Chapter 19 Transport Properties
Chapter 19 Transport Properties
Chapter 19 Transport Properties
19 Transport Properties
Chapter 19
Viscosity
19.1. In a normal adult at rest the average speed of flow of blood through the aorta is 0.33 m s–1. The radius of the aorta is 9 mm and the
viscosity of blood at body temperature, 37 °C, is about 4.0 × 10–3 kg m–1 s–1. Calculate the pressure drop along a 0.5 m length of the
aorta.
Solution
19.2. A typical human capillary is about 1 mm long and has a radius of 2 μm. If the pressure drop along the capillary is 20 Torr,
a. calculate the average linear speed of flow of blood of viscosity 4.0 × 10–3 kg m–1 s–1;
b. calculate the volume of blood passing through each capillary per second; and
c. estimate the number of capillaries in the body if they are supplied by the aorta described in Problem 19.1.
Solution
*19.3. The viscosity of ethylene at 25.0 °C and 101.325 kPa is 9.33 × 10–6 kg m–1 s–1. Estimate
a. the molecular diameter,
b. the mean free path,
c. the frequency of collisions ZA experienced by a given molecule, and
d. the collision density ZAA.
Solution
19-2
Chapter 19: Transport Properties Viscosity
*19.4. For nonassociated liquids the fluidity φ (i.e., the reciprocal of the viscosity) obeys to a good approximation an equation of the
Arrhenius form
φ = Ae− E /RT
a
19-3
Chapter 19: Transport Properties Viscosity
19.7. a. The activation energy for the fluidity of n-octane is 12.6 kJ mol–1 and the viscosity at 0 °C is 7.06 × 10–4 kg m–1 s–1. Estimate the
viscosity at 40.0 °C, assuming the Arrhenius equation to apply.
b. A better temperature law for the viscosity of n-octane has been found to be
η = A(T/K)–1.72exp(543/(T/K)
where T is expressed in kelvins.
Make another estimate of the viscosity at 40 °C. What is the effective activation energy at 20 °C?
Solution
*19.8. Over its entire liquid range the viscosity of water is represented to within 1% by the following empirical formula:
where t is the value of the temperature in degrees Celsius. Make a better estimate of the viscosity of water than obtained by the use
of the Arrhenius equation (Problem 19.4b).
To what activation energies does this empirical expression correspond at
a. 20 °C?
b. 100 °C?
Give a qualitative explanation for the difference between the two values.
Solution
*19.9. Consider a hypothetical gas in which the molecules have mass but no size and do not interact with each other.
a. What would be the viscosity of such a gas?
b. Suppose instead that the molecules have zero size but attract one another. What can you then say about the viscosity?
c. If they repel one another, what would the viscosity be?
d. Give a clear explanation of your conclusions in all three cases.
Solution
19-4
Chapter 19: Transport Properties Diffusion
Diffusion
19.10. The molecular diameter of the helium atom is 0.225 nm. Estimate, at 0 °C and 101.325 kPa,
a. the viscosity of the gas,
b. the self-diffusion coefficient,
c. the mean speed of the molecules,
d. the mean free path,
e. the collision frequency ZA, and
f. the collision density ZAA.
Solution
19.11. Calculate the mean square distance traveled by a molecule of H2 at 20 °C and 101.325 kPa in 10 s (D = 1.005 × 10–4 m2 s–1).
Solution
19.12. Solutions of (a) glucose (D = 6.8 × 10–10 m2 s–1) and (b) tobacco mosaic virus (D = 5.3 × 10–12 m2 s–1) were maintained at a
constant temperature of 20 °C and without agitation for 100 days. How far would a given molecule of each be expected to diffuse in
that time?
Solution
19.13. Estimate the diffusion coefficient of cupric sulfate in water at 25 °C from the molar conductivities given in Table 7.3 (p. 291).
Solution
19.14. Estimate the diffusion coefficient of sodium acetate in water at 25 °C from the following mobility values:
Solution
19-5
Chapter 19: Transport Properties Sedimentation and Diffusion
19.15. The diffusion coefficient for horse hemoglobin in water is 6.3 × 10–11 m2 s–1 at 20 °C. The viscosity of water at 20 °C is 1.002 × 10–3
kg m–1 s–1 and the specific volume of the protein is 0.75 cm3 g–1. Assume the hemoglobin molecule to be spherical and to obey
Stokes’s law, and estimate its radius and the molecular weight.
Solution
19.16. If the diffusion coefficient for insulin is 8.2 × 10–11 m2 s–1 at 20 °C, estimate the mean time required for an insulin molecule to
diffuse through a distance equal to the diameter of a typical living cell (≈ 10 μm).
Solution
*19.17. A colloidal particle is spherical and has a diameter of 0.3 μm and a density of 1.18 g cm–3. Estimate how long it will take for the
particle to diffuse through a distance of 1 mm in water at 20 °C (η = 1.002 × 10–3 kg–3 m–1 s–1; the density of water at 20 °C = 0.998
g cm–3). (See also Problem 19.21.)
Solution
Sedimentation and Diffusion
19.18. Diphtheria toxin was found to have, at 20 °C, a sedimentation coefficient of 4.60 Svedbergs and a diffusion coefficient of
5.96 × 10–7 cm2 s–1. The toxin has a specific volume of 0.736 cm3 g–1, and the density of water at 20 °C is 0.998 g cm–3. Estimate a
value for the molecular weight of the toxin.
Solution
19.19. A protein has a sedimentation coefficient of 1.13 × 10–12 s–1 at 25 °C and a diffusion coefficient of 4.2 × 10–11 m2 s–1. The density of
the protein is 1.32 g cm–3 and that of water at 25 °C is 0.997 g cm–3. Calculate the molecular weight of the protein.
Solution
*19.20. A protein of molecular weight 60 000 has a density of 1.31 g cm–3 and in water at 25 °C (ρ = 0.997 g cm–3; η = 8.937 × 10–4 kg m–1
s–1) it has a sedimentation coefficient of 4.1 × 10–13 s–1. Calculate the frictional coefficient f
a. from the sedimentation coefficient, and
b. by the use of Stokes’s law.
Suggest a reason why the two values are not quite the same.
Solution
19-6
Chapter 19: Transport Properties Sedimentation and Diffusion
*19.21. How long will it take the particle from Problem 19.17 to sediment a distance of 1 mm in the earth’s gravitational field (g = 9.81 m s–2)?
Solution
*19.22. An aqueous colloidal solution contains spherical particles of uniform size and of density 1.33 g cm–3. The diffusion coefficient at 25
°C is 1.20 × 10–11 m2 s–1; make an estimate of the sedimentation coefficient (ρ(H2O) = 0.997 g cm–3; η(H2O) = 8.937 × 10–4 kg m–1 s–1).
Solution
19.23. At 20 °C, γ-globulin has a sedimentation constant of 7.75 × 10–13 s, a diffusion coefficient in water of 4.8 × 10–11 m2 s–1, and a
density of 1.353 g cm–3. The density of water at 20 °C is 0.998 g cm–3.
a. Estimate the molecular weight of γ-globulin.
b. Assuming the Stokes-Einstein equation to apply, estimate the radius of the protein molecule. The viscosity of water at 20 °C is
1.002 × 10–3 kg m–1 s–1.
