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David R. Gaskell

Preliminaries

‡ Settings

Off@General::spellD

**‡ Physical Constants Needed for Problems
**

ü Heat Capacities The generic heat capcity c 105 bT Å Cp = a + ÅÅÅÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ ; T2 103 The heat capacities of various elements and compounds are CpAgs = Cp ê. 8a Ø 21.30, b Ø 8.54, c Ø 1.51<; CpAgl = Cp ê. 8a Ø 30.50, b Ø 0, c Ø 0<; 20.75 T2 CpAl = Cp + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. 8a Ø 31.38, b Ø -16.4, c Ø -3.6<; ÅÅÅÅÅÅ 106 CpAll = Cp ê. 8a Ø 31.76, b Ø 0, c Ø 0<;

— General::spell1 : Possible spelling error: new symbol name "CpAll" is similar to existing symbol "CpAl".

CpAl2O3 = Cp ê. 8a Ø 117.49, b Ø 10.38, c Ø -37.11<; CpCaO = Cp ê. 8a Ø 50.42, b Ø 4.18, c Ø -8.49<; CpCaTiO3 = Cp ê. 8a Ø 127.39, b Ø 5.69, c Ø -27.99<; CpCord = Cp ê. 8a Ø 626.34, b Ø 91.21, c Ø -200.83<; 2.26 T2 CpCr = Cp + ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ÅÅ ê. 8a Ø 21.76, b Ø 8.98, c Ø -0.96<; Å Å 106 CpCr2O3 = Cp ê. 8a Ø 119.37, b Ø 9.30, c Ø -15.65<;

2

Notes on Gaskell Text

—

General::spell1 : Possible spelling error: new symbol name "CpCO" is similar to existing symbol "CpCaO".

CpCO = Cp ê. 8a Ø 28.41, b Ø 4.10, c Ø -0.46<;

CpCO2 = Cp ê. 8a Ø 44.14, b Ø 9.04, c Ø -8.54<; 9.47 T2 CpCu = Cp + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. 8a Ø 30.29, b Ø -10.71, c Ø -3.22< ; Å Å 106 CpDiamond = Cp ê. 8a Ø 9.12, b Ø 13.22, c Ø -6.19<; 17.38 T2 CpGraphite = Cp - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. 8a Ø 0.11, b Ø 38.94, c Ø -1.48<; ÅÅÅÅÅÅ 106 CpH2Og = Cp ê. 8a Ø 30.00, b Ø 10.71, c Ø -0.33<; N2 over range 298-2500K CpN2 = Cp ê. 8a Ø 27.87, b Ø 4.27, c Ø 0<; O2 over range 298-3000K CpO2 = Cp ê. 8a Ø 29.96, b Ø 4.18, c Ø -1.67<;

—

General::spell : Possible spelling error: new symbol name "CpO2" is similar to existing symbols 8CpCO2, CpN2<.

Si3N4 over range 298-900K 27.07 T2 CpSi3N4 = Cp - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. 8a Ø 76.36, b Ø 109.04, c Ø -6.53<; ÅÅÅÅÅÅ 106 SiO2 (alpha quartz) for 298-847K CpSiO2Q = Cp ê. 8a Ø 43.93, b Ø 38.83, c Ø -9.69<; CpTiO2 = Cp ê. 8a Ø 73.35, b Ø 3.05, c Ø -17.03<; CpZra = Cp ê. 8a Ø 22.84, b Ø 8.95, c Ø -0.67<;

— General::spell1 : Possible spelling error: new symbol name "CpZrb" is similar to existing symbol "CpZra".

CpZrb = Cp ê. 8a Ø 21.51, b Ø 6.57, c Ø 36.69<;

CpZraO2 = Cp ê. 8a Ø 69.62, b Ø 7.53, c Ø -14.06<;

— General::spell1 : Possible spelling error: new symbol name "CpZrbO2" is similar to existing symbol "CpZraO2".

CpZrbO2 = Cp ê. 8a Ø 74.48, b Ø 0, c Ø 0<;

ü Enthalpies at 298K and Enthalpies of Transitions Here are some enthalpies at 298. For compounds, these are enthalpies for formation from elements. The enthalpies of pure elements are taken, by convention to be zero. HAl2O3 = -1675700;

Notes on Gaskell Text

3

HAlmelt = 10700; HCaO = -634900; HCaTiO3 = -1660600; HCH4 = -74800; HCr2O3 = -1134700; HCO2 = -393500; HDiamond = 1500; HH2Og = -241800; HO2 = 0; HSi3N4 = -744800; HSiO2Q = -910900; HTiO = -543000; HTiO2 = -944000; HTi2O3 = -1521000; HTi3O5 = -2459000; Transformation Zr(a) to Zr(b) DHZratob = 3900; Transformation Zr(a)O(2) to Zr(b)O2 DHZrO2atob = 5900; Formation of Zr(a)O(2) HZraO2 = -1100800; ü Entropies at 298K There are absolute entropies of some elements at compounds at 298K SCaO = 38.1; SCaTiO3 = 93.7; SN2 = 191.5; SO2 = 205.1; SSi3N4 = 113.0; SSiO2Q = 41.5;

massN = 14. massFe = 55. massF = 19 . B -> -0. STi2O3 = 77.4. massO = 16.7.6.. ü Vapor Pressure vapor = -A ê T + B Log@TD + C A C .98. massH = 1.85. ü Molecular Weights massAl = 26. SZra = 39.97.38 .ÅÅÅÅ + B Log@TD T Hg for the range 298-630K lnvapHgl = vapor ê. C -> 17. SZraO2 = 50.31. massCu = 63.007.94. STi3O5 = 129.2. massAu = 196.08.55. massCr = 52. STiO2 = 50.04.795. massMn = 54.0. massTi = 47.4 Notes on Gaskell Text STiO = 34. 8A -> 7611 .88. massC = 12. . massCa = 40. massZn = 65. massSi = 28.008. massMg = 24.6.168< .

It is interesting to note that the first steam engines were invented in 1769. 8A -> 33440 . one is normally not that interested in heat and work. lnvapCO2s = vapor ê. Thus the practical engineering was done without knowledge of thermodynamics and well before the theory of the heat engine was developed. C -> 21. Finally. the water is exhasted to the environment or in a cyclic engine it can be condensed and recyled to the heating chamber or boiler Boiler at T 1 Engine Work Done Exhaust at T 2 Steam power plant or steam engine Condenser An early goal for thermodynamics was to analyze the steam engine and to figure out the maximum amount of work that could be done for an engine operating between the input temperature T1 and the output temperature T2 . He was a French engineer and wrote one paper. B -> 0. C -> 23. B -> -1. In material science. phase transformations. The steam is then used to turn an engine which does work. in a steam engine heat is supplied to water to create steam. C -> 37. 8A -> 45390 . B -> 0.27.Notes on Gaskell Text 5 lnvapSiCl4 = vapor ê. lnvapMn = vapor ê. heated. are important. Some important effects are chemical reactions (such as oxidation). Some of the most important work on thermodynamics of heat engines was done by Nicholas Carnot around 1810.68< . lnvapZn = vapor ê. Chapter 1: Introduction and Definition of Terms ‡ History Thermodynamics began with the study of heat and work effects and relations between heat and work. that introduced the “Carnot” cycle and helped explain the maximum efficiency of heat engines. formation of solutions. 8A -> 15250 . but interested more the state of matter and how things might change when mixed. pressurized. Some early thermodynamics problems were for very practical problems.96< . refrigerators. 8A -> 3116 .01< . etc. Reflections on the Motive Power of Heat. It can be said that the invention of the steam engine spawned the development of thermodynamics or that the steam engine did much more for thermodynamics than thermodynamics ever did for the steam engine. 8A -> 3620 .255. thermodynamics has much wider applicability. lnvapFe = vapor ê. Although analysis of devices like steam engines. . For example.93< . etc.. combustion engines. C -> 16. C -> 10. B -> -1. B -> -3.02.79< .

Normally. It is found that when only a few of these variables are fixed. At sufficient low temperatures. a multi-component. It has been observed that when P and T are fixed that V always has a unique value. the thermodynamic state of a system is uniquely fixed when a small number of macroscopic.6 Notes on Gaskell Text Other issues might include response of materials to stress. The system is any collection of objects that we choose to analyze. the entire state of the system is also fixed. In heat engines with gases and liquids. The state of a system can be defined by specifying the masses. but in more practical terms is the environment of the system. Instead. volume. will they mix or phase separate. For example.. In other words. Early thermodynamics was on heat (thermo) and work (dynamics) effects. Fortunately such detailed knowlege is not required. they only depend on the current state and not the path the system took to reach the current state. positions. The surroudings is the rest of the universe.g. . it is possible to deviate from equilbrium for long times. a semiconductor alloy. Thus. The three key variables are pressure. The surroundings can supply heat to the system or do work on the system. our main interest in such systems is the equilibrium state of the system. and temperature. T. Thermodynamics is concerned only with the equilibrium state of matter and not in the rate at which matter reaches the equlibrium state. or magnetic filed. TD . Once P and T are known. independent variables are fixed. and T are all known as state variables. we do not have such detailed knowledge because there will always be a large number of particles (e. Our interest is in understanding the system. ‡ Concept of State Matter contains elementary particles such as atoms and molecules. V (and all other properties in this simple example) are determined. In other words. 1023 molecules in 1 mole of molecules). Such a state is called the microscopic state of the system. V. For example. ‡ System and Surroundings The universe is divided into the System and the Surroundings. stress. Such an equation is called an equation of state. Alternatively. equilibrium is often reached very fast and the rate of reaching equilibrium is very fast. multiphase ceramic. and volume. accelerations) of all of the particles in the system. will remain in the non-equilibrium glassy state. electrical field. the changes in the matter are more interesting than the heat and work effects. Given the microscopic state. In material science. The system and surroundings interact be exchanging heat and work. the system may give off heat (supply heat to the surroundings) or do work on the surroundings.g. temperature. a blend of polymer molecules. the equilibrium state will not be realized on any practical time scale. strain. P and T are the independent variables and V is a function of P and T: Volume = V@P. particularly problems dealing with solids or condensed matter. and how will they respond to externally applied stimuli such as pressure. consider a gas or a liquid of constant composition such as a pure gas or liquid. The “dynamics” part refers to work effects and not to rates of processes. or a mixutre of gases in a container. Some examples of material science type systems are a metalllic alloy in a crucible. or magnetic fields. The study of the rates of processes is known as “kinetics. A detailed thermodynamic analysis of glass polymers (a difficult problem) would predict that the polymer should exist in a different state than it actually does. however. strain. a polymer glass well below its glass transition is a non-equilibrium structure. electrical fields. the polymer. however. V. P. will there by phase transitions. will the components react. P.” In material science. we could deduce all the properties of the system. velocities. it is possible to define a macroscopic state of the system by specifying only a few macroscopic and measurable variables such as pressure. temperature. and all modes of motion (e.

ü More than Two Independent Variables Pure gases and liquids are particularly simple because their state depends only on two independent variables. the matter might experience various states of stress and strain. n1 . and strain e (instead of V). the strain components are a function of T and the stress components StrainComponent = εi @T. stress and strain are tensors with 6 independent coordinates. composition. For example. however. stress can be written as a function of temperature and strain StressComponent = si @T. the stress-strain relations will also depend on the compositions of the material and typically on the geometry of the structure. the natural variables are temperature. and composition. εi .. For a pure solid. T. this new equation of state could be done instead as an equation for P in terms of V. T. P =. n2 D . V =. or similarly as an equation for T in terms of P. . For interactions of matter with other stimuli suich as electric or magnetic fields. TD . n1 . V.Notes on Gaskell Text 7 The use of P and T as the independent variables is simply a matter of choice and is done usually because P and T are easy to control and measure. si . and composition: Pressure = P@V. If the material is not a pure material. stress s (instead of P). The volume of the system will depend not only on P and T. Unlike P and V which are scalar quantities. More complicated systems require more variables. For solids. but the number required is always relatively small. the equations of state will also depend on the intensity of those fields. or to use P and V is independent variables and define the system by an equation of state for temperature: Temperature = T@P. T. εi D . V. In general. These equations of state are the thermomechanical stress-strain relations for a material. VD . It would be equally acceptable to define V and T as the independent variables and define the system by an equation of state for pressure: Pressure = P@V. The simplest examples involve only two variables. si D . where εi and si are components of stress and strain. the variables are limited to P. but also on which gases are present. Thus. and applied fields. T =. such as a composite material. the volume of a mixture of two gases will depend on the P and T and the compositions of the two gases or Volume = V@P.. in summary. the thermodynamic state can also be expressed as an equation of state that is a function of a relatively small number of variables. . n2 D . Alternatively. T. For most problems encountered in thermodynamics. Pressure or volume are all that are needed to define mechanical stimuli on a gas or a liquid. where n1 and n2 are the number of moles of the two gases. Other systems require more variables. As above.

TD Note: blue text is these notes is Mathematica output after evaluating an input expression in red. TD . i where i and f are the initial and final values of T and P. The total differential in f (df) is given by ∑f df = ‚ J ÅÅÅÅÅÅÅÅÅÅÅ N dxi . . the partial derviatives for the total differentials themselves often have physical significance.T] for a pure gas depends on only two variables and has the total differential dV = ∑P V@P. Let f @x1 . TD is the change in volume per degree at constant pressure which is thermal expansion of the matter. In other words.T] as an mathematical function of P and T. TD α = ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ ÄÄÄÄÄÄÄÄÄÄÄ ÄÄÄÄÄÄÄÄ Ä . In thermodynamics. In Mathematica notation. TD VH0. TD dT dT VH0. x2 . i=1 where ∑xi fmeans the partial derivative of f with respect to xi while all other variables (here x j π xi ) are held constant.T] For example.8 Notes on Gaskell Text ü Multivariable Mathematics An equation of state is a function that defines one variable in terms of several other variables.. ü Example: V[P. Many input expressions are followed be semicolons which simple supresses uninteresting Mathematica output. TD dP + ∑T V@P. we are often concered with how something changes as we change the independent variables.1L @P. V@P. this total differential is written as n n df = ‚ ∑xi f dxi . xn D be a function of n variables x1 to xn . Thus equations of state follow the rules of mutlivariable mathematics. Any change in volume due to a change in T and P can be calculated by integrating dV: f DeltaV = ‡ „ V . ∂T V@P. TD ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ V@P. In the dV expression.1L @P. the equation of state V[P. they often correspond to measurable quanties. Thermal expansion coefficient is normalized to give . In general. TD + dP VH1. Å ∑xi i=1 where the partial derivative is taken with all x j π xi being held constant. This expression for dV is simply treating V[P. A general analysis of such a problem can be written down purely in mathematical terms. ∑T V@P. This Mathematica notation will be used throughout these notes which were prepared in a Mathematica notebook.0L @P.. In thermodynamics we are usually dealing with physical quantities.

dV = . Although all systems tend towards equilibrium. In such problems.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ V@P. Sometimes the physical significance is not clear. TD Many thermodynamic relations involve writing total differentials functions and then evaluating the physical significance of the terms. ü Equilibrium As stated before. TD .Notes on Gaskell Text 9 Likewise. After normalizing and adding a minus sign to make it positive.0L @P. compressibility is . TD In terms of thermal expansion and compressibility. Equilibrium is the state of the system when the variable reaches the value it should have as defined by the equation of state. There are some thermodynamic quantities that are not state variables.T] defined by the equation of state. These concepts will be discussed later. It depends only on the independent variables (P. The two most important are heat and work. TD VH1. and perhaps others) and not on the path taken to get to the variables. For example V is a state variable. thermodynamics always deals with the equilibrium state of matter. They are driven there by natural tendencies to minimize energy and to maximize entropy.dP b V@P. b =.T]. One good example to be encountered later in this course is chemical potential. . V@P. If we take Tc as the temperature on the centigrate scale and let V0 a0 = dV/dT. The heat supplied to a system or the work done by a system depend on the path taken between states and thus by definition. Equilibrium is reached when after changing P and T to some new values. In other words dV/dT is constant at constant pressure. For example. a pure gas has an equation of state V[P. thermodynamics says nothing about the rate at which they will reach equilibrium. TD dP + a V@P. ü State Variables A state variable is a variable that depends only on the state of a system and not on how the system got to that that state. the total differential for volume becomes: a =. the partial derivative is defined as having having physical significance or it becomes a new thermodynamic quantity. TD ÅÅÅÅÅÅÅÅ . where V0 and a0 are the volume and thermal expansion coefficient at 0˚C.ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ ÄÄÄÄÄÄÄÄÄÄÄ ÄÄÄÄÄÄÄÄ Ä . . heat and work are not state variables. then volume at any other temperature on the centigrate scale is found by integration . The previous sections define equations of state for matter. There are many thermodynamic state variables and they are very important in thermodynamics. TD dT dT a V@P. T. may not approach equilibrium on a pratical time scale. ∑P V@P. ∂P V@P. particularly condensed solids as encountered in material science. Some systems.b V@P. ü Equation of State of an Ideal Gas Charles’s law is that volume is proportional to temperature (which is true no matter what temperature scale is used) at constant pressure. TD is the change in volume due to pressure at constant temperature which is the compressibility of the matter. TD β = . the volume becomes equal to the V[P. All systems naturally proceed towards equilibrium.

It is physcially impossible to have negative volume. TcD 1 99Tc Ø . the equation of state for V for n moles of gas is T V = n R ÅÅÅÅÅÅ P nRT ÅÅÅÅÅÅÅÅÅÅÅ Å P The thermal expansion coefficient of an ideal gas is . . In 1802. These observations lead to the absolute or Kelvin temperature T defined by 1 1 T = Tc + ÅÅÅÅÅÅÅ ê. V = SimplifyAV ê. Guy-Lussac measured a0 to be ÅÅÅÅ1ÅÅÅÅ or Å 267 1 absolute zero to be at -267˚C. V0E 0 But. More accurate experiments later (and today) show that a0 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ or absoloute zero 273. Combining the laws of Boyle and Charles. this result implies that the volume will become zero when Solve@V == 0 . constant = P ÅÅÅÅÅÅ T PV ÅÅÅÅÅÅÅÅ T The constant for one mole of gas is defined as the gas constant R. Thus. an ideal gas can be defined by V V =.15 + Tc On the absolute scale 1 T =.ÅÅÅÅÅÅÅ E a0 a0 T V0 Thus the volume is zero at T=0 and increases linearly with T (as observed experimentally).15 to be at -273.ÅÅÅÅÅÅÅ == a0 and become negative if Tc drops lower.10 Notes on Gaskell Text Tc V = CollectAV0 + ‡ H1 + a0 TcL V0 V0 a0 „ T .15. Boyle found that at constant T that V is inversely proportional to P. Tc -> T .15 273.. thusw Tc = -1/a0 must define the lowest possible temperature or absolute zero. a0 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å Å a0 273.

V = . Thus. thus P V or work or energy has units liter-atm. we can write V = . dV = a V dT . 1 liter-atm is .ÅÅÅÅÅÅÅÅÅÅ V 1 ÅÅÅÅ P Thus for the special case of an ideal gas.Notes on Gaskell Text 11 ∑T V a = ÅÅÅÅÅÅÅÅÅÅ Å V 1 ÅÅÅÅ T The compressibility of an ideal gas is ∑P V Å b = . When R was first measured.. Solve A V == n R ÅÅÅÅÅ . P was measured in atm and V in liters. SI units for energy is Joules. in SI units. TE P PV 99T Ø ÅÅÅÅÅÅÅÅ == nR P = . . ‡ Units of Work and Energy P V has units of Force/Area X Volume = Force X length. PE Å P nRT 99P Ø ÅÅÅÅÅÅÅÅÅÅÅ == Å V T Solve A V == n R ÅÅÅÅÅÅ .082057 . In these units. R must have units of energy/degree/mole. These are the units of work or energy. with units liter-atm/(degree mole). 1 atm is oneatm = 101325.. R is Rla = 0.b V dP dP V dT V . T = .ÅÅÅÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅÅÅÅ Å Å P T Equations of state for P and T can be solved by simple rearrangement T V = . N ê m2 . . Because 1 liter is 1000 cm3 or 10-3 m3 . . Also..

etc.Choice of components is arbitrary. The relative proportions of phases in twophase regions are given by the lever rule.239 24. in SI units of J/(degree mole). In each zone. two phases can coexist. ‡ Phase Diagrams and Thermodynamics Components A Phase diagram is a 2D representation that plots the state of a system as a function of two independent variables.325 Rla In cgs units with energy units of egs = 10-7 J. On lines. Example of unary is water phase diagram. At triple points. Systems are characterized by the number of components and the type of phase diagrams depend on the number of components. Thus. mass is an extensive property. Intensive variables do not depend on the size such as pressure and temperature. fourcomponent (quarternary). two-component (binary). Binary diagrams add composition as a third variable. For example..12 Notes on Gaskell Text onela = oneatm 10-3 101. The complete phase space is 3D. Similarly.325 Joules. 2D binary plots are sections of the 3D curves. Zones can be single phase solutions or two-phase regions. . the gas constant is Rerg = RSI 107 1. the gas constant is RSI = Rla onela 101. one state is the most stable state.01325 µ 109 Rla Finally. Extensive variables can be changed into intensive variables by dividing them by the mass or number of moles. Then. or V) together with the composition variable. there are . ‡ Extensive and Intensive Properties Properties (or state variables) are extensive or intensive. Unary diagrams usually use two variables like P and T. the volume per mole or molar volume is an intensive variable of a system. The first law of thermodynamics connects the two energy units and allows one to relate heat and work energy or to relate calories and Joules. Such intensive variables are often called specific or molar quantities.2167 Rla Note that in early studies of work and heat. by mass per unit volume or density is an intensive property.239 cal/J. Examples are one-component (unary). The gas constant using calories as the energy unit is Rcal = RSI . calories were used for heat energy and Joules (or an equivalent F X length) for work or mechanical energy. three-component (ternary). Extensive variables depend on the size of the system such as volume or mass. Binary diagrams are usually for one variable (T. three phases can coexist. P.

