Adsorption: Chem Academy

CHEM ACADEMY 1 Adsorption (Solution)
ADSORPTION
EXERCISE - I
Single Answer Correct Type
1. (a) Reaches a constant giving value.
Q
2. l n   vs. Q
P
 Q  1
CHEM ACADEMY
K 
Q

 1 Q  P
1 Q 
 k 
P  k 
Q
ln    ln k  ln(1  Q)
P
Q  1
ln(1  Q)  ln(1)  ln(Q)

=O–Q
ln(1  Q)   Q
Q
ln    ln ln K  Q
P
y = C + mx
slope = –1
3. Refer to Text.
4. Extent of adsorption of a gas on a solid is favoured at low temperature and high pressure.
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5. Factor affecting adsorption of a gas over a solid surface-
(a) Temperature (b) Critical temperature
(c) Pressure (d) Nature of gas
(e) Nature of surface area (f) Extent of surface area
6. Physical adsorption with T Chemical adsorption
Eq.
x
7.  kp1/ n
m
x 1
log  log k  log P
m n
1
Slope of line =
n
8. CHEM ACADEMY
(c) The value of
1
n
is between 0 to 1 all cases
9. (b) NH3 > CO2 > H2

Refer Q.11
10. All are correct
11. Extent of adsorption is maximum for a Polar gas over a non-polar gas due to stronger interaction in
Polar species than in a non-polar gas.
NH3  Polar
H2, N2, O2  Non-Polar
 Max. Adsorption  NH3 (a)
Among polar or non-polar, secondary factor is molecular weight.
H 2  N 2  CO  CH 4  CO 2  HCl  NH 3  SO 2
Order:     
Non  polar Polar
Adsorption of CH4 is favoured over CO, due to its larger surface area per molecule.
Extent of adsorption of NH3 is favoured over HCl due to H-bonding.
12. Refer to Text
13. Refer to Text
14. Refer to Text
15. Sorption: A process when adsorption and absorption takes place simultaneously.
16. Vander Waal interactions exists in case of physical adsorption.
17. Langmuir adsorption isotherm (in terms of freundlich adsorption)
x

m
x
 k 3
m
x  kP 
 k3  
m  1  kP 
x  ap 
 
m  1  bp 
P 1  b.P

x/m a
P 1 b
  .P
x/m a a
x
18.
m
 kP1/ n
x
CHEM ACADEMY
1
log
x
m
log  log k  log P
m n
log P
x 45º
log
19. m
log P
x 1
Using: log  log K  log P
m n
1 1
Slope = tan 45º = 1
n n
x
 kP1/ n
m
x
 kP
m
x
 (10)(0.5)
m
5
 10   5g
10
20. Proceed as in the last example, we have
 15  103 J mol1 
  (1013 s) exp 
 (8.314 J K 1mol1 )(1000 K) 
 
 (1013 s)e1.81  6.11013 s
0.5 100
21. Number of moles in 0.5 M, 100 mL solution =  = 0.05 moles
1000
Number of moles in 0.49 M, 100 mL solution = 0.049 moles
Hence, Number of moles adsorbed = 0.050 – 0.049 = 0.001 moles
= 10–3 × 6.02 × 1023 = 6.02 × 1020 molecules
Total Area
Surface area adsorb by each molecules = No. of molecules
CHEM ACADEMY
=
3.01102
6.02 10 20
m2
1
 1018
2
= 0.5 × 10–18 = 5 × 10–19 m2
22. vmono = 130 cm3 g–1 = 0.130 dm3 g–1; Vm = 22.144 dm3 mol–1
6.022 1023 mol1
Number of molecules contained in vmono = 3 1
 0.130dm3g 1  3.49 10 22 g 1
22.414 dm mol
Area of cross section of one molecule = 0.162 (nm)2 = 0.162 × 10–18 m2
 Area of covered by 3.49 × 1022 molecules, viz,
surface area = 0.162 × 10–18 m2 × 3.49 × 1022 g–1 = 565.8 m2 g–1
c d
23. 2   [Gibbs adsorption equation]
RT dc
(1.00 104 mol dm 3 )(103 dm3 m 3 )
 1 1
(0.080N m 2 mol1 )
(8.314 J K mol )(298K)
= 3.2 × 10–6 mol m–2
The average surface area available for each molecule
1
 6 2 23 1
 5.2 1019 m 2
(3.2 10 mol m )(6.022 10 mol )
24. K = 3.75 kPa–1 ;  = 10% = 0.1
Using, Langmuir adsorption isotherm-
   1
k 
1   P
 0.1  1
P  kPa 1
 1  0.1  3.75
1 1
  kPa
9 3.75
= 29.6 Pa
25. Since, Adsorption is an Exo-thermic process. So, on increasing temperature, rate of physical
adsorption decreases.
26. During adsorption, entropy of gas decreases.
27. Adsorption of methylene blue on activated charcoal at 25°C is an example of physical adsorption,
which is accompanied by a decrease in enthalpy.
28. Refer to Text.
x 1
29. log

