Analytical Chemistry II

Mashile TR
School of Natural and Applied Sciences,
Sol Plaatje University
Office # 111 Laboratory Science
Building
Tel: 053 491 0276
Outline

• What is Analytical Chemistry??

• Quantitative Classical Methods of Analysis

• Approach to Electroanalytical Methods

Athletes are monitored and must control their caffeine intake to ideally achieve urinary
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approximate this urine concentration in a normal healthy adult male. One cup of regular coffee
contains about 100-mg of caffeine that can produce a urine concentration of 1.5mg/ml in 2-3
hours
What is Analytical Chemistry??
• What problem needs solving?
• How do I solve the problem?
• Qualitative or quantitative???
• How do I ensure that my solution is reliable???
• What sort of errors exist in measurement
• Have I accounted for the errors?
• Is my method accurate and precise??
– Student t tests? ,
– F-test? ,
– Q-test?
– Confidence intervals? Absolute error, standard deviation,
coefficient of variation
Types of Classical Wet Methods

• Gravimetric analysis:
– involves measurement of mass of analyte e.g
precipitation with specific counter ions e.g.
AgCl; Ag+ + Cl- = AgCl(s) white ppt
• Volumetric analysis:
– measurement of vol of reagent soln that reacts
completely with analyte e.g. neutralization
AcidH++ baseOH- = H2O + salt
Gravimetric Analysis
• There are two approaches to this method:
– Precipitation Gravimetry
• Analyte is precipitated out of a solution and is converted to a
compound of known composition which is then weighed.
Using stoichiometry the concentration of the analyte in the
sample can be determined

– Volatilization gravimetry
• Analyte is volatilized to a gas of known chemical composition
which is then weighed.
Precipitation Gravimetry
• The idea is to chose a precipitation reagent that
will give quality precipitate. What is a good
quality precipitate?
– Consisting of large particles i.e. easy to filter and
wash
– Analyte should not be lost during
treatment….therefore low solubility
– Pure…no contaminants, and stable i.e. unreactive
– Of known chemical composition
 How do we get good precipitates?
• By controlling experimental conditions
– We can have large particle size ppts; crystalline
or
– Small particle size ppts; colloidal suspensions
• Experimental variables that need to be
controlled
– Precipitate solubility
– Temperature
– Reactant concentration
– Rate of mixing the reactants
• Relative supersaturation QS

S

Where Q is the conc of solute at any instance

S is its equilibrium solubility
When Relative supersaturation is large; then
colloidal suspension is formed
When Relative supersaturation is small, then
crystalline ppts forms
ACID-BASE TITRATION CURVES
• VOLUMETRIC ANALYSIS
– includes any analytical procedure which
involves the measurement of volumes of
reactants. A common volumetric method of
analysis is titration.
– End point in a titration is the point at which the
indicator changes its colour indicating that the
reaction is complete
– Equivalence point is the point at which a
stoichiometric amount of the titrant has been
added and the reaction is complete.
 Standard solution
• Standard solution is a solution of accurately
known conc.

• One of the two solutions used in a titration is a

standard solution.

• A standard solution is prepared by dissolving an

accurately weighed quantity of a highly pure
chemical (1o standard) & diluting to an accurately
known volume in a volumetric flask.
• If a chemical is not sufficiently pure, a stock
solution of approximately the desired
concentration is prepared and this is
standardized by titrating a weighed quantity of
a primary standard with it.
 Primary standard
• Primary standard is a highly pure chemical used
for preparing a standard solution or for
standardizing a solution of approximately known
concentration.
 Classification of Titrimetric
Methods
• Titrimetric Methods are classified into four classes:
• Acid -Base Titrations
– When the solutions used in a titration are an acid
and a base, the titration is called acid-base
titration.
• Precipitation titrations
– If the titrant forms an insoluble product with the
analyte (test substance) during the titration, the
titration is called precipitation titration.
• Redox Titrations
– When the solutions used in a titration are
reducing agent and oxidising agent, the
titration is called reduction -oxidation titration
or redox titration.

• Complexometric Titrations
– If the titrant reacts with metal ions forming very
stable, water soluble complex, the titration is
called complexometric titration.
 Titration Curves
• The best way to follow the course of an acid-base
titration is to measure the pH as the titration
progresses & to plot a titration curve of pH versus
volume of titrant or pH versus percent
neutralization.
• Different titration curve involve the
following:

– (i) Strong acid versus strong base;

– (ii) Weak acid versus strong base;

– (iii) Strong acid versus weak base; &

– (iv) Weak acid versus weak base.

