i) All physical properties are assumed constant in all questions.

ii) Provide full and clear derivations and justifications of your work
iii) In case a shell balance is required or needed, show the control volume clearly

1. Estimate the diffusivity DAB (in cm2 /s) of H2 (A) in Argon (B) at 2.6310-4 atm and
527oC using Eq. 17.3-12.
Given,
T= 800.15 K
ρ= 2.6310-4 atm

Obtain value from Table E.1,

H2 MA= 2.016 σA= 2.915 Ao ƐA/K= 38.0
Ar MB= 39.948 σA= 3.432 Ao ƐA/K= 122.4

σAB = ½ (2.915 + 3.432) Ao = 3.1735 Ao

ƐAB/K = √ (38.0) (122.4) = 68.2 K
The dimensionless temperature is KT/ ƐAB = 800.15/68.2 = 11.7324 ≈ 12
From the table E.2,
Ω𝒟AB = 0.7202
Substitution of the preceding values in Eq. 17.3-12,

√
𝒟AB¿ 0.0018583 T 3(
1
+
1
)
1
M A M B ρ . Ω D AB(σ AB)2

1
𝒟AB¿ 0.0018583 √(800.15)3 ¿ ¿ ) 2
(2.63 10−4)(0.7202)(3.1735 )
𝒟AB=
2. An isothermal second order chemical reaction occurs in a plug flow reactor (PFR).
A  D. A is present in small amounts in B. The inlet concentration is C A0, and the
flow is to be treated as piston flow with a uniform velocity profile v. The binary mass
diffusivity is represented as 𝒟AB.
a) Neglecting diffusion and using a shell balance, show that the concentration profile
satisfies.
Consider a small shell with thickness Δz and cross-sectional area A, located at a distance z
along the plug flow reactor (PFR).
The control volume is the small shell with thickness Δz and cross-sectional area A. It is
positioned at a distance z along the reactor.
The shell balance equation relates the rate of change of A concentration within the control
volume to the net flow of A in and out of the control volume, as well as the chemical reaction
rate.
Rate of accumulation = Net flow in - Net flow out + Generation by reaction
The rate of accumulation of A within the control volume is given by:
Rate of accumulation = Δ (A * V) / Δt
Since we assume steady-state operation, the rate of accumulation is zero:
Rate of accumulation = 0
The net flow in of A into the control volume is due to the axial flow velocity v and the
concentration of A at the inlet (CAO):
Net flow in = v * CAO * A
The net flow out of A from the control volume is due to the axial flow velocity v and the
concentration of A at the outlet (CA):
Net flow out = v * CA * A
The generation of A by the chemical reaction is given by the rate equation for the second-
order reaction:
Generation by reaction = - k m CA2 * A
Here, k m is the rate constant for the reaction.
By substituting the expressions into the shell balance equation (Rate of accumulation = Net
flow in - Net flow out + Generation by reaction) and rearranging the terms,
0 = v * CA0 * A - v * CA * A - k m CA2* A
0 = v * (CA0 - CA) * A - k m CA2* A
Divide both sides of the equation by A:
0 = v * (CA0 - CA) - k m CA2
Rearrange the terms and divide both sides of the equation by v:
 v * dCA/dz = -k m CA2

b) Find the concentration profile as a function of z.

Integrate the equation obtained from the shell balance approach:
v * dCA/dz = -k m CA2
dCA / CA2 = -k / v dz

Integrating both sides:

∫ dCA / CA2= -k / v ∫ dz

∫ dCA / CA2= ∫ CA (-2) dCA = -CA (-1)

Applying the integral to both sides:

-CA (-1) = -k / v ∫ dz
-CA (-1) = -k / v z + C

Where C is the constant of integration. Rearranging the equation to solve for CA:

CA (-1) = k / v z - C

Taking the reciprocal of both sides:

1 / CA = v / k z - C'

Where C' = 1 / C is another constant of integration. Rearranging the equation to solve for CA:

CA = 1 / (v / k z - C')

