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Question number One.

A water solution containing a valuable solute is colored by small amounts of


impurity 9.6 (impurity/Kg Solution). The impurity is to be removed by
adsorbing on Carbon. In a series of laboratory test the following equilibrium
relation has been established.

X Y
(Impurity/Kg Carbon) (Impurity/Kg Solution)
200 0.7
400 1.7
600 4.0
800 6.3
1000 8.6

It is desired to remove 90% of impurity from Solution. Calculate the amount of


adsorbent you need for a 1000Kg of Solution in a Single Stage process.

Solution

The problem above can be represented schematically as Figure 1.0 showing the
colored water solution inlet, the adsorbent inlet, the Lean Solution and the
Solution outlet.
Lean Solution
Mass of Absorbent = M kg
C = 9.6(1- 0.9)
q0 =

ADSORBER

Solution with Impurity q (per 1000Kg of Solution)


C0 = 9.6(Impurity/Kg Sol.)
S = 1000Kg
q = q (Impurity/Kg Carbon)

Figure 1.0
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Using Material Balance in Figure 1.0:

(Mass of Impurity) (Change in Concentration)

= (Mass of Adsorbent) (Change in Concentration of Adsorbent).

Therefore:

M (q – q0) = S ( C0 – C )

Where S= 1000Kg

C0= 9.6 (Impurity/Kg Solution)

C = 0.96 (Impurity/Kg Solution)

M = Mass of Adsorbent (Kg) = Unknown

q = Unknown

q0 = 0 (Impurity/Kg Carbon)

Hence

M (q – 0) = 1000 (9.6 – 0.96)

M q = 1000 X 8.64

Using the equilibrium data,

X(q) Y (C) Mass ratio


Impurity Impurity Impurity Log q Log C
Kg Carbon Kg Solution Kg Solution
200 0.7 0.00350 2.301030 -0.154901
400 1.7 0.00425 2.602060 0.230449
600 4.0 0.00667 2.778151 0.602060
800 6.3 0.00788 2.903090 0.799341
1000 8.6 0.00860 3.000000 0.934498
0 9.6 - - -

From the equation of line, the slope = 0.619

Using the Freundlich equation

Lnqe = lnKf + (1/n)lnCe

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lnKf = Lnqe – (1/n)lnCe

where: 1/n = Slope

qe= 600

Ce = 4.0

Hence lnKf = ln(600) – 0.619ln(4.0)

lnKf =6.39693 – 0.85811

lnKf =5.5388137

Kf = e(5.5388)

Kf = 254.376

Therefore the resulting Freundlich Isotherm is Lnq = lnKf + (1/n)lnCe

Lnq = ln(254.376) + 0.619lnC

For q at the Spent adsorbent Stream we use C = 0.96

Hence Lnq = lnKf + (1/n)lnCe becomes,

Lnq = ln(254.376) + 0.619ln(0.96)

Lnq = 5.5135449

q=248.0288

From the materials balance equation: M q = 1000 X 8.64

M q = 8640

M = 8640/248.0288

M = 34.83466 Kg Carbon

Therefore the amount of adsorbent needed for a 1000Kg of Solution in a Single


Stage process is 34.83466 Kg

Slope M (Kg Carbon) Kf R2


0.619 34.83466 254.376 0.992

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Question number Two
It is desire to determine the adsorption capacity of activated carbon produced
from animal bone. In the studies, Cr(VI) solution (1000 mg.L-1) was prepared
by mixing 2.827 g of K2Cr2O7 in 1 L of de-ionized water. Adsorption capacity
of activated carbon animal was determined by contacting 1g (100 gL-1) with 300
ml metal solutions of known concentration (10–60 mgL-1) in 500 ml Erlenmeyer
flasks, shaken on an orbital shaker at 120 rpm for 60 min at room temperature
(25°C), followed by centrifugation at 500 rpm for 5 min to separate activated
carbon animal from the Cr (VI) solution. Rate of Cr(VI) adsorption by activated
carbon animal was determined by analyzing residual Cr(VI) ions in the
supernatant after contact periods of 10, 20, 30, 40, 50 and 60 min. The solid
phase mass was varied between 0.2 and 0.6 g adsorbent. Adsorption capacities
were obtained using a mass balance equation:
(Co – Ce)V
qe =
m

Where: qe = the equilibrium adsorption capacity per gram dry weight of the
adsorbent (mg/g).

