EP204 part 2: Thermodynamics and Kinetic Theory

Ref: Serway, Physics for Scientists and Engineers (4th ed.)

- chapters 19, 20, 21 (Temperature, Heat and the First Law of Thermodynamics, the
Kinetic Theory of Gases)
Lectures 1 to 3: Temperature, Zeroth Law of Thermodynamics, Thermometers and
temperature scales, Constant Volume gas thermometer and the Kelvin scale, thermal
expansion of solids and liquids, macroscopic description of an ideal gas.

Thermodynamics - relationships between bulk (macroscopic) properties of systems, eg.

volume, temperature, pressure, specific heat capacity.
Kinetic Theory of Gases explains bulk properties at the atomic/molecular scale
(microscopic).
Temperature and the Zeroth Law of Thermodynamics:
Firstly, we should distinguish between the temperature we sense and the temperature that is
objectively measured using some form of thermometer the former is quite often
misleading. Eg. bare feet on stone or tiled flooring on a cold winter morning; this feels much
colder than walking on a rug or a carpet, but if the stone and rug are in the same room, then
both have the same temperature. The reason they feel different is because stone conducts
heat better than carpet, which leads to heat flowing out of your feet faster on the stone floor.
This rapid heat loss makes you feel cold, but can give the wrong impression as regards the
temperature of the object you are touching.
For the same reason, a windy day at 6C feels much colder than a calm day at 6C because
moving air removes our body heat faster (the wind chill factor).
Conclude: humans are not reliable thermometers.
To understand temperature, we must define thermal contact and thermal equilibrium.
Thermal contact: consider two objects, at different temperatures, inside an insulated box (i.e.
no heat flow permitted into or out of the box). Energy will be exchanged between the
objects. This flow of energy which occurs because of the temperature difference is HEAT,
i.e. heat is energy in motion. Such objects are in thermal contact if heat can be exchanged
between them.
Thermal equilibrium: if objects are in thermal contact, and there is no net heat flow between
them, then the objects are in thermal equilibrium.
Zeroth law: consider objects A and B, not in thermal contact, and a third object C (a
thermometer). To find out if A and B would be in thermal equilibrium if they were in contact
with each other, first bring C in contact with A and wait for the temperature to stabilize
now record the temperature. Then bring C in contact with B, and again record the
temperature once thermal equilibrium is reached; if the two readings are the same, then A
and B are in thermal equilibrium.

If objects A and B are separately in thermal equilibrium with object C, the A and B are in
thermal equilibrium with each other if placed in thermal contact.
This Zeroth Law (so-called as its necessity was realized after the first law had become
well established) is used to define temperature: two objects in thermal equilibrium are at the
same temperature. Conversely, if objects have different temperatures then they are not in
thermal equilibrium.
Thermometers and Temperature Scales:
Thermometer makes use of change of some physical property as a function of temperature:
e.g. change in volume of a liquid, change in length of a solid, change in pressure of a gas (at
constant volume), change in resistance of a conductor, etc.
A thermometer must be calibrated, typically using two points:
i)
mixture of water and ice in thermal equilibrium at a pressure of one atmosphere
ice point of water gives 0C,
ii)
mixture of water and steam in thermal equilibrium at a pressure of one
atmosphere (1Atm) steam point of water gives 100C.
Example: mercury thermometer note levels of liquid in the capillary tube at 0C and
100C, and then divide the span into 100 equal segments. Each segment equals one degree.
(diagram: two-point calibration of mercury thermometer)
Problems with this approach:
i)
we are assuming a linear relationship between L and T this is not always true
(particularly if we move far below or far above the calibration points),
ii)
particular thermometers have a limited range (e.g. mercury freezes at -39C;
ethanol boils at 79C, so cannot use an alcohol thermometer to measure the
boiling temperature of water).
Ideally, we wish to have a universal thermometer whose readings are independent of the
substance used, and whose response is linear over a wide range of temperatures.

