CHM 212: GENERAL INFORMATION

ANALYTICAL CHEMISTRY Dr. K. Pokpas

PRECIPITATION (ARGENTOMETRIC) TITRATIONS Office: Rm 3.25 (3rd floor Chemical Sciences Building)
© Dr. K. Pokpas - 2020 Email: kpokpas@uwc.ac.za

Consultation:
All consultations are to be scheduled via email to ensure that the lecturer is
able to assist you.
Textbook:
Fundamentals of Analytical Chemistry, 9th Edition, Skoog, West, Holler, Crouch
Course Resources:
All relevant resources can be found on the iKamva interactive website under
the Lecture Content tab in the “CHM 212: Analytical Chemistry” page.

REMINDER: Test, See Course Ouline

Adapted from slides by PGLB

OUTLINE DEFINITION

CHM 212 serves as an introduction to Analytical Chemistry with an emphasis on • A special type of titrimetric procedure which involves the formation of precipitates
wet chemical methods of analysis. during the course of titration. The titrant reacts with the analyte forming an insoluble
 Statistical Analysis
material and the titration continues till the very last amount of analyte is consumed.
 Gravimetric Analysis
The first drop of titrant in excess will react with an indicator resulting in a color
 Volumetric Analysis
 Titrations in Analytical Chemistry (Chapter 13) change and announcing the termination of the titration.
 Principles of Neutralization Titrations (Chapter 14)
 Complex Acid/Base Systems (Chapter 15)
 Applications of Neutralization Titrations (Chapter 16)
 Complexation and Precipitation Reactions and Titrations (Chapter 17)
 Redox Titrations

PRECIPITATION TITRATIONS SOLUBILITY

• Quantitative precipitation can be used for volumetric determination (stoichiometric).
• The titration involves precipitation are called precipitation titrations • Solubility product is the product of the concentration of ions in the saturated solution of a sparingly soluble salt
as AgCl is constant at a given temperature.
• Two types:
• When the ionic product exceeds the solubility products the solution is super saturated and precipitation will
• Direct occur.
• Indirect (Back Titration) • When the ionic product is less than the solubility product the solution is unsaturated.
• Precipitate must be practically insoluble. • In quantitative analysis, excess precipitating agent is always employed to ensure complete precipitation.

• Precipitation must be rapid – precipitate formation usually relatively slow.

• Possible to detect equivalent point – evolving the rxn is apparent, but the end-point is obscured, hazy.
• Method based on precipitation of insoluble silver is known as Argentiometry.
• Halogens can be determined by precipitation as sparingly soluble mercurous salts HgCl2 and HgI2 is called
as mercurometry.
SOLUBILITY PRODUCT SOLUBILITY CHART

SOLUBILITY RULES WHAT DO WE NEED TO KNOW – ARGENTOMETRIC TITRATIONS

• Argentometric titrations are titrations using AgNO3 as titrant i.e. in the
burette
• Silver precipitates are usually insoluble
• Concentration changes are measured as the p function of the dominant
ion of the salt (precipitate) that is formed
• One ion of the salt is always Ag+ and the other is usually a halide Cl-, Br-, F-
etc. – precipitates form rapidly
• Therefore the concentrations in these types of calculations are expressed as
pAg, pCl, pBr etc depending on at what stage of the titration we are. You
will not be calculating pH!!
• Special indicators that adsorb onto the precipitate or form a complex just
after equilibrium (i.e. first drop after equilibrium) give the colour change

SILVER PRECIPITATES LEARNING OUTCOMES

Calculating pX and pAg at
Calculating pX before equilibrium Calculating pAg after
equilibrium equilibrium

AgNO3 + X-  AgX + NO3

Mohr indicator Volhard indicator
• Chemical • Chemical equation
equation for for indicator
indicator Fajan’s indicator
• gives colour change
• colour change • Chemical equation
• Special conditions
• Special conditions for indicator
• Colour change
• Special conditions
 TITRATION CURVES OF AgNO3 ARGENTOMETRIC TITRATION CURVES
Plots of titration curves are normally sigmoidal curves consisting of pAg (or pAnalyte i.e. pX)  In argentometry, the titration curve usually plots pAg against the added titrant volume. Note, that an
versus volume of AgNO3 solution added increasing pAg means strongly decreasing [Ag+]. During the titration, the precipitate equilibrium determines

Q:
pAg.
 Example: 50 mL 0,1 M KSCN sample 0,1 M AgNO3 titrant
Ksp, AgSCN = 4,9 x 10-13

