the mixture of gasoline and air in a cylinder is
compressed from 1.0 atm to 9.5 atm prior to ignition. If the uncompressed volume of the
cylinder is 410 mL, what is the volume in milliliters when the mixture is fully
compressed.

(PV)intial = (PV)final = nRT

(PV)intial = (PV)final
(PV)intial / Pfinal = Vfinal
(1 atm)(410 mL) / 9.5 atm = Vfinal
43 mL= Vfinal

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 Ideal gas Law
Test yourself
1. How many moles of methane gas, CH4, are in a storage tank with a volume of 1.00×105 L
at STP? How many grams.

2. An aerosol spray can with a volume of 350 mL contains 3.2 g of propane gas (C3H8) as
propellant. What is the pressure in atmospheres of gas in the can at 20 ℃.

3. A helium gas cylinder of the sort used to fill balloons has a volume of 43.8 L and a
pressure of 1.51×104 kPa at 25 ℃. How many moles helium are in the tank?

4. What final temperature (℃) is required for the pressure inside an automobile tire to
increase from 2.15 atm at 0 ℃ to 2.37 atm, assuming the volume remain constant ?

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 Ideal gas Law
Stoichiometric relationship with gases

➢It is necessary to calculate amounts of gaseous reactants as it is with solids, liquids

and solutions
➢This calculations apply ideal gas law in which three of four variables are known.

➢Ideal gas law can be rearranged to solve for density.

➢Density = m/V = PM/RT, M = molar mass
➢Lets look at worked example 10.6 and do practice 10.11

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Ideal gas Law

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Ideal gas Law

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Test yourself
1. Propane gas (C3H8) is used as a fuel in rural areas. How many liters of CO2 are formed
at STP by the complete combustion of the propane in a container with a volume of 15.0
L and pressure of 4.5 atm at 25℃ ? The unbalanced equation is

C3H8(g) + O2(g) CO2(g) + H2O(l)

2. A typical high-pressure tire on a bicycle might have a volume of 365 mL and a pressure
of 7.80 atm at 25 ℃. Suppose the rider filled the tire with helium to minimize weight. What
is the mass of the helium in the tire?

3. What is the density in g/L of ammonia at STP if the gas in a 1.00 L bulb weighs 0.672 g
at 25 ℃ and 733.4 mm Hg pressure?

4. A foul-smelling gas produced by the reaction of HCl with Na2S was collected, and a 1.00
L sample was found to have a mass of 1.52 gat STP. What is the molecular mass of the gas?

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 Partial pressure and Daltons law
➢ Just as the gas laws apply to all pure gases, regardless of chemical identity, they also
apply to mixtures of gases.

➢ What is responsible for pressure in a gas mixture ?

- Because the pressure of a pure gas at constant temperature and volume is proportional
to its amount (P= nRT/V).

- The pressure contribution from each individual gas in a mixture is also proportional to
its amount in the mixture. Ptotal = P1+ P2+ P3 +P4 at constant temperature and volume.
Ptotal = (n1+ n2+ n3 +n4)(RT/V)

➢ Dalton’s law of partial pressures states: the total pressure of a mixture of gases is
the sum of their individual partial pressures
PTotal = PA + PB + ....
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 Partial pressure and Daltons law
➢ The concentration of any individual component in a gas mixture is usually expressed
as a mole fraction (X).

➢ The mole fraction is the ratio of the number of moles of a given component to the
total moles of all components.

Mole Fraction (X)= moles of component/total moles of mixture

For a mixture of A, B, … substances, the mole fraction of substance i (Xi) is

nA
XA = , ni = moles of i
n A + nB + ... + nZ
P1= X1×Ptotal
This provides a convenient way to `partition’ the total pressure of a mixture of gases.
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 Partial pressure and Daltons law
Example
At an underwater depth of 250 ft, the pressure is 8.38 atm. What should the
mole percent of oxygen in the diving gas be for the partial pressure of
oxygen in the gas to be 0.21 atm, the same as in air at 1.0 atm ?

X1= P1/Ptotal

X1= 0.21 atm/8.38 atm

X1= 0.025
Percent of O2= 0.025 × 100 = 2.5%

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 Partial pressure and Daltons law
Test yourself
1. What is the mole fraction of each of component in a mixture of 12. 45 g of H2, 60.67 g
of N2, and 2.38 g of NH3?