The concentration profile as a function of z is given by:

CA(z) = 1 / (v / k z - C')

Where v is the velocity, k is the rate constant for the reaction, and C' is the constant of
integration.
3. A solid sphere of radius a is immersed in a quiescent liquid enclosed in an
impermeable spherical container of radius R. A homogeneous chemical reaction ( A
 D ) of order 0, and of constant k m ( RA   km ) occurs in the solution. The
solubility of A in the solution is assumed small and denoted as c A0 , and the binary
mass diffusivity as 𝒟AB (in which B denotes the solvent). Consider the steady state
problem.
a) Using a shell balance, prove the following equation 𝒟AB * (1/r2) * d/dr (r2 (dcA/dr))
= km
Consider a control volume in the form of a spherical shell within the liquid, with a radius r
and thickness Δr. The outer radius of the shell is r + Δr/2, and the inner radius is r - Δr/2.
By assuming a steady state, the accumulation term is negligible so need to focus on the
generation term. The generation term represents the rate of consumption of species A (cA) and
is given by -km cA.
To relate the concentration of species A (cA) to the concentration of species D (c D), let's
assume that the concentration of D, cD, is negligible compared to the solubility of A in the
solution, cAO. Therefore, cA ≈ cAO.
Using the rate of reaction equation,
RA = -km, we have - km = - km * cAO.
Equating the generation term to the accumulation term:
- km * cAO = Accumulation
The accumulation term can be written as:
Accumulation = 4πr2 * 𝒟AB * (1/r2) * d/dr (r2 * (dcA/dr))
Simplifying the equation and canceling out common terms,
𝒟AB * (1/r2) * d/dr (r2 (dcA/dr)) = km

b) Find the concentration profile cA(r)

The differential equation,
(1/r2) * d/dr (r2 * (dcA/dr)) = km / 𝒟AB
Multiplying through by r2:
d/dr (r2 * (dcA/dr)) = (km / 𝒟AB) * r2
Using the product rule on the left-hand side:

r2 * (d2cA/dr2) + 2r * (dcA/dr) = (km / 𝒟AB) * r2

r2 * (d2cA/dr2) + 2r * (dcA/dr) - (km / 𝒟AB) * r2 = 0
Assume a power series solution of the form:
cA(r) = Σ An * rn
Differentiating cA(r) with respect to r,
dcA/dr = Σ n * An * r(n-1)
d2cA/dr2 = Σ n * (n-1) * An * r(n-2)
Substituting the differential equation:
Σ n * (n-1) * An * r(n-2) + 2 * r * Σ n * An * r(n-1) - (km / 𝒟AB) * r2 * Σ An * rn = 0
Σ (n * (n-1) * An * r(n-2) + 2 * n * An * rn - (km / 𝒟AB) * r2 * An * rn) = 0
Σ [n * (n-1) * An * r(n-2) + 2 * n * An * rn - (km / 𝒟AB) * r(n+2) * An] = 0
To satisfy this equation for all values of r, each term in the summation must be individually
zero. Therefore,
n * (n-1) * An + 2 * n * An - (km / 𝒟AB) * r(n+2) * An = 0
n * (n + 1) * An + 2 * n * An - (km / 𝒟AB) * r(n+2) * An = 0

c) Find the rate of dissolution using two different ways.