m
CHEM ACADEMY
 log k  log P
n
Y = c + mx
 x
 log  vs(log P) gives a straight line.
 m
30. Refer to text.
31. The variation of pressure with temperature for given amount of adsorption, is called
“Adsorption Iso-stere”.
x
‘T’ vs ‘P’ at constant  
m
32. Refer to text
33. Refer to Q. No. 11
34. Refer to Q. No. 11
35. Refer to text.
B C
A
x
36.  
m
O P
x
OA     (P)1
m
1
x
AB     (P) n
m
x
BC     (P)0
m
x x
m m
37.
T T
Physical Adsorption Chemical Adsorption
T3
x CHEM ACADEMY T2
T1 x 1
38. m Since,   
m T
Hence, On increasing temperature, extent of adsorption decreases.

T 1 > T2 > T3
x 1
39. log  log k  log P
m n
1
m  tan 45º  1 
n
Log k = c = 0.6020  k=4
1
x
Hence,    k.(P) n
m
x 1
   (4)  (1)  4
m
40. Refer to Q. No. 37.
41. Saturation Stage
42. Correct answer is (d)
44. Refer to Text
   1
46. 'P'   
1   k
 0.95  1
  kPa
 1  0.95  0.9
0.95 1
  kPa  21.1
0.05 0.9
47. At saturation, if pressure is further increased multilayer formation takes place.
x 1
48. log  log k  log C
m n
1
M  slope  0 
n
49.
50.
Repeated
CHEM ACADEMY
On increasing temperature, extent of adsorption decreases.
So G becomes more positive from a negative value.
51. For a gas, represented by “An”
Langmuir adsorption Isotherm is described by
1
(kP) n
 1
1  (kP) n
When n = 2
kP

1  kP
52. Langmuir Isotherm
60mg
53. Number of moles of CH3COOH =
60 g mol1
CH3COOH
60 10 3 g
M.wf = 24 + 4 + 32 = 60 g mol–1 = = 10–3 moles
60 g mol1
Now, 100 m2 contains  –3
 10 moles
103
1m2 contains 
 2
 105 moles
10
1 cm2 (or 10–4 m2) will adsorb = 10–5 × 10–4 = 10–9 moles
54. Refer to Text.
55. Freundlich Adsorption equation is
x 1
P n n>1
m
x 1
 KP n
m
x 1
log  log KP n
m
log mx  log K  n1 log P
y c mx
|log (x/m)|
|log P|
CHEM ACADEMY slope = 1/n intercept = log K.
Correct option is (D)

EXERCISE - II
One or More Than One Correct Answer Type
# Except Q.No. 5 & 10, Rest all questions are based on peculiar properties of Adsorption, which are
already described in the Literature part and are also discussed in Ex. I.
5. (b) According to Freundlich
1
x
 k.(P) n
m
(d) According to Langmuir Adsorption Isotherm-
x x
   k '. (Proportionality constant)
m m
x  kP 
 k '.   k = distribution co-efficient
m  1  kP 
x a.P
 k´. k = a
m 1  bP
k=b
10. a, b, d
N2 is Physically adsorbed at low temperature (83 K) and chemically adsorped at high temperature
(773 k).
EXERCISE - III
Numerical Answer Type and Subjective Questions
1. K = 0.36 kPa–1
P = 1 kPa
   1
k 
1   P
kP
 
1  kP
0.36 1
  = 0.265
1  (1)(0.36)
   1
2. Now, k  Langmuir adsorption isotherm in terms of volume
1   P
 kP 
  
 1  kP 
CHEM ACADEMY
1 1  kP


kP
1 1
 1
 kP
V Vmono 1
   1
Vmono V kP
 Vmono 1 
  1 
 V k.P 
P
Multiplying by V
mono
P P 1
 
V Vmono k.Vmono
Y = MX + C
1
Slope 
Vmono
P/v(P0 – P)
3.
P/P0
4.   0e Ea / RT
(a) Ea = 15 kJ mol–1
 15 103 Jmol1 
  (1013 s) exp 
 (8.314 J K mol )(298K) 
 1 1
 
 (1013 s)e6.05  4.2 1011 s
(b) Ea = 150 kJ mol–1
 150  103 J mol1 
  (1013 s) exp 
 (8.314 J K mol )(298K) 
 1 1
 
 (10 13 s)e60.5  1.9 1013 s  600, 000 years
5. Repeat
6.
CHEM ACADEMY
 2 is equal to N/(NAA) where N is the number of molecules contained in a film of area A.
2 


