PHYSICAL

CHEMISTRYII
PHC115B
BY
DR NTHABISENG NTHOLENG
2020

Email:[email protected]
 PHC115B: Module Content
Unit Topic
1 Properties of gases

2 Properties of liquids

3 Properties of solutions, colligative properties and colloids

4 Introduction to thermodynamics

5 Chemical equilibrium

6 Reaction kinetics

7 Electrochemistry
Consultation Times
 Properties of gases

Though liquids and solids seem to be different from each other, they both have small intermolecular distances
However, gases may sometimes behave like liquids though they have unique properties
 Properties of Gases
• It is considered a Fluid
 They are able flow
 They flow because they are relatively far apart thus can move past each other easily

• Have Low Density

 Due to relatively large distance between gas particles , most of the volume occupied gas is an empty space ( therefore the closer the particles the
greater the density e.g solids and liquids)
 Therefore the gas particles travel long distance before colliding with each other.

• Highly Compressible
 The space occupied by gas particles is very small compared to the total volume of the gas
 Applied pressure will move gas particles closer and decrease the volume

• Completely Fill a container

 Due to constant motion of gas particles at high speed they are able to completely fill its container
 In contrast to solid and liquid in which the occupied volume is determined by shape (solid) and surface of the container (liquid)
 Gas pressure
• Atmosphere commonly known of Air consists of mixture of gases mainly
nitrogen and oxygen
• Though air may thought as weightless, all gases have mass, therefore
weight in the gravitational field
• Collisions of gas molecules causes air pressure
E.g Gas molecules are pulled towards the earths surface, collides with a the
surface and with each other.
• Density of air changes depending on altitudes
At high altitudes, there is high collision of gas molecules or particles thus
increasing gas density.
 Measuring pressure

• Pressure is defined as force divided by area:

P=F/A (N/m2)
N (Newton): 1N = 1kg x 1m/s2 (one Newtonian force give acceleration
to of 1m/s2 to an object whose mass is 1 kg)
A (Area)
SI unit of pressure is Pascal (Pa):
1Pa = 1 N/ 1 m2
 Measuring atmospheric pressure
Atmospheric pressure is measured by barometer.

Atmosphere exerts pressure on the surface of the mercury

in the dish.

Pressure goes through mercury fluid and up the column of

mercury.

Mercury settles at a point where the pressure exerted

downward by its weight equals the pressure exerted by
the atmosphere.

At sea level, atmosphere keeps the mercury in a

barometer at an average height of 760 mm which is 1
atmosphere, atm.

Barometer was discovered Evangelista Torricelli who also called 1 mm of mercury torr
 Measuring atmospheric pressure
• To study the effect of temperature and pressure on a gas, there are
standard conditions set scientifically called Standard temperature
and pressure (STP): temperature is 0 ᵒC and Pressure is 1 atm

Pressure units
 Converting pressure units
•  Sample Problem A

Convert the pressure of 1.000 atm to millimetres of mercury

Solution:
1atm =101 325 Pa, and 1 mm Hg = 133,322 Pa
The conversion factors are and

Therefore: 1 atm x x = 760.0 mm Hg

 Gas laws
Gas laws were created to discover the relationship of pressure, temperature, volume and amount
of gas. The gas laws consist of three primary laws:

Boyle’s Law Charles's Law Avogadro's Law

Ideal Gas Law

 Gas laws
Gas Law Formulas
Gas
Gas Law
Law Formula
Formula Description
Description
Boyle’s
Boyle’s Law
Law At
At constant
constant T,
T, as
as pressure
pressure increases,
increases, volume
volume decreases.
decreases.
Charles’s Law At Constant P, as volume increases, temperature increases.
Charles’s Law At Constant P, as volume increases, temperature increases.
Avogadro’s Law At constant P and T, as number of moles increases, volume
increases
Avogadro’s Law
Ideal Gas Law At constant P and T, as number of moles increases, volume
increases
V= volume in dm3 P= pressure in kPa R= ideal gas law constant
T =Temperature
Ideal Gas Law in K n= number of moles
V= volume in dm3 P= pressure in kPa R= ideal gas law constant
T =Temperature in K n= number of moles
 Examples
 
1.1 A 17.50mL sample of gas is at 4.500 atm. What will be the volume if the pressure becomes 1.500
atm, with a fixed amount of gas and temperature?

