Exam 2022 Desember

Task 1 Heat and mass balances

Si has a high latent heat. Si is researched as a high temperature Latent Heat Phase Change
Material (LH-PCM) in Thermal Energy Storage batteries.
a. How much energy in kJ will be stored at the melting temperature during melting
and discharged during cooling per kg Si according to the figure.

M(Si)=28.1 g/mol, B=10.8 g/mol, M(O)=16 g/mol

1000 𝑔 𝑆𝑖
𝑔 =35.6 mol
28.1
𝑚𝑜𝑙

Latent heat = heat of fusion: ∆𝑓𝑢𝑠𝑖𝑜𝑛 𝐻 ° = 50 𝑘𝐽/𝑚𝑜𝑙

𝑘𝐽 35.6𝑚𝑜𝑙 1780𝑘𝐽
∆𝑓𝑢𝑠𝑖𝑜𝑛 𝐻 ° = 50 ∙ =
𝑚𝑜𝑙 𝑘𝑔 𝑘𝑔

B has an even higher latent heat, and SiB alloys is hence proposed as the Phase Change
Material. One way to produce this material is to use Si to reduce B2O3 to B and SiO2.
b. Si + xB2O3 = SiO2 + yB , what is X and Y
To balance the equations: x=2/3 and y=4/3
c. How many kgs Si will be oxidized per kg B produced.
M(Si)=28.1 g/mol, B=10.8 g/mol, M(O)=16 g/mol

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 1000 𝑔 𝐵
1kg B=1000g B: 𝑔 = 92.6𝑚𝑜𝑙
10.8
𝑚𝑜𝑙

3 𝑔
92.6𝑚𝑜𝑙 ∙ ∙ 28.1 = 1951𝑔 = 1.95 𝑘𝑔 𝑆𝑖
4 𝑚𝑜𝑙

d. The Gibbs energy is shown in the figure. The Gibbs energy for this reaction is quite
independent of the temperature, why?

Temperature (°C)
1400 1450 1500 1550 1600 1650 1700 1750
20

10

0
ΔG°(kJ)

-10

-20

-30

-40
𝑑𝐺
= −𝑆
𝑑𝑇
The slope of Gibbs energy versus temperature is the negative entropy. The entropy of a reaction
is high if there are different amount of gas species on the reaction versus product side. Since
there is no gas in this reactions, and all species are in the liquid state, the slope is quite flat.

e. Si and B is totally miscible in the alloy and SiO2 and B2O3 is totally miscible in the
liquid slag. The activity coefficients are 1 for all species. For a 10mol% B and 90
mol%Si (XB=0.1 and XSi=0.9), what will be the mol%B2O3 in the slag at 1550°C. As
the slag will contain mainly %SiO2 one can assume that X(SiO2)=1

−∆𝐺° 4500
𝐾 = 𝑒𝑥𝑝 ( ) = 𝑒𝑥𝑝 ( ) = 1.35
𝑅𝑇 8.314 ∙ (1550 + 273)

4⁄ 4⁄
𝑎(𝑆𝑖𝑂2 ) ∙ 𝑎(𝐵2 𝑂3 ) 3 𝑋(𝑆𝑖𝑂2 ) ∙ 𝑋(𝐵) 3
𝐾= 2⁄ = 2⁄
𝑎(𝑆𝑖) ∙ 𝑎(𝐵) 3 𝑋(𝑆𝑖) ∙ 𝑋(𝐵2 𝑂3 ) 3

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 4⁄
𝑋(𝑆𝑖𝑂2 ) ∙ 0,1 3
1.34 = 2⁄
0.9 ∙ 𝑋(𝐵2 𝑂3 ) 3

𝑋(𝑆𝑖𝑂2 )
26,0 = 2⁄
𝑋(𝐵2 𝑂3 ) 3
3⁄
1 2
𝑋(𝐵2 𝑂3 ) = ( ) = 7.5 ∙ 10−3
26,0

f. How would you calculate the energy this process requires ending up with 10 mol and
90 mol Si and 100 mol SiO2 in HSC. You do not have to calculate it, just describe the
method.

OUT sheet
10 mol B at 1550°C
90 mol Si at 1550°C
7.5 mol SiO2 at 1550°C

In sheet:
5 mol B2O3 at 25°C
90+7.5 mol Si at 25 °C
HSC will then calculate the difference in enthalpy between the in and out materials and that is
the energy that is required.