Solution
*19.24. A sample of human hemoglobin had a sedimentation constant of 4.48 Svedbergs in water at 20 °C and a diffusion coefficient of 6.9
× 10–11 m2 s–1. The specific volume of human hemoglobin is 0.749 cm3 g–1, and the density of water at 20 °C is 0.998 g cm–3.
a. Estimate the molecular weight of human hemoglobin.
b. How far would a molecule diffuse in 1 minute?
c. Neglect diffusion and estimate how far a molecule would sediment in 1 minute.
d. In a centrifuge rotating at 15 000 rpm, how far would a molecule sediment in 1 minute if it were 20 cm from the center of
rotation?
e. Assume the molecule to be spherical and estimate its radius by the use of the Stokes-Einstein equation.
f. Estimate the radius from the molecular weight and the density.
Solution
19-7
Chapter 19: Transport Properties Sedimentation and Diffusion
*19.25.In the first decade of the twentieth century Jean Perrin carried out important investigations on the sedimentation, in the gravitational
field, of particles of gamboge, mastic, and other paint pigments. Consider particles of density 1.2 g cm–3 and of the following radii:
a. 1 mm
b. 0.1 mm
c. 10 μm
d. 1 μm
e. 10 nm
In each case, assuming Stokes’s law to apply, estimate the distance the particle would sediment in 1 hour, in water at 20 °C
(viscosity, η = 1.002 × 10–3 kg m–1 s–1 and density 0.998 g cm–3).
f. In the case of the particle having a radius of 10 nm, what speed of rotation in an ultracentrifuge would be required to bring about a
sedimentation of 1 mm in 1 hour? Take the distance from the axis of rotation to be 10 cm.
Solution
*19.26. Perrin also carried out, using pigment particles, experiments on Brownian movement in which he determined distances traveled by
individual particles in various periods of time. For each of the particles of five different radii mentioned in the previous problem,
estimate the diffusion coefficient and the average distance traveled in 1 hour. Take the water temperature again as 20°C and use the
data of Problem 19.25.
Solution
*19.27. A pure protein in water is centrifuged to equilibrium at 25 °C and at 25 000 rpm. At distances of 8.34 cm and 9.12 cm from the axis
of rotation the concentrations of the protein are measured to be 3.52 g cm–3 and 22.49 g cm–3, respectively. The specific volume V1
of the protein is 0.78 cm3 g–1, and the density of water at 25 °C is 0.997 g cm–3.Calculate the molecular weight of the protein.
Solution
*19.28. A protein has a molecular weight of 1 000 000 and a specific volume of 0.81 cm3 g–1. In an ultracentrifuge at 25 °C, what speed of
revolution is required to produce at equilibrium a concentration ratio of 20/1 at distances 10.00 cm and 9.00 cm from the axis of
revolution? The density of water at 25 °C is 0.997 g cm–3.
Solution
19-8
Chapter 19: Transport Properties Essay Questions
Essay Questions
19.29. Explain how the rate of diffusion through a membrane depends on
a. the size of the diffusing substance, and
b. its solubility in the membrane.
19.30. Explain clearly the different mechanisms involved in the viscosity of gases and the viscosity of liquids.
19-9
Chapter 19: Transport Properties Solutions
Solutions
19.1. In a normal adult at rest the average speed of flow of blood through the aorta is 0.33 m s–1. The radius of the aorta is 9 mm and the
viscosity of blood at body temperature, 37 °C, is about 4.0 × 10–3 kg m–1 s–1. Calculate the pressure drop along a 0.5 m length of the
aorta.
Solution:
Required: ΔP
To solve this problem we will use Eq. 19.10, the Poiseulle Equation.
dV ( P1 − P2 )π R 4
=
dt 8η l
8η l dV
ΔP = ⋅
π R 4 dt
To find the volume rate of flow, we find the area of the cross section of the aorta and multiply by the rate of blood flow through the aorta.
dV
= A × vblood
dt
A = π raorta
2
dV
= π raorta
2
vblood
dt
dV
( )( )
2
= π 9 × 10−3 m 0.33m s −1
dt
dV
= 8.397 48 × 10−5 m3 s −1
dt
19-10
Chapter 19: Transport Properties Solutions
ΔP = 65.18518519 kg m –1 s –2
1 kg m –1 s –2 = 1 Pa
ΔP = 65 Pa
dV
Required: vblood , , number of capillaries
dt
a. To calculate the average linear speed of blood flow, we use Eq. 19.10,
dV ( P1 − P2 )π R 4
=
dt 8η l
The volume rate of flow is found from the area of the cross section of the aorta multiplied by the rate of blood flow through the aorta.
19-11
Chapter 19: Transport Properties Solutions
dV
= A × vblood
dt
A = π raorta
2
dV
= π raorta
2
vblood
dt
ΔPπ R 4
π raorta
2
vblood =
8η l
ΔP π R 4
vblood =
8η l π raorta
2
R = raorta
ΔPR 2
vblood =
8η l
Pa
ΔP = 20 Torr × 133.3
Torr
1 kg m –1 s –2 = 1 Pa
( 20 ×133.3kg m s )( 2 ×10 )
2
–1 –2 −6
m
vblood =
8 ( 4.0 × 10 kg m s )(1× 10
–3 –1 –1 −3
m)
vblood = 3.3325 × 10 –4 m s −1
vblood = 3.3 × 10 –4 m s −1
19-12
Chapter 19: Transport Properties Solutions
dV
= π raorta
2
vblood
dt
dV
( )( )
2
= π 2 ×10−6 m 3.3325 × 10 –4 m s −1
dt
dV
= 4.187 74 ×10−15 m3 s −1
dt
dV
= 4.2 ×10−15 m3 s −1
dt
c. To calculate the number of capillaries, we divide the volume of flow through the aorta (from Problem 19.1) by the volume of flow
through the capillaries.
dV dV
Number of capillaries = aorta ÷ capillaries
dt dt
8.397 48 × 10−5 m3 s −1
Number of capillaries =
4.187 74 × 10−15 m3 s −1
Number of capillaries = 20 052 513128
Number of capillaries = 2.0 ×1010
19-13
Chapter 19: Transport Properties Solutions
*19.3. The viscosity of ethylene at 25.0 °C and 101.325 kPa is 9.33 × 10–6 kg m–1 s–1. Estimate
a. the molecular diameter,
b. the mean free path,
c. the frequency of collisions ZA experienced by a given molecule, and
d. the collision density ZAA.
