Physical & chemical treatment

processes of water and waste

Lecture 3 Mass transfer & pH,
alkalinity and hardness
WAT - E2120
Anna Mikola TkT D Sc (Tech)
Lecture outline
Lecture on gas transfer Lecture on pH, alkalinity and
- Mass transfer hardness
- Theory Demo exercises
- Important equations Independent exercises
- Practical applications

Demo exercises
Independent exercises
Mass transfer - basics
- Basic mass transfer
- Transfer of material from equation (Fick’s first law)
one homogenous phase to
another
- Concentration increases in
one phase and decreases in =−
the other
- Driving force is pressure or - r = mass transfer rate
concentration gradient - Dm = diffusion coefficient
- Transfer stops at - C = concentration of
equilibrium constituent being
- No conversion reactions!! transferred
- x = distance

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Mass transfer between different
phases
Phase equilibria Type of process Examples of
processes
Gas à solid Adsorption Activated carbon
Liquid à solid Ion exchange Selective removal of
compounds
Gas à liquid Absorption Addition of gases to
water, NH3 scrubbing
in acid
Solid à liquid Desorption Sediment scrubbing
Solid à gas Reactivation of GAC
Liquid à gas Evaporation Drying
Gas stripping Removal of gases

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So familiar phenomena..

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Mass transfer basics

Diffusion Convection
- Caused by chemical - Due to bulk motion of the
potential difference (= fluid
gradients), often - Can work in favour of or
concentration against diffusion
- Mainly caused by Brownian
motion of molecules
- Fick’s law = substances
move from more
concentrated area to less
concentrated area

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 Diffusion coefficient
- Increases when particle size
decreases
=
- Increases when viscosity of
the liquid decreases
- Increases when temperature
increases R universal gas law constant
- In turbulent flow regime T temperature
replaced by coefficient of ɣ dynamic viscosity
dispersion rP radius of particle
N Avogadro’s number

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 Henry’s law
The amount of gas dissolved pg= xg
in liquid is directly
proportional to the pressure of
the gas in the solution
mole fraction of gas
in air
The equilibrium or saturation
concentration is different for H Henry’s law constant
different gases PT total pressure
The equilibrium concentration xg mole fraction of gas
depends also on temperature in water
and on liquid

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Principle of Henry’s law

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Henry’s constants for different gases

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Application of Henry’s law

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Example of saturation concentration of
oxygen in water
What is the saturation
concentration of oxygen in Saturation concentration =
water at 25°C and 1 atm? (2,73 x 10-4 mole / l)(32 g/mol) =
Hpc = 769 l atm/molO2 8,74 mg/l
Air contains 21% of oxygen à
pg = 0,21 mole 02/mole air
From Henry’s law
= pg = 2,73 x 10-4 mole / l

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Example of saturation concentration of
oxygen in water
What is the saturation One liter of water contains 55,6
concentration of oxygen in mole
water at 20°C and 1 atm? = xg = 5,11 x 10-6
Hpm = 41100 atm
Air contains 21% of oxygen à
pg = 0,21 mole 02/mole air ng + nw ≈ 55,6 à ng ≈ 2,84 x 10-
4 mole / l
From Henry’s law
Saturation concentration =
= pg = 5,11 x 10 mole gas (2,84 x 10-4 mole / l)(32 g/mol) =
-6

/ mole water 9,09 mg/l

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Saturation
concentration of
oxygen in clean
water

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Gas-liquid mass transfer
Often described with two-film
theory
- Assumes gas film and liquid
film on both sides of the
interface
- Assumes that the bulk-
liquid and bulk-gas are
perfectly mixed
- Under steady-state
conditions the rate of mass
transfer in gas film must be
equal to liquid film
Optionally surface-renewal
model
- surface is randomly
replaced
Or penetration model
- unsteady mass transfer
during the contact time of
gas/liquid

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The two-film theory

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 Absorption of gases to liquid 1/2
From Fick’s first law Usually overall coefficients KL
and KG are used
= − = ( − ) KL is used if liquid film
resistance controls
kG gas film mass transfer coeff
kL liquid film mass transfer coeff Mass transfer rate per unit
volume is obtained by
multiplying by area A and
From Henry’s law dividing by the volume V

= ( − ) = (Cs - Ct) = KLa(Cs - Ct)

Cs saturation concentration
Ct concentration at time t

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Absorption of gases 2/2

A mass balance for an open The desorption of gases:

basin:

=
Accumulation = rate of mass
transfer + inflow – outflow
Initial state is supersaturation
(C0 – Cs)
From = KLa (Cs – Ct)

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Air bubbles in a reactor basin – a
researcher approach
Concentration
Pressure
Bubble size

Temperature
Flow pattern
Viscosity
Resistance due to surfactants
etc.

