The South African Breweries Section : 9.

8
Page : 1 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

1. INTRODUCTION
a) This method determines the amount of oxygen consumed from acidified potassium
dichromate in the oxidation of organic matter present in an aqueous solution (such as
brewery effluent). This approximates the oxygen theoretically required for complete
oxidation of carbonaceous matter to carbon dioxide (CO 2) and water (H2O).
b) COD levels in effluent impacts on the cost of processing brewery effluent by
municipalities.
c) Effluent discharged by a brewery typically originates from cleaning in the following
areas:
- Brewhouse.
- Fermentation.
- Maturation.
- Filtration.
- Packaging.
- Maltings (when applicable).
In order to identify the main contributor(s) to the overall load, each of these areas may
have to be assessed.
d) In the analysis the COD is measured in terms of the amount of potassium dichromate
reduced by the sample during 2 hours of refluxing in a medium of boiling sulphuric acid
(H2SO4) and in the presence of a silver sulphate (Ag2SO4) catalyst.
e) Chloride ions interfere, being precipitated as silver chloride (AgCl) and is subject to
unpredictable oxidation when Ag2SO4 is used on the catalyst. Chloride ions are removed
by complexing them with mercuric sulphate.
f) Auto-oxidation of the dichromate and organic impurities in the reaction system can be
accounted for by running a test/reagent blank with each batch of samples.
g) The test is not applicable only to effluent however, and can be used elsewhere, e.g.
Pasteurisers.
h) References :
i) Merck SQ 118 Photometer Manual.
ii) The Merck COD test pamphlet.
 The South African Breweries Section : 9.8
Page : 2 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

2. HEALTH AND SAFETY

2.1 HAZARDS
a) Sulphuric acid (H2SO4) is corrosive and destroys living tissue.
b) The test kit chemicals and reagents contain potassium dichromate and mercuric
sulphate which are toxic substances.
2.2 SAFETY REQUIREMENTS
a) H2SO4 : Face shield and acid-proof apron and gloves.
b) Test kit : Surgical gloves.
c) Heat resistant gloves.

2.3 PRECAUTIONS
a) H2SO4
 Never add water to this acid. Add the acid slowly to the water.
 The listed protective clothing must be worn when working with this acid.
 Store in an acids cupboard.
b) COD Test Kit
 Avoid eye and skin contact.
 Store in a safe secure place.
 The cell content (after testing) must not be disposed of into the drain.

3. APPARATUS
3.1 EQUIPMENT REQUIRED
a) Merck SQ 118 photometer.
b) Merck thermoreactor TR 300.
c) Merck cell rack Cat.No. : 14710.
d) Analytical balance.
e) Blender.
f) Volumetric flasks, 500 and 1000 ml.
g) Measuring cylinder, 500 ml.
h) Positive displacement pipette, 1-5 ml (Brand).
i) Tissues.
 The South African Breweries Section : 9.8
Page : 3 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

3.2 EQUIPMENT PREPARATION

3.2.1 Thermoreactor
a) Switch on the TR 300 thermoreactor.
b) Set the temperature selector to 148°C.
c) Set the timer to 20 minutes. When the yellow indicator lamp goes out, the
temperature has reached 148°C. The TR 300 thermoreactor is now ready for
use.

3.2.2 SQ 118 Photometer

a) Switch on the SQ 118 photometer.

b) Press the key.

c) Enter the method number e.g.
COD Range 10-150 Method 28
COD Range 100-1500 Method 29
COD Range 500-10 000 Method 112
The SQ 118 photometer is now ready for calibration.

3.3 EQUIPMENT MAINTENANCE

The halogen lamp on the photometer requires replacement only when fused. Part no.
14723.

3.4 CALIBRATION
a) Press the blank value key . 0
b) Wait until “reaction time” or “measure blank” appears on the display.
c) Place the reaction cell containing the blank (with a white cap) in the cell
compartment.
Note: Ensure that the vertical line is facing the operator.
d) Press the key. The blank value is displayed.
e) Remove the blank cell. The SQ 118 photometer is now ready for use.

3.5 STORAGE
 The South African Breweries Section : 9.8
Page : 4 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

4. CHEMICALS
4.1 CHEMICALS REQUIRED
a) Potassium hydrogen phthalate GR, Cat no. 4876.
b) COD cell test kits :
COD Range 500-10 000 mg/l Cat no.: 14555.
COD Range 10-150 mg/l Cat no.: 14540 (optional).
COD Range 100-1500 mg/l Cat no.: 14541 (optional).
c) Sulphuric acid, AR.

