Molecular Theory of Matter
The molecular theory of matter is based upon a set of assumptions. Predictions made
upon the basis of these assumptions are tested experimentally to determine whether
the theory is tenable.
The fundamental assumptions made in the molecular theory are that all matter is made
up of molecules which are in constant motion. In a gas, Newton’s laws of motion are
assumed to hold. In collisions between molecules, the laws of conservation of
momentum and conservation of kinetic energy hold. The molecules exert forces upon
each other, which depend upon the distance between them.
The pressure of a gas is given by the expression
P=1/3 nmv2
The Boltzmann constant k is the ratio of the universal gas constant R to Avogadro’s
number No, k = R/No.
The average kinetic energy per molecule is proportional to the Kelvin temperature of the
gas. ½ mv2 = 3/2 kT
The mean free path l of a molecule is the average distance it travels between
successive collisions. l = 1/π√2nd2
where d is the diameter of the molecule and n is the number of molecules per unit
volume,
In a Maxwellian distribution of speeds the
average speed v is greater than the most probable speed vp, and the rms speed Vrms is
greater than the average.
Cohesion is the attraction between like molecules, while adhesion is the attraction
between unlike molecules.
Diffusion takes place because the molecules of a gas or liquid move between the
molecules of the substance that is being penetrated.
Osmosis is one-way diffusion through a semi- permeable membrane.
Brownian movements are motions of small particles that are bombarded by
molecules.
There is a direct relationship between the rate of cooling of a substance and the size of
crystals formed. Rapid cooling produces tiny crystals and | slow cooling produces larger
crystals.
Problem Sets
1. How many molecules are there in1mg of ethane? The molecular mass of ethane is
30 g/mol.
2. Calculate the rms speed of a hydrogen molecule at 20°C and 70.0 cm Hg when the
density molecules of hydrogen at 0°C is 0.089 g/L.
2.1 Calculate the rms speed of methane molecules at a temperature of — 120°C.
Methane has a molecular mass of 16 g/mol.
3. Compute the rms speed of oxygen molecules at 0°C and 76.0cm Hg when the
density is
1,429 g/l.
4. What is the velocity of a molecule of methane gas at 37°C. Molecular mass of
methane
is 16 g/mol.
5. Find the temperature at which the rms velocity of an oxygen molecule equals that of a
hydrogen molecules which is at a temperature of 300°K.
Thermal Expansion
The temperature of an object is that property which determines the direction of flow of
heat between it and its surroundings.
Our subjective idea of temperature is obtained from the sensation of warmth or cold that
we experience on touching an object.
Thermal equilibrium exists when there is no net transfer of heat between two objects.
Any inanimate object without a built-in heating system will eventually attain the
temperature of the environment.
A thermometer scale is established by choosing a simple relation between a
measurable physical property and temperature, the zero of the scale being fixed by
assigning a numerical value to an easily reproducible temperature (triple point of water).
A thermometric property of matter is a property that varies predictably with an increase
or decrease in heat energy.
The expansivity is the fractional change (in length or in volume) per degree change in
tem- perature. The units, per C° or per F°, must be expressed.
The expansion of a material is equal to the product of the expansivity, the original size
(length or volume), and the temperature change
The pressure coefficients of expansion and the volume expansivities of all gases are
approximately equal to 1/273 per C°. The general gas equation is
1. A copper bar is 8.0 ft long at 68°F and has an expansivity α68, = 9.3 x 10-*/F. What is
its increase in length when heated 10 110°F?
2. A steel plug has a diameter 10.000cm at30.0°C. At what temperature will the
diameter be 9.986 cm?
ΔL = LαΔt
Volume Expansion - The volume expansivity for a material is the change in volume per
unit volume per degree rise in temperature,
where B is the average volume expansivity, Vt is the volume at temperature t, Vo the
volume 0°C, and Δt the temperature change.
There is a simple approximate relation between the linear expansivity for an isotropic
solid and the corresponding volume expansivity
This relation can be derived by consideration of the expansion of a cube of the material:
V, = Vo (1+βΔt) = L03(1+αΔt)3’. If the right-hand side of this equation is expanded and
terms in α2? And α3are neglected.