2. What is the total pressure in atmosphere and what is the partial pressure of each
component if the gas mixture in problem 9.14 is in a 10.00 L steal container at 90 ℃ ?

3. On a humid day in summer, the mole fraction of gaseous H2O (water vapor) in the air
at 25 ℃ can be as high as 0.0287. Assuming the total pressure of 0.977 atm, what is the
partial pressure in atmospheres of H2O in the air ?

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 Kinetic molecular theory of gases
The kinetic molecular theory is based on the following assumptions:
1.A gas consists of tiny particles, either atoms or molecules moving at random

2.The volume of the particles is negligible compared to the total volume of the gas.
Most of the volume of a gas is empty space.

3.Collisions among particles are perfectly elastic. That is, the total kinetic energy of the
gas particles is constant at constant temperature.
4.Gas particle act independently of one another, exert neither attractive nor repulsive
forces on one another.
5.The average kinetic energy of the molecules is proportional to the temperature of the
gas in kelvins
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 Kinetic molecular theory of gases
➢The average kinetic energy of the molecules is proportional to the temperature of the
gas in kelvins.
➢The Total Ek of a mole of a gas particles equals 3RT/2 and the average Ek per particle
is thus 3RT/2NA , where NA is the Avogadro,s number.
➢Therefore the average speed of a gas at a given temperature is

➢ u2 = 3RT/mNA or u = (3RT/M)1/2,
M= mass/moles (molecular mass)

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 Kinetic molecular theory of gases
Test yourself
1. Calculate the average speed of a nitrogen molecule in m/s on hot day summer (T=
37℃) and on a cold day in winter (T=-25℃).

2. At what temperature does the average speed of an oxygen molecule equal that of
an airplane moving at 580 mph?

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 Diffusion and Effusion: Graham’s Law
➢Gases mix rapidly when they come in contact.
➢This mixing of different gas molecules by random molecular motion with frequent
collision is called Diffusion.
➢A process in which gas molecules escape without collisions through a tiny hole into
vacuum is called Effusion.
➢Diffusion is the spontaneous intermingling of the molecules of one gas with another
➢Effusion is the movement of gas molecules through a tiny hole into a vacuum
➢The rates of both diffusion and effusion depend on the speed of the gas molecules
➢The faster the molecules, the faster diffusion and effusion occur

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Diffusion and Effusion: Graham’s Law

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 Diffusion and Effusion: Graham’s Law
➢Graham studied effusion and found that the effusion rate of a gas is inversely
proportional to the square root of its mass (m)
➢This is known as Graham’s law

1
effusion rate  (constant P and T )
m
comparing two gases at same T and P
effusion rate ( A) mB
=
effusion rate ( B ) mA

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 Diffusion and Effusion: Graham’s Law
➢Graham’s law requires that the rate of effusion for the different gases be compared
at the same temperature and pressure

➢When different gases have the same temperature, they have the same average
kinetic energy

➢The average kinetic energy can be expressed in terms of the average of the
velocities squared or root mean square

➢For the two gases labeled 1 and 2

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 Diffusion and Effusion: Graham’s Law
KE1 = KE2
1 1
m1 v1 = m2 v22 rearranging
2

2 2
v12
2
=
m2
or with vi () rms
 vi2
v2 m1
(v ) =
m2
(v )
1 rms

2 rms m1
➢ Note that heavier gases move slower than lighter gases

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Test yourself
1. The rate of effusion of Argon was measured to be 0.218 mol/s at a certain temperature.
Calculate the rate of effusion for helium gas.

2. Which gas in each of the following pairs diffuses more rapidly, and what are the relative
rates of diffusion ?
(a)Kr and O2
(b)N2 and C2H2

3. What are the relative rates of diffusion of the three naturally occurring isotopes of neon,
20Ne, 21Ne, and 22Ne?

4. An Unknown gas is found to diffuse through a porous membrane 2.92 times more slowly
than H2. What is the molecular mass of the gas?
5. An Unknown gas is found to diffuse through a porous membrane 4 times more faster than
O2. What is the molecular mass of the gas?
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