Task 2 Solutions
Task 2a)

a) The ideal entropy of mixing 𝛥𝑖𝑑

𝑚𝑖𝑥 𝑆 is dependent of the temperature only. Δ

It is dependent only on the amount of moles of the components and not of the temperature. This
can be seen from its mathematical expression 𝛥𝑖𝑑
𝑚𝑖𝑥 𝑆 = −𝑅(𝑋𝐴 𝑙𝑛𝑋𝐴 + 𝑋𝐵 𝑙𝑛𝑋𝐵 )

b) The Gibbs of mixing can be expressed based on the following equation for every
solution 𝛥𝑚𝑖𝑥 𝐺 = 𝑅𝑇(𝑋𝐴 𝑙𝑛𝑋𝐴 + 𝑋𝐵 𝑙𝑛𝑋𝐵 )
This is to describe ideal solutions.
c) The excess Gibbs energy of a regular solution is independent of temperature
This is true and can be seen from the definition of the excess Gibbs energy of a regular solution, that is
∆exc
mix Gm = Ωx1 x2

d) The partial molar Gibbs energy of a component in a solution is independent on the

choice of the standard state

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True. The partial molar Gibbs energy 𝐺̅𝑖 of a component in a solution is independent of the choice
of the standard state. This can be seen from the following equation: 𝐺̅𝑖 = 𝐺 𝑜 + 𝑅𝑇𝑙𝑛𝑎𝑖 . The
values of Go and ai depend on the standard state chosen.
e) When a solute B obeys Henry’s law, the solvent A obeys Henry’s law as well.
False. Raoults law behavior of the solvent follows as a consequence of Henry’s law behavior of
the solute. As such solvent follows Raoult’s law.
Task 2b)
Assume that the melt Pb-Bi exhibit regular solution behavior. At 700K the 𝑎𝑃𝑏 is 7.79E-01 for
𝑋𝑃𝑏 = 0.2. Calculate the value of Ω for the system and calculate the activity of Bi in the liquid
solution of 𝑋𝐵𝑖 = 0.7 at 900K.
𝑎𝑃𝑏 7.79𝑒−01
𝛾𝑃𝑏 = = = 3.9
𝑋𝑃𝑏 0.2
(𝑅𝑇𝑙𝑛𝛾𝑃𝑏 ) 8.314 ∗ 700 ∗ 𝑙𝑛3.9
𝛺= 2 = = 12096.6 𝐽
𝑋𝐵𝑖 0.82
Since a regular solution is assumed:
2
𝛺 ∗ 𝑋𝑃𝑏
𝑙𝑛𝛾𝐵𝑖 = = 0.15
𝑅𝑇
𝑎𝐵𝑖 = 0.81
Task 2c)

XZn 0.04 0.06 0.11 0.31 0.59 0.75 0.81 0.95

ΔmixHm 443 654 1126 2455 2700 2177 1775 550

The table show the integral molar enthalpy of a zinc (Zn) and cadmium (Cd) solution at 723K

Would you describe the solution by the regular solution model? Show by calculations.

𝑋𝑍𝑛 0.04 0.06 0.11 0.31 0.59 0.75 0.81 0.95

𝛥𝑚𝑖𝑥 𝐻𝑚 443 654 1126 2455 2700 2177 1775 550
𝑋𝐶𝑑 0.96 0.94 0.89 0.69 0.41 0.25 0.19 0.05
Ω 11536.5 11595.7 11501.5 11477.3 11161.6 11610.7 11533.5 11578,9

We see that Ω is almost constant so the solution can be described with the regular
solution model. The average 𝛺 = 11499.5. This can also be seen if we plot the
𝛥𝑚𝑖𝑥 𝐻𝑚 with 𝑋𝑍𝑛 , that is almost symmetrical to 0.5 composition.

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Task 2d)

The standard molar mixing enthalpy for a liquid mixture of A and B at 800K is given by the
following equation:

ΔmixHm∘ = xA∙ xB ∙[Ω + 313∙(xA - xBl)]

Where the XA and xB is the mol fraction of A and B in the liquid mixture. The regular
solution constant Ω is10300 J/mol. Cp(Bl)800K=29.8 J/Kmol and Cp(Al)800K=30.3 J/Kmol

0.625 mol liquid B and 0.375 mol liquid A was mixed at temperature T1 and after mixing, the
temperature obtained a temperature of 800 K. This was done in an adiabatic wessel.

Assume an ideal molar mixing entropy for the liquid A-B solution at 800K. Calculate Gibbs
molar mixing energy, ΔmixGom, for a liquid solution where xB = 0,625.

Løsning:

We assume that the standard molar entropy of mixing is ideal and we then have the following
equation for the standard molar integral Gibbs energy of mixing at xTl = 0.625 and 700 K:

ΔmixGom = ΔmixHom - T·ΔmixSom = ΔmixHom + RT·[xPb ·lnxPb + xTl ·lnxTl] =

= xPb∙xTl ∙[12600 + 313∙(xPb - xTl)] + RT·[xPb ·lnxPb + xTl ·lnxTl] =

= 0.375·0.625·[10300 + 313 (0.375 - 0.625)] + 8.314·800·[0.375·ln0.375 + 0.625·ln0.625] =

= 2396 - 4400 = - 2004 J/mol

Comment: The negative value for ΔmixGom indicates that the mixing reaction “goes to the right”.

