Alkalinity and the Carbonate System

Sam Miller
3/21/13
Lab-6 & 7

Abstract
We are to become knowledgeable of strong acid and its weak conjugate base, and the
concepts of alkalinity and buffer intensity. From this knowledge gathered it can be determined
whether or not total alkalinity can indirectly determine pH and if so it is comparable with the
measured pH from the meter. This is true for the pH that the values are comparable some error
did occur when calculating the results. A comparison of titration curves was also done for each
sample to demonstrate buffer capacity, allowing for comparison of the five samples to better
determine which solution has the highest buffer capacity. Buffer intensity was also computed and
compared for each standard trial and helps determine what the minima and maxima for the buffer
system.

Introduction
Total alkalinity of a solution can be defined as its acid neutralizing capacity; another way
to define this is the amount of acid required per liter to lower the pH. Most if not all surface
water is principally determined by the carbonate system the following equation can be used to
determine the concentration by a charge balance method using of units of eq/L

HC O3

OH

+
H
Total Alkalinity=

(1)

Before this several titrations must be done the first three are to be a standardization of the
sulfuric acid and the following equation was used to determine the normality of the acid from
this titration.
A xB
=N , Normality
53.00 x C

(2)

Were A is equal to Na2CO3 weighed into the 1 L flask, B is equal to mL of Na2CO3

solution taken for the titration and finally C is equal to mL acid used. Some important points to
note is that when titrations were being done phenolphthalein indicator was used after the pH
dropped below 8.3 the next indicator to be used was methyl orange indicator and titrate to the
desired pH of 4.3. A dilution must also be done and the following equation was used in regards to
this calculation.
M i V i=M F V F

(3)

When determining the total alkalinity of the sample the following equation was used to
determine the value in mg CaCO3/L.

Alkalinity =

A x N x 50,000
mL sample

(4)

Were A is the mL of standard acid used and N is the normality of the acid. Were ml of
sample is the amount of solution that was titrated.
Methods
When starting several dilutions will need to be made using equation (3) the amount of
each solution that will be needed to be used can be determined because the initial concentration
and final concentration and volume are known. By starting with 0.1N H2SO4 this dilution was
done by adding 2.8mL of concentrated sulfuric acid to 500mL of deionized water, then dilute to
1L. The second dilution will then be prepared by taking the 0.1N H2SO4 and diluting it to 0.02N
H2SO4 final volume of about 1L about 5mL of 0.1N H2SO4 is needed for this dilution. Two other
dilutions were prepared by other groups and initial concentration was not known but the final
concentration should be around 250mL of 1.0M NaOH and 250ml of 1.0M NaHCO3. Then a
solution using 1.06 g of dry Na2CO3 add that to 500 mL of water then fill to 1L. This solution
will be used to standardize the sulfuric acid.
The reason to standardize the sulfuric acid is accurately determine what the actual
normality of the sample was so that to accurately do several calculations later in the experiment.
This standardization is done by the titration of 0.02N H2SO4 with the sodium bicarbonate solution
that was prepared. This process will be done three times and was titrated to a pH of 4.3. Once
this is done using equation 2 the actual normality of the sulfuric acid can be determined.

After the standardization has been completed create 5 different samples. Sample A is a
dilution of 1M NaOH so that the final concentration is 0.003M NaOH and a final volume of 1L
of water. Sample B will be the 3 mL of NaHCO3 and 3 mL of 1M NaOH 1L of water. Sample C
is the dilution of 3 mL of 1M NaHCO3 to 1L of water. Sample D will be 3 mL of 1M NaHCO3
and 5 mL of 1M NaOH to 1L of water. Sample E will be 4 mL of 1M NaHCO3 and 3ml of 1M
NaHCO3. Once each sample has been prepared a 50 mL volume of each sample will be titrated
phenolphthalein will be used as an indicator to 8.3 pH and once this pH has been reached add the
Methyl orange which experiences a color change at 4.3 pH. When phenolphthalein indicator is
added the color does not change then record pH and add the methyl orange.
Results
Table 1: Standardization Results and values for Na2CO3

Table 2: Normality of H2SO4

Figure 1: pH vs. ml Acid demonstrates the buffer capacity of the solution

Figure 2: pH vs. showing the buffer capacity of solution allowing for a comparison of the pKa1
and pKa2

