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Gas and Electrolyte Diffusion Presentation

This document describes experiments to determine the diffusion coefficients of a gas (acetone) and electrolyte (NaCl solution) through theoretical analysis and experimental setup. For the gas experiment, the diffusion coefficient determined experimentally had good agreement with the correlation equation. However, for the electrolyte experiment, the experimental and correlated diffusion coefficients differed by 56.12% which is attributed to the effects of convection caused by the magnetic stir bar disturbing the diffusion process.

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969 views21 pages

Gas and Electrolyte Diffusion Presentation

This document describes experiments to determine the diffusion coefficients of a gas (acetone) and electrolyte (NaCl solution) through theoretical analysis and experimental setup. For the gas experiment, the diffusion coefficient determined experimentally had good agreement with the correlation equation. However, for the electrolyte experiment, the experimental and correlated diffusion coefficients differed by 56.12% which is attributed to the effects of convection caused by the magnetic stir bar disturbing the diffusion process.

Uploaded by

szulkipeli
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Gas and Electrolyte

Diffusion Experiment
Chemical Engineering 310
Dr. David Keffer, PIC Group #1
Brad Jaquith
John Robert Yates
Performed 11/09/2004 Luke Stewart
Presented 11/30/2004
Objectives
 Determine the diffusion coefficient of a gas by
evaporation from a liquid surface

 Determine the diffusion coefficient of a 2M


solution of NaCl in distilled water

 Compare experimental values with correlation


equations
Introduction/Background
 Diffusion is a process of mass transfer in
which a fluid moves from an area of higher
concentration to an area of lower
concentration, as a result of the fluid’s
kinetic properties, until an equilibrium is
established.
Experimental Setup/Data Acquisition -
Gas Diffusion
 Acetone is placed in a capillary tube which is
then inserted into the apparatus (see Figure 1).

 Maintained at a constant temperature of 40oC by


the heater, measurements of the level of the
acetone remaining in the capillary are taken
every 3600 seconds (or one hour) for use in
determining the diffusion coefficient.
Figure 1 -Gaseous Diffusion Apparatus

(source: ChE 310, Gaseous Diffusion Coefficients Apparatus Instruction Manual, 1999)
Experimental Setup/Data Acquisition -
Electrolyte Diffusion
 A 2M solution of NaCl is poured into the cell and
the bubbles are removed (see Figure 2).

 The cell is placed inside a CSTR to induce a


dynamic equilibrium at the point of the
measurements.

 Conductivity measurements are made by the


computer-controlled data acquisition system for
the determination of the diffusion coefficient.
Figure 2-Electrolyte Diffusion Apparatus

(source: ChE 310, Gaseous Diffusion Coefficients Apparatus Instruction Manual, 1999)
Determination of Diffusion Coefficient for a
Gas (Acetone) from Experimental Data
 Assuming constant T and P, the total concentration at the top of the
capillary is given by

cT,1 = N/V = p/RT.

 The concentrations of acetone and air are

cB,1 = xB,1 * cT,1


cA,1 = xA,1 * cT,1

 Then at the gas/liquid interface, the total concentration is

cT,1 = N/V = p/RT = cT,2


Cont’d
 Raoult’s Law states:
zApAvap(T) = xA,2p

 Assuming pure acetone, zA is 1, so that the concentration of acetone


and air at the gas/liquid interface is

cB,2 = xB,2 * cT,2 = cT,2[p-pAvap(T)]/p


cA,2 = xA,2 * cT,2 = cT,2[pAvap(T)/p]

 The equations for the molar flux due to diffusion of A at point 2 and
for the molar flux due to the evaporation of A at point 2 are:

NA,2= cT,2*DAB*(cA,2 – cA,1)/(cB,Im*L)

NA,2 = (ρA/MWA)*(dL/dt)
Cont’d
 Since the rate of diffusion of a gas and the rate of evaporation of the liquid are
the same, these two equations can be equated. Rearranging into the form of the
integral, integrating from to to t and Lo to L, and rewriting:

2cT,2*DAB*MWA*(cA,2 – cA,1)*(t-to)/(ρA*cB,lm) = (L-Lo)2 + 2(L-Lo)Lo

 Further rearranging leads to:

(t-to)/(L-Lo) = S(L-Lo) + 2SLo,

where S = ρA*cB,lm/(2cT,2*DAB*MWA*(cA,2 – cA,1)

 As the equation above indicates, this is a linear function of the form y=mx+b, and
when (t-to)/(L-Lo) is plotted as a function of L-Lo, the slope is S. Thus, the
diffusion coefficient can be derived from the equation for S above to give:

DAB= ρA*cB,lm/(2ScT,2*MWA*(cA,2 – cA,1)


Determination of Diffusion Coefficient of an
Electrolyte (NaCl) from Experimental Data
 Fick’s Law describes mass transfer due to diffusion:

 For a binary mixture, the mole fractions sum to 1, so the gradients are
inversely proportional:

 Therefore DAB=DBA=D and Fick’s Law is written for one diffusivity:

 The mole fraction gradient can be written as a differential, and assuming


constant molar concentration,

J*A = -D(∂cA/∂z)
Cont’d
 Assuming the measured conductivity is linearly
proportional to the concentration of salt:
k = CMcsalt
 Rearranging,
csalt = (1/CM)(k)

 From the mass flow balance on salt:

V(∂csalt/∂t) = in

 Differentiating the csalt equation and substituting into the


above equation gives:

J*A = in/area = V(1/CM)*(∂k/∂t)*(4/πd2N)


Cont’d
 Approximating the concentration gradient as:

(cA,2 – cA,1)/(z2-z1)

 Considering point 1 on the salt-rich side and


point 2 on the salt-lean side, the distance is the
membrane thickness L.

 Substituting in L in the above equation gives:

J*A = -D(-cA,1/L)
Cont’d
 Equating the previous equation with the J*A equation on the previous
slide gives:

V(1/CM)*(∂k/∂t)*(4/πd2N) = -D(-cA,1/L)

 Solving for D yields:

D = 4LV/(cA,1CMπd2N) * (∂k/∂t)

which is of the form y=mx, such that when conductivity (k) is plotted
against time (t), the slope is equal to (∂k/∂t), and D can be
evaluated.
Determination of Diffusion Coefficient
for Acetone from Correlation Equations
 Diffusivity in Gas Mixtures is given by the Fuller, Schettler, and
Giddings Correlation:

DAB = (0.00143T1.75)/(PMAB1/2[(ΣV)A1/3 + (ΣV)B1/3]2)

where MAB = 2/((1/MA)+(1/MB)).

 ΣV = summation of atomic and structural diffusion volumes from


Table 3.1 of Separation Process Principles, Seader and Henley.
Determination of Diffusion
Coefficient in Electrolyte Solutions
 The diffusion coefficient of a single salt in an aqueous solution can
be estimated from the Nernst-Haskell equation:

(DAB)∞ = (RT[(1/n+)+(1/n-)])/(F2[(1/λ+)+(1/λ-)])

Where n+ and n- = valences of the cation and anion, respectively


λ+ and λ- = limiting ionic conductances given in Table 3.5, Seader and
Henley
F = Faraday’s Constant = 96,500 C/g-equiv
T = Temperature, K
R = gas constant = 8.314 J/mol-K
Table of Results
Comparison of Experimental and Correlated Results
in the Electrolyte Diffusion Experiment

Type Diffusion Coefficient Standard Deviation Percent Error


(m2/s) (m2/s) (%)
------------ --------------------- ------------------- ---------------
Experimental 2.5136e-009 1.0991e-011 56.12
Correlated 1.6100e-009

Comparison of Experimental and Correlated Results


in the Gaseous Diffusion Experiment

Type Diffusion Coefficient Standard Deviation Percent Error


(m2/s) (m2/s) (%)
------------ --------------------- -------------------- ----------------
Experimental 1.1142e-005 2.6872e-007 4.56
Correlated 1.1674e-005
Conclusions
 Diffusion Coefficient in the gaseous
diffusion experiment compared very well to
the correlation – 4.56% error

 Liquid Diffusion Coefficient did not


compare as well – 56.12% error
Possible Explanation of Error in the
Electrolyte Diffusion Experiment

 The diffusion coefficient is dependent on the


position of the magnetic stir bar. Magnetic Stir
bar causes diffusion by convection when we are
measuring the diffusion by conduction. In our
experimental setup, the stir bar position was at
the 8 o’clock position on a clock face.

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