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Where are thermodynamics relevant in a LWR?

Pressure-temperature-volume properties (equations of state); water, UO2

Vapor pressures: fuel, coolant, fission products

Thermal properties: the specific heat; coefficient of thermal expansion Phase diagrams; single component, binary and higher order

Chemical and physical state of fission products in fuel

Tendency of hydrogen to form hydrides in cladding and carbon to form carbides in steel Susceptibility of metals and alloys to aqueous corrosion

Response of uranium dioxide stoichiometry to the oxygen potential of the environment

Point-defect populations in solids

Review of Basic Thermodynamics

1. Basic Thermodynamic Properties 2. First Law of Thermodynamics 3. Second Law of Thermodynamics 4. (Third Law of Thermodynamics) 5. Single Component Phase Equilibria 6. The Gibbs Phase Rule

7. Solution Thermodynamics
8. Binary Phase Diagrams and the Lever Rule 9. Ternary Phase Diagrams

1. Basic Thermodynamic properties

Five fundamental thermodynamic properties: * *

Three derived thermodynamic properties:

* Intensive properties -- independent of the system size

e.g., v=V/n specific volume an intensive property
Also: H = H/n, g = G/n (n = # of moles)
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The heat capacities (also called specific heats):

The coefficient of thermal expansion a and the coefficient of compressibility b:

2. First Law of Thermodynamics

The First law of thermodynamics is an empirical observation, never refuted, that the change in the internal energy of a closed system resulting from addition of heat and performance of work is given by:

U = Q - W

(eq. 1.7)

where U = U(final) - U(initial) = change in system internal energy Q = heat added to the system W = work done by the system (e.g., mechanical, chemical, electrical)

U + Usurr = 0

3. Second Law of Thermodynamics

S Q T

In an isolated system, for any spontaneous process the entropy will either increase or remain the same.

S+Ssurr 0

Where equality applies to reversible processes, i.e., at equilibrium

Combining the 1st and 2nd laws of thermodynamics:

du = Tds - pdv dh = Tds + vdp

dg = -sdT + vdp
df = -sdT - pdv
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Arrive at the following relations at fixed temperature: dG = -SdT + Vdp = dH TdS SdT = dH TdS

dF = -SdT pdV = dU TdS SdT = dU TdS

Note that dH = dU pdV V dp = dU d(pV) For solid phases, dU ~ dH, use H and U interchangeably.

From S+Ssurr 0 in an isolated system,

can derive dG 0 (~dF 0) in an isothermal system.

The criterion for equilibrium: F / G is minimized

Free Energy vs. T across Tm for a Solid and a Liquid

Gliq

Gsolid

Tm temperature

Whether a substance will be solid, liquid or gaseous, depends on which phase has the lowest Gibbs free energy. When two phases coexist, their specific Gibbs free energies are equal.
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Important application:

Saturation pressure (or vapor point) The pressure at a corresponding T at which liquid boils into its vapor phase or a solid sublimate into its vapor phase

(eq. 1.19a)

(eq. 1.19b)

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Phase Diagram of a Pure Substance

(eq. 1.19a)

(eq. 1.19b)

(eq. 1.22)

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Phase Diagram of a Pure Substance and The Gibbs Phase Rule

6. Gibbs Phase Rule:

F=C+2P

Components: distinct chemical species whose quantities can be independently varied. Phases are regions of a system in which all properties are uniform and are distinct from other regions in the same system. Degrees of freedom (F) are the number of system variables (e.g., properties, composition) that can be independently specified without changing the phase(s).

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7. Solution Thermodynamics
Solution: a homogeneous solid or liquid system of two or more components

Mole Fraction of a component:

For an ideal solution*

(A and B are the constituent elements, xA and xB, their concentrations q is the intensive quantity of any property)

*A binary solution of A and B is ideal if the average of the A-A and B-B intermolecular forces is just equal to the strength of the A-B interaction.

The chemical potential:

When q=entropy, an additional term appears on the r.h.s.:

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For a non-ideal solution:

Regular solution Simplest form of a non-ideal solution: assume a random distribution of A and B

W Is obtained by assigning fixed energies to each A-A, A-B and B-B bonds.

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Raoults law (for an ideal solution):

Henrys Law (for a nonideal solution):

The Henrys law constant, kHA, is the product of the composition-independent activity coefficient of A in solution and the saturation pressure of pure A. In the concentration range where A follows Henrys law, component B must obey Raoults law. 15

8. Binary Phase Diagrams and the Lever Rule

(note: contrary to the implication in the text, this is not the correct U-Zr phase diagram) alloy composition

The lever rule:

solid composition liquid composition 16

The phase diagram is determined by the phases free energies

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The Eutectic Phase Diagram

Eutectic Point

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19

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Lever rule applied to a binary system

Point 1
Point 2
b starts to form. Phase b first forms with a composition of 96 weight% B. The green dashed line below is an example of a tie-line. A tie-line is a horizontal (i.e., constant-temperature) line through the chosen point, which intersects the phase boundary lines on either side.

Liquid only

C
C = 65 weight% B

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Lever rule applied to a binary system

Point 3

C
C = 65 weight% B

C1 58 weight% B C2 92 weight% B fraction of solid b (65 - 58) / (92 - 58) 20 weight% fraction of liquid (92 - 65) / (92 - 58) 80 weight%

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Lever rule applied to a binary system

Point 4

C
C = 65 weight% B

C3 48 weight% B C4 87 weight% B fraction of solid b (65 - 48) / (87 - 48) 44 weight%. As the alloy is cooled, more solid b phase forms. The remainder of the liquid becomes a eutectic phase of a+b fraction of eutectic 56 weight%

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Lever rule applied to a binary system

Point 5

C
C = 65 weight% B

C5 9 weight% B C6 91 weight% B fraction of solid b (65 - 9) / (91 - 9) 68 weight% fraction of solid a (91 - 65) / (91 - 9) 32 weight%

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The Iron-Carbon Phase Diagram

Wt% C

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9. The Ternary Phase Diagram

In ternary systems (involving 3 components), Gibbs phase rule predicts a maximum of: F = C-P+2 = 3-1+2 = 4

degrees of freedom when only a single phase is present. In depicting these diagrams usually both pressure and temperature are held constant and the composition variables plotted against each other on a triangular diagram:

25
50 75 B

75 50

25
50 75 25 weight or mole percent C C

Locate the point on the above ternary phase diagram where the system consists of 25% A and 50% B.
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cB = 25%

A 25 50 75 50 25 50 75 25 weight or mole percent C C

cA = 25%

75
B
cC = 50%

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Example of a ternary phase diagram

of NaCl, KCl, H2O at a fixed pressure of 1 atm

1500 C liquid solution isothermal slice at o 25 C 0 oC 1413 oC

solid solution

KCl

H 2O

NaCl
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Ternary phase diagram for Fe, Cr, Ni at 400C showing commercial alloys related to PWR steam generators

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