BEFORE THE EQUIVALENCE POINT:

pAg is controlled by the remaining SCN- concentration
AT THE EQUIVALENC POINT:
pAg can be directly calculated from Ksp
AFTER THE EQUIVALENCE POINT:
The points on the curve can be calculated, given the analyte concentration, AgNO3 concentration and the pAg is controlled by the excess Ag+
appropriate Ksp

Q: Example: Derive a titration curve for the reaction of 40.00 mL of 0.050 M NaBr with 0.0998 M Ag NO3.
AgNO3 + NaBr  AgBr (s) + ( NaNO3)
Note: AgBr is the sparingly soluble salt formed, with Ksp = 5.2 x 10-13… very low solubility
Skill : calculate equivalence volume as before: C1V1= C2 V2; with V2 = 20.00 mL

INITIALLY: pBr = -log (0.05) = 1.3

pAg = undefined, because no Ag from AgNO3 has been added from the burette yet.

Before equilibrium: After addition of 5 mL: Br in the conical flask is in excess compared to Ag+ added from the burette

[Br-] = (40 x 0.05) – (no moles AgNO3 added) = = (2 – 0.499)/ 45

Total volume (40+5)
[Br-] = 0.0334 M
pBr = - log 0.0334 = 1.48
Typically we want to plot pAg for the entire titration curve. So even thoughwe cannot calculate pAg from the concentration and
volumes provided, we can obtain pAg from Ksp, the equilibrium expression

Q:
AgBr(s)  Ag+ + Br-
Ksp = [Ag][Br] = 5.2 x 10-13
-log Ksp = -log[Ag] + -log[Br] = 12.28 pAg + pBr = 12.28
pAg = 10.80
Exercise: Calculate pAg at 10, 15 and 18 mL in the same way i.e. first calculate pBr, then substract from pKsp to get pAg

Q:
Example: Derive a titration curve for the reaction of 40.00 mL of 0.050 M NaBr with 0.0998 M Ag NO3.

AgNO3 + NaBr  AgBr (s) + ( NaNO3)

TITRATION CURVE
 AT EQUIVALENCE: Actually we have already done this…. Remember… we have
VolAgNO3 added, mL pAg pBr
 We have already calculated equivalence volume: 20.04 mL 0 - 1.3
I’m sure
you got it
5 10.8 1.48 right???
 We have equilibrium concentrations of pAg and pBr i.e. pAg + pBr = 12.28 10 10.58 
18  
20.04 6.14 6.14
21 2.8  Summary:
 The only additional step is to remember that [Ag] and [Br] must be equal at equilibrium i.e. 25 2.1 10.16
30 1.84  (i) Know your equivalence volume
pAg = pBr = 12.28 = 2x (ii) Before equivalence [X] is in excess
and solving for x, we get: pAg = pBr = 6.14 We can now plot typically pAg vs volume AgNO3 added. so we calculate pX, directly
(iii) After equivalence[Ag] is in excess
 AFTER EQUIVALENCE: i.e. at 21.00 mL, AgNO3 is now in excess and so we calculate pAg directly and pBr from the so we calculate pAg directly
pKsp expression (iv) At equilibrium pAg = pX
[Ag] = (21x0.0998)- (40x0.05) equivalence
pAg (v) pAg and pX are related by the Ksp
40 + 21 expression, so if either one is know

Q:
[Ag] = 1.57 x 10-3 the other can be calculated
pAg = 2.8 , and if you want
pBr = 9.48
Exercise: Calculate pAg and pBr after We are able to construct a table as follows: VolAgNO3
CALCULATING THE TITRATION CURVE STEPS

Q:
Step 1: Calculate the volume of AgNO3 needed to reach the equivalence point.
 Calculate the titration curve for the titration of 50.0 mL of 0.0500 M NaCl with 0.100 M
Tips: shows that we need 25.0 mL of Ag+ to reach the equivalence point.
AgNO3.
Step 2: Calculate pCl before the equivalence point (determine the concentration of
unreacted NaCl).
–
 Ag+(aq) + Cl−(aq) ⇌ AgCl(s) Tips: Before the equivalence point the titrand, Cl , is in excess. The concentration of
– +
unreacted Cl after adding 10.0 mL of Ag which corresponds to a pCl of 1.60.
 When the equilibrium constant of the reaction is so large:
Step 3: Calculate pCl at the equivalence point (use Ksp for AgCl to calculate the
 K = (Ksp)−1 = (1.8 ×10−10)−1 = 5.6 × 109
concentration of Cl–). At the titration’s equivalence point, concentrations of Ag+ = Cl–. To
 Assume that Ag+ and Cl– react completely. calculate the concentration of Cl– we use the Ksp expression for AgCl; thus solving for x
gives [Cl−] as 1.3 × 10–5 M, or a pCl of 4.89.

