Fundamentals of Combustion

MEO581

Introduction to
Mass Transfer

Dr. Aditi Sengupta

Department of Mechanical Engineering
IIT (ISM) Dhanbad
Email: [email protected]
 Rudiments of Mass Transfer
• Mass transfer is complex, even though it is a fundamental topic of chemical engineering.

• Open a bottle of perfume, shortly, presence of perfume molecules in immediate vicinity of bottle
can be detected.

• At a later time, perfume odor is everywhere in the room.

• Processes whereby perfume molecules are transported from region of high concentration near the
bottle, to a region of low concentration, far from bottle – subject of mass transfer.

• Like heat and momentum transfer, mass is transported by molecular and/or turbulent processes.

• Molecular processes are relatively slow and operate on small spatial scales

• Turbulent transport depends upon velocity and size of eddy carrying transported material.
 Mass Transfer Rate Laws: Fick’s Law

• Fick’s Law of Diffusion: Describes rate at which one species diffuses through the other.

• For case of 1D binary diffusion, Fick’s law on a mass basis

𝑑𝑑𝑌𝑌𝐴𝐴
𝑚𝑚̇ 𝐴𝐴" = 𝑌𝑌𝐴𝐴 𝑚𝑚̇ 𝐴𝐴" + 𝑚𝑚̇ 𝐵𝐵" − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴
𝑑𝑑𝑑𝑑
Mass flow of Mass flow of species A Mass flow of species A
species A per unit associated with bulk associated with molecular
area flow per unit area diffusion per unit area

where 𝑚𝑚̇ 𝐴𝐴" is the mass flux of species A and 𝑌𝑌𝐴𝐴 is the mass fraction.

• Mass flux is defined as mass flow rate of species A per unit area perpendicular to the flow: 𝑚𝑚̇ 𝐴𝐴" =
𝑚𝑚̇ 𝐴𝐴′ /A (unit – kg/s-m2)

• Binary diffusivity, 𝒟𝒟𝐴𝐴𝐴𝐴 is a property of the mixture and has unit of m2/s.
 Mass Transfer Rate Laws: Fick’s Law
𝑑𝑑𝑌𝑌𝐴𝐴
𝑚𝑚̇ 𝐴𝐴" = 𝑌𝑌𝐴𝐴 𝑚𝑚̇ 𝐴𝐴" + 𝑚𝑚̇ 𝐵𝐵" − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴
𝑑𝑑𝑑𝑑

Species A is transported by two means:

1. First term on RHS represents transport of A resulting from bulk motion of fluid
2. Second term represents diffusion of A superimposed on the bulk flow.

• In absence of diffusion, we obtain 𝑚𝑚̇ 𝐴𝐴" = 𝑌𝑌𝐴𝐴 𝑚𝑚̇ 𝐴𝐴" + 𝑚𝑚̇ 𝐵𝐵" = 𝑌𝑌𝐴𝐴 𝑚𝑚̇ " = Bulk flux of species A

𝑑𝑑𝑌𝑌𝐴𝐴
• Diffusional flux adds an additional component to flux of A: 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 = Diffusional flux of
𝑑𝑑𝑑𝑑
"
species A, 𝑚𝑚̇ 𝐴𝐴,𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑

• Constant of proportionality is −𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 , suggesting that species A preferentially moves from

region of high concentration to region of low concentration.
 Mass Transfer Rate Laws: Fick’s Law

The general form of Fick’s law is

𝒎𝒎̇ "𝑨𝑨 = 𝑌𝑌𝐴𝐴 𝒎𝒎̇ "𝑨𝑨 + 𝒎𝒎̇ "𝑩𝑩 − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 𝜵𝜵𝒀𝒀𝑨𝑨

where bold symbols are vector quantities. Now, to represent the same in molar form, we define:

𝑵𝑵̇ "𝑨𝑨 = 𝜒𝜒𝐴𝐴 𝑵𝑵̇ "𝑨𝑨 + 𝑵𝑵̇ "𝑩𝑩 − 𝑐𝑐𝒟𝒟𝐴𝐴𝐴𝐴 𝜵𝜵𝝌𝝌𝑨𝑨

where 𝑵𝑵̇ "𝑨𝑨 is the molar flux (kmol/s-m2) of species A. 𝝌𝝌𝑨𝑨 is the mole fraction, and c is mixture molar
concentration (kmolmix/m3).

