TUTORIAL PROBLEMS FOR SURFACES AND COLLOIDS

CHEM3011, semester 1, 2012 (Developed by Dr. Ron Haines)

1.

2.

Calculate the surface area per gram of a catalyst that adsorbs 103 cm 3 of nitrogen
(measured at 1 atm and 0C) per gram of catalyst in order to form a monolayer. The
adsorption was carried out at 195C and the effective area occupied by a nitrogen
molecule at this temperature is 16.2 1020 m2.
(448 m2 g1)
The following data show the amount of hydrogen gas adsorbed per gram of a nickel
catalyst at 25C, for various pressures of H2. The volumes are corrected to 25C and 1
atm.
Pressure /105 Pa
Volume adsorbed/ cm3
g

0.005 0.010 0.015 0.02

0.03

0.05

0.10

0.15

0.48

1.07

1.20

1.33

1.40

0.68

0.83

0.93

(a) Show that the data fit a Langmuir adsorption isotherm:

3.

4.

and evaluate the constants.

(Vm = 1.43 cm3 g1; b = 98 105 Pa1 )
(b) Given the area of an adsorbed hydrogen molecule is 13 1020 m2, calculate the
specific area of the nickel in m2 g1.
(4.6 m2 g1 )
Study the two experimentally determined isotherms below, then answer the questions
following them.

(a) Which of the two isotherms indicates that the maximum adsorption occurs when a
monolayer of adsorbate molecules is formed? Which isotherm is typical of multi
layer adsorption?
(b) Which of the two isotherms could best be described by the Langmuir isotherm?
(c) Which theoretical isotherm would most likely describe isotherm (ii) above?
(d) Can you tell from the apparent adsorption isotherm whether chemisorption or
physisorption is occurring?
(a) Describe the types of intermolecular forces responsible for physisorption of a gas
on a solid.
(b) Describe the types of intermolecular forces responsible for chemisorption of a gas
on a solid.
(c) A commonly used (though not necessarily foolproof) criterion for judging whether
chemisorption or physisorption is occurring is to look at the enthalpy of adsorption.
Values more negative than 40 kJ mol1 indicate chemisorption, values less

CHEM3011 Surfaces and Colloids, Tutorial Problems (2012) Page 1

5.

6.

negative than 25 kJ mol1 indicate physisorption. Why should the transition lie in
this particular range of enthalpy changes?
The data below show the amount of ethyl chloride adsorbed on a sample of charcoal
at 0C at several pressures.
p/torr

20

50

100

200

300

grams adsorbed

3.0

3.8

4.3

4.7

4.8

(a) Using the Langmuir isotherm, determine the fraction of the surface covered at
each pressure.
(b) If the area of the ethyl chloride molecule is 0.260 nm 2 what is the surface area of
the charcoal?
((a) 0.61, 0.77, 0.87, 0.95, 0.97 (b) 1.2 104 m2)
The data below show the volume of gaseous butane (corrected to 0C and 1 atm)
adsorbed on a 1 gram sample of nickel oxide at 0C and at several pressures.
p/kPa