Solution:
Required: d , λ , Z A , Z AA
mu
d=
2 2πη
19-14
Chapter 19: Transport Properties Solutions
8kBT
u=
πm
M
m=
NA
( ) (
M = 2 12.011 g mol−1 + 4 1.00794 g mol−1 )
M = 28.053 76 g mol−1
28.053 76 g mol−1
m= −1
× 10−3
6.022 × 10 23
mol
m = 4.658 55 ×10−26 kg
u=
( )
8 1.381× 10−23 J K −1 ( 298.15 K )
π ( 4.658 55 ×10−26 kg )
u = 474.415 795 5 m s −1
d=
( 4.658 55 ×10 kg )( 474.415 795 5 m s )
−26 −1
2 2π ( 9.33 ×10 kg m s ) –6 –1 –1
d = 5.16317 × 10 –10 m
d = 5.16 × 10 –10 m
19-15
Chapter 19: Transport Properties Solutions
n P
=
V RT
n 101 325 Pa
=
V (
8.3145 J K −1 mol−1 ( 298.15 ))
n
= 40.873 860 75 mol m −3
V
N
= 40.873 860 75 mol m −3 × 6.022 ×1023 mol−1
V
N
= 2.461 42 ×1025 m −3
V
1
λ=
( ) ( 2.461 42 ×10 )
2
2π 5.16317 ×10 –10
m 25
m −3
λ = 3.430 17 ×10 –8 m
λ = 3.43 ×10 –8 m
uA
ZA =
λ
474.415 795 5 m s −1
ZA =
3.430 17 ×10 –8 m
Z A =13 830 675103 s −1
Z A = 1.38 × 1010 s −1
19-16
Chapter 19: Transport Properties Solutions
19-17
Chapter 19: Transport Properties Solutions
*19.4. For nonassociated liquids the fluidity φ (i.e., the reciprocal of the viscosity) obeys to a good approximation an equation of the
Arrhenius form
φ = Ae− E /RT
a
T = 0.0 °C
⎛ −E ⎞ ⎛ −10.9 × 103 J mol−1 ⎞
exp ⎜ a ⎟ = exp ⎜ −1 −1 ⎟
⎝ RT ⎠ ⎝ 8.3145 J K mol × 273.15 K ⎠
⎛ −E ⎞
exp ⎜ a ⎟ = 8.234 485 424 × 10−3
⎝ RT ⎠
T = 40.0 °C
⎛ −E ⎞ ⎛ −10.9 × 103 J mol−1 ⎞
exp ⎜ a ⎟ = exp ⎜ −1 −1 ⎟
⎝ RT ⎠ ⎝ 8.3145 J K mol × 313.15 K ⎠
⎛ −E ⎞
exp ⎜ a ⎟ = 1.520 131 7 ×10−2
⎝ RT ⎠
19-18
Chapter 19: Transport Properties Solutions
Since we are told viscosity has the inverse relationship to the fluidity φ , we calculate the viscosity at 40.0 °C as,
19-19
Chapter 19: Transport Properties Solutions
T = 20.0 °C
⎛ −E ⎞ ⎛ −18 × 103 J mol−1 ⎞
exp ⎜ a ⎟ = exp ⎜ −1 −1 ⎟
⎝ RT ⎠ ⎝ 8.3145 J K mol × 293.15 K ⎠
⎛ −E ⎞
exp ⎜ a ⎟ = 6.205 331 937 × 10−4
⎝ RT ⎠
T = 40.0 °C
⎛ −E ⎞ ⎛ −18 × 103 J mol−1 ⎞
exp ⎜ a ⎟ = exp ⎜ −1 −1 ⎟
⎝ RT ⎠ ⎝ 8.3145 J K mol × 313.15 K ⎠
⎛ −E ⎞
exp ⎜ a ⎟ = 9.944 936 073 × 10−4
⎝ RT ⎠
6.205 331 937 × 10−4
η40.0o C = η20.0o C ×
9.944 936 073 × 10−4
6.205 331 937 × 10−4
η40.0o C = 1.002 ×10−3 × −4
kg m −1 s −1
9.944 936 073 ×10
η40.0o C = 6.252 169 501×10−4 kg m −1 s −1
η40.0 C = 6.25 ×10−4 kg m −1 s −1
o
19-20
Chapter 19: Transport Properties Solutions
19.5. At 20.0 °C the viscosity of pure toluene is 5.90 × 10–4 kg m–1 s–1. Calculate the intrinsic viscosities of solutions containing 0.1 g dm–3
of polymer in toluene and having the following viscosities:
a. 5.95 × 10–4 kg m–1 s–1
b. 6.05 × 10–4 kg m–1 s–1
c. 6.27 × 10–4 kg m–1 s–1
These solutions are sufficiently dilute that the reduced specific viscosity can be taken to be the intrinsic viscosity.
Solution:
Required: [η ]
Since we are told that the reduced specific viscosity can be taken to be the intrinsic viscosity, we solve using Eq. 19.31,
1 η −η 0
reduced specific viscosity = ⋅ ≡ [η ]
ρ η0
a.
1 5.95 × 10 –4 kg m –1 s –1 − 5.90 ×10 –4 kg m –1 s –1
[η ] = ⋅
0.10 g dm −3 5.90 × 10 –4 kg m –1 s –1
[η ] = 0.084 745 763 dm3 g −1
[η ] = 8.5 ×10–2 m3 kg −1
b.
1 6.05 ×10 –4 kg m –1 s –1 − 5.90 ×10 –4 kg m –1 s –1
[η ] = ⋅
0.10 g dm −3 5.90 ×10 –4 kg m –1 s –1
[η ] = 0.254 237 288 dm3 g −1
[η ] = 0.25 m3 kg −1
19-21
Chapter 19: Transport Properties Solutions
c.
1 6.27 × 10 –4 kg m –1 s –1 − 5.90 ×10 –4 kg m –1 s –1
[η ] = ⋅
0.10 g dm −3 5.90 × 10 –4 kg m –1 s –1
[η ] = 0.627 118 644 dm3 g −1
[η ] = 0.63 m3 kg −1
19-22
Chapter 19: Transport Properties Solutions
*19.6. Suppose that solutions (a) and (c) in Problem 19.5 correspond to polymers of molecular weights 20 000 and 40 000, respectively.
Assuming the Mark-Houwink equation 19.33 to apply, make an estimate of the molecular weight of the polymer in solution (b).
Solution:
Required: M b
[η ] = kM rα
19-23
Chapter 19: Transport Properties Solutions
Using y = mx + b , we can use the coordinate of log M a and log [ηa ] to determine the intercept b.
19-24
Chapter 19: Transport Properties Solutions
19.7. a. The activation energy for the fluidity of n-octane is 12.6 kJ mol–1 and the viscosity at 0 °C is 7.06 × 10–4 kg m–1 s–1. Estimate the
viscosity at 40.0 °C, assuming the Arrhenius equation to apply.
b. A better temperature law for the viscosity of n-octane has been found to be
η = A(T/K)–1.72exp(543/(T/K)
where T is expressed in kelvins.
Make another estimate of the viscosity at 40 °C. What is the effective activation energy at 20 °C?
Solution:
Required: η 40.0 ° C using the Arrhenius equation and the equation above, Ea
a. To solve this problem, we use the same procedure using in Problem 19.4.