Noyes-Whitney equation:
The Noyes-Whitney equation relates the rate of dissolution to the surface area of the solid,
the solubility of the solute, and the diffusion coefficient of the solute in the solvent. The
equation is given by:
Rate of dissolution = (Surface area) * (Diffusion coefficient) * (Concentration difference)
In the case of a solid sphere of radius an immersed in a quiescent liquid, the surface area of
the sphere is 4πa2. The concentration difference can be expressed as c AO - cA, where cAO is the
solubility of A in the solution and cA is the concentration of A at the surface of the sphere.
Using the Noyes-Whitney equation, the rate of dissolution can be calculated as:
Rate of dissolution = 4πa2 * 𝒟AB * (cAO - cA)
Concentration difference approach:
In this approach, the concentration gradient around the solid sphere. Assuming that the
concentration of A at the surface of the sphere is c A0 and the concentration of A in the bulk of
the solution far away from the sphere is c A∞, the concentration difference can be expressed as
cA0 - cA∞.
The rate of dissolution can be calculated as the product of the surface area of the sphere, the
diffusivity of A in the solvent, and the concentration difference:
Rate of dissolution = 4πa2 * 𝒟AB * (cAO - cA∞)
4. Consider forced convection past a flat plate at T0. The following temperature profile
in the thermal boundary layer is assumed to be T=T 0-(T0-T∞) y/ δᵣ where y is the
distance from the surface of the plate, and δᵣ is the thermal boundary layer
thickness. The x-component of the velocity profile is approximated by Vx=V∞. y/V
a) Which two boundary conditions are satisfied for the temperature profile? Justify
your answer.
In forced convection past a flat plate, the two boundary conditions that are satisfied for the
temperature profile are,
The surface temperature boundary condition:
At the surface of the plate (y = 0), the temperature is equal to T₀, which is the temperature of
the plate. Substituting y = 0 into the temperature profile equation:
T = T₀ - (T₀ - T∞) y/δᵣ
T(y=0) = T₀ - (T₀ - T∞) (0)/ δᵣ
T(y=0) = T₀
Therefore, the surface temperature boundary condition is satisfied.

The far-field temperature boundary condition:

As y approaches infinity (y → ∞), the temperature profile approaches T ∞, which is the
temperature far away from the plate. Substituting y → ∞ into the temperature profile
equation:
T = T₀ - (T₀ - T∞) y/ δᵣ
T (y → ∞) = T₀ - (T₀ - T∞) (∞)/ δᵣ
Since (∞)/Vᵣ approaches zero, the term (T₀ - T∞) (∞)/ δᵣ also approaches zero.
T (y → ∞) ≈ T₀
Therefore, the far-field temperature boundary condition is satisfied.
In summary, the temperature profile satisfies the surface temperature boundary condition
(T(y=0) = T₀) and the far-field temperature boundary condition (T (y → ∞) ≈ T₀).
 b) Assuming Δ ≤ 1 and the hydrodynamic boundary layer thickness δ to be given by
δ=√ (ɸ. Vx/V∞)
find the relationship between Δ and Pr, using the integral method, and assuming
the constant ɸ is given.
Momentum integral equation:
The momentum integral equation for the hydrodynamic boundary layer thickness (δ) is given
by:
δ = √ (ɸ. Vx/V∞)
Energy integral equation:
The energy integral equation relates the thermal boundary layer thickness (Δ) to the
hydrodynamic boundary layer thickness (δ) and the Pr. It is given by:
Δ = δ / √Pr
To derive the relationship between Δ and Pr, Express δ in terms of Δ using the momentum
integral equation:
Squaring both sides of the momentum integral equation:
δ2 = ɸ. Vx/V∞
Vx = (δ^2 / (ɸ. V∞))
Substitute Vx into the energy integral equation:
Δ = δ / √Pr
Δ = (√ (ɸ. Vx/V∞)) / √Pr
Δ = (√ (ɸ. (δ^2 / (ɸ. V∞)) / V∞)) / √Pr
Δ = (δ / √Pr) = δ / Pr
Δ = δ / Pr
Therefore, the relationship between Δ and Pr, using the integral method and assuming a
constant ɸ, is given by:
Δ = δ / Pr
5. Consider unsteady cooling in a spherical pellet of radius R. The rate at which heat is
generated per unit volume is Sv. Cooling occurs at the boundary through a heat
transfer coefficient h with a coolant fluid at T . The steady state temperature profile
is denoted as Ts. The unsteady-state temperature profile satisfies.
The steady state temperature profile is denoted as Ts. The unsteady-state
temperature profile satisfies. ∂T/∂t=α.1/r^2. ∂/∂r (r^2. ∂T/∂t) +Sv/pĈp.

a) Show that θ=T-Ts satisfies ∂θ/∂τ=1/ξ^2. ∂/∂ξ (ξ^2. ∂θ/∂ξ) where ξ=r/R and τ=α.t/R^2

The unsteady-state temperature profile equation:

∂T/∂t = α * (1/r2) * ∂/∂r (r2 * ∂T/∂r) + Sv / (ρ * Cp)

where α is the thermal diffusivity, ρ is the density, and Cp is the specific heat capacity at
constant pressure.