Most problems we ever encounter can be solved from these basic principles. Internal energy often has a nice physical significance. Chapter 2: The First Law of Thermodynamics ‡ Ideal Gas Change of State ü Change in Internal Energy ∑U ∑U Because H ÅÅÅÅÅÅÅÅ LT = 0 for an ideal gas an H ÅÅÅÅÅÅÅÅ LV = n cv for an ideal gas. sometimes. the total differential for internal energy for ∑V ∑T any change of state of an ideal gas is dU = n cv dT. The second law defines limits on heat and work in processes. Some thermodynamic problems require an absolute value of entropy. and entropy. First law connected heat and work and clarified conservation of energy in all systems. because it has less apparant physical significance than internal energy. that direct use of internal energy and entropy can be difficult. however. The principles of thermodynamics is are nearly fully defined after defining the laws of thermodynamics.P1 V1 = DHPVL. The rest of the study of thermodynamics is application of those principles to various problems. It turns out. For an ideal gas. The second law also lead to the definition of entropy. entropy is the degree of mixed-upedness.Notes on Gaskell Text 13 ‡ Overview Zeroth law of thermodynamics defines temperature. The key new energy term that developed from the first law is internal energy. Thus internal energy can also be written as cv DU = ÅÅÅÅÅÅÅ D HPVL . Entropy was slow to be accepted. it significance is less apparant. Instead. R .T1 . we define new functions called free energy . Gibbs free energy is the most common term needed for chemical and material science problems that are typically encounted in various states of applied temperature and pressure. internal energy. The total change in internal energy is thuys always given by: T2 DU = ‡ n cv „ T T1 -n cv T1 + n cv T2 which can be rewritten as cv DU = ÅÅÅÅÅÅÅ n R DT . It was used to define the efficiency of heat engines.Gibbs free energy or Helmholz free energy. In particular. The first law says energy is conserved.T1 ) = P2 V2 . R where DT = T2 . Rougly speaking. All systems try to minimize energy and maximize entropy. but it makes no statement about the possible values of heat and work. the third law of thermodynamics defines the entropy of a pure substance at absolute zero to be zero. These new energies perform the same function as other thermodynamics functions. n R(T2 . but that are physcially much more relevant to typical problems of chemistry and material science.

DU = DH = 0 for an isothermal process.14 Notes on Gaskell Text ü Change in Enthalpy Once the change in internal energy is known. The actually value of q and w will depend on whether the process is conducted reversibly or irreversibly. Isobaric Process The definition of enthalpy is the it is equal to the heat during a constant pressure or isobaric process. Isothermal Process Because U is a function only of T for an ideal gas. w = q . 2. all that can be said about q and w for an isothermal process is q = w . thus q = DH . This section gives some results for heat and work during some common processes: 1. however. The values for heat and work during a change of state. Adiabatic Process The definition of an adiabatic process is that q=0. These results also follow from the general results by using DT = D(PV) = 0 for an isothermal process. will depend on path. In general. for an ideal gas c p . thus q = DH. R The previous sections gave results for DU and DH for any change of state in a ideal gas.cv = R which leads to H ÅÅÅÅÅÅ + 1L = ÅÅÅÅpÅÅ . w = -DU . thus all the change in U is caused by work or: q = 0 . Isometric Process In an isometric process volume is constant which means w=0. w = 0 . the change in enthalpy is easily found from cv DH = DU + D HPVL = J ÅÅÅÅÅÅÅÅ + 1N D HPVL R cv But. For a reversible process q and w can be calculated from P dV work as V2 q = w = ‡ P „V . V1 which using the ideal gas equation of state becomes V2 q = w = ‡ V1 nRT ÅÅÅÅÅÅÅÅÅÅÅ „ V Å V -n R T Log@V1 D + n R T Log@V2 D . The total change in enthalpy can be written two R R ways as: c cp DH = ÅÅÅÅÅÅÅ D HPVL .DU. 3. DH = R ü Heat and Work in Various Processes cp ÅÅÅÅÅÅÅ n R DT. Heat and work are thus: q = DU . Work is found thethe first law as w = q . 4. w = D HPVL .

T1 -> 298 .9 J . Rla Ø 0. w = ‡ P „V .08948< Finally. Thus. Rla -> 0.3144 . we can write V2 q = w = n R T LogA ÅÅÅÅÅÅÅ E . DH = 0 . this constant will convert liter-atm energy units to Joule energy units. P1 Ø 10. will be given by an equation of state only for reversible processes. R Ø 8. subs P1 -23330. w can be calculated for the P dV integral and q from the first law of thermodynamics.3144. DU = 0 . P2 5. we need to know P as a function of V throughout the process. T1 Ø 298. however. ü 1. V1 To do these calculations. The number of moles can be calculated from the starting state: P 1 V1 nmols = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. nums . R -> 8. q = w = V1 P1 n R T LogA ÅÅÅÅÅÅÅ E . Any Processes For any other process. n Ø 4. P. P2 -> 1 . All results are given in Joules: laToJ = 101. Å Rla T1 subs = Append@nums. n -> nmolsD 8V1 Ø 10. Here are some constants defined in a table used to get numerical results: nums = 8V1 -> 10 . Isothermal Process In an isothermal process for an ideal gas. P2 Ø 1.082057 < . ‡ Numerical Examples V1 liters or and ideal gas at T1 and P1 are expanded (or compressed) to a new pressure P2 .082057. This result applies for both reversible and irreversible processes. thus heat and work are equal and given by: P2 q = w = n R T1 LogA ÅÅÅÅÅÅÅ E J ê.Notes on Gaskell Text 15 or because PV = constant.325 . Reversible. we can write V2 V2 q = DU + ‡ V1 P „V . P1 -> 10 .

g -> 5 ê 3D 2 -15246. g -> 5 ê 3 Å V2 = j ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ z j z n Rla k P2 { P1 V 1 P2 I ÅÅÅÅÅÅÅÅÅÅÅÅÅ M P ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ2 ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ Å n Rla 5ê3 3ê5 For an ideal gas cv = 3R/2. T2 < ê.P1 V1 L laToJ ê.16 Notes on Gaskell Text ü 2. 118.7 or . thus 3 DU = ÅÅÅÅ n R HT2 . Thus the final state has 1êg g P2 V2 i P1 V1 y Å .99 or we can use 3 DU = ÅÅÅÅ HP2 V2 . and P V g is a constant. subs 2 -9147. g -> 5 ê 3DD 839.636< The work done is dw = -DU 9148.P1 V1 L laToJ ê.02 For an ideal gas c p = 5R/2. the final temperature and volumes were ad2 = N@8V2 .02 For some numeric results. Append@subs. T2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. g -> 5 ê 3D 2 -9148.T1 L ê. Append@subs. thus the enthalpy change is 5 DH = ÅÅÅÅ HP2 V2 . Reversible Adiabatic Expansion In an adiabatic expansion q = 0.8107. Append@subs.

99 (ii) Get to P2 V2 T2 by isometric process followed by isothermal process. . T2 =.T1 L ê. Rla Ø 0.T1 L ê. DU for isothermal step is zero (because of the ideal gas). T1 Ø 298.8107. The constant volume step is same as above and thus obviously gives the same result.66667< ü Altenate Paths to End of Adiabatic Expansion (i) Get to P2 V2 T2 by isothermal process followed by constant volume process. the initial and final states for the adiabatic process are V2 =. sub2 2 -9147.T1 L ê. P2 Ø 1.636. . g Ø 1. sub2 2 -13678. we only need to know the intermediate temperature given by P2 V 1 Å Ti = ÅÅÅÅÅÅÅÅÅÅÅÅÅ . n Ø 4. sub2 2 -9147.99 (iv) Get to P2 V2 T2 by isometric process followed by constant pressure process. The enthalpy change for the constant pressure step is simply the same as before 3 DU = ÅÅÅÅ n R HT2 . sub2 = Join@subs. T2 Ø 118. T2 -> ad2@@2DD. DU for isothermal step is zero (because of the ideal gas).082057.3144. For isometric process. g -> N@5 ê 3D<D 8V1 Ø 10.T1 L ê. 8V2 -> ad2@@1DD .Notes on Gaskell Text 17 5 DH = ÅÅÅÅ n R HT2 . V2 Ø 39. the first step has 3 DUi = ÅÅÅÅ n R HTi .08948. The constant volume step has the total DU which is 3 DU = ÅÅÅÅ n R HT2 . subs 2 -15246. P1 Ø 10. n Rla Thus.8 The internal energy change in the second step is .7 For numerical results in the subsequent examples. R Ø 8. DU for isothermal step is zero (because of the ideal gas). (iii) Get to P2 V2 T2 by isothermal process followed by constant pressure process.

84 Thus total energy change is DU = DUi + DUii -9147. n Rla The internal energy change is thus 3 DUi = ÅÅÅÅ n R HTi . sub2 2 -54456. a.1 The initial conditions are init = 8T1 -> 300 . The final temperature of the constant pressure process is P1 V 2 Å Ti = ÅÅÅÅÅÅÅÅÅÅÅÅÅ .Ti L ê.3144 .4 The constant volume step has: 3 DUii = ÅÅÅÅ n R HT2 .99 (comment) These same examples are given in the text. Rla -> 0. sub2 2 4530.18 Notes on Gaskell Text 3 DUii = ÅÅÅÅ n R HT2 . V1 -> 15 . For several of the steps the text calculates DH first and then subtracts D(PV) to get DU. P1 -> 15 . Reversible isothermal expansion to 10 atm pressure .082057 < . R -> 8.Ti L ê.4 The total energy change is DU = DUi + DUii -9147. sub2 2 45308.99 (v) Get to P2 V2 T2 by constant pressure process followed by constant volume process. DU can be calculated directly from the same information used to first get DH. ‡ Problems ü Problem 2.T1 L ê. This extra work is not needed because in all cases.

They are given by (using PV = nRT): V2 q = w = 101. init -5119.88 The heat work done for his adiabatic process is .1314 The final temperature is T1 P2 V2 T2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. Reversible adiabatic expansion to P=10 atm. DU = 0 for an isothermal process (U only a function of T). Finally DH=0 because DU=0 and PV = constant.5 R „ T ê. init Å T1 Rla 9. Append@init. The final volume is 1êg g i P1 V1 z j ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ y Å ê.325 P1 V1 LogA ÅÅÅÅÅÅÅ E ê. DU=0 and q=w. init Å P 1 V1 255.13999 Thus the total change in internal energy is T2 dU = ‡ T1 n 1. b.085 The number of moles is P1 V1 n = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. g -> 5 ê 3DE V2 = NAj z k P2 { 19.5 For isothermal process. V2 = NA ÅÅÅÅÅÅÅÅÅÅÅÅ ê.84 For an ideal gas. initE Å P2 22.Notes on Gaskell Text 19 Final volume is P1 V1 P2 = 10 . init V1 9243.

init -8533.84 b. n = 1 .88 The change in enthalpy is dH = dU + 101.325 . onela = 101.P1 L onela R 6809. Finally return to initial state along specific curve V1 w = onela ‡ 2 V1 H0.3144 .P1 V1 L ê.2 The starting conditions and a calculation of the initial volume are: T1 = 273 .0006643 V2 + 0. cp = ÅÅÅÅÅÅÅÅ . Rla = 0. V1 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å 2 2 P1 22. 3R 5R n Rla T1 ÅÅÅÅ cv = ÅÅÅÅÅÅÅÅ .9 The total change in U on returning to initial state is .325 HP2 V2 . P1 = 1.20 Notes on Gaskell Text q = 0 .V1 L onela 2269. c.082057 .6 w = P1 H2 V1 . Doubling of volume at constant pressure cp q = dH = ÅÅÅÅÅÅÅ P1 H2 V1 .51 w=0. w = -dU 5119. Then double the pressure at constant volume cv q = dU = ÅÅÅÅÅÅÅ 2 V1 H2 P1 .15 ü Problem 2.6667L „ V -3278. R = 8.4016 a.V1 L onela R 5674.

P1 = 1 . Because PVg is constant and initial state has PVg =1.P2 VL ê. and T=373 K.2 V1 2 P1 L onela R -10214.242142 The last step (adiabatic) has w = -DU or cv w3 = .Notes on Gaskell Text 21 cv dU = ÅÅÅÅÅÅÅ HV1 P1 .5 . T1 = 373 .5 atm to volume V.V2L -0. cv -> 1.2 ü Problem 2.363213 Work can also be calculated by integrating with P = 1 ê g5ê3 : . V1 = 1 . adiabatic compression to 1 atm returns to initial volume.082057.3 Initial state is P=1 atm. V = H1 ê P2L1êg ê.032672 First expand gas isothermally to twice the volume or to V=2 liters and P=0.51572 Total work done in first step (an isothermal process) is w1 = N@n R T1 Log@2DD 0.ÅÅÅÅÅÅÅ HP1 V1 . The number of moles is P1 V1 R = 0. P2 = 0.693147 The second step (at constant pressure) is w2 = P2 HV .3 Thus. V=1 liter. 8g -> 5 ê 3< 1.5 R R -0. Now cool at constant P=0. n = ÅÅÅÅÅÅÅÅÅÅÅÅÅ Å R T1 0. Finally. final volume must be V2 = 2 .5 atm. heat is q = dU + w -13493.

4 The total change in internal energy with supplied q and w are DU = 34166 . T = 273 . thus the total change in temperature is DU DT = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ H2L H1. The final temperature is thus Tfinal = 300 + DT 1621. a. ü Problem 2.3144 . The initial volume is T V = n 0. DU = n cv DT. R = 8.1216 32950 For an ideal gas.5L H8.89561 ü Problem 2.3144L 1321.325 Hw1 + w2 + w3L 8.22 Notes on Gaskell Text V1 w3alt = ‡ V 1 ÅÅÅÅÅÅÅÅÅ „ x Å 5ê3 x -0.325 8.5 The initial conditions are n = 1 .2112 .4016 The 832 J of work at constant pressure causes volume to change by DV = 832 ê 101.082057 ÅÅÅÅ P 22.363213 The total work in Joules is w = 101. P = 1 .

9799.082057 . 3000< c. T1 = 300 . 21. The value of cp (for this one mole) and cv are 3000 2168 9cp = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .V2) isobaric to (P2. R = 0.171 The PV diagram for the cylic process is (P1.067 b.6128 Final temperature is V2 T2 = P ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅ ÅÅÅÅÅÅÅÅ n 0. V2 = 10 V1 246. n = 10 .6171 After changing along a straight line to P2 = 1 atm. constant volume to (P1.V1). Internal energy and enthalpy are 8 DU = 3000 . cv = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = Å Å T2 .832 .Notes on Gaskell Text 23 Thus final volume is V2 = V + DV 30.6 The initial volume is T1 P1 = 10 . the volume increases by a factor of 10 to P2 = 1 .T 829. V1 = n R ÅÅÅÅÅÅÅ P1 24.082057 373.T T2 .V1) is plotted as follows . DH = 3000 < 82168.V1) to (P2.6655< ü Problem 2.

24 Notes on Gaskell Text 12 10 8 6 4 2 0 0 50 100 150 200 250 300 Volume (liters) The work done is the area of the triangle and it is positive work done by the gas. Isothermal compression to P4 = 1 .906 b.V1L H101. T2 = T1 . R = 0. T3 = 100 + 273 . Isothermal expansion to P = 0. V2 = n R ÅÅÅÅÅÅÅ P2 48. After conversion to Joules. Isobaric expansion to T3 = 100C T3 P3 = P2 .082057 . P1 = 1.2145 c. V3 = n R ÅÅÅÅÅÅÅ P3 61.325L 2 101020. V1 = n R ÅÅÅÅÅÅÅ P1 24. T1 = 25 + 273 .453 a.7 The intial conditions are T1 n = 1 . the total work is 1 w = ÅÅÅÅ H9L HV2 . ü Problem 2.5 gives T2 P2 = 0.5 .

T5 = 100 + 272 .07222 P Finally. d.6. . Isobaric compression to initial state P7 = P6 . the constant volume steps do no work.6073 d.8 The PV diagram traces a circle or radius r=5.07222 . The work is the area of the circle (converted to Joules) Pi H25L H101. Isobaric compression to 25C returns the gas to its initial state (state 1 above).26582 The second process traces a squate on a PV diagram: a. V6 = V5 . PD 88P Ø 0. equate to (minus) initial work and solve for P Solve@walt == -w .V1L + P7 HV7 . P6 = P .325L 7958. After returning to the intial state.05 The volume as a function of pressure has two possible values . The total work for these four steps are V2 V4 w = n R T1 LogA ÅÅÅÅÅÅÅ E + P2 HV3 . Thus the total work is walt = P1 HV5 .V2L + n R T3 LogA ÅÅÅÅÅÅÅ E + P4 HV1 .5252 b.297486<< ü Problem 2. Change pressure at constant volume to P P = . the total work comes from the isobaric steps only. V4 = n R ÅÅÅÅÅÅÅ P4 30. T4 = T3 .V6L 6. c. V7 = V1 . Isobaric expansion to 100C T5 P5 = P1 . V5 = n R ÅÅÅÅÅÅÅ P5 30.Notes on Gaskell Text 25 T4 P4 = 1 .V4L V1 V3 -4.

PlotA9P ÅÅÅÅÅÅÅÅ .10L2 "################################ # 25 . 5.5355339059327373` nR 1116.H-10 + PL2 "############################### # 25 . 15<E nR nR 1000 800 600 8 10 12 14 Ü Graphics Ü The maximum occurs on the V1 curve at V1 SolveADAP ÅÅÅÅÅÅÅÅ . P ÅÅÅÅÅÅÅÅ = .HP .10L2 V2 = 10 10 - "################################ # 25 .H-10 + PL2 The temperature during the cycle can be plotted V1 V2 n = 2 .26 Notes on Gaskell Text P = .HP . V1 = 10 + 10 + "############################### # 25 . PE nR 88P Ø 13. R = 0. P -> 13.5355<< which is gives a maximum temperature or V1 Tmax = P ÅÅÅÅÅÅÅÅ ê.082057 . .36 The minimum occurs on the V2 curve at . 8P. PE == 0.

dSD -dU . the minimum temperature is V2 Tmin = P ÅÅÅÅÅÅÅÅ ê.46447 nR 254. T1 V1 Using R = Cp . Cv = 3 R ê 2 g = Cp ê Cv = 5 ê 3.636 Chapter 3: The Second Law of Thermodynamics ‡ Problems ü Problem 3. . For this isothermal change . T2 = P2 V2 ê R . 8P Ø 6. PE == 0.Cv . this 3 P2 V2 g Å DS = ÅÅÅÅ R LogA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ E . Simpler expressions hold in some special cases.53553 I<.Notes on Gaskell Text 27 V2 SolveADAP ÅÅÅÅÅÅÅÅ .1 For any reversible change in state with variables U and V. expression can be reworked into T1 = P1 V1 ê R.P dV . the total differential for entropy can be written as dSform = Solve@dU == T dS .46447<< Taking the real root. + 3.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ == T For one mole of an ideal gas we can rewrite this as RT SimplifyAdSform ê. P -> ÅÅÅÅÅÅÅÅ =E V dV R dT Cv Å 99dS Ø ÅÅÅÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅÅÅÅÅÅÅ == Å T V which integrates upon a change in V and T to T2 V2 DS = Cv LogA ÅÅÅÅÅÅÅ E + R LogA ÅÅÅÅÅÅÅ E . P1 V1 g 2 This result applies to any change in state of an ideal gas. P -> 6.53553 I<. 9dU -> Cv dT . PE nR 88P Ø 5. 8P Ø 5. a.dV P 99dS Ø .3.

R -> 8. DU2 = ÅÅÅÅ R HT2 . DH2 . 2078. For a constant volume change in pressure DS ê.72 .7631 b. DH2 = ÅÅÅÅ R HT2 . depending on which one is easier: 3 3 DU1 = ÅÅÅÅ HP2 V2 . which mean q = DU = 1247 J.64465 ü Problem 3. 9. g -> 5 ê 3< 5. For a reversible adiabatic change.16.3144. T1 -> 300 . 2 2 3 P2 V 2 g T2 3ê2 V2 Å g Å Å DS1 = ÅÅÅÅ R LogA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ E . 8R -> 8. qrev = 0 and thus DS=0.3144< 81247. V2 -> 3 V1 < V1 3653. Thus V2 q = w = R T LogA ÅÅÅÅÅÅÅ E ê. R -> 8. V1 -> V . V2 -> 3 V1 . But here the process is reversible.28 Notes on Gaskell Text DS ê. 8T2 -> T1 .P1 V1 L . 2 2 5 5 DH1 = ÅÅÅÅ HP2 V2 .2 Some generic results for the change in a state function for one mole of an ideal monatomic gas are given below. temperature remains constant.3144< 80. the state functions results are the same as part a. T -> 400 .T1 L .1343< For free expansion there is no work (w=0) and thus because DU=0. V2 -> 2 V . c. w=0. Here we only need to know that the temperature changes from 300K to 400K at constant volume stepb = 8DU2 . b.58786< Because this process is at contant volume. 8T2 -> 400 . V1 -> V2 . For free expansion of ideal gas.T1 L . P2 -> 5 . q=0. 0. g -> 5 ê 3< -8. DS2 < ê. DS is also obviously zero because PVg is constant during a reversible adiabatic processes. For any isothermal expansion to triple the volume. DS2 < ê. Thus stepa = 8DU2 . 8P1 -> 10 . P2 -> 5 . DS2 = R LogA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ E . R -> 8. From the general equation above. DH2 .6. Here the volume triples.P1 V1 L . either can be used. 8P1 -> 10 . R -> 8. c.3144 . 3.3144 . V2 -> V1 . There are two results for each term. 2 P1 V 1 T1 3ê2 V1 a.

41< . V2 -> 300 V1 ê 400. T1 E 2 T1 88T1 Ø 299. H. thus the temperature change is q DT = ÅÅÅÅÅÅÅÅÅ ê. DS2 < ê. DS -> 14. w = q + 1247.2 a.72 .72 .831.97976< The book solution has a sign error in DS.16. 3653.. DH2 . The total changes in U.3144< 8-1247. Using the DS for one mole of an ideal gas at constant pressure we can solve SolveA 5R T2 DS == ÅÅÅÅÅÅÅÅ LogA ÅÅÅÅÅÅÅ E ê. we only need to known that at constant pressure V is proportional to T which implies V2 = 300 V1 ê 400: stepd = 8DU2 . 0.12. and S during these steps are stepa + stepb + stepa + stepd 80. R -> 8.6. Thus we only need to solve .8767< The total amount of heat and work are 81247 + 3653.01 From the entropy change we can calculate the absolute temperatures as well. For an isothermal expansion of an ideal gas q=w.6 .945<< Or T1 = 300 K and T2 = 600 K. T2 -> T1 + DT. 8T2 -> 300 . 8q -> 6236 .3144 .2078. q = C p DT. 8R -> 8.44< 82822.. 2822.44 Notice that all calculations were done without ever calculating the actual volumes and pressures during the processes.16 -831. -5. 15. For the state functions. At constant pressure q is equal to DH and work follows from that results: q = -2078.28< ü Problem 3. For one mole of an ideal gas at contant pressure. T1 -> 400 .Notes on Gaskell Text 29 d.3144< Å 5 ÅÅÅ R 2 300. R -> 8. and C p = 5 R ê 2.6 . -2078. b.

a Tf .79 + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å . qrev -> 1729< . we have to solve an integral equation by equating heats Cp = a + b T .97 10-3 T . The heat transferred into the cold block is Tf qcold = ‡ Cp „ T 273 b T2 74529 b f Å -273 a .4.6825 ü Problem 3.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + a Tf + ÅÅÅÅÅÅÅÅÅÅ Å Å 2 2 This heat must equal the heat leaving the hot body Tf qhot = .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ + 0.00197 T 3 T T2 1000+273 DH = ‡ Cp „ T 25+273 42747.30 Notes on Gaskell Text qrev SolveADS == ÅÅÅÅÅÅÅÅÅ ê.017<< ü Problem 3. TE Å T 88T Ø 300.ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ Å 2 2 Equate and solve for T f : .92 106 T-2 + 8.763. 8DS -> 5. the final temperature will be the average of the two initial temperature.20 108 T-3 8. If the heat capacity is independent of temperature. If the heat capacity is a function of temperature.‡ Cp „ T 373 139129 b b T2 f 373 a + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å . Heat flow is an integral of the constant-pressure heat capacity.2 µ 108 4.7 1000+273 DS = ‡ 25+273 Cp ÅÅÅÅÅÅÅ „ T T 59.5 The two blocks of copper will exchange heat until they reach the same temperature.79 + 1. however.92 µ 106 50.4 For this problem we need to integrate C p for enthalpy or CP ê T for entropy where Cp = 50.

