Hanna Instruments HI 4115 User Manual

HI 4115

SILVER/SULFIDE

COMBINATION

HI 4015

SILVER/SULFIDE

Instruction Manual

HI 4015HI 4015

HI 4015

HI 4015HI 4015
HI 4115HI 4115

HI 4115

HI 4115HI 4115

Silver/Sulfide Ion

Selective Electrode

Half-cell
Combination

1

HI 4015 Silver/ Sulfide Half-cellHI 4015 Silver/ Sulfide Half-cell

HI 4015 Silver/ Sulfide Half-cell

HI 4015 Silver/ Sulfide Half-cellHI 4015 Silver/ Sulfide Half-cell
HI 4115 Silver/ Sulfide CombinationHI 4115 Silver/ Sulfide Combination

HI 4115 Silver/ Sulfide Combination

HI 4115 Silver/ Sulfide CombinationHI 4115 Silver/ Sulfide Combination
ElectrodeElectrode

Electrode

ElectrodeElectrode

I. I.

Introduction:Introduction:

I.

Introduction:

I. I.

Introduction:Introduction:
The Hanna HI 4015 and HI 4115 are ion selective elec­trodes designed for the measurement of Silver/ Sulfide ions
in aqueous solutions. The HI 4015 is a solid state half-cell
sensor that requires a separate reference. The HI 4115 is a
combination ion selective electrode.

IIII

SpecificationsSpecifications

II.

Specifications

IIII

SpecificationsSpecifications

Type: Solid State electrode with

a Silver/ Sulfide pellet.

Ion(s) measured: Silver (Ag+), Sulfide (S2-)

Measurement range: Silver 1.0 M to 1 X 10

-6

M

(107,900 to 0.11 ppm)

Sulfide 1.0 M to 1 X 10

-7

M

(32,100 to 0.003 ppm)

Theory of OperationTheory of Operation

III. III.

Theory of Operation

III.

Theory of OperationTheory of Operation

III. III.

::

:

::
The HI 4015 or HI 4115 Silver/ Sulfide electrodes are po­tentiometric devices used for the rapid determination of free
silver or sulfide ions. They can be used as an indicator
following the progress of a halide titration with silver ni­trate. Sulfide ion determinations are made in ground wa­ters, soils and paper liquors. The electrode functions as a
sensor or ionic conductor. The HI 4015 requires a separate
reference electrode to complete its electrolytic circuit. The HI
4115 has a double junction reference electrode incorpo­rated in its design. The silver/ silver- sulfide pellet is prac­tically insoluble in the test solutions being measured and
produces a potential change due to changes in the sample’s
ion activity. When the ionic strength of the sample is fixed
by the addition of ISA, the voltage is proportional to the
concentration of silver or sulfide ions in solution and the
electrode follows the Nernst equation.

E= E

+ 2.3 RT/nF log A

a

ion

E= observed potential

Ea= Reference and fixed internal voltages

Interfering ions: Mercury must be absent.

Ions that complex with
measured species will re­duce measured ion con­centrations.

Operating Temperature: 0-80°C

Operating pH: 2-8 pH (For Silver)

12-14 pH (For Sulfide)

Dimensions: 12 mm (OD) X 120 mm

nominal insertion
(0.47” X 4.72”)

Connection: BNC

2

R= gas constant (8.314 J/K Mol)

n= Charge on ion (2- for sulfide), (1+ for silver)

A i=ion activity in sample

T= absolute temperature in K

F= Faraday constant (9.648 x 10

4

C/mol)

3

IV. IV.

Design elements of the HI 4015 and HI 4115Design elements of the HI 4015 and HI 4115

IV.

Design elements of the HI 4015 and HI 4115

IV. IV.

Design elements of the HI 4015 and HI 4115Design elements of the HI 4015 and HI 4115

electrodeselectrodes

electrodes

electrodeselectrodes

Cap

HI 4015

SILVER/SULFIDE

Sensor
Handle

V. Equipment required:V. Equipment required:

V. Equipment required:

V. Equipment required:V. Equipment required:

• Hanna HI 5315 Double Junction Reference Electrode

with HI 7072 Fill Solution for use with HI 4015.

