Total Hardness of Star Series

Method Note Total Hardness of

Surface Fresh Water M-1028-E 03/05 RevB Surface Fresh Water

Calibration and Analysis Total Hardness Introduction

1. Allow all the standards and the samples to attain room temperature for precise measurements since the Surface Fresh Hardness is the presence in water of calcium, magnesium, iron, and other divalent cations. Hardness
measurement is temperature sensitive. Water is one of the most important aspects of water quality. This procedure provides rapid, uncomplicated
2. Calibrate the meter using the 10 ppm and 100 ppm standards, stirring the standards at a uniform rate. determinations of the surface water hardness with divalent cation electrode.
Ion Selective
3. Place both electrodes and stirrer into the beaker with the 10 ppm with the electrode tip fully immersed Electrode (ISE)
in the solution. The stirrer should be positioned slightly below the tip of the electrode. Press the Recommended Equipment Cat. No.
STIRRER key on the meter to turn the stirrer on. Press the CALIBRATE key.
Total Hardness Application Package
4. Wait for a stable reading (1-2 minutes). Enter standard value of 10 using UP and DOWN arrow (includes all items with a Cat. No.) 1010129
keys and the DECIMAL/DIGIT key.
1. 4-Star benchtop pH/ISE meter 1115000
5. Press the CALIBRATE key to accept the 10 ppm standard and press the STIRRER key to turn the
stirrer off. 2. Divalent Cation electrode 9332BNWP
6. Rinse electrode and stirrer thoroughly with deionized water and blot dry. 3. Reference electrode 900100
7. Place the probes and stirrer into the beaker with the 100 ppm standard with the electrode tip fully 4. Orion benchtop stirrer (or magnetic stir plate and bar) 096019
immersed in the solution. The stirrer should be positioned slightly below the tip of the electrode. 5. Benchtop electrode stand 1110001
Press the STIRRER key on the meter to turn the stirrer on. 6. Beakers (150 mL)
8. Wait for stable reading (1-2 minutes). Enter standard value of 100 using UP and DOWN arrow 7. Graduated cylinder (100 mL)
keys and the DECIMAL/DIGIT key.
8. Volumetric flask (100 mL)
9. Press the MEASURE key to accept the 100 ppm standard and to move to the measure mode of the
meter. Press the STIRRER key to turn the stirrer off.
Required Solutions Cat. No.
10. Rinse electrode and stirrer thoroughly with deionized water and blot dry.
11. Place the probes and stirrer in a prepared sample with the electrode tip fully immersed in the solution. 1 Water Hardness Standard, 100ppm as CaCO3 923206
Press the MEASURE key on the meter; the stirrer will turn on. The ISE: mg/L icon will flash as the 2. Reference Electrode Filling Solution 900011
measurement is being made. The ISE:mg/L icon will become solid and the display value will freeze 3. 1 M Sodium Hydroxide
when a stable reading is achieved. This value is logged and printed automatically and the stirrer turns
off automatically. 4. 1 M Hydrochloric acid
12. Repeat steps 10 and 11 for additional samples. Remember to rinse the electrode with deionized water 5. Deionized water
between measurements. Upon completion of samples, rinse the electrode with deionized water and
store the electrode according to instructions in the Storage section of this method note. Calibration Standard Preparation
1. Using a graduated cylinder, transfer 100 mL of the 100 ppm as CaCO3 standard into a beaker.
2. Prepare a 10 ppm as CaCO3 standard by pipetting 10 mL of the 100 ppm standard into a 100 mL
volumetric flask. Dilute to the mark with deionized water. Mix well.

Sample Preparation
1. Adjust the pH of the sample solution to pH 7 - 10 with sodium hydroxide or hydrochloric acid.
2. Using a graduated cylinder, measure 100 mL of the sample into a beaker.
3. Repeat for additional measurements.

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 Total Hardness of
Surface Fresh Water

Results Meter Setup - 4 Star

Five samples of surface fresh water from a pond were collected and measured for hardness. The results are For initial meter setup, follow the steps on the Quick Reference Guide that is attached to the meter itself.
expressed as parts per million (ppm) equivalent to calcium carbonate. Hardness of the analyzed samples is The Quick Start Guide also contains a layout of the meter keypad for reference. The words in this method
about 45 - 46 ppm. According to USA Oce of Water Quality this surface water must be considered as soft represented in all capital letters, such as POWER, indicate a key on the meter, and words in quotations such as
(range 0 - 60 ppm). Unit indicate information on the meter display.
Surface Water ppm (mg/L) CaCO3 1. Connect the electrode to the meter.
Sample # 1: 47.7 2. Connect the reference probe to the meter.
Sample # 2: 45.8 3. Connect the stirrer to the meter.
Sample # 3: 45.0 4. Press the POWER key on the meter to turn meter on.
Sample # 4: 46.2 5. Note that the arrow on the left of the screen indicates the active line. If not the top line is not active, press
the LINE SELECTION key to change the selected line to the top line.
Sample # 5: 45.8
6. Press the SETUP key. Use the UP or DOWN keys to enter ISE Setup. Press the LINE SELECTION
key to select the bottom line. Press UP or DOWN arrow keys to select 3 for rES. Press LINE
Mean: 46.1 SELECTION key to accept setting.
Standard Deviation: 1.0 7. Press LINE SELECTION key to select middle line, and press DOWN arrow key to select nLln.
%CV: 2.16 8. Press the LINE SELECTION key to select the bottom line. Press UP or DOWN arrow keys to select
off for nLln. Press LINE SELECTION key to accept setting.
Electrode Storage 9. Press LINE SELECTION key to select middle line, and press DOWN arrow key to select rAng.
1. The sensing module should be kept in the glass vial until it is to be used. The assembled electrode can 10. Press the LINE SELECTION key to select the bottom line. Press UP or DOWN arrow keys to select
be stored in calcium standard (e.g. 100ppm). For long periods disassemble the electrode, rinse with HigH for rAng. Press LINE SELECTION key to accept setting.
deionized water, blot dry, and store the module in its vial. 11. Press LINE SELECTION key to select middle line, and press DOWN arrow key to select Unit.
2. The Orion 900100 reference electrode may be stored between sample measurements in its filling solution. 12. Press the LINE SELECTION key to select the bottom line. Press UP or DOWN arrow keys to select
Deionized water is also acceptable storage solution. The filling solution inside the electrode should not be mGL for Unit. Press LINE SELECTION key to accept setting.
allowed to evaporate and crystallize. For longer storage periods, drain the Orion 900100 completely, rinse 13. Press MEASURE key to return to measurement mode.
with deionized water, and store dry.
If all steps were followed correctly the meter display will show three digits in the top line and ISE: mg/L to the
Equipment Setup right of the top line. The meter and electrode are now ready for calibration.
Electrode Setup - Divalent Cation electrode
Note: The Orion Benchtop Stirrer must be turned on in General Instrument Setup before analysis, please see the Quickstart
1. Remove the electrode sensing module from the plastic vial package. Make sure the rubber washer is in Guide for instructions.
place on the sensing module. Remove the electrode handle from the box.
2. Screw the sensing module into the electrode body until finger tight.
3. Soak the divalent cation electrode overnight in a 100 ppm as CaCO3 standard adjusted to pH 7-10
with NaOH.
4. Fill the reference electrode according to instructions in the reference electrode instruction manual,
substituting Orion Cat. No. 900011 Filling Solution for the Orion Cat. No. 900001 Filling Solution that
is provided with the reference electrode. Do not use the filling solution shipped with reference electrode
because it contains sodium chloride, which will interfere with water hardness measurement.

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