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7.1 KINETIC MOLECULAR THEORY OF MATTER

Solids, liquids, and gases are easily distinguished by using four common physical properties of matter:
(1) Volume and shape
(2) Density
(3) Compressibility - is a measure of the change in volume of a sample of matter resulting from a pressure
change.
(4) Thermal expansion - is a measure of the change in volume of a sample of matter resulting from a
temperature change.

KINETIC MOLECULAR THEORY OF MATTER is a set of five statements used to explain the physical behavior
of the three states of matter (solids, liquids, and gases).
The basic idea of this theory is that the particles (atoms, molecules, or ions) present in a substance,
independent of the physical state of the substance, are always in motion.

The five statements of the kinetic molecular theory of matter follow.

Statement 1: Matter is ultimately composed of tiny particles (atoms, molecules, or ions) that have definite
and characteristic sizes that do not change.
Statement 2: The particles are in constant random motion and therefore possess kinetic energy. Kinetic
energy is energy that matter possesses because of particle motion. An object that is in motion
has the ability to transfer its kinetic energy to another object upon collision with that object.
Statement 3: The particles interact with one another through attractions and repulsions and therefore
possess potential energy.
Potential energy is stored energy that matter possesses as a result of its position, condition,
and/or composition. The potential energy of greatest importance when considering the
differences among the three states of matter is that which originates from electrostatic
interactions among particles.
An electrostatic interaction is an attraction or repulsion that occurs between charged
particles. Particles of opposite charge (one positive and the other negative) attract one
another, and particles of like charge (both positive or both negative) repel one another.
Further use of the term potential energy in this text will mean potential energy of electrostatic
origin.
Statement 4: The kinetic energy (velocity) of the particles increases as the temperature is increased. The
average kinetic energy (velocity) of all particles in a system depends on the temperature;
kinetic energy increases as temperature increases.
Statement 5: The particles in a system transfer energy to each other through elastic collisions.

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7.2 KINETIC MOLECULAR THEORY AND PHYSICAL STATES
1. Solid
- has dominance of potential energy over kinetic energy.
- The particles in a solid are drawn close together in a regular pattern by the strong cohesive forces
present

Characteristic properties of solids

1. Definite volume and definite shape.
2. High density. The constituent particles of solids are located as close together as possible
3. Small compressibility.
4. Very small thermal expansion. An increased temperature increases the kinetic energy (disruptive forces),
thereby causing more vibrational motion of the particles. Each particle occupies a slightly larger volume,
and the result is a slight expansion of the solid. The strong, cohesive forces prevent this effect from
becoming very large.

2. Liquid
- Physical state characterized by potential energy (cohesive forces) and kinetic energy (disruptive
forces) of about the same magnitude. It consists of particles that are randomly packed but relatively
near one another

Characteristic properties of liquids

1. Definite volume and indefinite shape.
2. High density. The particles in a liquid are not widely separated; they are still touching one another.
Therefore, there will be a large number of particles in a given volume— a high density.
3. Small compressibility. Because the particles in a liquid are still touching each other, there is very
little empty space. Therefore, an increase in pressure cannot squeeze the particles much closer
together.
4. Small thermal expansion.

3. Gas
- Physical state characterized by a complete dominance of kinetic energy over potential energy.
- Attractive forces among particles are very weak and, as a first approximation, are considered to be
zero. As a result, the particles of a gas move essentially independently of one another in a totally
random manner.

The kinetic theory explanation of the properties of gases follows the same pattern for solids and liquids:
1. Indefinite volume and indefinite shape.
2. Low density.
3. Large compressibility. Particles in a gas are widely separated; essentially, a gas is mostly empty
space. When pressure is applied, the particles are easily pushed closer together, decreasing the
amount of empty space and the volume of the gas.
4. Moderate thermal expansion. An increase in temperature means an increase in particle velocity.
The increased kinetic energy of the particles enables them to push back whatever barrier is
confining them into a given volume, and the volume increases.

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7.3 GAS VARIABLES
The behavior of a gas can be described reasonably well by simple quantitative relationships called gas laws.

Gas law is a generalization that describes in mathematical terms the relationships among the amount,
pressure, temperature, and volume of a gas.

Gas laws involve four variables:

1. Amount (n)
2. Pressure (P); units = torr, atm, kPa or mm Hg
3. Temperature(T); units= K
4. Volume (V); units= mL or L

Pressure is the force applied per unit area on an object, the total force on a surface divided by the area of
that surface.

