GRAVIMETRIC ANALYSIS OF A CHLORIDE SALT

Report Submitted by: Ronald Milner

Laboratory partner: Kiesha Mantik
Lab Performed: February 16th, 2012
Group: Thursday Afternoon, Group F
Date submitted: March 14th, 2012
Purpose: To determine the chloride content of an unknown soluble salt while illustrating the techniques
involved in gravimetric analysis.

Theory: In order to find the chloride content of an unknown soluble salt, that chloride can first be
extracted from the solution in the form of a precipitate. While some substances are easily soluble in
water due to molecular properties, others are not. These properties can be taken advantage of when
trying to isolate a particular ion. By implementing a reaction that for all intensive purposes goes to
completion, the Cl- ion can be reacted with other ions to form an insoluble substance. This new
substance will precipitate out of solution. With the use of stoichiometry, the chloride content of the new
substance can be calculated. Commonly the formation of silver chloride is used to find the
concentration chloride ions.

Precipitation of Chloride Ion by Addition of Silver Ion:

Ag+(aq) + Cl-(aq) => AgCl(s)

Though it is assumed that the above reaction goes to completion due to AgCl(s)'s extreme insolubility,
some AgCl(s) does in fact dissolve. This solubility can be shown by calculating the solubility product
Ksp.

(1) AgCl(s) => Ag+(aq) + Cl-(aq) Ksp = [Ag+(aq)][Cl-(aq)] = 1.6 x 10-10

While silver chloride will be in equilibrium with its ions in the solution, because Ksp is so small, the
dissolved ions can be considered negligible. When AgNO3 is added to a solution containing containing
Cl- ions, a displacement reaction is undergone and the Ag+ and Cl- ions will precipitate out quickly as
AgCl(s), until all of the Cl- is consumed (assuming Cl- is the limiting reagent).

A small amount of salt will be left in solution, depending on the amount of excess Ag+ added to
solution. Because maximum solubility will occur when there is no excess Ag+ ion present, the Ksp value
can be used to calculate the remaining Cl- in worst case conditions.

With no excess Ag+, [Ag+] = [Cl-]; let both = x

Ksp = [Ag+(aq)][Cl-(aq)] = 1.6 x 10-10

[x][x]=1.6 x 10-10
x =1.3 x 10-5
Because the formation of solid happens so fast, it precipitates as what is referred to as a colloid.
The particles are extremely small because there is no time for crystal formation. In order to collect the
precipitate without losses through the filter apparatus, the colloid can be encouraged to form larger and
more crystalline pieces with gentle heating and stirring in the presence of nitric acid. The precipitate
will turn into larger masses leaving behind a semi-clear liquid. The nitric acid prevents reversion of the
newly formed solid pieces to colloid state. The precipitate can then be filtered and massed for
calculation.

Factors leading to high results for Cl- ion: Due to the rapid precipitation of AgCl(s) to the colloid state,
other ions can become trapped at the same time. For this reason precipitation is carried out slowly in an
acidic solution. The acid solution resists interference from anions of weak acids (such as CO3-2) which
can also form precipitates with present silver ions. While there is need for some excess of silver ions, a
large excess can result in extra unwanted precipitates with silver and other ions in the solution.
Examples of interfering ions include any present negative ion that would have a low solubility when
combined with silver. Interfering ions could precipitate with the excess Ag+ in the solution resulting in a
higher mass of precipitate. Incomplete washing or drying of precipitate can encourage these errors by
allowing for .

Factors leading to low results for Cl- ion: The silver chloride precipitate decomposes back into its ions
in the presence of light.

(2) AgCl(s) => Ag(s) + (1/2)Cl2(g)

This results in a violet colour appearing on the precipitate due to the accumulation of silver. While this
can happen rapidly in strong light, the decomposition will happen mainly on the surface of the
precipitate with the inside being protected by the reacted coating formed on the outside, so the effects
should not be too great.

If the decomposition should occur with significant excess Ag+, soluble CIO3- can be formed resulting in
a low yeild of precipitate, as some Cl- ions will be lost through the filtration apparatus..

(3) 3Cl2(g) + 3H20(l) + 5Ag+(aq) => 5AgCl(s) + CIO3-(aq) + 6H+(aq)

Calculating Chloride % by Weight:

By equation 1: AgCl(s) => Ag+(aq) + Cl-(aq)

number of moles AgCl = number of moles Cl- so:

1) Convert mass of precipitate (AgCl) into mols:

Mols AgCl = (grams AgCl)/ (grams/mol AgCl)

2) Convert moles of chloride ion to mass:

Mass Cl- = (number of mols Cl-)x(grams/mol Cl-)

3)Use mass of Cl- to calculate % by mass of original sample:

% Cl = (Mass Cl- / Mass sample)x100%

Losses: In order to make sure that certain unwated ions are removed from the precipitate, the sample is
rinsed with both 100ml of water and 3 5ml portions of acetone. Because AgCl does have a very small
solubility in water, rinsing with water may cause some losses through the filter apparatus. The worst
case losses can be calculated using the Ksp value.