19-25
Chapter 19: Transport Properties Solutions
T = 0.0 °C
⎛ −12.6 ×103 J mol−1 ⎞
exp ( − Ea / RT ) = exp ⎜ ⎟
⎜ ( 8.3145 J K −1 mol−1 ) ( 273.15 K ) ⎟
⎝ ⎠
exp ( − Ea / RT ) = 3.895 402 × 10 −3
T = 40.0 °C
⎛ −12.6 ×103 J mol−1 ⎞
exp ( − Ea / RT ) = exp ⎜ ⎟
⎜ ( 8.3145 J K −1 mol−1 ) ( 313.15 K ) ⎟
⎝ ⎠
exp ( − Ea / RT ) = 7.912 639 816 × 10 −3
T = 0.0 °C
⎛ 543 ⎞
T −1.72 exp ( 543 / T ) = ( 273.15 )
−1.72
× exp ⎜ ⎟
⎝ 273.15 ⎠
19-26
Chapter 19: Transport Properties Solutions
To calculate the activation energy we use the fluidity. The fluidity can be expressed as,
1 ⎛ −4515 J mol−1 ⎞
= A−1 (T / K )
1.72
φ= exp ⎜ ⎟
η ⎝ RT ⎠
19-27
Chapter 19: Transport Properties Solutions
d ln φ
Ea = RT 2
dT
4515 J mol−1
ln φ = 1.72 ln (T / K ) −
RT
d ln φ 1.72 4515 J mol −1
= +
dT T RT 2
d ln φ 1.72 RT + 4515 J mol−1
=
dT RT 2
⎛ 1.72 RT + 4515 J mol−1 ⎞
Ea = RT 2 ⎜ ⎟
⎝ RT 2 ⎠
( )( )
Ea = 1.72 8.3145 J K −1 mol−1 293.15 K + 4515 J mol−1
19-28
Chapter 19: Transport Properties Solutions
*19.8. Over its entire liquid range the viscosity of water is represented to within 1% by the following empirical formula:
where t is the value of the temperature in degrees Celsius. Make a better estimate of the viscosity of water than obtained by the use
of the Arrhenius equation (Problem 19.4b).
To what activation energies does this empirical expression correspond at
a. 20 °C?
b. 100 °C?
Give a qualitative explanation for the difference between the two values.
Solution:
Given: empirical formula, T = 20 °C, T = 100 °C
Required: η water , Ea
In problem 19.4b, we make an estimate at T = 40.0 °C . We are also given, η 20 °C = 1.002 ×10 –3 kg m –1 s –1 Using the empirical formula, our
improved estimate is,
19-29
Chapter 19: Transport Properties Solutions
ln ⎜ ⎟=
⎝ η (40 C) ⎠ 109.0 + 40
D
149.0
3.1556 ( 20.0 ) + 1.925 ×10−3 ( 400 )
ln η40 DC = ln (1.002 ×10 kg m s ) −
–3 –1 –1
149.0
ln η40 DC = −6.905 757 276 − 0.428 738 255
η 40 C = e−7.334 495 531
D
d ln φ
Ea = RT 2
dT
d ln η
Ea = − RT 2
dT
From the empirical relationship, with
T = t + 273.15
a (T − 293.15 ) + b (T − 293.15 )
2
ln ηt = ln η20 °C −
T − 164.15
where a = 3.1556, b =1.925 ×10−3
d ln η
=−
( a + 2b (T − 293.15) ) (T − 164.15) − a (T − 293.15) − b (T − 293.15) 2
(T − 164.15)
2
dT
19-30
Chapter 19: Transport Properties Solutions
×
( 293.15 K − 164.15)
2
( )
Ea = 8.3145 J K mol−1 ( 293.15 K )
2
×
(3.1556 + 2 ( 1.925×10 ) ( 293.15 K ) − 586.3 ( 1.925×10 )) ( 293.15 K − 164.15)
−3 −3
( 293.15 K − 164.15)
2
Ea = 17 478.661 5 J mol−1
Ea = 17.5 kJ mol−1
×
( a + 2b ( 373.15) − 586.3b ) ( 373.15 − 164.15) − a ( 373.15 − 293.15) − b ( 373.15 − 293.15) 2
( 373.15 − 164.15)
2
Ea = 12 168.606 04 J mol−1
Ea = 12.2 kJ mol−1
19-31
Chapter 19: Transport Properties Solutions
*19.9. Consider a hypothetical gas in which the molecules have mass but no size and do not interact with each other.
a. What would be the viscosity of such a gas?
b. Suppose instead that the molecules have zero size but attract one another. What can you then say about the viscosity?
c. If they repel one another, what would the viscosity be?
d. Give a clear explanation of your conclusions in all three cases.
Solution:
Given: a – d
Required: clear explanations
a. In a hypothetical gas in which the molecules have no size, there are no collisions and there no exchanges of momentum between
molecules. If there are no forces between the molecules, two layers can move past each other freely, and the viscosity is zero.
b. If the molecules have no size but attract one another, a force is required to move one layer past another. The gas will therefore have a
viscosity. Increasing the temperature will increase the molecular speeds and will decrease the viscosity, as in a liquid.
c. If the molecules have no size but repel one another, a force again will be required to move one layer past another. There will again be a
viscosity, which decreases with increasing temperature.
19-32
Chapter 19: Transport Properties Solutions
19.10. The molecular diameter of the helium atom is 0.225 nm. Estimate, at 0 °C and 101.325 kPa,
a. the viscosity of the gas,
b. the self-diffusion coefficient,
c. the mean speed of the molecules,
d. the mean free path,
e. the collision frequency ZA, and
f. the collision density ZAA.
Solution:
Given: d = 0.225 nm, T = 0 °C, P = 101.325 kPa
Required: η , D, u , λ , Z A , Z AA
M
m=
NA
4.0026 g mol−1
m= −1
× 10−3 kg g −1
6.022 × 10 23
mol
m = 6.646 63 × 10−27 kg
19-33
Chapter 19: Transport Properties Solutions
( )( )
1/ 2
⎡ 6.646 63 × 10−27 kg 1.381× 10−23 J K −1 ( 273.15 K ) ⎤
η=⎣ ⎦
( 0.225 ×10 )
2
π 3/ 2 −9
m
η =1.77627 ×10−5 kg m −1 s −1
η =1.78 ×10−5 kg m −1 s −1
D=
( )(
1.77627 × 10−5 kg m −1 s −1 1.381×10−23 J K −1 ( 273.15 K ))
( 6.646 63 ×10 −27
)
kg (101 325 Pa )
−5 −1
D = 9.949 13 × 10 m s 2
D = 9.95 × 10−5 m 2 s −1
19-34
Chapter 19: Transport Properties Solutions
8kBT
u=
πm
u=
( )
8 1.381× 10−23 J K −1 ( 273.15 K )
π ( 6.646 63 ×10−27 kg )
u = 1 202.172 472 m s −1
u = 1.20 × 103 m s −1
n P
=
V RT
V
=
(
8.3145 J K −1 mol−1 273.15 K )( )
N (
(101 325 Pa ) 6.022 ×1023 mol−1 )
V
= 3.722 03 × 10−26 m3
N
Therefore the mean free path is,
3.722 03 × 10−26 m 3
λ=
( )
2
2π 0.225 ×10−9 m
λ = 1.654817375 ×10−7 m
λ = 1.65 ×10−7 m
19-35
Chapter 19: Transport Properties Solutions
2π d A2 u A N A
ZA = (SI unit :s −1 )
V
Which we recognize as,
uA
ZA =
λ
1 202.172 472 m s −1
ZA =
1.654 82 ×10 –7 m
Z A = 7 264 683 644 s −1
Z A = 7.26 ×109 s −1
19-36
Chapter 19: Transport Properties Solutions
19.11. Calculate the mean square distance traveled by a molecule of H2 at 20 °C and 101.325 kPa in 10 s (D = 1.005 × 10–4 m2 s–1).
