Académique Documents
Professionnel Documents
Culture Documents
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)
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:
Completeness of
precipitation
HNO3 Washing
White powdery
Tested positive for Washing
substance with fine complete
performed twice,
crystals
precipitation
washings testing
positive for
Precipitate
Description
Precipitate was
slightly purple
powdery
substance.
completion. No
visible particles
remained.
Partner sample
White powdery
Tested positive for Washing
substance with fine complete
performed twice,
crystals
precipitation
washings testing
positive for
completion. No
visible particles
remained.
Precipitate was
slightly purple
powdery
substance.
Data:
Values
Partners Values
59.49 %
59.49 %
Sample Mass
Required AgNO3
Crucible Mass
Oven Temperature
25 minutes
25 minutes
5 minutes
5 minutes
Mass Precipitate
Mass Cl-
2507.91+/- .50 %
% Error
4476.13 %
4445.45 %
Avg % Error
4511.65%
4511.65%
Relative Spread
3.96 ppt
3.96 ppt
% Cl- by Weight
-
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 ClSample 1: (.1259 +/- .0001 g)(.55) = .069245 +/- .0001 g Cl-
Partner's sample: (.1264g +/- .0001 g)(.55)= .06952 +/-.0001 g ClConvert grams of Cl- to moles
(g Cl-)/(g/mol Cl-) = moles ClSample 1: (.069245 +/- .0001 g)/(35.5 g/mol) = .001950563 +/- 2.81x 10-6 moles ClPartner'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 ClSample 1: (.0892883059 +/- 1.40x10-6 moles)(35.5 g/mol)= 3.17 +/- 4.95 x 10-5 g ClPartner's sample: (.0892276026 +/- 1.40 x 10 -6 moles)(35.5 g/mol) =3.17 +/- 4.95 x 10-5 g ClCalculating 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.