Thermodynamics

SOME DEFINITIONS:
• THERMO – related to heat
• DYNAMICS – the study of motion
• SYSTEM – an object or set of objects
• ENVIRONMENT – the rest of the universe
• MICROSCOPIC – at an atomic or molecular level
• MACROSCOPIC – at a level detectable by our senses

THERMODYNAMICS
 is the study of the relationship between heat and motion.
 is a macroscopic description of the properties of a system
using state variables (e.g. volume, temperature, pressure)

Atoms are in constant motion, which increases with temperature.

 The Phases of Matter
+ - + - + - - +
- + - + - + - + -
- - + - + - + + -
-- + - + - + + -
-- + - + - + + -
-- + - + - + + -
-- + - + + + -
+- + - + - + + -
-- + - + -+ -
-- + - + - + + -
+ - + - + - + -

Solid Liquid Gas or Vapor Plasma

Increasing Temperature
Solids and liquids composed of atoms joined together at distances
of about 10-10 m by attractive electrical forces. In gases, vapors
and plasmas, the atoms, molecules or ions are in random motion.
 Temperature
Temperature
• is a measure of how hot or cold an object is.
• is measured by a thermometer.

Thermometers are based on physical properties of

objects that change with temperature, for example:
 volume of a liquid
 length of a solid
 pressure of a gas
 electrical resistance of a solid
 electrical potential difference between two solids.
 Common Temperature Scales
Fahrenheit:
• Based on the ability of farm animals to survive for
extended periods without attention.
(0F is the coldest and 100F is the hottest).

Celsius or Centigrade:
• Based on the physical properties of water on the
earth’s surface at sea level (0C is the freezing point
and 100C is the boiling point).

T(C) = (5/9)[T(F) – 32]

T (F) = (9/5)T(C) + 32
 Zero’th Law of Thermodynamics
Our experience tells us that objects placed in contact
will eventually reach the same temperature. We say
that they are then in thermal equilibrium. This is the
basis for
The Zero’th Law of Thermodynamics:
If two objects A and B are in thermal equilibrium
with a third object C, then A and B are in thermal
equilibrium with each other.

Objects or systems in thermal equilibrium have the

same temperature. This is the physical basis for the
definition of temperature.
 Questions
• Is it possible for two objects to be in
thermal equilibrium if they are not
touching each other?

• Can objects that have different

temperatures be in thermal equilibrium
with each other?
 Thermal Expansion
Most materials expand when heated:
 The average distance between atoms increases as
the temperature is raised.
 The increase is proportional to the change in
temperature (over a small range).
Consider an object of length Li at temperature Ti
 If the object is heated or cooled to temperature Tf
Lf – Li = α Li (Tf – Ti) or ΔL = α Li ΔT
α = coefficient of linear expansion [ºC-1]
(α is a property of the material)
Thermal Expansion of Solids and Liquids

Material α (ºC -1) For the same temperature

change, the thermal
Glass 9 x 10-6 expansion of liquids is
much greater than that
Concrete 12 x 10-6 of solids (> 10 times).

Copper 17 x 10-6
Area Expansion:
Lead 29 x 10-6 ΔA = 2α Ai ΔT

Mercury 1.8x 10-4

Volume Expansion
Gasoline 3.2 x 10-4 ΔV = 3α Vi ΔT
 Example: Thermal Expansion
Problem 17-8.
A concrete highway is built of slabs
12 m long (20 ºC). How wide
should the expansion cracks
between the slabs be (at 20 ºC) to
prevent buckling if the range of
temperature is –30 ºC to +50 ºC ?
 Liquid water has an unusual property.
• Water contracts when
Density of Water
heated from 0ºC to 4ºC,
then expands when
1 heated from 4 ºC to
100 ºC.
0.99
• Just above the freezing
g/(cm**3)

0.98 point, the coldest (and

least dense) water rises
0.97 to the surface, and
0.96 lakes freeze from the
surface downward.
0.95 • This unusual property
0 4 12 20 50 100
permits aquatic life on
Temperature in Celsius earth to survive winter!
 Thermal Stress
• Heat can stress materials if no allowance is
made for thermal expansion:

1 F
L  L0 E = Young’s Modulus
E A
L   L0 T Thermal Expansion
1 F
L0   L0 T
E A
F
  ET Thermal Stress
A
 Review Questions
• When a cool mercury or alcohol
thermometer is inserted into boiling water,
it will initially indicate a lower
temperature before the reading starts to
increase. Explain.

