Chapter 19 Transport Properties

CHAPTER
19 Transport Properties
LAIDLER . MEISER . SANCTUARY

Physical Chemistry
Electronic Edition
Problems and Solutions

Chapter 19: Transport Properties Viscosity
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
*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
where A and Ea are constants.

a. For liquid CCl4 the viscosity at 0.0 °C is 1.33 × 10–3 kg m–1 s–1 and the activation energy Ea is 10.9 kJ mol–1. Estimate the
viscosity at 40.0 °C.
b. The Arrhenius equation does not apply well to associated liquids such as water, but it can be used over a limited temperature
range. At 20.0 °C the viscosity of water is 1.002 × 10–3 kg m–1 s–1 and the activation energy for fluidity 18.0 kJ mol–1. Estimate the
Solution
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
*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
19-3
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:
⎛ η (20 DC) ⎞ 3.1556(t − 20.0) + 1.925 ×10−3 (t − 20.0) 2

ln ⎜ ⎟=
⎝ η (t C) ⎠ 109.0 + t
D
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:
Na+: 5.19 × 10–4 cm2 V–1 s–1

CH3COO–: 4.24 × 10–4 cm2 V–1 s–1
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
*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
*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:
Given: vblood = 0.33m s −1 , raorta = 9 mm, η = 4.0 ×10 –3 kg m –1 s –1 , l = 0.5 m
Required: ΔP
To solve this problem we will use Eq. 19.10, the Poiseulle Equation.
dV ( P1 − P2 )π R 4
=
dt 8η l
Rearranging for ΔP we get,
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
Solving for ΔP we get,
8 ( 4.0 ×10 –3 kg m –1 s –1 ) ( 0.5 m )

ΔP = (8.397 48 ×10 −5
m3 s −1 )
π ( 9 ×10 m )
−3 4
ΔP = 65.18518519 kg m –1 s –2
1 kg m –1 s –2 = 1 Pa
ΔP = 65 Pa
Back to Problem 19.1 Back to Top

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:
Given: l = 1 mm, r = 2μ m, ΔP = 20 Torr, η = 4.0 ×10 –3 kg m –1 s –1
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
dV
= A × vblood
dt
A = π raorta
2
dV
= π raorta
2
vblood
dt
Rearranging to solve for vblood we obtain,
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
b. The volume of blood flow is defined above as,
19-12
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
*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:
Given: T = 25.0 °C, P = 101.325 kPa, η = 9.33 ×10 –6 kg m –1 s –1
Required: d , λ , Z A , Z AA
a. The molecular diameter is given in Eq. 19.15 as,

mu
η=
2 2π d 2
And therefore d is,
mu
d=
2 2πη
We calculate u from Table 1.3 as,
19-14
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
Solving for the diameter, we obtain
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
b. The mean free path is given in Chapter 1 by Eq. 1.68

V
λ=
2π d A2 N A
From the ideal gas law,
19-15
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
Therefore the mean free path is,
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
c. The expression for ZA is also found in Chapter 1 as Eq. 1.66,

2π d A2 u A N A
ZA = (SI unit :s −1 )
V
Which we recognize as,
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
d. From Eqs. 1.59 and 1.61,

1 N
Z AA = Z A
2 V
1
( )(
Z AA = 13 830 675103 s −1 2.461 42 × 1025 m −3
2
)
Z AA = 1.702 16 ×1035 m −3 s −1
Z AA = 1.70 ×1035 m −3 s −1
19-17
*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
where A and Ea are constants.

