Name: _______________________________

Student ID: ___________________________

Food Technology Programme

FTE2012 (MOLECULES TO MATERIALS)
Time-Limited Mid-Semester Lecture Assignment
Wednesday, 27th October 2021, 11:00 am
Time allowed: 90 minutes
Instructions:
• You may print-off this Assignment in the first 10 minutes.
• You must have Zoom video on yourself and your workspace open at
all times during the Assignment.
• Answer ALL questions in Section A & any TWO (2) question in
Section B.
• Write your answers in the spaces provided, or on separate sheets, if
you do not have a printer.
• Write your name and Student ID number at the top of each page (in
the space provided). If answering on separate sheets of paper, begin
each question on a new sheet headed with your name and Student ID
(matriculation) number and also write the question number on each
page.
• At end of this Assignment, upload to the DropBox, as in the
Instructions, along with the Declaration.

TOTAL MARKS: 45

Lists of fundamental constants and thermodynamic and mathematical formulae are

given on the last two (2) pages of this Assignment.
Name: _______________________________

Student ID: ___________________________

Section A: Answer ALL questions (Total marks: 35)

1. [10 marks]
Phosphoric acid, H3 PO4 (aq), is a polyprotic acid that is commonly used as a food acid, and
in industrial applications (e.g. etching concrete and rust prevention). Considering only the
first deprotonation, in aqueous solution the phosphoric acid dissociates to give dihydrogen
phosphate:
H3 PO4 (aq) + H2 O ⇋ H2 PO4 (aq)− + H3 O+ (aq) 𝐾a1 = 7.25 × 10−3
𝛼 2 𝑐𝛾±2 [H3 O+ ]
𝐾𝑎1 = 𝛼=
1−𝛼 𝑐
(a) (3 marks)
Calculate the degree of dissociation, 𝛼, and pH, for a 0.010 M solution of phosphoric
acid [you may assume for now that the mean activity coefficient, 𝛾 , is equal to one
for a 0.010 M solution of phosphoric acid].

Alpha = 0.85 (approx); 0.56 exact (-0.5 no noting assumptn)

(-1 arith error – e.g. no sqrt)
pH = 2.07 (approx); 2.23 (exact) (-1 no pH)
No-one was penalised for not noting their assumption that alpha << 1 (whicvh it’s
not. Most people successfully solved the quadratic equation.

(b) (2 mark)
The degree of dissociation of phosphoric acid is affected by the ionic strength.
“Isotonic” sports drinks have an electrolyte concentration roughly equal to 0.15 M
NaCl.
Calculate the mean activity coefficient for a 0.15 M NaCl solution.
Ionic strength, I = 0.15 (for 1:1 electrolyte I = Molarity)
(-0.5 arith error in I)
Log  = -0.509*|1*-1|sqrt(0.15/m ) o

= 0.197;
 = 0.64 (-0.5 not exponentiated)

(c) (2 marks)
Calculate the degree of dissociation and pH for a 0.010 M solution of phosphoric
acid in a 0.15 M NaCl solution. Note any simplifying assumptions, and briefly
explain why the pH changes for phosphoric acid in isotonic saline solutions.

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 2

Name: _______________________________

Student ID: ___________________________

Alpha = 1.34 (approx; impossible value); alpha = 0.75 (exact)

(no penalty of missed impossible value)
pH = 1.87 (approx); pH 2.13 (exact)
(Missing explanation -0.5)
Without exception, those who used the simplifying assumption (alpha << 1) failed to
note that alpha > 1 is impossible.

NOTE added 2022:

Using exact value of alpha (0.75) AND activity coefficient of 0.64 (omitted in answer
above to part (c)) gives
a(H+) = 0.75*0.010*0.64 = 0.048 and pH = 2.32.
This pH should be the same as that calculated in part (a), if the activity coefficient had
been included and not assumed to be 1.0. If the activity coefficient is calculated from the
extent of dissociation (alpha = 0.56), giving concentration of dihydrogen-phosphate and
H+ ions of 0.010*0.56 from which ionic strength (0.01*0.56) and activity coefficient
((0.92) can be calculated, then pH = 2.29  2.32 (but definitely not 2.13).
Several people have worked very carefully through this problem!!!