Table 3: Results from each sample Titration and measured pH

Table 4: values for sample A through E

Table 5: Total alkalinity and calculated pH

Table 6: Comparison of calculated pH vs. measured pH

Figure 3: pH vs. ml Acid demonstrates the buffer capacity each of the samples

Figure 4: Diprotic Acid buffer system

Table 7: pKa1 comparison pKa2

Discussion
The reason that the initial titration trials were done was so that to determine the actual
normality of the acid once all three titrations were done and the pH was measured the average

can be taken of the calculated normality was used as the overall normality of acid. The normality
of the acid was calculated using equation (2).
1.06 x 20 mL
=0.026 N
53.00 x 16.2

(2)

Once the normality has been determined you can use equation (4) to determine the total
alkalinity of each sample. Then once the total alkalinity has been calculated you can convert this
value from Ca(CO)3mg/L to eq/L once that is done you can use equation (1) to determine the
[H+] value. By making the assumptions that certain species are negligible due to the trace
amounts. Using the concentration given for the dominate species of each sample. Once
simplified sample A will look like the following.
+
H
0.00209=0.003
+
H
0.00091=

Once that this has been determined you can easily determine the pH based on the
alkalinity value using log (H+).
log ( 0.00091) =3.04 pH
When looking at the figure the diprotic acid represents the minima and maxima pKA
values these values are 6.37 and 10.33 respectfully. Then when looking at the pH vs. graph for
the 2 high peaks on the graph represents the minima and maxima pKA value this comparison is
done in table 6.

When measuring the sample the reason that you would carry this reaction out to 4.3 pH
instead of 8.3 pH because when looking at the pKA1 it is 6.37 pH meaning to compare these
values you would need to titrate below that range. Another point to note is that when titrating
below this point is assumed that the reaction is no longer carbonates dominate but hydrogen
dominant meaning that this must be the tipping point for the buffer no longer present. Alkalinity
by definition is the capacity of water to neutralize an acid. Acidity by definition is the level of
acid in substances such as water. The importance of measuring the alkalinity in terms of water
quality is to better understand how much acid a solution can take in without the pH changing.
The reason that the carbonate system is so important in water quality and water treatment would
be because a carbonate buffer system is an extremely strong buffer system and is resistant to a
drop of pH. The methods used in the stranded methods handout, when titrating supposed to
titrate to a pH of 0.3 and in our lab the pH we titrated to 4.3. The error that was caused from this
was from the total alkalinity values which needed to be determined 0.3 pH so this would create a
potential error in the calculation in the sample. A possible source of error during the experiment
was an improper calibration of the pH meter. When using the meter pH was not done dropping
and the pH meter to stabilize getting incomplete results. Another problem that was present in the
lab was to ignore certain species when determining total alkalinity this could have caused the
hydrogen concentration to be smaller allowing for more accurate pH readings. Another
assumption to make note of was that the concentrations that were used when calculating total
alkalinity were taken from the lab handout and from those assumptions some potential problems
that could have occurred were that these values are not correct causing change in the total [H+]
concentration.

When looking at figure 3 you can determine what solution makes for the best buffer of
the system. How this was determined was by looking at each curve and which one has the least
amount of change of pH vs. change in mL of acid. After looking it can be determined based on
the data from figure 3 that the best buffer system would be sample B.

Conclusion
The final analysis of the data has determined that the error in the calculation was caused
by a possible miss calibration or not waiting for the pH meter to finish reading. There could have
also been errors in the calculation based on some improper assumptions made when calculating
the data. While some possible errors did occur in calculations it is still possible to show the
comparison in total alkalinity and pH in the solution. Based on the titration curve it can be
determined that sample B is the most resistant to change in pH based on the amount of acid to
the solution. Another point to note would be that a carbonate system was one of the most
important buffer systems in the world because of its high alkalinity. So even though there were
some calculation and assumptions that might have been incorrectly it is still possible to
determine what system is the most ideal buffer capacity.

Bibliography
Lab note
Class slides; Week 6 ENV 330-Sp2013-Class
Alkalinity lecture, Holly Frederick; 3/04/13 - 3/22/12, room 223