The Constant-volume Gas Thermometer and the Kelvin Temperature Scale:

In a gas thermometer, temperature readings are nearly independent of the gas used.
(diagram: constant-volume gas thermometer)
Suppose T increases => pressure of gas in bulb rises => it pushes mercury below zero mark
on fixed scale. The position of the reservoir is now adjusted until the mercury level is back at
the zero mark => the volume of gas in the bulb is held constant. The height h in the open
column is then a measure of the pressure of the gas. This is the principle of the constant
volume gas thermometer. It could be calibrated using the ice point and steam point of
water, as discussed above.

It is found that the thermometer readings are almost independent of the type of gas used,
provided:
i)
the gas pressure is low,
ii)
T is well above the point where the gas liquefies.
Even with slight differences, however, it is found that in every case when the calibration
curve is extrapolated to the point of zero pressure, the temperature at which this occurs is
always the same, namely 273.15C.
(diagram: extrapolation of p-T curves for constant-volume gas thermometer)
This significant temperature is used as the basis of the Kelvin Temperature Scale, which sets
273.15C as its zero point (0K). For convenience, the size of the degree on the Kelvin scale
is the same as that of the Celsius (centigrade) scale. Note that, by convention, the degree
symbol () is not used for the Kelvin scale. To convert from one scale to the other, use:
TC = TK 273.15
e.g. T = 373.15K converts to T=100C, i.e. the boiling point of water (at a pressure of
1Atm).
Temperatures on the Kelvin scale are also known as absolute temperatures.
The existence of this fundamental absolute zero temperature permits a new procedure for
calibrating thermometers. Before, we needed two points to find the relationship
L = aT + b
where L is the length of the mercury column (for example), and a and b are the slope and
intercept of the linear relationship between column length and temperature. As there are two
unknowns (a and b) we need two independent calibration points. However, if we use
absolute zero as one of our calibration points, then b is zero (zero intercept) and we simply
have that
L = aT
so that we only require one calibration point to determine the slope a.
(diagram: single-point calibration procedure using the absolute scale)
The single point that was officially adopted in 1954 is the triple point of water, which is a
unique temperature at which liquid water, water vapour, and ice can coexist in equilibrium.
It occurs when the pressure is about 608Pa (0.6% of atmospheric pressure 4.58mm Hg,
where 1Atm is 760mm Hg), and on the Celsius scale it corresponds to a temperature of
0.01C, i.e. 273.16K. Note that it is just slightly above the temperature of the ice point (as
measured at a pressure of 1Atm = 1.01x105Pa). This triple point of water is used as it can be
readily reproduced in laboratories in different locations.

The scale based on 0K and the triple point at 273.16K is called the thermodynamic
temperature scale. The SI unit of temperature is the kelvin and is defined as (1/273.16) of
the temperature of the triple point of water.
The Fahrenheit scale:
An older temperature scale (devised by Fahrenheit in 1714); now obsolete (except in the
USA). Fahrenheit set 100 to be the temperature of the human body, and set 0 to be the
lowest temperature that he could then achieve (corresponding to about -18C). The ice and
steam points on this scale have values of 32.0C and 212.0C. Note that there are therefore
180 degrees between these two calibration points, and so the Fahrenheit degree is almost
half the size of the Celsius or Kelvin degree. To convert from Celsius to Fahrenheit, use
TF = (9/5)TC +32
e.g. if TC = 100, then TF = (900/5) + 32 = 212.
The Fahrenheit scale is not used in scientific work and will not be mentioned again in this
course.

Thermal Expansion of Solids and Liquids:

Most solids/liquids expand when heated (important exception water; see below).
Reason asymmetric shape of potential energy curve associated with binding between atoms
in solids (similar PE curve is used in liquids, but packing is usually looser).
(diagram: binding energy curve)
If solid has no thermal energy, atoms are stationary and separations = Ro (see diagram). Now
suppose solid is heated so that the potential energy is raised from Eo to E1: atoms now
vibrate between R1 and R2.
But (R2 Ro) > (Ro R1) because of asymmetrical shape of curve => atoms spend more time
in region (R2 Ro) than in region (Ro R1) => mean separation increases => solid expands.
(Note: if curve were symmetrical, then the mean separation would stay at Ro even if the
amplitude of vibrations increases due to heating i.e. no expansion).
Provided the expansion is small compared to the initial dimensions, the change in any
dimension is approximately proportional to the first power of the change in T, i.e.
L T
If the object has initial length Lo, then it is also found that
L Lo
(this makes sense the more atomic separations along the length, the more will be the
overall expansion)