a. For liquid CCl4 the viscosity at 0.0 °C is 1.33 × 10–3 kg m–1 s–1 and the activation energy Ea is 10.9 kJ mol–1. Estimate the
b. The Arrhenius equation does not apply well to associated liquids such as water, but it can be used over a limited temperature
range. At 20.0 °C the viscosity of water is 1.002 × 10–3 kg m–1 s–1 and the activation energy for fluidity 18.0 kJ mol–1. Estimate the
Solution:
Given: CCl4 : η0.0 °C = 1.33 ×10 –3 kg m –1 s –1 , Ea = 10.9 kJ mol –1 , T = 40.0 °C
T = 20.0 °C, η = 1.002 ×10−3 kg m −1 s −1
Required: η 40.0 °C , for CCl4 and water
a. Since A is a constant, we first calculate e− Ea /RT at each temperature,
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
Since we are told viscosity has the inverse relationship to the fluidity φ , we calculate the viscosity at 40.0 °C as,
8.234 485 ×10−3

η40.0 °C = η0.0 °C ×
1.520 131 7 ×10−2
8.234 485 ×10−3
η 40.0 °C = 1.33 ×10 –3 kg m –1 s –1 ×
1.520 131 7 × 10−2
η 40.0 °C = 7.204 55 ×10 –4 kg m –1 s –1
η 40.0 °C = 7.20 ×10 –4 kg m –1 s –1
b. Repeating the same procedure above for water, we get,
19-19
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
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:
Given: T = 20.0 °C, η pure = 5.90 ×10 –4 kg m –1 s –1 , ρ = 0.1 g dm –3
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
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
*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:
Given: Problem 19.5, M a = 20 000 g mol−1 , M c = 40 000 g mol−1 , Eq.19.33
Required: M b
The Mark-Houwink equation, given by Eq.19.33 is
[η ] = kM rα
If it is obeyed, a plot of log [η] against log Mr will be a straight line.

Taking the logarithms of the solutions to Problem 19.5 gives,
log [ηa ] = log ( 0.084 745 763)

log [ηa ] = −1.071882 007
log [η b ] = log ( 0.254 237 288 )
log [η b ] = −0.594 760 753
log [ηc ] = log ( 0.627 118 644 )
log [ηc ] = −0.202 650 288
The logarithms of the molar masses,
log M a = log ( 20 000 )

log M a = 4.301 029 996
log M c = log ( 40 000 )
log M c = 4.602 059 991
Since we assume a linear relationship the slope will be,
19-23
log [ηc ] − log [ηa ]

m=
log [ M c ] − log [ M a ]
−0.202 650 228 − ( −1.071 882 007 )
m=
4.602 059 991 − 4.301 029 996
m = 2.887 525 474
Using y = mx + b , we can use the coordinate of log M a and log [ηa ] to determine the intercept b.
log [ηa ] = m × log M a + b

−1.071 882 007 = 4.301 029 996 × 2.887 525 474 + b
b = −13.491 212 568
the molar mass will then be,
log [ηb ] = m × log M b + b

−0.594 760 753 = 2.887 525 474 × M b + ( −13.491 212 568 )
log M b = 4.466 264 254
M b = 104.466 264 254
M b = 29 259.321 7 g mol−1
M b = 2.9 ×104 g mol−1
19-24
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:
Given: Ea = 12.6 kJ mol –1 , η0.0 °C = 7.06 ×10 –4 kg m –1 s –1
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
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
3.895 402 × 10−3

η 40.0 °C = η0.0 ° C ×
7.912 639 816 × 10−3
⎛ 3.895 402 ×10−3 ⎞
η 40.0 °C = ( 7.06 × 10−4 kg m −1 s −1 ) × ⎜ −3 ⎟
⎝ 7.912 639 816 ×10 ⎠
η 40.0 °C = 3.475 646 404 ×10−4 kg m −1 s −1
η 40.0 °C = 3.48 ×10−4 kg m −1 s −1
b. Using the equation above, we get a better estimate.