For a gas, the force that creates pressure is that which is exerted by the gas molecules or atoms as they
constantly collide with the walls of their container.

Barometers, manometers, and gauges are the instruments most commonly used to measure gas
pressures.
A barometer is a device used to measure atmospheric pressure. The
essential components of a simple barometer (picture).

Atmospheric pressure is expressed in terms of the height of the barometer’s

mercury column, usually in millimeters of mercury (mm Hg).
Another name for millimeters of mercury is torr, used in honor of
Evangelista Torricelli (1608–1647), the Italian physicist who invented the
barometer.
1 mm Hg = 1 torr

Example: Atmospheric pressure varies with the weather and the altitude. It
averages about 760 mm Hg at sea level, and it decreases by approximately
25 mm Hg for every 1000-ft increase in altitude. The pressure unit
atmosphere (atm) is defined in terms of this average pressure at sea level.
By definition,

1 atm = 760 mm Hg = 760 torr

Another commonly used pressure unit is pounds per square inch (psi or
lb/in2 ). One atmosphere is equal to 14.7 psi.
1 atm = 14.7 psi

The three fundamental gas laws discover the relationship of pressure, temperature, volume, and amount of
gas.
1. Boyle's Law tells us that the volume of gas increases as the pressure decreases.
2. Charles' Law tells us that the volume of gas increases as the temperature increases.
3. Avogadro's Law tells us that the volume of gas increases as the amount of gas increases.
4. Ideal gas law is the combination of the three simple gas laws.

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7.4 BOYLE’S LAW: A PRESSURE-VOLUME RELATIONSHIP
- The first to be discovered relates gas pressure to gas volume. It was formulated over 300 years ago, in 1662,
by the British chemist and physicist Robert Boyle.

A. Boyle’s law states that the volume of a fixed amount of a gas is inversely proportional to the pressure
applied to the gas if the temperature is kept constant.

Doubling the pressure cuts the volume in half; tripling the pressure reduces the volume to one-third of its
original value; quadrupling the pressure reduces the volume to one-fourth of its original value; and so on.

The mathematical equation for Boyle’s law is:

P₁ x V₁ = P₂ x V₂
** P₁ and V₁ are the pressure and volume of a gas at an initial set of conditions
** P₂ and V₂ are the pressure and volume of the same sample of gas under a new set of conditions, with the
temperature and amount of gas remaining constant

Did you know!

Boyle’s law explains the process of breathing. Breathing in occurs when the diaphragm flattens out
(contracts). This contraction causes the volume of the thoracic cavity to increase and the pressure within
the cavity to drop (Boyle’s law) below atmospheric pressure. Air flows into the lungs and expands them,
because the pressure is greater outside the lungs than within them. Breathing out occurs when the
diaphragm relaxes (moves up), decreasing the volume of the thoracic cavity and increasing the pressure
(Boyle’s law) within the cavity to a value greater than the external pressure. Air flows out of the lungs. The
airflow direction is always from a high-pressure region to a low-pressure region

Using Boyle’s Law to Calculate the New Volume of a Gas

1. A sample of O₂ gas occupies a volume of 1.50 L at a pressure of 735 mm Hg and a temperature of 25°C.
What volume will it occupy, in liters, if the pressure is increased to 770 mm Hg with no change in
temperature?

Solution
A suggested first step in working gas law problems that involve two sets of conditions is to analyze the given
data in terms of initial and final conditions.

Step 1: step 2:

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2. A sample of oxygen gas has a volume of 425mL when the pressure is equal to 387kPa. The gas is
allowed to expand into a 1.75L container. Calculate the new pressure of the gas.

P1=387kPa
V1=425mL
V2=1.75L=1750mL
P2=V?

First, rearrange the equation algebraically to solve for P2.

P₁V₁= P₂V₂ (Boyle’s Law)

P₁V₁ = P₂V₂
V₂ V₂
P₁xV₁ 387kPa x 425ml
P₂ = = = 94.0 kPa
V₂ 1,750ml

7.5 CHARLE’S LAW: A TEMPERATURE-VOLUME RELATIONSHIP

Charles’s law states that the volume of a fixed amount of gas is directly proportional to its Kelvin
temperature if the pressure is kept constant

A balloon filled with air illustrates Charles’s law. If the balloon is placed near a heat source such as a light
bulb that has been on for some time, the heat will cause the balloon to increase visibly in size (volume).
Putting the same balloon in the refrigerator will cause it to shrink.

