Ezperciment 8

UV PHOTOCHEMICAL REACTOR
AIM:

To determinethe first order rate constant for the Photocatalytic oxidation of HCOOH
THEORY:

UV Photo catalytic detoxification has shown great promise for the treatment of ground water.
industrial wastewater and contaminated air and soil. In some cases such as removal of colour and
reduction of COD in industrial wastewater is one of the most effective treatments available.
Indoor experiments can be conducted with UV lamps using Ti0; as catalyst and UV radiations
from 300 to 400 nm wavelength.
Photocatalytic oxidation is a process were a semiconductor upon adsorption of a photon acts as a
catalyst in producing reactive radicals, mainly hydroxyl radicals, which in turn, can oxidize
organic compounds and totally mineralize thein. This way organic molecules get decomposed to
CO H,0 and mineral acids.Ti0; is one of the most favoured photo catalysts due to its excellent
activity, insolubility under most-conditions, non-toxicity and photo stability.
The energy needed to activate T0: is 3.2 ev, which corresponds to near UV radiation of a
wavelength of 380 nm or less.

Pathways and mechanism for photocatalytic oxidation and reduction are given below:
When a photon with an energy equal to or more than the band gap of Ti02 is absorbed on its
surface, it causes excitation of an electron from the valence band (vb) to the conduction band
(cb). forming a 'positive hole' in the valence band. Both the hole and the electron are highly
energetic and hence highly reactive. The excited electron and the positive hole,either recombine
and release heat, or migrate to the surface, where they react with adsorbed molecules and either
causes a reduction or oxidation of the adsorbate.

TO: hy --T02 ('ecb + hole* cb)

TO ('ecb + hole vb)> TO,+ heat
H,0>OH +H+

Hole vb+ OH ads OH

O2+ e cb O:
O+ 2H ag H0,+ 02

Oxidation of organics:
OH + Organics + O > Products (CO, H20etc)
 KINETICMODEL:
The rate of photolytic degradation depends on:
Illumination intensity
Catalyst type and dosage
Oxvgen congentration
pH
Cone, of organic reactant
Effect of temperature is small
Destruction rates of organics in photo catalytic oxidation can be modelled by Langmuir
Hinshelwood kinetic model expressed as:
dc KjK, C
dt 1+K,C

C= bulk solute concentration

K=reaction rate constant

K= equilibrium adsorption constant

t- time

For low solute concentrations, Equation (1) reduces to

dc
dt
=K, K;C= KC

Equation 2 is used to determine the apparent rate constant.

Batch type UV-detoxification set up can be used to determine the reaction rate constant K for
any organic solute.

Contaninated water (HCOOH + Water) is stored in the tank and is

reactor, which is illuminated by 3 or 4 UV tubes pumped through a UV
water coming out of the reactor is mixed with enclosed in a glass tube. The partially treated
the water in the tank. The
the mixed concentration in the tank
reaches an
prOcess continues until
acceptable level.
The reaction rate constant
(apparent rate constant, Kap) can be
Eq-2 using the concentration time determined from either Eq-1 or
history in the tank. The apparent rate
the volume constant is corrected for
correction as:
 1+x

K=Kap
Where o VR Volume of reactor

V Volume of Tank

dCT
dt
= KapCt

S-dc, =Kap S, dt

(4)
In=Kapt
DESCRPTION:

in the
The set-up is used to study a photo' photo catalytic reaction using a UV source provided
batch/
form of an UV tube. This set-up can be used to carry out a parameter study under
continuous flow condition. A photo catalyst like TO; can be used. This set-up can also be used
The
to study the mineralization of liquid effluent industrial streams & for purification of water.
set-up consists of reactor with inside reflecting surface. An UV source surrounding glass/ quartz
cylinder is placed centrally in the reactor.
UTILITIES REQUIRED:
1. Water supply and drain
2. Electricity-0.5kw, Single 0
3. Instruments, laboratory wares and chemicals required for analysis a per the system
adopted
CHEMICAL REQUIRED:
1. Formic Acid
2. Titanium dioxide
3. Hydrogen peroxide
EXPERIMENTAL PROCEDURE:
Lof
I. Prepare a 5 Lsolution of 500 ppm HCOOH by dissolving 2.5 gm of HCOOH in 5
distilled water.
determine the
2. Using standard N/10 NaOH solution and pheno phthalein as indicator,
with standard
exact concentration of HCOOH in water by titrating 50 ml of sample
NaOH.
in the tank (TO2 =0.6%
3. Weight 3gm of T02 and mix it with the 5 1 of acid solution
wt/vol)
appropriate level (5 LPH to 20
4. Start the pump and fix the flow rate of acid water at some
to the UV
LPH) and allowthe liquid to pass though the reactor. Start the power supply
tubes and simultaneously start thestopwatch.
and mix it thoroughly
5. Once the liquid comes out of the reactor, direct it to the acid tank
with tank fluid.
time and determine the
6. Collect 50 ml sample form the tank fluid at regular interval of
concentration of HCOOH by titrating it with standard N/ 10NaOH.
7. Repeat step 6, by collecting samples at 15-30 minutes interval.
8. You may repeat step 3 to 7for different TiO2 loading (0.2% to 0.05%)
ppm to l00
9. You may repeat steps I to 7 for different initial acid concentrations (500
ppm)
Steps 8 and 9 will help youo study the effect of T¡0; loading and initial feed concentration (Co)

respectively.

STANDARD DATA:

UV Source 30 W/ 16 W

Reactor With inside reflective surface

Effective volume of reactor I-1.5 L

Feed Tank Material SS 304. Capacity 5 L

Feed Circulation
Magnetic Pump made of Polypropylene.
Maximum working temperature is 80°C.
Flow Measurement Rotameter, Eureka/ IEPL/Mannix make
Sampl1ng points are providing at inlet & outlet of reactant line.

Control panel comprising of

Standard make on off switch, main Indicator, fuse, variable current supply to UV source etc. A
good quality painted rigid MS structure is provided to support all the parts.
FORMULA:

Reactor residence time per pass

T=
'R/o= min
Initial concentration of HCOOH in feed = Co

= Nx 46= gms/1

Plot in (Cor C) vs t

Slope = Kap
And o =VR/ VT

K = Kap X (1l+oc) /x
:K min-!

Based on different experiments runs you may report the

results as:
% Degradation = 0-C X 100
Co
Observations &Caleulations:
Standard Data:
UV tubes
=4 nos., 8 watt each with flux

=13.5 W/m² for each tube length of 12"

H02 added
=0.1-0.5 m/l of solution
Effective volume of the reactor, \VR = 1470 cm3

Volume of the liquid in the tank, VT

Amount of HCOOH(AR) added to 5 Iof distilled water =2.5 gms.
Amount of T02 added to 5 Lof distilled water =3 gms (0.6 wt/vol %)

Normality of std. NaOH used = N/10

Mol. Wt of HCOOH = 46

Mol. Wt of NaOH = 40

Volume of initial feed liquid(without T,O:) taken for titration= ml

Indicator Pheno/ phthalein

Volume of N/10NaOH used for titration =V= ml

i. (VN,) HCOOH =(V,N,) HCOOH

N, = GMEQ/ LTR

: initial concentration ofHCOOH in feed Co

NËx 46 = gms/1
Run No-1: Record

Volume of N/10 NaOHused (V> ml) for 50ml of sample from

feced tank at regular time interval:
Time (min) V2(ml) Cone, Of Co/C In(Co/C)
HCOOH gm/1, C
(V2/500x 46)

Plot In( Co/C)vst

Draw a straight line through the origin. Determine the slope of the line.

Slope= Kap=

And

= Vr/ VT = 1,47/5= 0.294

K = KapX (1+) /a = x (1+ 0.294)/ 0.294
:.K= min!

% Degradation Co-C X 100

Co
Note:

Specific grade of TiO is to be used as catalyst.

Youmay add HO; initially to aid photo catalysis.
T02 may be activated (in an oven) before use.
PRECAUTION& MAINTNANCE INSTRUCTIONS:
carefully.
1. Always prepare chemical for the experiment very handle with carefully.
skin so
2. Formic acid isa hazardous chemical to your
in the feed mixture.
3. Titrate the feed mixture before adding TiO;
Outlet of the reactor should thoroughly mix with in the tank until it will oscillate the
4.
concentration.

TROUBLE SHO0TING:
shake it
concentration of sample is fluctuating it means mixing is not proper so
1. If the
after 2-3 min.
shown on the panel so change that.
2. If anytube was fused simply