7.543

11.852

16.448

20.260

22.959

V/cm3

16.46

20.72

24.38

27.13

29.08

(a) Using the BET isotherm, calculate the volume of butane adsorbed (measured at
0C and 1 atm) when the NiO is covered by a monolayer. The vapour pressure
above a thick layer of liquid butane on NiO is 103.24 kPa.
(b) If the crosssectional area of a single butane molecule is 44.6 1020 m2, what is
the surface area per gram of NiO powder?
((a) 27.7 cm3 (b) 331 m2)
7.
From a consideration of Gibbs energy, explain why a drop of liquid will take on a
spherical shape in the absence of any external forces.
8.
An early morning mist is clearing at an air temperature of 10C. The saturated vapour
pressure of water is 1227 N m2 and its surface tension is 74.55 mN m 1, both at this
temperature. Calculate the vapour pressures of two mist droplets with diameters 20
nm and 200 nm.
(1375 Nm2, 1242 Nm2)
9.
(a) According to the Kelvin equation, will the vapour pressure inside a small bubble of
vapour contained in a liquid be higher or lower than the vapour pressure above a
flat surface of the liquid?
(b) If one relies on the formation of bubbles of pure vapour, the temperature required
to induce boiling in water at atmospheric pressure is almost 200C. Explain this in
terms of the Kelvin and Laplace equations.
(c) Explain the effect of the addition of porous solids (such as boiling chips) to the
liquid in this context.
10. The surface tension of toluene at 20C is 0.0284 N m 1 and its density at this
temperature is 0.866 g cm3. What is the radius of the largest capillary that will permit
the liquid to rise 2 cm?
(0.0334 cm)

11. Sap was once thought to rise up the trunk of a tree mainly by capillary action. How
narrow would the internal channels in the trunk have to be to allow the sap to rise to
the top of a 30m high tree? Assume the density of the sap is 1.0 g cm 3, the contact
angle is zero and the surface tension, = 73 103 N m1.
(radius = 0.5 m)
12. Surface and interfacial tensions can be used to determine whether one liquid will
spread over another, or form isolated drops on the surface.

CHEM3011 Surfaces and Colloids, Tutorial Problems (2012) Page 3

The work of cohesion (WA) is the work required to separate a cylinder of pure liquid A
into two cylinders. This requires the formation of two new surfaces of unit area and so
WA = 2A where A is the surface tension of the liquid.
The work of adhesion (WAB) is the work required to separate two cylinders of liquids A
and B joined by an interface of unit area, WAB = A + B AB where AB is the
interfacial tension between the two liquids.
A liquid, A, will spread on another liquid, B, if the initial spreading coefficient S (= WAB
WA) is positive or zero, that is, if the liquid A adheres more strongly to liquid B than it
coheres to itself.
At 20C the interfacial tension between benzene and water is 35 mN m 1. For water
= 72.75 mN m1, and for benzene = 28.85 mN m1. Calculate:
(a) the work of cohesion for benzene and for water,
(b) the work of adhesion between benzene and water,
(c) the initial spreading coefficient for benzene on water. Will benzene spread over
water?
((a) benzene: 57.7 mJ m2, water: 145.5 mJ m2 (b) 66.6 mJ m2 (c) 8.9 mJ m2)

13. An insoluble monolayer of the diethyl ester C 2H5OOC(CH2)11COOC2H5 was spread on

water at 1C and values of surface pressure () and area per molecule (A) were
recorded during a compression and are listed in the table below. Plot against A, and
interpret the resulting graph. By plotting A versus at low surface pressures (say <
1 mN m1) obtain an approximate value of the Boltzmann constant.
A/nm2molec.1 /mN m1

A/nm2molec.1 /mN m1 A/nm2molec. /mN m1

1

0.19
15.4
1.00
10.0
5.67
0.6
0.24
14.1
1.36
5.0
7.00
0.5
0.31
14.0
1.60
3.3
8.88
0.4
0.71
13.5
2.00
2.0
18.5
0.2
0.82
13.5
3.10
1.0
37.8
0.1
0.92
11.6
4.06
0.8
14. (a) It is found that 0.106 mg of stearic acid (CH 3(CH2)16COOH) covers 500 cm2 of
water surface at the point where the surface pressure just begins to rise rapidly as
the surface area is reduced. Estimate the crosssectional area per stearic acid
molecule. Given the density (0.85 g cm 3) of stearic acid and assuming the total
volume of stearic acid remains constant when it is dispersed into the monolayer,
calculate the thickness of the film.
(2.23 1019 m2 molecule1, 2.5 nm)
(b) One hundred grams of oleic acid (CH3(CH2)7CH=CH(CH2)7COOH), which forms a
condensed film on water, is poured on the surface of a lake, where the spreading
film can be seen if the water is rippled in the wind. The crosssectional area of
oleic acid is about 22 1020 m2. What will be the maximum diameter in meters of
a circular film produced from 100 g of acid?
(244 m)
15. The following surface tensions () were measured for aqueous solutions of npentanol
at 20C:
c /mol dm3 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.08 0.10