thus

L Lo.T

or
or

L = .Lo.T
note do not confuse (proportional to) with (alpha)
(L Lo) = .Lo(T To)

where L is the final length, T the final temperature, To is the initial temperature, and is the
proportionality constant (coefficient of linear expansion).
Units of :
[m] = [m].[C] => must have units of C-1 or K-1
NB expansion acts on all dimensions of an object - think of it as being similar to a
photographic enlargement. Eg. when a circular washer is heated, both the outer radius of the
washer and the radius of the hole expand the hole is enlarged.
(diagram: enlargement of washer on heating)
For most substances, > 0 => expansion as T increases
Solids typical ~ 10-5 K-1
Relationship between linear and volume expansion coefficients:
As all of the dimensions of a solid or liquid expand when T is increased (in most cases) it is
evident that the overall volume must expand:
V = .Vo.T
where is the volume expansion coefficient. There is a simple relationship between and
for a solid:
consider object shaped like a solid box, with side lengths l,w,h such that the initial volume is
Vo = l.w.h
If T now increases by T, the volume changes by V:
Vo+V = (l+l).(w+w).(h+h) = (l+lT).(w+wT).(h+hT)
(because w = .w.T etc., from above)
=> Vo+V = (l.w.h)(1+T)3
= Vo(1 + 3T + 3(T)2 + (T)3 )
Divide across by Vo:
1 + V/Vo = 1 + 3T + 3(T)2 + (T)3
We know that is small, so for relatively small T we can say that
T >> (T)2 >> (T)3
so that

V/Vo ~ 3.T

But V = .Vo.T
and so

= 3.

Similarly it can be shown that the change in area of a plate is

A = 2.Ao.T
where the factor 2 is the number of dimensions involved (2 for area; 3 for volume).

Thermal switch Bimetallic strip:

An application of thermal expansion exploits differences in values of to make a thermal
switch in electrical circuits:
e.g. (steel) = 1.1x10-5K-1 and (brass) = 1.9x10-5K-1 => brass expands more than steel for
the same value of T. Suppose a strip of brass and a strip of steel are bonded together the
strip will curve as it is heated because of the different expansion rates. This curvature is used
in thermostats to control switching on/off of heating supply (e.g. in hot-water boilers).
(diagram: bimetallic strip and mode of use as a circuit breaker)
Example: expansion of railroad track suppose steel railroad track has length = 30m at T =
0C. What is L when T = 40C?
Coefficient of linear expansion for steel: = 1.1x10-5K-1
L = .L.T
= (1.1x10-5)(30)(40-0) = 1.3x10-2m => L at 40C is 30.013m
The track has therefore expanded by more than 1cm, and this must be allowed for during
construction to prevent buckling.
Note: it is not necessary to convert from C to K in a problem such as this, as we are
working with a temperature difference, which will be the same on either scale. There are
other situations, however, where it is essential to convert to the absolute scale (whenever you
are calculating ratios of temperatures, or when you are working with a single temperature in
isolation, such as in the Stefan-Boltzmann radiation law). Simple rule if in doubt, always
convert all temperatures to the absolute scale.

Expansion of water as a function of temperature:

Most solids and liquids expand as T is increased; the volume expansion coefficient for
liquids is typically ten times that of solids, but the range of values is large in both categories
(e.g. for aluminium is 7x10-5K-1; for ethanol is 1.1x10-3K-1). The typical value for
water is lower about 2x10-4K-1 at 20C but at low temperatures the volume expansion

coefficient of water becomes negative, i.e. cold water contracts when heated between 0C
and 4C (at a pressure of 1Atm). Thus water has a maximum density at 4C; above that
temperature water behaves in a manner similar to other liquids.
(diagram: density profile of water in vicinity of density maximum at 4C)
The mechanism responsible for this density anomaly in liquid water is presumably the same
as that responsible for the anomalous phase change in water at 0C: solid water is less dense
than liquid water ice floats on water which is most unusual (very few other substances
exhibit this anomalous behaviour; examples are bismuth, gallium, silicon). In the case of
water, the anomaly is thought to arise due to a balance between optimal packing of the
molecules and optimisation of directional hydrogen bonding which leads to a less dense
structure. The direct consequence of both the 4C liquid anomaly and the freezing anomaly
is that colder water stays near the surface, and ice forms and stays near the surface. Without
these anomalies, lakes would freeze from the bottom up.

