Installation procedure

8810 - ORP

SULPHIDE

0 - 1 mg/l S 2-

03/2001 621 = 997 = 125

Rev . H
 2-
8810 - ORP - Sulphide 0 - 1 mg/l S

Content

1. APPLICATION
1.1 Basic configuration
1.2 Principle of the measurement
1.3 Calibration principle

2. PROGRAMMING
2.1 Programming menu
2.2 PM XXXX
2.2.1 Application
2.2.2 Options
2.2.3 Adjust I out
2.2.4 Unit.
2.3 Titration parameters
2.4 Cycle parameters
2.5 Sample conditioning
2.6 Chemical cleaning
2.7 General test
2.8 Sequence
2.9 Analog outputs
2.10 Example of programming

3. STARTING UP
3.1 Initial calibration
3.2 Start up
3.3 Process calibration
3.4 Reading calibration parameters

4. REAGENT PREPARATION
4.1 R1 = Titration: Silver nitrate
4.2 R2 = Conditioning: NaOH
4.3 R3 = Cleaning: NaOH + EDTA
4.4 Calibration solution

Page 2 / 9
 2-
8810 - ORP - Sulphide 0 - 1 mg/l S

- 8810 ORP analyser - Installation procedure -

- Sulphide 0-1 mg/l S2 - -

1. APPLICATION :

1.1 Basic configuration : Refinery WWTP

Range 0 - 1 mg/l sulphide

Detection limit 0.05 mg/l
Working electrode Ion Selective Electrode Sulphide, P/N: 368490,00000
Reference electrode Type 8483, with Ag/AgCl, gelified electrolyte, P/N= 368483,00000
Software version ORP N 6.13 or higher
Required equipment One additional conditioning pump (several P/N available),
Heating (P/N: 368810,76000), dark tubing kit (P/N: 368810,84000),
chemical cleaning (P/N: 368810,56000)

Option External sample measurement (P/N: 368810,65000)

1.2 Principle of the measurement :
The cell of the analyser is automatically filled with a
constant and reproducible volume of sample. After
alkaline conditioning, sulphide are titrated directly
by a solution of silver. The titration is followed by an
Ion Specific Electrode Sulphide.
The titration curve is increasing from a potential of
-500 mV and up to +200 mV with a maximum
deviation around +130 mV. The exact determination
of the END POINT of the curve, is calculated by the
analyser (Auto-End point).
Low level sulphide analysis impose the so-called
two points calibration type to determine slope and
asymmetry. On a regular basis (once a week
maximum, once a month minimum), perform any of
the following calibration mode to your convenience.
a. MANUAL = Manual introduction of two
STANDARD injections, directly in the reactor vessel
of the analyser.

b. PROCESS = The analyser perform two separate

1.3 Calibration principle titration on rinsing water and process sample. Grab
each fluid during sampling phase and determine
On this application, automatic calibration is not concentration value in the laboratory.
possible because of the great instability in time of
sulphide solutions. No sulphide solution is accurate
after couple of days.

Page 3 / 9
 2-
8810 - ORP - Sulphide 0 - 1 mg/l S

2. PROGRAMMING: AUTO SYS CAL : NO (press ENTER)

2.1 Programming menu: CLEANING : YES (press ENTER)

Connect the analyser to the power supply. SAMPLE COND. : YES (press ENTER)

O Switch on the red button on the front panel. CAL 2 PTS : YES (press ENTER)

O Press SELECT to enter the main menu. GRAB SAMPLE : (YES or NO) depends if option
External sample measurement was purchased
O Press the UP/DOWN keys to select
SAMPLE TIME : XXX s usually 030 depends
(press ENTER)
"PROGRAMMING".
on volumetric pump flow (press ENTER).
O Press ENTER and hold on 5 seconds to enter the
PROGRAMMING menu. ZINC : NO (press ENTER)

T C : XXX.X C usually 025.0 depends on

HEATING : YES (press ENTER)
2.2 PM XXXX
application (press ENTER)
O Select "PM XXXX" with the scrolling keys.
NITROGEN : NO (press ENTER)
O Press ENTER.
DILUTION : NO (press ENTER)
O Enter 4000 with the scrolling keys.

O Press SELECT to change the digit.

2.2.3 ADJUST I out :
O Enter 4600 with the scrolling keys.
O At first, place a multimeter in series with your
O Press SELECT to change the digit. chart recorder or DCS and select with the scroll
down key ADJUST Iout and press ENTER.
O Enter 4670 with the scrolling keys.
O With the scroll down key, select the analogue
output range (0-20 or 4-20 mA) and press ENTER.
OUT : (0 or 4) ... 20 mA (press ENTER).
REMARK
If you enter a wrong code, you will be back O With the scroll down key, adjust the analogue
into the main menu. output origin.
OUT : (0 or 4) mA XXX (press ENTER).

