Circulating Water Testing

Following tests are performed on Circulating Water testing

 pH
 Hardness
 Chloride ion
 Alkalinity

1) pH Testing
Calibration:
 Turn on the pH meter.
 Click on the “Mode” and then click on “yes”.
 P1 will appear on screen.
 Wash the electrode with DM water and add standard solution of pH “6.86” in the
beaker. When screen shows “Ready” it means electrode has detected the pH .
 Click on “Yes” again “P2” will appear. Wash the beaker again with DM water and add
solution of pH of “9.20”. When screen shows “Ready” Click “Yes”.
 Calibration Curve will appear. It must be more than 90 %.

Testing:
 Turn on the pH meter.
 Wash the electrode and beaker with DM water.
 Add sample water in the beaker and place the electrode in it.
 When “ready” appears on screen it means result has been displayed.
 Wash the electrode again and put it in 3M KCl solution.

Precautions:
 Place the electrode in 3M KCl solution to prolong the efficiency of electrode.
 Wash the electrode before and after every test.
 Use the electrode with care because it can be easily broken.
 Rinse the beaker with sample water after washed by DM water.
 2) Hardness of Water by EDTA Titration
This method is carried out with the reference of GB6909.1-86

Purpose
To determine the concentrations of Ca2+ and Mg2+ ions in the circulating cooling water.
Determination of hardness is very important. Water containing harness when goes inside the
condenser for cooling, the temperature of circulating water increases. Following reaction will
happen:
Ca (HCO3 )2 CaCO3 + CO2 +H2O
Calcium carbonate is insoluble in water and will deposit on the pipes and cause scaling.
Disadvantages of Hardness
 Hardness can cause scaling inside the condenser and cooling tower.
 It can deposit on the pipes in the condenser and reduce the heat transferring efficiency.
Flowing area will be reduced by continuous deposition of calcium carbonate and
magnesium hydroxide so cooling will be the worse in the cooling tower.

Working Principle
One of the factors that establish the quality of a water supply is its degree of hardness. The hardness of
water is defined in terms of its content of calcium and magnesium ions. Since an analysis does not
distinguish between Ca2+ and Mg2+, and since most hardness is caused by carbonate deposits in the earth,
hardness is usually reported as total parts per million calcium carbonate by weight. Water hardness
can be readily determined by titration with the chelating agent EDTA
(ethylenediaminetetraacetic acid). This reagent is a weak acid that can lose four protons on
complete neutralization; its structural formula is below.

HOOC-CH2 CH2-COOH
NCH2-CH2N
HOOC-CH2 CH2-COOH

Ethylenediaminetetraacetic Acid (EDTA, or H4Y)

The four acid sites and the two nitrogen atoms all contain unshared electron pairs, so that a
single EDTA ion can form a complex with up to six sites on a given cation. The complex is
typically quite stable, and the conditions of its formation can ordinarily be controlled so that it
contains EDTA and the metal ion in a 1:1 mole ratio. In a titration to establish the concentration
of a metal ion, the EDTA that is added combines quantitatively with the cation to form the
complex. The end point occurs when essentially all of the cation has reacted.

In this experiment you will standardize a solution of EDTA by titration against a standard
solution made from calcium carbonate, CaCO3. EDTA solution is used to determine the
hardness of an unknown water sample. Since both EDTA and Ca2+ are both colorless, it is
necessary to use a rather special indicator to detect the end point of the titration. The indicator
you will employ is called Eriochrome Black T, which forms a rather stable wine-red complex,
MgIn-, with the magnesium ion. A tiny amount of this complex will be present in the solution
during the titration. As EDTA is added, it will complex free Ca2+ and Mg2+ ions leaving the
MgIn- complex alone until essentially all of the calcium and magnesium has been converted to
chelates. At this point, the EDTA concentration will increase sufficiently to displace Mg2+ from
the indicator complex; the indicator reverts to an acid form, which is sky blue, and this
establishes the end point of the titration.

