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Perform titrations.
Discuss concepts of alkalinity and buffering.
Measure alkalinity of water samples.
Estimate the concentration of Total Inorganic Carbon (i.e., sum of carbonate
system species) from alkalinity measurements.
References
1Davis, M.L., & Cornwell, D.A. (2008). Introduction to environmental engineering.
Dubuque, IA: McGraw-Hill Companies.
2Davis, M.L., & Masten, S.J. (2004). Principles of environmental engineering and
science. New York, NY: McGraw-Hill, pp. 64-73.
3Sawyer, C.N., McCarty, P.L., & Parkin, G.F. (2003). Chemistry for environmental
engineering and science. Boston: McGraw-Hill.
4U.S. Environmental Protection Agency. (n.d.). Effects of Acid Rain - Surface Waters and
Aquatic Animals. Retrieved from
http://www.epa.gov/acidrain/effects/surface_water.html.
Background
Alkalinity quantifies the ability of water to resist the effects of added acid; that is,
alkalinity counters added acid to prevent the pH from dropping (to some degree). Thus
alkalinity is sometimes called acid neutralizing capacity. The importance of the alkalinity
of natural waters received considerable attention when the negative effects of acid rain
were observed in the 1960s and 1970s.
For typical natural waters, the carbonate system is the predominant source of alkalinity,
although the presence of other weak acids (and weak bases) can also contribute. For
example, as water seeps through the soil and contacts rocks and minerals, it picks up
humic acids, borate, silicic acid, and hydrolyzed metal ions that contribute to alkalinity.
In some stages of sewage processing, the presence of organic acids and ammonia from
microbial activity contributes to the alkalinity of wastewater. The theory and experiments
presented in this lab focus on the main source of alkalinity, the carbonate system
(carbonate and bicarbonate ions, carbonic acid and dissolved carbon dioxide).
Theory
Since alkalinity is acid neutralizing capacity, alkalinity of a solution is quantified by
measuring how much strong acid must be added to lower the pH. Recall that pH reflects
+
how much acid ( H ion) is present: pH = 7 is neutral, pH < 7 is acidic, pH > 7 is basic
+
(in a base there is more hydroxide OH ion than H ion; pH = 0 is an extremely
If acid is added to pure water (initially pH = 7), the pH will readily drop, directly
+
reflecting the presence of more H ion because pure water has negligible acid
neutralizing capacity. If the water has appreciable alkalinity, added acid can be absorbed
+
(i.e., neutralized), so more H must be added to bring about a drop in pH compared to
2
+
pure water. The carbonate ion CO 3 will readily absorb H in the following
reaction:
2 HCO3
++CO 3
H
Thus the presence of carbonate can neutralize added acid until all carbonate is converted
to bicarbonate HCO3 , but at that point further added acid can be absorbed in the
reaction:
H 2 CO 3
++ HCO3
H
If enough acid is added, only carbonic acid ( H 2 CO 3) will remain of the carbonate
group, and the acid neutralizing capacity will have been exhausted.
Since the above reactions are reversible, the carbonate group can also provide some
ability to prevent the rise in pH if base is added. This effect is called acidity, essentially
the opposite of alkalinity. If a water solution is simultaneously somewhat resistant to
change in pH either up or down, it is said to be buffered (i.e., concurrently having
appreciable alkalinity and acidity). Any weak acid/base group can provide alkalinity &
acidity & buffering qualities to water, but the carbonate group has a unique role.
Contact of natural waters with the atmosphere means that carbon dioxide can dissolve,
providing a source of carbonic acid via this reaction:
CO2 + H 2 O H 2 CO 3
Rocks formed in ancient seabed environments have significant limestone content
(carbonate minerals such as CaCO 3 ), so water seeping through the soil typically picks
up carbonate and bicarbonate ions. The influence of the atmosphere (acidic, from carbon
dioxide) and of the earth (basic, from carbonate minerals) combine to provide a degree of
moderation in the pH of most natural waters. For example, most lakes and streams are
between pH 6 and 8. Exceptions can be due to unusually high influx of acid or base
and/or naturally low alkalinity. For example, the bedrock of mountains in the U.S.
northeast is granitic, a poor source of alkalinity compared to limestone (which is
abundant in Florida). Acid rain caused many lakes and streams in that region to have pH
low enough to kill aquatic life. Air pollution rules have since alleviated this problem.
Alkalinity is an important parameter in engineered processes as well. A common
technique to control reactions is to adjust the pH down or up; the alkalinity or the acidity,
respectively, would be measured to calculate how much acid or base must be added. In
other reactions the carbonate interferes with added chemicals, so the alkalinity may affect
the efficiency of the process.
Measuring Alkalinity
Since alkalinity is dominated by the carbonate system, the conventions for measuring
alkalinity go hand in hand with the action of carbonate group members in the process. If
the initial pH is above 10.5, the first added acid will be neutralized by simply reacting
OH
with the hydroxide
ions present, but starting at pH 10.5 the dominant actor in
2
absorbing acid is carbonate CO 3 , absorbing added acid until it is exhausted by about
pH of 8.3. Similarly, bicarbonate HCO3 absorbs acid starting at about pH 8.3 but is
exhausted by about pH 4.5. These characteristics of the behavior when acid is added lead
to the definitions listed in Table 1 for hydroxide alkalinity, carbonate alkalinity, and total
alkalinity ( ALK Total ) . Note that these names can be confusing. For example, carbonate
2
alkalinity is not due solely to the action of CO ; rather it is based on the quantity of
3
acid neutralized by hydroxide and carbonate plus any other weak acids/bases present that
can absorb added acid down to pH 8.3.
