Experiment.

EDTA Titration of Ba2+ Modified 09/05/2019

Experiment. EDTA Titration of Ba2+ of a) unknown metal sulfate and b) unknown BaCl2

Objective: The most common multivalent metal ions in natural waters are Ba2+ in an) known sample of BaCl2 and b) from the filtrate
from experiment 1 In this experiment, the total concentration of barium ions that can react with EDTA with the assumptions that
EDTA reacts 1:1 with metal (Ba2+) ions. In a separate experiment, the unknown from experiment 1 will be analyze via EDTA titrimetry
and compared to the results obtain so far.

***USE ONLY DEIONIZED WATER (NOT DISTILLED WATER!)THROUGHOUT THE ENTIRE EXPERIMENT***

Equipment Chemicals
250-mL Erlenmeyer flask (3) Buffer (pH 10): Add 142 mL of 28 wt % aqueous NH3 to 17.5 g of NH4Cl and dilute to 250 mL with water.
50-mL Buret
0.01xx M EDTA solution
Ring-stand and hardware
Desiccator
Eriochrome black T indicator: Dissolve 0.2 g of the solid indicator in 15 mL of triethanolamine plus
400-mL Beaker
5 mL of absolute ethanol. Add a minimum amount of Mg+2 ion so that the indicator starts with a
500-mL Vol. Flask
red hue
250-mL Vol. flask
1.0-mL Vol Pipette
Test Sample: Filtrate from Experiment 1.
100-mL Grad cylinder
Hot plate Known solutions: 1 L of solution containing 15–25 g of BaCl2 plus 38 mL of 12 M HCl. Each student will
need 100 mL of this solution.

Safety and Waste Disposal

Place all waste in the appropriate waste container. Do not pour any material down the drain. Dispose of nitrile gloves in the
appropriate container.

Discussion: The molar mass of the cation in an unknown sulfate salt was determine by gravimetric isolation in experiment 1. In that
experiment, Excess barium was added to the unknown solution and barium sulfate precipitated under acidic conditions. The unreacted
barium in the mother liquor pass through the filtration process and is found in the filtrate. The excess barium ion is analyzed in this
experiment.

In this experiment, the Ba2+ in the filtrate from experiment 1 will be determined by titration of ethylenediaminetetracetate, EDTA.
To ensure your technique is correct, a controlled sample, will also be determine by titration of an EDTA. The percent error will be
reported as a result.

EDTA is a hexadentate ligand that sequesters or chelate all metal ions in solution except group I and NH4+. There is an experimental
error of about 1% however, which is acceptable due to the "fuzzy" endpoints in this titration. See Fig 1.

As a chelating agent, EDTA can form several bonds to a single metal ion. Chelating
agents are multi-dentate ligands. A ligand is a substance that binds with a metal ion
to form a complex ion. Multi-dentate ligands are many clawed, holding onto the metal
ion to form a very stable complex. EDTA can form four or six bonds with a metal ion
thus the term hexadentate.
Erio-T indicator or Eriochrome Black-T indicator is used in this titration. as an endpoint indicator. When it is chelated or acidifies, it
produces a Bright Pink-Red solution. When it is not chelated and is under basic conditions, it is Blue. Figure 2 below shows a series of
color change when the end point is reached in this titration. There is a 1-drop difference of 0.01 M EDTA between the first and
second illustration and between the second and third illustration. Two or three seconds were allowed for colors in the second and
third pictures to develop after adding the additional drop. In each case the solution was thoroughly mixed. This color change from
wine red to violet to blue is due to the compact nature of the complex.

Figure 2: Titration of barium ion and EDTA with

Figure 1: Fuzzy nature of endpoint
Erio-T or Eriochrome Black-T indicator
A weak complexometric indicator name Eriochrome black T (EBT) is added before titration to visualize the presence of barium in
solution. The compound weakly binds to any metal cation (Ba+2) present in solution forming a bright red colored solution. When
Eriochrome black-T (EBT) is not bound to the barium ion, it produces a bright blue solution.

Because EDTA is a very strong complexing agent and strongly binds to metals in 1:1 ratio, any metal ions in solution will prefer to bind
to EDTA. The resulting complex, M[EDTA] is colorless. In this experiment, any metal ions bound to EBT indicator will be “stolen” and
will bind to EDTA instead. As EDTA react with the barium in Ba[EBT], the resulting solution changes from red to blue, indicating all
barium has reacted and the reaction is complete.
Experiment. EDTA Titration of Ba2+ Modified 09/05/2019
PROCEDURE
A. Titration of a known BaCl2 sample.

1A. The EDTA has been prepared and standardize for you. Record the concentration in your notebook. Remember to do a bank
titration after each part (A, B & C) below. The blanks are prepared so that they have the same matrix as the actual samples but
without the analyte.

2A. Before you proceed, you should practice finding the end point several times by adding a little tap water in a clean beaker and
titrating with EDTA. Save a solution at the end point to use as a color comparison for other titrations.

