Chemical Process Industries (lab)

Department of Chemical Engineering Course No. Ch.E-201

Wah Engineering College wahcantt.

EXPERIMENT# 01

Experiment Title: Water analysis

Objectives:

1. Determine the ppm of total alkalinity in the given sample of water,

2. Point out the type of alkalinity in the given sample of water.

Apparatus required: Water sample, N/50 HCl, methyl orange, phenolphthalein, measuring flask, burette,
funnel.

Chemicals required: N/50 HCl, methyl orange, phenolphthalein

Procedure:

Take 100 ml of given water sample using 100ml of measuring or volumetric flask .
Transfer the water sample in measuring flask. Add 1 to 2 drops of phenolphthalein indicator. Fill the
burrette with N/50 HCl. Solution.

Note down the initial burette reading. On addition of phenolphthalein into water sample the pink colour is
formed. Titrate pink colur water solution against N/50 HCl solution, till the pink colour vanish.

Take 100ml of tap water add 1 to drops of methyl orange titrate it against N/50 HCl solution, till end
point is achieved, which is pink colour is achieved. Take three readings.

Reagents

The reagents needed include the indicator and the acid used for the titration. The acid is N/50
hydrochloric acid, which is the same as 0.02 N HCL acid. The indicator for the total alkalinity test will
be:

 Methyl orange or methyl purple indicator, in a 50 to 100 mL dropping bottle. Store the
solution in a dark place.

And for the phenolphthalein alkalinity test, you will need the following indicator:

 Phenolphthalein indicator, in a 50 to 100 mL dropping bottle.

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 Chemical Process Industries (lab)
Department of Chemical Engineering Course No. Ch.E-201
Wah Engineering College wahcantt.

In either test, a pH meter can be used instead of an indicator, if so desired. If using a pH meter, do not
add the indicator in step 3 of the procedure below. In step 4, the acid is added not until a color change
occurs but until the pH reaches the desired endpoint - 4.5 for the total alkalinity test or 8.3 for the
phenolphthalein alkalinity test.

Total Alkalinity Procedure

1. Clean the burette and fill almost to the top with N/50 sulfuric acid. Then run some acid to
waste until the "zero" mark is reached. This should leave the stopcock and tip of the
burette full of the solution.
2. Measure out 100 mL of the water to be tested and pour into a clean white porcelain
evaporating dish.
3. With a dropping bottle, add 2 or 3 drops of methyl orange or methyl purple indicator to the
sample and stir. When alkalinity is present, the solution becomes yellow when methyl
orange is added or becomes green when methyl purple is added. (Note: When a high
chlorine residual is present, the chlorine bleaches the color and makes the determination of
endpoint difficult. The chlorine may be removed using sodium thiosulfate, or an additional
indicator may be added.)
4. Slowly and carefully add N/50 sulfuric acid from the burette to the contents of the dish
until the faintest pink coloration appears - that is, until the color of the solution is no longer
yellow. While adding the acid, the solution should be gently stirred with the stirring rod. It
is often advantageous to set up two 100 mL samples, adding methyl orange to each and
acid to only one while the other is held alongside so that the colors may be compared and
the color change to pink can be better recognized. (Note: When using methyl purple, the
color is changed to purple. A gray tint precedes the end point and warns the operator of its
approach.)
5. Record the volume of sulfuric acid used to reach the endpoint.

6. Calculate the total alkalinity, as follows:

T. alk. = (mL of acid) × (10 ppm/mL)

For example, if 1.5 mL of acid were used in the titration, then the total alkalinity would be:

T. alk. = (1.5) × (10) = 15 ppm CaCO3

(Note that this simple formula requires that you use the exact acid concentration and sample volume listed
in this procedure. If you use different values, you must calculate the alkalinity as follows:

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 Chemical Process Industries (lab)
Department of Chemical Engineering Course No. Ch.E-201
Wah Engineering College wahcantt.

This more complicated equation can also be used to calculate phenolphthalein alkalinity.)

Phenolphthalein Alkalinity Procedure

1. Clean the burette and fill almost to the top with N/50 sulfuric acid. Then run some acid to
waste until the "zero" mark is reached. This should leave the stopcock and tip of the
burette full of the solution.
2. Measure out 100 mL of the water to be tested and pour into a clean white porcelain
evaporating dish. Stir the sample.
3. With a dropping bottle, add 5 drops of phenolphthalein indicator to the sample and stir.
When phenolphthalein alkalinity is present, the solution becomes pink. No color indicates
the phenolphthalein alkalinity is zero and that the test is complete. No color also indicates
that free carbon dioxide is present, and the same sample may be used to test for carbon
dioxide.
4. If pink color results after the indicator is added, slowly and carefully add N/50 sulfuric acid
from the burette to the contents of the dish until the coloration disappears. While adding
the acid, the solution should be gently stirred with the stirring rod.
5. Record the volume of sulfuric acid used to reach the endpoint.

6. Calculate the phenolphthalein alkalinity, in ppm, as follows:

P. alk. = (mL of acid) × (10 ppm/mL)

For example, if 2.4 mL of acid were used, the phenolphthalein alkalinity would be:

P. alk. = (2.4) × (10) = 24 ppm CaCO3

Corrosive Water

lkalinity is important in the water treatment plant because it promotes coagulation and inhibits corrosion.
Here, we will be concerned with the amount of alkalinity which must be present in the finished water to
prevent corrosion in the pipes of the distribution system.