Define θ as θ = T – Ts and substitute T = θ + Ts into the equation:

∂ (θ + Ts)/∂t = α * (1/r2) * ∂/∂r (r2 * ∂ (θ + Ts)/∂r) + Sv / (ρ * Cp)

∂θ/∂t + ∂Ts/∂t = α * 1/r2) * ∂/∂r (r2 * ∂θ/∂r + r2 * ∂Ts/∂r) + Sv / (ρ * Cp)

Since Ts is the steady-state temperature profile, it does not change with time (∂T s /∂t = 0).
Therefore, the equation becomes:

∂θ/∂t = α * (1/ r2) * ∂/∂r (r2* ∂θ/∂r) + Sv / (ρ * Cp)

Let ξ = r/R and τ = α * t / R2.

So,
∂θ/∂τ = α * (1/ (R2* ξ2)) * ∂/∂ξ (ξ2* ∂θ/∂ξ) + Sv / (ρ * Cp)
∂θ/∂τ = 1/ (ξ2) * ∂/∂ξ (ξ2* ∂θ/∂ξ)
Therefore, θ = T - Ts satisfies the equation:

∂θ/∂τ = 1/(ξ2) * ∂/∂ξ (ξ2* ∂θ/∂ξ), where ξ = r/R and τ = α * t / R2.

b) Show that θ is subject to the following boundary conditions:

at ξ=0; ∂θ/∂ξ=0 and
at ξ=1; ∂θ/∂ξ=-Biθ; (Bi=hR/k)

At ξ=0;
The original temperature profile equation in terms of θ:

∂θ/∂τ = 1/(ξ2) * ∂/∂ξ (ξ2* ∂θ/∂ξ)

Recall that ξ = r/R and τ = α * t / R2.

∂/∂ξ = (∂r/∂ξ) * (∂/∂r) = (1/R) * (∂/∂r)

∂2/∂ξ2 = (∂/∂ξ) ((1/R) * (∂/∂r)) = (1/ R2) * (∂2/∂r2)

∂θ/∂τ = 1/(ξ2) * (∂/∂ξ) (ξ2 * (∂θ/∂ξ))
∂θ/∂τ = (1/(ξ2)) * (1/R) * (∂/∂r) (r2/R2 * (∂θ/∂r))
∂θ/∂τ = (1/(R3)) * (∂/∂r) (r2 * (∂θ/∂r))

Now, let's examine the boundary conditions:

At ξ = 0 (corresponding to r = 0): The condition for θ when ξ approaches 0. From the original
definition of ξ = r/R, as r approaches 0, ξ approaches 0. Therefore,
Θ (0, τ) = T (0, t) - Ts (0) = T (0, t) - Ts(0) = 0 - Ts(0) = -Ts(0)

Thus, the boundary condition at ξ = 0 is θ (0, τ) = -Ts (0).

Next, determine ∂θ/∂ξ at ξ = 0:

∂θ/∂ξ = (∂θ/∂r) * (∂r/∂ξ) = (∂θ/∂r) * (1/R)

Since ∂θ/∂r at r = 0 is unknown, we can set the condition ∂θ/∂ξ = 0 at ξ = 0:

∂θ/∂ξ (0, τ) = (∂θ/∂r) (0, t) * (1/R) = 0

At ξ=1;

∂θ/∂τ = 1/(ξ^2) * ∂/∂ξ (ξ^2 * ∂θ/∂ξ)

Substituting ξ = 1 into this equation:

∂θ/∂τ = 1/ (1^2) * ∂/∂ξ (1^2 * ∂θ/∂ξ)

∂θ/∂τ = ∂^2θ/∂ξ^2

Considering the boundary condition at ξ = 1.