Bulk flow: First, we express total mass flux of binary mixture:

𝑚𝑚̇ " = 𝑚𝑚̇ 𝐴𝐴" + 𝑚𝑚̇ 𝐵𝐵"

Mixture mass flux on LHS is total mixture flow rate per unit area perpendicular to flow – same as
thermodynamics/fluid mechanics!
 Mass Transfer Rate Laws: Fick’s Law
Diffusional Flux:

Assuming 1D flow, we can substitute for individual species mass fluxes

" "
𝑑𝑑𝑌𝑌𝐴𝐴 "
𝑑𝑑𝑌𝑌𝐵𝐵
𝑚𝑚̇ = 𝑌𝑌𝐴𝐴 𝑚𝑚̇ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 + 𝑌𝑌𝐵𝐵 𝑚𝑚̇ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
or
𝑑𝑑𝑌𝑌𝐴𝐴 𝑑𝑑𝑌𝑌𝐵𝐵
𝑚𝑚̇ " = (𝑌𝑌𝐴𝐴 + 𝑌𝑌𝐵𝐵 )𝑚𝑚̇ " − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑

For a binary mixture, 𝑌𝑌𝐴𝐴 + 𝑌𝑌𝐵𝐵 = 1, thus:

𝑑𝑑𝑌𝑌𝐴𝐴 𝑑𝑑𝑌𝑌𝐵𝐵
−𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 =0
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
"
i.e. sum of diffusional fluxes of the species is zero. Overall mass conservation requires that ∑ 𝑚𝑚̇ 𝑖𝑖,𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 =0
 Mass Transfer Rate Laws: Fick’s Law
"
Condition of ∑ 𝑚𝑚̇ 𝑖𝑖,𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 = 0 only holds

- for assumption of a binary gas

- assuming species diffusion is a result of concentration gradients only (ordinary

diffusion)

Real mixtures of interest in combustion contain many components

Gradients of temperature and pressure can also cause species diffusion – thermal
diffusion (Soret) and pressure diffusion effects

Exercise: What is the physical interpretation of bulk flux vs diffusional flux in cardiovascular system of human body?
 Mass Transfer Rate Laws: Molecular Basis of Diffusion

• To obtain insight into molecular processes that result in macroscopic

laws of mass diffusion (Fick’s law), we apply concepts from kinetic
theory of gases.

• Consider a stationary (no bulk flow) plane layer of a binary gas mixture
having

- rigid, non attracting molecules

- same molecular mass of species A and B

• Concentration gradient:

- exists in gas layer in x-direction

- small enough that mass fraction varies linearly over few λ.
Schematic diagram illustrating mass diffusion
of species A molecules from a region of high
concentration to low concentration.
 Mass Transfer Rate Laws: Molecular Basis of Diffusion
• We define average molecular properties derived from kinetic theory:

where kB is Boltzmann’s constant, mA the mass of a single A molecule, nA/V is the number of A
molecules per unit volume, ntot/V the total number of molecules per unit volume, and σ the diameter of
both A and B molecules.
 Mass Transfer Rate Laws: Molecular Basis of Diffusion

Assuming no bulk flow for simplicity, net flux of A molecules at x-plane is difference between flux
of A molecules in positive x-direction and in negative x-direction:

" "
𝑚𝑚̇ 𝐴𝐴" = 𝑚𝑚̇ 𝐴𝐴, +𝑥𝑥 −𝑑𝑑𝑑𝑑𝑑𝑑 − 𝑚𝑚̇ 𝐴𝐴, −𝑥𝑥 −𝑑𝑑𝑑𝑑𝑑𝑑

which, when expressed in terms of collision frequency becomes

𝑚𝑚̇ 𝐴𝐴" = (𝑍𝑍𝐴𝐴" )𝑥𝑥−𝑎𝑎 𝑚𝑚𝐴𝐴 − 𝑍𝑍𝐴𝐴" 𝑥𝑥+𝑎𝑎

𝑚𝑚𝐴𝐴

Net mass flux Number of A Mass of

Number of A Mass of
of species A molecules single
molecules single
crossing plane at molecule
crossing plane at molecule
x originating
x originating
from plane at x+a
from plane at x-a
per unit time and
per unit time and
area
area
 Mass Transfer Rate Laws: Molecular Basis of Diffusion
1 𝑛𝑛𝐴𝐴 𝑚𝑚𝐴𝐴 1
Using density, 𝜌𝜌 = 𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡 ⁄𝑉𝑉𝑡𝑡𝑡𝑡𝑡𝑡 to relate 𝑍𝑍𝐴𝐴" to mass fraction of A molecules: 𝑍𝑍𝐴𝐴" 𝑚𝑚𝐴𝐴 = 4 𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡
𝜌𝜌𝜈𝜈̅ = 𝑌𝑌𝐴𝐴 𝜌𝜌𝜈𝜈̅
4

Substituting into net flux equation and treating mixture density and mean molecular speeds as constants, we get