Ksp = 1.6 x 10-10 mol/L

1) Calculating the amount of AgCl than can be dissolved in 100ml of water:

Losses in mols = (Ksp)(.1L)
= 1.6 x 10 -11 mols

2) converting to grams

(1.6 x 10-11mol)(143.32 g/mol) = 2.3 x 10-9 g lost

Therefore in the worst case scenario, 2.3 x 10-9g or precipitate can be lost by rinsing with 100 ml of
water.

Procedure:

To begin the lab, the sample of unknown salt was obtained and the sample number and true %
Cl- by mass recorded. A hotplate was then prepared and set to heat to setting 5. While the hotplate was
preheating, .1259g of unknown salt was then weighed by difference in a 250 ml glass beaker. 100 ml of
distilled water was then added to the unknown sample and 1ml of HNO3 was added by a TA. The
solution was then stirred. The necessary amount of AgNO3 needed for reaction was calculated as 19.5
ml along with an additional 5ml excess and 3ml for later use. The needed AgNO3 was then obtained
from a TA. The calculated value of AgNO3 along with 5ml excess was added to the 250ml beaker
containing the unknown sample and placed on the hotplate. The solution and precipitate was heated,
with gentle stirring at intervals in order to encourage crystal formation. Several times the solution was
overheated, releasing too much steam. When overheating occurred, the beaker was removed and the
temperature of the hotplate was reset before placing the beaker back in its original position. When the
majority of the precipitate had collected in larger pieces and the solution was semi-clear, the solution
was tested for completeness of reaction with the previously collected 3ml of AgNO3. No precipitate
formed and the reaction appeared complete. The 250 ml beaker was then placed in a drawer to cool out
of direct light. The mass of the crucible was recorded as 19.3836 g and initials were written it in order
to keep track of different samples. While the solution was cooling, 30ml of 0.1 M HNO3 was collected
from a TA for later use. Once the solution was slightly warmer than room temperature it was filtered
using a vacuum filter apparatus. 10 ml of the 0.1 M HNO3 was added to the beaker and swirled, being
used to dislodge precipitate into the crucible/filtering apparatus. This process was done twice and the
filtered solution was emptied into a waste beaker before the final rinse. The beaker containing
precipitate was then rinsed into the crucible once more with the remaining HNO3. This filtered solution
was then moved into a small test tube, and tested for completeness by a TA. The solution tested positive
for completion and a lack of silver ions. The precipitate was then washed twice with 5ml squirts of
acetone. The crucible was then placed in a desiccator and taken to a TA who placed the crucible in a 97
degree oven. After 25 minutes, the crucible was removed and massed along with the precipitate as
32.1804g. This experiment was done twice side by side in order to compare results.

Observations:

Sample ID: 338

Sample Completeness of HNO3 Washing Precipitate
Description precipitation Description
Sample White powdery Tested positive for Washing Precipitate was
substance with fine complete performed twice, slightly purple
crystals precipitation washings testing powdery
positive for substance.
 completion. No
visible particles
remained.
Partner sample White powdery Tested positive for Washing Precipitate was
substance with fine complete performed twice, slightly purple
crystals precipitation washings testing powdery
positive for substance.
completion. No
visible particles
remained.

Data:
Values Partners Values
True Value % Cl- by Weight 59.49 % 59.49 %
Sample Mass 0.1259 +/- .0001 g .1264 +/- .0001 g
Required AgNO3 24.5 +/- .02 ml 24.6 +/- .02 ml
Crucible Mass 19.3836 +/- .0001g 19.5381 +/- .0001 g
Oven Temperature 97.0 +/- .2 degrees Celcius 97.0 +/- .2 degrees Celsius
Time precipitate in oven 25 minutes 25 minutes
Precipitate cooling time 5 minutes 5 minutes
Mass Crucible with Precipitate 32.1804 +/- .0001g 32.3262 g +/- .0001 g
Mass Precipitate 12.7968 +/- .0002g 12.7881 g +/- .0002 g
Mass Cl- 3.17 g +/- 4.95 x 10-5 3.17 g +/- 2.95 x 10-5
% Cl- by Weight 2517.87 +/- .50 % 2507.91+/- .50 %
-
Average Cl % by weight of two 2512.89 +/- .50 % 2512.89 +/- .50%
trials
% Error 4476.13 % 4445.45 %
Avg % Error 4511.65% 4511.65%
Relative Spread 3.96 ppt 3.96 ppt

Calculations:

Calculating required AgNO3:

From equation (1) in theory, ratio Ag to Cl has 1 to 1 molar ratio. Assuming the sample is 55%
chloride by weight:

