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Definitions
Phase(P) -State matter which is uniform throughout not only in chemical composition but also in physical state J. Willard Gibbs
Solid
Alloys (sometimes its difficult to tell this - microscopic examination may be necessary {dispersions uniform on macroscopic scale})
Liquid
Miscible liquids are one phase Immiscible liquids are multiple phases (P>1)
Gas
Definitions
Heterogeneous and homogeneous systems Systems with one phase are homogeneous Systems with more than one phase are heterogeneous Constituent- a chemical species (ion or molecule which is present Component (C) - chemically independent constituents of a system C = #of independent chemical constituents - # of distinct chemical reactions
#of independent chemical constituents = total # of constituents minus the number of any restrictive conditions (charge neutrality, material balance etc.)
Counting Components
Example: CaCO3(s) CaO(s) + CO2(g) Phases: P = 2 solid + 1 gas = 3 Component: C = 3 consitiuents - 1 reaction = 2 Example: Consider the system NaCl, KBr and H2O. Suppose you can also isolate the following from it KCl(s), NaBr(s), NaBr. H2O(s), KBr. H2O(s), and NaCl. H2O(s)
Phases: P = 5 solid
Components:
There are 8 constituents You can write the following reactions four: NaCl + KBr KCl + NaBr; NaCl + H2O NaCl. H2O KBr + H2O KBr. H2O; NaBr + H2O NaBr. H2O Conditions: 1 -Material balance moles of KCl = moles of NaBr + NaBr. H2O
Remember you must count reactions which actually occur not those which could occur Consider a system in which we has the following : O2(g), H2(g),
H2O(g) If conditions are such O2(g) + H2(g) H2O(g) does not occur, C=3 If conditions are such (T, catalyst) O2(g), H2(g) H2O(g) occurs, then
C=3components -1reaction =2
If conditions are such (T, catalyst) O2(g), H2(g) H2O(g) occurs and you impose
the condition that all the hydrogen and oxygen come from dissociation of water, then C=3 constituents - 1 condition -1 reaction = 1
Phase Rule
In discussing phase equilbria, you need only consider intensity factors (temperature, pressure, and concentration) Only certain of these can be varied independently Some are fixed by the values chosen for the independent variables and by the requirements of thermodynamic equilibrium
Number of variables which can be varied independently without changing the number of phases is called the degrees of freedom of the system
The number of degrees of freedom or variance of a system, F, is related to the number of components(C) and number of phases(P)
F=C-P+2
In any system the number of intensive variables are: pressure, temperature plus the mole fractions of each component of each phase.
i.e. JP1= JP2= JP3= JP4= JP5.{there are P-1 such equations} Since there are C components, equilibrium requires that there are C(P-1) equations linking the chemical potentials in all the phases of all the components F = total required variables - total restraining conditions F = P(C-1) + 2 - C(P-1) = PC - P + 2 -CP + C = C- P + 2
Specified by temperature and pressure and occurs at 1 point (called the triple point)
If one phase is present, F = 2 that is P and T can be varied independently This defines an area in a P,T diagram which only one phase is present If two phases are present, F = 1 so only P or T can be varied independently. This defines a line in a P, T diagram
Cooling Curve
A B 100C Liquid Cooling Temp. Solid f reezing C 0C Solid Coolin g D Gas Cooling Gas Condensing
You can generate a cooling curve @ constant pressure (isobar) from previous phase diagram Halts occur during 1st order phase transitions (e.g. freezing)
Time
Experimental Measurements
Phase changes can be measured by performing DTA (differential thermal analysis) on samples
In DTA sample is heated vs. a reference 1st order transitions can be measured even when they cant be observed
Maximum value for F is 2 If T is constant one degree of freedom is pressure and the other is mole fraction
Phase diagram (Constant T) is map of pressure and compositions at which each phase is stable
If P is constant one degree of freedom is temperature and the other is mole fraction
Phase diagram (Constant P) is map of temperature and compositions at which each phase is stable
Both Useful
p = pA + pB = xApA * + xBpB * But xB = (1-xA)so xApA * + xBpB * = xApA * + (1-xA) pB * = pB * + xA(pA * -pB *)
The composition of the vapor is given by Raoults law so the mole fraction in the gas phase, yA and yB is
yA = pA/p and yB = pB/p {also yA = 1-yA) From above yA = xApA * /[pB * + xA(pA * -pA *)]
If pA * /pB *= pA/B then yA = (xA * pA/B) /(1+ (xA * pA/B) - xA ) Or yA = (xA * pA/B) /(1+ (xA *( pA/B - 1) )
p*/p*=1000
A B
p*/p*=10 p*/p*=50
A B A B
0.6
p*/p*=4
A B A
p*/p*=2
B
p*/p*=1 A B
0.4
This shows the vapor is richer in the more volatile component If B is non volatile then yB = 0
Assume the composition on the x axis is the overall composition, zA (as mole fraction)
In Liquid region zA = xA In vapor Region region zA = yA In between two phases present F=1 so at given pressure compositions are fixed by tie lines
A vertical line represents a line of constant composition or isopleth Until pressure = p1sample is liquid vapor phase composition is a1 At p1, vapor composition is given by tie line to vapor curve At p2 vapor composition is a2, liquid composition is a2 and overall composition is a At p3 vitually all the liquid is vapor and trace of liquid has composition given by tie line to liquid
The composition of each phase is given by the each end of the tie line The relative proportion of each phase is given by the length of the tie line
nl = nl or n= nl / l
Temperature-Compositions
Assume A more volatile than B Region between two curves is 2-phase region F=1 (pressure is fixed) At given temperature compositions are fixed by tie lines Region outside lines composition & temperature variable Heat liquid with composition a1 Hits boiling curve, vapor has composition a2, liquid a2 (=a1) vapor is richer in more volatile component Distillation Vapor condensed (a2-a3) New vapor @ concentration a3 (richer still) New condensate @a4 etc until nearly pure liquid obtained
Distillation/Theoretical Plates
A theoretical plate is a vaporization-condensation step Previous example has 3 theortetical plates If the two curves move closer together, more theoretical plates are required to achieve same degree of separation
As vapor is removed you move to right up the curve until you reach point b At b liquid boils with constant composition
Called an azeotrope (unchanging Gr.)
