Lab 3:

Alkalinity

Introduction

Alkalinity is a measure of the capacity of a solution to neutralize a strong acid. We
can calculate the amount of alkalinity in water by titrating the sample water with an
acid, using an indicator to determine when the sample water's pH has dropped to a
certain level - the endpoint.
Titration does not tell us the actual types of alkalinity present in the water (though we
can make an educated guess, as discussed below.) So we cannot report our results as
ppm of carbonate, bicarbonate, etc. Instead, we report the amount of alkalinity
as calcium carbonate equivalent, which is the amount of alkalinity in terms of its
equivalent value of calcium carbonate. This is the same unit of measurement we will
use to measure hardness, as you will learn in a later lab.
The pH of water determines what type(s) of alkalinity can be found in the water. By
performing two different alkalinity tests with different endpoint pH values, we are
able to estimate the proportions of carbonate, bicarbonate, and hydroxide alkalinity in
the water. The two tests also help us determine whether the water is corrosive and
whether it is caustic. This page will present the lab procedures for testing both total
and phenolphthalein alkalinity and for using these test results to calculate all of the
factors mentioned above.




Equipment
25 or 50 mL burette, graduated in 0.1 mL
burette support
100 mL graduated cylinder
rubber-tipped stirring rod, or magnetic stirrer and stir bar
white porcelain evaporating dish, 4.5 inches in diameter


Reagents
The reagents needed include the indicator and the acid used for the titration. The acid
is N/50 sulfuric acid, which is the same as 0.02 N sulfuric 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.
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 CaCO
3


(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:

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 CaCO
3





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 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 CaCO
3
, should not be greater than:

15 ppm + (0.4 T. alk.)

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

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 25C (77F).

Limits of alkalinity for various pH ranges
pH Range
Limit for Total Alkalinity
(ppm as CaCO
3
)
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 CaCO
3
). (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.




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, 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 We
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 CaCO
3
(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:
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 CaCO
3
)
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? __________________