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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