1
𝑚𝑚̇ 𝐴𝐴" = 𝜌𝜌𝜈𝜈(𝑌𝑌
̅ 𝐴𝐴,𝑥𝑥−𝑎𝑎 − 𝑌𝑌𝐴𝐴,𝑥𝑥+𝑎𝑎 )
4
𝑑𝑑𝑌𝑌𝐴𝐴 𝑌𝑌𝐴𝐴,𝑥𝑥+𝑎𝑎 −𝑌𝑌𝐴𝐴,𝑥𝑥−𝑎𝑎 𝑌𝑌𝐴𝐴,𝑥𝑥+𝑎𝑎 −𝑌𝑌𝐴𝐴,𝑥𝑥−𝑎𝑎
Since we assumed a linear concentration distribution, = =
𝑑𝑑𝑑𝑑 2𝑎𝑎 4𝜆𝜆/3

Solving the above equation for concentration difference and substituting into net flux equation for A molecules:

1 𝑑𝑑𝑌𝑌𝐴𝐴
𝑚𝑚̇ 𝐴𝐴" = − 𝜌𝜌𝜈𝜈𝜆𝜆
̅
3 𝑑𝑑𝑑𝑑
�
𝜈𝜈𝜆𝜆
From this, we can define binary diffusivity 𝒟𝒟𝐴𝐴𝐴𝐴 as, 𝒟𝒟𝐴𝐴𝐴𝐴 = 3
 Mass Transfer Rate Laws: Molecular Basis of Diffusion

Using definition of mean molecular speed, mean free path and ideal-gas equation of state PV =
nkBT, one can obtain 𝒟𝒟𝐴𝐴𝐴𝐴 as
1/2
2 𝑘𝑘𝐵𝐵3 𝑇𝑇 𝑇𝑇
𝒟𝒟𝐴𝐴𝐴𝐴 =
3 𝜋𝜋 3 𝑚𝑚𝐴𝐴 𝜎𝜎 2 𝑃𝑃
or
𝒟𝒟𝐴𝐴𝐴𝐴 ∝ 𝑇𝑇 3/2 𝑃𝑃−1

Mass flux of species A depends on product 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 for which, 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 ∝ 𝑇𝑇 1/2 𝑃𝑃0

In many analyses of combustion, this weak temperature dependence is neglected and 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 is
treated as a constant.
 Species Conservation
• We use rate law of species transport (Fick’s law) to develop a basic species mass conservation
expression.

• Let us consider a 1D control volume which is a plane layer with thickness, ∆𝑥𝑥

• Species A flows into and out of control volume as a result of combined action of bulk flow and
diffusion.

• Within CV, species A may be created or destroyed due to chemical reactions.

 Species Conservation
• Net rate of increase in mass of A within CV relates to mass fluxes and reaction rate as follows:

𝑑𝑑𝑚𝑚𝐴𝐴,𝑐𝑐𝑐𝑐
= 𝑚𝑚̇ 𝐴𝐴′′ 𝐴𝐴 𝑥𝑥 − 𝑚𝑚̇ 𝐴𝐴′′ 𝐴𝐴 𝑥𝑥+∆𝑥𝑥 + 𝑚𝑚̇ 𝐴𝐴′′′ 𝑉𝑉
𝑑𝑑𝑑𝑑
Rate of increase Mass flow Mass flow Mass production
of mass of A of A into the of A out of rate of species A
within control control the control by chemical
volume volume volume reaction

where the species mass flux is 𝑚𝑚̇ 𝐴𝐴′′ , and 𝑚𝑚̇ 𝐴𝐴′′′ is the mass production rate of species A per unit volume
(𝑘𝑘𝑘𝑘𝐴𝐴 ⁄𝑚𝑚3 𝑠𝑠).

Mass of A within the control volume is 𝑚𝑚𝐴𝐴,𝑐𝑐𝑐𝑐 = 𝑌𝑌𝐴𝐴 𝑚𝑚𝑐𝑐𝑐𝑐 = 𝑌𝑌𝐴𝐴 𝜌𝜌𝑉𝑉𝑐𝑐𝑐𝑐 and volume, 𝑉𝑉𝑐𝑐𝑐𝑐 = 𝐴𝐴∆𝑥𝑥, so above
equation can be rewritten as:

𝜕𝜕(𝜌𝜌𝑌𝑌𝐴𝐴 ) 𝜕𝜕𝑌𝑌𝐴𝐴 𝜕𝜕𝑌𝑌𝐴𝐴

𝐴𝐴∆𝑥𝑥 = 𝐴𝐴 𝑌𝑌𝐴𝐴 𝑚𝑚̇ ′′ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 − 𝐴𝐴 𝑌𝑌𝐴𝐴 𝑚𝑚̇ ′′ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 + 𝑚𝑚̇ 𝐴𝐴′′′ 𝐴𝐴∆𝑥𝑥
𝜕𝜕𝜕𝜕 𝜕𝜕𝑥𝑥 𝑥𝑥
𝜕𝜕𝜕𝜕 𝑥𝑥+∆𝑥𝑥
 Species Conservation