/mN m1

72.6

64.6

60.0

56.8

54.3

51.9

49.8

46.0

43.0

CHEM3011 Surfaces and Colloids, Tutorial Problems (2012) Page 5

Calculate surface concentrations and the average area occupied by each adsorbed
molecule for bulk concentrations of 0.01, 0.02, 0.04, and 0.08 mol dm 3. Plot a A
curve for the adsorbed npentanol monolayer and compare it with the corresponding
curve for an ideal gaseous film.
(for c= 0.01 mol dm3, 2.2 106 mol m2, A 0.75 nm2)

16. The following surface tensions were measured for aqueous solutions of the nonionic
surfactant CH3(CH2)9(OCH2CH2)5OH at 25C.
Conc. / 104 mol L1

0.1

/ mN m1

63.9 56.2 47.2 41.6 34.0 30.3 29.8 29.6 29.5

0.3

1.0

2.0

5.0

8.0

10.0 20.0 30.0

Determine the critical micelle concentration and calculate the area occupied by each
adsorbed surfactant molecule at the critical micelle concentration.
(9 104 mol L1, approx. 4 1019 m2)

17. The concentration of Na2SO4 required to flocculate a hydrated ferric oxide sol is
0.0092 mol L1 but a very much lower concentration of K3Fe(CN)6 is required.
(a) What is the sign of the charge on the particles of the original sol ?
(positive)
(b) Calculate the approximate concentration of KCI required to flocculate the sol. (0.59
M)

18. Given that for an aqueous solution of a symmetrical electrolyte at 25C

/m1 = 0.329 1010/m1 M1/2 (where c is in mol L1 and M = mol L1)

where
c = concentration,
Z = ionic charge number,
= reciprocal of thickness of the double layer in m 1,
calculate the thickness of the diffuse electric double layer for a negatively charged
solid surface in contact with the following aqueous solutions at 25 C:
(a) 0.1 mol L1 KCl
(1.0 nm)
1
(b) 0.001 mol L
KCl
(10 nm)
1
(c) 0.1 mol L
MgSO4
(0.48 nm)
19. The zeta potential () of a particle of radius a, suspended in a medium of viscosity
and permittivity is related to the electrophoretic mobility uE by the equations:
uE = /1.5 (Hckel equation, for a < 0.1)
uE = /
(Smoluchowski equation, for a >100)
The reciprocal of the thickness of the double layer in a 1:1 electrolyte (such as KCl)
can be calculated from:
/m1 = 0.329 1010/m1 M1/2 (where c is in mol L1 and M = mol L1)
where
c = concentration,
Z = ionic charge number,
= reciprocal of thickness of the double layer in m 1,
The electrophoretic velocity of a nonconducting particle, diameter 6 106 m,
dispersed in 1 103 mol L1 aqueous KCl solution was found to be 27.7 106 m s1
in a potential gradient of 10 Vcm1. The viscosity of the medium is 1 103 kg m1s1
and its permittivity is 7.999 1010 F m1. (Note: F stands for Farad, the SI unit of
capacitance; F m1 is the SI unit of permittivity)
(a) Calculate uE
(27.7 109 m2 V1 s1 )

CHEM3011 Surfaces and Colloids, Tutorial Problems (2012) Page 7

(b) Which of the two given equations should be used to estimate the zetapotential of
the particle?
(Smoluchowski)
(c) Use the chosen equation to estimate the zetapotential of the particle. (35 mV)

CHEM3011 Surfaces and Colloids, Tutorial Problems (2012) Page 9