Traditionally alkalinity was measured by acid titration using an indicator that changed
color at the appropriate pH. Phenolphthalein turns from pink to transparent at about the
endpoint for carbonate alkalinity (pH 8.3) and Methyl Orange changes from yellow to
orange at about the endpoint for total alkalinity (pH 4.5). Technological developments
have brought the cost of electronic pH meters down, so the pH may be monitored directly
during the titration without the use of indicators.
Table 1. Listing of the formal definitions of the different types of alkalinity and the acidneutralizing species for each. Note that the terminology and definitions may be applied to
any system with acid neutralizing capacity, even if the system does not contain the
2
carbonate group (which would be unusual, but in such case just omit CO and
3
HCO3 from the last column).
Name
hydroxide (or
caustic) alkalinity
carbonate
alkalinity
Operational Definition
the amount of strong acid (moles/L) required
to lower the pH of a sample to
10.5
the amount of strong acid (moles/L) required
to lower the pH of a sample to
8.3
primarily OH
2
OH , CO 3 , other
species that may be
present
total alkalinity
( ALK Total )
OH , CO 3 ,
equivalents applies to bases too, since a base provides a hydroxide ion OH which
will eventually cause one H+ to be transferred. Normality and Molarity (moles per liter)
may be related by a factor n in the formula N=nM , as demonstrated in the
examples shown below.
For an acid solution, n is the number of H+ provided per formula unit of acid.
e.g.: 0.5 M HCl = 0.5 N HCl solution because for hydrochloric acid, n = 1.
e.g.: 0.5 M H2SO4 = 1 N H2SO4 solution because for sulfuric acid, n = 2.
For a basic solution, n is the number of OH- provided per formula unit of base.
e.g.: 0.5 M NaOH = 0.5 N NaOH solution because for caustic soda, n = 1.
e.g.: 1.0 M Ca(OH)2 = 2.0 N Ca(OH)2 solution because for calcium hydroxide, n
= 2.
Be aware that the term equivalent can have other meanings in situations other than
acid/base reactions. Because it can be ambiguous, some authorities discourage its use, but
it is included here because it is widely used in alkalinity and other chemistry applications.
Table 2. Equipment and reagents.
Equipment
pH meter/electrode
Magnetic stirrer with stirring bars
Buret
Pipets
Beakers
Funnel
Volumetric Flask
Definitions:
Reagents
Standard sulfuric acid, approximately 0.02
N (need ~100 mL per team).
Phenolphthalein indicator solution.
Methyl orange indicator solution.
Standard pH buffer solutions:
pH 4.01, pH 7.00
NaHCO3
Na2CO3
Approximately 100 mL of each sample per
student team.
Procedure
There are 2 samples to be analyzed: lab tap water, a solution of 2 x 10-3 M NaHCO3 and a
solution of 2 x 10-3 M Na2CO3. For each sample you will titrate using the pH meter to
display the pH directly. Calibrate electrode using pH buffer solutions and instructions
provided.
1. Youneedtwosolutionsthatyouwillmakefromthesolid.Everyonewillshare,so
electsomeonetomakeoneorbothofthem.Thefinalconcentrationthatyouwantin
aliterofsolutionisthatprovidedabove(confirmwithTA).
1. Rinse buret with sulfuric acid and fill using the funnel. Record the concentration of
titrant as indicated on the bottles provided: __________. (You will need this for your
data analysis.)
2. Collect data points for a titration curve.
a. Place 50 mL of Solution A in a clean beaker. Add magnetic stir bar and place
on magnetic stirrer to mix. Measure the initial pH with the pH meter and
record the value in your lab book. For greatest ease of measuring titrant, it is
recommended to make sure the starting position of titrant is zero.
b. Add an appropriate increment of acid titrant (0.3-1 mL at a time is
recommended. You want to have 3 readings per pH unit at least), and record
the amount added (i.e., record the actual amount, even if it is not precisely in
the planned increments). Record the pH after allowing a few seconds of
stirring to ensure complete mixing of the titrate and the titrant.
c. Add another increment of acid titrant, recording the cumulative amount of
titrant added, pausing and recording the pH.
d. Repeat previous step until pH of 3.5 is reached. Note that a pH versus acid
plot titration curve will be made from this data, so an effort should be made to
obtain at least three readings per pH unit.
3. Discard wastes as instructed by the TA. Rinse the beaker and stir bar several times
with DI water, then place on a clean paper towel at your station to dry. Rinse the
buret several times with DI water and place upside-down on the buret stand with
the petcock open.
Starting
position
(mL)
Ending
position
(mL)
Vadded
(mL)
Sample:_____________________
pH
Starting
position
(mL)
Ending
position
(mL)
Vadded(mL)