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Assignment 2

This document contains a multi-part assignment on thermodynamics and phase equilibria. It includes questions on: 1) Expressions for partial molar properties of a binary solution and changes in chemical potential with pressure. 2) Equilibrium vapor pressure calculations using standard entropy of vaporization. 3) Conditions for spinodal decomposition and determining spinodal and miscibility gaps. 4) Minimum alloy compositions to prevent oxidation using standard free energies of formation. 5) Stepwise reduction reactions and calculating standard free energy changes. 6) Evaluating partial pressures using standard free energies of formation. 7) Calculating equilibrium constants from tabulated data and determining heats of reaction. 8) Determining

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83 views5 pages

Assignment 2

This document contains a multi-part assignment on thermodynamics and phase equilibria. It includes questions on: 1) Expressions for partial molar properties of a binary solution and changes in chemical potential with pressure. 2) Equilibrium vapor pressure calculations using standard entropy of vaporization. 3) Conditions for spinodal decomposition and determining spinodal and miscibility gaps. 4) Minimum alloy compositions to prevent oxidation using standard free energies of formation. 5) Stepwise reduction reactions and calculating standard free energy changes. 6) Evaluating partial pressures using standard free energies of formation. 7) Calculating equilibrium constants from tabulated data and determining heats of reaction. 8) Determining

Uploaded by

sushil kumar
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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NE241 - Assignment 02

Feb 27, 2024

Question 1 - Thermodynamics Parameters of Binary Solu-


tion
Part A:
The expression of partial molar Gibbs free energy of a A-B system is given as follows:

o o T
g = xA gA +xB gB +kT (xA log(xA )+xB log(xB ))+ΛxA xB (3150xA +2300xB )(1− ) (1)
4000

Where Λ ≡ (cal)/(Avogardo’s conatant) is some energy per atom constant, and gA 0 and
0
gB are the molar gibbs free energy of pure A and B atom respectively. What will be the
expressions of partial molar entropy, enthalpy and chemical potential of B atom in A-B
solution.

Part B:
An iron-Carbon alloy system is held at a temperature of 1273K and 1 atm pressure with
a carbon content of xC = 0.05. If the pressure is increased by 2000 times, what will be
the change in the chemical potential of the carbon. The molar volume and isothermal
compressibility of the alloy can be estimated as follows:

v = 7.32xF e + 3.73xC + 0.15xF e xC Cm3 /mol (2)

β = (1.09xF e + 1.92xC ) × 10−11 P a−1 (3)

1
Question 2 - Equilibrium Vapour Pressure
Mercury’s boiling point is 630K. What will be the equilibrium vapour pressure of mercury
at room temperature. [∆vap S o = 22.47 cal/mol/k]

Question 3 - Spinodal Decomposition


The molar Gibbs free energy of an A-B binary solution can be expressed as follows.

g(xB ) = kT (xA logxA + xB logxB ) + ΩxA xB (4)

Ω is temperature independent positive constant.

Part A:
Will the solution undergo spinodal decomposition when xB = 0.5 and at low enough
T.

Part B:
Evaluate the composition range xB,s,min (T ) < xB < xB,s,max (T ) for which the solution
can undergo spinodal decomposition. Also, calculate the critical temperature over which
the spinodal gap vanishes.

Part C:
At temperature less than critical temperature, if the composition is outside spinodal gap,
is the system at global minimum on free energy vs composition graph. Draw a common
tangent figure and estimate the miscibility gap xB,m,min (T ) < xB < xB,m,max (T ). Outside
the miscibility gap the A-B can stay as a single phase, but inside they coexists as a mixture
of A-rich and B-rich phase. Only write the equation necessary to determine xB,m,min (T )
and xB,m,max (T ), no need to solve them. Also, is the miscibility gap always greater than
the spinodal gap below critical temperature?

Question 4 - Oxidation prevention


Part A:
We are interested in making a Ag-Au alloy to prevent oxidation of Ag to Ag2 O at room
temperature and in air. At room temperature, logγAg ∞ ≈ −5 and the Gibbs free energy of

Ag2 O formation is -2500 Cal/mol. Oxygen content of air is 20.8%. What is the minimum
amount of gold required in the alloy to prevent the oxidation.