η = A (T / K ) exp ⎡⎣543 (T / K ) ⎤⎦
−1.72
T = 0.0 °C
⎛ 543 ⎞
T −1.72 exp ( 543 / T ) = ( 273.15 )
−1.72
× exp ⎜ ⎟
⎝ 273.15 ⎠
19-26
T −1.72 exp ( 543 / T ) = 4.706 868 453 × 10−4

T = 40.0 °C
⎛ 543 ⎞
T −1.72 exp ( 543 / T ) = ( 313.15 )
−1.72
× exp ⎜ ⎟
⎝ 313.15 ⎠
T −1.72 exp ( 543 / T ) = 2.886 486 719 ×10−4
2.886 486 719 ×10−4
η40.0 °C = η0.0 °C ×
4.706 868 453 ×10−4
⎛ 2.886 486 719 ×10−4 ⎞
η40.0 °C = ( 7.06 ×10−4 kg m −1 s −1 ) × ⎜ −4 ⎟
⎝ 4.706 868 453 ×10 ⎠
η40.0 °C = 4.329 544 461×10−4 kg m −1 s −1
η40.0 °C = 4.33 ×10−4 kg m −1 s −1
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 ⎠
The activation energy at 20 °C is, by definition,
19-27
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
Ea = 8707.320 561 J mol−1

Ea = 8.71 kJ mol−1
19-28
*19.8. Over its entire liquid range the viscosity of water is represented to within 1% by the following empirical formula:
⎛ η (20 DC) ⎞ 3.1556(t − 20.0) + 1.925 ×10−3 (t − 20.0) 2

ln ⎜ ⎟=
⎝ η (t C) ⎠ 109.0 + t
D
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
⎛ η (20 DC) ⎞ 3.1556 ( 40 − 20.0 ) + 1.925 ×10−3 ( 40 − 20.0 )

2
ln ⎜ ⎟=
⎝ η (40 C) ⎠ 109.0 + 40
D
3.1556 ( 20.0 ) + 1.925 ×10−3 ( 400 )

ln (1.002 ×10 kg m s ) − ln η 40 DC =
–3 –1 –1
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
η40 C = 6.526 33 ×10 –4 kg m –1 s –1

D
η40 C = 6.53 ×10 –4 kg m –1 s –1

D
To find the activation energies, we use the definition
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
( a + 2bT − 586.3b )(T − 164.15) − a (T − 293.15 ) − b (T − 293.15)

2
d ln η
=−
(T − 164.15)
2
dT
19-30
a. At T = 20.0 °C , the activation energy is,

( )
Ea = 8.3145 J K mol−1 ( 293.15 K )
2
( a + 2b ( 293.15 K ) − 586.3b ) ( 293.15 K − 164.15) − a ( 293.15 K − 293.15) − b ( 293.15 K − 293.15) 2
×
( 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
b. At T = 100.0 °C , the activation energy is,

( )
Ea = 8.3145 J K mol−1 ( 373.15 K )
2
×
( 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
*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
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
a. To find viscosity, we use Eq. 19.16,

(mk T )1/ 2 (mkBT )1/ 2
η = 3/B2 2 =
π d π 1/ 2σ
For the helium atom, the mass is given by,
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
Solving for η we get,
19-33
( )( )
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
b. We calculate the self-diffusion coefficient from Eq. 19.57,

η = ρD
η
D=
ρ
mN mP
ρ= =
V kBT
η kBT
D=
mP
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
c. We calculate u from Table 1.3 as,
19-34
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
d. The mean free path is given in Chapter 1 by Eq. 1.68

V
λ=
2π d A2 N A
From the ideal gas law,
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
e. The expression for ZA is also found in Chapter 1 as Eq. 1.66,
19-35
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
f. From Eqs. 1.59 and 1.61,

1 N
Z AA = Z A
2 V
1
( )( )
−1
Z AA = 7 264 683 644 s −1 3.722 03 × 10−26 m3
2
Z AA = 9.759 03 × 1034 m −3 s −1
Z AA = 9.76 × 1034 m −3 s −1
19-36
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:
Given: H 2 : P = 101.325 kPa, t = 10 s, D = 1.005 ×10 –4 m 2 s –1
Required: x2
From Eq. 19.48, the mean square distance is given by,
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
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
From Eq. 19.48, the mean square distance is given by,
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
For the virus,
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
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
From Table 7.3, we obtain the molar conductivities,
λ1 = 56.6 Scm 2 mol –1