3A. Weigh out the 0.3xx total mass of your solid BaCl2 known. If the Barium chloride is a dihydrate salt, weigh 0.35x g. Record your
mass to the nearest 0.1 mg. Dissolve the BaCl2 in a minimum of deionized water and then transfer to a 100-mL volumetric flask and fill
to the mark with deionized water. Mix thoroughly. Be sure that all of the solid dissolves in this stock solution.

4A. Draw 3, 25mL aliquot samples and place each aliquot in 250mL Erlenmeyer flasks. To each sample, add 3 mL of pH 10 buffer and 6
drops of Eriochrome black T indicator. To the first 25-ml solution, titrate with EDTA from a 50-mL buret and note when the color
changes from wine red to blue.

5A. Repeat the titration with the next two remaining samples to find an accurate value of the total atomic mass of the barium in the
original solid known. Perform a blank titration with 25 mL of distilled water and subtract the value of the blank from each result.
Remember that the blanks are prepared so that they have the same matrix as the actual samples but without the analyte.

B. Titration of filtrate from experiment 1.

6B. For each trial from experiment 1, there should be a precipitate that is saved. Take this filtrate and record the total volume. If
possible, reduce the volume to 25mL by heating over a hot plate. You will be given instructions on the amount of filtrate to analyze.
Take this aliquot and place in an 250mL Erlenmeyer flask. To each sample, add 3 mL of pH 10 buffer, 6 drops of Eriochrome black T
indicator and 50mL of distilled water. To the first filtrate, titrate with EDTA and note when the color changes from wine red to blue.

7B. Repeat the titration with the next two remaining samples to find an accurate value of the mass of barium. Calculate the mass of
barium in each aliquot of the filtrate.

C. Titration of the unknown metal sulfate salt from experiment 1.

8C From the results of experiment #1, determine the mass necessary of your unknown to prepare100mL of a 15.x mM solution.
Prepare the unknown solution similar to procedure A above. Be sure that all of the solid dissolves in this stock solution.

9C. Draw 3, 25mL aliquot samples and place each aliquot in 250mL Erlenmeyer flasks. To each sample, add 3 mL of pH 10 buffer and 6
drops of Eriochrome black T indicator. To the first 25-ml solution, titrate with EDTA from a 50-mL buret and note when the color
changes from wine red to blue. Use your data to calculate the moles of the metal and the atomic weigh of the metal in your unknown.
Calculate the moles of metal in each aliquot analyzed.

10C. Upon completion of the experiment, discard all solution in a chemical waste bottle and wash out the glassware. Be sure to dry
your buret in the upside down position.
Calculations –
Analysis: Analyte Ba2+
The reaction of Ba2+ ions with H2EDTA2- takes place with a 1:1 stoichiometric ratio: Ba2+ + H2EDTA2- D BaH2EDTA.
At the end point of the titration, 1-equivalent of Ba2+ reacts with one equivalent of H2EDTA2-.
1 eqv Ba2+ = 1 eqv H2EDTA2-; equivalent Ba2+ = [H2EDTA2-] • Vol EDTA

Recall that the analyte (we call this unknown) was prepared by taking all the solid and dissolving it in a 100-mL volumetric
flask. Next a 25-mL aliquot (call this the analyte) of this solution was titrated against EDTA. Note that the analyte moles is
equal to the EDTA moles n at the equivalent point.

A. The mass and % Ba2+ in unknown solid:

Moles of Ba2+ in 25mL Sample = ⎡⎣H 2EDTA2- ⎤⎦ • ⎡⎣Vol EDTA ⎤⎦ = mol H 2EDTA2- = mol Ba2+in 25 - mL Analyte

137.327 g Ba2+
Mass of Ba2+ in 25mL of unknown = mol Ba2+ ⋅ = __ g Ba2+
!##1.0
#"moL
### $
Molar Mass Ba2+

100mL
Mass of Ba2+ in original unknown = g Ba2+ ⋅ = __ g Total Ba2+
25
# mL
!" #
$
Dilution Fator

Mass Ba2+
Percent Ba in original unknown =
2+
= % Ba2+in unknown
Total Mass Unknown

B. Molar mass of metal sulfate salt from Expt #1 based on back titration of barium.
The excess barium unreacted from experiment 1 is determine from this experiment and subtracted from the total barium that was
used in experiment #1. The difference is the moles of barium that reacted with the sulfate ions in experiment #1 which can be used
to determine the molar mass of the unknown.

Moles of Ba2+ in filtrate = ⎡⎣H 2EDTA2- ⎤⎦ • ⎡⎣Vol EDTA ⎤⎦ = mol H 2EDTA2- = mol Ba2+in filtrate Analyte

___mol BaCl2
Moles of Ba2+used in eperiment#1 = M BaCl2⋅V BaCl2 = ⋅ _ L BaCl2 = ___ moles Ba2+
1-L

Moles of Ba2+ react with SO4 2- in Expt #1 = Moles of Ba2+used in Extp# - moles filtrate from Expt#2

Moles of SO4 2- in Expt #1 = moles Ba2+ reacted with sulfate Expt#2

Mass unk Expt 1

Molar Mass Unknown =
moles Ba2+ reacted with SO4 2- Expt#2

Atomic Mass Unknown Expt #1 = Molar Mass Unknown - Molar Mass SO4 2- ion.