• Hanna HI 4222 pH/ISE/mV meter or other suitable

ion or pH/mV meter. (Note: log/linear graph paper is
useful if an ISE (ion) meter is not available).

• Hanna HI 180 Magnetic Stirrer or equivalent with

Teflon coated stirring bars (HI 731320). (Note: iso­late beakers from stirrer motor heat by placing insu­lating material such as foam or cork between them).

• Hanna HI 76404 Electrode Holder or equivalent.

• Plastic beakers (HI 740036P) or other suitable mea-

surement vessel.

Sensing
Membrane

Upper Cap

Upper
Threads

O-Ring

Ceramic Junction
on Inner Stem

Liquid junction

Spring

Fill Hole

O-Ring and
Plug

Outer Sleeve

Sensing
Membrane

VI. VI.

Solutions Required for CalibrationSolutions Required for Calibration

VI.

Solutions Required for Calibration

VI. VI.

Solutions Required for CalibrationSolutions Required for Calibration
Select appropriate Hanna Instruments standard and ISA
from the list below:

0.1 M Silver Standard, 500 mL HI 4015-01
ISA for Silver measurement, 500 mL HI 4000-00
SAOB for Sulfide measurement, 500 mL HI 4015-00
Note: For Sulfide standard, see directions that follow.

Silver Standards
For Molar solutions:
Using volumetric pipettes and glassware make serial dilu­tions of HI 4015-01 to approximately bracket the concen­tration of the samples. Standards with concentrations

-3

< 10

M should be prepared daily. Store in dark plastic
bottles.
Two mL of Hanna ISA for Halide electrodes (HI 4000-00)
should be added to 100 mL of sample or standard.
For ppm solutions:
Prepare 1078.7 ppm Silver standard by diluting HI 4015­01: Pipette 100 mL standard to a 1 liter volumetric flask.
Add deionized water to volume. Using additional pipettes
and glassware make serial dilutions of this 1078.7 ppm
standard to bracket the sample concentra-

4

5

tions. Standards with concentrations < 100 ppm should
be made daily.

Solutions for Sulfide Measurements
SAOB, Hanna HI 4015-00 : Add content of SAOB reagent
B bottle to the bottle with SAOB reagent A. Cap bottle
and mix well until completely dissolved. Reagent that is
brown has been oxidized and should be discarded.

Sulfide Standards:
Sulfide standards are susceptible to air oxidation and
therefore are not commercially available.
Sulfide stock solution: Weigh approximately 100 gram of
reagent grade Sodium Sulfide nonahydrate
(Na2S·9H2O) into a 1 liter volumetric flask that contains
a volume of distilled or deionized /deareated water.
Swirl to dissolve, bring to volume, then transfer to a
tightly sealed 1 L container with minimal head space
and allow solution to equilibrate overnight.

133.5 ppm standard (approximate concentration):
Transfer 5.00 mL stock solution and 250 mL Sulfide
Antioxidant buffer SAOB (Hanna HI 4015-00) to a to
500 mL volumetric flask. Mix well then bring to volume
with distilled or deionized /deareated water. Hanna HI
4015-00 SAOB, should be clear to pale straw in color
after mixing. Note: higher concentrations of standard can
also be prepared and titrated if samples are greater in
concentration. The sensor is useable from 32,100 to

0.003 ppm.
Determine exact concentration of the prepared standard
by doing a titration with Lead Perchlorate standard (user
prepared) on a weekly basis. The exact concentration of
the standard is found by titrating 10 mL of the standard
with 0.01 M Lead Perchlorate standard; (Pb(ClO4)2 ).
Pb2++ S

2-

> PbS
Use the electrode pair as an indicator for S2- to determine
the endpoint. See Section XII.

Calculate as follows:
Weekly standard in Molar concentration

VV

= Volume of the standard sulfide solution used

V

VV

s. s.

s.

s. s.

C (moles/liter)= (0.01) *

(10 mL)
VV

V

= Volume of the Lead Perchlorate titrant used to reach

VV

t t

t

t t

V

/ V

t

s.

endpoint (mL))
Weekly standard in ppm
C (ppm)= (0.01) *32.07

V

/ V

t

s.

