Gravimetric Analysis of Chloride Introduction

Gravimetric analysis is a method for determining the amount of a chemical present by converting
it, through a chemical reaction, into another of known chemical composition, which can be
isolated and weighed.

In this experiment we will determine the composition of an unknown chloride salt (XCl), by
reacting chloride and silver ions to produce a silver chloride precipitate. The silver chloride is
then filtered out and weighed. Based on the known stoichiometric ratios of the silver chloride
reaction 1:1 we can determine the amount of chloride initially present in our metal sample.

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

We will begin our experiment by first adding a weighed sample of our unknown XCl sample to
water, the XCl will disassociate in the water into Cl- and X+ ions:

XCl (s) + H2O (aq) -> X+ (aq) + Cl- (aq) + H2O (aq)

A 1M solution of AgNO3 is added to serve as the source for our Ag+ ions, as AgNO3 is added
AgCl will precipitate out of the solution. AgNO3 is added until no more AgCl precipitates out
of solution, the initial quantity of Cl- ions present serves as the limiting agent to our reaction. The
amount of excess AgNO3 added is not important, once all of the AgCl has precipitated out of
solution. We then filter out our AgCl precipitate, and weigh it.

From the mass of our AgCl precipitate we can determine how many moles of AgCl were
produced:

Moles of AgCl = weight of AgCl / GMW of AgCl = weight of AgCl / 143.32

We can determine the % of Cl- present in our unknown:

Moles of Cl- = moles of AgCl

Weight of Cl- in XCl sample = (moles of Cl-)x(atomic weight of Cl- = 35.4527)

% Cl- in sample = (weight of Cl- in XCl sample / weight of XCl sample) x 100 %

Procedure

Step 1: Obtain unknown, in a 250 ml Beaker add 5 g of unknown chloride XCl.

Step 2: Add water to XCl, fill beaker to 100ml level by adding water, stir solution until XCl is
completely dissolved.
Step 3: Add Concentrated Nitric Acid, add 1 ml of concentrated acid to XCl solution.

Step 4: Add 1M AgNO3: Obtain a 100ml graduated cylinder and fill with 1M AgNO3, add
AgNO3 to XCl solution in 5 to 25 ml increments. A precipitate of AgCl will form and gradually
settle. Continue to add AgNO3 until no more precipitate forms. To verify that the reaction is
complete check the chemical properties of the beaker (by double-clicking on it) and confirm that
all of the XCl (in solution) has been consumed.

Step 5: Filter and weigh AgCl : Obtain a 250ml Erlenmeyer flask and add a filter (Buchner
funnel), pour the contents of the beaker into the flask. Remove the filter from the Erlenmeyer
flask (by again selecting the filter menu or button) and save the solid contents in a watch glass.
Weigh the sample and record the result. *

*Note that in an actual lab the AgCl filtered precipitate would need to be dried to remove excess
water, however in this simulation the filtered precipitate is free of water.

Observations:

Initial unknown chloride sample weight (g):

Weight of AgCl precipitate:
Approximate volume of AgNO3 solution added (ml):

Moles of AgCl = ( AgCl precipitate mass/143.32 ):

Weight of Cl- in XCl sample = (moles of AgCl)x(atomic weight of Cl- = 35.4527) :
% Cl- in sample = (weight of Cl- in XCl sample / weight of XCl sample) x 100 % :

What happened as excess AgNO3 solution was added to the XCl solution ?
1
THEORY
SALT CONTENT BY TITRATION

When we talk about an industrial brine solution we are referring to a solution of predominantly
sodium chloride (NaCl) salt in water. The brine may include other components such as solids,
oil, dissolved gas, or other negative and positive ions, but it is mainly salt dissolved in water.
We know that the presence of salt lowers the resistance of water and this lowered resistance
allows current flow from the cathode to the anode, via ions. Remember that electron flow goes
via a conductor from the anode to the cathode. From Ohm’s law we know that if the resistance is
low then the current may flow, thus completing the circuit and enhancing corrosion. From your
own experience you can compare the corrosion of boats and fishing tackle in fresh water to that
in ocean water. It is ions like Na+ and Cl- that lower the resistance and carry the corrosion
current.

Brine solutions are very common. Ocean water, oil patch formation waters and some heat
transfer fluids in refrigeration systems are brine solutions. Corrosion in these environments is
severe and if measures are not taken, early failures of equipment will occur.

Although brine solutions are mostly sodium chloride (NaCl) in water, other chemical compounds
can react, like salt, to cause corrosion. Brine waters from Saskatchewan, that are in contact with
potash formations, can have large concentrations of potassium chloride (KCl). Chlorides (Cl-),
bromides (Br-) and iodides (I-) are anions that behave identically by lowering the resistance of
solutions.