Tf D ÅÅÅÅÅÅÅÅ C +C 99Tf Ø E ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅ == 1 2 Log@T1 D C 1 +Log@T2 D C2 .597977 In other words. the process was irreversible because entropy increased.32 K. 8a -> 22. Assuming constant heat capacities. b -> 0.64. The total work then becomes w = q 2 .47 The total change in entropy (considering both bodies) is 323.6 The engine will stop producing work when it reaches its equilibrium temperature of T f .64. The quantity of heat transferred is q = qcold ê.51<. 8Tf Ø 323.Tf L .318<< The second root is the correct one or T f = 323.32 T DS = ‡ 273 0.00628< 1233. the entropy changes from the reservoirs is Tf Tf C C1 2 ÅÅÅÅÅÅÅ „ T + ‡ ÅÅÅÅÅÅÅ „ T T T T2 DS = ‡ T1 -Log@T1 D C1 + Log@Tf D C1 . ü Problem 3. 8a -> 22.00628< .T1 L.q1 C2 HT2 .Tf L . 8Tf -> 323.‡ ÅÅÅÅÅÅÅ „ T ê. b -> 0.32 373 Cp Cp ÅÅÅÅÅÅÅ „ T .00628< T 323. b -> 0. the total entropy change (reservoirs plus engine) must be zero. The engine operates in a cycle and thus must have no entropy change. a -> 22.32.C1 H-T1 + Tf L In this reversible engine. the high-temperature bath will expel heat q2 = C2 HT2 .To reach this temperature. Tf D 88Tf Ø -7533. The engine will expel heat to the low temperature bath of q1 = C1 HTf .Notes on Gaskell Text 31 Solve@qcold == qhot ê.64.Log@T2 D C2 + Log@Tf D C2 The final temperature to make T f zero is found by solving Solve@DS == 0 .

a. When there are 2 moles of A in chamber 1. The total differental in entropy (again assuming an ideal gas) is P dV RT dS = ÅÅÅÅÅÅÅÅÅÅ ê. These ideal gases do not interact and thus the total energy change is the sum of entropy changes for each type of gas: DS = R Log@2D + R Log@2D 2 R Log@2D or R Log[4] as given in the text. the entropy change for that gas doubles giving: DS = 2 R Log@2D + R Log@2D 3 R Log@2D or R Log[8] as given in the text.1 When an ideal gas expands (reversible or irreversibly) the temperature remains constant and therefore internal energy remains constant. Chapter 4: The Statistical Interpretation of Entropy ‡ Problems ü Problem 4. . Chamber 1 has 1 mole of A and chamber 2 has 1 mole of B. P -> ÅÅÅÅÅÅÅÅ Å T V dV R ÅÅÅÅÅÅÅÅÅÅ Å V Integrating over any volume change gives V2 DS = ‡ V1 R ÅÅÅÅ „ V V -R Log@V1 D + R Log@V2 D or V2 DS = R LogA ÅÅÅÅÅÅÅ E . V1 Physically entropy increases when the volume increases. b.32 Notes on Gaskell Text This result is equivalent to the answer in the book.

S. ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 1136 1478 . DSZrO2atob = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ .R LogA ÅÅÅÅ E 3 2 which combines to R Log[32/27].Zr .SO2. and 3rd Law of Thermosynamics ‡ Problems ü Problem 6.1 The heat of transformation for Zr(b) + O(2) to Zr(b)O(2) at 1600K is given by the following equation which starts with the heat of transformation at 298K and then integrates DCp from 298 to 1600K accounting for phase transitions or Zr (a->b) at 1136K and ZrO2 (a->b) at 1478 K. Cp. When one chamber has 2 moles of A and the other has 1 mole of A.CpO2L „ T 1600 DHZrO2atob + ‡ 1478 -1. This problem is best solved by first moving the partition to equalize pressures.O(2). we integrate Cp/T and include entropy of the required transitions. When each chamber has 1 mole of A. The system is still at equilibrium and thus DS=0.CpZrb .CpZra . Notice that DH for the Zr (a->b) transition is entered with a minus sign because those components are on the left side of the reactions: 1136 DH = HZraO2 + ‡ DHZratob + ‡ 298 HCpZraO2 . the two chambers will be at different pressures and removing the partition will causes changes and a non-zero change in entropy. Thus the total change in entopy can be calculated from the initial change in volumes done to equalize pressures: 2ê3 1ê3 DS = 2 R LogA ÅÅÅÅÅÅÅÅÅÅÅÅ E + R Log A ÅÅÅÅÅÅÅÅÅÅÅ E Å 1ê2 1ê2 4 3 2 R LogA ÅÅÅÅ E . When each chamber has gas A.CpO2L „ T + HCpZrbO2 . 1/2) to the position where the side with 2 moles of A is twice as large as the side with 1 mole of A (2/3. The entropy of transitions come from DH ê Ttr DSrxn = SZraO2 . Chapter 6: Cv.08659 µ 106 For the entropy of reaction. removing the partition does not change anything.SZra .Notes on Gaskell Text 33 c. 1/3). DHZratob DHZrO2atob DSZratob = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . d. This move will equalize pressure such that the subsequent removal of the partition can be done with DS=0.CpZrb .CpO2L „ T - 1478 1136 HCpZraO2 . H. Here it is moved from the middle (1/2. The entropy of reaction at 298K comes from absolute entropies of ZrO(2) . we can not use the methods in parts a and b because they no longer act independently.

thus the reaction to form CO from diamond is more exothermic (larger positive number on the left).HCaO .Hgr1000 637.CpCaOL „ T .CpO2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å „ TE ÅÅÅÅÅÅÅÅ T 1600 DSZrO2atob + ‡ 1478 -177.CpTiO2 .3 These compounds have no transitions between 298K and 1000K.CpO2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å „ T ÅÅÅÅÅÅÅÅ T 1478 1136 CpZraO2 . ü Problem 6.CpZra .2 For entropy of the reaction we first need 298 HCpCaTiO3 .1 The enthalpy of diamond is CpDiamond „ T 298 Hdia1000 .5 The enthalpy of diamond at 1000K is 1000 Hdia1000 = HDiamond + ‡ 12467.2 The enthalpy of graphite at 1000K is 1000 Hgr1000 = ‡ CpGraphite „ T 298 11829.CpZrb .523 higher than that of graphite.HTiO2 -81700 1000 DHrxn1000 = DHrxn + ‡ -80442.CpZrb .34 Notes on Gaskell Text 1136 DS = NADSrxn + ‡ DSZratob + ‡ 298 CpZraO2 .CpO2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å „ T + ÅÅÅÅÅÅÅÅ T CpZrbO2 . The initial heat of formation at 298K is DHrxn = HCaTiO3 .977 ü Problem 6.

Heating to T=x give x DHbyTemp = ChopA‡ CpCu „ TE 298 322000.0427<. T Ø 298=z z 3 4 k { 10 10 „P 707.493 i y j Å Å jVCu H1 .493 10^-4 for thermal expansion (or by dividing the result given in the text by 10). 9VCu Ø ÅÅÅÅÅÅÅÅÅÅÅÅ .916<.916 The book calculated the pressure effect to cause the enthalpy to increase by 707 J.493 i y j Å Å jVCu H1 .498 10^-4.09 0. the 10^-3 on VCu converts cm^3 to liters: Solve@DHbyTemp == DHbyPressure . The Handbook of Chemistry and Physics gives the thermal expansion of Copper as as 0.alphaCu TL ê. Using the correct thermal expansion changes the above results to: DHbyPressure = 101.4 The change in enthalpy of Cu by heating at constant pressure is integral of the constant pressure heat capacity.005355 x2 ÅÅÅÅÅ x Using (dH/dP)T = V(1 . 9VCu Ø ÅÅÅÅÅÅÅÅÅÅÅÅ . 8x Ø 5297. xD 88x Ø 35.SCaO .41 + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + 30.03431 298 CpCaTiO3 .325 1000 ‡ 1 7.0.29 x .325 converts liter-atm to J.CpTiO2 . This answer can be obtained by using 0. Thus the text gave the wrong value in the problem. but used the correct value to derive the solution.132 . 8x Ø 323.239 The 101.STiO2 5. -9631.44<< The correct root is the middle one or T = 323. the change in enthalpy at constant temperature from 1 to 1000 atm is DHbyPressure = 101. alphaCu Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . T Ø 298=z z 3 3 k { 10 10 „P 612.alphaCu TL ê. alphaCu Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . 1000 DSrxn1000 = NADSrxn + ‡ 7.alpha T).CpCaO ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ „ TE ÅÅÅÅÅÅÅÅ T ü Problem 6.Notes on Gaskell Text 35 DSrxn = SCaTiO3 .09 0.325 1000 ‡ 1 7.

HO2 SO2 9HTi2O3 . 8x Ø 5293.ÅÅÅÅÅÅÅÅÅÅ .0645 Assume need to add excess of Cr2O3 (add moleCr of Cr2O3) or that all the Al gets used up in the reaction.5 DH and DS can be found form enthalpies and entropies of each compound in the reactions.35< HO2 SO2 93 HTiO2 .ÅÅÅÅÅÅÅÅÅÅ .(moleAl/2) moles of Cr2O3. -80.66044 µ 107 . ü Problem 6.2 HTiO.54783 µ 107 .6395<.HTi3O5. -94. H-18. 8x Ø 327. and moleCr .5322 + moleCrL -2.5322 + moleCrL The enthalpy of the initial components at 700 C (=973 K).ÅÅÅÅÅÅÅÅÅÅ .2 STiO= 2 2 8-435000.972063.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ z jHCr2O3 + ‡ j z 2 k {k 298 298 { -2. moleAl or Cr.75< HO2 SO2 92 HTi3O5 .909<. 2 STi3O5 .3 HTi2O3. was . 3 STiO2 .15< ü Problem 6.ÅÅÅÅÅÅÅÅÅÅ . The total enthalpy of these products (none of which have transitions between 298K and 1600K) is 1600 1 y i z j CpAl2O3 „ Tz + HProducts = ÅÅÅÅ moleAl jHAl2O3 + ‡ z j 2 298 { k 1600 1600 moleAl y i y i z CpCr „ T + j Å Å zj CpCr2O3 „ Tz moleAl ‡ jmoleCr . accounting for the melting transition of Al at 943K.6* The balanced reaction is Cr2O3 + 2Al -> Al2O3 + 2Cr.935209.ÅÅÅÅÅÅÅÅÅÅ . xD 88x Ø 34. The initial number of moles of aluminum are 1000 moleAl = NA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ E Å Å massAl 37. STi2O3 . H-18.STi3O5= 2 2 8-373000.36 Notes on Gaskell Text Solve@DHbyTemp == DHbyPressure . -75.3 STi2O3= 2 2 8-355000.85<< The middle root is the book solution.ÅÅÅÅÅÅÅÅÅÅ . The products then contain moleAl/2 moles of Al2O3.

moleAns ÅÅÅÅÅ 1000 818. ÅÅÅÅ J-251326.05378 µ 106 moleCr The moles of Cr2O3 required to balance these enthalpies is moleAns = Solve@HProducts == HInitialD 88moleCr Ø 118. ü Problem 6. a. The reaction is CH4 + 2 O2 -> CO2 + 2 H2O.7 The adiabatic flame temperature can be found by finding out at what temperature the total enthalpy of the products is equal to the enthalpy of the initial material. ÅÅÅÅ J-409921.00452 AFT2 N + ÅÅÅÅÅ 3 AFT 2 33000.11638 µ 106 . constant pressure conditions. the required mass is moleCr H3 massO + 2 massCrL ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ê.8 kg. + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + 44.0).Notes on Gaskell Text 37 973 i 943 y j z HInitial = moleAl j‡ CpAl „ T + HAlmelt + ‡ CpAll „ Tz + j z 943 k 298 { 973 y i z j CpCr2O3 „ Tz moleCr jHCr2O3 + ‡ z j 298 { k 1.1.005355 AFT2 N Å Å 3 AFT . Enthalpy of starrint components is HCH4 HInitial = ÅÅÅÅÅÅÅÅÅÅÅÅ Å 3 74800 . AFT + 0.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å 3 The enthalpy of the products at the flame temperature is HProducts = AFT AFT 1 i y 2 i y z z j j ÅÅÅÅ jHCO2 + ChopA‡ CpCO2 „ TEz + ÅÅÅÅ jHH2Og + ChopA‡ CpH2Og „ TEz 3 k { 3 k { 298 298 1 854000.78<< In kilograms.14 AFT + 0.0546< This result is higher than the book solution of 14. This method works because total enthalpy is conserved for adiabatic. The starting components at 298K 2/3 O2 and 1/3 CH4 (ratio O2 to CH4 of 2. + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + 30. The final components are 1/3 CO2 and 2/3 H20.

0983<. 8AFT Ø 1.524 0.38 Notes on Gaskell Text Solve@HInitial == HProductsD 88AFT Ø -11586.<.524 XN2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ 10.14 AFT + 0.0950209 The enthalpy of the starting components is HInitial = XCH4 HCH4 -7107. AFT + 0. 8AFT Ø 4747.524 0.190046 1 XCH4 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å Å 10.56 After all the CH4 reacts with all the O2 to form XO2 or H20 and XCH4 of CO2.87 AFT + 0. the enthalpy at the flame temperature is y i z j CpCO2 „ TEz + HProducts = XCH4 jHCO2 + ChopA‡ { k 298 AFT AFT AFT i y j z XO2 jHH2Og + ChopA‡ CpH2Og „ TEz + XN2 ChopA‡ CpN2 „ TE k { 298 298 0. 8AFT Ø 2330.524 XO2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ 10.1<.86 + 27.21 9.524 0.00452 AFT2 N + ÅÅÅÅÅ AFT 33000.0950209 J-409921. b.39<< The correct root is the last one or the flame temperature is 2330K.005355 AFT2 N Å Å AFT Solve@HInitial == HProductsD 88AFT Ø -12360. . 0.14<< The correct root is the last one or the flame temperature is 4747K. For the reaction in air starting with one total mole of reactants.002135 AFT2 L + 854000. the fractions are . 0. + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + 30.714933 H-8494.714933 .02066<. 8AFT Ø 1. + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + 44.79 9.190046 J-251326.

Notes on Gaskell Text 39 ü Problem 6. The DG of the reaction at 800K found by integration (and there are no transitions in the compounds) or 800 800 DelCp i y j z DelCp „ T . c Ø 2<< .3 CpO2.277741 These results differ from the book answer which gets a much larger error between the two methods. The DGsimp agrees with the book. 1 + a == b + c. 3 + a == 2 b + c<D 88a Ø 3. b Ø 2.DG800L err = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ DG800 -0.800 jDSrxn + NA‡ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ „ TEz Å j z T 298 k { DG800 = DHrxn + ‡ 298 -1.9221 µ 106 The DCp for the reaction is DelCp = 2 CpN2 + 3 CpSiO2Q .3 SO2 -220.800 DSrxn -1. ü Problem 6.81126 µ 106 The percent error cause by ignoring the DCp terms is 100 HDGsimp .8* The DG of the reaction at 298K is DHrxn = 3 HSiO2Q .9 Solve@83 + a == b + 2 c.HSi3N4 -1987900 DSrxn = 3 SSiO2Q + 2 SN2 .CpSi3N4 . but the DG800 in the book is different.8163 µ 106 If DCp was assumed to be zero.SSi3N4 .298 DSrxn -1. the DG would be calculated as DGsimp = DHrxn .8 DGrxn = DHrxn .

The MW or cordierite is MWCord = 18 massO + 2 massMg + 4 massAl + 5 massSi 584. c Ø 2. Hca Ø -3293200.10 The heat required to melt cordierite per mole is 1738 qmelt = ‡ CpCord „ T 298 979799.74 Thus. . Some books have them as 7.4. These notes give the solutions to the 8 problems in common to all books. b Ø 2.40 Notes on Gaskell Text DH298 = c Hcc + b Hcb .2 to 7. Sca Ø 144. Scc Ø 198.8 DG298 = DH298 .298 DS298 62211. b Ø 2.Hc1 ê. Some books have 9 problems that correctly correspond to the 9 solutions. Hc1 Ø -6646300. Scb Ø 202. 8a Ø 3. Hcb Ø -4223700.8. Sc1 Ø 241. c Ø 2.a Hca .8.6 ü Problem 6. others have them as 7.a Sca . Hcc Ø -3989400< 99700 DS298 = c Scc + b Scb .Sc1 ê.3< 125.67561 µ 106 Chapter 7: Phase Equilibria in a One-Component System ‡ Problems All third editions of Gaskell have 9 problems. Other books (probably early printings of the thrid edition) are missing the problem that goes with the first solution and have an extra problem that has no solution. 8a Ø 3.1 to 7.5.9. the heat required (in J) to heat 1 kg from 298K to 1738 K is qmelt 1000 totalHeat = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅ ÅÅÅÅÅÅÅÅ MWCord 1.

the P and T will remain on the transition curve but the vapor pressure will change with temperature. T -> 280D 0. 8T Ø 2. Equating to vapor pressure and solving gives a condensation temperature of Tcondense = Solve@Log@PcoolD == lnvapSiCl4 .139656 The pure vapor pressure at 280K would be RT Ppure = ÅÅÅÅÅÅÅÅÅÅÅÅ ê. the percentage that has condensed must be .2(3) We assume that SiCl4 vapor behaves as a ideal gas. P will be Pfinal = Exp@lnvapSiCl4 ê.082057. Once the vapor-liquid equilibrium is reached at constant volume. 8R -> 0. the vapor will condence when Pcool becomes equal to the vapor pressure at that T.082057 Å Vfix 0. the total volume is R 350 Vfix = ÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. the pressure as a function of temperature is RT Pcool = ÅÅÅÅÅÅÅÅÅÅÅÅ ê.082057 Å 1 28.Notes on Gaskell Text 41 ü Problem 7. At 350K.01306 µ 107 << The first root is the physcially correct one.1(2) The vapor pressure of Hg at 100C (373K) is Exp@lnvapHgl ê.00285714 T By this cooling path. T -> 280< Å Vfix 0. TD 88T Ø 328.382<.72 When cooled at this fixed volume.000354614 ü Problem 7. T -> 373D 0.8 Thus. R -> 0. At the final temperature of 280K. R -> 0.

-5.0.25.79< ê. T -> 800 833. T -> 3330. DHsub = R T ^ 2 dlnPdT ê.9281.31443 25907. the cross at the triple point of Solve@ -15780 ê T . -15250 ê T . the DHvap. at the triple point is .755 Log@TD + 19. DHsub.42 Notes on Gaskell Text Ppure .66169< Thus the first must be the vapor pressure of solid zinc.196<< Above this temperature.543 ü Problem 7.325 converts the result fo Joules) ü Problem 7.255 Log@TD + 21. the vapor pressure of the solid will be higher (for a given T.25 == -15250 ê T . (Also.4(5) From the Clausius-Clapeyron equation for a liquid-vapor transition where the vapor volume is assumed to be much larger than the liquid volume R T2 Å DHvap = 101.0.3(4) Equating the two curves and solving.255 Log@TD + 21.325 ÅÅÅÅÅÅÅÅÅÅ dPdT ê. Table A-4 gives the second equation as the vapor pressure curve for liquid Zn).755 Log@TD + 19. R -> 8. TD .8 Thus. (The leading constant of 101. the liquid-vapor curve is below the solid-vapor curve). dPdT -> 3. Taking 800K for example. the two curves give 815780 ê T .1. or the heat of sublimation is dlnPdT = D@lnvapCO2s.082057.Pfinal Fraction = 100 * ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅ Ppure 82. P -> 1 .79D 88T Ø 712.72 10-3 < 342976.5(6) From the Clausius-Clapeyron equations. ü Problem 7. P 8R -> 0.1.

T -> 273 .2885 Solid CO2 is referred to as “dry ice” because the triple point is at Exp@lnvapCO2sD ê.6(7)* From the Clapeyron equation (after converting volumes to liters. R -> 8. looking up melting transition properties of lead. Thus under atmospheric conditions.1413 which is above 1 atm. DHPb -> 4810 ê 101.852 If the temperture of the melting point changes by 20 (dT = 20). solid CO2 vaporizes into gaseous CO2 . ü Problem 7.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ T The constant is found from the triple point Solve@lnPvap == lnvapCO2s ê. and converting DH to liter-atm): DHPb dPdT = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ ê.3888<< Thus.2 .Notes on Gaskell Text 43 DHvap = DHsub . T -> 273 + 25 T 4. ÅÅÅÅÅÅÅÅ Tm HVl . at 25C. constD 88const Ø 11. the vapor pressure curve for the liquid is -DHvap lnPvap = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + const ê. DHmelt -> 8330 17577.56.92 * 10-3 . the pressure must change by: Vl -> 19.13 lnvapCO2l = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ + 11.56. 8Vs -> 18.3888 ê.2944 or the actual pressure is Pvap = Exp@lnvapCO2lD 73.31443 Å Å RT 2114.8 Assuming DHvap is constant.DHmelt ê.13 const . -2114. Tm -> 600 .2 5.VsL 143.325< .47 * 10-3 . T -> 273 .