𝜕𝜕(𝜌𝜌𝑌𝑌𝐴𝐴 ) 𝜕𝜕𝑌𝑌𝐴𝐴 𝜕𝜕𝑌𝑌𝐴𝐴

𝐴𝐴∆𝑥𝑥 ′′
= 𝐴𝐴 𝑌𝑌𝐴𝐴 𝑚𝑚̇ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 ′′
− 𝐴𝐴 𝑌𝑌𝐴𝐴 𝑚𝑚̇ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 + 𝑚𝑚̇ 𝐴𝐴′′′ 𝐴𝐴∆𝑥𝑥
𝜕𝜕𝜕𝜕 𝜕𝜕𝑥𝑥 𝑥𝑥
𝜕𝜕𝜕𝜕 𝑥𝑥+∆𝑥𝑥

Dividing through by 𝐴𝐴∆𝑥𝑥 and taking the limit as ∆𝑥𝑥 → 0,

𝜕𝜕(𝜌𝜌𝑌𝑌𝐴𝐴 ) 𝜕𝜕 𝜕𝜕𝑌𝑌𝐴𝐴
=− 𝑌𝑌𝐴𝐴 𝑚𝑚̇ ′′ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 + 𝑚𝑚̇ 𝐴𝐴′′′
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕

For a steady flow, we get

𝑑𝑑 𝑑𝑑𝑌𝑌𝐴𝐴
− ′′
𝑌𝑌𝐴𝐴 𝑚𝑚̇ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 + 𝑚𝑚̇ 𝐴𝐴′′′ = 0
𝑑𝑑𝑑𝑑 𝑑𝑑𝑥𝑥

This is the steady, 1D form of species conservation for a binary gas mixture.
 Species Conservation
Steady, 1D form of species conservation for a binary gas mixture:

𝑑𝑑 𝑑𝑑𝑌𝑌𝐴𝐴
− ′′
𝑌𝑌𝐴𝐴 𝑚𝑚̇ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 + 𝑚𝑚̇ 𝐴𝐴′′′ = 0
𝑑𝑑𝑑𝑑 𝑑𝑑𝑥𝑥

This assumes species diffusion occurs only as result of concentration gradients, i.e. only ordinary
diffusion is considered

For multi-dimensional case, above equation can be generalized as

𝑚𝑚̇ 𝐴𝐴′′′ − 𝜵𝜵 � 𝒎𝒎̇ ′′

𝑨𝑨 = 0

Net rate of Net flow of species A

production of species out of control
A by chemical volume, per unit
reaction, per unit volume
volume
 Stefan Problem
Consider liquid A, maintained at a fixed height in a glass cylinder

A mixture of gas A and gas B flow across the top of the cylinder.

If conc. (A) in flowing gas < conc. (A) at liquid-vapor interface, driving force for mass transfer exists.

Species A will diffuse from liquid-gas interface to open end of cylinder.

 Stefan Problem

If we assume a steady state exists, and assuming B is insoluble in liquid A, then there will be no net
transport of B in tube, producing stagnant layer of B in column.

Mathematically, overall conservation of mass for the system is expressed as

𝑚𝑚̇ ′′ 𝑥𝑥 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑚𝑚̇ 𝐴𝐴′′ + 𝑚𝑚̇ 𝐵𝐵′′

As, 𝑚𝑚̇ 𝐵𝐵′′ = 0, we have 𝑚𝑚̇ ′′ 𝑥𝑥 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑚𝑚̇ 𝐴𝐴′′

 Stefan Problem

Fick’s law expression becomes

𝑑𝑑𝑌𝑌𝐴𝐴
𝑚𝑚̇ 𝐴𝐴′′ = 𝑌𝑌𝐴𝐴 𝑚𝑚̇ 𝐴𝐴′′ − 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴
𝑑𝑑𝑑𝑑

Rearranging and separating variables, we obtain

𝑚𝑚̇ 𝐴𝐴′′ 𝑑𝑑𝑌𝑌𝐴𝐴

− 𝑑𝑑𝑑𝑑 =
𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 1 − 𝑌𝑌𝐴𝐴

Assuming 𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 to be constant, above equation can be integrated to yield

𝑚𝑚̇ 𝐴𝐴′′
− 𝑥𝑥 = − ln 1 − 𝑌𝑌𝐴𝐴 + 𝐶𝐶
𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴
where C is constant of integration.
 Stefan Problem

Now, we need a boundary condition

𝑌𝑌𝐴𝐴 𝑥𝑥 = 0 = 𝑌𝑌𝐴𝐴,𝑖𝑖

We can eliminate C and obtain the mass-fraction distribution after removing logarithm by exponentiation:

𝑚𝑚̇ 𝐴𝐴′′ 𝑥𝑥
𝑌𝑌𝐴𝐴 𝑥𝑥 = 1 − 1 − 𝑌𝑌𝐴𝐴,𝑖𝑖 exp
𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴

The mass flux of A, 𝑚𝑚̇ 𝐴𝐴′′ can be found by setting another boundary condition, 𝑌𝑌𝐴𝐴 𝑥𝑥 = 𝐿𝐿 = 𝑌𝑌𝐴𝐴,∞

𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 1−𝑌𝑌𝐴𝐴,∞
Thus, 𝑚𝑚̇ 𝐴𝐴′′ = 𝑙𝑙𝑙𝑙
𝐿𝐿 1−𝑌𝑌𝐴𝐴,𝑖𝑖

Larger diffusivities thus produce larger mass fluxes.

 Stefan Problem

To see effects of concentrations at interface and at top of tube, let mass fraction of A in free stream flow
be zero.

Let the interface mass fraction, 𝑌𝑌𝐴𝐴,𝑖𝑖 vary from zero to unity

At small values of 𝑌𝑌𝐴𝐴,𝑖𝑖 , dimensionless mass flux is proportional to 𝑌𝑌𝐴𝐴,𝑖𝑖 .

For 𝑌𝑌𝐴𝐴,𝑖𝑖 > 0.5, mass flux increases rapidly.

 Liquid-Vapor Interface Boundary Conditions
• In the Stefan problem, we assumed the gas-phase mass fraction of
diffusing species at the liquid-vapor interface, 𝑌𝑌𝐴𝐴,𝑖𝑖 as a known
quantity

• In reality, measuring this mass fraction is difficult

• Can be measured by assuming equilibrium exists between liquid

and vapor phases of species A

• Partial pressure of species A on gas side of interface must equal saturation pressure associated with
temperature of liquid, i.e.,
𝑃𝑃𝐴𝐴,𝑖𝑖 = 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 (𝑇𝑇𝑙𝑙𝑙𝑙𝑙𝑙,𝑖𝑖 )

• Partial pressure can be related to mole fraction of species A, 𝜒𝜒𝐴𝐴,𝑖𝑖 = 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 /𝑃𝑃 and to the mass fraction
as:
𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 (𝑇𝑇𝑙𝑙𝑙𝑙𝑙𝑙,𝑖𝑖 ) 𝑀𝑀𝑊𝑊𝐴𝐴
𝑌𝑌𝐴𝐴,𝑖𝑖 =
𝑃𝑃 𝑀𝑀𝑊𝑊𝑚𝑚𝑚𝑚𝑚𝑚,𝑖𝑖
 Liquid-Vapor Interface Boundary Conditions
𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 (𝑇𝑇𝑙𝑙𝑙𝑙𝑙𝑙,𝑖𝑖 ) 𝑀𝑀𝑊𝑊𝐴𝐴
𝑌𝑌𝐴𝐴,𝑖𝑖 =
𝑃𝑃 𝑀𝑀𝑊𝑊𝑚𝑚𝑚𝑚𝑚𝑚,𝑖𝑖

From the above expression, it is clear that problem has transformed to one of
finding temperature at interface.

Interface temperature can be found by energy balances for liquid and gas
phases and solving with appropriate boundary conditions (including those at
interface)

In crossing liquid-vapor boundary, we maintain continuity of temperature, i.e.

𝑇𝑇𝑙𝑙𝑙𝑙𝑙𝑙,𝑖𝑖 𝑥𝑥 = 0− = 𝑇𝑇𝑣𝑣𝑣𝑣𝑣𝑣,𝑖𝑖 𝑥𝑥 = 0+ = 𝑇𝑇(0)

and energy is conserved at interface.

 Liquid-Vapor Interface Boundary Conditions

Heat is transferred from gas to liquid surface, 𝑄𝑄𝑔𝑔−𝑖𝑖

Some of this energy goes into heating the liquid, 𝑄𝑄𝑖𝑖−𝑙𝑙 , while remainder causes
the phase change

Energy balance is expressed as

𝑄𝑄̇ 𝑔𝑔−𝑖𝑖 − 𝑄𝑄̇ 𝑖𝑖−𝑙𝑙 = 𝑚𝑚̇ ℎ𝑣𝑣𝑣𝑣𝑣𝑣 − ℎ𝑙𝑙𝑙𝑙𝑙𝑙 = 𝑚𝑚ℎ

̇ 𝑓𝑓𝑓𝑓

or

𝑄𝑄̇ 𝑛𝑛𝑛𝑛𝑛𝑛 = 𝑚𝑚ℎ

̇ 𝑓𝑓𝑓𝑓

This can be used to calculate net heat transferred to interface if evaporation

rate, 𝑚𝑚̇ is known.