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 3

Name: _______________________________

Student ID: ___________________________

(d) (2 marks)
Phosphoric acid has three pKa values: 2.16, 7.21 and 12.32. Explain why phosphoric
acid is a good buffering agent at pH 7.21 but a poor buffering agent 4.7. At which
other pH is phosphoric acid a poor buffering agent?
Good buffering at pKa  1 (-1 poor explanation)
~9.7 +/- 0.3 (-1 wrong pH)
Many people threw away a mark by not answered the question about pH and poor
buffering.
(e) (1 mark)
Salts of phosphoric acid, such as KH2PO4 and K2HPO4, are widely used as a
biological buffer for solutions of proteins. You want to buffer at pH 7.2 a 10 mM
solution of the milk protein -lactoglobulin. What concentration of phosphate buffer
would you choose? Note: at phosphate concentrations greater than ~750 mM your
protein will precipitate out of solution

>50 mM as bLg is multiply charged (polyvalent) and this contributes strongly to

ionic strength.
Nobody really nailed this – but we had mentioned elsewhere that proteins because of
charged side chains carry substantial charge. At pH 7.2, -lactoglobulin carries sa
positive charge of ~ +11.

2. [5 marks]

(a) (2 marks)
A surfactant was added to an aqueous solution in contact with air and the change in
surface energy with surfactant concentration, Δ𝛾, was found to be −23 mJ m−2, for a
surfactant concentration of 𝑐 = 0.01 mol L−1. Calculate the surface excess of the
surfactant. The temperature is 25 oC
−Δ𝛾 𝑐𝑗
Γ𝑗 = ×
𝑅𝑇 𝑐 o

Surface excess = -(-23x10-3 J m-2 )x(0.01/1)/(8.314 J mol-1 K-1 x298 K)=9.3x10-8 mol
m-2

Several equations were found – no penalty for using equation where ln (c/co) was
used.

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 4

Name: _______________________________

Student ID: ___________________________

(b) (1 mark)
Give a sketch that shows the relative concentrations of the surfactant in bulk solution
and at the interface.

concentration

Distance from interface

rfaceinterfaceinterfaceconcentrat
ion – many sketched oil drop with surfactant
Almost nobody gave a sketch like above
(c) (2 mark)
The surfactant molecule is palmitic acid, C15H31COOH.

Roughly sketch (squiggly lines are OK) how palmitic acid molecules might arrange
at an air-water interface.

(-1 mark if not so oriented)

What interactions does the palmitic acid make with the water molecules?

Hydrogen bonds: -COOH....:OH2 and -C(OH)=O:...HOH

(-1 mark H bonds not mentioned)

3. [3 marks]

(a) (2 marks)
Briefly describe the difference between a gel and a colloid.
Gel two continuous phases – cross-linked polymer (e.g. jelly, yoghurt)
FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 5
Name: _______________________________

Student ID: ___________________________

Colloid continuous phase and a discontinuous phase (milk: water and casein
micelles, etc.); surface charge repels particles to stabilise emulsion
(Need additional point beyond core definition to 2/2)

Almost everyone gave the same definition “....solvent permeates...” You are
supposed to answer in your own words.

(b) (1 mark)
A log-log plot of viscosity against polymer concentration is shown below.
Describe, possibly using a sketch, the polymer structure that would be
expected in the region marked II.

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 6

Name: _______________________________

Student ID: ___________________________

4. [10 marks]

Brownian
Sedimentation
vB
Velocity

vs
vB = vs

Particle Radius

(a) (1 mark)
Mark on the diagram above the curve that corresponds to Brownian motion and the
curve that corresponds to sedimentation.
(b) (1 mark)
Briefly describe the forces involved in sedimentation.
Gravity vs viscous force; gravity depend on density difference between particles and
solvent

(c) (2 marks)
Sketch the curve(s) on the diagram above that would result if the viscosity of the
system increases, keeping density, gravitational force and temperature constant.
Does this increase in viscosity increase or decrease the critical radius?
See above: Brownian motion unaffected by viscosity – see equation below
Sedimentation velocity decreases with increasing viscosity
Critical radius increases with increasing viscosity – see equation below.
9𝑘𝑇
Brownian motion: 𝑣𝐵 = √
4𝜋𝑎3 𝜌𝑑

2𝑟 2 (𝑝𝑑 −𝑝𝑐 )𝑔
Sedimentation: 𝑣𝑠 =
9
1
 93 2kT  7
a =  
 2 4  (  −  )2 g 2 
Critical radius:  d d c 

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 7

Name: _______________________________

Student ID: ___________________________

I am not a mind reader -- many people failed to note which curve was associated
with increased viscosity. Many people also sketched correctly, but then said critical
radius decreased instead of increased. Remarkably few people turned to the
equations quoted above. Many people also sketch a change in Brownian speed – this
is not affected by change in viscosity – see equation for vB.