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Air bubbles in a reactor basin – an
engineer approach
In practice the oxygen transfer
rate is calculated
R = α KLa ( ∞− )
α is the correction factor for KL
taking into account the
difference between clean water
and process water (e.g.
wastewater)
ß is the correction factor for
the saturation concentration in
process water
Note: here a is the surface area
of bubbles per unit volume.
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Examples of gas liquid transfer
applications
Stripping of gases – packed VOC removal
towers From water: stripping,
activated carbon adsorption
From soil: soil vapor extraction

Fliteway technologies
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 Examples of gas liquid transfer
applications
Aeration
CO2 stripping

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 Examples of gas liquid transfer
applications
Scrubbers – towers, plates,
Ozone diffusion
venturis
What is affecting the aeration
efficiency with bottom diffused air
- Water depth
- Aerator type
- Bubble size
- Aerator density and
coverage (flow
conditions)

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 Ammonia absortion and stripping
Nitrogen and phosphorus harvesting from different concentrated
liquid waste streams (Post doc Surendra Pradhan)

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GHG emission studies from advanced
nutrient removal processes
Comprehensive inventory of N2O emissions from an
advanced WWTP and implementation of N2O in the plant
wide process model

Department of Built Environment

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Demo exercise – Desorption of
benzene
A quantity of benzene was , ( )
spilled into a water storage Thus =
basin. Estimate the time
required for the concentration Solving for time
to drop by 50% due to
KLa t = ln 2
volatilization.
t = 0,69 / KLa
It can be assumed that the
concentration of benzene in KLa for benzene 0,144 m/h
the atmosphere is 0 à à T = 4,8 h
= ( )

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pH, alkalinity,
hardness

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pH - basics
Water dissociates on H+ and When acid is added to water, it
OH- ionizes and H+ increases and
For pure water consequently OH- must
{H+}{OH-} = Kw = 10-7 x 10-7 = decrease in order to keep the
10-14 ionization equilibrium
pH = -log {H+}
At pH 2 à {H+} = 10-2 Strong acids/bases are
At pH 10 à {H+} = 10-10 strongly ionized, week acids /
bases are poorly ionized

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Relevance of pH in treatment
processes
pH control
- Removal of CO2 by aeration
- The most commonly used
alkaline reagents are (Ca(OH)2),
(NaOH), (Na2CO3) e.g. pH
control for nitrification
- Sulphuric and hydrochloric
acids (H2SO4, HCl) are used to
increase the acidity of the
water, i.e.decrease the pH,
e.g.in coagulation,
neutralisation

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 Alkalinity - basics
Alkalinity is the acid Hydroxide alkalinity can be
neutralization capacity calculated from pH
Mainly due to salts of weak Hydroxide alkalinity =
( )
acids and strong bases
Most important:
Hydroxide OH-
Carbonate CO3 2- [OH-] 1 mole/l = 50000 mg/l of
CaCO3
Bicarbonate HCO3-
Less important: phosphates,
silicates…

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Calculation and measurement of
alkalinity
+ − −
[ ] + alkalinity (mol/l) = − +2
+

Alkalinity is measured by titration with sulfuric acid

Usually given as mmol/l (= meq/l)
Other units of alkalinity: equivalent CaCO3

Acidity: usually caused by CO2 in the water, also

mineral acidity
CO2 from the atmosphere and from biological
processes

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Application of alkalinity in treatment
processes
- Chemical coagulation – CO2 – alkalinity – pH
sufficient alkalinity needed - interactions
- Water softening Example: removal of CO2 to
- Corrosion control increase pH – what is the effect
- Langelier saturation index of alkalinity?
- Aggressive index
- Buffer capacity, especially in
biological processes

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Hardness - basics

Reflects the nature of ( )

geological formations
Caused by multivalent metallic =

cations mainly Ca2+ , Mg2+

Expressed as mmol/l, German
hardness (dH) or equivalents EW = equivalent weight
CaCO3 In this case atomic weight
mmol/l = 100x mg/l CaCO3 divided by the usual valence

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Consequences and removal of
hardness
- Ineffectiveness of soap Hardness can be removed by
- Scale formation especially removing Ca and Mg
in warm environments Methods:
(boilers, heating system - Precipitation and filtration
pipes…) - Ion exchange
- Causes clogging, material
damages and heat losses
- Protects against corrosion

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Demo example on pH

How much will the hydrogen-

ion concentration change if pH pH 7 à [H+] = 10-7 mol/l =
decreases of one unit? 0,0000001
pH 6 à [H+] = 10-6 mol/l =
pH = - log [H+] 0,000001

One unit in pH corresponds to Increase in [H+] = 0,0000009

10-fold change in hydrogen-ion mol/l
concentration.

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