UNIVERSITY OF GHANA

DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING

MTEN 202: KINETICS PROCESSES AND SURFACE PHENOMENON
(2 CREDITS)

Homework 1

Question 1
Using the Kelvin equation, calculate the pore radius which corresponds to capillary condensation
of nitrogen at 77 K and a relative pressure of 0.5. Allow for multilayer adsorption on the pore
wall by taking the thickness of the adsorbed layer on a non-porous solid as 0.65 nm at this
relative pressure. List the assumptions upon which this calculation is based. For nitrogen at 77 K,
the surface tension is 8.85 mNm-1 and the molar volume is 34.7 cm3 mol-1.

Solution
The Kelvin equation is given by:
𝑃𝑟 2𝛾 𝑉𝑚 cos 𝜃
𝑅𝑇 ln ( ) = −
𝑃𝑜 𝑟
Solving for r (which is the radius of the droplet) is given by:
2𝛾 𝑉𝑚 cos 𝜃
𝑟=−
𝑃
𝑅𝑇 ln (𝑃𝑟 )
𝑜
2 × 8.85 × 10−3 × 34.7 × 10−6 × cos 0
𝑟=− = 1.384𝑛𝑚
8.314 × 77 × ln(0.5)
The pore radius = the radius of the droplet plus the size of the droplet adsorbed on the wall
surface.
The pore radius = 1.384 nm + 0.65 nm= 2.03 nm

The assumptions are:

1. A zero contact angle

2. A closed cylindrical pores

3. A constancy of γ with r,

4. An equivalence of multilayer adsorption at flat and curved surfaces.

1
Question 2
At 20°C the surface tension of benzene is 28.9 mN m-1 and its molar volume is 89.2 cm3 mo1-1.
Determine the relative pressures at which condensation of benzene vapour should begin in a
cylindrical capillary of radius 10 nm if the capillary is

(a) closed at one end

(b) open at both ends.

Assume zero contact angle and neglect adsorption on the walls of the capillary.

Solution
(a) closed at one end
Solving using the Kelvin equation which is given by:
𝑃𝑟 2𝛾 𝑉𝑚 cos 𝜃
𝑅𝑇 ln ( ) = −
𝑃𝑜 𝑟
Solving for ln(Pr/Po) which is given by:
𝑃𝑟 2𝛾 𝑉𝑚 cos 𝜃
ln ( ) = −
𝑃𝑜 𝑅𝑇 𝑟
𝑃𝑟 2 × 28.9 × 10 × 89.2 × 10−6 × cos 0
−3
ln ( ) = − = −0.2116
𝑃𝑜 8.314 × 77 × 10 × 10−10

𝑃𝑟
( ) = 0.8092 ≈ 0.81
𝑃𝑜

(b) open at both ends

Solving using the Kelvin equation which is given by:
𝑃𝑟 𝛾 𝑉𝑚 cos 𝜃
𝑅𝑇 ln ( ) = −
𝑃𝑜 𝑟
Solving for ln(Pr/Po) which is given by:
𝑃𝑟 𝛾 𝑉𝑚 cos 𝜃
ln ( ) = −
𝑃𝑜 𝑅𝑇 𝑟
𝑃𝑟 28.9 × 10 × 89.2 × 10−6 × cos 0
−3
ln ( ) = − = −0.2116
𝑃𝑜 8.314 × 77 × 10 × 10−10

𝑃𝑟
( ) = 0.8996 ≈ 0.90
𝑃𝑜

2
Question 3
The following data refer to the adsorption of n-butane at 273 K by a sample of tungsten powder
which has a specific surface area (as determined from nitrogen adsorption measurements at 77
K) of 6.5 m2g-1.

Relative pressure (p/po) 0.04 0.10 0.16 0.25 0.30 0.37

Volume of gas adsorbed/cm3 (s.t.p.) g-1 0.33 0.46 0.54 0.64 0.70 0.77

Use the BET equation to calculate a molecular area for the adsorbed n-butane at monolayer
coverage and compare it with the value of 32.1 x 10-20 m2 estimated from the density of liquid
butane.
Solution

V(cm3/g) V(m3/g) (1/V)×(P/Po-1) g/cm3 (p/po)

0.33 0.00000033 126262.6263 0.04
0.46 0.00000046 241545.8937 0.1
0.54 0.00000054 352733.6861 0.16
0.64 0.00000064 520833.3333 0.25
0.7 0.0000007 612244.898 0.3
0.77 0.00000077 762729.3342 0.37

900000 -3
slope = 1.9067E6 cm
-3
intercept = 48353.5311 cm
750000
-3

600000
P/V(Po-P) cm

450000

300000

150000

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40

(P/Po) dimensionless

Figure-3.1: A graph expressing the linear relationship of BET plot of n-butane on W-powder.

