Lecture 1: The First Law

of Thermodynamics
 The first law of thermodynamics

For fixed n we only need to know two properties (T,V) to describe the system

The task of thermodynamics is to calculate these partial derivatives in terms of

measurable quantities.
 The first law of thermodynamics

Constant Volume:
 Joule Free Expansion of Gases

Joule designed an experiment to find out whether or not gases cool on expansion

Thermometer

gas vacuum
Joule Free Expansion of Gases
constant internal
energy

measured in the experiment

Joule coefficient
 Results of Joule Experiment

For ideal gas:

The internal energy of ideal gas depends only on temperature U(T)

For isothermal expansion or compression

of ideal gas

For change in state of ideal gases

Joule experiment is not valid for real gases

 Enthalpy

Chemical reactions usually take place at constant pressure. Enthalpy is a useful

function of state under these condition H(T, p).

The change in the enthalpy of a system is equal to the amount of heat exchanged
by the system at constant pressure.
Joule-Thomson expansion

Cp
estimates this quantity
 1 2

Joule-Thomson is a constant enthalpy process

Joule-Thomson expansion

constant enthalpy, dH = 0
Joule-Thomson Coefficient

Chain rule

will be derived later from

fundamental equations
 Mathematical Interlude

Cyclic relations:
Joule-Thomson coefficient for ideal gases
Relationship between heat capacities at constant p and V

Use H=U+pV
 Changes in Internal Energy at Constant Pressure

Internal pressure

expansion coefficient

Isothermal compressibility
Relationship between heat capacities at constant p and V

Will derive later from

fundamental equations

Universally true: can apply to any substance

Relationship between heat capacities for ideal gas
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