Determination of phenol and Sulphate in municipal wastewater

Objectives To determine Phenol & Sulphate concentration in wastewater sample.

Theoretical concept: Phenols are defined as hydroxyl derivatives of benzene, and its condensed nuclei occur in domestic and
industrial wastewaters, natural wastes and potable water supplies. Odoriferous and objectionable tasting chlorophenols are
formed as a result of chlorination of water containing phenol. Phenols may be present in raw water owing to the discharge of
wastewaters from coke distillation plants, the petrochemical industry and numerous other industries where phenols serve as
intermediates. They are also present in municipal wastewaters. Presence of phenols may lead to objectionable taste in
chlorinated drinking water and hence its monitoring is essential. Phenols can be removed from drinking water by super-
chlorination (chlorine-dioxide or chloramines treatment) ozonation and activated carbon adsorption.

Sulphate is widely distributed in nature and may be present in natural water in concentrations ranging from a few to several
thousand milligrams/L. Sulphates are of considerable concern because they are indirectly responsible for two serious problems
often associated with the handling and treatment of wastewater. Odour and sewer corrosion problem result from the reduction
of sulphates to hydrogen sulphide under anaerobic conditions. Sulphate ion is precipitated in an acetic acid medium with barium
chloride so as to form barium sulphate crystals of uniform size. The crystal formation is enhanced in the presence of an acetic
acid buffer solution containing magnesium chloride, potassium nitrate, sodium acetate and acetic acid. Light absorbance of the
BaSO4 suspension is measured by photometer and SO4- concentration is determined by comparison of the reading with a
 Apparatus and Reagents
• Magnetic stirrer, Nephelometer or Spectrophotometer, Distillation apparatus, pH meter, Funnels, Nessler tubes, short
or long form
• A) Sulphate
• Buffer solution A: Dissolve 30 g magnesium chloride, 5 g sodium acetate, 1 g potassium nitrate and 20 ml acetic acid in
500 ml distilled water and make up to 1000 ml.
• Buffer solution B (required when the sulphate concentration of sample is less than 10 mg/l): Dissolve 30 g magnesium
chloride, 5 g sodium acetate, 0.111 g sodium sulphate and 20 ml acetic acid in 500 ml distilled water and make up to
1000 ml.
• Barium chloride: crystals of 20 to 30 mesh size. In standardization uniform turbidity is produced with this mesh range
and the appropriate buffer.
• Standard sulphate solution: Dissolve 0.1479 g anhydrous Na2SO4 in distilled water and dilute to 1000 ml.
• B) Phenol
• Phosphoric acid solution: Dilute 10 mL of 85% H PO to 100 mL with distilled water.
• Copper sulfate solution: Dissolve 100 g CuSO4•5H O in distilled water and dilute to 1L.
• Buffer solution: Dissolve 16.9 g NH Cl in 143 mL conc. NH OH and dilute to 250 mL with distilled water. Two ml
should adjust 100 ml of distillate to pH.
• Amino antipyrine solution: Dissolve 2 g of 4AAP in distilled water and dilute to 100 ml.
• Potassium ferricyanide solution: Dissolve 8 g of K Fe(CN) in distilled water and dilute to 100 ml.
• Continue
Stock phenol solution: Dissolve 1.0 g phenol in freshly boiled and cooled distilled water and dilute
to 1 liter. 1 ml = 1 mg phenol.
Working solution, A: Dilute 10 ml stock phenol solution to 1 liter with distilled water. mL = 10 µg
phenol.
Working solution B: Dilute 100 ml of working solution A to 1000 mL with distilled water. 1 mL = 1
µg phenol.
Ferrous ammonium sulfate: Dissolve 1.1 g ferrous ammonium sulfate in 500mL distilled water
containing 1 mL conc. H2SO4 and dilute to 1 liter with freshly boiled and cooled distilled water.
• C) Preparation of calibration curve
• Take 100 mL distilled water in a 500 mL glass stoppered conical flask or iodine flask. Add 50 mL
stock phenol solution and 10 mL 0.1N bromate-bromide solution followed by 1 mL
concentrated HCl and swirl gently.
• If brown colour of free bromine does not persist, add 10.0 mL portions bromate-bromide
solution until it does. Put the stopper tightly and keep it for 10 minutes.
• Add 1 g Kl, keep flask stoppered, swirl and again keep it for some time.
• Prepare a blank in the same manner using distilled water and 10 mL 0.1N bromate-bromide
solutions.
• Titrate blank and sample with 0.025 N sodium thiosulphate using starch as an indicator.
Calibration curve for Phennol
 Procedure for Sulphate determination