3
 1
𝑉𝑚 =
𝑠𝑙𝑜𝑝𝑒 + 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡

1
𝑉𝑚 =
1.9067 × 106 𝑔𝑚−3 + 48353.5311 𝑔𝑚−3

𝑉𝑚 = 5.11495 × 10−7 𝑚3 /𝑔

The molecular area of the adsorbed molecule, s (m2):

𝑆𝐵𝐸𝑇 𝑉
𝑠=
𝑉𝑚 𝑁𝐴 𝑎

6.5 𝑚2 /𝑔 × 2.2414 × 10−2 𝑚3 𝑚𝑜𝑙 −1

𝑠= = 47.30 × 1020 𝑚2
5.11495 × 10−7 𝑚3 /𝑔 × 6.022 × 1023 𝑚𝑜𝑙 −1

4
Question 4
The following data refer to the adsorption of nitrogen on 0.92 g of a sample of silica gel at 77 K,
p being the pressure and V the volume adsorbed:

p/kPa 3.7 8.5 15.2 23.6 31.5 38.2 46.1 54.8

V/cm3 (s.t.p.) 82 106 124 142 157 173 197 227

Saturated vapour pressure (PO) = 101.3 kPa.

Plot the adsorption isotherm and use the BET equation to calculate a specific surface area for the
silica gel sample, taking the molecular area of nitrogen as 16.2 x 10-20 m2.

Solution
V(cm3) V(m3/g) (1/V)×(P/Po-1) (g/m3) p (kPa) po (kPa) (p/po)
82 8.91304E-05 425.3298681 3.7 101.3 0.036525173
106 0.000115217 794.9739753 8.5 101.3 0.083909181
124 0.000134783 1309.804803 15.2 101.3 0.150049358
142 0.000154348 1967.843095 23.6 101.3 0.232971372
157 0.000170652 2644.498385 31.5 101.3 0.310957552
173 0.000188043 3219.405843 38.2 101.3 0.37709773
197 0.00021413 3900.169205 46.1 101.3 0.455083909
227 0.000246739 4776.27777 54.8 101.3 0.540967423

5000
3
slope=8537.66994 g/cm
3
4000 intercept=45.2029 g/cm
-3
P/V(Po-P) cm

3000

2000

1000

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
(P/Po) dimensionless

Figure-4.1: A graph expressing the linear relationship of BET plot of nitrogen on silica gel.

5
 1
𝑉𝑚 =
𝑠𝑙𝑜𝑝𝑒 + 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡

1
𝑉𝑚 =
8553.68897 𝑔𝑚−3 + 43.30993 𝑔𝑚−3

𝑉𝑚 = 0.000116511 𝑚3 /𝑔

The specific surface area, SBET (m2):

𝑠 𝑉𝑚 𝑁𝐴
𝑆𝐵𝐸𝑇 =
𝑉

16.2 x 10−20 m2 × 0.000116511 𝑚3 /𝑔 × 6.022 × 1023 𝑚𝑜𝑙 −1

𝑠= = 506.279 𝑚2 /𝑔
2.2414 × 10−2 𝑚3 𝑚𝑜𝑙 −1 × 0.92 𝑔

6
Question 5
The following data list volumes of ammonia (reduced to s.t.p.) adsorbed by a sample of activated
charcoal at 0°C:

Pressure /kPa 6.8 13.5 26.7 53.1 79.4

Volume / cm3 g-1 74 111 147 177 189

Show that the data fit a Langmuir adsorption isotherm expression and evaluate the constants.

Solution

V(cm3) V(m3/g) P/V p (kPa) p (Pa)

74 0.000074 91891891.89 6.8 6800
111 0.000111 121621621.6 13.5 13500
147 0.000147 181632653.1 26.7 26700
177 0.000177 300000000 53.1 53100
189 0.000189 420105820.1 79.4 79400

3
8 slope=4519.15179 m
4x10
3
intercept=60812800 Pa/m

8
3x10
P/V (Pa/m )
3

8
2x10

8
1x10

0 20000 40000 60000 80000

P (Pa)

Figure-5.1: A graph expressing the linear fit relationship of the Langmuir adsorption isotherm
for ammonia on activated charcoal.

7
Evaluating the constants:
1
𝑠𝑙𝑜𝑝𝑒 (𝑔) =
𝑉𝑚
1 1
𝑉𝑚 = = = 𝟎. 𝟎𝟎𝟎𝟐𝟐𝟏𝟐𝟖 𝒎𝟑 𝒐𝒓 𝟐𝟐𝟏. 𝟐𝟖 𝒄𝒎𝟑
𝑠𝑙𝑜𝑝𝑒 4519.1518 𝑚−3

1
𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 (𝐼) =
𝑎 𝑉𝑚
1 1
a= = 3 3
= 𝟕. 𝟒𝟑𝟏 × 𝟏𝟎−𝟓 𝑷𝒂−𝟏
𝐼 𝑉𝑚 60812800 𝑃𝑎/𝑚 × 0.00022128 𝑚

Note
Due by Tuesday March 5, 2019. Please submit personally to me in class. A late submission
will attract a penalty of 10% loss of the total marks each day.