Solution:
Required: x2
x 2 = 2 Dt
x 2 = 2 Dt
x2 = (
2 1.005 ×10 –4 m 2 s –1 ) (10 s )
x 2 = 0.044 833 024 m
x 2 = 4.5 cm
19-37
Chapter 19: Transport Properties Solutions
19.12. Solutions of (a) glucose (D = 6.8 × 10–10 m2 s–1) and (b) tobacco mosaic virus (D = 5.3 × 10–12 m2 s–1) were maintained at a
constant temperature of 20 °C and without agitation for 100 days. How far would a given molecule of each be expected to diffuse in
that time?
Solution:
Given: Dglucose = 6.8 ×10 –10 m 2 s –1 , Dvirus = 5.3 × 10 –12 m 2 s –1 , T = 20.0 °C, t = 100 days
Required: x2
x 2 = 2 Dt
x 2 = 2 Dt
Converting the time in days to time in seconds we can solve for the mean square distance,
t = 100 × 24 × 60 × 60
t = 8 640 000 s
x 2 glucose = (
2 6.8 ×10 –10 m 2 s –1 ) (8 640 000 s )
x 2 glucose = 0.108 399 262 m
x 2 glucose = 11 cm
x 2 virus = (
2 5.3 ×10 –12 m 2 s –1 ) (8 640 000 s )
x 2 virus = 0.009 569 953 m
x 2 virus = 0.96 cm
19-38
Chapter 19: Transport Properties Solutions
19.13. Estimate the diffusion coefficient of cupric sulfate in water at 25 °C from the molar conductivities given in Table 7.3 (p. 291).
Solution:
Given: T = 25 °C, Table 7.3
Required: D
To solve this problem, we follow the example set by Example 19.4
Using Eq. 19.73, at 25 °C,
RT D
D= λ
F 2 zi
D=
(8.3145 J K mol ) ( 298.15 K ) λ (Ω
−1 −1
D −1
cm 2 mol−1 )
( 96500 C mol ) ( 2 ) −1 2
D =1.331 03 ×10−7 λ D J Ω −1 C −2 cm 2
D =1.331 03 ×10−7 λ D cm 2 s −1
For Cu2+,
(
D+ = 1.331 03 ×10−7 ( 56.6 ) )
D+ = 7.533 6 ×10−6 cm 2 s –1
For SO42–,
19-39
Chapter 19: Transport Properties Solutions
( )
D− = 1.331 03 ×10−7 ( 80.0 )
D− = 1.064 82 ×10−5 cm 2 s –1
2 D+ D−
D=
D+ + D−
2 × ( 7.533 6 ×10−6 cm 2 s –1 )(1.064 82 ×10−5 cm 2 s –1 )
D=
7.533 6 ×10−6 cm 2 s –1 + 1.064 82 ×10−5 cm 2 s –1
D = 8.824 13 ×10−6 cm 2 s −1
D = 8.82 ×10−6 cm 2 s −1
19-40
Chapter 19: Transport Properties Solutions
19.14. Estimate the diffusion coefficient of sodium acetate in water at 25 °C from the following mobility values:
Required: D
To solve this problem we use Eq. 19.72,
kBT
D= ui
Q
Since the charge on 1 mole of an equivalent ion QL, is 96 500 C mol-1, we can write Eq. 19.72 as,
RT
D= ue
Q
D=
(8.3145 J K mol ) ( 298.15 K ) u
−1 −1
(96500 C mol ) −1
e
For Na+,
(
D+ = 0.025 688 789 V ) ( 5.19 ×10 –4
cm 2 V –1 s –1 )
D+ = 1.333 25 ×10−5 cm 2 s –1
For CH3COO–,
(
D− = 0.025 688 789 V ) ( 4.24 ×10 –4
cm 2 V –1 s –1 )
D− = 1.089 2 ×10−5 cm 2 s –1
19-41
Chapter 19: Transport Properties Solutions
2 D+ D−
D=
D+ + D−
2 × (1.333 25 ×10−5 cm 2 s –1 )(1.089 2 ×10−5 cm 2 s –1 )
D=
1.333 25 ×10−5 cm 2 s –1 + 1.089 2 ×10−5 cm 2 s –1
D = 1.198 93 ×10−5 cm 2 s –1
D = 1.20 ×10−5 cm 2 s –1
19-42
Chapter 19: Transport Properties Solutions
19.15. The diffusion coefficient for horse hemoglobin in water is 6.3 × 10–11 m2 s–1 at 20 °C. The viscosity of water at 20 °C is 1.002 × 10–3
kg m–1 s–1 and the specific volume of the protein is 0.75 cm3 g–1. Assume the hemoglobin molecule to be spherical and to obey
Stokes’s law, and estimate its radius and the molecular weight.
Solution:
Required: r , M
kBT
D=
6π rη
kBT
r=
6πη D
r=
(1.381×10 −23
J K −1 ) ( 293.15 K )
6π (1.002 ×10 –3 kg m –1 s –1 )( 6.3 × 10 –11 m 2 s –1 )
r = 3.402 31×10 m –9
r = 3.4 × 10 –9 m = 3.4 nm
To get the molar mass, we first calculate the volume, assuming the molecule is perfectly spherical.
19-43
Chapter 19: Transport Properties Solutions
4
V = π r3
3
4
( )
3
V = π 3.402 31×10 –9 m
3
V = 1.649 72 × 10 –25 m3
V
M= NA
Vspecific
1.649 72 × 10 –25 m3
M=
0.75 × 10 m g
–6 3 –1 (
6.022 ×1023 mol−1 )
M = 132 461.7981 g mol−1
M = 1.3 ×105 g mol−1
19-44
Chapter 19: Transport Properties Solutions
19.16. If the diffusion coefficient for insulin is 8.2 × 10–11 m2 s–1 at 20 °C, estimate the mean time required for an insulin molecule to
diffuse through a distance equal to the diameter of a typical living cell (≈ 10 μm).
Solution:
Required: t
The mean time can be obtained from From Eq. 19.48,
x 2 = 2 Dt
x2
t=
2D
(10 ×10 m)
−6 2
t=
2 ( 8.2 ×10
–11
m 2 s –1 )
t = 0.609 756 098 s
t = 0.61 s
19-45
Chapter 19: Transport Properties Solutions
*19.17. A colloidal particle is spherical and has a diameter of 0.3 μm and a density of 1.18 g cm–3. Estimate how long it will take for the
particle to diffuse through a distance of 1 mm in water at 20 °C (η = 1.002 × 10–3 kg–3 m–1 s–1; the density of water at 20 °C = 0.998
g cm–3). (See also Problem 19.21.)
Solution:
Required: t
The mean time can be obtained from Eq. 19.48,
x 2 = 2 Dt
x2
t=
2D
D=
(1.381×10 −23
J K −1 ) ( 293.15 K )
6π (1.002 × 10 –3 kg m –1 s –1 )(1.5 × 10−7 m )
D = 1.428 97 ×10 –12 m 2 s –1
19-46
Chapter 19: Transport Properties Solutions
(10 m)
−3 2
t=
2 (1.428 97 × 10 –12 m 2 s –1 )
t = 349 902.085 4 s
t = 3.5 × 105 s
19-47
Chapter 19: Transport Properties Solutions
19.18. Diphtheria toxin was found to have, at 20 °C, a sedimentation coefficient of 4.60 Svedbergs and a diffusion coefficient of 5.96 × 10–
7
cm2 s–1. The toxin has a specific volume of 0.736 cm3 g–1, and the density of water at 20 °C is 0.998 g cm–3. Estimate a value for the
molecular weight of the toxin.