(d) (3 marks)
Sketch on the diagram below, the curve(s) that would result if temperature was
increased. Mark clearly the critical radius. Explain your decisions.

vB
Velocity

vs
vB = vs

Particle Radius

Black lines: Small decrease in viscosity with increasing temperature – shifting

sedimentation curve to left. Increase in Brownian motion directly with temperature,
shifting brownian motion curve to right. Critical radius increases, as quantified in
equation above
(-1 Wrong curve for brownian motion)
(-1 for not referring to eqn for Brownian motion)
(-1 not marking critical radius)
(+0.5 if effect on viscosity correctly mentioned)
(-0.5 for incorrect drawing of viscosity change)

Again, I was left to guess which curves were associated with the increased
temperature.

(e) (3 marks)
Brominated palm oil drops (pd = 1150 kg m-3) of radius 100 nm (a) are placed
in a centrifuge where g = 1000 m s-2. The continuous phase is water (pc = 1000
kg m-3). The emulsion viscosity, , is 1.00 mPa s. Assume the emulsion is
stabilised. Temperature = 298 K
(i) Calculate the sedimentation velocity of the drops. In the absence of Brownian
motion, what is the direction of sedimentation?

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 8

Name: _______________________________

Student ID: ___________________________

Vs = 2*(100x10-9)2(1150-1000)(1000)/(9*1x10-3) = 3.3x10-7 m s-1

(-1 for every error of conversion)

Droplets sink

Most people failed to note that the droplets sink. No penalty was levied.
(ii) What is the critical radius at which Brownian speed equals sedimentation
velocity?

r(critical) = ((93*0.0012*1.38x10-23*298.15)/(24*3.1416*1150*(1150-1000)2*10002 )(1/7)

= 3.02x10-6 m
Or take vS and put into equation for VB.

5. [7 marks]
(a) (1 mark)
The potential energies of interaction are illustrated for an emulsion that is stable, an
emulsion that coalesces and an emulsion that flocculates. Label each of these curves.

Stable

Flocculates

Unstable

(b) (2 marks)
For the emulsion that is stable, what have you assumed about thermal energy, RT?
Illustrate this on the diagram above.
Potential VTotal >> RT . Red arrow in diagram.
Hardly anybody got this correct
(c) (2 marks)

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 9

Name: _______________________________

Student ID: ___________________________

If the maximum potential energy of interaction is +3.5 kJ mol-1, is this emulsion

stable at room temperature of 293 K? Justify your answer.
RT = 8.134*293 = 2.4 kJ/mol. The emulsion is only slightly stabilised with respect to
thermal energy, so expect to see flocculation over time.

Hardly anybody calculated RT( = 2.5 kJ /mol) to compare with 3.5 kJ/mol. With RT
similar to VTotal the emulsion is somewhat unstable.

(d) (2 marks)
Nanoparticles are coated in citric acid, a tricarboxylic acid. At neutral to basic pH
the particles stay separated but at pH ~3.5, the particles start to coalesce. Give a
brief description for this behaviour.

At neutral to basic pH the citric acid is deprotonated. The nanoparticles bear an overall
negative charge and therefore repel each other.

At low pH, citric acid becomes fully protonated and neutral. Thus, the nanoparticles
will start to coalesce.

Nobody explicitly noted that citric acid is a carboxylic acid (or even any sort of acid)
and at low pH carboxylic acids get protonated. At best vague statements about zeta
potentials of change in charge.

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 10

Name: _______________________________

Student ID: ___________________________

Section B: Answer any TWO (2) of the following questions 6-9

(Total marks: 10)
6. [5 marks]
(a) (3 marks)
Use the Kelvin equation and the information below to calculate the ratio of vapour
pressure inside a tiny cavity in bulk water with a cavity radius of 100 nm, 𝑝vap (cavity)
∗
to the vapour pressure of the same liquid with a flat surface, 𝑝vap at 𝑇 = 298 K.

