Hanna Instruments HI 4004 User Manual
HI 4104
CALCIUM
COMBINATION
HI
4000-50
SENSOR HANDLE
Instruction Manual
HI 4004HI 4004
HI 4004
HI 4004HI 4004
HI 4104HI 4104
HI 4104
HI 4104HI 4104
Calcium Ion
Selective Electrode
Half-cell
Combination
1
HI 4004 Calcium Half-cellHI 4004 Calcium Half-cell
HI 4004 Calcium Half-cell
HI 4004 Calcium Half-cellHI 4004 Calcium Half-cell
HI 4104 Calcium Combination ElectrodeHI 4104 Calcium Combination Electrode
HI 4104 Calcium Combination Electrode
HI 4104 Calcium Combination ElectrodeHI 4104 Calcium Combination Electrode
I. I.
Introduction:Introduction:
I.
Introduction:
I. I.
Introduction:Introduction:
The Hanna HI 4004 and HI 4104 are ion selective electrodes designed for the measurement of calcium ions in
aqueous solutions. They utilize a replaceable sensing module that contains an organic polymer membrane that is
sensitive to calcium ions. The HI 4004 is a half-cell electrode that requires a separate reference. The HI 4104 is a
combination ion selective electrode.
IIII
SpecificationsSpecifications
II.
Specifications
IIII
SpecificationsSpecifications
Type: PVC membrane with
organic ion exchanger
Ion measured: Calcium (Ca
2+
)
Measurement range: 1.0 M to 3 X 10
-6
M
40080 to 0.12 ppm
Interference:
Organic solvents and cationic detergents must be absent.
Ratio of interfering ion to Ca
2+
must be less than the
ratio indicated below:
15000 for Na+sodium
7000 for Mg3+magnesium
700 for Ni2+nickle
300 for Fe
2+
ferrous
250 for Al3+aluminum
2+
+
4
-
ammonium
lead
200 for NH
35 for Cu2+cupric
0.001 for Pb
Operating Temperature: 0-40°C
Operating pH: 4 to 10 pH (see Section
XIII)
Dimensions: 12 mm (OD) X 120 mm
nominal insertion
(0.47” X 4.72”)
Connection: BNC
2
III. III.
Theory of OperationTheory of Operation
III.
Theory of Operation
III. III.
Theory of OperationTheory of Operation
::
:
::
The HI 4004 and HI 4104 calcium electrodes are potentiometric devices used for the rapid determination of free calcium ions in water, sea water and beverages. The electrode
functions as a sensor or ionic conductor. The HI 4004
requires a separate reference electrode to complete its electrolytic circuit. The HI 4104 is a combination electrode with
a Ag/AgCl reference electrode with gel stabilized Cl- electrolyte in it’s inner chamber. The external reference chamber
is refillable. The PVC membrane used on the sensor is
impregnated with the organic ion exchanger.
This organic ion exchanger is considered a carrier ionophore
in that it is capable of shielding and carrying the charged
calcium ion in it’s polar cage freely through the apolar
regions of the membrane. A charge imbalance developes
between the test solution and internal cell of the sensor.
This voltage changes in response to the sampleís ion activity. When the ionic strength of the sample is fixed, the
voltage is proportional to the concentration of nitrate ions in
solution. The sensor follows the Nernst Equation:
E = E
+ 2.3 RT/nF log A
a
ion
E = observed potential
Ea = Reference and fixed internal voltages
R = gas constant (8.314 J/K Mol)
n = Charge on ion (2+)
A
= ion activity in sample
ion
T = absolute temperature in K
F = Faraday constant (9.648 x 104 C/equivalent)
3
IV. IV.
Design elements of the HI 4004 and HI 4104Design elements of the HI 4004 and HI 4104
IV.
Design elements of the HI 4004 and HI 4104
IV. IV.
Design elements of the HI 4004 and HI 4104Design elements of the HI 4004 and HI 4104
electrodeselectrodes
electrodes
electrodeselectrodes
Cap
HI
4000-50
HANDLE
R
SENSO
Sensor
Handle
O-Ring
Sensing
module
Upper Cap
Upper
Threads
O-Ring
Ceramic Junction
on Inner Stem
Liquid junction
Spring
Fill Hole
O-Ring and
Plug
Outer Sleeve
Sensing Module
4
V. V.
Equipment required:Equipment required:
V.
Equipment required:
V. V.
Equipment required:Equipment required:
• The HI 4004 requires the Hanna HI 5315 Double
junction reference electrode with HI 7082 as external
electrolyte.
• 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
magnetic stirring bars (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.
VI. VI.
Solutions RequiredSolutions Required
VI.
Solutions Required
VI. VI.
Solutions RequiredSolutions Required
Standards for Calcium Measurements
0.1 M calcium standard,500 mL HI 4004-01
Ionic Strength Adjuster
ISA, 500 mL HI 4004-00
Conditioning and Storage Solution
Calcium storage solution, 500 mL HI 4004-45
Using volumetric pipettes and glassware make dilutions to
bracket the concentration of the samples. Store samples in
plastic bottles. Standards with concentrations < 10
-3
should be prepared daily.
Two mL of Hanna ISA HI 4004-00 should be added to
100 mL sample or standard.
M
VIIVII
General GuidelinesGeneral Guidelines
VII.
General Guidelines
VIIVII
General GuidelinesGeneral Guidelines
• Ensure the o-ring is installed on modules before
screwing into the sensor handle or inner stem.
O-Ring
5
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