Gravimetric Determination of Chloride in a Soluble Salt Mixture

(Source: http://www.nmt.edu/~fletcher/labs/lab!/"ab!#Grabimetric#$nal#Cl.html%

A gravimetric determination is an analysis in which the critical measurement is mass. In this
particular experiment you will exhaustively precipitate a selected analyte and then measure its mass to
determine the amount of the analyte originally present in the unknown. A century ago almost all of
analytical chemistry was concerned with gravimetric determinations. Today, faster and simpler procedures
have replaced older wet chemical analysis methods. In order for a gravimetric analysis to work, the
precipitate must fulfill the following conditions:

! Its solu"ility must not "e large enough to cause significant error #very low $sp!.
%! The precipitate must "e a particulate, large crystal solid.
&! It must "e sufficiently pure and in a form suita"le for drying and weighing.
'! Its stoichiometry, and prefera"ly its solu"ility product, must "e known.


(olu"ility )roduct and the *ommon Ion +ffect

The ideal gravimetric precipitation will have only a very small amount of sample remaining in
solution. (ince we will use an analytical "alance, we should try to have a precipitation in which less than
,. mg of sample will remain in solution. -or a typical precipitation with .to. stoichiometry

/
0
0 A
.
/A

the solu"ility can then "e defined as

$
sp
1 2/
0
32A
.
3

$sp is a constant that depends on the temperature and allows you to calculate the solu"ility of the analyte
under a given set of conditions. In gravimetric precipitations, a slight excess of the precipitating reagent is
usually added. This excess has the effect of further reducing the solu"ility of the desired species "y the
common ion effect causing more of the precipitate to form.

*ommon )ro"lems

If the concentration of a desired compound is high or if the total concentration of salts in the
solution is too high, then the concentration terms in the $sp e4uation should "e replaced "y activity terms.
The effect of high salt concentrations is to reduce the tendancy of ions to com"ine into compounds and
precipitate, which increases the solu"ility of the salt.

*hemical e4uili"rium may also have an effect. Ions in e4uili"rium with the precipitate may also
"e involved in other e4uili"ria, reducing their effective concentration. -or instance, in the presence of a
slight excess of ammonia, silver ions form complexes with ammonia preventing the precipitation of silver
chloride.

*o.precipitation of other salts having low solu"ility in the presence of the precipitating agent will
increase the 4uantity of precipitate. 5ikewise, adsorption of other chemical species from solution onto the
surface of the precipitate will increase its mass and lead to errors. This is more likely when the surface area
of the precipitate is large.

)hysical *haracteristics

(o that the precipitate may "e efficiently filtered and collected, it must have a sufficiently large
particle si6e. )recipitation occurs in two stages, nucleation and crystal growth. 7ucleation is the process
of particle formation and is dependant on a solution that is supersaturated with material. *rystal growth
results from the continuing deposition of material onto the particles.

To ensure that large filtera"le particles are o"tained the num"er of nucleation sites that are
formed must "e limited. This is achieved "y mixing the reagents slowly so that the level of supersaturation
is never too high. In addition, if the temperature is raised the solu"ility is increased and the level of
supersaturation is reduced. 5arge particles are then formed through crystal growth as the solution cools.

In this experiment you will have a sample of chloride unknown, which you will dissolve in
distilled water. To this you will incrementally add silver nitrate. The silver and the chloride will react to
form insolu"le silver chloride which will then "e filtered and its mass determined. -rom the mass of silver
chloride, you can determine the num"er of moles of Ag*l formed, which will allow you to calculate the
num"er of moles and the mass of chloride in the unknown.

)re.5a" *alculations 8 /9(T "e completed and checked "efore "eginning the experiment

The unknown sample contains "etween ', and :,; solu"le chloride. Assuming a mass of a"out
,.% grams of unknown sample, a ,.% / solution of silver nitrate and a total final volume of a"out %, m5,
calculate the volume of silver nitrate solution that should "e added to insure that 4uantitative precipitation
#<==.=;! of the chloride is o"tained. Ignore diverse ion effects and competitive e4uili"rium. The $sp of
silver chloride is .> x ,
.,
at %?*. @I7T: to determine if the precipitation is 4uantitative, determine if
A2#moles silver added! 8 #moles silver remaining!3B#moles silver added!CD,,; is greater than or e4ual to
==.=;. If it is, then the precipitation is 4uantitative.


&xperimental

Eeagents and +4uipment Ee4uired

. *hloride 9nknown: provided, store in a dessicator
%. 7itric Acid, concentrated
&. (ilver 7itrate, ,.% /: dissolve %.F g Ag7G& in :? m5 distilled water
'. )recipitate wash solution: add % m5 conc nitric acid to %?, m5 distilled water
?. & sintered.glass filtering cruci"les #Hooch!