4.2 REAGENT PREPARATION

4.2.1 Standard Stock Solution(10 000 mg/l COD)
a) Weigh out 8,50 g potassium hydrogen phthalate, and transfer to a 1000 ml
volumetric flask.
Note: Potassium hydrogen phthalate dried for 2 hours at 105°C, and
cooled in a desiccator.
b) Dissolve in about 200 ml purified water.
c) Carefully add 2,5 ml concentrated sulphuric acid.
d) Make up to volume with purified water.

4.2.2 Standard Working Solution (5 000 mg/l COD)

a) Measure 500 ml of the stock solution using a measuring cylinder.
b) Pour into a 1 000 ml volumetric flask.
c) Make up to volume with purified water.
Note: i) The shelf life of this solution is one month.
ii) This solution is used for verification that all systems and
chemicals are working for a test in the range 500-
10 000 mg/l.
iii) If methods 28 or 29 (i.e. the lower COD ranges) are used, a
working standard is prepared as per the relevant test kit
pamphlet.

4.3 DISPOSAL
See Health and Safety.
 The South African Breweries Section : 9.8
Page : 5 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

5. METHOD
5.1 SAMPLE PREPARATION
Note: Prepare and analyse immediately after sampling.
a) Homogenise the sample using a blender.
b) Samples with a chloride concentration greater than 10 000 mg/l must be diluted with
purified water prior to the COD determination.
c) COD values are invalid if the sample pH is outside the range 2,0-12,0. In this case
adjust the sample pH with a molar solution of either sulphuric acid or sodium
hydroxide to fall within the required pH range.
d) Samples where the COD value is greater than 10 000 mg/l are repeated on a sample
diluted with purified water.

5.2 TEST METHOD

Note: i) With chloride concentrations between 2 500 and 10 000 mg/l the
photometric measurement should be taken with the cell contents still
having a temperature of at least 60°C.
ii) Photometric measurement of turbid solutions gives false - high COD
readings. Re-dissolve the precipitated matter by re-heating in the
thermoreactor and repeat the photometric measurement with the cell
temperature at 602,5°C.
a) Pipette 1 ml de-ionised water (blank), sample or working standard, using a positive
displacement pipette, into separate reaction cells.
Note: Allow these liquids to run carefully down the inside of the tilted
reaction cell.
b) Tightly attach the screw caps to the reaction cells.
c) Mix the content of the reaction cell.
Note: Wear safety gloves - the cell becomes warm.
d) Insert the reaction cells into the pre-heated thermoreactor and place the safety shield
in position.
e) Set the timer to 120 minutes.
f) Once the thermoreactor heater has switched off, remove the hot reaction cells from
the heating block.
g) Allow the cell to cool down in the cell rack.
Note: DO NOT COOL DOWN WITH COLD WATER.
h) After 10 minutes, shake the cell 10 times.
 The South African Breweries Section : 9.8
Page : 6 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

5.2 TEST METHOD (Continued)

i) Return the reaction cell to the cell rack and allow to cool down to approximately 20-
40°C.
Note: Calibrate the photometer as per section 3.4 above.
j) Insert the sample cell into the cell compartment with the vertical line facing the
operator.

k) Press the key.

l) Read and record the displayed COD value.
Note: Visually check that the sample is not turbid. If it in turbid, reheat to
approx. 60°C.
m) Remove sample cell from the compartment.
n) Insert the cell containing the standard working solution and conduct steps (j) to (l)
above.

5.3 CALCULATIONS
a) Undiluted samples.
COD mg/l = displayed value.
b) Diluted samples.
COD mg/l = displayed value x dilution factor.

6. VERIFICATION
a) Results are only valid if the displayed COD of the relevant working standard is within
5% of the prepared concentration.
Note: Degradation of the working solution will be noted when these COD values
are monitored.
b) Verification Routines - Refer to Volume X, Section 3.12.

7. COMPETENCY TEST
 The South African Breweries Section : 9.8
Page : 7 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

7. COMPETENCY TEST

FORMATIVE ASSESSMENT CHECKLIST

Date : Candidate Name :

Position : Department Name :
Unit :
Element :
Assessor 1 : Assessor 2 :