Cu 2+
2
λ1 = 80.0 Scm 2 mol –1

SO24−
2
For Cu2+,
(
D+ = 1.331 03 ×10−7 ( 56.6 ) )
D+ = 7.533 6 ×10−6 cm 2 s –1
For SO42–,
19-39
( )
D− = 1.331 03 ×10−7 ( 80.0 )
D− = 1.064 82 ×10−5 cm 2 s –1
Using Eq. 19.74,
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
19.14. Estimate the diffusion coefficient of sodium acetate in water at 25 °C from the following mobility values:
Na+: 5.19 × 10–4 cm2 V–1 s–1

CH3COO–: 4.24 × 10–4 cm2 V–1 s–1
Solution:
Given: T = 25 °C, ue, Na + = 5.19 ×10 –4 cm 2 V –1 s –1 , ue , CH COO – = 4.24 ×10 –4 cm 2 V –1 s –1 mobility

3
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
D = ( 0.025 688 789 V ) ue
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
Using Eq. 19.74,
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
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:
Given: D = 6.3 × 10 –11 m 2 s –1 , T = 20 °C, η = 1.002 ×10 –3 kg m –1 s –1 , Vspecific = 0.75 cm3 g –1
Required: r , M
Stokes law is given by Eq. 19.77 as,
kBT
D=
6π rη
Solving for r, the radius of the hemoglobin molecule we get,
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
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
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:
Given: D = 8.2 × 10 –11 m 2 s –1 , T = 20 °C, x = 10 μ m
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
*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:
Given: d = 0.3 μ m, ρ = 1.18 g cm –3 , x = 1 mm, T = 20 °C,
η = 1.002 ×10 –3 kg m –1 s –1 , ρ water = 1.18 g cm –3
Required: t
The mean time can be obtained from Eq. 19.48,
x 2 = 2 Dt
x2
t=
2D
Stokes law gives D in Eq. 19.77 as,

kBT
D=
6π rη
d
r = = 1.5 × 10−7 m
2
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
Solving for t, we get,
(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
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:
T = 20 °C, s = 4.60 ×10−13 s, D = 5.96 ×10 –7 cm 2 s –1 , Vspecific = 0.736 cm 3 g –1 , ρ = 0.998 g cm –3
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)
( 5.96 ×10 –11

( (
m 2 s –1 ) 1 − 0.736 cm3 g –1 ) ( 0.998 g cm )) –3
M = 70.862 894 28 J mol−1 m −2 s 2

1 J = 1 kg m 2 s −2
M = 70.9 kg mol−1
M = 70.9 ×103 g mol−1
19-48
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
*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:
Given: T = 25 °C, M = 60 000 g mol−1 , ρ protein = 1.31 g cm −3 , s = 4.1×10 –11 s –1 ,

ρ H O = 0.997 g cm –3 , η = 8.937 ×10 –4 kg m –1 s –1
2
Required: f from a and b

a. To calculate the frictional coefficient from the sedimentation coefficient, we use Eq. 19.86,
(1 − V2 ρ )mω 2 x υ
υ= , where s = 2 from Eq. 19.87.
f ω x
Therefore we get the frictional coefficient as,
(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
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
Using r, we now solve for f.
19-51
(
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
*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:
Given: Problem 19.17, x = 1 mm, g = 9.81 m s –2
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
The speed is therefore,
⎛ 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
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
*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:
Given: d = 1.33 g cm –3 , T = 25 °C, D = 1.20 × 10 –11 m 2 s –1 ,

ρ H2O = 0.997 g cm –3 , ηH2O = 8.937 ×10 –4 kg m –1 s –1
Required: s
To find the sedimentation coefficient, we will use Eq. 19.89,
(1 − V2 ρ )m
s=
6πη r
We find the radius using Stokes Law, Eq. 19.77,
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
The mass of each particle is calculated using volume and density,
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
The sedimentation coefficient is,
⎛ 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
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:
Given: T = 20 °C, s = 7.75 × 10−13 s, D = 4.8 ×10−11 m 2 s −1 , ρ =1.353 g cm −3 ,
ρ H O = 0.998 g cm –3 , η = 1.002 ×10 –3 kg m –1 s –1