Solution:
Given:
Required: M
The molar mass is given by the Svedberg equation, Eq. 19.93,
RTs
M=
D(1 − V2 ρ )
Substitution into this equation gives the molar weight of the toxin.
M=
(8.3145 J K −1
)(
mol−1 293.15 K ) ( 4.60 ×10 −13
s)
19-48
Chapter 19: Transport Properties Solutions
19.19. A protein has a sedimentation coefficient of 1.13 × 10–12 s–1 at 25 °C and a diffusion coefficient of 4.2 × 10–11 m2 s–1. The density of
the protein is 1.32 g cm–3 and that of water at 25 °C is 0.997 g cm–3. Calculate the molecular weight of the protein.
Solution:
Given:
T = 25 °C, s = 1.13 ×10−12 s, D = 4.2 ×10 –11 m 2 s –1 , ρ protein = 1.32 g cm −3 , ρ H2O = 0.997 g cm –3
Required: M
1
We solve this problem in the same manner as Problem 19.18, making the substitution for V2 as .
ρ protein
RTs
M=
D(1 − V2 ρ )
Substitution into this equation gives the molar weight of the protein .
M=
(8.3145 J K −1
)( )
mol−1 298.15 K (1.13 ×10−12 s )
⎛
( 4.2 ×10 m s ) ⎜⎜1−
–11 2 –1
(
0.997 g cm –3 ) ⎞⎟
⎜ 1.32 g cm −3 ⎟⎟
⎝ ⎠
−1
M = 272.565 894 9 kg mol
M = 2.7 × 105 g mol−1
19-49
Chapter 19: Transport Properties Solutions
*19.20. A protein of molecular weight 60 000 has a density of 1.31 g cm–3 and in water at 25 °C (ρ = 0.997 g cm–3; η = 8.937 × 10–4 kg m–1
s–1) it has a sedimentation coefficient of 4.1 × 10–13 s–1. Calculate the frictional coefficient f
a. from the sedimentation coefficient, and
b. by the use of Stokes’s law.
Suggest a reason why the two values are not quite the same.
Solution:
(1 − V2 ρ )m
s=
f
(1 − V2 ρ )m
f =
s
To solve for f we first calculate the mass of the protein.
M
m=
NA
60.000 kg mol−1
m=
6.022 ×1023 mol−1
m = 9.963 47 ×10−23 kg
19-50
Chapter 19: Transport Properties Solutions
1
Using the substitution for V2 as .
ρ protein
⎛
(
0.997 g cm –3 ⎞ )
⎟⎟ ( )
⎜1 − ⎟ 9.963 47 ×10−23 kg
⎜⎜ 1.31 g cm −3
f =⎝ ⎠
4.1× 10 –13 s –1
f = 5.806 3 × 10 –11 kg s –1
f = 5.8 ×10 –11 kg s –1
b. To solve for the frictional coefficient from Stokes Law, we use Eq. 19.76,
f = 6π rη
We assume the protein is perfectly spherical and use the volume of the sphere to find r.
m
V=
ρ
9.963 47 × 10−23 kg
V=
1.31× 103 kg m −3
V = 7.605 7 ×10−26 m3
4
V = π r3
3
1/3
⎛ 3V ⎞
r =⎜ ⎟
⎝ 4π ⎠
1/3
⎛ 3 × 7.605 7 × 10−26 m3 ⎞
r =⎜ ⎟
⎝ 4π ⎠
−9
r = 2.628 35 × 10 m
19-51
Chapter 19: Transport Properties Solutions
(
f = 6π 2.628 35 × 10−9 m ) (8.937 ×10 –4
kg m –1 s –1 )
f = 4.427 68 ×10−11 kg s –1
f = 4.43 ×10−11 kg s –1
The two values are not quite the same since in the Stokes calculation, we assumed that the molecule is perfectly spherical.
19-52
Chapter 19: Transport Properties Solutions
*19.21. How long will it take the particle from Problem 19.17 to sediment a distance of 1 mm in the earth’s gravitational field (g = 9.81 m s–2)?
Solution:
Required: t
The limiting rate of sedimentation is given by Eq. 19.85 as,
(1 − V2 ρ )mg
υ=
6π rη
To solve for v we first calculate the mass of the particle using volume and density,
m
ρ=
V
⎛4 ⎞
m = ⎜ π r3 ⎟ ρ
⎝3 ⎠
4
( )( )
3
m = π 1.5 × 10−7 m 1.18 ×103 kg m −3
3
m = 1.66819 ×10−17 kg
⎛ 0.998 g cm −3 ⎞
⎜1 −
⎜ 1.18 g cm −3
( )(
⎟ 1.66819 ×10−17 kg 9.81 m s –2
⎟
)
υ= ⎝ ⎠
(
6π 1.5 ×10−7 )(
m 1.002 × 10 –3 kg m –1 s –1)
υ = 8.909 28 ×10−9 m s –1
19-53
Chapter 19: Transport Properties Solutions
Since speed is the distance travelled over time, the particle sediments a distance of 1 mm in,
d
υ=
t
d
t=
υ
1×10−3 m
t=
8.909 28 × 10−9 m s –1
t = 112 242.497 6 s
t = 1.12 × 105 s
19-54
Chapter 19: Transport Properties Solutions
*19.22. An aqueous colloidal solution contains spherical particles of uniform size and of density 1.33 g cm–3. The diffusion coefficient at 25
°C is 1.20 × 10–11 m2 s–1; make an estimate of the sedimentation coefficient (ρ(H2O) = 0.997 g cm–3; η(H2O) = 8.937 × 10–4 kg m–1 s–
1
).
Solution:
Required: s
To find the sedimentation coefficient, we will use Eq. 19.89,
(1 − V2 ρ )m
s=
6πη r
kBT
D=
6π rη
kT
r= B
6πη D
r=
(1.381×10 −23
J K −1 ) ( 298.15 K )
6π ( 8.937 ×10 –4 kg m –1 s –1 )(1.20 × 10 –11 m 2 s –1 )
r = 2.036 83 ×10 –8 m
19-55
Chapter 19: Transport Properties Solutions
m
ρ=
V
⎛4 ⎞
m = ⎜ π r3 ⎟ ρ
⎝3 ⎠
4
( ) (1.33 ×10 )
3
m = π 2.036 83 ×10 –8 m 3
kg m −3
3
m = 4.707 64 × 10−20 kg
⎛ 0.997 g cm −3 ⎞
⎜1 −
⎜ 1.33 g cm ⎟⎠
−3
(
⎟ 4.707 64 ×10−20 kg )
s= ⎝
( )(
6π 8.937 × 10 –4 kg m –1 s –1 2.036 83 ×10 –8 m )
s = 3.43517 ×10 –11 s
s = 3.44 × 10 –11 s
19-56
Chapter 19: Transport Properties Solutions
19.23. At 20 °C, γ-globulin has a sedimentation constant of 7.75 × 10–13 s, a diffusion coefficient in water of 4.8 × 10–11 m2 s–1, and a
density of 1.353 g cm–3. The density of water at 20 °C is 0.998 g cm–3.
a. Estimate the molecular weight of γ-globulin.
b. Assuming the Stokes-Einstein equation to apply, estimate the radius of the protein molecule. The viscosity of water at 20 °C is
1.002 × 10–3 kg m–1 s–1.