• Filter the sample if it is turbid and adjust the temperature between 15 to 30˚C.
• Measure 100 ml sample into a 250 ml Erlenmeyer flask.
• Add 20 ml buffer solution and mix in a stirring apparatus.
• While stirring add a spoonful of BaCl2 crystal and the timing immediately.
• Stir for 60 ± 2 sec at constant speed.
• After stirring period is over, pour solution into a absorption cell of photometer and measure turbidity at 5 ±0.5
min.
• Estimate SO4 concentration in sample by comparing turbidity reading with a calibration curve prepared by
carrying SO42- standards through the entire procedure.
• Space standards at 5 mg/L increments in the 0 to 40 mg/L SO42- range.
• Correct for sample color and turbidity by running blanks to which BaCl2 is not added.
• Follow the Link : https://www.youtube.com/watch?v=ve53HN9za7E Gravimetric Method
• https://www.youtube.com/watch?v=-7qUHmwFfMc Turbidity Method
 Procedure for phenol determination
• Measure 500 mL sample into a beaker, add 50 mL phenol-free distilled water, lower the pH to 4.0 with
H3PO4 solution using methyl orange as an indicator.
• Add 5 mL CuSO4 solution & Transfer to distillation flask and collect 500 mL distillate using measuring
cylinder as receiver.
• If the distillate is turbid repeat the same procedure as above. Omit addition of H3PO4 and CuSO4 if the
preserved sample is used.
• Take 100 mL distillate or an aliquot of the distillate containing not more than 0.5 mg phenol and dilute
to 100 mL in a 250 mL beaker.
• Prepare a 100 mL distilled water blank and a series of 100 mL phenol standards containing 0.1, 0.2, 0.3,
0.4 and 0.5 mg phenol.
• Add 2.5 mL 0.5N NH4OH solution in each and adjust the pH to 7.9 ± 0.1 with phosphate buffer and
dilute to 100 mL in a 250 mL beaker.
• Add 1 mL 4-aminoantipyrine solution and 1 mL K3Fe (CN)6 solution in each flask and mix well.
• Measure the absorbance of each after 10 minutes against blank at 500 nm.
• Follow the Link for Phenol: https://www.youtube.com/watch?v=oir6sB-
XqzY&ab_channel=PravendraTomar%5BPTSir%5DIITJEE%2CNEET and
• https://www.youtube.com/watch?v=iqZWvs8vpF8&ab_channel=sandhyanaykinde
• https://www.youtube.com/watch?v=q0rtKY4Bx4s
 Calculations:
SO4 in mg/L = mg SO42- X 1000/ ml of sample
Calculation of the concentration of phenol solution as follows:
mg/L phenol = 7.842 [(A x B) – C]
A = mL thiosulphate for blank
B = mL bromate-bromide solution used for sample divided by 10
C = mL thiosulphate used for sample
Use of calibration curve,
µg/L, phenol = [(A /B) x 1000]
Where:
A = mg phenol in sample (estimated from calibration curve)
B = mL original sample
 Results and discussion
• Concentration of SO4 in mg/L =
• Concentration of phenol in µg/L=
• Environmental Significance:
• Discharge of phenolic compounds without treatment may lead to
serious health risks to humans, animals, and aquatic systems.
Phenolic compounds are highly toxic even at low
concentrations. Their presence in streams and other waterways will
cause foul smell and will adversely affects the fish tissues and other
aquatic lifes.
• Water containing appreciable amount of sulphates forms hard scale
in boilers and heat exchangers. Sulphates also causes odour and
corrosion of sewer in anaerobic conditions because it gets converted
to hydrogen sulphide.