Conversely, if 𝑄𝑄̇ 𝑛𝑛𝑛𝑛𝑛𝑛 is known, evaporation rate can be determined.

 Example 1
Liquid benzene (𝐶𝐶6 𝐻𝐻6 ), at 298K, is contained in a 1-cm-diameter glass tube and maintained at a level
10 cm below the top of the tube, which is open to the atmosphere. The following properties of benzene
are given:
𝑇𝑇𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 = 353𝐾𝐾 @ 1 𝑎𝑎𝑎𝑎𝑎𝑎
𝑘𝑘𝑘𝑘
ℎ𝑓𝑓𝑓𝑓 = 393 @𝑇𝑇𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏
𝑘𝑘𝑘𝑘
𝑘𝑘𝑘𝑘
𝑀𝑀𝑀𝑀 = 78.108
𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘
𝜌𝜌𝑙𝑙 = 879 𝑘𝑘𝑘𝑘/𝑚𝑚3
2
𝑚𝑚
𝒟𝒟𝐶𝐶6 𝐻𝐻6 −𝑎𝑎𝑎𝑎𝑎𝑎 = 0.88 × 10−5 @298𝐾𝐾
𝑠𝑠
A. Determine the mass evaporation rate (kg/s) of the benzene.
B. How long does it take to evaporate 1cm3 of benzene?
𝑚𝑚2
C. Compare the evaporation rate of benzene with that of water. Assume 𝒟𝒟𝐻𝐻2 𝑂𝑂−𝑎𝑎𝑎𝑎𝑎𝑎 = 2.6 × 10−5
𝑠𝑠
 Example 1
Solution:
A. Find 𝑚𝑚̇ 𝐶𝐶6𝐻𝐻6 . Given configuration represents the Stefan problem.

𝜌𝜌𝒟𝒟
̅ 𝐶𝐶6𝐻𝐻6−𝑎𝑎𝑎𝑎𝑎𝑎 1 − 𝑌𝑌𝐶𝐶6 𝐻𝐻6,∞
𝑚𝑚̇ 𝐶𝐶′′6𝐻𝐻6 = 𝑙𝑙𝑙𝑙
𝐿𝐿 1 − 𝑌𝑌𝐶𝐶6𝐻𝐻6,𝑖𝑖

𝑀𝑀𝑀𝑀𝐶𝐶6𝐻𝐻6 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 (𝑇𝑇𝑙𝑙𝑙𝑙𝑙𝑙,𝑖𝑖 )

We know that 𝑌𝑌𝐶𝐶6𝐻𝐻6,𝑖𝑖 = 𝜒𝜒𝐶𝐶6 𝐻𝐻6,𝑖𝑖 𝑀𝑀𝑀𝑀 , where 𝜒𝜒𝐶𝐶6𝐻𝐻6,𝑖𝑖 =
𝑚𝑚𝑚𝑚𝑚𝑚,𝑖𝑖 𝑃𝑃

𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 (𝑇𝑇𝑙𝑙𝑙𝑙𝑙𝑙,𝑖𝑖 ) 𝑑𝑑𝑑𝑑 ℎ𝑓𝑓𝑓𝑓 𝑑𝑑𝑑𝑑

To evaluate , we integrate the Clausius-Clapeyron equation, = 𝑅𝑅 2
𝑃𝑃 𝑃𝑃 𝑢𝑢 ⁄𝑀𝑀𝑀𝑀𝐶𝐶6 𝐻𝐻6 𝑇𝑇

𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 ℎ𝑓𝑓𝑓𝑓 1 1 393000 1 1

= 𝑒𝑒𝑒𝑒𝑒𝑒 − − = 𝑒𝑒𝑒𝑒𝑒𝑒 − − = exp −1.93 = 0.145
𝑃𝑃(= 1𝑎𝑎𝑎𝑎𝑎𝑎) 𝑅𝑅𝑢𝑢 ⁄𝑀𝑀𝑀𝑀𝐶𝐶6𝐻𝐻6 𝑇𝑇 𝑇𝑇𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 8315⁄78.108 298 353

So, 𝑃𝑃𝑠𝑠𝑠𝑠𝑠𝑠 = 0.145 atm and 𝜒𝜒𝐶𝐶6𝐻𝐻6,𝑖𝑖 = 0.145. The interface molecular weight is

𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚,𝑖𝑖 = 0.145 78.108 + 1 − 0.145 28.85 = 35.99𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

where simplified composition of air is assumed.

