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Expt3 PDF
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EXPERIMENT 3.
ACID-BASE TITRATIONS: DETERMINATION OF
CARBONATE BY TITRATION WITH HYDROCHLORIC ACID
BACKGROUND
Carbonate Equilibria
In this experiment a solution of hydrochloric acid is prepared, standardized
against pure sodium carbonate, and used to determine the percentage of
carbonate in a sample.
An aqueous solution of hydrochloric acid is almost completely dissociated into
hydrated protons and chloride ions. Therefore, in a titration with hydrochloric
acid the active titrant species is the hydrated proton. This species is often written
H3O+, although the actual form in solution is more correctly (H2O)n H+. For
convenience we designate it simply H+.
Carbonate in aqueous solution acts as a base; that is, it is able to accept a proton to
form bicarbonate ion.
2-
CO3
H+ <==========> HCO-3
(1)
HCO3
+ H+ <==========> H2CO3
(2)
Equilibrium expressions for the dissociation of bicarbonate and carbonic acid may
be written
2[H+] [CO3 ]
K2 =
(3)
[HCO-3]
and
[H+] [HCO-3]
K1 =
[H2CO3]
(4)
where K1 and K2 are the first and second acid dissociation constants for H2CO3;
the experimentally determined values are K1 = 3.5 x 10-7 and K2 = 5 x 10-11.
When successive protonation reactions such as (1) and (2) occur, the extent to
which the first reaction proceeds before the second begins depends on the
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CO3
+ OH-
(5)
Here water acts as an acid, providing a proton to carbonate ion, the base. The
equilibrium constant for this reaction may be written
-
Kb =
[HCO3] [OH- ]
2-
(6)
[CO3 ]
Figure 1.
Curve for
the titration
of carbonate
with hydrochloric
acid.
Multiplying the right side of Equation (6) by [H+]/[H +], we see that K b is equal to
Kw/K2, where Kw is the dissociation constant for water.
Kw = [H+] [OH- ] = 10-14 at 25C
(7)
1
Reactions of ions of a solute with water often are called hydrolysis reactions. They are more
properly considered, however, as simply another example of a Bronsted acid-base reaction in
which water acts as an acid or a base.
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and K2 is the second dissociation constant for carbonic acid [Equation 3]. If the
initial concentration of carbonate and the values of Kw and K 2 are known, [OH - ]
can be calculated from
Kw
K2
[HCO3] [OH- ]
2[CO3 ]
(8)
Assume that the equilibrium for Equation (5) lies far to the left, so that the
carbonate ion concentration is still essentially 0.1 M. Since bicarbonate and
hydroxide are formed in equimolar amounts,
-
[HCO3 ] = [OH- ]
(9)
10-14
[OH- ]2
=
0.1
5 x 10-11
(10)
(11)
and
10-14
4.5 x 10-3
= 2.2 x 10-12 M
(12)
so the pH is 11.7.
(13)
does not occur to an appreciable extent; that it does not can be verified by
substituting the value for [H+] found in Equation (12) in Equation (4) and
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2-
confirmed because Equations (9) and (11) show that [HCO3 ] is less than 5% of
2-
[CO3 ] .
Kw
Note from this discussion that K
= Kb, or K w = K2Kb. Thus, if Ka for an acid
2
HA is known, K b for the corresponding base A - can be calculated in aqueous
solutions. An acid HA and base A - are called a conjugate acid-base pair; HA is
the conjugate acid of A- and A- the conjugate base of HA.
pH at Point B. At Point B in Figure 1,
1
2
for each mole of carbonate. The solution now contains an equimolar mixture of
carbonate and bicarbonate. We can calculate the pH at this point by rearranging
Equation (3) to
-
[H+] =
[HCO3] K2
2-
(14)
[CO3 ]
Since the bicarbonate and carbonate concentrations are equal, the hydrogen ion
concentration is equal to K2, and the pH is 10.3.
Accurate calculations of concentrations of species during titrations must include
the effect of dilution by the titrant, but thus far those caused by the addition of
hydrochloric acid have not been considered.