Step 4: Calculate pCl after the equivalence point (calculate the concentration of excess AgNO3 and 9.00
then calculate the concentration of Cl– using the Ksp for AgCl). 8.00
7.00
After the equivalence point: calculate the concentration of excess Ag+ and then use the Ksp
6.00
expression to calculate the concentration of Cl–. For example, after adding 35.0 mL of titrant or a
5.00
pCl of 7.81. Additional results for the titration curve.
pCl

4.00
Volume of Volume of 3.00
pCl pCl
AgNO3 (mL) AgNO3 (mL) 2.00
0 1.30 30 7.54 1.00
5 1.44 35 7.82 0.00
10 1.60 40 7.97 0.00 10.00 20.00 30.00 40.00 50.00 60.00
15 1.81 45 8.07 Volume of AgNO3
20 2.15 50 8.14
Titration curve for the titration obtained.

CHALLENGE CHALLENGE

 50 mL 0,1 M KSCN sample 0,1 M AgNO3 titrant, Ksp,

Q: AgSCN = 4,9 x 10-13

 Construct a titration curve using 0, 10, 25, 50, 75, and 100 Q: Calculate the titration curve for the titration of 50.0
mL of 0.0500 M NaCl with 0.100 M AgNO3 .
mL of added titrant.
EFFECT OF KSP ON TITRATION CURVES METHODS IN PRECIPITATION TITRATION

Detection of end point:

Chemical
NOTE: -Complexation Type - Mohr’s method
Smaller values of Ksp -Adsorption – Fajan’s method
give much sharper -Back titration – Volhard method
breaks at the end point.
Sensors –Potentiometric or amperometric

The chemical types are also classified into:

1. Indicators reacting with titrant forming specific color.
2. Adsorption indicators.

SEVERAL PRECIPITATION TITRATION SEVERAL PRECIPITATION TITRATION

-MOHR METHOD- -MOHR METHOD-
• Direct titration
This method utilizes chromate as an indicator which forms a 2nd precipitate after equivalence
The method is applicable to the determination of Cl- and Br-, but not for I- or SCN-. • Basis of endpoint: formation of a colored
secondary precipitate
Titration: Ag+ (aq) + Cl- (aq)  AgCl (s)
End point: Ag+ (aq) + CrO4 (aq)  Ag2CrO4 (s) • Indicator: Soluble chromate salt (Na2CrO4,
K2CrO4)
2-

The first drop of excess Ag+ will react with the chromate indicator (reddish precipitate) after all Cl- Note : Two precipitates are formed at equilibrium
has been consumed to formed AgCl.
1. The desired precipitate between Ag and the
This method can incur relatively greater titration error because it is difficult to observe the red color halide ion Cl or Br (white)
(Ag2CrO4 precipitate) over the yellow color (CrO2- ion). At present, this method is not widely used as
other end point detection method are now available. 2. And the indicator precipitate Ag2CrO4 (brick
red)

SEVERAL PRECIPITATION TITRATION SEVERAL PRECIPITATION TITRATION

-MOHR METHOD- -MOHR METHOD

• Has to be performed at a neutral or weak basic

Endpoints for Argentometric Titrations solution of pH 7-9 (or 6-10)

Precipitation Type - Mohr’s method

• In a lower pH (acid solution)
• Ag2CrO4 precipitation in neutral pH solution.
CrO42- (aq) + H + (aq)  H2CrO4
• Product is colored. H2CrO4 ↔ 2 H+ (aq) + CrO4 2-(aq)
• Colour forms just after AgCl or Ag I forms .
• Small error involved. • In a higher pH (basic solution)
Ag+ (aq) + OH- (aq)  AgOH (s)
MOHR METHOD – COMPLEX FORMATION MOHR’S METHOD

• Addition of silver ions

Ksp AgCl = 1.82 x 10-10 Ksp = x2 Remember: AgCl  Ag+ + Cl- • Formation of AgCl (white precipitate)
[Ag+] = 1.35 x 10-5 M Before • Chromate indicator  faint yellow
endpoint color
Ksp Ag2CrO4 = 1.1 x 10-12 = [Ag+]2[[CrO4-2] Remember : Ag2CrO4  2Ag+ + CrO4-2
[CrO4-2] = (1.1 x 10-12)/ (1.35 x 10-5) • All Cl- has been comsumed
• Excess Ag+ react with chromate ion
[CrO4-2] = 6 x 10-3 M At the  slight reddish colour
endpoint
Solubility of [CrO4-2] >>[Ag+] therefore AgCl precipitates first and the [CrO4-2] can be adjusted to
retard the formation of Ag2CrO4-2 (brick red colour) until AgCl in solution reaches equivalence.
Points to note during titration: • Increase formation of silver chromate
After (stronger reddish precipitate)
• Acidity of the medium important: Empirically pH 7-10 works best. If Too acidic then Cr2O7-2 endpoint,
Clear yellow colour of chromate
(dichromate) is formed and if Too alkaline then Ag2O is formed (s). indicator solution before addition of excess Ag+
any silver nitrate

SEVERAL PRECIPITATION TITRATION

-MOHR METHOD- MOHR METHOD

The problem should be pay attention to:

• The consumption of the indictor : 5 x 10-3 mol/L .