2
Required: M, r
1
a. We solve this problem in the same manner as Problem 19.18, making the substitution for V2 as .
ρ
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
b. To estimate radius, we use the Stokes-Einstein equation, Eq.19.77

kT
D= B
6π rη
kT
r= B
6πη D
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
*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)
( 6.9 ×10 –11

( (
m 2 s –1 ) 1 − 0.749 cm3 g –1 ) ( 0.998 g cm ))–3
M = 62.675 385 94 J mol−1 m −2 s 2

1 J = 1 kg m 2 s −2
M = 62.7 kg mol−1
M = 62.7 ×103 g mol−1
19-59
b. Using Einstein’s equation, Eq. 19.48, the molecule would diffuse,

x 2 = 2 Dt
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
Therefore the distance travelled is,

d = vt
(
d = 4.394 88 ×10−12 m s −1 ) ( 60 s )
d = 2.636 93 ×10−10 m
d = 2.64 × 10−10 m
d. The rate of sedimentation in an ultracentrifuge is given by Eq. 19.87

υ = sω 2 x
The speed of revolution ω is
⎛ 15 000 rpm ⎞
ω =⎜ –1 ⎟
× 2π
⎝ 60 s min ⎠
ω = 1 570.796 327 rad s –1
19-60
The rate of sedimentation, with x = 20 cm is,
υ = ( 4.48 ×10−13 s )(1 570.796 327 rad s –1 ) ( 0.2 m )

2
υ = 2.210 79 ×10−7 m s –1

d = vt
(
d = 2.210 79 × 10−7 m s −1 ) ( 60 s )
d = 1.326 47 ×10−5 m
d = 1.33 × 10−5 m
e. To estimate radius, we use the Stokes-Einstein equation, Eq.19.77

kT
D= B
6π rη
kT
r= B
6πη D
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
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.
19-62
*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:
Given: ρ = 1.2 g cm –3 , r , t = 1 h, T = 20 °C, η = 1.002 ×10 –3 kg m –1 s –1 , ρ water 0.998 g cm –3
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
The mass of the particle is calculated as,

m =Vρ
4
m = π r3ρ
3
4
( )( )
3
m = π 1×10−3 m 1.2 g cm −3 = 1200 kg m −3
3
m = 5.026 55 × 10−6 kg
19-63
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
The rate of sedimentation in a gravitational field is therefore,
v = 9.81 m s −2 × 0.044 799 29 s

v = 0.439 481 038 m s −1

d = vt
(
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
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
v = 9.81 m s −2 × 4.479 929 ×10 –4 s

v = 4.394 8103 8 × 10 –3 m s −1
(
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
ν = 9.81 m s −2 × 4.479 929 031×10−6 s

ν = 9.394 810 379 ×10−5 m s −1
(
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
v = 9.81 m s −2 × 4.479 929 ×10 –8 s

v = 4.394 8103 8 ×10 –7 m s −1
(
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
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
v = 9.81 m s −2 × 4.479 929 ×10 –12 s

v = 4.394 8103 8 × 10 –11 m s −1
(
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
f. The rate of sedimentation in an ultracentrifuge is given by Eq. 19.87

υ = sω 2 x
The rate of sedimentation is,
1× 10−3 m
υ=
3600 s
υ = 2.777 78 ×10−7 m s −1
The sedimentation coefficient is calculated as,
19-67
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
This leads to,
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
*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
The diffusion coefficient is given by Eq. 19.77 as,
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
Using Einstein’s equation, Eq. 19.48,
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
*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
V1 = 0.78 cm3 g –1 , ρ water = 0.997 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 )
Solving for ω we get,
25 000 rpm
ω= × 2π
60 s min −1
ω = 2617.993 878 rad s −1
Taking the density of the protein as a measure of the concentration, we solve.]
⎛ 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
*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
We can solve for ω using Eq. 19.98,
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 −1

in rpm,
ω=
( 201.552 775 1 rad s ) × 60 s −1
2π
ω = 1924.687 227 rpm
ω = 1.9 ×103 rpm
19-72

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CHAPTER

LAIDLER . MEISER . SANCTUARY

Problems and Solutions

where A and Ea are constants.