Charles’s law, stated mathematically, is

where V1 is the volume of a gas at a given pressure, T1 is the Kelvin temperature of the gas, and V2 and T2
are the volume and Kelvin temperature of the gas under a new set of conditions, with the pressure
remaining constant.

Using Charles’s Law to Calculate the New Volume of a Gas

1. A sample of the gaseous anesthetic cyclopropane, with a volume of 425 mL at a temperature of 27°C, is
cooled at constant pressure to 20°C. What is the new volume, in milliliters, of the sample?
Solution
First, we will analyze the data in terms of initial and final conditions.
V1 = 425 mL V2 = ? mL
T1 = 27°C + 273 = 300 K T2 = 20°C + 273 = 293 K

We know three of the four variables in the Charles’s law equation, so we can calculate the fourth, V₂. We will
rearrange Charles’s law to isolate V₂ (the quantity desired) by multiplying each side of the equation by T₂

Charles’s law is consistent with kinetic molecular theory. When the temperature of a gas increases, the
kinetic energy (velocity) of the gas molecules increases.

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7.6 COMBINED GAS LAW

Boyle’s and Charles’s laws can be mathematically combined to give a more versatile equation than either of
the laws by themselves.

Combined gas law states that the product of the pressure and volume of a fixed amount of gas is directly
proportional to its Kelvin temperature. The mathematical equation for the combined gas law is

Using this equation, we can calculate the change in pressure, temperature, or volume that is brought about
by changes in the other two variables.

Using the Combined Gas Law to Calculate the New Volume of a Gas

1. A sample of O₂ gas occupies a volume of 1.62 L at 755 mm Hg pressure and a temperature of 0°C.
What volume, in liters, will this gas sample occupy at 725 mm Hg pressure and 50°C? Solution?

Solution:

2. Suppose you have a sample of gas at 303K in a container with a volume of 2L and pressure of
760mmHg. The sample shifts to a temperature of 340 K and the volume increases slightly to 2.1L.
What is the pressure of the sample now?

Solution:
Here we are looking at two different states. The original state with subscript 1, and the second state
with subscript 2. First, write out the variables we know:

1. We know all the variables except P2. We can also tell we are looking at a
before and after state, so we want to use the following equation.

Interchange

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7.7 IDEAL GAS LAW

Ideal gas law is a gas law that describes the relationships among the four variables temperature, pressure,
volume, and molar amount for a gaseous substance at a given set of conditions. Mathematically, the ideal
gas law has the form
PV = nRT

Pressure (P) measured in atmosphere

Volume (V) is measured in Liters
The number of moles of gas (n) is the moles of gas content
Temperature (T) measured in kelvin
Gas constant (R) is a constant that converts the units. (0.082)
The value of the ideal gas constant (R) varies with the units chosen for pressure and volume. With
pressure in atmospheres and volume in liters, R has the value
PV 0.082 atm· L 0.082 atm· L
R= nT = or R=
mole · K mole · K

Using the Ideal Gas Law to Calculate the Volume of a Gas

The colorless, odorless, tasteless gas carbon monoxide, CO, is a by-product of incomplete combustion of any
material that contains the element carbon. Calculate the volume, in liters, occupied by 1.52 moles of this gas
at 0.992 atm pressure and a temperature of 65°C.

Solution
This problem deals with only one set of conditions, so the ideal gas equation is applicable. Three of the four
variables in the ideal gas equation (P, n, and T ) are given, and the fourth (V) is to be calculated.

P = 0.992 atm n = 1.52 moles

V= ? L T = 65°C = 338 K

Rearranging the ideal gas equation to isolate V on the left side of the equation gives
𝑛𝑅𝑇
V=
𝑃
Because the pressure is given in atmospheres and the volume unit is liters, the R value 0.0821 is valid.
Substituting known numerical values into the equation gives
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Note that all the parts of the ideal gas constant unit cancel except for one, the volume part. Doing the
arithmetic yields the volume of CO.

7.8 DALTON’S LAW OF PARTIAL PRESSURES

Dalton’s law of partial pressures states that the total pressure exerted by a mixture of gases is the sum of
the partial pressures of the individual gases present. A partial pressure is the pressure that a gas in a mixture
of gases would exert if it were present alone under the same conditions. Expressed mathematically, Dalton’s
law states that
P Total = P1 + P2 + P3 + ….

Solution:

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