Using volumetric pipettes and glassware make dilutions
daily from the titrated standard whose value has been
determined. Choose standards to bracket the concentra­tion of the samples.
50 mL of HI 4000-00 ISA should be added to each 100
mL flask of standard before being brought to volume.

VIIVII

General GuidelinesGeneral Guidelines

VII.

General Guidelines

VIIVII

General GuidelinesGeneral Guidelines

• Calibration standards and sample solutions should

have the same ionic strength. ISA or SAOB should be
added to both samples and standards in the same
ratio.

• Calibration standards and sample solutions should

be at same temperature.

• Thermally insulate beaker with standard or sample

from magnetic stirrer.

• Calibration standards and sample solutions should

be stirred at the same rate using identically sized TFE
coated stir bars.

• Rinse electrode pair with distilled or deionized water

between samples and gently dab off using soft
disposable absorbent toweling. Do not rub sensor sur­face.

• Presoaking silver sensor in a dilute standard

(<10-3M) will help to optimize response.

• A scratched, pitted, or tarnished pellet surface can

cause drift, poor repeatability or a loss of low level
response. Restore optimum response can be by
removing the damaged surface with the microabrasive
strip HI 4000-70.

6

7

• Avoid large changes in temperature (thermal shock)

as it may damage the sensor.

• Avoid leaving electrode in SAOB containing solutions

for long periods of time as it will damage the elec­trode.

VIII. VIII.

Electrode PreparationElectrode Preparation

VIII.

Electrode Preparation

VIII. VIII.

Electrode PreparationElectrode Preparation

HI 4015

1. Remove protective cover from sensor tip.

2. Prepare reference electrode by filling outer electrolyte

reservoir with HI 7072.

3. Place sensor and reference electrodes into electrode

holder and connect cable connectors to meter.

HI 4115

1. Unwrap plastic film seal found over ceramic junction

on inner stem and discard. This is only used for ship­ping and long term storage.

2. Rinse inner stem with deionized water making certain

to wet the o-ring found on the inner stem.

6. Holding the body of the electrode gently press upper
cap with your thumb. This permits the fill solution to
drain out of the body. Release cap and verify elec­trode returns to its original position. (You may need to
gently assist for this to occur).

E

N

ID
F

IO

L

T

U

A

/S

IN

R

5

B

E

1

M

1

S

4

O

IL

I

C

S

H

Water

Deionized

Parafilm

3. Reassemble electrode by gently pushing the inner
assembly into the outer body, sliding spring down
cable, and screwing cap into place.

4. Remove fill hole cover and o-ring on fill hole spout.

5. Using the dropper pipette provided, add a few drops
HI 7072 fill solution to the electrode, wetting the o­ring and rinsing out the fill solution chamber.

8

Remove

7. Tighten the electrode cap onto the body and fill elec­trode body until fill solution volume is just below fill
hole.

8. Position electrode in a Hanna HI 76404 electrode
holder (or equivalent) and connect plug to meter.

9

IX. IX.

Quick Check of Electrode SlopeQuick Check of Electrode Slope

IX.

Quick Check of Electrode Slope

IX. IX.

Quick Check of Electrode SlopeQuick Check of Electrode Slope

++

+

++

AgAg

Ag

AgAg

• Connect sensors to pH/mV/ISE meter.

• Place meter in mV mode.

• Place 100 mL of deionized water into a beaker with

stir bar.

• Place electrode (s) into prepared sample.

• Add 1 mL of a standard (0.1 M or 1078.7 ppm stan-

dard) to beaker. Record the mV value when stable.

• Add an additional 10 mL of standard to the solution.

Record the mV when reading has stabilized. This
value should greater than the previous noted (more
positive).

• Determine the difference between the two mV values.

An acceptable value for this slope is 56 ± 4 mV. If
sensor does not have appropriate mV change, correc­tive action must be taken.

2-2-

2-

2-2-

SS

S

SS

• Connect sensors to pH/mV/ISE meter.

• Place meter in mV mode.

• Place 50 mL of deareated water into a beaker with 50

mL of the premixed SAOB, Hanna HI 4015-00. Add
stir bar and mix thoroughly.

• Place electrode (s) into prepared sample.

• Add 1 mL of the titrated standard to beaker. Record

the mV value when stable.

