CH E 534 Fundamentals of Oil Sands Extraction (Winter 2021)

Assignment 3

Due date: March 14, 2021 (Sunday) at 17:00. Upload your solution, in the form of a pdf file, on eClass.
• No late submission is accepted.
• Handwriting assignment.
• Answers without clear explanation or analysis will not be graded.
• Illegible work will not be graded.
Note: weight: 22.5% of final mark on assignments, i.e., maximum final mark = 9 marks.

Q1(30 marks)
Answer the following questions by placing a tick besides the most probable answer. Please note that in
order to discourage guessing, the final mark will be based on subtracting incorrect answers from the

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correct answers.

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Q Statement TRUE FALSE
A surfactant with a very low Hydrophile-Lipophile Balance (HLB) value (e.g.

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1-4) is expected to have a high solubility in water.
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In oil sands extraction pH range, the detachment of bitumen droplets from
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sand grain surface in water is thermodynamically unfavourable.
If the contact angle θ is larger than zero, thermodynamically air bubble will
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attach on bitumen in water spontaneously.

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Natural surfactants in bitumen benefits both bitumen liberation and

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aeration in extraction process.
Natural surfactants in bitumen is insoluble in water, thus, adding NaOH
5 can ionize the natural surfactant to facilitate the migration of natural
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surfactant to bitumen/water interface.

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Decreasing bitumen-water interfacial tension is unfavorable for bitumen

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aeration with air bubbles.
Decreasing bitumen-water interfacial tension is unfavorable for bitumen
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liberation from sand grains.

If the surface tension of a liquid in air is less than the interfacial tension of
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the liquid and solid, the liquid could spread on solid surface in air.
Increasing oil sands ore slurry pH by adding NaOH is favorable for bitumen
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liberation from sand grains and bitumen aeration with air bubbles.
Reducing the air bubble size increases the collision efficiency between air
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bubble and bitumen droplet
Surfactant A has a HLB value of 12, and surfactant B has a HLB value of 6.
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The mixture of A and B at volume ratio of 1:1 gives the HLB value of 9.

12 Surface tension is a net attraction force that is parallel to the surface.

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 In general, small air bubbles facilitate bubble-bitumen attachment upon
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collision.
Surfactant molecules prefer to adsorbed at surface or interface in
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comparison to the bulk phase before critical micelle concentration.
If liquid 1 and liquid 2 are miscible, the interfacial tension of liquid 1 and 2
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is 0.

Q2. (10 marks)

The following are the interfacial tensions for the various two-phase surfaces formed by n-octane, water,
and mercury: for n-octane-water, 𝛾 = 50.8 mJ.m−2; for n-octane-mercury, 𝛾 = 375 mJ.m−2. The surface
tension of n-octane, water and mercury is 21.8, 72.8, and 484 mJ.m-2, respectively. Assuming that only
van der Waal interaction between molecules of the hydrocarbon (i.e., 𝛾(𝑛−𝑜𝑐𝑡𝑎𝑛𝑒/𝑎𝑖𝑟) = 𝛾 𝑣𝑑𝑤 ), use
Fowkes Equation to estimate (1) 𝛾 𝑣𝑑𝑤 for water and mercury, and (2) interfacial tension of water and

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mercury.

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Q4. (15 marks)
The interfacial tension of bitumen in contact with sand and water is measured to be 90 and 20 mN/m,

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respectively. The interfacial tension of sand and water is 75 mN/m. The surface tension of sand, water
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and bitumen is determined to be 36, 72.8 and 30 mN/m, respectively. You are asked to:
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1) Calculate the contact angle of a pure water droplet on sand in air; calculate the work of adhesion of
water to sand and cohesion of water in air; and defense or oppose the water spreads on sand surface in
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air spontaneously.
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2) Calculate the water contact angle of a bitumen droplet on sand in water; calculate the work of
adhesion of bitumen to sand and cohesion of bitumen in water; and defense or oppose the bitumen
spreads on sand surface in water spontaneously.
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3) What is the critical contact angle that bitumen droplet spreads on the air bubble surface (i.e., full
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engulfment)?

Q3. (20 marks)

The surface tension of water is 72 mN/m at 25 °C.
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(1) Calculate the Laplace pressure of an air bubble in water with a diameter of 2 cm;
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(2) Assuming to add a non-ionic surfactant (e.g. Sorbitan alkanoate, page 114 in textbook) with a
concentration of 2mM, to the water to stabilized the air bubble. At this concentration, we have a
positive excess. As an average, each surfactant molecule occupies a surface area of 0.7 nm2. Estimate
the change in pressure inside the air bubble with the diameter of 2 cm;

(3) If the surfactant is sodium stearate (page 114 in textbook) with the same concentration and surface
excess to sorbitan alkanoate in Q3.2, what would be the change in pressure inside the air bubble with
the diameter of 2 cm?

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 Q5. (25 marks)
Liberation of bitumen from sand grains is a critical step in bitumen recovery from mineable oil sands. In
a water-based bitumen extraction system, a bitumen cap on a sand grain immersed in water is shown in
the figure below. Clearly a small equilibrium angle of 𝜃, known as contact angle measured at three
phase contact (TPC) point is beneficial for bitumen liberation. The value of contact angle is determined
collectively by the interfacial energies of bitumen-water (𝛾𝑏/𝑤 ), bitumen-sand (𝛾𝑏/𝑠 ) and sand-water
(𝛾𝑠/𝑤 ). For such a system, you are asked to:

(1) show with detailed steps that the energy change (dG) associated with the inward displacement
of TPC point by dR from the solid profile to the dotted profile of bitumen cap at a given
temperature and pressure is given by (5 marks)
𝑑𝐺 = 2𝜋𝑅𝑑𝑅[𝛾𝑠/𝑤 − 𝛾𝑏/𝑠 + 𝛾𝑏/𝑤 cos 𝜃] (1)

where R is the radius of contact area circle of bitumen cap on the sand;

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(2) show that the equilibrium contact angle is linked with interfacial energy by
𝛾𝑏/𝑠 −𝛾𝑠/𝑤

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cos 𝜃 = 𝛾𝑏/𝑤
(2)

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(3) show that equilibrium contact angle, 𝜃, is equal to 0 when the work of adhesion of bitumen on

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sand in water (Wad) is zero.
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(4) sketch the variation of the contact angle defined in Equation (2) with pH.
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(5) explain the possible ways that caustic addition can help improve bitumen liberation by referring
to equation (2) (you are encouraged to make sketches to assist your answer).
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