• If the concentration of the K2CrO4 is too high, the end point is advance,
result is low

• If the concentration of the K2CrO4 is too low ,the end point is delay,
result is high .K2CrO4 exert titration produce positive error, the
measured concentration is low, it need a blank test.

SEVERAL PRECIPITATION TITRATION

CHALLENGE -VOLHARD METHOD-
This method is to determine Cl- by titrating with Ag+ using back titration. First, Cl- is
precipitated by excess standard AgNO3 (known quantity).

Q:
Ag+ (aq) (excess) + Cl- (aq)  AgCl (s)
 A 0.4179 g sample containing chloride and inert material is titrated
with 0.1012 M AgNO3, requiring 34.99 mL to reach the Ag2CrO4
The precipitate is isolated and the excess Ag+ is titrated with standard thiocyanate
end point. Titration of a blank sample consumes 0.32 mL of the
(KSCN) solution in the presence of Fe3+.
AgNO3 titrant. Determine the Wt% chloride (M.M. = 35.453 g/mol)
in the sample. Ag+ (aq) + SCN- (aq) = AgSCN (s)

After all of the Ag+ has been consumed, the SCN- reacts with Fe3+ to form a red complex.
Fe3+ + SCN- =Fe(SCN)2+
The indicator system is very sensitive and usually good results are obtained.
 SEVERAL PRECIPITATION TITRATION SEVERAL PRECIPITATION TITRATION
-VOLHARD METHOD -VOLHARD METHOD

Problem 1: The end point slowly fades because AgCl is more soluble than
AgSCN. The AgCl slowly dissolves and is replaced by AgSCN.
This problem can be overcome by :
• Filter off the solid AgCl and only the Ag+ left in the filtrate.
• Add a few mL of C6H5NO2 with the AgCl precipitate and shake.
Problem 2: Possibility of Fe3+ to hydrolyze to form Fe(OH)3 under alkaline
conditions.
This problem can be overcome by :
• Perform titration under slightly acidic conditions.
Endpoints for Argentometric Titrations
• Chemical method for silver analyses
• Volhard’s method using thiocyanate , CNS-, as titrant.
• Iron (III) is the indicator as it forms a red complex ion with
thiocyanate , CNS-, Fe(CNS)2+
• The method can be adapted to Chloride analyses.
• AgNO3 is added in excess. The AgCl precipitate is often filtered off.
Then the excess Ag+ backtitrated with thiocyanate , CNS-.
• Iron (III) acts as the indicator as above.

VOLHARD METHOD VOLHARD METHOD

• Addition of SCN- ion

• Formation of silver thiocyanate precipitate
Before
endpoint • Faint yellow colour observed

• All Ag+ completely consumed

• Excess SCN- react with Fe3+ ions
At the • Ferric ammonium sulfate indicator  slight orange/red colour
endpoint

• Further formation of ferric thiocyanate (stronger dark red colour)

After endpoint
(excess of SCN−)

FAJAN’S METHOD – ADSORPTION BEFORE EQUIVALENCE - FAJAN

Fajan’s method uses an adsorption indicator which is an organic compound (typically a

dye) that tends to adsorb onto the surface of the precipitate. Usually these dyes are weak
acids/ bases which dissociate in aqueous medium
Example: Flourescein (weak acid) – (which we will write as Hflo in short form)
Application: for the detection of Cl- with AgNO3
Weak acid behavior: HFlo + H2O  H+ + Flo-
- pH of 6 and more favors dissociation of the acid
- the solution turns yellow/green after equilibrium
 Initially the precipitate is colloidal and less than 1 um in diameter. This is undesirable for gravimetric analysis
but advantageous for an adsorption indicator method.
 Precipitates have a tendency to adsorb “their own” ions to the surface to form what is known as the primary
adsorption layer, i.e., AgCl preferentially adsorbs Ag+ or Cl-, whichever happens to be in excess.
 A colloidal precipitate has a very large surface area and, therefore, presents an abundance of room for adsorption.
Before the equivalence point of the titration of Cl- with Ag+, the Cl- ion is in excess and forms the primary
adsorption layer on the surface of the AgCl precipitate. The particles have a negative surface charge and
repel each other; the colloid is stabilized by this.
 The indicator ion, In- , is also repelled and stays well away from the surface.
 Because the particles are negatively charged, they attract cations that are in solution more strongly than anions.
 Thus there is weakly bound secondary adsorption layer consisting of the cation that forms the most
insoluble chloride to AgCl (probably Na+); these ions form the secondary adsorption layer.
 FAJAN METHOD POST EQUIVALENCE - FAJAN