7(8) The information that the point P = 1 atm and T = 36K is on the a-b transition tells you that line is the one below the triple point. For the other two lines DS ê 101.99 SolveA0 == .25.043 + 0. 8DS -> 1. You are also given the slopes of the lines emanating from the triple point by using the Clapeyron equation: DS ê 101. we find the boiling point by solving for T when P=1: 6613.3045D == lnPvap ê. ü Problem 7.59 + 1. B Ø 12. DV -> 0. 8A. T -> 520< .165< ÅÅÅÅÅÅÅÅ DV 10-3 277.94<< . DV -> 0.325 slopeab = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ê.7669 DS ê 101. then -A lnPvap = ÅÅÅÅÅÅÅÅ + B . Log@.03 (Note: this result differs slightly from the book answer of 2822 atm).ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + 12.9310D == lnPvap ê.325 slopebg = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ê. 8DS -> 4.043< ÅÅÅÅÅÅÅÅ DV 10-3 1053. B<D 88A Ø 6613.6477<< Then.44 Notes on Gaskell Text dP = dPdT dT ê.8(9) We assume DHvap is a constant.165< ÅÅÅÅÅÅÅÅ DV 10-3 74.325 slopeag = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ê. ü Problem 7.325 and 10-3 convert slope to atm/K.6477 . TE ÅÅÅÅÅ T 88T Ø 522.25. 8DS -> 4.99.098 A sketch of lines emanating from a triple point with these slopes is given in the text.48 The factors 101. T -> 478 .59. dT -> 20 2877. T We can find the constants by solving Solve@8Log@. DV -> 0.

TR = T/Tcr.a V + R T V2 99P Ø . V.a V + R T V2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅ .2): . and T defined as PR = P/Pcr. and Tcr: crit = Solve@8Pcr == Pform .VL V2 At the critical point.Notes on Gaskell Text 45 Chapter 8: The Behavior of Gases ‡ Calculations with van der Waals Equation for a Non-Ideal Gas ü Critical Conditions for a van der Waals Gas Solving the van der Waals equation for P in terms of T and V gives a SolveAJP + ÅÅÅÅÅÅÅ N HV . Vcr.a Vcr + R Tcr Vcr2 . 0 == D@Pform. VcrD.1.9 VR + 8 TR VR2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ ÅÅÅÅÅÅÅÅ VR2 H-1 + 3 VRL Here is a plot of several isothermal curves around the critical point (TR = . 8Vcr.VL V2 Thus the van der Waals equation for P is Pform = P ê. Tcr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .7. we solve the following three equations for Pcr. and 1.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å == ÅÅÅÅÅÅ Hb .8.0. we rewrite the van der Waals equations using reduced P. critE@@1DD ÅÅÅÅÅÅÅÅ ÅÅÅÅÅ 2 Pcr VR Vcr . 8T -> Tcr .. V -> Vcr< a b . Tcr<D a 8a 99Pcr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . Vcr Ø 3 b== Å 27 b2 27 b R ü Plots of P vs T and V For convenience.VcrL Vcr To find the critical condtions. 8Pcr.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Hb . The result is 1 R TR Tcr a PR = SimplifyA ÅÅÅÅÅÅÅÅÅÅ J ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å . 0 == D@Pform. this form gives Pform = Pform ê. Vcr.1.9. %@@1DD a b .bL == R T .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å N ê. and VR = V/Vcr.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ 2 ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Hb .b VR Vcr2 3 ..1. PE V2 a b . 2<D<.

6 + .1 i . 5<D 4 3 2 1 1 2 3 4 5 -1 Ü Graphics Ü Here is a 3D plot: . TR -> . 6<DD . 8VR.46 Notes on Gaskell Text Plot@Release@Table@PR ê. 1. . 8i.4.

. PlotPoints -> 60. 8TR.7 Ü SurfaceGraphics Ü 0.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ ÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅ 2 R Tcr TR R Tcr TR Vcr VR R Tcr TR Vcr VR . 8VR.7. AxesLabel -> 8"VR". T -> TR Tcr . PlotRange -> 8-1.8 VR 3 4 0.5.4. 4<D 4 PR 2 1. 8P -> PR Pcr .9 TR ü Compressibility Factor Z as function PR and TR Solving the van der Waals equation for z = PV/RT gives a Pb ab z = 1 .1 0 1 1 2 0.ÅÅÅÅÅÅÅÅÅÅÅ Å Å RT R T V2 RTV z2 = z ê. ClipFill -> None . "TR". 4<. "PR"<.ÅÅÅÅÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å Å RTV RT R T V2 bP ab a 1 + ÅÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . 1. V -> VR Vcr< b Pcr PR ab a 1 + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ 2Å . .Notes on Gaskell Text 47 Plot3D@PR.2<.

4. 1DD .9 VR + 8 TR VR2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ ÅÅÅÅÅÅÅÅ VR2 H-1 + 3 VRL VRroots = Solve@PR == PReq . 1. Table@Log@10.5 0.2.6. PR -> 10x < . 6<D . 12. 2.48 Notes on Gaskell Text z3 = z2 ê. z4D ê. 6. 10. 8. 8TR -> .5 1 -0. 8x. VRD . 14. 1.2 -0. 20D<D 0. 1. 8i. 1.8 + . Here is a plot of z vs PR for TR = 1. Plot@Release@ 8Table@Log@10.8. -1. 8<D<D . critE@@1DD ÅÅÅÅÅÅÅÅ ÅÅÅÅÅ 2 Pcr VR Vcr . we can solve the van der Waals equation for VR and take the first root (the real root): 1 R TR Tcr a PReq = SimplifyA ÅÅÅÅÅÅÅÅÅÅ J ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å .4. 1.b VR Vcr2 3 .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å N ê. 8TR -> 2 i .2 i . 1. and 16. z4D ê.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅ 8 TR 8 TR VR 8 TR VR To express in terms of PR and TR. 8i. crit @@1DD PR 3 9 1 + ÅÅÅÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ2Å .2 -1 -0. VRroots@@1.4 Ü Graphics Ü . Now substitute back (the expressions are very long and therefore not shown): z4 = z3 ê. PR -> 10x < . Log@10.

"Z"<. AxesLabel -> 8"Log PR". TR = T/Tcr. 20D<. PlotPoints -> 60. and VR = V/Vcr. z4D ê. -1. Log@10. The result is . We rewrite the van der Waals equations using reduced P.6. 8TR.5 0 0.4 0.2 -0. PR -> 10x . 1.5 Log PR 1 5 TR 1 Ü SurfaceGraphics Ü ‡ Problems ü Problem 8.4<. ClipFill -> NoneD 0. 16<.4 10 -1 -0.1 a.Notes on Gaskell Text 49 Here is a 3D plot of the "compressibility" surface: Plot3D@Log@10. 8x. "TR". PlotRange -> 8-0. and T defined as PR = P/Pcr. V. 0.2 Z 0 -0.

we need to solve for an increase in Gsoln using Solve @ H1 ê 2L RT H nA Log@XA D + nB Log@XB DL == RT H nA Log@XA D + nB Log@XB D + HnA + nB L Log@PDL . The maximum increase in entropy occurs when there are equal parts of each gas. TRD H-1 + 3 VRL H3 + PR VR2 L 99TR Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å == ÅÅÅÅÅÅÅÅÅ 8 VR2 Note that this equation for TR does not depend on a or b.15)). in reduced variables. b. Mixing of ideal gases is puring due to entropy effects.9 VR + 8 TR VR2 PR == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ ÅÅÅÅÅÅÅÅ VR2 H-1 + 3 VRL A nicer form results by solving for TR: Solve@% .b VR Vcr2 8a a Å 9Pcr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . From partial molar results (eq.2 a.1 c. This problem is solved in the text (see page 197): ü Problem 8. PR == SimplifyA ÅÅÅÅÅÅÅÅÅÅ J ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å .. At the critical point Pcr Vcr a 8a Z = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. PD 2 Hn +n LÅÅÅÅÅÅÅÅ 99P Ø E ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ == A B -Log@XA D nA -Log@XB D n B . Tcr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .50 Notes on Gaskell Text 1 R TR Tcr a PR =. ÅÅÅÅÅÅÅÅ ÅÅÅÅÅ 2 Pcr VR Vcr . Vcr Ø 3 b=E 2 27 b R 27 b 3 . all van der Waal gases follow the same equation of state. the free energy of the solution is Gsoln = nA GA0 + nB GB0 + RT H nA Log@XA D + nB Log@XB D + HnA + nB L Log@PDL GA0 nA + GB0 nB + RT HLog@XA D nA + Log@XB D nB + Log@PD HnA + nB LL Because GA0 and GB0 are for constants that do not depend on subsequent increase in temperture. b. (8. thus. Tcr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . Vcr Ø 3 b= Å Å Å Å R Tcr 27 b2 27 b R 3 ÅÅÅÅ 8 This result is somewhat higher the results for real gases in Table 8. 9Pcr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅ .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å N ê.

8P -> 200 . the number of moles in an ideal gas under the stated conditions is nideal = Solve @ P V == n R T ê. R -> 0. ü Problem 8. V V2 P -> 100 .180158 . V V2 P -> 50 .1238.36 . XB -> 0.8319 At constant volume.478 + 1238.1.5 .100284 . nE 88n Ø 564. A B ÅÅÅÅ + ÅÅÅÅÅÅÅ ê.473<< For an van der Waals gas.Notes on Gaskell Text 51 % ê.394608<< PV SolveA ÅÅÅÅÅÅÅÅ == 1 + RT 8A -> -.03025. If you pay by the container. 8XA -> 0. V -> Vtank< .03025.0.478 . 8V Ø 0. Pressure is given by the virial expansion.082057.0318. you would prefer the van der Waals gas because you would get more moles per dollar.5 . b -> 0. These come from solving PV SolveA ÅÅÅÅÅÅÅÅ == 1 + RT 8A -> -. nD 88n Ø 510. B -> . T -> 460<E 88V Ø 0.41421<< ü Problem 8. If you pay by the mole. so all we need are the initial and final volumes.n bL == n R T ê. 8r -> .082057. 8V Ø 0. T -> 460<E 88V Ø 0.233434 I<.13 I<.082057. the van der Waal gas has more moles.265.100284 + 0. B -> .889<. T -> 300 .3 The volume of the tank is Vtank = Pi r2 l 103 ê. 8V Ø 0. Å z j z V2 { k R -> 0.233434 I<. T -> 300 . 8n Ø 705. R -> 0. the number of moles would be n2 a y i j nvander = Solve A jP + ÅÅÅÅÅÅÅÅÅ z HV .159419 I<.082057.159419 I<. nA -> nB < 88P Ø 1. R -> 0.265. 8n Ø 705.180158 + 0. l -> 2< 62.4 We need to integrate pressure over the volume change.176895<< . A B ÅÅÅÅ + ÅÅÅÅÅÅÅ ê. you would prefer the ideal gas because it would be cheaper. V -> Vtank< .0. 8P -> 200 . a -> 1. 8V Ø 0.13 I<< From the real root.

5. First the calculations is done using the virial expansion . VcrE ê.082057< V 82. Pcr -> 77. the van der Waals constants for the gas are a 8a SolveA9Pcr == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . V -> 0. To find work done by the gas.7.082057. T -> 500. R -> 0.4776 The corresponding ideal gas has pressure Pideal = RT ÅÅÅÅÅÅÅÅ ê. Using the van der Waals equation with the above determined constants gives RT a ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å . Pcr -> 77. From the critical temperature and pressure. Note that A and B were divided by 10^3 and 10^6.5< Pvander = 65.325 ‡ 1384. b Ø 0. j z V V2 V3 { k .176895 8A -> -.6 This problem asks for work calculated three different ways. b Ø 0. to convert to units of liters.03025.0567833<< b. R -> 0.bL V2 8a Ø 6.3946087 ü Problem 8. Tcr == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ =.7 . R -> 0. 8T -> 500. R -> 0. b<E ê. The critical volume comes from the critical compressibility ratio or Pcr Vcr 3 SolveA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ == ÅÅÅÅ . Å 2 27 b 27 b R 8Tcr -> 430.77306.0567833. we integrate P from V1 to V2 or to find the work done on the gas we reverse the integration and go from V2 to V1.8.082057< 88Vcr Ø 0. ÅÅÅÅÅ HV . The result (after convertion to joules) is A B y i1 R T j ÅÅÅÅ + ÅÅÅÅÅÅÅ + ÅÅÅÅÅÅÅ z „ V ê.52 Notes on Gaskell Text We take the real roots for the actual volume.082057< 88a Ø 6. B -> .77306. respectively.057 ü Problem 8.5 a.17035<< c. Å Å R Tcr 8 8Tcr -> 430.265.082057. V -> . 8a.ÅÅÅÅÅÅÅ ê.8. T -> 460< work = 101.7. R -> 0.

2461. T -> 298. T -> 298. n -> 100< wVirial = 101. A -> 0. Finally. n -> 100< Å V 272203. A -> 0. PD nRT 99P Ø . If the gas is a van der Waal gas.n bL 8R -> 0.082057. To find fugacity from a virial expansion.Notes on Gaskell Text 53 Solve@P V == n R T H1 + A PL .00064. ü Problem 8. ÅÅÅÅÅÅÅÅ 10 V . Solve the equation and take the non-zero root: .325 ‡ 301097. n -> 100< 30 30 wvander = 101. or by directly integrating the ideal gas result: 30 wIdeal = 101. a -> 0. the work is nRT n2 a y i j ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ j z ÅÅÅÅÅÅÅÅ .564 b. the ideal gas result can come for either above result by setting extra constants to zero.ÅÅÅÅÅÅÅÅÅÅ z „ V ê.7 a. it is easiest to integrate (Z-1)/P which here is simple the constant A=0.082057.00064< 688.00064: P lnfoverP = ‡ A „ P ê. 8Z -> 1 + A P< 0 AP The fugacity at 500 atm is: fug = P Exp@A PD ê.02668. 8R -> 0.325 ‡ 309394.A n R T 8R -> 0. j z V2 { 10 k HV . T -> 298. Positive work must be done on a system to compress it).325 ‡ 10 nRT ÅÅÅÅÅÅÅÅÅÅÅ „ V ê. (Note: the book has -301 kJ which must be to work done by the gas.082057. b -> . 8P -> 500.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ == AnRT-V nRT ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ „ V ê.

9 The extra free energy change due to a nonideal gas is extraDG = DG . PD ê.XAL2 W XA2 ÅÅÅÅÅÅÅÅ Å aB = gB H1 .00064 For the non-ideal gas fug DG = R T LogA ÅÅÅÅÅÅÅÅÅÅÅÅ E ê.DGideal 791. we assume that W H1 . 8R -> 8. RT RT lnaA = lngA + Log@XAD . lngB = ÅÅÅÅÅÅÅÅÅÅÅÅÅ .04<< c. 8R -> 8.275 Chapter 9: The Behavior of Solutions ‡ Regular Solutions ü Activities In a regular solution.54 Notes on Gaskell Text Solve@2 P == P Exp@A PD .XAL .2 The ideal gas result is 500 DGideal = R T LogA ÅÅÅÅÅÅÅÅÅÅ E ê. It will be seen later to be assumed to be independent of temperature.XAD . A -> 0. We can plot the activity coefficients of A and B for various values of W: . 8A -> 0.00064< 1. where W is a constant. T -> 298< 1 15397.00064< 88P Ø 0<. but it may depend on pressure.3144 . aA = gA XA . 8P -> 1.XAL2 W XA2 ÅÅÅÅÅÅÅÅ Å gA = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ E . The fugacity at 1 atm is fug1 = P Exp@A PD ê. lngA = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ . lnaB = lngB + Log@1 . 8P Ø 1083. T -> 298< Å fug1 16189.3144 . gB = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅ E . RT RT W H1 .

8W.6 0. 3. T -> 1<D.8 0.6 0.8 1 X .2 Ü Graphics Ü 0. 8R -> 1 .2 1 0. 8XA.4 0.4 0.Notes on Gaskell Text 55 Plot@ Release@Table@aA . -5. 0. AxesLabel -> 8"XA ". 1<. "aA "<D aA 1.2 0. 1<D ê.

1<D ê.56 Notes on Gaskell Text Plot@ Release@Table@aB . 8R -> 1 .8 0. AxesLabel -> 8"XA ".6 0. T -> 1<D.2 1 0. . 1<.6 0. 8W.2 Ü Graphics Ü 0.8 1 XA ü Free Energy of Mixing The free energy of mixing is DGm = R T H XA Log@aA D + H1 .XAL Log@aB DL . 0.4 0.4 0. 8XA. -5. "aB "<D aB 1. 3.2 0.

6 0.4 0. DGm may be positive or negative.5 -1 -1. T -> 1<D. 8W. 8R -> 1 .5 -2 Ü Graphics Ü Note that DGm is always symmetric about XA = 0. 1<.8 1 XA -0. positive values are solutions that will not mix. When W>0. 1<D ê. When W<0. 8XA. 0. -5.Notes on Gaskell Text 57 Plot@ Release@Table@DGm .2 0. many real solution are not symmetric. "DGm "<D DGm 0.5. DGm is always negative and the two components disolve. AxesLabel -> 8"XA ". Here is blow up for some positive W: .5 0. 5.

5.4 0.6 0.5.5 : Solve@DGm == 0 ê.8 1 X -0.1 Ü Graphics Ü A critical value of W is when DGm=0 at XA=0.05 0.1 0. "DGm "<D DGm 0.5<D ê. . If will split Log@aA D into Log[XA] + Log@gA D we can separately calculate the ideal free energy of mixing and the excess free energy of mixing.5. 8XA. T -> 1< .XAL lngB LD -H-1 + XAL XA W We can also calculate DGm directly from the activity coefficient. WD — Solve::ifun : Inverse functions are being used by Solve. 88W Ø 2. 2. 8XA -> 0.15 0. 1<.05 -0. The results are: . 0. 3. R -> 1. 8R -> 1 . 8W.2 0. so some solutions may not be found.58 Notes on Gaskell Text Plot@ Release@Table@DGm . AxesLabel -> 8"XA ". T -> 1<D.77259<< ü Excess Free Energy of Mixing The excess free energy of mixing is given by DGmXS = Simplify@R T H XA lngA + H1 .

0.R XA Log@XAD which. here for just A) is DGmA = Simplify@R T lnaA D H-1 + XAL2 W + R T Log@XAD ü Excess Entropy of Mixing If W is assumed to be independent of temperature.XAL IntegrateA lngA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . XA< . Assumptions -> 8XA < 1.XAL2 -H-1 + XAL XA W Finally. 8XA.XAL Log@-XAD IntegrateA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ . the partially molar free energy of mixing (for A or B.XAL ∑T lngB LD 0 The total entropy of mixing can be calculated from activity of just A using the partial molar entropy of mixing which is DSmA = -R HlnaA + T ∑T lngA L -R Log@XAD DSm = FullSimplifyAH1 . -XA. XA< . XA > 0<EE ÅÅÅÅÅÅÅ H1 . Assumptions -> 8XA < 1.XAL IntegrateA DSmA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .R T HXA ∑T lngA + H1 . XA > 0<EE ÅÅÅÅÅÅÅ H1 . is just the ideal entropy of mixing. Assumptions -> XA > 0EE H1 + XAL2 R T H-H-1 + XAL Log@1 . 8XA.Notes on Gaskell Text 59 DGmid = SimplifyAR T H1 . if we ignore the complex term (?). 0< .XAD + XA Log@XADL DGmXS = SimplifyAR T H1 . the excess entropy of mixing is obviously zero from DSmXS = -∑T DGmXS 0 We can also calculate excess entropy for the excess entropy of mixing formula derived in class DSmXS = Simplify@ -R HXA lngA + H1 . . 0.XAL lngB L . 8XA.XAL2 R H-1 + XAL H-I p + Log@-1 + XADL .

"DHm "<D DHm 1 0.6 0.2 0.XAL ∑T lngB LD -H-1 + XAL XA W Thus. the sign of W is also the sign of the enthaply effect. -5.5 -1 Ü Graphics Ü If W gets sufficiently positive.60 Notes on Gaskell Text ü Excess Enthalpy of Mixing The excess enthalpy of mixing can easily be calculated from DGmXS and DSmXS: DHmXS = DGmXS + T DSmXS -H-1 + XAL XA W which is simply equal to the excess free energy of mixing. Some plots of excess enthalpy (which are actually total enthalpy of mixing) are: Plot@ Release@Table@DHmXS. AxesLabel -> 8"XA ". 8R -> 1 . We can also use the formula derived in class DHmXS = Simplify@ -R T2 HXA ∑T lngA + H1 . The total enthalpy of mixing can be calculated from activity of just A using the partial molar enthalpy of mixing which is . 1<D ê. 1<. T -> 1<D.5 0. the resulting positive enthalpy will eventually overwhelm the ideal entropy of mizing causing the free energy of mixing to be positive or causing the components to be insoluable. 0.8 1 XA -0. 8W. 8XA. 5.4 0.

XA > 0<EE ÅÅÅÅÅÅÅ H1 . 8XA. lngA = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ .23 to suggest W is linear in T.XAL ∑XA DGmXSD H-1 + XAL2 Hk0 + T k1 L . 9.XAL ∑T lngB LD -H-1 + XAL XA k0 Notice that at constant temperature both DGmA and DHmA are proportional to XB 2 . ü Partial Molar Quantities Partial molar results can be derived from Gibbs-Duhem analysis DGmAXS = Simplify@DGmXS + H1 .XAL IntegrateA DHmA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .Notes on Gaskell Text 61 DHmA = -R T2 ∑T lngA H1 . however. If we take the results in Fig 9.XAL lngB LD -H-1 + XAL XA Hk0 + T k1 L DSmXS = Simplify@ -R HXA lngA + H1 .23) suggest that a T (which is proportional to W) is not constant but rather decreases with temperature.XAL ∑T lngB LD H-1 + XAL XA k1 DHmXS = Simplify@ -R T2 HXA ∑T lngA + H1 .XAL2 W DHm = FullSimplifyAH1 . The proportionality constants. lngB = ÅÅÅÅÅÅÅÅÅÅÅÅÅ . XA< . are different which means they are not equal and furthermore the entropy change must differ from ideal results.XAL lngB L . Assumptions -> 8XA < 1. RT RT The problem is solved by finding just the excess terms. we can derive new non-ideal solution results using W H1 .R T HXA ∑T lngA + H1 . 0.XAL2 -H-1 + XAL XA W ‡ Regular Solutions with Temperature Dependence Some experimental results in the text (see Fig. DGmXS = Simplify@R T HXA lngA + H1 .XAL2 W XA2 ÅÅÅÅÅÅÅÅ Å W = k0 + k1 T .