• Add an additional 10 mL of standard to the solution.

Record the mV when reading has stabilized. This
value should less than the previous noted (more nega­tive).

• Determine the difference between the two mV values.

An acceptable value for this slope is -28± 4 mV for
freshly made solution. Solution exposed to air will be
degraded and lower slopes will be observed. If sensor
does not have appropriate mV change, corrective ac­tion must be taken.

X. X.

Corrective actionCorrective action

X.

Corrective action

X. X.

Corrective actionCorrective action

• Verify protective cap has been removed.(HI 4015)

• Verify plastic film has been removed from inner

stem.(HI 4115)

• Verify electrodes are connected properly to meter and

meter is powered.

• Verify dilute standards are freshly made and stored.

Remake solutions if appropriate.

• Verify SAOB was added to sulfide standards and they

have been stored appropriately. Remake solutions if
necessary.

• If the silver sensor slope just misses the suggested

slope window, soaking the sensor in a dilute standard
may solve the problem. (Choose a dilute value equal
or less than 10

-3

M).

• A scratched sensing surface can be polished with HI

4000-70 polishing strip. Cut off approximately 1
inch of the micro-abrasive strip. Wet the frosted side
with deionized water and place against damaged
membrane of the electrode. Place your thumb against
the shiny backing and slowly rotate back and forth
while applying gentle pressure. Check to see if small
scratches have been eliminated and coatings have
been removed. Rinse in deionized water and dab
dry. Continue polishing until you are satisfied with
the surface.
Warning: Silver Sulfide dust is considered corrosive.
Protective hand coverings is strongly recommended
during this procedure.

• If dark deposits appears on polishing strip move the

paper slightly and continue polishing.

• If the membrane is damaged, the response becomes

extremely sluggish, or the slope of the electrode has
decreased significantly, and procedures above have
not helped, the sensor should be replaced.

10

11

XI. XI.

Direct Calibration and MeasurementDirect Calibration and Measurement

XI.

Direct Calibration and Measurement

XI. XI.

Direct Calibration and MeasurementDirect Calibration and Measurement
The direct calibration technique is a simple procedure for
measuring many samples. A direct reading ISE meter (HI
4222 or equivalent) determines concentration of the un­known by a direct reading after calibrating the meter with
the standards. The meter is calibrated with two or more
freshly made standards that are in the linear measurement
range of the unknowns. Unknowns are read directly. At
very low levels of silver, special precautions must be em­ployed for reproducible measurements. Water used for
standards must be free of halides and sensors and glass­ware must be rinsed repeatedly with this water to prevent
carry over. Plastic beakers are recommended. In the region
where the electrode response appears curved, more calibra­tion points are needed, and calibration will need to be
repeated more frequently. See “Procedure for Silver” be-
low for additional instructions.
A pH/mV meter in mV mode with semi-log graph paper
may also be used. Two or more freshly prepared standards
that are in the measurement range of the unknowns are
measured in mV mode on the meter.
These values are plotted on the semi-log paper and the
points are connected to form a straight-line curve. When
samples are measured, their mV values are converted to
concentration by following the mV to the concentration axis
on the semi-log plot.

Procedure for Silver

1) Follow sections VIII and IX to prepare sensors for

measurement.

2) Follow section VI to prepare standard solution. Stan-

dards should bracket and fall within the range of
interest.
Two mL HI 4000-00 ISA is added to 100 mL of both
samples and standards for measurements equal or
above 10-4M silver. At concentrations equal or less
than 10-4M silver, prepare a separate calibration curve
and use 1 mL of a diluted ISA in sample and stan-

dards. Add stir bar and mix thoroughly and continu­ously before taking measurements. A lower level ionic
strength adjuster is prepared by diluting HI 4000-00
ISA (20 mL diluted to 100 mL). This should be used
at a dose of 1 part per 100 parts sample or standard.
Sample ionic strengths will be approximately 10-2M.

3) Follow section VII to optimize test set-up.

4) During calibration it is best to start with lower concen­tration samples first. Wait for a stable measurement
before recording values. Slightly longer equilibra­tions are required at lower concentrations .

5) To prevent carry over and contamination of samples,
rinse sensors with deionized water and dab dry be­tween samples.