The titration is carried out at a pH of 10, in an NH3-NH4+ buffer, which keeps the EDTA (H4Y)
mainly in the half-neutralized form, H2Y2-, where it complexes the Group IIA ions very well
but does not tend to react as readily with other cations such as Fe 3+ that might be present as
impurities in the water. To overcome this problem masking agent such as L-cysteine and
Triothanolamine is added. Taking H4Y and H3In as the formulas for EDTA and Eriochrome
Black T respectively, the equations for the reactions that occur during the titration are as
follows.

main reactions H2Y2-(aq) + Ca2+(aq) → CaY2-(aq) + 2 H+(aq)

H2Y2-(aq) + Mg2+(aq) → MgY2-(aq) + 2 H+(aq)
at end point H2Y2-(aq) + MgIn-(aq) → MgY2-(aq) + HIn2-(aq) + H+(aq)
wine red sky blue

Hardness due to Ca2+(aq) ion is determined by a separate titration at a higher pH, by adding
NaOH solution to precipitate Mg(OH)2(s), using hydroxynaphthol blue (Calcon) as indicator.

Experimental Procedures:
Apparatus:
 50-mL burette
 250-mL Erlenmeyer flasks
 100-mL graduated cylinder
 10-mL pipet

Chemicals
 pH 10 ammonia/ammonium chloride buffer (570 ml NH4OH + 67.5 g NH4Cl and dilute to
1000 mL with water.
 disodium EDTA dehydrate (0.010M)
 sodium hydroxide solution (2.0 M)
 L- Cysteine (10g/L)
 Triethanolamine (1+4)

Indicators:
 Calcon indicator
 Erichome Black T

Determination of Total Hardness:

1. Take 100 ml of sample water into a conical flask.
2. Add 3 ml of L- Cysteine solution (to mask the interference of Mercury).
3. Add 3 ml of Thiethanolamine (to mask the interference of Aluminum ions)
4. Add 5 ml buffer solution (used to resist the pH to 10) followed by 3 drops of Eriochrome
Black T indicator solution.
5. Titrate with 0.01 M EDTA until the solution turns from wine red to sky blue with no hint of
red (save the solution for color comparison).
6. Repeat the titration to obtain two concordant results.

Results:
Determination of total hardness
Trial 1 2
Final burette reading/cm3
Initial burette reading/cm3
Volume used/cm3
Average volume of 0.01 M EDTA used/cm3

Determination of Concentration of Ca2+ Ions

1. Take 100 ml of sample water into a conical flask.
2. Add 5 ml of NaOH solution, swirl the solution and wait for a couple of minutes to completely
precipitate the magnesium ions as Mg(OH)2.
3. Add a pinch of hydroxynaphthol blue also known as calcon indicator (exact amount to be
decided by the intensity of the resulting colored solution) and titrate with EDTA until purple
color changes to sky blue.
Note: NaOH is added to make the pH 12.
4. Repeat the titration to obtain two concordant results.

Determination of concentration of Ca2+(aq) ions

Trial 1 2
3
Final burette reading/cm
Initial burette reading/cm3
Volume used/cm3
Average volume of 0.01 M EDTA used/cm3

Calculation
Volume of EDTA used Concentration of EDTA
Hardness mmol/l= 1000
Volume of sample taken
 3) Determination of Chloride Ion by Mohr method
This method is performed in accordance with the GB6905.1-86
Purpose:
The purpose of this test is to check the amount of chloride ion present in the water sample. Chloride
ion is harmful for the power industry. The presence of chlorides significantly aggravates the
conditions for pitting corrosion of most metals (including stainless steels, aluminum, aluminum
alloys, and high-alloyed materials) by enhancing the formation and growth of the pits through an
autocatalytic process.
Working Principle:
The sample to be analysed is adjusted to a pH of 8.3 and titrated with silver nitrate solution in the
presence potassium chromate indicator. The end point is indicated by the development and
persistence of the brick-red silver chromate.
Reaction:
Ag+ + Cl- AgCl (White ppts)
+ -
2Ag + CrO4 Ag2CrO4 (Brick Red ppts)
Mohr method usually works in pH range of 6.5-9.0. Phenolphthalein indicator is added to check if
pH is greater than the required pH.
If pH is high brownish silver hydroxide will form and mask the end point. If pH is low chromate is
converted into dichromate and will disturb the end point. Good stirring is required during the test
because poor agitation can lead to end point neither sharp nor reproducible.
Apparatus:
 50-mL burette
 250-mL Erlenmeyer flasks
 100-mL graduated cylinder
 10-mL pipet

Reagents:
 1/2 H2SO4 0.1 M (Take 2.7174 ml of concentrated H2SO4 (98%) into 1000 ml of water.)

 Phenolphthalein Indicator: (10g / L)

 Dissolve 1.0 g of Phenolphthalein in 50 ml of ethyl alcohol (95 %) and dilute to 100 ml with
demi water.

 Potassium chromate Indicator solution.