 Example 1
Solution:
A. The interface benzene mass fraction is, then
78.108
𝑌𝑌𝐶𝐶6𝐻𝐻6,𝑖𝑖 = 0.145 = 0.3147
35.99

For isothermal, isobaric conditions, we can estimate mean gas density in the tube by using ideal-gas law and mean
mixture molecular weight as:
𝑃𝑃
𝜌𝜌̅ =
(𝑅𝑅𝑢𝑢 ⁄𝑀𝑀𝑀𝑀)⁄𝑇𝑇
where
1 1
𝑀𝑀𝑀𝑀 = 𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚,𝑖𝑖 + 𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚,∞ = 35.99 + 28.85 = 32.42
2 2
Thus,
101325
𝜌𝜌̅ = = 1.326𝑘𝑘𝑘𝑘/𝑚𝑚3
(8315⁄32.42)⁄298
We can now evaluate benzene mass flux:

1.326(0.88 × 10−5 ) 1−0

𝑚𝑚̇ 𝐶𝐶′′6𝐻𝐻6 = 𝑙𝑙𝑙𝑙 = 1.167 × 10−4 ln 1.459 = 4.409 × 10−5 𝑘𝑘𝑘𝑘⁄𝑠𝑠 − 𝑚𝑚2
0.1 1 − 0.3147
 Example 1
Solution:
From this, we can calculate evaporation rate of benzene as:
𝜋𝜋𝐷𝐷 2 𝜋𝜋(0.01)2
𝑚𝑚̇ 𝐶𝐶6 𝐻𝐻6 = 𝑚𝑚̇ 𝐶𝐶′′6𝐻𝐻6 = 4.409 × 10−5 = 3.46 × 10−9 𝑘𝑘𝑘𝑘/𝑠𝑠
4 4

B. Find the time needed to evaporate 1 cm3 of benzene. Since the liquid level is maintained, the mass flux is constant
during the time to evaporate the 1 cm3

𝑚𝑚𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝜌𝜌𝑙𝑙𝑙𝑙𝑙𝑙 𝑉𝑉 879 × 10−6 5 𝑠𝑠 = 70.6 ℎ𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜

𝑡𝑡 = = = = 2.54 × 10
𝑚𝑚̇ 𝐶𝐶6𝐻𝐻6 𝑚𝑚̇ 𝐶𝐶6 𝐻𝐻6 3.46 × 10−9

C. Find 𝑚𝑚̇ 𝐶𝐶6𝐻𝐻6 /𝑚𝑚̇ 𝐻𝐻2𝑂𝑂 . To find 𝑚𝑚̇ 𝐻𝐻2𝑂𝑂 , we need to follow the process in A.

However, the problem is simplified since we can use the steam tables to find Psat at 298K rather than using Clausius-
Clapyeron equation.

3169
From the steam tables, Psat (298K) = 3.169 kPa, So, we have 𝜒𝜒𝐻𝐻2𝑂𝑂,𝑖𝑖 = 101325 = 0.03128
 Example 1

Solution:
Interface mixture molecular weight is 𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚,𝑖𝑖 = 0.03128 18.016 + 1 − 0.03128 28.85 = 28.51 𝑘𝑘𝑘𝑘/𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

Thus,
𝑀𝑀𝑀𝑀𝐻𝐻2𝑂𝑂 18.016
𝑌𝑌𝐻𝐻2𝑂𝑂,𝑖𝑖 = 𝜒𝜒𝐻𝐻2𝑂𝑂,𝑖𝑖 = 0.03128 = 0.01977
𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚,𝑖𝑖 28.51

The mean molecular weight and mean density in the tube are

1 1
𝑀𝑀𝑀𝑀 = 𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚,𝑖𝑖 + 𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚,∞ = 28.51 + 28.85 = 28.68
2 2

101325
𝜌𝜌� = = 1.173 𝑘𝑘𝑘𝑘/𝑚𝑚3
(8315⁄28.68 )⁄298

where we assume air outside the tube is dry.

 Example 1

Solution:
The evaporation flux is then

′′
1.173(2.6 × 10−5 ) 1−0
𝑚𝑚̇ 𝐻𝐻2 𝑂𝑂
= 𝑙𝑙𝑙𝑙 = 3.05 × 10−4 0.01997 = 6.09 × 10−6 𝑘𝑘𝑘𝑘/𝑠𝑠𝑠𝑠2
0.1 1 − 0.01977

So,
2 2
′′
𝜋𝜋𝐷𝐷 𝜋𝜋(0.01)
𝑚𝑚̇ 𝐻𝐻2 𝑂𝑂 = 𝑚𝑚̇ 𝐻𝐻2 𝑂𝑂 4
= 6.09 × 10−6 = 4.785 × 10−10 𝑘𝑘𝑘𝑘/𝑠𝑠
4

Thus, we have
𝑚𝑚̇ 𝐶𝐶6𝐻𝐻6 3.46 × 10−9
= = 7.23
𝑚𝑚̇ 𝐻𝐻2𝑂𝑂 4.785 × 10−10
 Droplet Evaporation
• Problem of evaporation of a single liquid droplet in a quiescent environment is the Stefan problem
for spherically symmetric coordinate system

• Figure defines spherically symmetric coordinate

system.

