Chemistry 231
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Chemistry 231. Chapter 3 – Enthalpy and Internal Energy: The Importance of State Functions. The Properties of the Pressure, P. Let’s examine the pressure of any system as a function of T and V. The Isothermal Compressibility. For a fluid system or a solid Isothermal Compressibility.

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Chemistry 231

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Chemistry 231

Chapter 3 – Enthalpy and Internal Energy: The Importance of State Functions


The Properties of the Pressure, P

Let’s examine the pressure of any system as a function of T and V


The Isothermal Compressibility

  • For a fluid system or a solid

    • Isothermal Compressibility


Coefficient of Thermal Expansion

  • For solids and fluid systems

    • The coefficient of thermal expansion


The Final Expression

Assume that we will write pressure as a function of T and V


The Properties of U

In general, we write U as a function of T and V


Isothermal Changes in U

Examine the second partial derivative


The Joule Experiment

O

O

O

O

C

C

F

F

50

120

100

40

30

80

20

60

10

40

0

20

10

0

20

20

30

40

40

60

50

A

T1, Vm,1, P1

B

Stirrer

Thermal insulation

Valve


The Joule Coefficient

is known as the Joule coefficient, J.

The partial derivative


Internal Energy and the Joule Coefficient

The change in the internal energy under isothermal conditions is related to the Joule Coefficient


Relating CP and CV

  • In general

For an ideal gas


The Properties of H

In general, we write H as a function of T and P


The Constant Pressure Heat Capacity

Define the constant pressure heat capacity, CP


Isothermal Changes in H

Examine the second partial derivative


The Joule-Thomson Experiment

Thermal insulation

O

O

O

O

C

O

C

O

O

O

F

F

C

C

F

F

50

120

50

120

100

40

100

40

30

80

30

80

20

20

60

60

10

10

40

40

0

0

20

20

10

10

0

0

20

20

20

20

30

30

40

40

40

40

60

50

60

50

T2, P2, Vm,2

T1, P1, Vm,1

Porous Plug


The Joule-Thomson Coefficient

is known as the Joule-Thomson coefficient, JT.

The partial derivative


Relating H to the Joule-Thompson Coefficient

The change in the enthalpy under constant pressure conditions is related to the Joule-Thomson Coefficient


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