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Chapter 19 Thermodynamics. What is Entropy? What is chemical spontaneity?. First Law. E nergy cannot be created nor destroyed , it only changes form Gets converted (high quality to low) or transferred from system to surroundings. How does this occur?. Spontaneously Nonspontaneously.

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chapter 19 thermodynamics

Chapter 19Thermodynamics

What is Entropy?

What is chemical spontaneity?

first law
First Law
  • Energy cannot be created nor destroyed, it only changes form
  • Gets converted (high quality to low) or transferred from system to surroundings
how does this occur
How does this occur?
  • Spontaneously
  • Nonspontaneously

Spontaneous Processes

  • Spontaneous processes are those that can proceed without any outside intervention.
  • The gas in vessel B will spontaneously effuse into vessel A, but once the gas is in both vessels, it will not spontaneously return to vessel B.
spontaneous processes
Spontaneous Processes

Processes that are spontaneous in one direction are nonspontaneous in the reverse direction.


Spontaneous Processes

  • Processes that are spontaneous at one temperature may be nonspontaneous at other temperatures.
  • Above 0 C it is spontaneous for ice to melt.
  • Below 0 C the reverse process is spontaneous.
reversible really
Reversible? Really?
  • Reversible – change occurs in such a way that system/surroundings can be restored by EXACTLY reversing the original change
  • Irreversible – cannot be reversed to restore
  • Heat Flow is irreversible
  • P. 789
  • Spontaneous Process is irreversible!
  • Like total energy, E, and enthalpy, H, entropy (S) is a state function.
  • Therefore,

S = S finalS initial

  • Entropy can be thought of as a measure of the randomness of a system.
  • It is related to the various modes of motion in molecules.

The more disordered, or random, the system is, the larger the value of S.

isothermal entropy changes




Isothermal Entropy Changes

At constant temperature (an isothermal process), the change in entropy is equal to the heat that would be transferred if the process were reversible divided by the temperature:

2 nd law of thermodynamics
2nd Law of Thermodynamics
  • Entropy of the universe increases for spontaneous processes
  • Entropy of the universe does not change for reversible processes
  • Turn to pg. 791
2 nd law of thermodynamics1
2nd Law of Thermodynamics

In other words:

For reversible processes:

Suniv = Ssystem + Ssurroundings = 0

For irreversible processes:

Suniv = Ssystem + Ssurroundings > 0

2 nd law of thermodynamics2
2nd Law of Thermodynamics

These last truths mean that as a result of all spontaneous processes the entropy of the universe increases.


Entropy on the Molecular Scale

  • Ludwig Boltzmann described the concept of entropy on the molecular level.
  • Temperature is a measure of the average kinetic energy of the molecules in a sample.

Statistical thermodynamics is a field that uses statistics and probability to link the microscopic and macroscopic world.


Entropy on the Molecular Scale

  • Molecules exhibit several types of motion:
    • Translational: Movement of the entire molecule from one place to another.
    • Vibrational: Periodic motion of atoms within a molecule.
    • Rotational: Rotation of the molecule on about an axis or rotation about  bonds.
entropy on the molecular scale
Entropy on the Molecular Scale
  • Boltzmann envisioned the motions of a sample of molecules at a particular instant in time.
    • This would be like taking a snapshot of all the molecules.
  • He referred to this sampling as a microstate of the thermodynamic system.
entropy on the molecular scale1
Entropy on the Molecular Scale
  • Each thermodynamic state has a specific number of microstates, W, associated with it.
  • Entropy is S= k *lnW

where k is the Boltzmann constant, 1.38  1023 J/K.

entropy on the molecular scale2

SS= kln



Entropy on the Molecular Scale
  • The change in entropy for a processis:

S= klnWfinalklnWinitial

  • Entropy increases with the number of microstates in the system.
entropy on the molecular scale3
Entropy on the Molecular Scale
  • The number of microstates and, therefore, the entropy tends to increase with increases in
    • Temperature.
    • Volume.
    • The number of independently moving molecules.