XA ∑XA DHmXSD XA2 k0 ‡ Subegular Solutions Subregular solution models are derived by letting W vary with composition.XAL ∑XA DHmXSD H-1 + XAL2 k0 DHmBXS = Simplify@DHmXS . W = a + b H1 .XAL . DGmXS = W XA H1 .62 Notes on Gaskell Text DGmBXS = Simplify@DGmXS . 9XB Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ == ÅÅÅÅÅ 3b 3b Some plots are on page 262 of the text. This change will make the curves no loner symmetrical about XA=0.XAL ∑XA DSmXSD -H-1 + XAL2 k1 DSmBXS = Simplify@DSmXS .5.XA ∑XA DSmXSD -XA2 k1 DHmAXS = Simplify@DHmXS + H1 . Solve@∑XB DGmXS2 == 0. The simplest model is to let W be linear in XB but we introduce this linear dependence in the excess free energy (for simplicity) instead of in the activity coefficient of A (this other method could be used if desired).XAL Ha + b H1 .XB .XAL XA This excess free energy will have minima and/or maxima depending on the values of a and b. XBD è!!!!!!!!!!!!!!!!!!!!!!!!! ! è!!!!!!!!!!!!!!!! !! !!!!!!!! -a + b . XA -> 1 . Here is a sample: .XALL H1 .a2 + a b + b2 -a + b + a2 + a b + b2 99XB Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ =. These occur where the derivative is zero or at DGmXS2 = DGmXS ê.XA ∑XA DGmXSD XA2 Hk0 + T k1 L DSmAXS = Simplify@DSmXS + H1 .

6 0.4 0.8 1 XB -500 -1000 -1500 -2000 Ü Graphics Ü . -2000. 2000<D ê. AxesLabel -> 8"XB ".Notes on Gaskell Text 63 Plot@ Release@Table@DGmXS2 . -10000.2 0. 1<. 8b. a -> -4000D. "DGm XS "<D DGm XS 0. 0. 8XB.

AxesLabel -> 8"XB ". 2000<D ê. -2000.4 0.64 Notes on Gaskell Text Plot@ Release@Table@DGmXS2 .8 1 XB Ü Graphics Ü . 8XB. "DGm XS "<D DGm XS 0. -10000. 1<. 8b.2 -200 -400 -600 -800 -1000 -1200 -1400 0. a -> 0D. 0.6 0.

2 -200 -400 -600 Ü Graphics Ü The excess entropy is 0. 8b. 2000<D ê. 0. 8XB.6 0.Notes on Gaskell Text 65 Plot@ Release@Table@DGmXS2 .2 b XAL .XAL XA ü Partial Molar Quantities Partial molar results can be derived from Gibbs-Duhem analysis DGmAXS = Simplify@DGmXS + H1 . "DGm XS "<D DGm XS 800 600 400 200 XB 0.XALL H1 . a -> 4000D. Finally. the excess enthalpy is simply equal to the excess free energy.XAL ∑XA DGmXSD H-1 + XAL2 Ha + b . AxesLabel -> 8"XB ". or by a calculation: DHmXS = DGmXS + T DSmXS Ha + b H1 . -10000.8 1 DSmXS = -∑T DGmXS 0 It is still zero because there is no temperature dependence in a and b and therefore DGmXS is independent of temperature. 1<. -2000.4 0.

2 b XAL ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ RT or.2 b H-1 + XALL XA2 ü Activity Coefficients The activity coefficients can be derived from the partial molar free energies DGmAXS Å Å lngA = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ RT H-1 + XAL2 Ha + b .XAL ∑XA DHmXSD H-1 + XAL2 Ha + b .2 b XAL DHmBXS = Simplify@DHmXS .‡ ÅÅÅÅÅÅÅÅÅÅÅ „ XAE Å Å XA2 XA2 1 H-1 + XAL2 Ha + b .2 b H-1 + XALL XA2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅ RT Alternatively we can calculate lng A from Gibbs-Duhem results: XA lng lngB B lngAcalc = SimplifyA-H1 .2 b H-1 + XALL XA2 DSmAXS = Simplify@DSmXS + H1 .XA ∑XA DHmXSD Ha .XAL XA ÅÅÅÅÅÅÅÅÅÅÅ .XAL ∑XA DSmXSD 0 DSmBXS = Simplify@DSmXS .XA ∑XA DSmXSD 0 DHmAXS = Simplify@DHmXS + H1 . we can calulate lngB from Gibbs-Duhem results: .66 Notes on Gaskell Text DGmBXS = Simplify@DGmXS .2 b XAL ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ RT DGmBXS Å Å lngB = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ RT Ha . vice-versa.XA ∑XA DGmXSD Ha .

XAL XA J1 .XAL ∑XA DGmXSD H-1 + XAL2 Ha + b .2 b H-1 + XALL XA2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅ RT ‡ Subegular Solutions with Temperature Dependence We can add temperautre dependence to subregular solutions by adding a third parameter to give T W = Ha + b H1 .ÅÅÅÅ N t .XAL T Ha + b H1 .XALL J1 . ü Partial Molar Quantities Partial molar results can be derived from Gibbs-Duhem analysis DGmAXS = Simplify@DGmXS + H1 .XALL H1 .XAL XA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + ‡ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ „ XAE 2 H1 .tL .XAL XA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ t DHmXS = Simplify@DGmXS + T DSmXSD -H-1 + XAL XA Ha + b .2 b H-1 + XALL XA2 HT . DSmXS = -∑T DGmXS Ha + b H1 .ÅÅÅÅ N t For fixed temperature.2 b XAL HT . DGmXS = W XA H1 .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ t DSmAXS = Simplify@DSmXS + H1 .XAL2 0 Ha . For constant composition W is now linear in T.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ t DGmBXS = Simplify@DGmXS .tL .Notes on Gaskell Text 67 XA lngA lngA lngBcalc = SimplifyA-H1 .XAL H1 .2 b XAL ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ t . This temperature dependence will lead to non-zero excess entropy of mixing. W is linear in XB (as above for subregular solutions).XAL ∑XA DSmXSD H-1 + XAL2 Ha + b .XA ∑XA DGmXSD Ha .b XAL (Note: the book calculated excess entropy and enthalpy incorrectly).XALL H1 .

XAL XA ÅÅÅÅÅÅÅÅÅÅÅ .tL . we can calulate lngB from Gibbs-Duhem results: XA lngA lngA lngBcalc = SimplifyA-H1 .tL .tL .XAL XA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + ‡ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ „ XAE 2 H1 .XAL ∑XA DHmXSD H-1 + XAL2 Ha + b .tL .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ RTt .2 b H-1 + XALL XA2 HT .XAL H1 .XA ∑XA DHmXSD Ha .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ RTt or.2 b XAL HT .XAL2 0 Ha .2 b XAL DHmBXS = Simplify@DHmXS .68 Notes on Gaskell Text DSmBXS = Simplify@DSmXS . vice-versa.2 b H-1 + XALL XA2 HT .XA ∑XA DSmXSD Ha .2 b XAL HT .‡ ÅÅÅÅÅÅÅÅÅÅÅ „ XAE Å Å XA2 XA2 1 H-1 + XAL2 Ha + b .2 b H-1 + XALL XA2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅ t DHmAXS = Simplify@DHmXS + H1 .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ RTt Alternatively we can calculate lng A from Gibbs-Duhem results: XA lng lngB B lngAcalc = SimplifyA-H1 .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ RTt DGmBXS Å Å lngB = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ RT Ha .2 b H-1 + XALL XA2 ü Activity Coefficients The activity coefficients can be derived from the partial molar free energies DGmAXS Å Å lngA = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ RT H-1 + XAL2 Ha + b .

you can design a non-ideal solution by writing down an expression for excess free energy of mixing. Binary Solution ü Ideal Solution Starting Point The subsequeent calculations will only be for excess functions.XAL Log@1 . P for pressure. Express everything using XA.XAL2 + d H1 . and XA for mole fraction of component A.XAL3 L T ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ lngA = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ RT b Ha + c P + ÅÅÅ L HH1 . and mole fraction.XAL2 + d H1 . As above. enter a function for lng A using T for temperature. and XA. dividing this result by R T gives lngA . For example. P. it should approach 0 (or activity coefficient of 1) as XA->1 and should approach a Henry's law coefficient as XA->0.XAD + XA Log@XADL DSmid = Simplify@-∑T DGmidD -R H-H-1 + XAL Log@1 .XADL R T HH1 . To plot total function.XAD + XA Log@XADL DHmid = Simplify@DGmid + T DSmidD 0 ü Start From Activity Coefficient or Excess Free Energy You can design a non-ideal solution by writing down any function for activity coefficient of component A that tells how it depends on temperature. pressure.XAL3 L T ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ ÅÅÅÅÅÅÅÅ RT Alternatively. we can calculate the partial molar excess free energy of A. for XB. these excess functions should be added to the following ideal solutions results: DGmid = R T HXA Log@XAD + H1 .Notes on Gaskell Text 69 ‡ Create Your Own Non-Ideal. this function should be a function of T . . Note: whatever function you select. use (1-XA) instead. we could try b j z DGmXS = R T i + ÅÅÅÅ y Sin@p XAD ja z T{ k b R Ja + ÅÅÅÅ N T Sin@p XAD T From the excess free energy. To create a solution. b Ha + ÅÅÅ + c PL HH1 .XAL Log@1 .

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DGmXS + H1 - XAL ∑XA DGmXS lngA = SimplifyA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ E ÅÅÅÅÅÅÅÅ Å RT Hb + a TL Hp H-1 + XAL Cos@p XAD - Sin@p XADL - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ ÅÅÅÅÅÅÅÅ T Now both approaches have been expressed in terms of lngA . The remainder of this section thus derives all terms for the solution from that result. Here the sample results are based on the first lngA given above. Result based on DGmXS could easily be created by reevaluating all equations. Activity Coefficients: Using the Gibbs-Duhem equation and its application for calculating activity coefficients, we can calculate lngB from lng A using the following form of the “alpha” equation (which has been transformed from the equation in the text to be an integral of XA instead of over XB):

XA lngA lngA ÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ „ XAE lngB = SimplifyA-H1 - XAL XA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + ‡ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ 2 H1 - XAL H1 - XAL2 0

Hb + Ha + c PL TL XA2 H-2 + d H-3 + 2 XALL - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 2 R T2 Excess Functions: Using the above activity coefficients we can easily calculate all excess functions. The simplest method is to calculate DGmXS first and then differentiate it to find the other functions. Alternatively, the other excess functions could be determined directly from activity coefficients. DGmXS = Simplify@R T HXA lngA + H1 - XAL lngB LD Hb + Ha + c PL TL H-2 + d H-2 + XALL H-1 + XAL XA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ Å 2T DSmXS = Simplify@-∑T DGmXSD b H-2 + d H-2 + XALL H-1 + XAL XA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ 2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 2T DHmXS = Simplify@DGmXS + T DSmXSD H2 b + Ha + c PL TL H-2 + d H-2 + XALL H-1 + XAL XA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ 2T DVmXS = Simplify@∑P DGmXSD 1 ÅÅÅÅ c H-2 + d H-2 + XALL H-1 + XAL XA 2 Partial Molar Excess Functions: Using the “method of tangents” which was calculated from the Gibbs-Duhem equation, we can calculate partial molar excess functions from each of the above excess functions: DGmAXS = Simplify@DGmXS + H1 - XAL ∑XA DGmXSD Hb + Ha + c PL TL H-1 + d H-1 + XALL H-1 + XAL2 - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ T

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DGmBXS = Simplify@DGmXS - XA ∑XA DGmXSD Hb + Ha + c PL TL XA2 H-2 + d H-3 + 2 XALL - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 2T DSmAXS = Simplify@DSmXS + H1 - XAL ∑XA DSmXSD b H-1 + d H-1 + XALL H-1 + XAL2 - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ 2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅ ÅÅÅÅÅÅÅÅ T DSmBXS = Simplify@DSmXS - XA ∑XA DSmXSD b H2 + d H3 - 2 XALL XA2 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅÅ 2 T2 DHmAXS = Simplify@DHmXS + H1 - XAL ∑XA DHmXSD H2 b + Ha + c PL TL H-1 + d H-1 + XALL H-1 + XAL2 - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ T DHmBXS = Simplify@DHmXS - XA ∑XA DHmXSD H2 b + Ha + c PL TL XA2 H-2 + d H-3 + 2 XALL - ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ 2T DVmAXS = Simplify@DVmXS + H1 - XAL ∑XA DVmXSD -c H-1 + d H-1 + XALL H-1 + XAL2 DHmBXS = Simplify@DVmXS - XA ∑XA DVmXSD 1 ÅÅÅÅ c H2 + d H3 - 2 XALL XA2 2 Alternate Methods: By using the various equations derived from the Gibbs-Duhem analysis, many of the ablve resutls could be calculated by alternate methods. For example, DGmXS can be calculated directly from lngA using DGmXS = SimplifyAR T H1 - XAL IntegrateA lngA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ , 8XA, 0, XA< , Assumptions -> 8XA < 1, XA > 0<EE ÅÅÅÅÅÅÅ H1 - XAL2 Hb + Ha + c PL TL H-2 + d H-2 + XALL H-1 + XAL XA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ Å 2T Plotting Parameters: The rest of this section is to plot the results for the above solution. To do those plots, you need to define some set of parameters. Using the following table command, create a table of tables where each element is a set of parameters for subsequent plots. To create different plots, redefine the parameters and execute the plot functions again.

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parameters = Table@8R -> 1, T -> 1, P -> 1 , a -> 1, b -> value, c -> -2 , d -> -2< , 8value, -3, 2, 1<D 88R Ø 1, T Ø 1, P Ø 1, a Ø 1, b Ø -3, c Ø -2, d Ø -2<, 8R Ø 1, T Ø 1, P Ø 1, a Ø 1, b Ø -2, c Ø -2, d Ø -2<, 8R Ø 1, T Ø 1, P Ø 1, a Ø 1, b Ø -1, c Ø -2, d Ø -2<, 8R Ø 1, T Ø 1, P Ø 1, a Ø 1, b Ø 0, c Ø -2, d Ø -2<, 8R Ø 1, T Ø 1, P Ø 1, a Ø 1, b Ø 1, c Ø -2, d Ø -2<, 8R Ø 1, T Ø 1, P Ø 1, a Ø 1, b Ø 2, c Ø -2, d Ø -2<< Activity Coefficients of Components A and B: Plot@ Release@XA Exp@lngA D ê. parameters D, 8XA, 0, 1<, AxesLabel -> 8"XA ", "aA "<D

aA 1.4 1.2 1 0.8 0.6 0.4 0.2 XA

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3 0.2 0.4 0.2 -0.4 0. AxesLabel -> 8"XA ".Notes on Gaskell Text 73 Plot@ Release@H1 . "aB "<D aB 1.2 1 0.2 0. 0.4 0.4 0.8 1 Ü Graphics Ü Excess and Total Free Energy of Mixing Plot@ Release@DGmXS ê.6 0.6 0.5 0. parameters D. 8XA. 1<.1 0.XAL Exp@lngB D ê. parameters D.6 0. 8XA.8 1 XA Ü Graphics Ü .6 0.8 0. 0. "DGmXS"<D DGmXS 0. 1<.2 XA 0.1 0. AxesLabel -> 8"XA ".

3 Ü Graphics Ü 0. 1<.8 Ü Graphics Ü Excess Entropy.8 1 XA .2 -0. 0.2 0.1 0. "DSmXS"<D DSmXS 0.1 -0.74 Notes on Gaskell Text Plot@ Release@DGmid + DGmXS ê. 8XA. parameters D. parameters D. Enthalpy. AxesLabel -> 8"XA ".3 0.2 -0.8 1 XA -0. 1<.4 0. 0.6 0. AxesLabel -> 8"XA ".6 0. and Volume Plot@ Release@DSmXS ê.2 0.4 -0.2 -0.6 -0.4 0. 8XA.4 0. "DGm"<D DGm 0.

8 1 Ü Graphics Ü . parameters D.05 XA 0. AxesLabel -> 8"XA ". 0.15 0.4 0. 1<. AxesLabel -> 8"XA ".6 0. 8XA. 1<.2 -0.2 -0. parameters D.1 0.8 0. "DVmXS"<D 0.Notes on Gaskell Text 75 Plot@ Release@DHmXS ê.2 0.6 0.6 0.4 0.4 0.25 0. 0. "DHmXS"<D DHmXS 1 0.2 0.8 1 XA DVmXS 0. 8XA.4 Ü Graphics Ü Plot@ Release@DVmXS ê.3 0.2 0.

py: From table A-5.1 a. thus the entropy change is just the entropy of the added component which.5 H1 + ÅÅÅÅÅÅÅÅÅÅÅÅÅ L massMn massMn To get activity.2< 59. Given the entropy of melring. Thus DStotal = DSm .5 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 1. It is stated that the solution is very large. the enthlapy of melting of Cr2 O3 for its melting point or DHm = DSm Tm ê. 8R -> 8. we need to find the vapor pressure of pure Mn. for 1 mole added. the pure pressure is pMnPure = Exp@lnvapMn ê. this is also the entropy of melting for Cr2 O3 (I do not know why the text simply did not include DHm for the Cr2 O3 in Table A-5 instead of using this arbitrary relation given in this problem). b. the partial pressure due to Mn gas comes from its mole fraction in the total gas which is stated to be at 1 atm: 1.638 ü Problem 9. 8Tm -> 2538< 117399. To get the total enropy change we add the entropy of melting to the entropy change on disolving the Cr2 O3 . T -> 1863D ElnvapMn Thus the activity is . This data suffices to calculate DSm as 107500 DSm = NA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ E Å Å 2324 46. Using the results in Table A-4.3144 .2 Assuming the gas is made up of 1 mole of argon gas and the evaporated Mn gas. DHm for Al2 O3 is 107500 J and its melting point is Tm=2324K.76 Notes on Gaskell Text ‡ Problems ü Problem 9. is just the partial molar entropy of that component.5 y i pMn = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ì j + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ z Å Å Å z j1 massMn massMn { k 1.R Log@XAD ê. this result is the total enthalpy change on disolving solid Cr2 O3 into the liquid solution.5 1. Assuming this enthalpy of melting is independent of temperature and that the solution is ideal (as stated) and therefore contributes no extra enthalpy effects. XA -> 0.2565 As stated in the problem. Enthal.

First we need to get the activities from the partial molar free energies . 4393. 4391.4. If the solution is regular than DGmXS should be W XA XB.75. 4388. This constant W does not prove the solution is regular.6. 395< . 925. W -> 4400 < 4400 XA2 c. T -> 1863 . The total free emergy of mixing is DGm = R T HXA Log@XAD + XB Log@XBDL + W XA XB ê. 1. 4404. 4391.3* a. 703. 4393. W -> 4400 < 4400 XB2 GFeMn = XA2 W ê.3144. 8XB -> 0.76.Notes on Gaskell Text 77 aMn = pMn ê pMnPure 1.5 H1 + ÅÅÅÅÅÅÅÅÅÅÅÅÅ L massMn massMn Finally. 925. 8XA -> 0. To prove that there would have to ba additional experiments showing that the entropy of mixing is zero and therefore the excess enthalpy is equal to the excess free energy (note: I think the book got W wrong and is off by a factor of 4).8 + 4400 XA XB d. 8R -> 8. 1054. XA -> 0. 9<E ÅÅÅÅÅÅÅÅÅ 0.0. 1100. 703. 4400. dividing by the mole fraction gives the activity coefficient: gammaMn = aMn ê XMn ê. XMn -> 0. 4404.67. 8i.89.75. Evalulating that ratio for the result in the book gives GmXS = 8395.4 ..6. 1054. The partial molar quantities for a regular solution are given by GFeXS = XB2 W ê.76. W -> 4400< -10424.5 3.89< Thus W is constant and equal to 4400 J. In other words.5 E-lnvapMn ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 1. XB -> 0.67.1 i H1 . E-lnvapMn ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 1. GmXS@@iDD Wtest = TableA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .5 H1 + ÅÅÅÅÅÅÅÅÅÅÅÅÅ L massMn massMn ü Problem 9.1 iL 84388. b. DGmXS/(XA XB) should be constant and equal to the regular solution interaction term.

XB -> 0.223144 +lnvapFe + ÅÅÅÅÅÅÅÅÅT 4400 XB 2 pMn = aMn pMnPure R ÅÅÅÅÅÅÅÅ E-1. T -> 1863. we have to use the methods of Chapter 6 to find the enthalpy required to heat 1 mole of Cu and 1 mole of Ag from 298K to 1356 K.60944 + ÅÅÅÅÅÅÅÅÅT 4400 XA 2 The pure vapor pressures are pFePure = Exp@lnvapFe ê. T -> 1863D ElnvapMn Finally. T -> 1863D ElnvapFe pMnPure = Exp@lnvapMn ê. T -> 1863. W -> 4400< R ÅÅÅÅÅÅÅÅ E-1.2 . Å RT 8R -> 8.78 Notes on Gaskell Text XB2 W aFe = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + Log@XADE ê.3144. First.60944 +lnvapMn + ÅÅÅÅÅÅÅÅÅT 4400 XA 2 (Note: all results above agree with the book solution if W=1052 instead of 4400 as found here).2 . XA -> 0. the partial vapor pressures over the solutions are pFe = aFe pFePure R ÅÅÅÅÅÅÅÅ E-0.3144. XB -> 0.8.4 The heat required is the total changein enthalpy.8. Accounting for 1356 DHCu = ‡ 298 CpCu „ T + DHmCu ê. 8DHmCu -> 12970< 12970 + 1058 CpCu . XA -> 0.223144 + ÅÅÅÅÅÅÅÅÅT 4400 XB 2 XA2 W aMn = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ + Log@XBDE ê. W -> 4400< R ÅÅÅÅÅÅÅÅ E-0. Å RT 8R -> 8. ü Problem 9.

these two liquids are mixed with the resulting excess enthalpy of DHXS = 2 HW XA H1 .90042.ÅÅÅÅÅÅÅÅÅÅ N == -2.XPbL2 W lnaPb = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ + Log@XPbD .41180 H1 . Here H1 .XSnL2 W ÅÅÅÅÅÅÅÅ aSn = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ + Log@XSnDE ê. W -> -4577. 8XA -> 0.XALL J1 . The method used here is to fit the data to a function and then use Mathematica methods to numercially integrate the results. use the appropriate formula for a regular solution. 8R -> 8.Notes on Gaskell Text 79 1234 1356 DHAg = ‡ 298 CpAgs „ T + DHmAg + ‡ 1234 CpAgl „ T ê. RT 8R -> 8.1< — — T General::ivar : Ha + b H1 . To find any other activity.XALL J1 . t 746 SolveA-2.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅT ÅÅÅÅÅÅÅÅÅÅ 4577. XSn -> 0. natural log of activity is given by H1 . t 746 Ha + b H1 . 8DHmAg -> 11090< 11090 + 122 CpAgl + 936 CpAgs Next.91< RÅÅÅÅÅÅÅÅ E-0.30259 + 0.3144. Å t 746 General::ivar : Ha + b H1 .055D .XAL XA ü Problem 9.6 This problem has to be solved by graphical or numerical integration which is hard to in Mathematica.XALL ê.XAL XA The total heat required is the sum of these three enthalpies DHCu + DHAg + DHXS 24060 + 122 CpAgl + 936 CpAgs + 1058 CpCu .91 H1-XSnL2 ü Problem 9. XPb -> 0.693147 .XALL J1 . WD ê.ÅÅÅÅÅÅÅÅÅÅ NE t b.3144.ÅÅÅÅÅÅÅÅÅÅ N is not a valid variable. ÅÅÅÅÅÅÅÅ RT We can thus find W by solving Solve@lnaPb == Log@0. W -> -20590< -41180 H1 . T -> 473 + 273.XALL J1 .ÅÅÅÅ N is not a valid variable. .5. T -> 473 + 273.5. For a regular solution.000130592 Ha + b H1 .5 a.