The Gas Laws
Considered the relation between pressure P and volume V when the temperature
remains constant, namely, that the product of pressure and volume is constant.
PV = k – Boyle’s Law
These two equations express Charles's laws: If the volume of a confined gas is
constant, the pressure is directly proportional to the absolute temperature, or P1/T1 =
P2/T2
If the pressure of a confined gas is unchanged, the volume is directly proportional to the
absolute temperature or V1/T1 = V2/T2
THE GENERAL GAS LAW
The three gas laws just stated can be combined into a single law that applies to
changes in conditions of a gas whether the factors change one at a time or
simultaneously.
P1V1/T1 = P2V2/T2 = k
This relationship can be written in a simpler form if we express the mass in kilomoles, n,
of the gas. A mole (mol) is defined as one molecular mass of the substance expressed
in grams. From chemistry we find that the molecular mass of oxygen is 32; thus 1 mol of
oxygen has a mass of 32 g. Also, 1 mol of hydrogen, which has a molecular mass of 2,
consists of 2 g. A kilomole is simply 1,000 mol of a gas.
By definition, then, n = m/W; where n is the number of kilomoles, m is the mass of the
gas expressed in grams, and W is the atomic mass of the gas. To find n for a particular
gas, we divide the mass of the gas by the atomic or molecular mass.
By experiment it has been found that when the constant k in the combined equation has
been measured for various kinds of gases,
PV/T = k =m/W (R) and PV/T = nR
where R is a constant called the universal gas constant which can. be used for all
low-density gases. Therefore, P, V, T, and n can be related to each other by what is
known as the general gas law: PV = nRT
The value of R depends upon the units selected for pressure and volume in the
equation, When n is in kilomoles and T in degrees Kelvin, R = 8,317 J/(kmol)(K*)
Equivalent values of the gas constant R expressed in different units may be useful for
reference:
R = 0.08205 |-atm/(mol)(K*)
= 8.317 x 107 ergs/(mol)(K*)
= 1.987 cal/(mol)(K°)
In using the general gas law it may be convenient to write it in other forms. If we divide
both sides of Eq. (20) by mT and express the result in terms of initial and final
conditions, we have P1V1/m1T1 = P2V2/m2T2
Or, since the density p = m/V, P1/p1T1 = P2/p2T2
The general gas law can be used to study any changes in the conditions of the gas so
long as absolute temperatures and complete (absolute) pressures are used. Gauge
pressures cannot be used in the gas law.
Example A.5,000-cm3 container holds 4.90g of a gas when the pressure is 75.0cm Hg
and the temperature is 50°C. What will be the pressure if 6.00 g of this gas is confined
in a 2,000-cm3 container at 0°C?
Example The weight-density of air at 32°F and 29.92 inHg pressure is0.081 1b/ft®.
What is – its weight-density at an altitude where the pressure is 13.73inHg and the
temperature is —40°F?
Example Air at pressure 14.7 Ib/in’ is pumped into a tank whose volume is 42.5 ft. What
volume of air must be pumped into make the gauge read 55.3 1b/in? if the temperature
is raised from 70 to 117°F in the process?
P1= 14,7 1b/in?
P2= 1477 1b/in? + 55.3 1b/in? = 70.0 1b/in3
T1= 70°F= 294°K
T2= 117°F = 320°K
Since m is constant,
Since 42.5 ft3 of air was in the tank at the beginning, the volume the added air would
occupy at atmospheric pressure is V = 199ft3 – 42.5ft3 = 157ft3
Volume Expansion
1. A gas having a volume of 100ft3 at 27°C is expanded to120ft3 by being heated at
constant pressure. To what temperature has it been heated to have this new volume?
2. A gas thermometer contains 100 cm3 of air at 20°C. At what temperature will the
volume of the air be 110 cm3.
3. The volume of a gas held at constant pressure increases from 4.0cm3 at 00C to 5.0
cm3? at 100°C. At what temperature will this gas occupy a volume of 4.6cm3?
4. An aluminum piston, having a diameter of 3,000 in at 0°C is designed to fit into a
steel cylinder with a clearance of 0.005 in (difference inradii) at0°C. What is the
maximum temperature at which the piston can operate?