10 103 Nm1
 4.04 106 mol m 2
RT (8.314 J K 1 mol1 )(298K)
A 1 1
    6 2 23  1
 4.11 1019 m 2  0.411 nm 2
N  2 N A (4.04 10 mol m )(6.022 10 mol )
7. From the equation

 /(103 N m 1 )  72.0  0.5 (c/mol dm–3) + 0.2 (c/mol dm–3)2
we get
d(  /103 N m 1 )
3
 0.5  0.4(c / mol dm 3 )
d(c / mol dm )
Thus, at c = 0.5 mol dm–3, we have
d
= (–0.5 + 0.4 × 0.5)(10–3 N m–1 mol–1 dm3)
dc
= – 0.3 × 10–3 N m–1 mol–1 dm3 = –0.3 × 10–6 N m2 mol–1
c d
hence,  
RT dc
(0.5 mol dm 3 )
 1 1
(0.3  106 N m 2 mol1 )
(8.314 J K mol )(298 K)
= 6.05 × 10–11 mol dm–3  6.05 × 10–12 mol cm–2
8. Let M be the molar mass of X. Thus,
(107 g)
Amount of X =
M
  *    0.20 dyn cm 1
Using the two dimensional ideal gas law,   RT , we have
RT (8.314 107 dyn cm K 1 mol1 )(298 K)
 
 0.20 dyn cm 1
= 1.239 × 1011 cm2 mol–1
Now for 200 cm2 surface area, the amount of the compound X is
(200 cm 2 )
11 2 1
 1.614 109 mol
(1.239 10 cm mol )
(107 g)
Hence,  1.614  109 mol
M
or CHEM ACADEMY
M
(107 g)
9
(1.614 10 mol)
 61.94 g mol1
9. From the two-dimensional ideal gas law   RT , we have

RT (8.314 N m K 1mol1 )(298 K)
 
 (0.005 N m 1 )
= 4.955 × 105 m2 mol–1
Amount of protein,
(0.001 g)
n
(60000 g mol 1 )
Area occupied by the amount n
 0.001 
 mol  (4.955  105 m 2 mol1 )  82.6 104 m 2 = 82.6 cm2.
 60000 
10. Repeat
11. Surface excess ‘  ’ = 3 × 10–10 mol dm–2
Temperature ‘T’ = 298 K.
(Vº) surface tension of pure solvent = 0.075 Nm–1
Using  ·   RT
RT  1
   
  
 RT  
= 8.314 J K–1 mol–1 × 298 K × 3 × 10–10 mol dm–2
= 7432.7 × 10–10 J dm–2
= 7.43 × 10–7 (N.m) dm–2
= 7.43 × 10–7 (N × (10 dm)) dm–2
Surface film Pressure   7.43 106 N dm 1

  Vº  V V = Surface tension of solution.
V = Vº – 
= 0.072 Nm–1 – 7.43 × 10–6 N (10–1 m)–1
= 0.072 – 7.43 × 10–5 Nm–1
= 0.0719 Nm–1
RT
12. 

RT

1 RT




CHEM ACADEMY
 0.01 Nm 1
Surface Excess '  '  RT 
8.314 Nm k 1 mol 1  298 K
= 4.04 × 10–6 mol m–2
13. surface film pressure = 1 Nm–1
RT


8.314 N m k 1 mol1  298K
= = 2.4776 × 103 m2 mol–1
1 N m 1
Hence, Number of moles occupying 2.48 × 103 m2 area = 1 mol
1
 Number of moles in 1 m2 area (104 cm2) = moles
2.48 103
1102
Number of moles in 100 cm2 area = moles
2.48 103 104
given mass
Number of moles = molar mass
‘w’ given mass = 0.4 × 10–5 × 242 = 97.6 × 10–5 = 9.76 × 10–4 g.
   1
14. P 
 1   k
 0.2  1
  kPa
 1  0.2  1.25
0.2 1000
  Pa
0.8 1.25
Pressure = 200 Pa
molecular wt.
15. Density = Molar volume
284 g mol 1
'Vm '  3
 302.13 cm3mol 1
0.94 g cm
302.13 cm3mol1
Volume occupied by 1 molecule = 23 1 = 50.187 × 10–23 cm3
6.02 10 mol
= 501.87 Å3
CHEM ACADEMY
1 cm = 108 Å
1 cm3 = 1024 Å3
Now, Volume = Area × thickness
Volume 501.87Å3
Thickness = = = 25.09 Å
Area 20Å 2

Adsorption: Chem Academy

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CHEM ACADEMY 1 Adsorption (Solution)

ln(1  Q)  ln(1)  ln(Q)

9. (b) NH3 > CO2 > H2

Hence, On increasing temperature, extent of adsorption decreases.

Correct option is (D)

7. From the equation

9. From the two-dimensional ideal gas law   RT , we have

Surface film Pressure   7.43 106 N dm 1

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