As vapor is removed you move to right down the curve until you reach point b At b liquid boils with constant composition Example ethanol-water boils at constant water content of 4 wt% @ 78C
If two liquids immiscible and in intimate contact then p is nearly the sum of vapor pressures of pure components (p = pA* +pB*)
mixture will boil when p = atmospheric pressure intimate contact (& trace level saturation maintained)
If two liquids immiscible and not in intimate contact then p for each is the vapor pressures of pure components (p = pA* and p = pB*)
Each will boil separately when respective pA* = atmospheric pressure and/or pB* = atmospheric pressure
Liquids miscible & solids immiscible Consider Cooling along isopleth from a1
At a2 pure B starts to come out of solution At a3 solution is mixture of B + Liquid with composition b3 (ratio by lever rule) At a4 liquid has composition e and freezes
e is called a eutectic
Eutectic Mol %B 64 81 55 69 89
Eutectics
In previous diagram, the eutectic (easily melted, Gr.) point is a temperature at which a mixture freezes without first depositing pure A or B
Like a melting point in that it it is a definite temperature Thats because, since C=2 and P=3, by Phase rule, F=0 A cooling (or heating) curve will have a halt at the eutectic temperature
If pure A and pure B are in contact a liquid will form at the eutectic temperature Examples
solder lead/tin (67/33) melting point 183C NaCl and water (23/77) melting point -21.1C
Maximum in phase diagram Phase diagram interpreted as before except now there are additional regions
High Power Density Nuclear Sources for Space Power & Propulsion
PBR - Schematic
Hot frit, nozzle, etc. Withstand H2 Environment ~2800 K 70 atmospheres Large Temperature Gradients 12K to Tmax over a few cm Multiple Thermal Cycles Long Exposure Times 10s minutes Launch Stresses Withstand Radiation Fields Not Affect Reactor Criticality
Fuel Same as general components Provide for adequate reactivity Optimize coating thickness and type to maintain criticality Maintain (Keff) No HfC coatings Maintain coolable geometry No large gaps between layers No particle clumping No reaction with other components, e.g. hot frit Minimum F.P. and U release Criticality and safety criterion
Large neutronic penalty for monolithic Re High radiation heating for monolithic Re Extensive alloying of Re with fuel coatings @ T > 2760 K
High cost 11BN required Unacceptable thermal decomposition (3 wt % in 10 min @ 2700 K Reaction with baseline ZrC fuel coating Potential for CTE mismatch between coatings and substrate
Pyrolytic BN
UC
HTGR - SiC PBR - ZrC Spongy layer Dense layer HTGR - UO2 PBR - UC
Pyrocarbon layer(s)
Inner kernel
Zirconium-Carbon
Compound melts into components Called the peritectic melting point One solid phase melts around the other
Isopleths a
b2-> b3 liquid phase with A + B b3 B reacts to form compound b3->b4 Solidcompound + liquid b5 solid A precipitates with compound
Zone Refining
Ultra high purity can be obtained by moving a small molten zone across a sample.
Impurities more soluble in liquid than solid so they continually move down the liquid front One end becomes purer while other end is dirtier Multiple passes can be used to achieve high purity
Triangle with each edge one line of binary phase diagram Usually temperature
Phase diagrams are usually given as a succession of surfaces at constant temperature To examine temperature variation you hold composition constant
2.6
cm cm
4.2
2
cm
4.2
4.2
1
cm
5.7 cm
A 100 % Component "A"
4.2 cm
To obtain relative amounts d rop a perpendicular to each axis Ratio of the lengths of lines is the ratio of compone nets Ratio A:B:C "1 " = 1:1:1 or 33% o f each component "2 " = 1.6:1:2.2 or 33 .6%A, 20.8%B, 45 .6%C