Lecture 2.

1: The First Law of Thermodynamics: Internal In contrast, work is the transfer of energy that makes
Energy use of organized motionin the surroundings.

Joule’s Experiments – The present day concept of heat Internal Energy – total energy of a system; total kinetic
and its “mechanical equivalent” work was developed by and potential energy of the constituents of the system.
James P. Joule in the 1840s - This does not include the kinetic energy arising
from motion of the system as a whole
Two parts of the “universe” - There is no thermodynamic definition –
System – the part of the world/universe of interest primitive
Surroundings – the region outside the system and were - a state function – a property with a value that
measurements are made depends only on the current state of the system
as described by a set of state variables
Classification of systems based on BOUNDARIES
1. Open system – matter and the energy it
contains can be transferred through the
boundary.
2. Closed System – matter can’t pass through but
non-flow-related energy can
3. Isolated system- neither matter nor energy can
Motional Degrees of Freedom
pass through the boundary
1. Translational
2. Rotational
Work – is done to achieve motion against an opposing
3. Vibrational
force
Equipartition theorem- for a sample at thermal
equilibrium, the average value of each quadratic
Energy – is the capacity to do work. When work is done
contribution to the energy is ½ kT.
on a system, its energy increases.

Molecular Interpretation of Internal Energy

Heat – when the energy of a system changes as a result
- The internal energy of a perfect gas is
of a temperature difference, this is the energy said to be
independent of its molar volume
transferred.
- As the temperature of the system is raised, the
1. Diathermic - Permit heat transfers
internal energy increases as the various modes
2. Adiabatic – Do not permit heat transfer
of motion become more highly excited
Exothermic reactions – processes that release energy as
heat (i.e., combustion)
First Law of Thermodynamics – although energy
Endothermic reactions – those where energy is
assumes many forms, the total quantity of energy is
acquired as heat.
constant, and when energy disappears in one form it
appears simultaneously in other forms

- The internal energy of an isolated system is

constant

Acquisitive convention
- W and q are positive if energy is transferred
Thermal motion – heating is the transfer of energy that INTO the system
makes use of disorderly, apparently random, molecular - Negative if LOST from the system
motion.
Expansion Work – which is the work arising from a
change in volume.

- If dz is positive but against an opposing force

dw<0 the internal energy of the system doing
the work decreases
Constant-Volume Calorimetry
Calorimeter constant (for the instrument):

- pex = 0 (free expansion) only for total vacuum

Through electricity:

Where:
Thermodynamic Reversibility I – constant current
Reversible change – is a change that can be reversed by ∆φ – potential difference
an infinitesimal modification of variable t – period of time
- Work is often calculated for the hypothetical
reversible processes combined with an Constant-Volume Heat Capacity, Cv
appropriate thermodynamic efficiency (as a
basis)
Characteristics:
- Infinitesimal change
- Never more than minutely removed from
equilibrium
- Traverses a succession of equilibrium states
- Frictionless
- Infinitely slow
- Restores the initial state of the system and Enthalpy – the energy supplied as heat at constant
surroundings pressure is equal to the change in another
thermodynamic property of the system.

*under constant pressure

- More work is obtained when the expansion is

reversible (the area is greater)
- The maximum work available from a system
operating between two states is obtained when
the change takes place reversibly.

CONSTANT-VOLUME SYSTEMS
- No work done by or on the system
WEEK 9
RELATION OF CP AND CV
- A smaller increase in temperature implies a
larger heat capacity
- the heat capacity at constant pressure is larger
than its heat capacity at constant volume (in
most cases) (CP > CV)

Adiabatic Processes
- Q=0; there is no transfer of heat
- Energy transfer as WORK only
- Lowered internal energy
- Decreased temperature
Adiabats- curves of pressure versus volume for
Adiabatic Changes in Temperature adiabatic changes; more steeply or rapidly compared to
The Change in Temperature isothermal processes

THE SECOND LAW OF THERMODYNAMICS: ENTROPY

Two fundamental properties of Thermodynamics:
1) Internal Energy (U)
2) Entropy (S)

Anything that can happen to the object can be classified

to spontaneity. It will happen on its own.
- The direct spontaneous change is determined
by the manner in which energy and matter is
determined by the second law of
- ISOTHERMAL EXPANSION thermodynamics
- ISOCHORIC COOLING - Energy associated due to motion becomes
∆U=CV∆T dispersed into thermal motion
**Eq 4-22 (PVT relationship in adiabatic circumstances) - heat directly into work.
- SIGNPOST: look for the direction of change that
leads to the dispersal of energy

∆U = Wad = Cv∆T Kelvin statement:

Adiabatic Changes in Pressure “No process is possible in which the sole result is the
For monoatomic perfect gas: absorption of heat from a reservoir and its complete
Cv,m= 3/2 R conversion to work”
Cp,m = 5/2 R - Hindi possible na lahat ng heat macconvert sa
Γmono = 5/3 work; There is energy lost

For a gas of nonlinear polyatomic molecules: Clausius statement:

Cv,m = 3R “Heat does not flow spontaneously from a cool body to
Cp,m = 4R a hotter body”
Γ = 4/3 - There must be energy input applied to the
system for this to happen; to cool.
Entropy ENTROPY AS A STATE FUNCTION
- Is not conserved Carnot cycle – named after French engineer Said Carnot
- Increases in the course of a spontaneous - Consists of 4 reversible stages in which a gas is
change expanded and compressed in various ways

-
- Stotal > 0 to be spontaneous

*find a reversible path between them, and integrate the

energy supplied as heat at each stage of the path
divided by T at which the heat is transferred
- Total entropy should be zero (0)

Carnot Efficiency

Statistical Definition (Entropy)

- atoms and molecules are distributed over the energy
states available to them in accord with the Boltzmann
distribution

Boltzmann formula (aka statistical entropy): Thermodynamic temperatures

The equation that enabled the definition of
thermodynamic temperature

Where:
k = 1.381 x 10-23 J/K
W = number of microstates The Clausius Inequality
- More work is done when a change is reversible
Microstates – makes the quantitative concepts of that when it is irreversible
disorder and “dispersal of matter and energy”
- The number of arrangements possible
- A more disorderly distribution of matter and a
greater dispersal of energy corresponds to a
greater number of microstates associated with
the same total energy
- Higher microstate, higher entropy
Trouton’s rule
 - A wide range of liquids give approximately the
same standard entropy of vaporization (~85 J/K
mol)
- Similar change in volume occurs when any
liquid evaporates and becomes a gas

Composite Processes
- More than one parameter changes

Debye extrapolation

THIRD LAW OF THERMODYNAMICS

Nernst heat theorem:
The entropy change accompanying any physical or
chemical transformation approaches zero as the
temperature approaches zero provided all the
substances involved are perfectly ordered (perfect
crystal)