8. 80.348307.1. 80. 1.935<. .55) we need to integrate XB/XA as a function of lngB.55): Here is the data from the problem as x-y pairs of moles fraction and activity of Cu (XB. 1. 1<.7. 8i. The frist point is left off because XB/XA is infinite when XA=0: eq955Data = aCuData@@i. Use Eq.2. 4.112212. 1. 80. 80.9.111111<. 80. 2DD gCuData = TableA9aCuData@@i. ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ = . 80. 1<. 0. 11<E ÅÅÅÅÅÅÅÅ Å 1 .955511. 80. this change scales the x axis by 2. 80. 2.9.11875<. . 3. 1DD. 80.025<. 81. 0.15 in the text (except that here I am using natural log instead of base 10 log.28093. 1. 2DDD. 2.7. 80.830<. 80.41667<. 80.211649. 80. 80.0526316<< Here is a plot of the points which is the same as Fig 9.8.<< For equation (9. 1DD TableA9Log@gCuData@@i. . . .70557.850<.575<. 11<E ÅÅÅÅÅÅÅÅ aCuData@@i. 80. 80. 8.6<. 8i. .780<.303): . 1DD 880. 0. 1.7492. 80. 2.865<.33333<. 80. 1. . 80.40<< . (9.23571<. 1. aB) (here B is for Cu and A is for Fe) aCuData = 881.2.6<. 81. .1. 9. 1.66<.03889<.<.<. 80. 80.810<.6.75<. 82.895<.<.aCuData@@i.4. 80. 1DD 881.3. This table divides the activity by mole fraction to get x-y pairs of (XB. 80. lngB).0381518. 0.720<.506818.05.428571<. 80. 2.666667<.5.07944. This tables has the x-y pairs for (XB/XA.5<.80 Notes on Gaskell Text a.25<.6. ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅ = .05. 0.3. 0. .gB): aCuData@@i. 80.5. 5. 80.4.

3. "XBêXA"<D XBêXA 8 6 4 2 0.57707 x + 2.577878 x3 x We next need the integration limits. x ^ 3<. eq955Fit = Fit@eq955Data. xD 0.49897 x2 . For now the upper limit is just lngB: lngB lngA = .17158 + 0.10935<< This the lower limit of the integration is 2.71542 + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ .283895 Log@0. 8x Ø 2.0.5 2 lngB To do calculations in Mathematica. The lower limit is the intercept of the XB/XA plot with the x axis.830274 + 0.84839 lngB + lngB2 L . xD 88x Ø -0. one method is to fit the data and then numerically integrate the fit function.0.06993 . Here the fit should include 1/x terms because the function looks like a 1/x plot.667313 I<. This table thus gives gA as a function of XB in x-y pairs (XB. we insert the data for lngB at each value of XB. 1.91747 + lngBL H-1.283895 1.667313 I<. + lngBD To convert to Fe activity coefficients.10935 0.5 Ü Graphics Ü 1 1.0. x. gA): .10935 which is lngB when XA=1.03553 µ 10-15 + lngBL H4.17158 .Notes on Gaskell Text 81 dp = ListPlot@eq955Data. Solving for where the fit is zero gives: lowlim = Solve@eq955Fit == 0 .144469 H-2. 8x Ø 1. x ^ 2. AxesLabel -> 8"lngB". 8x Ø 1. 81 ê x.2.‡ eq955Fit „ x 2.128116<.

00035<< Finally. 0.9. 80.93449<. 1. Exp@lngAD ê. 80.9. 1DD< .7.1. 80.9 in the text: ListPlot@Join@aCuData. 2.6. First we convert the activity coefficient data to x-y pairs of (XA. AxesLabel -> 8"XB".2.6 0. 80.8 0. (9. 10<D 880. Use Eq. 1.544468<. 0.82 Notes on Gaskell Text gFeData = Table@8gCuData@@i + 1. aFeDataD.853601<.gFeData@@i. 80.42267<.799783<. 80. 0.61) is the last equation on page 242 and it is not labeled.2 0.1. 1. 1. 80. 80.3.4.05. "activity"<. lngB -> eq955Data@@i.14507<. 1DD.61): Eq. (9. 1.5. 1<D activity 1 0. 0. 0. 1.04645<.44468<.4 0.4 0. we get activity by multiplying by XA = 1-XB: aFeData = Table@8gFeData@@i.2. 8i.881697<. 80. 0. 1. 3. 2DD H1 . 10<D 880. 80.67248<. 1DD. 80.6.25957<.719424<.5. 0. 1. 80. 0.6 0.03832<. 1DDL<.8.4.8. 80. 8i. This plot is identical to Fig 9. PlotRange -> 80.7.66594<. 80. 2. gFeData@@i. 5.950336<< Here is a plot of the activity of Fe as calculated and compared to activity of Cu.59712<. 80.3.05.8 1 XB b. 80.818581<. 80. 80.836241<.916058<.2 Ü Graphics Ü 0. 0.aB) which is the function that needs to be integrated: . 0.

1DD. 4<<D 4 3. 80. 2. 1 ê x. we do all the calculations in one step. 2.303. 80. 2.6.4. 80.95002<. thus we have to use exponential to get activity coefficient and multiply by XA to get activity or aA = XA Exp[lngA]: . (9.5 2 1. 80. 1. 80.81518<.3.2. 80. ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅ = . 1. 2.aA) where aA is calculation equation (9. 80.02727<.17692<. x ^ 2. 80.61). But.2. ap = ListPlot@eq961Data.8. 2DDD TableA91 . PlotRange -> 880.8053<.0315193 x . The 1/x is required to get a nice fit: eq961Fit = Fit@eq961Data.58653 x3 x Finally.30409<< Here is a plot of aB.35166<. It has the same form.5 0.18802 x2 + 2.5. but here I am using natural log instead of base 10 log. 80.Notes on Gaskell Text 83 eq961Data = Log@gCuData@@i. 1<.9.2 Ü Graphics Ü 0.gCuData@@i. 2. 2.8 1 Here is a good fit fuction. These x-y pairs are (XB. Thus the y axis here is scaled by a factor of 2. This should be the same as plot 9.gCuData@@i.95. x.15951<.4 0.17 in the text.00146<.7. xD 0. 1DDL2 880.6 0.197163 1. 8i. 81. 11<E ÅÅÅÅÅÅÅÅ H1 .95992<. 2. 80. 3.5 3 2.1.61) gives lngA.5 1 0. Eq.86931 + ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ .0. 2. x ^ 3<.

80. 80. 80.62<.067<< .6 0.4.2. 0.XAL XA alpha . 80. alpha -> eq961Data@@i. 1. . 80.5. 1<D activity 1 0. (9. 80.1.374<. aB) (here B is for Ni and A is for Fe) aNiData = 881.‡ 1 eq961Fit „ x ê.6.9 in the text: ListPlot@Join@aCuData. 1DD ExpA XA -H1 . 0.2.3. 80.eq961Data@@i. 0.4 0. 0. PlotRange -> 80. 0. 80.8 0. 1<. . aFe961D. .6 except the data is different and we need to veroiify that the function forms used to fit the results for numerical integration are god fitting functions a.2 Ü Graphics Ü 0.8. 80.8. "activity"<.6 0. 80.859137<.7.84 Notes on Gaskell Text aFe961 = TableA91 . 0. .816825<.207<. AxesLabel -> 8"XB".712799<. 0. . 80. 0.1. 80. 1DD.841623<.05.4. . Use Eq. 80.2 0. 80.7 This problem is identical to Problem 9.55): Here is the data from the problem as x-y pairs of moles fraction and activity of Ni (XB.9.283<.6.766<. 80. 2DD<E =. . 80.9. 0. .3. 8i.136<.790949<. 1DD . 0. 0.95813<< Here is a plot of data which again is identical to Fig 9.4 0.89<. 80. 10<E 880. eq961Data@@i.5.544856<.932132<.7. 80.8 1 XB ü Problem 9.900018<.877303<.485<. 8XA -> eq961Data@@i. .

1. 80. 8-0. 8i.7. 0. 1DD 881.aNiData@@i. ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ = . 80.9575<.5<.385662. lngB). 2. 0. 9. 80.6. 10<E ÅÅÅÅÅÅÅÅ Å 1 .400478.14 in the text (except for a scaling of 2.4 -0.346018. 2. 2DDD.290352.666667<.4. 8-0. 0.67<< For equation (9. 0.1 lngB To do calculations in Mathematica. .212781. 8-0.55) we need to integrate XB/XA as a function of lngB. This tables has the x-y pairs for (XB/XA.69<. 1DD.428571<.gB): aNiData@@i.2 -0. 80.33333<.988889<. 0.0434296. 0.3 Ü Graphics Ü -0. 2DD gNiData = TableA9aNiData@@i.Notes on Gaskell Text 85 This table divides the activity by mole fraction to get x-y pairs of (XB. 0.885714<.<.68<.3. 80. 80.9.111111<< Here is a plot of the points which is the same as Fig 9. 8-0. 8-0. 80.<. ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅ = .0111733.121361. AxesLabel -> 8"lngB".2. 4. one method is to fit the data and then numerically integrate the fit function.303 in the x axis because of use of natural log instead of base 10 log) dp = ListPlot@eq955Data. 1. 8-0.748<.<. 0. 1DD 88-0.371064.25<. 0. 10<E ÅÅÅÅÅÅÅÅ aNiData@@i. 8-0. 1. 0. 1<. Here the fit should include 1/x terms because the function looks like a 1/x plot.7075<. 0. The frist point is left off because XB/XA is infinite when XA=0: eq955Data = aNiData@@i. 8-0. 0. 80.808333<. 0. "XBêXA"<D XBêXA 8 6 4 2 -0. 8i.8. 1. 1DD TableA9Log@gNiData@@i.5. 80.

‡ eq955Fit „ x -0. The lower limit is the intercept of the XB/XA plot with the x axis.934413<. Re@Exp@lngAD ê. 80.2076 x2 + 55. 0. 0. 0. 0.4. 0. 80. 80. 80. 2DD H1 .86 Notes on Gaskell Text eq955Fit = Fit@eq955Data. we insert the data for lngB at each value of XB. 0.213922<.113199<. 81 ê x.899373<< Here is a plot of the activity of Fe as calculated and compared to activity of Ni.338615<. 0. 8x Ø 0. 1DDL<.411755 which is lngB when XA=1.8 in the text: . gA): gFeData = Table@8gNiData@@i + 1. 8i. 80. 80. lngB -> eq955Data@@i.713072<. 80.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅ + 13.3.2. x ^ 2.996371<. 8x Ø -0.217534 IL 13. gFeData@@i.411755 H-0.346932 I<. 80. x. 0.0. 1DDD< .7.1.147001 + 0. 1DD. xD 0. 0. x ^ 3<. + lngBD To convert to Fe activity coefficients.9. For now the upper limit is just lngB: lngB lngA = .gFeData@@i.7. 9<D 880.0692434 Log@0.4.346932 I<.0212219<< This the lower limit of the integration is -0. Solving for where the fit is zero gives: lowlim = Solve@eq955Fit == 0 . 80. 0.8155 x3 ÅÅÅÅÅÅÅÅ x We next need the integration limits.978622<.991411<.8.468087 .845 x + 38.473713<.3. 80.0692434 2. 0.467206<.95126 . 1.2.6. This plot is identical to Fig 9. 80.0.846538<.5. This table thus gives gA as a function of XB in x-y pairs (XB. 8i. xD 88x Ø -0. 8x Ø -0. 80.325358 + 0.5.1.0473713<.52373 µ 10-17 + lngBL H0.411755<. 80. 0. 1.147001 .9539 H7. 80. 0. 0.6.797097<.587173<. 0. 1. 0.565996<. 0. 80.693988<. 9<D 880.650056 + lngBL H0. 0. we get activity by multiplying by XA = 1-XB: aFeData = Table@8gFeData@@i.999303<< Finally. 1DD.262657 lngB + lngB2 L + 0. 80.9.8.

2 Ü Graphics Ü 0. . ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅ = .8 1 XB b.303 because of the use of natural logs instead of base 10 logs. -0.494417<< Here is a plot of aB. 1<D activity 1 0.1.16141<. This should be the same as plot 9. 80. 8i. It has the same form.2. -1.16 in the text.gNiData@@i.9. (9.08574<. 80.3. aFeDataD.8.61): Eq.Notes on Gaskell Text 87 ListPlot@Join@aNiData. -1.6. -0.6 0.96116<. 80. 2DDD TableA91 . 80. -1.7. 2. PlotRange -> 80.8 0. -0.11733<. 80.6 0. -0.4 0. "activity"<.4 0.34845<. Also the plot reversed the direction of the y axis and this this plot is also a mirror image of the book plot.aB) which is the function that needs to be integrated: eq961Data = Log@gNiData@@i. First we convert the activity coefficient data to x-y pairs of (XA. but scaled here by 2. (9. 10<E ÅÅÅÅÅÅÅÅ H1 . AxesLabel -> 8"XB". 1DD.5. -1. Use Eq. 80.32988<.4.602598<.757273<. 80.2 0.61) is the last equation on page 242 and it is not labeled. 1DDL2 880. -1. 80.gNiData@@i.

1. 0.8.XAL XA alpha .54183 x2 . 1DD ExpA-H1 . (9. 0. xD -0. The 1/x is required to get a nice fit: eq961Fit = Fit@eq961Data.4.2. x ^ 3<. 80. 80.113483<.8 1 Here is a good fit fuction.75 -1 -1.585182<. 8XA -> eq961Data@@i. 8-2. 0.465444<.76855 x3 Finally. 80.3. 80.25 -0. XA eq961Data@@i. 2DD<E =.4 0. 1.9.aA) where aA is calculation equation (9. 80.6. 1DD. 80.88 Notes on Gaskell Text ap = ListPlot@eq961Data.75 -2 Ü Graphics Ü 0.48737 x + 9. 0.8 in the text: .21594<. 0<<D 0. 9<E 880. But. 0. 1<. Eq.5 -0.339624<.4. 80.61) gives lngA. 80. 1DD .799316<.69424<.5 -1.6 0.61). 0.7.4.901121<< Here is a plot of data which again is identical to Fig 9. x ^ 2. 8i. PlotRange -> 880.25 -1. These x-y pairs are (XB. thus we have to use exponential to get activity coefficient and multiply by XA to get activity or aA = XA Exp[lngA]: aFe961 = TableA91 .5. 0. 0. we do all the calculations in one step. 81. alpha -> eq961Data@@i. 0.eq961Data@@i.‡ 1 eq961Fit „ x ê.689222 .2 -0.046974<. x.

AxesLabel -> 8"XB". R -> 8. The total enthalpy change is the partial molar enthalpy of the dilute substanct times the number of moles of the diluite substance. 8n -> 100.5. nA -> 1 j z k T { -840 R This result is negative and thus heat is released. In adiabatic conditions. this heat increased the temperature of the allow according to its heat capacity: Solve@n Cp DT == .2 Ü Graphics Ü 0.58z ê. 1<D activity 1 0.DHmA ê.8 1 XB ü Problem 9. "activity"<.nA R T2 ∑T j ÅÅÅÅÅÅÅÅÅÅÅÅ + 1.3144< .6 0.4 0. DTD 88DT Ø 2.4 0.2 0. PlotRange -> 80. aFe961D.8 0.6 0.36749<< This result is a factor of 10 lower than the book solution.Notes on Gaskell Text 89 ListPlot@Join@aNiData. Using the formula for partial molar enthalpy we find i -840 y Å DHmA = . Cp -> 29.8* When one mole of a substance is added to a large amount of a substance. . the dilute substance is in the Henrian limit while the other substance is in the ideal or Raoult's limit.

XNiL ∑XNi DGmXS lngNi = SimplifyA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å E ÅÅÅÅÅÅÅ RT H-2660 + TL H-1 + XNiL2 H2414 .XNiL XNiL Å 2660 The full activity coefficients are DGmXS + H1 .3 XZn3 Thus activity of Cd is when XCd=0.90 Notes on Gaskell Text ü Problem 9.XNiL + 38280 XNi .18 XNi + 4269 XNi2 L .3< 0.425 XZn2 + 0. a2 -> -.XNiL + 38280 XNi .XNiL XNi H24140 H1 .XNiL T H24140 H1 .ÅÅÅÅÅÅÅÅÅÅÅÅ N H1 . (9.10 This problem is most easily calculated using Eq.11* The activity coefficients can be calculated from the method of tangents applied to the excess free energy of mixing which is given as DGmXS = XNi H1 .61) lngZn = a1 XCd2 + a2 XCd3 a1 XCd2 + a2 XCd3 which is substituted into Eq. (9.XCdL XCd ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .XZn .XNiLL J1 .ÅÅÅÅÅÅÅÅÅÅÅÅ N Å 2660 T J1 .14230 XNi H1 .ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 266 R T .61) XCd lngZn lngZn lngCd = SimplifyA-H1 .875.875. 8XCd -> 0.3<DD 0.14230 H1 . a2 -> -0.577298 ü Problem 9.‡ Å ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ „ XCd E Å XCd2 XCd2 1 1 ÅÅÅÅ H-1 + XCdL2 H2 a1 + a2 + 2 a2 XCdL 2 Expand@Simplify@lngCd ê. a1 -> 0. a1 -> 0.5 is aCd = XCd Exp@lngCdD ê. 8XCd -> 1 .5.

2864 XNi + 4269 XNi2 L . TBm = 1563 . R -> 8.3144< 0. 8XNi -> 0.ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ Å 266 R T Thus. for CaF2 DHm DHm = 31200 . Chapter 10: The Phase Diagrams of Binary Systems ‡ Problems ü Problem 10.4506 From Table A-5. R -> 8.5 .3144< 0. because we do not know otherwise and the c p for these compounds are not given in Table A-2) gives .5 . Tm = 1691 . (10. the activities are aNi = XNi Exp@lngNiD ê.XNiL Exp@lngAuD ê.695454 The book must have interchanged the activities in the final provided answer. for MgF2 DHBm DHBm = 58160 .Notes on Gaskell Text 91 DGmXS . T -> 1100. 8XNi -> 0. DSm = NA ÅÅÅÅÅÅÅÅÅÅ E Tm 18.XNi ∑XNi DGmXS lngAu = SimplifyA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ E RT H-2660 + TL XNi2 H2423 .2105 Plotting the liquidus lines (using Eq.23)) and assuming DH and DS are independent of temperature.1* From Table A-5.872396 aAu = H1 . T -> 1100. DSBm = NA ÅÅÅÅÅÅÅÅÅÅÅ E Å Å TBm 37.

These results differ from the actual eutectic composition and from the answers in the text. which goes through the free energy of the eutectic composition. Relative to the unmixed liquids we compare the line connecting the pure solid states. 8T.54 1310 1320 1330 1340 1350 Ü Graphics Ü These plots intersect at the predicted eutectic temperature about 1328K and mole fraction CaF2 = 0. 1350<E 0. ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ Å RT RT R -> 8. 1300. ü Problem 10.54.3144E . at the eutectic composition. to the line connecting the pure solid states.56 0.2 1.58 0. as illustrated by the arrow in the following diagram: B(l) A(l) A(s) B(s) Thus using .92 Notes on Gaskell Text -DHm + T DSm -DHBm + T DSBm PlotAReleaseA9ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ E . 1 .ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅ E= ê.

T -> 636< 11194. with equal entropies of melting (as stated in the problem).2565 DGA = DHm . 8DHAu -> 12600 .46.46.TL ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅÅÅÅ 337 TAu . 8DHm -> 2538 DSA . 2.186. TSi -> 1685< z j k TSi { 10040 H1685 .XSiL DGAu ê.Notes on Gaskell Text 93 i TSi .T y DGSi = DHSi j ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ z ê.19) and (10.T DSm ê. TAu -> 1338< TAu 2100 H1338 .2565 T The phase diagram can be plotted (as a reversed plot of X A vs T instead of the more usual T vs X A ): . DSm -> DSA< 107500 .21). we have DHm DSA = NA ÅÅÅÅÅÅÅÅÅÅ ê. Associating A with Al2 O3 and B with Cr2 O3 .1 Note: some copies of the text has a mi-printed solution of 1119.T DSm ê. which is a factor of 10 too low. the liquidus and solidus lines are given be Eqs.TL ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅ 223 DG1 = XSi DGSi + H1 . Tm -> 2324<E Tm 46.3 For ideal solid and liquid solutions. (10. DSm -> DSA< 117399.2565 T DGB = DHm . ü Problem 10.T DGAu = DHAu J ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ N ê. 8DHSi -> 50200 . 8DHm -> 107500 . 8DHm -> 107500 . 8XSi -> . . The energy difference relative to the solids is zero because the liquid solution curve just touches the line between the solid states at the eutectic composition (see above figure).