• Will a grandfather clock that has been

calibrated at normal room temperature run
fast, slow or the same on a very hot day?
Absolute (Kelvin) Temperature Scale
The volume occupied by any gas at constant pressure is an
increasing linear function of temperature, that always
extrapolates to zero at –273.15 ºC (called absolute zero).

This is called
Charles’s Law
and is the basis
for the absolute
or Kelvin (K)
temperature
scale.
T(K) = T(ºC) + 273.15
 Absolute or Kelvin Temperature Scale
 The absolute or Kelvin scale is the true physical
temperature scale.

 T = -273.15 ºC = 0 K is the lowest temperature that

can be defined for any physical system.

 Absolute zero of temperature (0 K) is a theoretical limit

that can never be reached in a physical system.
 Experiments on Bose-Einstein Condensation in gases have
reached the nano-Kelvin (10-9 K) range (1998, 2001 Nobel
Prizes in physics)!

 The degree steps in the Celsius and Kelvin scales are

chosen to be the same: ΔT(ºC) = ΔT(K).
 Molecular Model of an Ideal Gas
• The number of molecules is large.
• The average separation between molecules
is large compared to their dimensions.
• The molecules obey Newton’s laws of motion
and move randomly.
• The molecules collide elastically with each
other and with the container walls.
• The forces between molecules are negligible
except during collisions.
• All the molecules of the gas are identical.
 Ideal Gas
 The relationship between the state variables,
pressure P, volume V and temperature T of a
system is called its equation of state.
 An ideal gas is one whose equation of state
is simple:
PV = nRT
n = number of moles (mole = 6.023 x 1023 molecules)
R = universal gas constant = 8.31 J/(mole K)
 Most gases near room temperature and
atmospheric pressure behave as ideal gases.
 Avogradro’s Number and Molar Mass
• NA = 6.023 x 1023 = Avogadro’s number

• 1 mole is the quantity of any substance that

contains Avogadro’s number of atoms or
molecules.

• The gram-molecular-weight M of a substance is

the mass of one mole (molar mass) of that
substance:
 Helium (He) M = 4 g/mole
 Nitrogen (N2) M = 28 g/mole
 Oxygen (O2) M = 32 g/mole
 Methane (CH4) M = 16 g/mole
 Equation of State of an Ideal Gas
• For a gas containing N atoms or molecules, the
number of moles n = N/NA.

• The ideal gas law:

PV = nRT = (N/NA)RT = N(R/NA)T = NkBT
where
kB = R/NA = 1.38 x 10-23 J/K (Boltzmann’s constant)

• The ideal gas law may be expressed:

PV = NkBT (N = number of atoms or molecules)
or
PV = nRT (n = number of moles)
 Applying the Ideal Gas Law
For a ideal gas:
INITIAL STATE (1) FINAL STATE (2)
P1, V1, T1, n1 P2, V2, T2, n2
P1V1 = n1RT1 P2V2 = n2RT2
R = P1V1/(n1T1) R = P2V2/(n2T2)

P1V1 P2V2 P1V1 P2V2

 or if n1 = n2 
n1T1 n2T2 T1 T2
general case closed container
 Example Problem
Problem 17-34.

If 18.75 mol of helium gas is at 10.0ºC and a

gauge pressure of 0.350 atm., calculate
a) The volume of the helium gas under these
conditions.
b) The temperature if the gas is compressed to
precisely half the volume at a gauge
pressure of 1.00 atm.
 Questions
• An ideal gas in a sealed bottle at temperature T
occupies a volume V, and exerts a pressure P on
the walls of the bottle. What will happen to the
pressure if the temperature is doubled?

• Instead of a sealed container, the gas is contained

in a test tube with a movable piston on one end.
The temperature is then halved. What will happen
to
a) the pressure?
b) the volume?