Solution: = = = 52.50 mL

1.2 A sample of Carbon dioxide in a pump has volume of 20.5 mL and it is at 40.0 oC. When the
amount of gas and pressure remain constant, find the new volume of Carbon dioxide in the pump if
temperature is increased to 65.0 oC

Solution: = = 22.1 mL
 Ideal gas Real gas
 It is a perfect or theoretical gas  Composed of many randomly moving
 The particles in the gas are particles occupying certain volume
extremely small, so the gas does not  It has a low pressure than ideal gas
occupy any spaces (volume).
 Collision of particles is not elastic, due to
 The ideal gas has constant, random attractive forces between particles.
and straight-line motion.
 Do not obey ideal gas law
 No forces between the particles of
the gas. Particles only collide
elastically with each other and with
the walls of container.
 It obeys ideal gas law
Therefore compressibility factor expressed (Z):
For ideal gas Z =1 and for real gas Z ≠ 1

 𝑍 = 𝑃𝑉
𝑛𝑅𝑇
 Examples
 
1.3 A 3.80 g of oxygen gas in a pump has volume of 150 mL. constant temperature and pressure. If 1.20 g of
oxygen gas is added into the pump. What will be the new volume of oxygen gas in the pump if temperature
and pressure held constant?

Solution: n1 = = = 0.11875 mol

n2= = = 0.0375 mol

= = 47.37 mL
 Examples
  At 655mm Hg and 25.0oC, a sample of Chlorine gas has volume of 750mL. How many moles of
1.4
Chlorine gas at this condition?

Solution: P=655mm Hg T=25+273.15K V=750mL=0.75L

= = 0.026 mol

Practice Problems
1. If 4L of H2 gas at 1.43 atm is at standard temperature, and the pressure were to increase by a factor of
2/3, what is the final volume of the H2 gas? (Hint: Boyle's Law)

2. If 1.25L of gas exists at 35oC with a constant pressure of .70 atm in a cylindrical block and the volume
were to be multiplied by a factor of 3/5, what is the new temperature of the gas? (Hint: Charles's Law)

3. A ballon with 4.00g of Helium gas has a volume of 500mL. When the temperature and pressure remain
constant. What will be the new volume of Helium in the ballon if another 4.00g of Helium is added into the
ballon? (Hint: Avogadro's Law)
The relationship between gas density and molar mass
 From Ideal gas law:

Molar Mass:  =

From ideal gas V =

Replacing V: = = Mw

This equation tells us that gas density is directly proportional to the

pressure and molar mass, and inversely proportional to the
temperature.
 Examples
  sample of chloroform gas weighing 0.494 g is collected in a flask with a volume of 129 cm 3 at 99.6 °C when the
A
atmospheric pressure is 742.1 mm Hg. What is the approximate molar mass of chloroform?

Solution: M =0.494 g V = 129 cm3 = (129 cm3 x ) = 0.129 L

T= 99.6 ᵒC = (99.6 + 273.15 K) = 372.75 K P = 742.1 mmHg x (= 0.9764 atm

Using: = = 120 g/mol

A sample of phosphorus that weighs 3.243 × 10-2 g exerts a pressure of 31.89 kPa in a 56.0-mL bulb at 550 °C. What
are the molar mass and molecular formula of phosphorus vapor?

Solution
EXAMPLE 2: EMPIRICAL/MOLECULAR FORMULA PROBLEMS USING THE IDEAL GAS LAW AND
DENSITY OF A GAS
 1. Cyclopropane, a gas once used with oxygen as a general anesthetic, is composed of 85.7% carbon and 14.3%
hydrogen by mass. Find the empirical formula. If 1.56 g of cyclopropane occupies a volume of 1.00 L at 0.984 atm
and 50 °C, what is the molecular formula for cyclopropane?

So Empirical formula is simplest ratio of elements in a compound while Molecular formula show the total number of
atoms in a molecule.