• The radius r is only coordinate variable

• Origin is at centre of droplet

• Droplet radius at liquid-vapor interface is denoted

by rs

• Very far from droplet surface (𝑟𝑟 → ∞), the mass fraction of droplet vapor is 𝑌𝑌𝐴𝐴,∞ .
 Droplet Evaporation

• Heat from ambient environment supplies energy

necessary to vaporize the liquid

• Vapor diffuses from droplet surface into the ambient

gas

• Mass loss causes droplet radius to shrink with time

until droplet is completely evaporated (rs = 0)

• We need to determine mass flow rate of vapor from

surface at any instant
Conservation laws required:
• Eventually, we can calculate droplet radius as a
• Droplet: mass and energy conservation
function of time and droplet lifetime.
• Droplet vapor/ambient gas mixture ( 𝑟𝑟𝑠𝑠 < 𝑟𝑟 < ∞ ):
Overall mass conservation, droplet vapor (species)
conservation, and energy conservation
 Droplet Evaporation

ASSUMPTIONS:

1. Evaporation process is quasi-steady eliminating need of dealing with PDEs

2. Droplet temperature is uniform and below boiling point of liquid.

3. Mass fraction of vapor at droplet surface is determined by liquid-vapor equilibrium at

droplet temperature

4. Thermophysical properties are constant

 Droplet Evaporation

We can find mass evaporation rate, 𝑚𝑚̇ and the droplet radius history, 𝑟𝑟𝑠𝑠 (𝑡𝑡) by writing
droplet vapor species conservation equation and droplet liquid mass conservation
equation.

Once we determine evaporation rate, 𝑚𝑚,̇ we can easily find drop size as function of time.

As in Stefan problem, species originally in liquid phase is species transported, while

ambient fluid is stagnant

Overall mass conservation is expressed as

 Droplet Evaporation
Species conservation for droplet vapor becomes

Substituting the above into mass conservation equation and rearranging to solve
for evaporation rate 𝑚𝑚̇ = 𝑚𝑚̇ 𝐴𝐴 yields

Integrating above expression and applying boundary condition that at droplet

surface, vapor mass fraction is 𝑌𝑌𝐴𝐴,𝑠𝑠

yields
 Droplet Evaporation

Evaporation rate can be determined by using the boundary condition,

𝑌𝑌𝐴𝐴 = 𝑌𝑌𝐴𝐴,∞ for 𝑟𝑟 → ∞, as:

The argument of the logarithm in above equation is used to define a

dimensionless transfer number, 𝐵𝐵𝑌𝑌 :

or
 Droplet Evaporation

Using the transfer number, 𝐵𝐵𝑌𝑌 , the evaporation rate is expressed as

• When transfer number is zero, evaporation rate is zero.

• As transfer number increases, so does the evaporation rate.

• From the appearance of mass-fraction difference 𝑌𝑌𝐴𝐴,𝑠𝑠 − 𝑌𝑌𝐴𝐴,∞ in its

definition, transfer number can be interpreted as “driving potential”
for mass transfer.
 Droplet Mass Conservation

We obtain droplet radius history by writing mass balance that states that rate
at which mass of droplet increases is equal to rate at which liquid is
vaporized:

where the droplet mass, 𝑚𝑚𝑑𝑑 , is given by

and V and D(=2𝑟𝑟𝑠𝑠 ) are droplet volume and diameter, respectively.

 Droplet Mass Conservation

Substituting droplet mass expression and evaporation rate into mass balance
of droplet diameter,

Expressing the same in terms of 𝐷𝐷 2 rather than D, we get

Thus, time derivative of square of droplet diameter is constant; i.e. D2 varies

linearly with t with slope −(8𝜌𝜌𝒟𝒟𝐴𝐴𝐴𝐴 /𝜌𝜌𝑙𝑙 )ln(1+BY). Slope is defined as
evaporation constant K:
 Droplet Mass Conservation

We can use above expression to find the time it takes a droplet of given
initial size to evaporate completely; i.e., the droplet lifetime, td. Thus,

which yields

or

This is the D2 law for droplet evaporation.

Droplet Mass Conservation
Example 2
 Example 2

We start by calculation of transfer number BY, which requires knowledge of mass

fraction at surface.

As in Example 1, we integrate the Clausius-Clapeyron equation to find the saturation

pressure at given droplet surface temperature.
 Example 2
For T = Tboil – 10 = 479.5K,
Example 2
Example 2