2
Part B:
How dry hydrogen gas should be, so that we can use it to heat Ti at 1600K without any
oxidation. At that temperature the gibbs free enrgy of formation of T iO, T iO2 , and H2 O
are -94600, -156300, and -37930 cal./mol. respectively.

Part C:
Chromium plates are bright annealed at 1000K in a wet hydrogen atmosphere. The pressure
of wet hydrogen is 1 atm. What should be the minimum water content in the hydrogen
gas , so that there is no oxidation of chromium. Will the annealed chromium plates be
oxidized when cooled to 500K.

2Cr + 3H2 O = Cr2 O3 + H2 (5)

∆Go = −91050 + 22.80T Cal (6)

Question 5 - Oxidation - Reduction


Part A:
The complete reduction of α − W O3 takes place in four successive stages, according to the
following reactions:
Step 01: 10W O3 + H2 = 10W O2.9 + H2 O; logK1 = −3792T + 4.8268

50 50 −1442.5
Step 02: 9 W O2.9 + H2 = 9 W O2.72 + H2 O; logK2 = T + 1.684

50 50 −801.7
Step 03: 36 W O2.72 + H2 = 36 W O2 + H2 O; logK3 = T + 0.8615

1 −2219
Step 04: 2 W O2 + H2 = 21 W + H2 O; logK4 = T + 1.5809

Find an expression for the standard free energy change for the complete reduction of
αW O3 , i.e. αW O3 + 3H2 = W + 3H2 O, as a function of temperature and, hence, calculate
its value at 1073K.

Part B:
Will a magnesia crucible decompose at 1273K in a vacuum of 0.01 atm?
Given: M gO = M g + 0.5O2 ; ∆Go = 145350 + 0.24T logT − 26.95T Cal

3
Question 6 - Partial pressure
Evaluate the partial pressure of Mg vapour at 1473K for the following reaction:
2M gO + 2CaO + Si = 2M g + 2CaO.SiO2 .

Given: 2M gO + Si = 2M g + SiO2 ; ∆Go = 152600 + 11.37T logT − 99.18T Cal


2CaO + SiO2 = 2CaO.SiO2 ; ∆Go = −30200 − 1.2T Cal.

Question 7 - Equillibrium Constant


Part A:
The equilibrium constants of the following reactions are given for various temperature:
Reaction 01: F eO + CO = F e + CO2 ; K1
Reaction 02: F eO + H2 = F e + H2 O; K2

T(K) 873 973 1073 1173 1873


K1 0.9 0.673 0.535 0.453 0.396
K2 0.332 0.422 0.499 0.594 0.668

Calculate the equilibrium constant of the reaction: CO + H2 O = CO2 + H2 at the above


temperatures. Also calculate the heat of reaction for the production of hydrogen from
carbon monoxide and water vapour, assuming it to be independent of temperature.

Part B:
The equilibrium constants for the decomposition of nickel oxide N iO = N i + 12 O2 are
1.514 ∗ 10−11 and 2.355 ∗ 10−8 at 527o C and 727o C respectively. Calculate the value of
the equilibrium constant at 627o C from the following data:

Cp,N iO = 11.18 + 2.02 ∗ 10−3 T cal/deg/mole in the range 292o - 1527o C


Cp,N i = 7.10 + 1.0 ∗ 10−3 T − 2.23 ∗ 105 T −2 cal/deg/mole in the range 357o C - M.P.
Cp,O2 = 7.16 + 1.0 ∗ 10−3 T − 0.4 ∗ 105 T −2 cal/deg/mole in the range 20o - 2727o C

Part C:
Calculate the equilibrium constant for the reaction N iO + H2 = N i + H2 O at 750o C from
the following data:

N i + 21 O2 = N iO; ∆Go = −58450 + 23.55T cal

4
H2 + 12 O2 = H2 O; ∆Go = −58900 + 13.1T cal

Could pure nickel sheet be annealed at 750o C in an atmosphere containing 95 percent


H2 O and 5 percent H2 by volume without oxidation?
NOTE: All the notations are represented in the same way as the class, unless mentioned
otherwise.

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