)rocedure

Clean Crucibles and bring to constant mass. +ach cruci"le should "e cleaned and rinsed
thoroughly with distilled water. If there are still stains on them, they will need to "e cleaned with acid.
+ach cruci"le needs to "e marked in some manner that will not "e ru""ed off, removed "y heating, or
change in mass. To dry, place the clean cruci"les in a "eaker 8 watch glass arrangement and place in the
oven at a"out ?* for week. Eemove the cruci"les with tongs #never touch cruci"les with your hands
or paper for the duration of the experiment! and allow them to cool for a few minutes "efore placing them
in a dessicator to cool to room temperature #%,.&, min!. Ieigh cruci"les to the nearest ,. mg. Eeturn
them to the oven for % hours or longer and repeat weighing procedure. This procedure should "e repeated
until two consecutive masses agree to within ,.& mg. It is extremely important that the cruci"les "e
treated exactly the same way during this procedure as they will "e treated when they contain the
precipitate. Jou will lose credit if you continue the experiment "efore your cruci"les reach constant mass.

7GT+: Jou need to use the same "alance throughout the course of this experiment. (witching "alances
when weighing the cruci"les will introduce error into your calculations and can "e a common cause of
cruci"les not coming to constant mass.


Dissolve and precipitate the unknown chloride sample. 'ecord the un(nown letter on the
assa) sheet and in )our noteboo(. *ailure to do so will result in no credit bein+ +iven for the
completion of this experiment and loss of partial credit for experiment ,. Ieigh three individual
portions of the dried unknown sample into three separate clean ',, m5 "eakers. +ach sample of unknown
should weigh a"out ,.% g, record its mass to ' decimal places. Add approximately ,, m5 of distilled
water to each "eaker to dissolve the sample. *arefully add, with the aid of a stirring rod, m5 of
concentrated nitric acid to each solution. A separate stirring rod should "e used with each solution and the
stirring rod should "e kept in the solution for the duration of the experiment. @eat the solution to a"out >,
*. Add the amount of silver nitrate calculated in the pre.la" calculation slowly in >., portions. 9se the
stirring rod to pour the solution down the side of the "eaker. (tir the solution carefully after each addition
of the silver nitrate solution. Any solution or precipitate lost during any of these steps will cause large
errors in the final value.

Allow for Crystal Growth. After completing the addition of silver nitrate, cover the "eaker #and
stirring rod! with a watch glass and store in your ca"inet until the following week.

Test for completeness. After the precipitate settles, test the clear supernatant solution for
remaining chloride ions "y adding a few drops of silver nitrate solution. If additional precipitate does not
form, the precipitation is complete. If precipitate does form, more silver nitrate solution must "e added and
the test for completeness must "e repeated. )erform this test some time during the week "etween la"
classes.

Filter the precipitate. Assem"le a suction flask and trap for filtration. There are only a few of
these, so you may need to wait until one is availa"le. Insert the cruci"le into the cruci"le holder on the
suction flask and apply a gentle suction to the filter assem"ly. To "egin filtration, hold the "eaker at an
angle so that the precipitate nestles in the lower corner of the "eaker and decant the supernatant solution
into the cruci"le. It is "est to pour the solution along the glass stirring rod to avoid missing the cruci"le or
loss of drops of solution. 7ever allow the level in the cruci"le to reach a"ove %B& full as the solution tends
to creep upward and particles may "e lost over the side of the cruci"le. Ihen almost all of the supernatant
is decanted through the cruci"le, wash the Ag*l precipitate in the "eaker with & or ' .%, m5 portions of the
precipitate wash solution. Add the wash solution, swirl the precipitate gently a"out the flask, and pour
solution to cruci"le.

Test filtrate for silver ions. *ollect a few m5 of the last portions of wash li4uid coming through
the cruci"le in a test tu"e. Add one or two drops of dilute @*l to this filtrate to test for remaining silver
nitrate. If no tur"idity #cloudiness! is o"served, the filtrate is ade4uately washed. If cloudiness is o"served,
wash the precipitate further. The filtrate can "e discarded down the drain with plenty of water.

Dry and weigh the precipitate. )lace the cruci"les in a "eaker 8 watch glass assem"ly as "efore
and allow to dry in the oven several days. Ieigh the cruci"les as you did earlier. Eepeat heating, cooling
and weighing until the mass of each cruci"le is constant to within ,.& mg. Gnce constant mass is
reached, discard the solid in the waste container provided. Ko not rinse solid down drain. Jou will lose
credit if you continue the experiment "efore your cruci"les reach constant mass.

Calculate percent chloride. Gn the "asis of the three separate results, calculate and report the
mean percent chloride in the unknown. *alculate the standard deviation, and the =,; confidence interval.
+liminate data using the L.test if needed. Turn in the assay sheet one week after the cruci"les.with.
precipitate reach constant mass.
7ame

Hravimetric Ketermination of (olu"le *hloride

(how a sample of all calculations on the "ack


-./.01.


/ass of 9nknown *l: % &


/ass of *ruci"le: % &


/ass of *ruci"le 0 Ag*l: % &


/ass of Ag*l: % &


; *l
.
in 9nknown: % &


Average ;*l
.
: s: =,:







Ihy is important to store the cruci"les in the dessicator after they are taken out of the oven "efore they are weighedM






@ow can you "e sure that you have precipitated all of the chloride as Ag*lM







@ow does the common ion effect affect the precipitation of Ag*lM Ihat is the common ionM