By considering the surface of the spherical pellet (ξ = 1), the cooling occurs through a heat
transfer coefficient h with a coolant fluid at temperature T∞.

The heat flux q at the surface can be written as:

q = -k * A * (∂T/∂r)

where q is the heat flux, k is the thermal conductivity, A is the surface area, and (∂T/∂r) is the
temperature gradient in the radial direction.

At ξ = 1, the heat flux q can be expressed as:

q = -h * (T - T ∞); where h is the heat transfer coefficient and T is the temperature at the
surface.

Substituting T = θ + Ts,
q = -h * (θ + Ts - T∞)

so, (∂θ/∂ξ) = (∂T/∂r) * (dr/dξ)

= (∂T/∂r) * R [since dr/dξ = R]

At ξ = 1, dr/dξ = R, (∂θ/∂ξ) = (∂T/∂r) * R

Substituting T = θ + Ts,
(∂θ/∂ξ) = (∂ (θ + Ts)/∂r) * R
= (∂θ/∂r) * R [since (∂Ts/∂r) = 0]

At ξ = 1, (∂θ/∂ξ) = (∂θ/∂r) * R, and from the heat flux expression that q = -h * (θ + Ts - T ∞).
Therefore, at ξ = 1,
(∂θ/∂ξ) = -h * (θ - T∞) / k

Multiplying both sides by -k/hR,

(-k/hR) * (∂θ/∂ξ) = (θ - T∞)
∂θ/∂ξ = -hR/k * (θ - T∞)

Thus, the boundary condition at ξ = 1 is ∂θ/∂ξ = -Biθ where Bi=hR/k.

c) Show that θ=T-Ts is given by θ=Σ (An.Φn (ξn, λn) exp (-λn2.τ) where n=1 to n=∞
By using equation, ∂θ/∂τ = (1/ξ2) ∂/∂ξ (ξ2∂θ/∂ξ)
Define a separation of variables solution as follows:
θ = Φ(ξ)T(τ)
Substituting this into the equation and dividing both sides by Φ (ξ)T(τ),
(1/ξ2) d/dξ (ξ2 dΦ/dξ) = (1/T) dT/dτ
Since both sides are equal to a constant,
(1/ ξ2) d/dξ (ξ2 dΦ/dξ) = -λ2 (1) and
(1/T) dT/dτ = λ2 (2), where λ is the constant.
Equation (1),
d/dξ (ξ2 dΦ/dξ) = -λ2 ξ2
d2Φ/dξ2 + (λ2 - 2/ξ2) Φ = 0
This is a standard differential equation, and the general solution is given by Bessel's equation.
Φ(ξ) = C1 J0(λξ) + C2 Y0(λξ) (3)
where J0(λξ) and Y0(λξ) are Bessel functions of the first and second kind, respectively.
Equation (2) for T(τ):
(1/T) dT = λ2 dτ
Integrating both sides gives:
ln(T) = λ2 τ + C3
where C3 is a constant of integration. Taking the exponential of both sides,
T = C4 exp (λ2 τ) (4)
where C4 = exp(C3).
Now, combining Equations (3) and (4),
θ = Φ(ξ)T(τ) = (C1 J0(λξ) + C2 Y0(λξ)) (C4 exp (λ2 τ))
θ = C1C4 J0(λξ) exp (λ2 τ) + C2C4 Y0(λξ) exp (λ2 τ)
Since λ is a constant, combine C 1C4 and C2C4 into new constants an = C1C4 and Bn = C2C4,
respectively. Therefore,
θ = Σ (An J0(λnξ) + Bn Y0(λnξ)) exp (λn2 τ)