• Figure 1 Titration curve- strong acid vs strong base
• During the greater part of the titration,
the pH changes gradually as the titrant is
added. At the equivalence point, however,
the pH changes abruptly; i.e, a small Amt
of titrant causes a pH change of several
units and then nearly levels off as more
titrant is added.
• The central point of the vertical portion of
the titration curve corresponds to the pH
at the equivalence point. The pH at the
equivalence point is 7, corresponding to a
neutral solution of sodium chloride.
• This would suggest the use of an indicator
such as bromothymol blue which has a
pH transition range of 6.0 -7.6.

• Looking more closely at the - shape of this

curve, however, we see that the steep
portion of the curve is very long.
• A single drop of 1.00 M NaOH changes the
pH by nearly six units. Therefore, any
indicator that has a colour transition range
within the vertical portion of the titration
curve is suitable for the titration.
 Examples of Indicator with transition pH and
colour changes:

• Indicator pH transition range Colour

change
• Methyl orange 3.1 -4.4 red -yellow
orange
• Methyl red 4.4 -6.2 red -yellow orange
• Bromothymol blue 6.0 -7.6 yellow -blue
• Phenolphthalein 8.2 -9.8 colourless -red
violet
• Since all these indicators have a colour
transition range within the vertical portion
of the titration curve, any of them can be
used in a titration of a strong acid with a
strong base. Acid-base titrations are
usually carried out with approximately
0.1 M titrant.
2) Titration Curve of a Weak Acid Titrated with a
Strong Base (e.g. Acetic acid vs NaOH)

• Figure 2: Titration curve- Weak Acid versus Strong Base

• In a titration of acetic (ethanoic) acid with
sodium hydroxide, the ions present in the
solution at the equivalence point are Na+
(neutral) and acetate (ethanoate) CH3COO-
(basic) ions as shown below:

• NaOH(aq) solution  Na(aq)+ + and OH(aq)-

• CH3COOH solution  CH3COOH molecules

 Titration Rxn:
CH3COOH(aq) + OH-(aq) ⇄ CH3COO- (aq + H2O(aq)

• The ethanoate ion reacts with water

(hydrolysis) forming the weak acid
CH3COOH and OH- ions as follows.

CH3COO- (aq + H2O(L ) ⇄ CH3COOH(aq) + OH-(aq)

• The OH- ions make the solution basic. Since
the reaction does not go to completion,
relatively few OH- ions are formed.

• The pH of the solution is >7 (about 9). The

indicator used must change colour close to
pH 9, which is the pH of the solution when
the reaction is complete.

• Phenolphthalein with pH transition range of

8.2 -9.8, changing from colourless to red
violet, is a suitable indicator for this titration.
• The pH of the solution corresponding to
the mid point of a titration of a weak acid
against a strong base is always equal to
pKa of the acid where Ka is the ionization
(or dissociation) constant of the acid and

• pKa = -Log Ka
Example # 01:

• The pH at the mid point of a titration of a

weak acid against a strong base is 5.60.
What is the ionization constant, Ka of the
acid?
 Answer # 01:
• pKa = pH at the mid point
= 5.60 (2 sig. fig.)
• pKa = -log10 Ka = 5.60

• Ionisation constant of the acid,

• Ka = 10-5.60
= 2.5 x 10-6
Example # 02:
• Titration of potassium hydrogen phthalate (KHP)
against sodium hydroxide (NaOH)

• Potassium hydrogen phthalate formula is KHC8H4O4

is represented as KHP for convenience.

• KHP solution contains K+ and HP- ions. HP-

(hydrogen phthalate ion) is weakly acidic. It ionizes
slightly:

HP- (aq) ⇄ H+(aq) + P2-(aq)

• The ionization constant, Ka of the acid, HP- is
given as: [ H ][P2 ]
Ka 
[HP ]

Since H+ ions and P2- ions are formed

[H ] in equal
 2

amounts, [H+] = [P2-] → Ka = [HP ] 

• [H+] can be calculated from the pH of KHP
solution.

• [HP-] is the same as the original Conc. of

KHP since the amount of HP- ionized is
negligible.
• Substituting the values of [H+] and [HP-] in
the above expression, Ka can be calculated.

• If KHP solution is titrated with a strong base

such as sodium hydroxide, the titration
reaction is:

KHP(aq) + NaOH(aq)  KNaP(aq) + H2O(aq)

• OR
HP-(aq) + OH-(aq)  P2-(aq) + H2O(L)
• The solution at the equivalence point
contains P2- ions. P2- ions undergo slight
hydrolysis:

P2-(aq) + H2O(aq) ⇄ HP-(aq) + OH-(aq)

• Since small amount of OH- ions are formed by
hydrolysis, the solution at the equivalence
point is slightly basic (pH > 7).