O With the scroll down key, adjust 20 mA :

OUT : 20 mA XXX (press ENTER).
2.2.1 APPLICATION :

O Press ENTER to select "APPLICATION".

O With the scroll down key, select INC. POT.

1PT. Press ENTER. REMARK
CAL TEMPERATURE and ADJUST ADC"
are POLYMETRON reserved menus.
For this application (millivolt range = - 700
2.2.2 OPTIONS : to + 300 mV), S1 to S5 jumpers must be:

O With the scroll down key, select "OPTION" and

1-0-0-1-1
press ENTER.
Enter or check the following information :

Page 4 / 9
 2-
8810 - ORP - Sulphide 0 - 1 mg/l S

2.2.4 UNIT : 2.5 SAMPLE CONDITIONING :

O With the scroll down key, select UNIT and O With the scroll down key select "SAMPLE
press ENTER. COND.", and press ENTER.
Enter and check the following information :
O Enter or check that the unit is in accordance with
usual practise (mg/l, USER = PPB S) and press REAGENT 1 : YES (press ENTER)
ENTER.
INJ. REAG. 1 : 060 s (press ENTER)
O Exit from PM XXXX by pressing SELECT.
TIME REAG.1 : 020 s (press ENTER)

REAGENT 2 : NO (press ENTER)

2.3 TITRATION PARAMETERS

O With the scroll up key, select "MEASUREMENT" 2.6 CHEMICAL CLEANING :

and press ENTER.
Enter or check the following information: O With the scroll down key select "CLEANING"
and press ENTER. Enter or check the following
AUTO END PT (press ENTER) information :

FREQUENCY : XXX usually 010 adjust to

keep a clean reactor vessel
Deviation : 019 mV (press ENTER)
(press ENTER)

SPRINKLER t. : XXX s usually 007 depends

END PT1 : + 0200 mV (press ENTER)

on rinsing water flow ( press ENTER)

REAG. INJ. t. : XXX s usually 005 adjust to

2.4 CYCLE PARAMETERS: keep a clean reactor vessel (press ENTER)

O With the scroll down key select "TIMING" and RESIDENC t : XXX s usually 030 adjust to
press ENTER. Enter or check the following keep a clean reactor vessel (press ENTER)
information:

SAMPLE TIME : XXX s usually 030 depends on

sample flow (press ENTER)

SPRINKLER N : X s usually 2 adjust to keep a

2.7 GENERAL TESTS :

clean reactor vessel (press ENTER) O With the scroll down key select "SERVICE" and

SPRINKLER t : XX s usually 07 depends on

press ENTER.

rinsing water flow (press ENTER) O With the scroll down key, switch on/off each
analyser subassembly for testing purposes.
INJECT TIME : 01 s (press ENTER)
O Pass to next subassembly by pressing ENTER.
DELAY t. : 07 s (press ENTER)

CYCLE TIME : XXX mn must be over 012 mn

depends on requested analysis frequency
REMARK

(press ENTER) When you are testing the pumps, let

them work until the reagents arrive in
LIM. TIT. t : XXX mn < or = to CYCLE TIME the vessel.
(press ENTER)

Page 5 / 9
 2-
8810 - ORP - Sulphide 0 - 1 mg/l S

2.7.1 Sample-taken volume:
Using a volumetric cylinder, adjust the level of the
siphon tube (if necessary) to capture exactly 100
ml in the reactor vessel.
! ! ! Exact volume of 100 ml is required to
achieve accuracy during calibration step ! ! !
Following instructions are the Standard Operation
Procedure to measure this volume. Drain the cell
(DRAIN), fill it with rinse water (SPRINKLER),
weight empty cylinder and place under the drain
valve connector, drain the cell (DRAIN) and
weight full cylinder.
The unit has been previously selected in the
UNIT submenu ( see chapter 2.2.4: Unit)
O With the scroll down key select "ZERO" and
adjust your chart recorder or DCS on the scale
origin.
O With the scroll down key select "FULL" and
adjust your chart recorder or DCS on full scale.
O With the scroll down key select "CONC" and
press ENTER.

3. STARTING UP :
2.7.2 Volumetric pump:
The exact flow is not critical. Verify the time 3.1 INITIAL CALIBRATION:
necessary for the pump to fill the cell and activate
the siphon tube (Usual value: 20 to 30 seconds). It is the first operation to do after the programming.
Input this value as "SAMPLE TIME : XXX" of
menu PM XXXX / OPTION / GRAB SAMPLE (see O With the scroll down key select CALIBRATION
chapter 2.2.3 options) and press ENTER.