The Bessel function Y0(λξ) is unbounded as ξ approaches zero, which is physically unrealistic
for the temperature profile. Therefore, we can assume that C2 = 0, leading to:
θ = C1C4 J0(λξ) exp (λ2 τ)
Express the Bessel function J0(λξ) in terms of Eigen functions and eigenvalues. as:
J0(λξ) = Σ (An Φn (ξ, λn))
where Φn (ξ, λn) represents the Eigen functions associated with the eigenvalues λn, and An
are constants to be determined.
Substituting this back into the expression for θ,
θ = C1C4 Σ (An Φn (ξ, λn)) exp (λ2 τ)
Since the sum and the exponential term do not depend on ξ, we can interchange the
summation and the exponential term:
θ = Σ (An Φn (ξ, λn) exp (λ2 τ)) (1)
where now Φn (ξ, λn) and An are given by:
Φn (ξ, λn) = J0(λnξ)
An = C1C4
Replace λ2 with λn2,
θ = Σ (An Φn (ξ, λn) exp (-λn2 τ)) (2), where n=1 to n=∞
where Φn (ξ, λn) = J0(λnξ) and An = C1C4.

Find an expression for Φn (ξ, λn) and write an equation satisfied by the eigenvalues λn.
The Eigen functions Φn (ξ, λn) can be expressed in terms of the Bessel function of the first
kind, denoted as Jν(z), Φn (ξ, λn) = J0(λnξ)
Substitute the separation of variables solution into the original partial differential equation:
∂θ/∂τ = (1/ξ2) ∂/∂ξ (ξ2 ∂θ/∂ξ)
By substituting θ = Φ(ξ)T(τ) and dividing both sides by Φ (ξ)T(τ),
(1/ξ2) d/dξ (ξ2 dΦ/dξ) = (1/T) dT/dτ
(1/ξ2) d/dξ (ξ2 dΦ/dξ) = -μ2
Where μ^2 represents the constant eigenvalue associated with the Eigen function Φn (ξ, λn).
In this case, since we have ν = 0, the Eigen functions Φn (ξ, λn) are given by:

Φn (ξ, λn) = J0(λnξ)

Substitute Φn (ξ, λn) into the ξ-dependent part of the equation:
(1/ξ2) d/dξ (ξ2 dΦn/dξ) + μ2 Φn = 0
(1/ξ2) d/dξ (ξ2 d(J0(λnξ))/dξ) + μ2 J0(λnξ) = 0.

d) The initial temperature is T0. Give an expression for the An coefficients as a function
of T0 and Ts.
The expression for θ as:
θ = Σ (An Φn (ξ, λn) exp (-λn2 τ))
At time τ = 0, the unsteady-state temperature profile is equal to the initial temperature,
Θ (ξ, τ=0) = T0
Substituting the expression for θ and setting τ = 0,
Σ (An Φn (ξ, λn) exp (-λn2 * 0)) = T0
Since exp (0) = 1,
Σ (An Φn (ξ, λn)) = T0
By considering the steady-state temperature profile, denoted as Ts. In the steady state, the
rate of heat generation Sv is balanced by the heat transfer through the boundary, resulting in a
constant temperature distribution. This means that θ = T - Ts = 0,
Σ (An Φn (ξ, λn) exp (-λn2 τ)) = Ts
Σ (An Φn (ξ, λn) exp (-λn2 τ)) - Ts = 0
Σ (An Φn (ξ, λn) exp (-λn2 τ)) = Ts
Since the expression holds for all values of τ, each term in the summation must individually
equal zero:
An Φn (ξ, λn) exp (-λn2 τ) = 0
As exp (-λn2 τ) is non-zero,
An Φn (ξ, λn) = 0
Since Φn (ξ, λn) ≠ 0 for a valid Eigen function, we can conclude that the coefficient An must
be zero:
An = 0

Therefore, the coefficients An are determined to be zero for all n. This implies that the initial
condition T0 and the steady-state temperature Ts do not contribute to the series expansion of
θ, and the expression becomes:
θ=0
This indicates that the unsteady-state temperature profile is identically zero in this case.