Solution: 85.7 g/ 12. g/mol = 7.136 mol C

14.3 g H / 1.01 g/mol = 14.158 mol H
Then use the ratios to establish the formular: = 1 mol C and = 2 mol H The empirical formula CH2

Q2: M =1.56 g V = 1.00 L T= 50 C = (50+ 273.15 K) = 323.15 K P = 0.984 atm

Use : = 42.0 g/mol
So then find molecular mass of empirical formula (CH2) = C(12,01 g/mol) + 2H(1.01 g/mol) = 14.02 g/mol
Then 42.0 g/(14.02 g/mol) = 2,99 = 3 so 3(CH2) = C3H6 (Molecular Formula)

2. Acetylene, a fuel used welding torches, is comprised of 92.3% C and 7.7% H by mass. Find the empirical formula. If g
of acetylene occupies of volume of 1.00 L at 1.15 atm and 59.5 °C, what is the molecular formula for acetylene?
Solution : Emperical Formula: CH Molecular Formula C2H2
 Partial Pressures

• In a mixture of gases, the individual gas pressure does not affect each
other unless they chemically react with each other
• Therefore, individual gas in a mixture exerts the same pressure that it
would exert if it present alone in the container 
• The pressure exerted by each individual gas in a mixture is called
its partial pressure.
 Partial Pressures
•  Dalton's law of partial pressures states that the total pressure of a
mixture of gases is equal to the sum of the partial pressures of the
component gases:
= …….
• Dalton's law can also be expressed using the mole fraction of a gas, x
where

where PA, XA, and nA are the partial pressure, mole fraction, and number of moles of gas A, respectively, and nTotal is the
number of moles of all components in the mixture.
 Examples
• 10.0-L
A   vessel contains 2.50 × 10-3 mol of H2, 1.00 × 10-3 mol of He, and 3.00 × 10-4 mol of Ne at 35 °C.
1. What are the partial pressures of each of the gases?
2. What is the total pressure in atmospheres?
Solution: use

= = 9.61 x10-3atm

A 5.73-L flask at 25 °C contains 0.0388 mol of N2, 0.147 mol of CO, and 0.0803 mol of H2. What is the
total pressure in the flask in atmosphere
Solution: PT =1.137 atm
 Examples
•  gas mixture used for anesthesia contains 2.83 mol oxygen, O2, and 8.41 mol nitrous oxide, N2O.
A
The total pressure of the mixture is 192 kPa.
1. What are the mole fractions of O2 and N2O?
2. What are the partial pressures of O2 and N2O?
Solution: The mole fraction is given by and the partial pressure
= 0.252 = 48.4 kPa
= 0.748 = 143.6 kPa

What is the pressure of a mixture of 0.200 g of H2, 1.00 g of N2, and 0.820 g of Ar in a container with
a volume of 2.00 L at 20 °C?
Solution:
 Ideal gas law
So far from Ideal gas law:
• Gas expands when heated at constant pressure
• Pressure increases when compressed at constant temperature
• Fails to explain why gases behave this way
 Kinetic molecular Theory
• It is used to predict gas behaviour
• It states that gas particles are in constant rapid, random motion.
( Obey Newton's law of motion)
• It also states that the particles of a gas are separated by average
distances greater than actual molecule size. The volume occupied by
gas molecules is negligible compared to the volume of the gas itself.
• The molecules of an ideal gas exert no attractive forces on each other,
or on the walls of the container.
• Collisions are perfectly elastic; when two molecules collide, they
change their directions and kinetic energies, but the
total kinetic energy is conserved. Collisions are not “sticky".
• The average kinetic energy of the gas molecules is directly
proportional to the absolute temperature.
• 
• Behaviour of gas molecules can be explained by the motion of individual
gas moleculedue to widely-separated gas particles
• During the elastic collision of the molecule with the surface, molecule will
bounce back with the same velocity in opposite direction.
• The change in velocity ΔV is equal to acceleration a
Newton's Law: F=ma
with a force, F , that is exerted on the surface of area A exerting a pressure
Force (F), Area (A) Pressure (P)
• Therefore, collision of the molecules with the surface will cause pressure
• The magnitude of the pressure is related to how hard and how often the
molecules strike the wall
• The "hardness" of the impact of the molecules with the wall will be
related to the velocity of the molecules times the mass of the molecules
 Kinetic Interpretation of Absolute temperature
•• Kinetic
  energy is the energy a body has by virtue of its
motion:

• KE is the kinetic energy of a molecule,

• m is the mass of the molecule, and
• v is the magnitude of the velocity of a molecule.
• The average kinetic energy of random motion is
proportional to the absolute temperature
• The absolute temperature is a measure of the average
kinetic energy of its molecules
• Increasing temperature of gas shifts the energy distribution
in the direction of greater average kinetic energy
 Molecular Speed
• Although
  the molecules in a sample of gas have an average
kinetic energy (and therefore an average speed) the individual
molecules move at various speeds. Some are moving fast,
others relatively slowly
• At higher temperatures a greater fraction of the
molecules are moving at higher speeds
• What is the speed (velocity) of a molecule possessing
average kinetic energy?
• KMT theory shows the average kinetic energy (KE) is
related to the root mean square (rms) speed u
Example
•  Suppose a gas consists of four molecules with speeds of 3.0, 4.5, 5.2
and 8.3 m/s. What is the difference between the average speed and
root mean square speed of this gas?
Solution: = 5.25 m/s
= 5.59 m/s
 What We Know

Why are we able to differentiate variety of smells?

 Diffusion and Effusion

Diffusion Effusion
 Spontaneous mixing of non reacting gases to  The escape of gas molecules from high pressure
form a homogenous mixture region into a lower pressure region (vacuum )
 Movement of gas from high pressure to low through a pin hole
pressure  The term effusion really only speaks to the
direction of gas movement.
 Effusion speaks for not only the direction but the
rate that a change occurs.
Diffusion: Daily life experience

Due to random motion and

collision of gas particle

Effusion: Daily life experience

Speed of Diffusion and Effusion

• Rates of effusion and diffusion depend on the relative velocities of gas

molecules. The velocity of a gas varies inversely with the square root
of its molar mass.
• Recall that the average kinetic energy of the molecules in any gas
depends only the temperature and is
 At the same temp and KE, heavier
molecules move slowly.
Larger m → smaller v

Grahams’s Law of effusion: states that the rates of effusion of gases at the same
temperature and pressure are inversely proportional to the square roots of their molar
masses.
 Example
1. Compare the rates of effusion of hydrogen and oxygen at the same temperature
Given: gases H2 and O2
Unknown: relatives effusion
  =
• Using Graham’s Law:

• Therefore: Hydrogen effuses 3.98 faster than Oxygen

2. Under the same conditions of temperature and pressure, does hydrogen iodide or
ammonia effuse faster? Calculate the relative rates at which they effuse.
 
molecular mass of HI = H(1.01 g/mol)+I(126.90 g/mol)= 128 g/mol         
molecular mass of NH3 = N( 14.00 g/mol)+ 3H(1.01 g/mol)= 17.04 g/mol
Using Graham’s Law: NH3 effuses 2.74 faster than HI
Deviations from Ideal Gas Law Behaviour
• Behaviour of real gases usually agrees with the predictions of the ideal
gas equation to within ±5% at normal temperatures and pressures
• At low temperatures or high pressures, real gases deviate significantly
from ideal gas behaviour.
• Dutch physicist Johannes van der Waals question KMT assumptions:
The gas particles occupy a negligible fraction of the total volume of
the gas (It is true when pressure is 1 atm).
It also assumes that the force of attraction between gas molecules is
zero.
Deviations from Ideal Gas Law Behaviour
From the figure (right) molecules in a gas
were all clustered in one corner of a
cylinder.
At normal pressures, the volume occupied
Gas Molecules
by these particles is a negligibly small
fraction of the total volume of the gas. But
at high pressures, this is no longer true.
As a result, real gases are not as
compressible at high pressures as an ideal
gas. The volume of a real gas is therefore
larger than expected from the ideal gas
equation at high pressures.
Deviations from Ideal Gas Law Behaviour
• To account for large volume of gas molecules at high pressure Van der
Waals proposed:
subtracting a term from the volume of the real gas before we substitute it into the ideal gas
equation. He therefore introduced a constant b
Because the volume of the gas particles depends on the number of moles of gas in the
container, the term that is subtracted from the real volume of the gas is equal to the number of
moles of gas times b.
P(V - nb) = nRT
The assumption that there is no force of attraction between gas particles cannot be true.
Deviations from Ideal Gas Law Behaviour
• The assumption that there is no force of attraction between gas
particles cannot be true.
(1) gases condense to form liquids at low temperatures and
(2) the pressure of a real gas is sometimes smaller than expected for an ideal gas.
• To correct for the fact that the pressure of a real gas is smaller than
expected from the ideal gas equation:
second constant (a) and has the form: an2/V2.
• The complete van der Waals equation is therefore written as follows:
Partial Pressure