Typi cal Li neari ty for HI 4015 & HI 4115

500

450

400

350

mV

300

250

200

150

012345678

for Si lver Measurement

-Log of Concent ration ( M)

Reg ula r Le vel

Low Level

12

13

Procedure for Sulfide

1) Follow sections VIII and IX to prepare sensors for
measurement.

2) Follow section VI to prepare standards / solution.
Standards should bracket and fall within the range of
interest.
Fifty mL HI 4015-00 ISA is added to the beaker with
50 mL sample or standard. Add stir bar and mix
thoroughly and continuously before making mea­surements. Protect these solutions from air and use
promptly.

3) Follow section VII to optimize test set-up.

4) During calibration it is best to start with lower concen­tration samples first. Wait for a stable measurement
before recording values. Slightly longer equilibra­tions are required at lower concentrations .

5) To prevent carry over and contamination of samples,
rinse sensors with deionized water and dab dry be­tween samples.

XII. XII.

Other Measurement TOther Measurement T

XII.

Other Measurement T

XII. XII.

Other Measurement TOther Measurement T

echniquesechniques

echniques

echniquesechniques
Known Addition (for Ag+or S2-)
An unknown concentration can be determined by adding a
known amount (volume and concentration) of measured
ion to a known volume of the sample. This technique is
called Known Addition. The method can use an ideal
sensor slope, but actual determined slopes at the tempera­ture of measurement should be used if known. This method
is preprogrammed in the Hanna HI 4222 pH/ISE/mV meter,
which simplifies the method greatly.This technique is use­ful for high ionic strength samples.
Example: Silver ion determination with known addition.

1. A 50 mL sample of unknown (Vsample) is placed in

a clean plastic beaker with a HI 4115 sensor. 2 mL of
HI 4000-00 ISA (V

)is added and the sample is

ISA

mixed well. The stable mV value (mV 1) is then re­corded.

2. 5 mL (Vstd) of 10-3M (Cstd) standard is added to the

beaker and the mV value increases. The unknown
silver concentration in the original sample (Csample)
can then be determined by the following equation.

Typical Linearity for HI 4015 & HI 4115

-680

-700

-720

-740

-760

mV

-780

-800

-820

-840

-860

01234567

for Sul fide Measurement

-Log of Conce ntration

14

C

C

=

sample

(V

(V

samp le+Vstandard+VISA

(V

sample+VISA

standardVstandard

∆E/S

)10

T

- (VS’)

)= V

)= V

S’

V

S’

V

sample

T

3. The procedure can be repeated with multiple samples.

Analyte Subtraction (S2-)
This method is based on a titration reaction, with the
electrode responsing to a reagent that reacts with the
sample being added.
A known concentration of sulfide in a sample can be
determined by using this method. A silver standard is
used as the reagent. Ions that complex with silver cannot
be present. These include Cl-, Br-, I- CN-, or SAOB. This
method assumes an ideal sensor slope, but actual

15

determined slopes at the temperature of measurement
should be used if known.
Example: Sulfide ion determination by sample subtrac­tion.

1) A volume of standard solution of silver reagent
(V

) (C

std

) plus ISA (V

std

) is placed in a beaker

ISA

with the sensor pair. The mV1 is recorded.

2) A known volume (V

) of the unknown sulfide

sam

sample is added (mV should change at least 10 –
30 mV). The new mV is recorded (mV2) and the
difference is calibrated using the equation below

∆mV = mV2-mV1 . S is the slope of the silver

electrode.

3) The unknown sulfide concentration in the sample
(C

) can then be determined by the following

sam

equation. For an example a sensor is placed into
100 mL of a 0.001 M Ag+ standard. 1.0 mL of
unknown was added. The mV changed 12.5 mV.
The unknown sulfide value is found to be 1 X 10
M. n= ½ because ½ mole of sulfide reactions
with 1 mole of silver ion.

Titration of Chloride
A silver electrode may be used as an indicator to follow
the progress of a chloride (or other halide) titration with
silver nitrate. The electrode can be used in colored
samples where other indicators suffer from interferences.
During the titration the sensor follows the decrease in the
halide concentration while small additions of silver
nitrate titrant are added. The silver reacts with the
chloride ions forming a precipitate of silver chloride. At
the stoichiometric end point, a large change in mV occurs
as the silver is in excess. Measurements may be
automated by use of the Hanna Titrator HI 901 or titrated
manually.

