Chapter 2 The Structure of Thermodynamics

Notes on Thermodynamics in Materials Science by Robert T. DeHoff (McGraw-Hill, 1993).

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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Thermodynamic Systems
System --- That portion (subset) of the universe that is under study. Surroundings --- Everything else. Usually, only the interaction with the immediate surroundings is relevant.

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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Classification of Systems
Unary versus Multicomponent --- How many unique chemical species? Homogeneous versus Heterogeneous --- How many unique phases? Closed versus Open --- Is matter exchanged with the surroundings? Non-reacting versus Reacting --- Can chemical reactions occur? Otherwise Simple versus Complex --- Are only chemical, thermal, or mechanical effects involved? Are fields, surfaces, or elastic effects involved?
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2.1 Classify the following thermodynamic systems: A solid bar of copper

Unary Homogeneous Closed Non-reacting Otherwise simple Multicomponent Heterogeneous Open Reacting Complex

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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2.1 Classify the following thermodynamic systems: A glass of ice water

Unary Homogeneous Closed Non-reacting Otherwise simple Multicomponent Heterogeneous Open Reacting Complex

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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2.1 Classify the following thermodynamic systems: An yttria stabilized zirconia furnace tube.
Unary Homogeneous Closed Non-reacting Otherwise simple Multicomponent Heterogeneous Open Reacting Complex

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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2.1 Classify the following thermodynamic systems: A styrofoam coffee cup (just the polymer)
Unary Homogeneous Closed Non-reacting Otherwise simple Multicomponent Heterogeneous Open Reacting Complex
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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

2.1 Classify the following thermodynamic systems: A styrofoam coffee cup (the polymer and enclosed gas)
Unary Homogeneous Closed Non-reacting Otherwise simple Multicomponent Heterogeneous Open Reacting Complex
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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

2.1 Classify the following thermodynamic systems: A eutectic alloy turbine blade rotating at 20,000 rpm:
Unary Homogeneous Closed Non-reacting Otherwise simple Multicomponent Heterogeneous Open Reacting Complex

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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Thermodynamic Properties
State Variables --- Values are determined by current condition & are independent of path. Process Variables --- Have meaning only for changing systems. Intensive Properties --- Have a value at each point in a system. May vary from point to point. Do not depend on the amount of matter. Extensive Properties --- Values apply to the whole system. Depend on the amount of matter.
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2.2 Without state functions thermodynamics would be useless. Discuss this assertion.
If there no state functions (like T, P, V, composition) then the behavior of all aspects of matter would depend explicitly on the history of the system. There would be no variables that, by themselves, explicitly describe the current condition of any system. Even the history experienced by the system could not be described in terms of some sequence of its properties.
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2.4 Why is heat a process variable?

Heat is fundamentally a flow of energy. Heat is transferred between two systems, or between parts of the same system. The rearrangement of the distribution of energy is accompanied by changes in at least some of the properties of the system. Such a change is a process
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09/19/2001

Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

Thermodynamic Properties
State Variables --- Values are determined by current condition & are independent of path. Process Variables --- Have meaning only for changing systems. Intensive Properties --- Have a value at each point in a system. May vary from point to point. Do not depend on the amount of matter. Extensive Properties --- Values apply to the whole system. Depend on the amount of matter.
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2.3 Determine which of the following properties of a thermodynamic system are extensive/intensive: The mass density.
M/L3 Kg/m3

Intensive

Extensive

Intensive

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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2.3 Determine which of the following properties of a thermodynamic system are extensive/intensive: The molar density.
M/L3 Moles/m3

Intensive

Extensive

Intensive

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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2.3 Determine which of the following properties of a thermodynamic system are extensive/intensive:
The number of gram atoms of alumina in a chunk of alumina. M Moles

Intensive

Extensive

Extensive

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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2.3 Determine which of the following properties of a thermodynamic system are extensive/intensive:
The potential energy of the system in a gravitational field. ML2/t2 J

Intensive

Extensive

Extensive

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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2.3 Determine which of the following properties of a thermodynamic system are extensive/intensive:
The molar concentration of NaCl in a salt solution. M/L3 Moles/m3

Intensive

Extensive

Intensive

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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2.3 Determine which of the following properties of a thermodynamic system are extensive/intensive:
The heat absorbed by a gas in a cylinder when it is compressed. M L2/t2 J

Intensive

Extensive

Extensive

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Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

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Thermodynamic Relations
Laws --- 0th, 1st, 2nd, 3rd Definitions --- Energy, , Compressibility, ... Coefficient Relations --- Z = Z(w,x,y,)
Z M w x , y ,...

Maxwell Relations ---

Z N x w, y ,...

Criteria for Equilibrium --- DS = maximum Conditions for Equilibrium --- Ta = Tb ,...
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

M N x w, y ,... w x , y ,...

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