 Dissolve 50 g of Potassium chromate K2CrO4 in 100ml of demi water, and add silver nitrate
AgNO3 until a slight red precipitate is produced. Allow the solution to stand, protected
from light, for at least 24 hrs. Then filter the solution to remove the precipitate, and dilute to
one litre with demi water.

 Silver Nitrate standard solution (0.025 N).

 Crush approximately 5 g of AgNO3 crystals and dry to constant weight at 40 °C. Dissolved
4.2473 g of the crushed, dried crystals in demi water dilute to one litre with demi water.
Standardize against the standard NaCl solution
Procedure:
 Take 10 ml of the sample into the conical flask having ml of water.
 Add few drops of Phenolphthalein indicator, if the color changes into pink, titrate in against
sulfuric acid.
 Add one ml of potassium chromate indicator and titrate it with AgNO3.
 Calculate the reading.
 Determine the amount of chloride ions in blank sample also.

Result Sheet:
Trial 1 2
3
Final burette reading/cm
Initial burette reading/cm3
Volume used/cm3
Average volume of Silver Nitrate used/cm3

Calculation:
I ml of AgNO3 = I mg of Chloride Ion

(V1- V0) 1.0

Chloride ion (ppm)= 1000
Volume of sample taken
Precaution:
This standard may involve hazardous materials, operation, and equipment. This standard does not
purport to address all of the safety problems associated with its use. It is the responsibility of the
user of this standard to establish appropriate safety and health practices and determines the
applicability of regulatory limitation prior to use.
 4) Determination of Total Alkalinity

This method is performed in accordance with standard GB6909.1-86.

Purpose:
The purpose of this test to determine the alkalinity of all types, majorly because of the bicarbonate
[HCO3-] and carbonate [CO3--].

Significance and Use:

Acidity and alkalinity measurement are used to assist in establishing levels of chemical treatment to
control scale, corrosion, and other adverse chemical equilibrium.
Level of acidity or alkalinity is critical in establishing solubility of some metals, toxicity of some
metals, and the buffering capacity of some waters.

Operating Principle:
The sample to be analyzed is adjusted to a pH of 8.3 and titrated with sulphuric acid solution in the
presence Methyl Red indicator. The end point is indicated by changing the Yellow color into Orange.

In fresh water, carbonate is almost completely converted into bicarbonate at pH 8.3, and that is the
purpose of phenolphthalein titrations, to determine alkalinity in freshwater due to carbonate only.
As the pH drops from 8.2 to about 7.5, the most important thing happening is that the carbonate is
converted into bicarbonate
As the pH drops to about 6, the main thing happening is that bicarbonate is getting converted into
carbonic acid. Also in this range, phosphate continues to take up protons:

As the pH drops to about 4, the bicarbonate becomes fully converted into carbonic acid. Also in this
range, phosphate continues to take up protons and ends up as mostly H2PO4-, but very little
phosphoric acid itself forms.

Apparatus:

 50-mL burette
 250-mL Erlenmeyer flasks
 100-mL graduated cylinder
 10-mL pipet

Reagents:

1- Methyl Red Indicator Solution (1.0 gm / L)

Dissolve 0.1 gm of water-soluble methyl red in water & dilute to100 ml.
2- Phenolphthalein Indicator: (10g / L)
 Dissolve 1.0 g of Phenolphthalein in 50 ml of ethyl alcohol (95 %) and dilute to 100 ml with
demi water.

3- ½ H2SO4 0.1 M
Take 2.7174 ml of concentrated H2SO4 (98%) into 1000 ml of water.

Procedure:

 Take 100 ml of water sample in the conical flask.

 Add few drops of Phenolphthalein indicator, if the color changes into pink, titrate in against
sulphuric acid. This is called phenolic alkalinity.
 Note the reading
 Add few drops of methyl red and titrate it against sulphuric acid. The yellow color will
change to orange. This is the end point.
 Note the reading carefully.

Results Sheet:
Burette Reading (ml) Total Volume
Volume of used (ml)
Sample No.
Sample Initial Final
Reading Reading

Calculation:

Volume of H2SO4 used Concentration of H2SO4

Alkalinity (mmol/l) = 1000
Volume of sample taken

Precaution:

This standard may involve hazardous materials, operation, and equipment. This standard does not
purport to address all of the safety problems associated with its use. It is the responsibility of the
user of this standard to establish appropriate safety and health practices and determines the
applicability of regulatory limitation prior to use.