Solution:
Required: M, r
1
a. We solve this problem in the same manner as Problem 19.18, making the substitution for V2 as .
ρ
The molar mass is given by the Svedberg equation, Eq. 19.93,
RTs
M=
D(1 − V2 ρ )
Substitution into this equation gives the molar weight of the protein .
M=
(8.3145 J K −1
)(
mol−1 293.15 K ) ( 7.75 ×10 −13
s)
⎛
( 4.8 ×10 m s ) ⎜1−
–11 ⎜ 2 –1
(
0.998 g cm –3 ) ⎞⎟
⎜ 1.353 g cm −3 ⎟⎟
⎝ ⎠
−1
M = 149.987 803 4 kg mol
M = 1.5 ×105 g mol−1
19-57
Chapter 19: Transport Properties Solutions
r=
(1.381×10 −23
J K −1 ) ( 293.15 K )
6π (1.002 ×10 –3 kg m –1 s –1 )( 4.8 ×10 –11 m 2 s –1 )
r = 4.465 53 × 10 –9 m
r = 4.5 ×10 –9 m
19-58
Chapter 19: Transport Properties Solutions
*19.24. A sample of human hemoglobin had a sedimentation constant of 4.48 Svedbergs in water at 20 °C and a diffusion coefficient of 6.9
× 10–11 m2 s–1. The specific volume of human hemoglobin is 0.749 cm3 g–1, and the density of water at 20 °C is 0.998 g cm–3.
a. Estimate the molecular weight of human hemoglobin.
b. How far would a molecule diffuse in 1 minute?
c. Neglect diffusion and estimate how far a molecule would sediment in 1 minute.
d. In a centrifuge rotating at 15 000 rpm, how far would a molecule sediment in 1 minute if it were 20 cm from the center of
rotation?
e. Assume the molecule to be spherical and estimate its radius by the use of the Stokes-Einstein equation.
f. Estimate the radius from the molecular weight and the density.
Solution:
Given: T = 20 °C, s = 4.48 ×10−13 s, D = 6.9 ×10 −11 m 2 s −1 , V2 = 0.749 cm3 g −1 , ρ H2O = 0.998 g cm −3
Required: a – f
To solve this problem, we can refer to Example 19.6 for extra help.
a. The molar mass is obtained from Eq. 19.93,
RTs
M=
D(1 − V2 ρ )
M=
(8.3145 J K −1
)(
mol−1 293.15 K ) ( 4.48 ×10 −13
s)
19-59
Chapter 19: Transport Properties Solutions
x2 = 2 Dt
x2 = (
2 6.9 × 10 –11 m 2 s –1 ) ( 60 s )
x 2 = 9.099 45 ×10 –5 m
x 2 = 9.1×10 –5 m
c. The sedimentation coefficient is the rate of sedimentation for an acceleration of gravity of unity. In a gravitational field of g = 9.8 m s–2
the rate of sedimentation is,
v = 9.81 m s −2 × 4.48 × 10−13 s
v = 4.394 88 × 10−12 m s −1
(
d = 4.394 88 ×10−12 m s −1 ) ( 60 s )
d = 2.636 93 ×10−10 m
d = 2.64 × 10−10 m
⎛ 15 000 rpm ⎞
ω =⎜ –1 ⎟
× 2π
⎝ 60 s min ⎠
ω = 1 570.796 327 rad s –1
19-60
Chapter 19: Transport Properties Solutions
υ = 2.210 79 ×10−7 m s –1
(
d = 2.210 79 × 10−7 m s −1 ) ( 60 s )
d = 1.326 47 ×10−5 m
d = 1.33 × 10−5 m
r=
(1.381×10 −23
J K −1 ) ( 293.15 K )
6π (1.002 ×10 –3 kg m –1 s –1 )( 6.9 ×10 –11 m 2 s –1 )
r = 3.106 46 ×10 –9 m
r = 3.1× 10 –9 m
f. Using molecular weight and the density we can make another estimate for the radius.
The mass of the molecule is given by,
19-61
Chapter 19: Transport Properties Solutions
M
m=
NA
62.675 385 94 kg mol−1
m=
6.022 × 1023 mol−1
m = 1.040 77 × 10−22 kg
Using density,
m
V=
ρ
(
V = 1.040 77 × 10−19 g ) ( 0.749 ×10 −6
m3 g –1 )
V = 7.795 39 × 10−29 m3
4
V = π r3
3
1/3
⎛ 3V ⎞
r =⎜ ⎟
⎝ 4π ⎠
1/3
⎛ 3 × 7.795 39 ×10−29 m3 ⎞
r =⎜ ⎟
⎝ 4π ⎠
−10
r = 2.650 02 ×10 m
r = 2.65 ×10−10 m
This is in reasonable agreement with the radius obtained in part e. The molecule is not in fact spherical, and the equation is more
satisfactory for larger particles.
Back to Problem 19.24 Back to Top
19-62
Chapter 19: Transport Properties Solutions
*19.25.In the first decade of the twentieth century Jean Perrin carried out important investigations on the sedimentation, in the gravitational
field, of particles of gamboge, mastic, and other paint pigments. Consider particles of density 1.2 g cm–3 and of the following radii:
a. 1 mm
b. 0.1 mm
c. 10 μm
d. 1 μm
e. 10 nm
In each case, assuming Stokes’s law to apply, estimate the distance the particle would sediment in 1 hour, in water at 20 °C
(viscosity, η = 1.002 × 10–3 kg m–1 s–1 and density 0.998 g cm–3).
f. In the case of the particle having a radius of 10 nm, what speed of rotation in an ultracentrifuge would be required to bring about a
sedimentation of 1 mm in 1 hour? Take the distance from the axis of rotation to be 10 cm.
Solution:
Required: d , v
a. To solve for the distance travelled, we need to calculate the sedimentation coefficient, given by Eq. 19.89,
(1 − V2 ρ )m
s=
6πη r
19-63
Chapter 19: Transport Properties Solutions
1
Making the substitution for V2 as , the sedimentation coefficient is,
ρ
⎛ 0.998 g cm −3 ⎞
⎜1 −
⎜ 1.2 g cm −3 ⎟
(
⎟ 5.026 55 × 10−6 kg )
s= ⎝ ⎠
( )(
6π 1.002 × 10 kg m –1 s –1 1× 10−3 m
–3
)
s = 0.044 799 29 s
(
d = 0.439 481 038 m s −1 ) (3600 s )
d = 1 582.131 737 m
d = 1.58 × 103 m
Repeating the same procedure for b – e we can solve for the distance of sedimentation.
19-64
Chapter 19: Transport Properties Solutions
b.
4
( )( )
3
m = π 0.1×10−3 m 1200 kg m −3
3
m = 5.026 55 × 10−9 kg
⎛ 0.998 g cm −3 ⎞
⎜1 −
⎜ 1.2 g cm −3
(
⎟ 5.026 55 ×10−9 kg
⎟
)
s= ⎝ ⎠
(
6π 1.002 ×10 –3 kg )(
m –1 s –1 0.1× 10−3 m )
s = 4.479 929 × 10 –4 s
(
d = 4.394 8103 8 × 10 –3 m s −1 ) (3600 s )
d = 15.821 317 37 m
d = 15.8 m
c.