Ce = the final or equilibrium concentration of Cr (VI) in the Solution (mg/L)

Co =Initial Concentration of Cr (VI) in the Solution (mg/L)

V = the Volume of the Solution (L)

M = the dry weight of the adsorbent (g).

From an experiment, the adsorbent dose and the percentage removal of Cr (VI)
ion is given in the table below;

Adsorption Percentage (%) Adsorbent dose (mg/L)


99.9355 150.523
99.9687 298.607
99.983 500.697

99.9873 601.742
99.9861 800.348
99.988 1000.7

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1. Compare the langmure and Frandlich isotherm model constants and
correlation coefficient for the adsorption of Cr (vi) on the animal bone
activated carbon.
2. Comment on the key parameters describing the two models
3. Determine the thermodynamics Parameters for the adsorption of Cr (vi)
4. Determine the intra-particle diffusion with Kinetic Parameters of
adsorption on to animal bone active carbon.

Solution
(Co – Ce)V
From the equation qe = we have the Calculated values of qe and Ce
m
using the equation
(Co – Ce)
Adsorption Percentage (%) = X 100
Co

Given that Co = 1000mg/L

The values are summarized in the table below

Adsorption Adsorbent dose Contact Equilibrium Equilibrium


Percentage (mg/L) periods concentration adsorption
(%) (mins) (mg/L) capacity(mg/g)
99.9355 150.523 10 990.0065 74.02630
99.9687 298.607 20 990.0031 74.05089
99.983 500.697 30 990.0017 74.06148

99.9873 601.742 40 990.0013 74.06467


99.9861 800.348 50 990.0014 74.06378
99.988 1000.7 60 990.0012 74.06519

In Adsorption, the adsorption isotherm shows how the adsorption molecules are
distributed between the liquid phase and the solid phase when the adsorption
process reaches an equilibrium state. Analysis of equilibrium adsorption data by
fitting different linear isotherm models is an important step to find the suitable
model that can be used for design purposes.

The studies of adsorption isotherms are carried out basically on two well-known
isotherms;

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1. The Langmuir adsorption isotherm models
2. The Freundlich adsorption isotherm models

The Langmuir isotherm assumes monolayer adsorption onto a surface


containing a finite number of adsorption sites of uniform strategies of
adsorption with no transmigration of adsorbate in the plane of surface.

While, the Freundlich isotherm model assumes heterogeneous surface energies,


in which the energy term in the Langmuir equation varies as a function of the
surface coverage.

The applications of these isotherms equation are compared by judging their


correlation coefficients R2.

Langmuir Adsorption Isotherm

This describes quantitatively the formation of a monolayer adsorbate on the


outer surface of adsorbent, and after that no further adsorption takes place.
Thereby, the Langmuir represents the equilibrium distribution of Chromium
ions between the solid and liquid phase. The Langmuir isotherm is valid for
monolayer adsorption onto a surface containing a finite number of identical
sites.

The model assumes uniform energies of adsorption onto the surface and on
transmigration of adsorbate in the plane of the surface. Based upon these
assumptions, Langmuir represented the following equation
q K𝐶
qe =
1+𝐾𝐶

Langmuir adsorption Parameters were determined by transforming the equation


above as:
Ce Ce K𝐿
= +
qe q 𝑚𝑎𝑥 qmax K𝐿

Where: Ce = the equilibrium concentration of adsorbate (mg/L)

qe = the amount of metal adsorbed per gram of the adsorbent at


equilibrium (mg/g)

qmax = maximum monolayer coverage capacity (mg/g)

KL = Langmuir isotherm Constant (L/mg).

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The values of KL and qe were computed from the slope and intercept of the
Langmuir plot of 1/qe versus 1/Ce. The essential features of the Langmuir
isotherm may be expressed in terms of equilibrium parameter R L, which is a
dimensionless constant referred to as separation factor or equilibrium parameter.