Exp@ ÅÅÅÅÅÅÅÅÅ DL Exp@ ÅÅÅÅÅÅÅÅÅ D RT RT RT ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ . A compositiong of X A = 0.Exp@ ÅÅÅÅÅÅÅÅÅ D H1 .94 Notes on Gaskell Text -DGB -DGB -DGA 1 . Tm -> 1240<E Å Tm 54.38 ü Problem 10. we have: Tm . TL For K2 O B2 O3 using data in the appendix. For Na2 O B2 O3 using data in the appendix. 2324.4 0.62 c. AxesLabel -> 8T. the answers are: a.3144E .8 0.Exp@ ÅÅÅÅÅÅÅÅÅ D RT RT RT RT R -> 8. 10. ÅÅÅÅÅÅÅÅ PlotAReleaseA9 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ -DGA -DGB -DGA -DGB Exp@ ÅÅÅÅÅÅÅÅÅ D . . we add the DGm of each component to the ideal DGmixing . d. ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ = ê. The initial composition of the melt is X A = 0.0323 H1240. 2538<.1. Melting is completed at 2443K. 8DHm -> 67000. The last formed solid has X A = 0. we have : .Exp@ ÅÅÅÅÅÅÅÅÅ D Exp@ ÅÅÅÅÅÅÅÅÅ D .T DGA = NADHm J ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ N ê.20d except they are symmetric about the middle.4 The liquid-liquid and solid-solid solutions resemble the curves in Fig. 8T. To find the total DG.6 0. XA <E XA 1 0. b.5begins to melt at 2418K.2 2400 Ü Graphics Ü 2450 2500 T Prodeeding graphically from this phase diagram (by expanding and plotting key sections).

4754 H1220.19) and (10.T DGB = NADHm J ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ N ê. exGe = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ E . The intention of this problem is to use Eq.20) for ideal solution liquidus mole fraction and solve for DHmGe as the only unknown. . we can solve for W using: XB W SolveALogA ÅÅÅÅÅÅÅ E + ÅÅÅÅÅÅÅÅ HXA . 8W -> 38095. XA RT 8XA -> 0.3144< -814.TL ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅÅÅÅ 337 Tm . 8T -> 1123 .5 DGA + 0.52 ü Problem 10. T -> 1794 + 273<E 88W Ø 38095. R -> 8. 8DHm -> 50200 . 8DHm -> DHmGe .5 DGB ê.24 when T=1794C. TL The total DG is then the following sum (which remembers to use 1/2 a mole for each component): DG = R T Log@0. Tm -> 1210< Å Å Tm H1210 .5 The only information we need to know is that the solution is regular with minima at XA=0.3144 . The free energies of melting of each component in terms of the enthalpies of melting are: Tm .6 a. 8DHm -> 62800. Tm -> 1685< Å Å Tm 10040 H1685 .XBL == 0 ê.20): -DGmSi -DGmGe exSi = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ E .T DGmGe = DHm J ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ N ê.95 ü Problem 10.8 . R -> 8.8<< Using the standard formula.Notes on Gaskell Text 95 Tm . Tm -> 1220<E Å Tm 51. Because the minima occur when the derivative of DGmixing is zero (see page 277). the critical temperature is W Tcr = ÅÅÅÅÅÅÅÅ ê.TL DHmGe ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅÅÅÅ 1210 The following two terms are the exponential terms in Eqs.3144< 2R 2290.T DGmSi = DHm J ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ N ê.76 . (10.1. R -> 8.24.5D + 0. Å Å Å RT RT . (10. XB -> 0.

96

Notes on Gaskell Text

Solving Eq. (10.21) for DHmGe gives: H1 - exGeL exSi SolveAXSil == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ê. ÅÅÅÅÅÅ exSi - exGe 8T -> 1200 + 273 , XSil -> 0.32 , R -> 8.3144< , DHmGeE 88DHmGe Ø 21529.2<< b. Similarly, Eq. (10.19) can be solved to give: 1 - exGe SolveAXSis == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ ê. ÅÅÅÅÅÅÅÅ exSi - exGe 8T -> 1200 + 273 , XSis -> 0.665 , R -> 8.3144< , DHmGeE 88DHmGe Ø 33114.2<< Comments: Part b gives the better result, but actually neither result is appropriate. Equations (10.19) and (10.20) are based on the assumption that both the liquid and the solid solutions are ideal. The problem says to assume that only one of them is ideal.Unfortunately, there is not enough information provided to find DHmGe when only one solution is ideal and the other is non-ideal.This problem is poorly written, but can the answers in the book can be obtained by using Eqs. (10.19) and (10.20) has shown above. ü Problem 10.7 Let XA1 be the mole fraction of MgO at the point of maximum soluability of MgO in CaO and let XA2 be the mole fraction of MgO at the point of maximum soluability of CaO in MgO. At XA1, the activity of MgO (which obeys Henry's law) is gA0 XA1 and in the Henry's limit we assume the activity of CaO is its mole fraction or (1XA1). Similar, at XA2, the activity of CaO is gB0(1-XA2) and the activity of MgO is XA2. Because these two compositions exist in equilibrium, we can equate the activities of the two components and solve for XA1 and XA2: Solve@8gA0 XA1 == XA2 , gB0 H1 - XA2L == H1 - XA1L< ê. 8gA0 -> 6.23 , gB0 -> 12.88< D 88XA1 Ø 0.14992, XA2 Ø 0.934<< The first answer is the maximum soluabiility of MgO in CaO. 1-0.934=0.066 is the maximum soluability of CaO in MgO.

**Chapter 11: Reactions Involving Gases
**

‡ Problems

ü Problem 11.1 For the reaction CO + (1/2) O2 -> CO2 , the free energy is given in the text as:

Notes on Gaskell Text

97

DGC = -282400 + 86.85 T -282400 + 86.85 T For the reaction H2 + (1/2) O2 -> H2 O, the free energy is given in the text as: DGH = -246400 + 54.8 T -246400 + 54.8 T Subtracting the former from the latter gives the free energy for the reaction H2 + CO2 -> H2 O + CO: DG = DGH - DGC 36000 - 32.05 T The equilibrium constant for this reaction at 900C (1173K) is -DG Kp = ExpA ÅÅÅÅÅÅÅÅÅÅ E ê. 8R -> 8.3144 , T -> 900 + 273< RT 1.17763 After starting with .5 mole fraction CO and .25 mole fraction CO2 nad H2 and reacting x mole fraction towards the right, we have the following final mole fractions (note total number of moles is constant at 1) mfs = 8XCO -> .5 + x, XCO2 -> .25 - x, XH2 -> .25 - x, XH2O -> x< ; Because P=1, the mole fractions are equal to the partial pressures and we just need to solve x H.5 + xL extent = SolveAKp == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ E H.25 - xL2 88x Ø 0.0683606<, 8x Ø 6.0612<< which gives final mole fractions or mfs ê. extent 88XCO Ø 0.568361, XCO2 Ø 0.181639, XH2 Ø 0.181639, XH2O Ø 0.0683606<, 8XCO Ø 6.5612, XCO2 Ø -5.8112, XH2 Ø -5.8112, XH2O Ø 6.0612<< Only the first solution is physcially possible and it agrees with the text. ü Problem 11.2 From section 11.6, the reaction SO2 + H1 ê 2L O2 -> SO3 has DG = -94600 + 89.37 T -94600 + 89.37 T

98

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After mixing 1 mole of SO2 and 1/2 mole of O2 , allowing x moles to reaction and equlibrating at 1 atm total pressure, the final mole fractions are 1-x .5 - .5 x x XSO2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ; XO2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ; XSO3 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ; ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 1.5 - .5 x 1.5 - .5 x 1.5 - .5 x Because total pressure is P=1 atm, these mole fractions are equal to partial pressures. The Kp for the reaction is -DG Kp = ExpA ÅÅÅÅÅÅÅÅÅ E ê. 8R -> 8.3144 , T -> 1000< Å RT 1.87579 We find x by solving XSO3 extent = SolveAKp == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅ , xE ÅÅÅÅÅÅÅÅ è!!!!!!!!! XSO2 XO2 88x Ø 0.463196<< If x moles reaction, the heat evolved is x H-DHL ê. 8x -> 0.4631956 , DH -> -94600< 43818.3

ü Problem 11.3 For the reaction CO + (1/2) O2 -> CO2 , the text gives: DGC = -282400 + 86.85 T -282400 + 86.85 T which leads to Kp at 1600C (1873K) of: -DGC KpC = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅ E ê. 8R -> 8.3144 , T -> 1600 + 273< Å RT 2182.81 For the reaction H2 + (1/2) O2 -> H2 O, the text gives: DGH = -246400 + 54.8 T -246400 + 54.8 T which leads to Kp at 1600C (1873K) of:

8R -> 8.3144 . nms x-y 1 + R + ÅÅÅÅÅÅÅÅÅÅÅ Å 2 Thus.Notes on Gaskell Text 99 -DGH KpH = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅ E ê. This information can be used to eliminate x or y. nms Å nm nm nm R-x x ÅÅÅÅÅÅÅÅÅÅ 9XCO Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅx-y . Here we eliminate y by solving elimy = Solve @XO2 == 10-7 ê. ÅÅÅÅÅÅÅÅÅÅ 1 + R + ÅÅÅÅÅÅÅ 1 + R + ÅÅÅÅÅÅÅ 2 2 y x-y 1-y ÅÅÅÅÅÅÅÅÅÅ XO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Åx-y ÅÅÅÅ . XCO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å .x. yD -2 . nO2 -> ÅÅÅÅÅÅÅÅÅÅÅ . XHOH Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ == ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 10000000 H1 + RL 10000000 H1 + RL . nO2 Ø ÅÅÅÅÅÅÅÅÅÅÅ .y. XCO2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅ . nCO2 -> R . pps. nHOH -> y= Å 2 x-y 9nCO Ø x. the mole fractions are as follows (note these are equal to the partial pressures because the total partial pressure is 1 atm): nCO nCO2 pps = 9XCO -> ÅÅÅÅÅÅÅÅÅÅ . nHOH Ø y= Å 2 The total number of moles is no longer constant. XH2 -> ÅÅÅÅÅÅÅÅÅÅ . T -> 1600 + 273< Å RT 10213. it is nm = nCO + nCO2 + nO2 + nH2 + nHOH ê. XO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .2 R + 9999999 x XH2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ . elimyD 9999999 x 9999999 HR .xL 1 99XCO Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å .x. XHOH -> ÅÅÅÅÅÅÅÅÅÅÅÅ = ê. We start with 1 mole of H2 and R moles of CO2 (thus the CO2 to H2 starting ratio is R). nH2 -> 1 .y. After allowing the CO2 reaction to back react by x moles and the H2 reaction to forward react by y moles. ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 10000000 H1 + RL 10000000 H1 + RL 10000000 10000001 + 2 R . nH2 Ø 1 . the mole fractions (which are equal to the partial pressures) are: xpps = Simplify@pps ê. XHOH Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅx-y = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ 1 + R + ÅÅÅÅÅÅÅ 2 H1 + R + ÅÅÅÅÅÅÅ L 1 + R + ÅÅÅÅÅÅÅ 2 2 2 We are told the partial pressure of O2 is 10-7 atm.2 R + 9999999 x 99y Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ == ÅÅÅÅÅÅÅÅ 9999999 In terms of x and R. XCO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅx-y . XH2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅx-y . nm nm nO2 nH2 nHOH XO2 -> ÅÅÅÅÅÅÅÅÅÅ .9999999 x -2 . the number of moles of all components are: x-y nms = 9nCO -> x. nCO2 Ø R .

pp .100 Notes on Gaskell Text Finally. 8x. % 888y Ø 0. pBr -> ÅÅÅÅÅÅÅÅÅÅ = ê. solving the two equilibria for the above two reactions for the two unknowns gives the final answer: SolveA è!!!!!!!! ! è!!!!!!!! ! 9XCO2 == XO2 KpC XCO . nms Å nm nm nm 1-x x x 9pLiBr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅ . xpps . the final reaction proceeds by extents x (given here) and elimy ê.x.4 From Table A-1. nBr Ø ÅÅÅÅ = 2 The total number of moles is nm = nLiBr + nLi + nBr ê. nLi Ø x. pBr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = Åx Åx ÅÅÅÅÅÅÅÅ x 1 + ÅÅÅ 1 + ÅÅÅ 2 H1 + ÅÅÅ L 2 2 2 We are told that the final partial pressure of Li is 10-5 atm which can be used to solve for x: elimx = Solve@pLi == 10-5 ê. nms x 1 + ÅÅÅÅ 2 Thus the final mole fractions (which are equal to the final partial pressures because the total pressure is 1 atm) are nLiBr nLi nBr pp = 9 pLiBr -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . we end with total numbers of moles of x nms = 9nLiBr -> 1 . R Ø 1.29064<< The required initial ratio is this R value. pLi Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅ .763573.x . xD 2 99x Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ == Å Å 199999 The final partial pressures are thus .42.09 T If we start with 1 mole of LiBr of which x moles dissociate. the free energy for the reaction LiBr -> Li + (1/2) Br2 is: DG = 333900 . pLi -> ÅÅÅÅÅÅÅÅÅÅ .42. R<E 88x Ø 0. XHOH == XO2 KpH XH2= ê.763572<<< ü Problem 11. nBr -> ÅÅÅÅ = 2 x 9nLiBr Ø 1 . nLi -> x .09 T 333900 .

37 T If x moles of an initial 1 mole of SO3 decompose we end up with the following numbers of moles: x nms = 9nSO3 -> 1 . R -> 8. pBr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ == Å Å Å Å 200000 100000 200000 which leads to an equilibrium constant of è!!!!!!!! ! pLi pBr Kp = NA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ ê. nSO2 -> x .2361 µ 10-8 < The temperature at which this is the correct equilibrium constant is found by solving -DG SolveA2. pSO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅ .xL Åx ÅÅÅÅÅÅÅÅ 9pSO3 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . nO2 -> ÅÅÅÅ = 2 x 9nSO3 Ø 1 .x .89.2361 10-8 == ExpA ÅÅÅÅÅÅÅÅÅ E ê. nSO2 Ø x. nO2 Ø ÅÅÅÅ = 2 The total number of moles is nm = nSO3 + nSO2 + nO2 ê. nms Å Å Å nm nm nm Px Px P H1 . TE Å RT 88T Ø 1770.3144 . pLi Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . pO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = x ÅÅÅÅÅÅ x 1 + ÅÅÅ 2 H1 + ÅÅÅ L 1 + ÅÅÅ 2 2 2 We can eliminate x from the given information about pO2: .37 T 94600 . elimx 199997 1 1 99pLiBr Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .89.Notes on Gaskell Text 101 ppf = pp ê.x. ppfE pLiBr 82. pO2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅ = ê. nms x 1 + ÅÅÅÅ 2 Thus the partial pressures (mole fractions time pressure P) are nSO3 P nSO2 P nO2 P pps = 9pSO3 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .83<< ü Problem 11. pSO2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .5 The decomposition reaction follows SO3 -> SO2 + (1/2) O2 with free energy DG = 94600 .

8R -> 8.114.533109 è!!!!!!!!! pSO2 pO2 SolveAKp == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅ ê. elimxD 88pSO3 Ø -0.9 T At 3000K. pps . the final partial pressures are: ppsf = Simplify@ pps ê. P Thus. xD 2. the free energy is DG = 945000 . P.05 ê. R -> 8. PE ÅÅÅÅÅÅÅÅ pSO3 88P Ø 0. we solve for the P required to make this pressures give the correct equilibrium constant: -DG Kp = ExpA ÅÅÅÅÅÅÅÅÅ E ê. we solve -DG SolveA0.6 For the reaction N2 -> 2N.102 Notes on Gaskell Text elimx = Solve@pO2 == . + 20. 99x Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅ == ÅÅÅÅÅÅÅÅ -1.114.0263067 == ExpA ÅÅÅÅÅÅÅÅÅ E ê.191944<< If the total pressure is changed to P=1 atm. the new Kp is è!!!!!!!! ! pSO2 pO2 Kp = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅ ê. the equiltibrium constant is .856<< ü Problem 11. P -> 1 ÅÅÅÅÅÅÅÅ pSO3 80.0263067< To find the temperature that gives this Kp. pO2 Ø 0. TE Å RT 88T Ø 790. ppsf .3144 . T -> 1000< Å RT 0. pSO2 Ø 0.9 T 945000 .15 + 1.05<< Finally. ppsf ê.1.3144 .

xL 2Px 9pN2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .0526316<< Thus the partial pressure become: ppf = pp ê.9 ê.53162 µ 10-11 a. PE 88P Ø 3.17846 µ 10-9 << ü Problem 11. pN -> ÅÅÅÅÅÅÅÅÅÅÅ = ÅÅÅÅÅÅ Å 1+x 1+x P H1 .Notes on Gaskell Text 103 -DG Kp = ExpA ÅÅÅÅÅÅÅÅÅ E ê. 8pp ê. pN Ø 0.3144 . x -> 2. 8x Ø 2. P -> 1< . we can solve for x pN2 elimx = SolveA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ == . the final partial pressures are H1 .94272 µ 10-6 b. Thus 2xP finalpN = ÅÅÅÅÅÅÅÅÅÅÅÅ ê.9 P.97137 µ 10-6 << The positive root is the correct one. elimx 88pN2 Ø 0. the free energy is . 8R -> 8. xE pN + pN2 88x Ø 0. ppf . If x moles of an initial 1 mole of N2 dissociates. If pN2 is 90% of the total pressure.xL P 2xP pp = 9pN2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . 8P -> 1 . pp . pN Ø ÅÅÅÅÅÅÅÅÅÅÅÅ = ÅÅÅÅÅÅ 1+x 1+x The value of x to reach equilibrium is pN2 SolveAKp == ÅÅÅÅÅÅÅÅÅÅ ê.1 P<< The pressure is found from pN2 SolveAKp == ÅÅÅÅÅÅÅÅÅÅ pN2 ê.7 From Table A-1. xE pN2 88x Ø -2. T -> 3000< Å RT 3.97137 µ 10-6 <.97137 10-6 < 1+x 5. for the reaction H3 ê 2L H2 + H1 ê 2L N2 -> NH3 .

pN2 Ø 0. pH2 Ø 0.676 which can be used to find the enthalpy .7 TL 2 1 ÅÅÅÅ H-87030 + 31. the x must be x elimx = SolveA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ == 0.xL P H3 x ê 2L P Hx ê 2L P pp = 9 pNH3 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . the pressure must be pNH3 SolveAKp == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ê. T -> 300 + 273 -110.7 T + 25. PE ÅÅÅÅÅÅÅÅ Å 3ê2 pH2 pN21ê2 88P Ø 13.2974<< b.2 . elimx 88pNH3 Ø 0. ppx .2 P<< To equal the equilibrium constant. pH2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . the entropy can be found from DS = -∑T DG ê. pN2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = ÅÅÅÅÅÅ ÅÅÅÅÅÅ ÅÅÅÅÅÅ 1+x 2 H1 + xL 2 H1 + xL If the mole fraction of N2 is 0.8 T Log@TDL 2 The equilibrium constant at 300C (575K) is -DG Kp = ExpA ÅÅÅÅÅÅÅÅÅ E ê. the partial pressures become ppx = pp ê.xL 3Px Px 9pNH3 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . T -> 300 + 273< Å RT 0.3144 . the final partial pressures are H1 . At 300C.666667<< Thus.2 P. xE ÅÅÅÅÅÅ 2 H1 + xL 88x Ø 0.0723638 If x mole of and initial 1 mole of NH3 dissociates.8 T Log@TD + 31.104 Notes on Gaskell Text 1 DG = ÅÅÅÅ H-87030 + 25. pN2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = ÅÅÅÅÅ 1+x 1+x 1+x P H1 .6 P.2. pH2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ . 8R -> 8.

elimxD -0. we solve for R by equating to the equilibrium constant: XPCl5 SolveAKp == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅ ê. we end up with the following mole fractions (which are also partial pressures when P=1 atm): R-x 1+x x pp = 9XPCl5 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .8 From Table A-1. XCl2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = ÅÅÅÅ ÅÅÅÅ ÅÅÅÅ 1+R+x 1+R+x 1+R+x R-x 1+x x 9XPCl5 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .7 ü Problem 11. the reaction PCl3 + Cl2 -> PCl5 has free energy DG = -95600 .2 T -95600 + 235. we can eliminate x by solving x elimx = SolveA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ == 0. RE ÅÅÅÅÅÅÅÅ XPCl3 XCl2 88R Ø 0. T -> 300 + 273 -50906. Starting with 1 mole of PCl2 and reacting x moles. + 0. the partial pressures are ppx = Simplify@pp ê. + 1. XPCl3 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .1 R 99XPCl5 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅ . XPCl3 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å .1 . xE ÅÅÅÅ 1+R+x 88x Ø 0.3144 .8 R 1.371542<< .1 atm. ppx . 8R -> 8. RL<< Thus. XCl2 Ø 0.94 T Log@TD + 235.90168 Let R be the startint ratio of PCl5 to PCl3 . XPCl3 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .7. XCl2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = ÅÅÅÅ ÅÅÅÅ ÅÅÅÅ 1+R+x 1+R+x 1+R+x If the final partial pressure of Cl2 is 0.Notes on Gaskell Text 105 DH = DG + T DS ê.94 T Log@TD At 500K.7. T -> 500< RT 1.1== ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 1+R 1+R Finally.111111 H1.1 + 0.2 T . the equilibrium constant is -DG Kp = ExpA ÅÅÅÅÅÅÅÅÅÅ E ê.

pO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ 2 ÅÅÅÅ .ÅÅÅ 2 2 2 2 a.ÅÅÅ L 5 . pN2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ x ÅÅ .ÅÅÅ 5 .ÅÅÅ 25 H5 . the equilibrium constant is -DG Kp = ExpA ÅÅÅÅÅÅÅÅÅ E ê. pp1E ÅÅÅÅÅÅÅÅÅ è!!!!!!!! pH2 pO2 88x Ø 1.xL P nm = 5 .ÅÅÅ L P H4 * 79 ê 100L P xP 100 2 ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .ÅÅÅ 5 . the final partial pressures (after x moles of reaction) are: x H1 . T -> 1200< Å RT 7. the free energy is: DG = -246400 + 54.ÅÅÅ L 2 2 2 2 The extent of reaction is nearly complete as found by solving pHOH SolveAKp == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ! ê.10839 µ 10-8 .ÅÅÅ L 79 P P H1 . pHOH Ø 0.ÅÅÅ 1-x x 79 25 2 9pH2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅ . pO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . % 88pH2 Ø 1.ÅÅÅ 5 . P -> 1 21 x ÅÅÅÅÅ .222222<< b.8 T At 1200K.9* From the text for the reaction H2 + H1 ê 2L O2 -> H2 O. ÅÅÅÅÅÅ 2 nm 4 * 21 x Å H ÅÅÅÅÅÅÅÅÅÅ . pN2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ x ÅÅ . At a total pressure of 10 atm.xL Px 25 ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 9pH2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . pHOH -> ÅÅÅÅÅÅÅÅÅÅ = ÅÅÅÅÅÅ pO2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ .106 Notes on Gaskell Text ü Problem 11.702222. pHOH Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅ = Åx x ÅÅÅÅÅÅ x 5 .8 T -246400 + 54. pHOH Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = Åx ÅÅÅÅÅÅÅÅ x Å x 5 . the partial pressures are: pp1 = pp ê.ÅÅÅ 25 H5 . the partial pressures are: . pN2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ nm nm nm 21 x P H ÅÅÅÅÅ .0755556. pp = 9 pH2 -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . At total pressure of 1 atm.29391 µ 107 If we mix 1 part H2 to 4 parts air.ÅÅÅÅ .<< which converts to final partial pressures of pp1 ê. pN2 Ø 0. pO2 Ø 0. 8R -> 8.3144 .