Statistical Analysis –
1. Report the mean, medium, standard deviations (s), relative standard deviation (RSD), variance (s2) and the 95%
confidence interval for your results.
2. Apply the student’s t test at the 95% confidence interval

3. Apply a Q-test or G-test to any suspected result (see below)

If any trials is thrown out, be sure you repeat the procedure so you have at least three trials so that statistical
analysis can be performed.
4. ts
Confidence interval = x +
n

5. Compare the results of this experiment to the previous experiment, Gravimetric determination of Ca. Apply the
Comparison of Means with Student’s t, Case2 (p76) Comparing Replicate Measurements. Do the two methods agree
within the 95% confidence interval?

Test for Outlier

Apply a Grubb’s Test and Q-Test for any suspected outliers at 95 % level. See page 83 of text for critical values for 95%
confidence. If your results show an anomalous data then use the Q-test to determine if the result should be rejected.

(Suspected Value - Nearest Value) | Questionable value - x |

Q= G calc =
(Suspected Value - Furthest Value) s
Experiment. EDTA Titration of Ba2+ Modified 09/05/2019
Table of Data, Results and Statistical Analysis:

Raw Data Analysis of Barium ion known and filtrate

Part A
Part A
1. Known number
13 Mass of Barium in Unknown
2 Concentration of EDTA
14 % of Barium in known (by mass)
3 Mass of known BaCl2 solid used 15 % Error
+
4 Total volume prepared for known Ba2 Solution

5 Volume Aliquot of known solution to be titrated Part B

5 Volume EDTA during titration 16 Moles of Barium excess

6 Volume EDTA for blank trials 17 Moles of Sulfate reacted expt #1

18 Molar mass of Sulfate salt expt #1
7 Q or G-Test (95%) of any outlier
19 Atomic weight of cation in metals sulfate
PartB

8. Unknown number of sulfate salt (from Expt1)

9. Trial identity for filtrate (1, 2 or 3) Statistical Analysis
10. Volume EDTA during titration
20. Averages and Standard deviations of all results
11 Volume EDTA for blank trials
21 Variance, RSD and CV of all results
12 Q-Test (95%) of any outlier
22 95% Confidence interval to

23 ttable and tcalc vs expt #1

Discussion-

The goal of this experiment was to determine A) amount of barium both in an known solid and B) the excess of barium unreacted from
experiment #1 to verify the results from experiment #1. Statistical analysis was applied to the results in this experiment for both
Parts A and B. A discussion of this experiment should include the accuracy and precision of this experiment compared to the EDTA
titration method. An analysis of a comparison of replicated measurement is performed and discussed.

Table of results should include -

Include in your summary table the following:

i) Mass of Ba2+ in the known solid, percentage of known in the solid and percent error.

ii) The molar mass of the unknown sulfate salt and the atomic weight of the cation in the salt.

iv) Mean, standard deviations, RSD and CV for each of the above results.

v) Student’s t at the 95% confidence interval as it applies to the results in this experiment.

vi) Application of a G and Q-test to any suspected result at the 95% level.

vii) ttable, tcalc, Conclusion on comparison of replicated measurements.

IMPORTANT NOTE

1. Eriochrome Black T Indicator. The color change of Eriochrome black T at the endpoint is rather subtle. It is not an abrupt change
from deep red to a dark blue; but rather it is from a light red (or pink) to a pale blue. At least one trial titration is recommended. (You
can always discard a "bad" value when you know there is a definite reason for a poor result. Make sure you indicate a possible problem
in your notebook at the time you observe it.)

If you have trouble distinguishing the endpoint, a "before" and an "after" flask are recommended. Prepare two 250-mL flasks in a
similar manner as your samples – except do not add your unknown. Instead, add an equal volume of deionized water to approximate the
volume of the sample aliquot (25 mL), the volume of EDTA titrant that would have been titrated into the flask. Add the indicator and
the ammonia buffer. To one flask (the "before" the endpoint flask) add a few drops of the Ba solution; to the other flask (the "after"
flask) add a small amount of EDTA solution to get just past the color change at the endpoint. Stopper the flasks and keep them
nearby for comparison of the colors. Titrate against a white background for better discrimination of colors.

Sometimes the Eriochrome black T solution goes bad because of air oxidation. If the endpoints seem very indistinct or slow to change
color to you, try a fresh bottle of indicator. Alternatively, try adding a small amount of solid Eriochrome black T mixture (1 g indicator
ground with 100 g NaCl). A small amount on the end of a spatula is sufficient.

Before Beginning the experiment-

To calculate the volume of Aliquot for part 2 of the analysis.

Unknown is in Group A

If the mass of unknown was about .2xxx g +/- .05 g, then use the formula to determine aliquot of the filtrate

Vol Filtrate * 0.40. = aliquot to analyze.

Unknown is in Group B

If the mass of unknow is about was abo+/- .3xxg +/- .05 g, then use

Vol Filtrate * 0.48. = aliquot to analyze

Unknown is in Group C

If the mass of unknow is about was abo+/- .3xxg +/- .05 g, then use

Vol Filtrate * 0.28. = aliquot to analyze