⎛ η (20 DC) ⎞ 3.1556(t − 20.0) + 1.925 ×10−3 (t − 20.0) 2

Na+: 5.19 × 10–4 cm2 V–1 s–1

Given: vblood = 0.33m s −1 , raorta = 9 mm, η = 4.0 ×10 –3 kg m –1 s –1 , l = 0.5 m

Rearranging for ΔP we get,

Solving for ΔP we get,

8 ( 4.0 ×10 –3 kg m –1 s –1 ) ( 0.5 m )

Back to Problem 19.1 Back to Top

Given: l = 1 mm, r = 2μ m, ΔP = 20 Torr, η = 4.0 ×10 –3 kg m –1 s –1

Rearranging to solve for vblood we obtain,

b. The volume of blood flow is defined above as,

Back to Problem 19.2 Back to Top

Given: T = 25.0 °C, P = 101.325 kPa, η = 9.33 ×10 –6 kg m –1 s –1

a. The molecular diameter is given in Eq. 19.15 as,

And therefore d is,

We calculate u from Table 1.3 as,

Solving for the diameter, we obtain

b. The mean free path is given in Chapter 1 by Eq. 1.68

From the ideal gas law,

Therefore the mean free path is,

c. The expression for ZA is also found in Chapter 1 as Eq. 1.66,

d. From Eqs. 1.59 and 1.61,

Back to Problem 19.3 Back to Top

where A and Ea are constants.

Given: CCl4 : η0.0 °C = 1.33 ×10 –3 kg m –1 s –1 , Ea = 10.9 kJ mol –1 , T = 40.0 °C

T = 20.0 °C, η = 1.002 ×10−3 kg m −1 s −1

Required: η 40.0 °C , for CCl4 and water

a. Since A is a constant, we first calculate e− Ea /RT at each temperature,

8.234 485 ×10−3

b. Repeating the same procedure above for water, we get,

Back to Problem 19.4 Back to Top

Given: T = 20.0 °C, η pure = 5.90 ×10 –4 kg m –1 s –1 , ρ = 0.1 g dm –3

Back to Problem 19.5 Back to Top

Given: Problem 19.5, M a = 20 000 g mol−1 , M c = 40 000 g mol−1 , Eq.19.33

The Mark-Houwink equation, given by Eq.19.33 is

If it is obeyed, a plot of log [η] against log Mr will be a straight line.

log [ηa ] = log ( 0.084 745 763)

The logarithms of the molar masses,

log M a = log ( 20 000 )

Since we assume a linear relationship the slope will be,

log [ηc ] − log [ηa ]

log [ηa ] = m × log M a + b

the molar mass will then be,

log [ηb ] = m × log M b + b

Back to Problem 19.6 Back to Top

Given: Ea = 12.6 kJ mol –1 , η0.0 °C = 7.06 ×10 –4 kg m –1 s –1

3.895 402 × 10−3

b. Using the equation above, we get a better estimate.

T −1.72 exp ( 543 / T ) = 4.706 868 453 × 10−4

The activation energy at 20 °C is, by definition,

Ea = 8707.320 561 J mol−1

Back to Problem 19.7 Back to Top

⎛ η (20 DC) ⎞ 3.1556(t − 20.0) + 1.925 ×10−3 (t − 20.0) 2

⎛ η (20 DC) ⎞ 3.1556 ( 40 − 20.0 ) + 1.925 ×10−3 ( 40 − 20.0 )

3.1556 ( 20.0 ) + 1.925 ×10−3 ( 400 )