02222.10* From Table A-1. the final partial pressures (which are the mole fractions when P=1 atm) are 1-x 1-x 1+2x pp = 9pH2 -> ÅÅÅÅÅÅÅÅÅÅÅ . pHOH Ø 2. pp . pN2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . 8x Ø 2.17. pHI Ø ÅÅÅÅ H1 + 2 xL= Å Å 3 3 3 a. P -> 10 21 x 10 H ÅÅÅÅÅ . Solving for x at equilibrium gives pHI2 SolveAKp == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê.3144 .17.ÅÅÅ L 10 H1 . 8R -> 8.Notes on Gaskell Text 107 pp10 = pp ê. pI2 -> ÅÅÅÅÅÅÅÅÅÅÅ .ÅÅÅ 2 2 2 2 The extent of reaction is nearly complete as found by solving pHOH SolveAKp == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ! ê.503553<. xE Å Å pH2 pI2 88x Ø 0.65 T -8370 . pp10E ÅÅÅÅÅÅÅÅÅ è!!!!!!!! pH2 pO2 88x Ø 1. the equilibrium constant is -DG Kp = ExpA ÅÅÅÅÅÅÅÅÅ E ê.ÅÅÅ 5 .46847<< The first root is the correct one. pO2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ x 2ÅÅÅÅÅÅ . pO2 Ø 0.ÅÅÅ L 5 .3454 After mixing and x moles of reaction. pHOH Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅ = ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ Å ÅÅÅÅÅÅÅÅ Åx x x 5 .<< which converts to final partial pressures of pp10 ê. the reaction H2 + I2 -> 2 HI has free energy DG = -8370 . T -> 1500< Å RT 16.xL 158 10 x 25 9pH2 Ø ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å .65 T At 1500K.50505 µ 10-8 .ÅÅÅ 5 H5 . ü Problem 11. pHI -> ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ = Å Å Å 3 3 3 1-x 1-x 1 9pH2 Ø ÅÅÅÅÅÅÅÅÅÅÅ .755556. % 88pH2 Ø 3. pI2 Ø ÅÅÅÅÅÅÅÅÅÅÅ . the the H2 pressures are slightly different. pN2 Ø 7. Thus the mole fractions (which at P=1 atm are the partial pressures) are .22222<< The O2 partial pressures agree with the solutions in the text.

503553 8pH2 Ø 0.3144 T pH2 pI2 88T Ø 918. pHI Ø ÅÅÅÅ == 7 7 7 This give the correct equilibrium constant at the solution to the following equation -DG pHI2 SolveAExpA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å E == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê.108 Notes on Gaskell Text pp ê. ppf . pI2 Ø ÅÅÅÅ . Now change the temperature such that pHI is five times pH2. pI2 Ø 0. the free energy is DG0 = -117600 + 170 T -117600 + 170 T But this is for CO2 at P=1 atm. for MgO + CO2 -> MgCO3 . b.165482.1 From Table A-1. x -> 0. xD 4 99x Ø ÅÅÅÅ == 7 The final partial pressure become ppf = pp ê. % 1 1 5 99pH2 Ø ÅÅÅÅ .466<< Chapter 12: Reactions Involving Pure Condensed Phases and Gases ‡ Problems ü Problem 12.165482. pHI Ø 0. TE ÅÅÅÅÅÅ Å Å 8. If we add the above reaction to the change in pressure reaction CO2 H1 atm) -> CO2 (P) which has DGP = R T Log@PD R T Log@PD The total DG for the reaction with CO2 at pressure is . Using this information we can eliminate Solve@pHI == 5 pH2 ê.669035< This answers differs from the solution in the text. pp .

DGlD 17490. DG<0 and the reaction proceeds to the right to form MgCO3 . TD 88T Ø 564.DGP -117600 + 170 T .2 Consider the two reactions.Notes on Gaskell Text 109 DG = DG0 .10.1 T The DHmelt is easily found from DHmelt = DGm ê.68<< b. The melting temperature is where these two free energies are equal: Solve@DGs == DGl .R T Log@PD The T for equilibrium when P=0. At temperature above this result. 8R -> 8.6<< At temperature below this result. . P -> 10-2 < . First Ni(s) + H1 ê 2L O2 -> NiO(s) with free energy (in Table A-1): 1 DGs = ÅÅÅÅ H-471200 + 172 TL 2 1 ÅÅÅÅ H-471200 + 172 TL 2 Second Ni(l) + H1 ê 2L O2 -> NiO(s) with free energy (in Table A-1): 1 DGl = ÅÅÅÅ H-506180 + 192. Subtracting these two reactions gives the reaction Ni(s) -> Ni(l) with free energy DGm = Simplify@DGs . MgCO3 will decompose.2 TL 2 1 ÅÅÅÅ H-506180 + 192. TD 88T Ø 1731. The DSmelt is found from . T -> 0 17490.01 is Solve@DG == 0 ê.2 TL 2 a.3144 . ü Problem 12.

3144.3 TL 3 4 2 The difference of these reactions gives a reaction for oxidation of Cr by water as is ÅÅÅÅ Cr + 2 H2 O -> ÅÅÅÅ Cr2 O3 + 3 3 2 H2 with DG = Simplify@DGCr .85 TL 2 H-247500 + 55. TE 2 88T Ø 420.1.957<< b. As in Problem 12. TD 88T Ø 461.1 ü Problem 12. we need to subtract the change in free energy due to reducing the O2 pressure.673<< ü Problem 12. P -> .ÅÅÅÅ R T Log@PD == 0 ê. + 53.85 TL 4 2 The chromium reaction (on molar oxygen basis) is ÅÅÅÅ Cr + O2 -> ÅÅÅÅ Cr2 O3 with 3 3 2 DGCr = ÅÅÅÅ H-1110100 + 247. In air (which is 21 percent O2 .4 The water reaction is 2 H2 + O2 -> 2 H2 O with DGH = 2 H-247500 + 55.3 TL 3 2 ÅÅÅÅ H-1110100 + 247. The decomposition temperature (or equilibrium temperature) is Solve@DG0 == 0 .3 For the reaction 2Ag + (1/2) O2 (1 atm) -> Ag2 O.21< . The new equilibrium temperature is 1 SolveADG0 .11 T -30540 + 66.11 T a. the free energy is DG0 = -30540 + 66.DGHD -245067.110 Notes on Gaskell Text DHmelt .DGm DSmelt = SimplifyA ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅ E ÅÅÅÅÅÅÅÅ Å T 10. 8R -> 8. the oxygen pressure is reduces.1667 T The equilibrium constant is .

0281339 . Thus.12.5 The two key reactions are H2 + Cl2 ->2HCl with DGH = -188200 .Notes on Gaskell Text 111 -DG K = ExpA ÅÅÅÅÅÅÅÅÅ E ê. the equilibrium constant should be -DG K = ExpA ÅÅÅÅÅÅÅÅÅ E ê.2 T The final equilbrium constant from the given composition pHCl2 Kq = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê.80 T -188200 .3144 .07< Å pH 0.DGSnD 144800.8 T and Sn + Cl2 -> SnCl2 with DGSn = -333000 + 118.0098 From DG. 8Pmax Ø 0.3144 .12. pHCl -> . this pressure is the maximum water pressure to which Cr can be heater without oxidizing. 8pH -> . 8R -> 8.5 .131. 8R -> 8. ü Problem 12.00132317<< If the pressure is above this value.4 T -333000 + 118. T -> 1500< Å RT 571174. PmaxE Å Pmax2 88Pmax Ø -0. the reaction is exothermic (DH = -245067 < 0). From the DG result above. DG will become negative and the Cr oxidation will proceed. T -> 900< Å RT 0. The water pressure (when the H2 pressure is 1 atm) at equilibrium is 1 SolveAK == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .4 T The difference of these reactions is H2 + SnCl2 -> 2HCl + Sn with DG = Simplify@DGH .00132317<. .

00063968 The only gas is Mg. ü Problem 12. the lower slope of the 2Fe + O2 -> 2 FeO line means the 2CO + O2 -> 2 CO2 line would have to be rotated to the left to regain equilibium.0252919<. This rotation to the left requires a lower pressure CO. ü Problem 12. The question can be answered. FeO and CO must react. 8R -> 8. There does not seem to be enough information to find the final composition unless one knows the starting composition of Ar and H2 (it is not supplied). 8pMg Ø 0. The text book answer gives the actual equilibrium answer. If the temperature is reduced. however.DGM + DGS -974300 + 179.31 T -67200 + 4.6 It is stated the Fe and FeO are in equilibrium with CO and CO2 at some ratio and at 1273K.7 The key reactions for Table A-1 are 2Mg(g) + O2 -> 2MgO(s) with DGM = 2 H-729600 + 204 TL 2 H-729600 + 204 TL 2 MgO(s) + SiO2 -> Mg2 SiO4 with DG2 = -67200 + 4. thus its pressure is Solve@K == pMg2 D 88pMg Ø -0. Thus in the reaction FeO + CO -> Fe + CO2 .112 Notes on Gaskell Text Thus the mixture is not at equilibrium.2 H-729600 + 204 TL The equilibirum contant at 1400 C is -DG K = ExpA ÅÅÅÅÅÅÅÅÅ E ê.3144 .0252919<< . T -> 1400 + 273< Å RT 0.31 T and Si + O2 -> SiO2 with DGS = -907100 + 175 T -907100 + 175 T The reaction in the problem 4MgO + Si -> 2Mg(g) + Mg2 SiO4 has DG = DG2 . without finding the final equilibrium.31 T . The FeO will eventually disappear. but they might be in error.

Notes on Gaskell Text

113

ü Problem 12.8 CaCO3 can decompose to a gas and a solid by CaCO3 -> CaO + CO2 with DG = 161300 - 137.2 T 161300 - 137.2 T The equilibrium constant is simply K=pCO2; thus -DG pCO2 = ExpA ÅÅÅÅÅÅÅÅÅ E ê. R -> 8.3144 Å RT

ÅÅÅÅÅÅÅÅ T E- ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅ

0.120273 H161300-137.2 TL

**The number of moles of CO2 created as a function of T is nmCO2 = pCO2 V ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. 8V -> 1 , R -> 0.082057< RT
**

0.120273 H161300 -137.2 TL

ÅÅÅÅÅÅÅÅ T 12.1867 E- ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ T

The initial number of moles of CaCO3 were 1 nmCaCO3 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ massCa + massC + 3 massO 0.00999201 1. We need to equate the number of moles of CO2 to CaCO3 and solve for T. That equation can not be solved for T, but a plot over T shows the final temperature to be about 1173

114

Notes on Gaskell Text

Plot@Release@8nmCO2, nmCaCO3<D, 8T, 1000, 1200<, PlotRange -> 80.009, .011<D

**0.011 0.01075 0.0105 0.01025 1050 0.00975 0.0095 0.00925 0.009
**

Ü Graphics Ü This result can be checked by calculating the number of moles of CO2 : nmCO2 ê. T -> 1173 0.0100083 2. The pressure in the vessel at 1000K is pCO2 ê. T -> 1000 0.0551011 3. At 1500K, all CaCO3 hasconverted to CO2 : thus nmCaCO3 R T p = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ ê. 8R -> 0.082057 , V -> 1 , T -> 1500< ÅÅÅÅÅÅÅÅ V 1.22987

1100

1150

1200

ü Problem 12.9 First consider the reaction CoO + SO3 -> CoSO4 which is given in Table A-1 with DG = -227860 + 165.3 T -227860 + 165.3 T The only gas here is SO3 , thus its pressure is determined by the the equilibrium constant

Notes on Gaskell Text

115

-DG K = ExpA ÅÅÅÅÅÅÅÅÅ E Å RT

R ÅÅÅÅÅÅÅÅ T E- ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ -227860 +165.3 T

**thus, the presure is 1 pSO3 = ÅÅÅÅ ê. 8R -> 8.3144 , T -> 1223< K 0.0798805
**

1 Next, this SO3 might decompose according to SO3 -> SO2 + ÅÅÅÅ O2 with 2

DGd = 94600 - 89.37 T 94600 - 89.37 T From the decomposition, the pressure of O2 must be exactly half the pressure of SO2 : 1 pO2 = ÅÅÅÅ pSO2 2 pSO2 ÅÅÅÅÅÅÅÅÅÅÅ Å 2 The equilibrium constant for the decomposition reaction is -DGd K = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅ E ê. 8R -> 8.3144 , T -> 1223< Å RT 4.24436 The final pressures are found from è!!!!!!!! pSO2 pO2 SolveAK == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅ , pSO2 E ÅÅÅÅÅÅÅÅ pSO3 88pSO2 Ø 0.612602<< The total pressure is thus pTotal = pSO3 + pSO2 + pO2 ê. % 80.998784< ü Problem 12.10

1 Consider the three reactions from table A-1: C + ÅÅÅÅ O2 -> CO with 2

87.96 T -202800 .87.14 T 1. xE Å pCOS 88x Ø 0.3144 . The problem means to remove sulfer from the COS. pp . the number of moles removed is pCO SolveAK4 == ÅÅÅÅÅÅÅÅÅÅÅÅ ê.DG2 + DG3 -59100 .9 + x< The equilibrium constant is -DG4 K4 = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅ E ê.9 + x< 8pCOS Ø 0.004 899.65 T 1 1 C + ÅÅÅÅÅ O2 + ÅÅÅÅ S2 -> COS with 2 2 DG2 = -202800 .00396403<< The percentage removed is 100 x ÅÅÅÅÅÅÅÅÅÅÅÅÅ ê. If x moles get removed the final partial pressures are: pp = 8pCOS -> . The pressure of S2 is calculated from reaction 3 and only one gas: .96 T 1 and Fe + ÅÅÅÅ S2 -> FeS with 2 DG3 = -150200 + 52. pCO -> .65 T -111700 . T -> 1000< Å RT 25130. Thus.9.55 T Then the reaction in the problem of COS + Fe -> CO + FeS has DG4 = DG1 .x.004 .55 T -150200 + 52. 8R -> 8.25.004 .116 Notes on Gaskell Text DG1 = -111700 . % Å .x . pCO Ø 0.1007< 2.9.

29067 µ 10-11 << ü Problem 12.1 V nAr = ÅÅÅÅÅÅÅÅÅÅ ê.3144 . 8R -> 0.9 V nHOH = ÅÅÅÅÅÅÅÅÅÅ . which leads to 1 SolveAK3 == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .0408948 + x In terms of x.x The Ar does not react. 8 R -> 0.082057 . x The x values at the two temperature determined from the two supplied mass loss rates . T -> 298< Å RT 0. T -> 298< Å RT 0. pS2 E Å è!!!!!!!! pS2 88pS2 Ø 6. 8R -> 8.082057.0368053 .x ê. T -> 1000< Å RT 126082. Thus the total number of moles of water is .massCa .11 In 1 liter (or 1 minute of time). the mass rate loss per hour rate = 60 x HmassCa + 2 massF . .Notes on Gaskell Text 117 -DG3 K3 = ExpA ÅÅÅÅÅÅÅÅÅÅÅÅ E ê.massOL 1320. V -> 1.9/(R T) moles of enter the reaction and we take x as the number of these moles that react to reach equilibrium.00408948 The moles of HF formed are nHF = 2 x 2x The total number of moles in the equilibrium mixture is nms = nHOH + nAr + nHF 0. thus it has the following constant number of moles . V -> 1.

118 Notes on Gaskell Text x1 = Solve@rate == expt ê. The final variation of free energy with temperature is DG = DH .03788 µ 10-7 << x2 = Solve@rate == expt ê.T DS 282275. expt -> 8. T -> 1100< 146961. Drawing a line through these two slopes. the entropy is -HG2 .10367 µ 10-10 nHF2 K2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ê. expt -> 2. 8R -> 8.28788 µ 10-6 << The equilibrium constants at the two temperatures are nHF2 K1 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ê. T -> 900 282275.013 and the enthalpy is DH = G1 + DS T ê.05074 µ 10-7 The G's at the two temperature are G1 = -R T Log@K1D ê.G1L DS = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 200 123. x2@@1DD ÅÅÅÅÅÅ nms nHOH 1.013 T .3144.3144. T -> 900< 171563.69 * 10-4 D 88x Ø 2.30 * 10-3 D 88x Ø 6. 8R -> 8. G2 = -R T Log@K2D ê. . x1@@1DD ÅÅÅÅÅÅ nms nHOH 1.123.

83742 µ 109 << . 1500<D -440000 -460000 -480000 -500000 -520000 -540000 -560000 900 1000 1100 1200 1300 1400 1500 Ü Graphics Ü The one with the steepest slope is obvious the gas oxidation (the largest -DS is caused by conversion of gas to solid). Similarly.Notes on Gaskell Text 119 ü Problem 12. 8T.8 T . 800. DGiii = -608100 . From the following solutions Solve@DGii == DGi .0 T . DGii = -759800 .13. let me know. DGiii<D . We can plot then all Plot@Release@8DGi .36 T Log@TD + 142. Another approach is to find the intersections of each. From the plot abve (and identifying the gas. the next steepest slope is the liquid oxidation. but it is not clear whcih of (i) and (iii) has the steeper slope. TD 88T Ø 1329. If you have a solution.12* It was not clear what the problem is asking or even if enough information is available.0.68<.13 The three reactions are DGi = -604000 .4 T Log@TD + 317 T .44 T Log@TD + 112. and solid oxidation from the slopes) the melting point is the highest intersection and the boiling point is the lowest intersection. 8T Ø 2. Thus. liquid. DGii .5. ü Problem 12. reaction (ii) is for the gas.

42 .8 atm minus the vapor pressure of Zn): nO2 P pO2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ nO2 + nN2 ê.xL ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 2.79 1.959<< we deduce the (ii) is the gas.pZn 0. The melting point and boiling point are Tm = 928 .x 0.120 Notes on Gaskell Text Solve@DGii == DGiii . and (i) is the solid. we find the non-negligible vapor pressure of Zn: pZn = Exp@lnvapZn ê. T -> 1030D 0.621319 H0.178681 1 The reacion Zn + ÅÅÅÅ O2 -> ZnO has 2 DG = -460200 + 198 T -460200 + 198 T in two moles of air (which as given elsewhere is 21% oxygen) has the following number of moles of O2 : nO2 = . ü Problem 12.x . Tb = 1372 . P -> .42 .8 .89<.58 The partial pressure of O2 and N2 come from mole fraction (between O2 and N2 ) using total pressure due to just those compounds (the given . TD 88T Ø 1371.x and moles of N2 nN2 = 2 * . (iii) is the liquid. 8T Ø 6.42 .95165 µ 106 << Solve@DGi == DGiii . TD 88T Ø 927.14 First. .

981684 ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ ÅÅÅÅÅÅÅÅ 2.2054 ü Problem 12.3144 . The mass oxidized is thus massOx = 2 * . Note the due to the high K.42<< Each mole of oxygen consummes 2 moles of Zn. T -> 1030< Å RT 9. .x The equilibirum constant is -DG K = ExpA ÅÅÅÅÅÅÅÅÅ E ê. P -> . ü Problem 12.9192 Comparing Zn vapor pressure to the two moles of air.8 .42 * massZn 54. the mass of Zn in the vapor is pZn massVap = 2 ÅÅÅÅÅÅÅÅÅÅ massZn .15* No solution.8 29.2 T with equilibrium constant at 600 K of . the reaction is essentailly complete and all oxygen is used up: 1 SolveAK2 == ÅÅÅÅÅÅÅÅÅÅ E pO2 88x Ø 0.2 T -152200 + 207.Notes on Gaskell Text 121 nN2 P pN2 = ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ Å ê.pZn ÅÅÅÅÅÅÅÅ nO2 + nN2 0. 8R -> 8.89965 µ 1012 which can be solved to get extent of reaction x.16* The reaction Hg(l) + H1 ê 2L O2 -> HgO(s) has DG = -152200 + 207.

0000139868. ÅÅÅÅÅÅÅÅÅÅ = 2 2 2 86. the partial pressure of N2 becomes pN2 = P . The vapor pressure of the liquid Hg is pHg = Exp@lnvapHgl ê.85 TL .387 Because O2 is the only gas.pHg ê. pO2E Å ! è!!!!!!!! pO2 88pO2 Ø 0.0000139868<< pO2 = 0.3144 .9934 µ 10-6 . 8R -> 8. ü Problem 12. ÅÅÅÅÅÅÅÅÅÅ .7 of the text which was not covered in class and will not be on the final exam. 0.547409 Finally.122 Notes on Gaskell Text -DG K = ExpA ÅÅÅÅÅÅÅÅÅ E ê. Final Exam ü Problem 1 The water reaction is 2 H2 + O2 -> 2 H2 O with DGH = 2 H-247500 + 55. it must develop partial pressure 1 SolveAK == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅÅ .726289< These results differe from those in the text. 0.273704.45258 The mole fractions are half these values (because there total pressure is 2 atm): pO2 pHg pN2 9 ÅÅÅÅÅÅÅÅÅÅ .85 TL 2 H-247500 + 55. P -> 2 1. T -> 600< Å RT 267. T -> 600D 0.17* This problem is related to section 12.pO2 .

DG will become negative and the Si oxidation will proceed. 8R -> 8.DGHD -412100.Notes on Gaskell Text 123 The silicon reaction (on molar oxygen basis) is Si + O2 -> SiO2 with DGSi = -907100 + 175 T -907100 + 175 T The difference of these reactions gives a reaction for oxidation of Si by water as Si + 2 H2 O -> SiO2 + 2 H2 with DG = Simplify@DGSi .40317 µ 1010 The water pressure (when the H2 pressure is 1 atm) at equilibrium is 1 SolveAK == ÅÅÅÅÅÅÅÅÅÅÅÅÅÅ . T -> 1600< Å RT 1.44199 µ 10-6 <. the reaction is exothermic (DH = -412100 < 0). + 63. From the DG result above. this pressure is the maximum water pressure to which Si can be heated without oxidizing. PmaxE Å Pmax2 88Pmax Ø -8. Thus.3144 . 8Pmax Ø 8.44199 µ 10-6 << If the pressure is above this value.3 T The equilibrium constant is -DG K = ExpA ÅÅÅÅÅÅÅÅÅ E ê. .

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