4
m = π (10 × 10−6 m ) (1200 kg m −3 )
3
3
m = 5.026 548 246 ×10−12 kg
⎛ 0.998 g cm −3 ⎞
⎜1 − ⎟ 5.026 548 246 × 10−12 kg
⎜ 1.2 g cm −3 ⎟
s= ⎝ ⎠
( )(
6π 1.002 × 10 kg m −1 s −1 10 × 10−6 m
−3
)
s = 4.479 929 031× 10−6 s
19-65
Chapter 19: Transport Properties Solutions
(
d = 4.394 8103 8 × 10 –5 m s −1 ) (3600 s )
d = 0.158 213 2 m
d = 1.58 × 10 –1 m
d.
4
( )( )
3
m = π 1× 10−6 m 1200 kg m −3
3
m = 5.026 55 × 10−15 kg
⎛ 0.998 g cm −3 ⎞
⎜1 −
⎜ 1.2 g cm −3 ⎟
(
⎟ 5.026 55 × 10−15 kg )
s= ⎝ ⎠
( )(
6π 1.002 ×10 kg m –1 s –1 1×10−6 m
–3
)
s = 4.479 929 × 10 –8 s
(
d = 4.394 8103 8 × 10 –7 m s −1 ) (3600 s )
d = 0.001 582 132 m
d = 1.58 × 10 –3 m
19-66
Chapter 19: Transport Properties Solutions
e.
4
( )( )
3
m = π 10 × 10−9 m 1200 kg m −3
3
m = 5.026 55 × 10−21 kg
⎛ 0.998 g cm −3 ⎞
⎜1 −
⎜ 1.2 g cm −3
(
⎟ 5.026 55 ×10−21 kg
⎟
)
s= ⎝ ⎠
(
6π 1.002 ×10 –3 kg )(
m –1 s –1 10 × 10−9 m )
s = 4.479 929 × 10 –12 s
(
d = 4.394 8103 8 × 10 –11 m s −1 ) (3600 s )
d = 1.582 13 × 10 –7 m
d = 1.58 × 10 –7 m
1× 10−3 m
υ=
3600 s
υ = 2.777 78 ×10−7 m s −1
19-67
Chapter 19: Transport Properties Solutions
4
( )( )
3
m = π 10 × 10−9 m 1200 kg m −3
3
m = 5.026 55 × 10−21 kg
⎛ 0.998 g cm −3 ⎞
⎜1 −
⎜ 1.2 g cm −3
(
⎟ 5.026 55 ×10−21 kg
⎟
)
s= ⎝ ⎠
(
6π 1.002 ×10 –3 kg )(
m –1 s –1 10 × 10−9 m )
s = 4.479 929 × 10 –12 s
υ
ω=
sx
2.777 78 × 10−7 m s −1
ω=
( 4.479 929 ×10 –12
)(
s 10 × 10−3 m )
ω = 2490.079 326 rad s −1
ω
(revolutions per second)
2π
= 396.308 4334 rps
= 23 778.506 rpm
2.38 ×104 rpm
19-68
Chapter 19: Transport Properties Solutions
*19.26. Perrin also carried out, using pigment particles, experiments on Brownian movement in which he determined distances traveled by
individual particles in various periods of time. For each of the particles of five different radii mentioned in the previous problem,
estimate the diffusion coefficient and the average distance traveled in 1 hour. Take the water temperature again as 20°C and use the
data of Problem 19.25.
Solution:
Given: Problem 19.25
Required: D, x2
kBT
D=
6π rη
Solving using the data from part a of the previous question we get,
kBT
D=
6π rη
D=
(1.381×10 −23
J K −1 ) ( 293.15 K )
(
6π 1.002 × 10 –3 kg m –1 s ) (10 ×10 m )
–1 –3
D = 2.143 46 × 10−16 m 2 s –1
D = 2.143 × 10−16 m 2 s –1
19-69
Chapter 19: Transport Properties Solutions
x 2 = 2 Dt
x2 = 2 Dt
x2 = (
2 2.143 46 ×10−16 m 2 s –1 ) (3600 s )
x 2 = 1.242 29 ×10−6 m
x 2 = 1.242 ×10−6 m
Repeating the above procedure for b – e, we summarize with the following results,
r/m D ×10−16 / m 2 s −1 x2 / μm
a. 10−3 2.143 1.242
b. 10−4 21.43 3.928
c. 10−5 214.3 12.42
d. 10−6 2143 39.28
e. 10−8 2.143 × 105 392.8
19-70
Chapter 19: Transport Properties Solutions
*19.27. A pure protein in water is centrifuged to equilibrium at 25 °C and at 25 000 rpm. At distances of 8.34 cm and 9.12 cm from the axis
of rotation the concentrations of the protein are measured to be 3.52 g cm–3 and 22.49 g cm–3, respectively. The specific volume V1
of the protein is 0.78 cm3 g–1, and the density of water at 25 °C is 0.997 g cm–3.Calculate the molecular weight of the protein.
Solution:
Given: T = 25 °C, 25 000 rpm, x1 = 8.34 cm, x2 = 9.12 cm, ρ1 = 3.52 g cm –3 , ρ 2 = 22.49 g cm –3
Required: M
We can calculate the molecular weight from Eq. 19.98,
2 RT ln(c2 /c1 )
M=
(1 − V2 ρ )ω 2 ( x22 − x12 )
25 000 rpm
ω= × 2π
60 s min −1
ω = 2617.993 878 rad s −1
⎛ 22.49 g cm −3 ⎞
(
2 8.3145 J K −1
mol −1
)( )
298.15 K ln ⎜
⎜ 3.52 g cm −3
⎟
⎟
M= ⎝ ⎠
(1 − ( 0.78 cm g ) ( 0.997 g cm )) ( 2617.993 878 rad s ) ((9.12 ×10
3 −1 −3 −1 2 −2
m ) − ( 8.34 ×10−2 m )
2 2
)
M = 4.430 571 965 kg mol−1
M = 4430.571 965 g mol−1
M = 4.43 ×103 g mol−1
19-71
Chapter 19: Transport Properties Solutions
*19.28. A protein has a molecular weight of 1 000 000 and a specific volume of 0.81 cm3 g–1. In an ultracentrifuge at 25 °C, what speed of
revolution is required to produce at equilibrium a concentration ratio of 20/1 at distances 10.00 cm and 9.00 cm from the axis of
revolution? The density of water at 25 °C is 0.997 g cm–3.
Solution:
Given: M = 106 g mol−1 , V2 = 0.81 cm3 g –1 , T = 25 °C, c2 /c1 = 20 /1, x1 = 10.00 cm, x2 = 9.00 cm
ρ water = 0.997 g cm –3
Required: ω
2 RT ln ( c2 c1 )
M=
(1 − V2 ρ ) ω 2 ( x22 − x12 )
2 RT ln ( c2 c1 )
ω=
(1 − V2 ρ ) M ( x22 − x12 )
ω=
(
2 8.3145 J K −1 mol−1 ) ( 298.15 K ) ln ( 20)
(1 − ( 0.81 cm g ) ( 0.997 g cm
3 −1 −3
)) (10 kg mol ) ((10.00 ×10 m ) − (9.00 ×10 m ) )
3 −1 −2 2 −2 2
ω=
( 201.552 775 1 rad s ) × 60 s −1
2π
ω = 1924.687 227 rpm
ω = 1.9 ×103 rpm
19-72