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RL =
1 + (1 + K L Co )

Where: Co = Initial concentration (mg/L)

qe = maximum monolayer coverage capacity (mg/g)

KL = Langmuir isotherm Constant

RL = Adsorption nature
The Adsorption nature indicates unfavorable, Linear or Favorable if 0 < RL < 1
and irreversible if RL = 0. From the data calculated in table 1, the RL is greater
than 0 but less than 1 indicating that Langmuir isotherm is favorable. Langmuir
Isotherm model was determined to be 35.714 mg/g, KL (Langmuir isotherm
constant) is 9.333 L/mg, RL (the separation factor) is 0.274 indicating that the
equilibrium adsorption was favorable and the R2 value is 0.999 proving that the
adsorption data fitted well to Langmuir Isotherm model.

qe (mg/g0 KL (g/L) R2
35.714 9.333 0.999
Langmuir Isotherm model.

Freundlich Adsorption Isotherm

Freundlich Isotherm is mostly used to describe the adsorption characteristics for


the heterogeneous surface. These data often fit the empirical equation proposed
by Freundlich:

qe = Kf Ce (1/n)

Where: Kf = Freundlich isotherm constant (mg/g);

n = adsorption intensity;

Ce = the equilibrium concentration of adsorbate (mg/L);

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qe = the amount of metal adsorbed per gram of the adsorbent at
equilibrium (mg/g).

Linearizing the equation we have;

lnKf = Lnqe – (1/n)lnCe

The constant Kf is an approximate indicator of adsorption capacity, while 1/n is


a function of the strength of adsorption in the adsorption process. When n = 1
then the partition between the two phases are independent of the concentration.
If value of 1/n is below one it indicates a normal adsorption. On the other hand,
1/n being above one indicates cooperative adsorption.

However, Kf and n are parameters characteristic of the adsorbent-adsorbate


system, which must be determined by data fitting and whereas linear regression
is generally used to determine the parameters of kinetic and isotherm models.
Specifically, the linear least-squares method and the linearly transformed
equations have been widely applied to correlate adsorption data where 1/n is a
heterogeneity parameter, the smaller 1/n, the greater the expected heterogeneity.
This expression reduces to a linear adsorption isotherm when 1/n = 1. If n lies
between one and ten, this indicates a favorable adsorption process. From the
data in the table below, it shows that the value of 1/n = 14.136 while n=0.068
indicating that the adsorption of Cr (VI) unto activated carbon animal is
favorable and the R2 value is 0.999.

n Kf R2
0.068 40.935 0.923
Freundlich Model.

To Determine the thermodynamics Parameters for the adsorption of


Cr(VI).

Thermodynamic parameters generally include change in the enthalpy (H°),


entropy (S°), and Gibbs free energy (G°) of a system. These are essential for a
further understanding of the effect of temperature on adsorption indicating
whether the adsorption processes occurs spontaneously or not. The effect of
temperature on adsorption in this study was investigated at a temperature of
25°C (298°K). G° values is negative at this temperatures indicating that Cr (VI)
adsorbed onto activated carbon was spontaneous and that the system did not
gain energy from an external source. Therefore, the magnitude of H° and G°
gives some information about the nature of adsorption process.
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∆G° = ∆H° − 𝑇∆S°

Where: R = 8,314 J/(mol.K) is the universal gas constant

T(°K) is the absolute solution temperature

The literature data show that a physical adsorption is characterized by values of


H° not more than 4.2Kj/mol and G° lower than 40 kJ /mol. According to the
calculated data, the adsorption of chromium six on to activated carbon is rather
physical adsorption than chemisorption.

To determine the intra-particle diffusion with Kinetic Parameters of


adsorption on to animal bone active carbon.

Tree simplified kinetic models were adopted to examine the mechanism of the
adsorption process. First, the kinetics of adsorption was analyzed by the
Lagergren pseudo-first-order equation as depicted below. The adsorption data
can be presented by the following equation:
𝐾𝑡
Log (qe – qt) = log qe -
2.303

Where: qe and qt are the amounts of Cr (VI) adsorbed (mg/g) at equilibrium and
at time t (min), respectively, and k (min-1) is the rate constant.

Values of k at ambient temperature were calculated from the plots of log (qe –
qt) versus t for initial concentrations of Cr(VI)kint (mg/(g. (min 1/2))) represents
the intra-particle diffusion rate constant and C is a constant (mg/g) which gives
information about the thickness of the boundary layer.