Property Value
Surface energy, 𝛾 [mJ m−2 ] 72.8
Molar volume, 𝑉m [cm3 mol−1 ] 18.0

∗ −2𝛾𝑉𝑚 (𝑙)
𝑝𝑣𝑎𝑝 = 𝑝𝑣𝑎𝑝 exp ( )
𝑟𝑅𝑇

p/p* = exp((-2*72x10-3*18x10-6)/(100x10-9*8.314*298))
= 0.989
(-1 for wrong sign)

(b) (2 marks)
If a sample of 100 nm water cavities was introduced into a sample of 10 nm water
cavities, what would you observe as the system approached equilibrium?

The little cavities would coalesce into the large ones due to Laplace pressure differences.

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 11

Name: _______________________________

Student ID: ___________________________

7. [5 marks]
(a) (1 mark)
Rank the three materials in the diagram below, A, B and C, in order of strength. Give
your reason(s) for your ranking.

A>B>C

(b) (1 mark)
Rank the three materials in the diagram below, A, B and C, in order of toughness.
Give your reason(s) for your ranking.

B > C > A (or B > A > C – as all depends on scale of axes)

A
B

(c) (3 marks)
Briefly explain how a biocomposite such as nacre or bone achieves toughness.

See notes

Many people failed to explicitly note that the organic component gives flexibility, but
has low strength and that the inorganic/mineral component gives strength, but although
strong it is brittle.

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 12

Name: _______________________________

Student ID: ___________________________

8. [5 marks]
(a) (3 marks)
The equation below describes the balance of interactions, illustrated in the Figure
alongside, controlling crystallisation:
4 3
G = r g + 4r 2
3
Briefly describe the terms in this
equation and use these to annotate the
diagram alongside.

From the above equation derive the following equations for ∆G* and r*:
16 3 
G* =  and r* = −2
3 ( g )2 g

See notes

If g = −100 kJ mol-1 m-3 and interfacial tension  = 0.25 J m-2, calculate the critical
radius at which G is a maximum. Calculate also G*.

r* = -2*0.25/-100000 = 5.0x10-6 m.

G* = (16/3)*3.1416*0.253/-1000002 = 2.6x10-11 J

This was well done for those who chose to do this question.

(b) (2 marks)
Define heterogeneous nucleation and briefly explain how this may aid nucleation
and control crystal growth, especially for biomineralisation. With respect to the
diagram above, what changes does heterogeneous nucleation cause to the magnitude
of G* and r*?

See notes—heterogeneous nucleation changes interfacial tension.

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 13

Name: _______________________________

Student ID: ___________________________

A number of answers went off into cloud cuckoo land. Words like complementary
interface were rare and many did not read question to comment on effect of delta-G*
and r*.

9. [5 marks]
(a) (2 marks)
The general formula for zeolites is [Mn+]x/n[AlO2]x[SiO2]y ∙ mH2O. What role does each of
the four components play?

See notes

There was frightening similarities of commentary, word for word identical, on the roles
of the four components.

A student reported the formulation of a zeolite as [Fe2+]3[AlO2]3[SiO2]7 ∙ 10H2O. Does

this formula make chemical sense?

Positive charge: (3x2)+(3x3)+(7x4)= +43

Negative charge: (2x3x-2)+(7x2x-2) =-40

Therefore not a valid formula.

(b) (3 marks)
Describe briefly how zeolites are used to separate mixtures of gases. In the adsorption
isotherms shown below, which pair of gases is best separated by this zeolite and which
pair is very poorly separated.

The graphs seemed to be open to two interpretations, so marks were generously

allocated here.However, with similar absorption profiles with time to equilibration, O2
and CO2 are poorly separated.

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 14

Name: _______________________________

Student ID: ___________________________

Best separated: methane and oxygen

Poorly separated: oxygen and carbon dioxide.