O With the scroll down key, select PRIMARY CAL

and press ENTER.
2.8 SEQUENCE:
O With the scroll down key, select MANUAL SYS
O With the scroll down key select "SEQUENCE" CAL and press ENTER.
and press ENTER.
O With the scroll down key, select FIX TIME and O When FILL CAL SOL 1 appears, gently poor
press ENTER. demineralised water (200 ml max.) in the reactor
O Input or check injection time of each pump that vessel to reach overflow of the siphon tube. Press
will occur during fix-time or stand-by procedure, ENTER.
as followed :
O Just after temperature and pH conditioning,
Inj. time P1 : 00s (press ENTER) quickly inject in the reactor vessel 1 ml of
Inj. time P2 : 00s (press ENTER) STANDARD solution (with a micro-pipette). For
Inj. time P3 : 00s (press ENTER) preparation see chapter 4.4 : calibration solutions.
Inj. time P4 : 00s (press ENTER)
O At the end of the titration, input or check
O If LOOP mode is requested, press ENTER CONC. 1: XXXXX (as the value of the
again on menu SEQUENCE. STANDARD solution divided by 100) and press
O With the scroll down key, select LOOP and ENTER.
press ENTER.
O When FILL CAL SOL 2 appears, gently poor
demineralised water (200 ml max.) in the reactor
vessel to reach overflow of the siphon tube. Press
2.9 ANALOGUE OUTPUTS : ENTER.

O With the scroll down key select "ANALOG O Just after temperature and pH conditioning,
OUT" and press ENTER. quickly inject in the reactor vessel 2 ml of
STANDARD solution (with a micro-pipette). For
Enter your desired range(for example: 0 -1 mg/l): preparation see chapter 4.4 : calibration solutions.

O At the end of the titration, input or check

START I1 : 0000. (press ENTER) CONC. 2: XXXXX (as the value of the
STANDARD solution divided by 50) and press
END I1 : 1.000 (press ENTER) ENTER.

OUT : Conc

Page 6 / 9

3.2 START UP THE ANALYSER :
Now you are ready to start your process.
O Press SELECT to exit from the PROGRAMMING
menu.
O With the scroll down key select "START", press
ENTER and let the analyser roll !
3.3 "PROCESS" CALIBRATION (If you have to
adjust the calibration slope).
O Press SELECT to access the main menu. Press
ENTER and the display will show If sure : ENTER.
Press ENTER to stop the analyser.
O Press SELECT to access the main menu and the
scroll down key until the display shows
PROGRAMMING.
O Press ENTER and hold on 5 seconds to enter the
PROGRAMMING menu.
O With the scroll up key, select CALIBRATION
and press ENTER.
O With the scroll down key, select SYSTEM CAL
and press ENTER.
O With the scroll down key, select PROCESS SYS
CAL and press ENTER.
O The system starts titrating using the rinsing water
(sulphide free) for the 1st point and the process
sample for the 2nd point.
O During each sampling phase, grab the solution at
the outlet of the siphon tube and send them for a
laboratory comparison measurement.
Page 7 / 9
2-
8810 - ORP - Sulphide 0 - 1 mg/l S
O After each titration, input or check:
CONC. 1 / 2: XXXXX (press ENTER)
as the concentration determined by laboratory
measurement.
O Follow instructions of chapter 3.2 STARTING
THE ANALYSER to launch the measuring mode.
3.4 READING CALIBRATION PARAMETERS
O At any moment, reading calibration parameters is
possible.
O Press SELECT to access the main-menu and the
scroll down key until display shows READING.
O Press ENTER and hold on 5 seconds to enter the
READING menu.
O Press the scroll down key until display shows
CAL PARAMETER and press ENTER.
O Press ENTER to read LAST CAL menu with
following information:
P / O / M / A / N letter indicates the calibration
mode. Respectively Process, On line, Manual,
Automatic, Primary.
S= XXX.X with value from 50% to 200%.
Co= X.XX with values from 0 to 999.
O Report the calibration parameters on a logsheet
and press ENTER.
O Press SELECT twice to come back to the
operating mode.