Oppgave 3 – Binære fasediagram

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Figure 1. The K-Na phase diagram

Et forenklet K-Na er skissert i Error! Reference source not found..

a) What is the formula of the intermediate K-Na phase and how does it melt.
It contain 66%Na and 22%K and would then be Na2K. It is an incongruently melting phase, which
means that it is not melting into a liquid with the same composition. The composition is then not
within the primary crystallization area of the phase.

b) What is the composition ranges of the primary crystallization area of the three solid phases
present (given in %Na).
0-29 %Na: K
29-58 %Na: Na2K
58-100 %Na Na

c) Use the phase law to describe the maximum number of phases that can coexist in a binary phase
diagram.
P+F=C+2-R
C-components, F-degree of freedom, P=phases and R is restrictions
Components are 2 that is K and Na
P+F=2+2=4 with no restrictions. If F=0, then P=4: 1 gas phase + 3 condenced phases. As F=0, the
points where you have 3 condensed phases coexisting is then the invariant points. Since F=0 it
alos measn that both temperature and composition of each phase is fixed.

d) Hvilke invariante punkter har vi dette fasediagrammet og hva skjer i disse punktene ved
oppvarming/avkjøling?

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Solution: There is 2 intermediate invariant points in this system:

1. Eutectic reaction at -7 °C: liquid = K(s) + Na2K(s) (liquid is given by the composition at the
eutectic point)
2. Peritectic reaction at 7 °C: liquid + Na(s)=Na2K(s) (liquid composition is given by the liquidus
and the composition of Na is given by the solidus)

The melting of K and Na is however also invariant points, so all together it is 4 invariant points.

e) Show on the figure, and calculate how much you have in each step of the cooling path, if you
start with a liquid given by the point X.

Solution:

Cooling of a liquid with composition x:

97.5 – 67 °C: no change in phase composition: it will be a liquid phase with

composition given by the point X.

67 - 7 °C: Na will start to precipitate and the liquid will contain a decreasingly
amount of Na given by the liquidus composition (red line in figure).

liquid(x) → liquid(p) + Na
𝑥 −𝑁𝑎 𝑥 −𝑝
100% 𝑝 −𝑁𝑎
= 48% 𝑝 −𝑁𝑎
= 52%

If you start with 100mol liquid(x) you now produce 48mol liquid(p) and mol Na

7 °C: liquid(p) + Na → Na2K

𝑁𝑎2 𝐾 −𝑁𝑎 𝑁𝑎2 𝐾 −𝑝
= 84% = 16% 100%
𝑝 −𝑁𝑎 𝑝 −𝑁𝑎

84% er 48mol
48𝑔
16% → 84%16%=9.1mol

Overall accountant

Na Na2K

Step 1 52mol 0mol

Step2 -9mol (48+9.1)=57.1mol

Total 43mol 57mol

Which fits quite nicely with 58% Na2K and 42% Na

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f) The Gibbs energy curves for the system A-B are shown in Figure 2. Draw the binary
phasediagram for the A-B system between the temperatures T1 and T6.

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Figure 2. Gibbs energy curves for the system A-B at 6 temperatures where T1>T2>T3>T4>T5>T6.

Solution (see Figure 3):

T1: The liquid phase has the lowest Gibbs energy over the entire composition area and will be the
stable phase.

T2: The liquid phase has the lowest Gibbs energy over the entire composition area and will be the
stable phase. The solid phase has now the same Gibbs energy at composition A and it means that we
are at the melting pint of A, both phases are present.

T3: The solid phase are stable up to xB=0.2, when 0.2<xB<0.6 a mixture of liquid and solid phase will
give the lowest Gibbs energy, at xB>0.6 the liquid phase will be stable and give the lowest Gibbs
energy.

T4: The solid phase are stable up to xB=0.6, when 0.6<xB<0.85 a mixture of liquid and solid phase will
give the lowest Gibbs energy, at xB>0.85 the liquid phase will be stable and give the lowest Gibbs
energy.

T5: The solid phase has the lowest Gibbs energy over the entire composition area and will be the
stable phase. The liquid phase has now the same Gibbs energy at composition B and it means that
we are at the melting pint of B, both phases are present.

T6: The solid phase has the lowest Gibbs energy over the entire composition area and will be the
stable phase.

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Figure 3. Gibbs energy curves for the system A-B at 6 temperatures where T1>T2>T3>T4>T5>T6 including the tangent
between the liquid and solid phase.

Figure 4. Phase diagram according to Gibbs energy given by Figure 3.

Task 4: MgO-SiO2-Al2O3 phase diagram

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a) Draw the Alkemade triangles in the diagram and add the temperature gradients on the
boundary lines (as the primary precipitation area of 4M5A2S are very small you don’t have
to add the arrows there.)

b) Show on the figure, and calculate how much of each phase you precipitate in each step of
the cooling path down to all the liquid is gone, if you start with a liquid given by the point a.

c) Show on the figure, and show the phases you precipitate in each step of the cooling path
down to all the liquid is gone, if you start with a liquid given by the point b. (You don't have
to calculate the amounts).

d) Draw the phase areas that you have in the SiO2-CaO-Al2O3 phase diagram at 1600° C,
describe the phases you have in the phase areas, and upload the drawing. (You can
abbreviate the CaO to C, SiO2 to S and Al2O3 to A)

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