+++++++++++++++++++++++++++++++++

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021 15

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Student ID: ___________________________

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FTE2012 Mid-Term Test
Internal

CONSTANTS

Boltzmann’s constant: 𝑘 = 1.38 × 10−23 J K −1

Avogadro′ s number: 𝑁𝐴 = 6.022 × 1023 mol−1
Gas constant: 𝑅 = 8.314 J K −1 mol−1
Standard gravity constant: 𝑔 = 9.8 m s−2
FORMULAE

1. Chemical potential and mixing of solutions

nA
m AIdeal = m A* + RT ln x A x A =:
nA + nB +…
…

m AReal = m A* + RT ln a A a A = g Ax A
D Excess
Mix G
= x A ln g A + x B ln g B
RT

Gibbs-Duhem Equations: å i nidmi = 0 nAdm A + nBdm B = 0

æ ö
For vapour behaving ideally: a = p A and m Real = m * + RT ln ç p A ÷
A A A *
p*A è pA ø
2. Ionic strength, activity and activity coefficient
mB
For solute: m B = m Æ Æ
B + RT ln aB = m B + RT ln g B
mÆ
I
log g ± = -0.509 | Z+ Z- |
mÆ
1 all ions
I=
2 i
å mi zi2 𝛼 = 𝑚𝑖 𝑧𝑖 𝛾±

3. Hydrostatic and osmotic forces

Osmotic pressure: p » i[B]RT ( M r ( A) in kg/mol)

Hydrostatic pressure: 𝜋 = 𝑑𝑔ℎ = 𝜌𝑔ℎ

4. Surface effects
Surface tension: w = g DA
æ g sg - g ls ö æ s ö
Wetting coefficient: k = cosq = ç ÷ = 1 +ç ÷ ( -1 < cosq < +1)
è g lg ø è g lg ø
Spreading coefficient: s = g sg - (g lg + g ls ) = g lg (cosq -1)

Laplace equation (cavity): 4pr pext +8pg r = 4pr pint pint = pext + 2g / r
2 2

Laplace equation (droplet): 4pr 2 pext = 4pr 2 pint +8pg r pext = pint + 2g / r
∗ 2𝛾𝑉𝑚 (𝑙)
Kelvin equation (droplet): 𝑝𝑣𝑎𝑝 = 𝑝𝑣𝑎𝑝 exp ( )
𝑟𝑅𝑇

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021

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FTE2012 Mid-Term Test
Internal

∗ −2𝛾𝑉𝑚 (𝑙)
Kelvin equation (cavity): 𝑝𝑣𝑎𝑝 = 𝑝𝑣𝑎𝑝 exp ( )
𝑟𝑅𝑇
r ghr 2g cosq
Capillarity: Dp = 2g / R = (2g cosq ) / r = r gh g= h=
2cosq r gr
n (s )
Surface excess: nJ = nJ (a ) + nJ ( b ) (
nJ (s ) = nJ - nJ (a ) + nJ (b ) ) GJ = J
s
𝑑𝛾 = − ∑ Γ𝑗 𝑑𝜇𝑗
𝑗
−Δ𝛾 𝑐𝑗
Γ𝑗 = ×
𝑅𝑇 𝑐 o

5. Movement of colloids and particles

Viscosity-average molecular weight: [h] = KMV

k BT
Stoke-Einstein equation: D =
6ph a
9𝑘𝑇
Brownian motion: 𝑣𝐵 = √
4𝜋𝑎3 𝜌𝑑

2𝑟 2 (𝑝𝑑 −𝑝𝑐 )𝑔
Sedimentation: 𝑣𝑠 =
9
1
 93 2kT  7
a =  
 2 4  (  −  )2 g 2 
Critical radius:  d d c 

7. Interparticle forces in emulsions:

− Aa
VA =
Attractive: 12H 0

Repulsive:

8. Rheology (stress and strain):

s ( stress) = m ( elastic constant ) ´ g (strain)

G"(w ) dg
In the limit, w ® 0, ® h given Newton’s Law of Viscosity: s = h
w dt
9. General formulae
Force: d𝐹 = 𝐴d𝑝 or 𝐹 = 𝑚𝑔
Area of a circle: 𝐴 = 𝑟 2
4
Volume of a sphere: 𝑉 = 3 𝜋𝑟 3

Surface area of a sphere: 𝐴 = 4𝜋𝑟 2

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021

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FTE2012 Mid-Term Test
Internal

FTE2012 Molecules to Materials Time-Limited Mid-Semester Lecture Assignment 2021

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