(sample mass)(55% chloride by mass) = g Cl-

Sample 1: (.1259 +/- .0001 g)(.55) = .069245 +/- .0001 g Cl-

Partner's sample: (.1264g +/- .0001 g)(.55)= .06952 +/-.0001 g Cl-

Convert grams of Cl- to moles

(g Cl-)/(g/mol Cl-) = moles Cl-

Sample 1: (.069245 +/- .0001 g)/(35.5 g/mol) = .001950563 +/- 2.81x 10-6 moles Cl-

Partner's sample: (.06952 +/- .0001 g)/(35.5 g/mol) = .0019583099 +/- 2.81 x 10-6 moles Cl-

# of mols Cl- = # of moles Ag+, so convert moles to ml.

(# of moles Ag+)/(moles/litre AgNO3)(1000 ml/L) = ml AgNO3

Sample 1: ((.00195063 +/- 2.81x10-6 moles)/(.10 moles/litre))(1000 ml/Litre) = 19.5 +/- .02 ml AgNO3
+ 5ml excess = 24.5 +/- 0.02 ml AgNO3

Partner's Sample: ((.0019583099 +/- 2.81x10-6 moles)/(.10 moles/Litre))(1000 ml/Litre)= 19.6 +/- .02
ml AgNO3 + 5ml excess = 24.6 +/- 0.02 ml AgNO3

Calculating mass Cl- from mass precipitate:

Convert mass precipitate (AgCl(s)) to moles

(mass precipitate (g))/(g/mol AgCl) = moles AgCl

Sample 1: (12.7968 +/- .0002 g)/(143.32 g/mol) = .0892883059 +/- 1.40x10-6 moles AgCl

Partner's sample: (12.7881 +/- .0002 g)/(143.32 g/mol) = .0892276026 +/- 1.40x10-6 moles AgCl

Because molar ratio of AgCl to Cl- is 1 to 1, convert moles Cl- to g

(# of moles Cl-)(g/mol Cl-)= g Cl-

Sample 1: (.0892883059 +/- 1.40x10-6 moles)(35.5 g/mol)= 3.17 +/- 4.95 x 10-5 g Cl-

Partner's sample: (.0892276026 +/- 1.40 x 10 -6 moles)(35.5 g/mol) =3.17 +/- 4.95 x 10-5 g Cl-

Calculating sample Cl- % by Weight:

((Mass Cl-)/(Mass Unknown Salt Sample))x100 = Cl- % by Weight of sample

Sample 1: ((3.17 +/- 4.95 x 10 -5 g)/(.1259 +/- .0001 g))x100 = 2517.87 +/- .50 % Cl- by Weight

Partner's Sample: ((3.17 +/- 4.95 x 10 -5 5)/(.1264 +/- .0001 g))x100= 2507.91 +/- .50% Cl- by Weight

Calculating Average of Trials

(Value 1 + Value 2)/2 = avg

(2517.87 +/- .50 % + 2507.91 +/- .50 %)/2 = 2512.89 +/- 50%
Calculating % Uncertainty:

% uncertainty = ((Uncertainty in value)/(value))x100

(.0002 g/3.17 g)x100 = 6.31 x 10 -5 %

Calculating % Error:

% Error= ((Calculated Value True Value)/(True Value))x100

Sample 1: ((2517.87% - 54.49%)/(54.49%))x100 = 4520.79 % Error

Partner's sample: ((2507.91% - 54.49%)/(54.49%)x100= 4502.51% Error

Average: (4520.79%+4502.51%)/2= 4511.65 %

Calculating Relative Spread:

Relative spread = (((High Cl- Value) (Low Cl- Value))/(avg))x1000 parts per thousand

(2517.87% - 2507.91%)/(2512.89)= 3.96 ppt

Discussion: The experiment yielded impossibly high results. The massive error is believed to be caused
by an error in massing the the crucibles used. The scale was not properly calibrated after weighing the
unknown sample by difference causing the mass of crucibles to be recorded as much to low. This
caused the weighing by difference of the precipitate to result in an extremely high mass, throwing off
calculations throughout. By comparison, the crucibles of colleagues weighed significantly more than
those used for this experiment. Had the results been high within a reasonable error, this could have
been caused by other reasons. The use of too much excess Ag+ when testing for completion could have
allowed for the formation of precipitate with present ions other than the Cl- ion. Improper washing of
the precipitate may have also allowed some of the unwanted ions to remain in the precipitate.

Conclusions: The sample number was 338 with a true % Cl- by weight of 54.49%. The calculated
average of % Cl- by weight was 2512.89 +/- .50% with a calculated uncertainty of 6.31 x 10-5 %. The
average % error (or accuracy of the experiment) between the calculated value and the real value was
4511.65%. The precision of the experiment was good, having a relative spread of 3.96 ppt between the
two trials.

Bibliography:

Archer D.W, Burk R.C, Wolff P.A, CHEM 1101: Chemistry for Engineers, Laboratory Manual
2011-2012, Department of Chemistry, Carleton, Ottawa, 41, 59-64.