Plot generated on Hanna HI 901 Titrator duringPlot generated on Hanna HI 901 Titrator during

Plot generated on Hanna HI 901 Titrator during

Plot generated on Hanna HI 901 Titrator duringPlot generated on Hanna HI 901 Titrator during
automated chloride titration using HI 4115automated chloride titration using HI 4115

automated chloride titration using HI 4115

automated chloride titration using HI 4115automated chloride titration using HI 4115
electrode.electrode.

electrode.

electrode.electrode.

-2

C

sample

n

*

=

n =

V

Std*CStd

V

std

Mole ratio of ions in sample that
react with 1 m ole of standard

-

+

V

ISA

16

V

Std*CStd

V

std

10

+

V

ISA

∆E/S

V

std+VISA+Vsam

*

V

Sam

C

S2-

= C

Pb2

17

+

Pb2

V

+

*

-

S2

V

Titration of Sulfide
A silver/sulfide electrode may be used as an indicator to
follow the progress of a sulfide titration with lead
perchlorate. The lead perchlorate should be 10 to 20
times greater in concentration than that of the sulfide
sample. The sample is first mixed with an equal volume
of SAOB. During the titration the sensor follows the
decrease in the sulfide concentration while small
additions of lead perchlorate titrant are added and react
with the sulfide ions. Permit sufficient time for solution
reaction and electrode equilibration. The largest mV
change for given increment is the endpoint.

XIII.XIII.

pHpH

XIII.

pH

XIII.XIII.

pHpH
For Silver measurements:
HI 4115 and HI 4015 electrodes may be used in solutions
with pH values between 2 and 8. Samples that fall
beyond this range should be adjusted with acid (HNO3) or
base (NaOH).
For Sulfide measurements:
Sulfide measurements are made in the presence of SAOB;
HI 4015-00 which adjusts the pH between 12 and 14 pH.

XV. XV.

Conversion tablesConversion tables

XV.

Conversion tables

XV. XV.

Conversion tablesConversion tables

++

+

++

For AgFor Ag

For Ag

For AgFor Ag

Multiply byMultiply by

Multiply by

Multiply byMultiply by

Moles/L (M) to ppm (mg/L) 1.0787 x 10
ppm (mg/L) to M (moles/L) 9.27x 10

2-2-

2-

2-2-

For SFor S

For S

For SFor S

-6

Moles/L (M) to ppm (mg/L) 3.207 x 10
ppm (mg/L) to M (moles/L) 3.12 x 10

-5

5

4

XIV. XIV.

Storage and Care of the HI 4015 andStorage and Care of the HI 4015 and

XIV.

Storage and Care of the HI 4015 and

XIV. XIV.

Storage and Care of the HI 4015 andStorage and Care of the HI 4015 and

HI 4115 sensorsHI 4115 sensors

HI 4115 sensors

HI 4115 sensorsHI 4115 sensors
The HI 4015 sensor can be stored in very dilute standards
(<10-4 M) for short periods of time and should be stored
dry with the protective cap on when not in use.
The model HI 4115 combination electrode can be left in
dilute standards (<10-4 M) for short time periods.
For long term storage, the electrode should be drained and
washed of salts with distilled or deionized water. Unscrew
the upper cap and move outer sleeve up cable. Wrap the
ceramic junction on the inner stem with Parafilm® or
other sealing wrap. Place the protective cap provided over
the sensor membrane. Store dry disassembled electrode in
storage box provided with electrode.

18

19

MAN4115 03/07

WARRANTY WARRANTY

WARRANTY

WARRANTY WARRANTY
Hanna Instruments Ion Selective Electrodes are warranted
to be free of defects in material and workmanship for 6
months from date of purchase when used for their intended
purpose and maintained according to instructions. If they
fail to work when first used contact your dealer immediately.
Damage due to accidents, misuse, misapplication, tampering
or lack of prescribed maintenance is not covered.

Hanna Instruments reserves the right to modify the design,
construction or appearance of its products without advance
notice.

20