4. REAGENT PREPARATION
Prepare 3 x 10 litres canisters of reagents R1, R2,
R3.
With all chemicals, respect safety
procedures and wear gloves and safety
glasses.
Remark: Estimated Shelves Life (ESL) of each
canister is indicated at the end of the preparation.
4.1 : R1 = TITRATION (10 litres):
-4
Ag NO3 5 x 10
Pipette 50 ml of 0.1 N silver nitrate solution and
introduce in a volumetric flask (2 or 5 litres). Dilute
to the volumetric mark with demineralised water.
Transfer into a dark 10 litres canister. Refill the
volumetric flask with demineralised water to reach
a total of 10 litres in the canister. Put the cap on the
canister and shake to mix. Label, date and place on
the analyser.
ESL of a sealed canister: 2 months.
ESL of an open canister: 1 month.
Silver Nitrate STOCK solution 0.1 N AgNO3
Commercially available. Alternatively, it can be
prepared using silver nitrate powder:
In a 1 litre volumetric flask, add about 700 ml of
demineralised water. Under stirring, dissolve 17 g of
silver nitrate (AgNO3, reagent grade).
Transfer into a dark or amber glass storage flask.
Label and date. Store at +5 C.
2-
8810 - ORP - Sulphide 0 - 1 mg/l S
4.2 : R2 = CONDITIONING (10 litres):
Sodium hydroxide (32%) 40 % v/v
In a 10 litre standard canister, add 6 litres of
demineralised water. Poor slowly and portionwise, 4
litres of concentrated sodium hydroxide solution
(NaOH, >32%, d240 = 1.35, reagent grade). Put the
cap on the canister and shake to mix. Indicate date
of preparation and place on the analyser.
Reagent R2 is added during conditioning by
activation of the pump 2. Duration of the injection is
programmable to reach a sample pH after
conditioning of 12 units (See chapter 2.5 Sample
conditioning).
Consumption: With 60 seconds injection, one
measurement every 20 minutes, the 10 litres
N
canister will last 40 days.
ESL of a sealed canister: 6 months.
ESL of an open canister: 2 months.
4.3 : R3 = CLEANING REAGENT (10 litres):
NaOH 5 % vol.
EDTA.4Na,4H2O 50 g/l
In a 10 litres standard batch, add 7 litres of
demineralised water. Add portionwise 500 ml of
concentrated sodium hydroxide solution (NaOH,
>32%, d240 = 1.35, reagent grade). Then poor 500 g
of Ethylene Diamine Tetra Acetic acid
Tetrasodium Tetrahydrate (C10H12N2Na4O8.4H2O,
pract., > 95%). Put the cap on the canister and
shake to mix. Indicate date of preparation and place
on the analyser.
Reagent R3 is added during chemical cleaning cycle
by activation of the cleaning pump (located on the
back side of the analyser). Duration of the injection
is programmable (chapter 2.5 Chemical cleaning)
to keep a clean reactor vessel.
Consumption: With 4 seconds injection, one
cleaning every measurement and one
measurement every 12 minutes, the 10 litres
canister will last 40 days.
ESL of a sealed canister: 1 year.
ESL of an open canister: 6 months.
Page 8 / 9

4.4 CALIBRATION SOLUTIONS (for 500 ml):
All sulphide solution preparation must be
performed under the hood to avoid
breathing noxious fumes.
Precise standards cannot be prepared by weighting
a salt because of the large and variable water of
hydration.
STOCK solution (500 ml):
variable S value (in g/l S2-)
Initial S value shall be 2.67 g/l S2-.
In a 500 ml volumetric flask, add about 200 ml of
demineralised water. Under stirring, dissolve 100 ml
of concentrated sodium hydroxide solution
(NaOH, >32%, d240 = 1.35, reagent grade). Add 17g
of D (-)-Isoascorbic acid (C6H8O6, reagent grade).
Weigh quickly and roughly 10 g of sodium
sulphide hydrate (Na2S.aq, reagent grade) and
Page 9 / 9
2-
8810 - ORP - Sulphide 0 - 1 mg/l S
transfer quickly into the volumetric flask. Close
securely the flask and stir until crystals totally
dissolve. Adjust to 500 ml with demineralised water.
Shake to mix and transfer into a dark or amber glass
storage flask. Label and date. Store at +5 C.
ESL of a storage flask: Maximum 6 months or S
value is below 0.2 g/l. Neutralise with appropriate
method.
1 / 200
STANDARD (200 ml): Sx in mg/l S2-
In a 200 ml volumetric flask, add about 100 ml of
demineralised water. Under stirring, dissolve 20 ml
of concentrated sodium hydroxide solution
(NaOH, >32%, d240 = 1.35, reagent grade).
Pipette 2 ml of STOCK solution and dilute to 200
ml with demineralised water. Close securely, label
and date. Use within the next hour.
Exact concentration must be determined by
laboratory titration. Use as is until (S x 1 / 200) is
down to 5 mg/l. Pipette another volume of STOCK
solution if necessary.
ESL of a sealed flask: less than 1 hour. Neutralise
with appropriate method.