Corrosive water results from low alkalinity, which tends to promote acidic water. Since coagulation uses

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 Chemical Process Industries (lab)
Department of Chemical Engineering Course No. Ch.E-201
Wah Engineering College wahcantt.

up alkalinity, operators must sometimes add lime or soda ash to water to prevent corrosive finished water.
However, there is no set amount of alkalinity which must be present in water to prevent corrosion.
Instead, the relation between alkalinity and pH is usually the determining factor as to whether or not the
finished water will be corrosive. The following three requirements must be met in order for treated water
to be non-corrosive:

1. The phenolphthalein alkalinity, calculated as CaCO3, should not be greater than:

15 ppm + (0.4 × T. alk.)

This requirement limits the permissible pH to about 10.6 at 25°C (77°F).

2. The normal carbonate alkalinity should not exceed 120 ppm. This requirement may be met by keeping
the total alkalinity within the limits suggested in the table below. These values apply to water at 25°C
(77°F).

Limits of alkalinity for various pH ranges

Limit for Total Alkalinity

pH Range
(ppm as CaCO3)
8.0 to 9.6 400
9.7 340
9.8 300
9.9 260
10.0 230
10.1 210
10.2 160
10.3 180
10.4 170
10.5 to 10.6 160

3. The total alkalinity should not exceed the hardness by more than 35 ppm (calculated at CaCO3). (You
will learn to measure hardness in the next lab.)

Does your water meet the first two criteria for being non-corrosive? You will need to test the pH of the
water to determine whether your water meets the second criteria. Record your answer in the Data section.

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 Chemical Process Industries (lab)
Department of Chemical Engineering Course No. Ch.E-201
Wah Engineering College wahcantt.

Caustic Water

Another problem related to alkalinity is caustic water, which causes a burning sensation when it is tasted.
Caustic water is caused hydroxide alkalinity. Perform the following calculations to determine whether
your water is caustic, and then record the result in the Data section.

1. Calculate:

C = (0.5) × (T. alk.)

2. Is phenolphthalein alkalinity greater than C? If so, the water is caustic.

Proportions of Alkalinity Sources

The primary causes of alkalinity in water are carbonate and bicarbonate, with hydroxide present in smaller
amounts. Once you measure both total and phenolphthalein alkalinity, you can calculate the approximate
amount of these three types of alkalinity using the table below:

When... Hydroxide Carbonate Bicarbonate

P=O 0 0 T
2P < T 0 2P T - 2P
2P = T 0 2P 0
2P > T 2P - T 2(T - P) 0
P =T T 0 0

( P= Phenolphthalein alkalinity; T = Methyl orange alkalinity)

We'll consider a couple of examples to help you use the table above. In the first example, our
phenolphthalein test showed no alkalinity (P=0) and the total alkalinity is 80 ppm as CaCO3 (T=80.) As
we can see from the table, when phenolphthalein alkalinity is 0, all alkalinity is bicarbonate. As a result,
our water contains 80 ppm bicarbonate alkalinity and 0 ppm hydroxide and carbonate alkalinity.

Let's assume that P=50 ppm and T=80 ppm. In this case, 2P is more than T, so we read the fourth row of
the table. We can calculate the components of the alkalinity as follows:

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 Chemical Process Industries (lab)
Department of Chemical Engineering Course No. Ch.E-201
Wah Engineering College wahcantt.

Hydroxide:
2P - T
2(50) - 80
20 ppm
Carbonate:
2(T - P)
2(80 - 50)
60 ppm

Bicarbonate:
0

So we can see that, in this second example, 20 ppm of the alkalinity results from hydroxide and 60 ppm of
the alkalinity results from carbonate. There is no bicarbonate alkalinity present in the sample.

It can sometimes be important to understand the various alkalinity components of water because they can
act differently. For example, hydroxide is the cause of caustic water. You should calculate the amount of
each type of alkalinity in your sample water and record the results of your calculations in the Data
section.

Data

Water Source mL of acid used Alkalinity (ppm as CaCO3)

Total alkalinity test
Phenolphthalein alkalinity test

1. What is the pH of the water? ______________________

2. Does the water meet the first two criteria for being non-corrosive? _________________________

3. Is the water caustic? ____________________

4. How much of the alkalinity is hydroxide? ________________

5. How much of the alkalinity is carbonate? __________________

6. How much of the alkalinity is bicarbonate? ___________________

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 Chemical Process Industries (lab)
Department of Chemical Engineering Course No. Ch.E-201
Wah Engineering College wahcantt.

Alkalinity:
The alkalinity of water is due to the presence of wide variety of salts of weak acids such as carbonates,
bicarbonates, phosphates, etc., and also due to the presence of weak and strong bases (due to
contamination with industrial wastes). The major portion of alkalinity in natural water is caused by the
presence of bicarbonates that are formed when water containing free carbon dioxide percolates through
soils containing calcium carbonates and magnesium carbonates.

CaCO3 + CO2 + H2O Ca (HCO3)2

The alkalinity of natural water may be taken as an indication of the concentration of hydroxides,
carbonates and bicarbonates.

The type and extent of alkalinity present in a water may be determined by titrating the water with a
standard acid to phenolphthalein end point (P) and continuing the titration to methyl orange end point (T)

The reactions taking place are as follows:

OH- + H+ H2O (i)

CO32- + H+ HCO3- (ii)

H CO3- + H+ H2O + CO2 (iii)

The volume of the acid used up to phenolphthalein end point P corresponds to the completion of equations
(i) and (ii) , while the volume of the acid used after P corresponds to the completion of equation (iii). The
total amount of acid used from beginning of the experiment corresponds to the total alkalinity present
which represents the completion of equations (i) to (iii).

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