 Beyond the equivalence point, Ag+ is in excess and the surface of the precipitate
becomes positively charged, with the primary layer being Ag+. These positively
charged colloidal particles will now attract the indicator anion and adsorb it
into secondary adsorption layer.
 The indicator forms a colored complex with silver ion, imparting a color to the
precipitate. Only at the surface is the silver ion concentration high enough for the
solubility product of the complex to be exceeded; this does not happen anywhere
else in the solution, and the color is therefore confined to the precipitate surface.

 Colour change observed:

Points to note during titrations
 Before Equivalence: AgCl: Cl- ( negative counter ion layer) which repels Flo- solution is
yellow/green  Adsorption is reversible, pH control is important to favour Hflo
dissociation Precipitate must be a colloidal type precipitate
 After Equivalence: AgCl: Ag+ (positive counter ion layer) attract Flo- red colour from
precipitate  High electrolyte concentration causes coagulation of the precipitate and
 Once the dye adsorbs onto the precipitate the precipitate has a slightly red colour, the must be avoided
solution colour actually disappears

SEVERAL PRECIPITATION TITRATION SEVERAL PRECIPITATION TITRATION

-FAJANS METHOD -FAJANS METHOD

• Addition of Ag+ to Cl- • Fluorescein and its derivatives – Endpoints for Argentometric Titrations
Before • Formation of colloidal AgCl weak acids.
equivalence
• Solution should be slightly alkaline,
point
so that indicator keep in anion Chemical:
form.
• Only slightly alkaline to avoid Ag+ is
At
• All Ag+ has been consumed converted to AgOH Adsorption – Fajan’s method
equivalence • Strong acids of other fluorescein
point derivatives (eosin) can be used in
acidic pH.
• A red dye attaches to the silver salt, on the surface of the analyte
• Anion dyes (fluorescein and its derivatives – adsorption • Simple method with reproducible precipitate particle.
After
indicator) adsorbed on AgCl surface
• Excess Ag+ react with FI-  reddish preciptate
results. • This happens only when the silver ion Ag+ is in excess, i.e. just after the
equivalence
point equivalence point.
FAJAN METHOD LIMITATION OF PRECIPITATION TITRATION

• A few number of ions such as halide ions (Cl-, Br-, I-) can
be titrated by precipitation method.

• Co-precipitation may be occurred.

• It is very difficult to detect the end point.

APPLICATIONS OF PRECIPITATION TITRATION APPLICATIONS OF PRECIPITATION TITRATION

1. The determination of the chlorine contained in natural water : 5. The precipitation can be observed when the salt is occurred and indicators is used to see
- Mohr and Volhard Method the pH range: mostly used for neutralization reactions

2. The determination of Silver contained in silver alloy:

6. Precipitation titration is used for such reaction when the titration is not recognized by
- Volhard method changing the colors. during the reaction a salt is precipitated as the titration is completed.
3. The determination of halogen contained in organic compounds such as food,
organochlorine pesticides, used Volhard method. 7. Precipitation titration is an Amperometric titration in which the potential of a suitable
indicator electrode is measured during the titration.
C6H6Cl6 + 3OH- = C6H6Cl3 + 3Cl- + 3H2O

8. It is used for determination of chloride by Mohr's Method using Silver nitrate.

4. The determination of sodium chloride contained in MSG: Mohr
method, no more than 20%
glutamate more than 95% grade level
glutamate more than 80% second level

PRECIPITATION TITRATION CURVE INVOLVING SILVER ION APPLICATIONS OF STANDARD SILVER NITRATE SOLUTIONS

 The most common method of determining the halide ion concentration of

aqueous solution

 To construct titration curve, 3 types of calculation are required, each of

which corresponds to a distinct stage in the reaction:
 Pre-equivalence
 Equivalence
 Post-equivalence
THANK YOU FOR WATCHING!
PLEASE FEEL FREE TO CONTACT YOUR LECTURER SHOULD YOU HAVE ANY QUESTIONS.