Assessment 1 2 3

COMPETENT NOT YET NOT

CHECKLIST COMPETENT ASSESSED

1.0 PRODUCT
I’d know that the end product is right and as
manualised if:-
1. Service record of the analytical balance and details
of servies conducted is available and current.
2. Maintenance records of the equipment are available
and current.
3. Calibration records of the equipment are available
and current.
4. Chemicals are stored and comply to "shelf life".
5. A "Change Management" record is available and
current.
6. Updated record of results is available.
Range of Variables:
Calibration equipment: SQ 118, thermoreactor, analytical balance and blender or vortex
mixer.
Maintenance equipment: SQ 118, thermoreactor and analytical balance.
Chemicals Storage Shelf-Life
Sulphuric Acid Acid cupboard N/A
COD Test Kit Safe secure place As supplier recommendations
 The South African Breweries Section : 9.8
Page : 8 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

7. COMPETENCY TEST (Continued)

FORMATIVE ASSESSMENT CHECKLIST (Continued)

COMPETENT NOT YET NOT

CHECKLIST COMPETENT ASSESSED

2.0 PROCESS
If the candidate did the job the correct way as
manualised he/she would:-
1. Adhere and comply to Health and Safety:
1.1 Sulphuric Acid: Safety glasses and gloves.
1.2 Test Kit: Surgical gloves, heat resistant
gloves.
2. Identify samples and glassware clearly for
traceability.
3. Prepare glassware:
3.1 Inspect, clean and dry.
3.2 Use dedicated tubes.
4. Quantitatively - Standard stock solution.
- Standard working solution.
5. Prepare the equipment:
5.1 Switch on the thermoreactor and set the timer
to 20 minutes. (Make sure 148°C
temperature is reached).
5.2 Switch on the SQ 118 photometer.
5.3
Press the key and enter the method
number (No. 28: 10-50, No. 29: 100-1500, No.
112: 500-1000).
5.4 Calibrate - press the blank key 0 .
5.5 Wait until "reaction time" or "measure blank"
appears on the display, then:
5.6 Insert the blank reaction cell (white cap) into
cell compartment, vertical line facing analyst.
5.7 Press key to display blank value (SQ
118 = calibrated).
6. Prepare samples:
6.1 Homogenise the sample using a blender.
6.2 Dilute samples if the chloride concentration is
greater than 10000 mg/l.
6.3 Adjust the pH if outside 2,0-12,0.
 The South African Breweries Section : 9.8
Page : 9 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER
 The South African Breweries Section : 9.8
Page : 10 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

7. COMPETENCY TEST (Continued)

FORMATIVE ASSESSMENT CHECKLIST (Continued)

COMPETENT NOT YET NOT

CHECKLIST COMPETENT ASSESSED

2.0 PROCESS (Continued)

7. Analyse samples:
7.1 Pipette 1 ml de-ionised water (blank), sample
or working standard into separate reaction
cells (allowing liquids to run carefully down the
inside of the tilted reaction cell).
7.2 Tightly attach the screw caps to the reaction
cells.
7.3 Mix the content of the reaction cell.
7.4 Insert the reaction cells into the pre-heated
thermoreactor (Temp. = 148°C).
7.5 Set timer to 120 minutes.
7.6 Remove cells from thermoreactor (if this has
switched off).
7.7 Shake each cell 10 times after 10 minutes
cooling and cool to 20-40°C.
7.8 Insert cell into compartment (vertical line
facing analyst) and press the key.
7.9 Read and record displayed COD value.
7.10 Check for turbidity, if present heat cell to
about 60°C and read COD value.
7.11 Repeat steps 7.8 to 7.10 for all samples and
the working standard.
8. Calculate all diluted samples.
9. Verify and validate results against verification
routines.
10 Record, report and communicate results.
3.0 KNOWLEDGE
A candidate who does this job should be able to:
1. Explain what COD measures.
2. Explain the impact of high COD to breweries.
 The South African Breweries Section : 9.8
Page : 11 of 10
BREWING MANUAL 1st Issue : Sep 1996
Vol. X - Analytical Methods Rev. Date : Jan 2000

SECTION 9.8 : DETERMINATION OF CHEMICAL OXYGEN

DEMAND (COD) BY SQ 118 PHOTOMETER

7. COMPETENCY TEST (Continued)

FORMATIVE ASSESSMENT CHECKLIST (Continued)

COMPETENT NOT YET NOT

CHECKLIST COMPETENT ASSESSED

3.0 KNOWLEDGE (Continued)

3. Explain the safety precautions that need to be
adhered to in this method.
4. Discuss why samples have to be prepared and
analysed immediately after sampling.
5. Explain why the samples have to be homogenised
on a blender.
6. Explain why the sample is cooled down to
approximately 20-40°C.
7. Explain what should be done if the sample is turbid
and why.

Competent : Not Yet Competent:

Comments :

Action Plan Follow up Dates

Assessor 1 Candidate
Sign. Sign.

Assessor 2
Sign.