Macroscopic description of an ideal gas:

Consider gas, mass m, contained in volume V at pressure P and temperature T how are
these quantities related? The equation relating such quantities is called an equation of state
and is usually rather complicated. However, for gases at very low pressure (or low density),
we find that the equation of state is simple ideal gas. Most gases at room T and
atmospheric P behave approx. as ideal gases.
Usual to express amount of gas in moles, n:
- 1 mole = 6.02x1023 molecules = NA Avagadros number
- n = m/M, where m=total mass (in grams) and M=molar mass in grams per mole.
Example: oxygen has atomic weight = 16, so molecular O2 has atomic weight = 32, and the
molar mass of molecular oxygen is 32 grams per mole.
Suppose an ideal gas is confined in a cylinder with a piston, such that the volume can be
varied (the amount of gas remains constant):
(diagram: gas in cylinder with piston)
We find that P 1/V for constant T (Boyles law)
and that V T for constant P (Charles law)
We can rewrite these as PV = constant, and V/T = constant (not the same constants)
or P1V1 = P2V2

and V1/T1 = V2/T2 in going from state 1 to state 2.

These can be combined into one formula:

PV/T = constant, or PV = const.T
To see why, consider P1V1/T1 = P2V2/T2

if T1 = T2 we get P1V1 = P2V2 (Boyles law retrieved from combined formula);

if P1 = P2 we get V1/T1 = V2/T2 (Charles law retrieved from combined formula).
This combined formula is the equation of state for an ideal gas, and is usually written as
PV = nRT

Ideal Gas Law

where n=number of moles, T is the absolute temperature (i.e. using the Kelvin scale), and R
is a constant which is the same for all (ideal) gases the molar gas constant or universal
gas constant
R = 8.31 J.mole-1.K-1

Molar Gas Constant

Example: calculate the volume occupied by one mole of an ideal gas at standard temperature
and pressure (STP).
STP is specified as 0C (273.15K) and 1Atm (1.013x105Pa) (1Pa = 1N.m-2)
NB. when using the ideal gas law you MUST convert T to the absolute scale (otherwise, at
STP you would get that PV=0 which would make no sense)
PV = nRT => V = RT/P, for n=1 mole
thus V = (8.31)(273.15)/(1.013x105) = 0.0224m3
(check for yourself that the units of nRT/P gives m3)
Recall that 1m3 = 1000 litres, so the volume occupied by 1 mole of
ideal gas at STP is 22.4 litre.
Example: ideal gas occupies a volume of 200cm3 at 20C and at a pressure of 100Pa how
many moles of gas are present?
V = 200cm3 = 2x10-4m3 (recall that 1m3 = 106cm3)
T = 20C = 293.15K
PV = nRT => n = PV/RT = (100)(2x10-4)/(8.31)(293.15) = 8.2x10-6mole
Number of molecules present?
1 mole contains NA molecules, so 8.2x10-6mole contains (8.2x10-6)(6.02x1023)
= 4.9x1018 molecules.

The ideal gas law can also be expressed in terms of the total number of molecules, N:
N = nNA, where n = number of moles, and NA is the Avagadro number.
Thus PV = nRT = (N/NA).RT

or

PV = NkT, where k = R/NA = 8.31/6.02x1023 = 1.38x10-23J.K-1

k is Boltzmanns constant, and is frequently encountered when discussing systems at the

atomic/molecular level (R, on the other hand, is used when discussing macroscopic systems).
Note that R, NA, and k are related if you know two of them, you can calculate the third.
P,V,T are called the thermodynamic variables of the system. If the equation of state of the
system is known, then one of the variables can always be expressed as a function of the other
two. Different systems may use different variables in the equation of state, e.g. for a wire
under tension at constant pressure, the appropriate variables would be the tension force, the
length of the wire, and the temperature of the wire.