CATIONS ANIONS SALT NAMES

Na+ + F- ---> NaF Sodium fluoride

Na+ + Cl- ---> NaCl Sodium chloride
Na+ + Br- ---> NaBr Sodium bromide
Na+ + I- ---> NaI Sodium iodide
K+ + F- ---> KF Potassium fluoride
K+ + Cl- ---> KCl Potassium chloride
K+ + Br- ---> KBr Potassium bromide
K+ + I- ---> KI Potassium iodide

All of the above sodium and potassium halide salts behave like sodium chloride in lowering the
resistance of a solution.
To determine the salinity of a water sample technologists use a silver nitrate titration. Silver
nitrate (AgNO3), is a soluble silver salt that reacts readily with all halide ions, namely, F-, Cl-, Br-
, and I-.

The silver cation reacts quickly with chloride (or any halide) to form an insoluble silver chloride
(AgCl) precipitate.

All silver halide salts are white to off-white and require an indicator to tell us when the
precipitation reaction is over. Potassium chromate (K2CrO4), is a suitable indicator since a slight
excess of AgNO3 causes a bright red precipitate of silver chromate, Ag2CrO4.

BALANCED CHEMICAL REACTIONS:

CONCENTRATION RELATIONSHIPS:

1 molar solution = 1 M = 1 mol solute

1 L solution

1 part per million = 1 ppm = 1 mg or 1 mg

1,000,000mg 1 L solution

1 L solution = 1 L x 1000 mL x 1 g x 1000 mg = 1,000,000 mg (for dilute solutions)

1L 1 mL 1g

MATHEMATICAL RELATIONSHIPS:

To calculate the molarity of a sodium chloride solution:

Molarity (NaCl) x Volume (NaCl) = Molarity (AgNO3) x Volume (AgNO3)

M1V1=M2V2

To calculate the parts per million of chloride ion:

 ppm Cl- = mole Cl- x 35.45 g/mole Cl- x 1000 mg/g
sample volume in litres

or

ppm Cl- = (Molarity of Cl-) x 35.45 g x 1000 mg

mol Cl- g

To calculate the parts per million of sodium chloride:

ppm NaCl = ppm Cl- x 58.44 g/mole NaCl

35.45 g/mole Cl-

or

ppm NaCl = (Molarity of NaCl) x 58.44 g x 1000 mg

mol NaCl g

PROCEDURE
1. Select “Hot Plate & Mag Stir” from the Equipment menu. Place 25.00 mL of an
unknown brine solution into a 100 mL beaker. Place the beaker on the magnetic stirrer.
Add 0.100 mL of potassium chromate. Select the magnetic stirrer and use the context
menu to set the stirring rate.

2. Carefully fill a 50.00 mL burette with standardized silver nitrate solution. Zero the
burette to 0.00 mL and position it over the 100 mL beaker.

3. Titrate the contents of the beaker with silver nitrate from the burette. Initially the silver
nitrate may be added rapidly with continuous stirring. At this point, large amounts of
white solid should be forming. Slow down subsequent additions of silver nitrate until a
faint brick red precipitate forms indicating the end of the titration.

4. Record all pertinent data on the data sheet. Read the burette volume to +/- 0.1 mL .

5. Repeat the titration until the final volumes agree to +/- 0.2 mL.

6. Fill in the remainder of the data sheet and perform all calculations.

BE CAREFUL WITH SILVER NITRATE SOLUTIONS

 Spills on your skin or the floor turn black on exposure to light. These stains are very
difficult to remove from floor tiles, without grinding off the finish. These stains on skin
take about a month for new skin to grow to replace the black stain.

REPORT

1. SHOW DETAILED CALCULATIONS FOR THE FOLLOWING:

 Molarity of salt (NaCl) in the unknown:

 ppm chloride (Cl-)in the unknown:

 ppm salt (NaCl) in the unknown:

1.1.1
1.1.2
1.1.3 QUESTIONS
1. Consider the conductance meter and the titration method of determining the salt content
of a brine sample. Discuss at least two advantages and two disadvantages of each
method.

2. A corrosion technologist pipetted a 50.00 mL sample of an unknown brine and titrated it

with 37.64 mL of 0.1024 M silver nitrate solution. Calculate the ppm salt (NaCl) in the
sample.

3. If a salty crude sample was analyzed to have 110.6 ppm salts, calculate the pounds of
salt per 1000 bbls of crude.

NAME: ____________________________

SECTION: _________________________ DATE: ______________________________

UNKNOWN INFORMATION : ___________________________________

SALT CONTENT OF A BRINE SOLUTION

CONCENTRATION OF STANDARDIZED SILVER NITRATE:____________________

Trial #1 Trial #2 Trial #3

Pipetted volume
Final burette reading
Initial burette reading
Volume titrated

AVERAGE OF 2 BEST TITRATION’S: ___________________________________