To correct calculations of
concentrations of the major components for dilution, multiply each calculated
concentration by the factor V/(V + ), where V is the volume of the original
solution and is the volume of hydrochloric acid added at any point. Although in
the present example the effect is slight, in many systems the correction is
significant.
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K1K2 =
(15)
[H+] [HCO3]
-7
K1 = 3.5 x 10 = (0.1) [50/(50 + 100)]
[H+]2
= 0.033
(16)
Therefore,
[H+] = 1.07 x 10-4 M = 10-3.97
(17)
(18)
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Figure 2. Effect of
removal of carbon
dioxide on pH
change the second
equivalence point
in a titration of
carbonate with
hydrochloric acid.
Band indicates
region of change
of indicator color.
Primary standards are stable, nonhygroscopic substances that react
quantitatively and are easy to purify and handle. A high equivalent weight is
advantageous because weighing errors are minimized. Among the excellent
primary standards available are potassium acid phthalate, benzoic acid, oxalic
2
In mammals the CO2 produced through biological oxidation is carried by the blood to the lungs,
where it is exchanged for oxygen. Part of the CO2 is present in the blood as H2CO3. Since the time
available in the lungs for exchange is short, the dissociation of H2CO3 to CO2 and H 2O is
accelerated by the enzyme carbonic acid anhydrase, a zinc-containing protein of high molecular
weight. Thus nature need not resort to either boiling or shaking.
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acid dihydrate, and sulfamic acid for standardizing bases and sodium oxalate,
tris(hydroxymethyl)aminomethane, 4-amino pyridine, and sodium carbonate for
standardizing acids. Pure anhydrous sodium carbonate, besides having all the
properties of a suitable primary-standard base, has the added advantage in this
experiment of being the same compound as the substance determined. This tends
to compensate for determinate errors in end-point selection.
PROCEDURE
Reagent List:
Unknown Sample - must be mixed thoroughly and dried
HCl concentrated - approx. 12M
sodium carbonate (Na2CO3) - must be dried
Bromocresol Green - indicator
Put a little less than 1 liter of distilled water into a clean 1-liter bottle. Calculate
the volume of 12 M HCl required to prepare 1 liter of 0.2 M HCl, and measure this
quantity into a small graduated cylinder. Transfer it to the bottle and mix
thoroughly. Label.
Na 2CO3 tends to absorb H2O from the air to form Na2CO3.H 2O, and CO 2 to form NaHCO3. At
least several hours of drying at 140C is necessary to remove all H2O and CO2.
4
Use a pencil or felt marking pen to label the container with the name or sample number of the
contents and with your locker number. The container may be placed inside a small glass beaker,
and a watch glass, raised with several bent portions of glass rod, placed on top for protection.
Avoid leaving chemicals or equipment in the drying oven longer than necessary, this not only
causes crowding, but increases the chance of equipment being broken or samples contaminated by
spilled chemicals.
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before the end point the titrant is best added in fractions of a drop.5
buret reading and add to it the buret calibration correction.
Record the
Calculate the molarity of the HCl solution. The procedure outlined in the
discussion of calculations below may be used as a guide. Relative deviations of
1
individual values from the average should not exceed about 2 parts per 1000.
CALCULATIONS
The percentage of Na 2CO3 in a sample can be calculated in two steps: (1) the
determination of the molarity of the HCl titrant from the standardization
titrations and (2) the calculation of the percentage of Na2CO3 from titrations of the
sample.
1.
(19)
moles HCl
liter
moles Na2CO3 x 2
(ml HCl/1000)
To deliver amounts less than 1 drop from a buret, first let a droplet form on the tip, and then touch
the tip momentarily to the inside wall of the flask. Rinse the wall with a small amount of distilled
water from a wash bottle to ensure that the titrant is washed into the solution. Do not rinse the tip of
the buret.
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(20)
(wt of Na2CO3) x 2
= (mol wt Na CO ) (ml HCl/1000)
2
3
The factor 2 required because each mole of Na2CO3 reacts quantitatively with
2 moles of HCl.
2.
=
Remember:
wt of Na2CO3 in sample
g sample
x 100
x 100
(21)
x 100