• Phenolphthalein with colour transition pH

range of 8.2 -9.8 is the suitable indicator for
this titration.

• The Titration curve for this reaction is similar

to that of the previous example of acetic acid
versus NaOH , given in Figure 2.
3) Titration Curve of a Weak Base Titrated
with a Strong Acid (e.g. NH3 vs HCl)
pH
50 cm3 of 0.1 M NH3
14 + 0.1M HCl

12

10

8
Equivalence
point
6

0
0 10 20 30 40 50 60 70
Volume of HCl added (cm3)

Figure 3: Titration curve - Weak Base versus Strong Acid

TITRIMETRY-PART II:
PRECIPITATION REACTIONS
• PRECIPITATE FORMATION TITRATION
– Mohr method for halides: Determination of
Chloride
• The chloride solution is titrated with a
standard solution of silver nitrate using
about 1 cm3 of a dilute solution of potassium
chromate as the indicator. During the
titration, the silver ions react with the
chloride ions forming a white precipitate of
silver chloride.
Ag+ (aq) + CI- (aq)  AgCl(s)

• When the precipitation of chloride is

complete, the first excess of silver nitrate
reacts with the chromate indicator forming a
red precipitate of silver chromate. The
appearance of a permanent red colour
indicates the end point.

2 Ag+ (aq) + CrO42- (aq)  Ag2CrO4(s)

• The end point is not very sharp due to the
presence of the white precipitate of silver
chloride.

• Some excess silver nitrate must be added to form

enough red precipitate of silver chromate to be
seen over the heavy white precipitate of AgCl.

• This makes it necessary to determine an

indicator blank and subtract this from the volume
of silver nitrate used in titrating the sample.
Calculation:
• Moles of AgNO3 used = Molarity of AgNO3 x
Volume (in dm3) of AgNO3

• Since Ag+ and CI- ions react in 1:1 mole ratio,

number of moles of CI- = number of moles of
Ag+
 Note:
• (i) The concentration of the chromate indicator is
important in this titration. If too much chromate is
added, the end point occurs before the equivalence point;
if not enough, the end point comes later.

• (ii) Acidity is also important in this titration. In acidic

solutions, part of the indicator is present as HCrO4-
instead of CrO42-; hence, more indicator is needed
to form a silver chromate precipitate. pH 8 is ideal
for this titration. More alkaline solution is not also
suitable because it may precipitate AgOH, due to
high Conc of OH-.
• Mohr method can be used for the
determination of bromide and iodide. The
precipitate in these cases i.e AgBr and
AgI, will be light yellow.
VOLHARD METHOD FOR HALIDES

• Determination of Chloride by Volhard Back -

titration method
• The Cl solution is acidified by dilute nitric acid.
A measured excess volume of standard Ag
nitrate solution is then added to the chloride
solution. The Ag+ ions react with the chloride
ions forming a white precipitate of AgCl.

• Ag+(aq) + Cl- (aq)  AgCl(s) + excess Ag+

• The AgCl precipitate is either filtered off or
shaken with a little nitrobenzene and the
excess Ag+ is back-titrated with standard
potassium thiocyanate solution using iron
(III) alum solution as indicator.

• During the titration, the silver ions

remaining in solution react with thiocyanate
ions forming a white precipitate of silver
thiocyanate.
(Titration reaction)

Ag+(aq) + SCN-(aq)  AgSCN(s)

• When the precipitation of AgSCN is complete,

the first excess of thiocyanate reacts with iron
(III) indicator forming a red complex in solution.
The red colour of the solution indicates the end
point.
• (End point reaction)

• Fe 3+
(aq)
+ SCN -
(aq)
 Fe(SCN)2+(aq)
 Calculation:
• Moles of Ag+ excess = Moles of SCN- used in
back-titration

• Moles of Ag+ reacting with Cl-

= Ag+ original -Ag+ excess

• Moles of Cl-
= Moles of Ag+ reacting with it
• In Volhard method for chloride, it is important to
separate the AgCl precipitate from the solution because
this precipitate can cause an error in the chloride
determination by reacting with thiocyanate back-titrant
forming AgSCN precipitate.

• This happens because AgCl precipitate is more soluble

than AgSCN precipitate.

AgCl(s) + SCN-(aq)  AgSCN(s) + Cl-(aq)

• This reaction consumes a lot of thiocyanate back-
titrant giving a high value for excess Ag+ and a low
value for Cl-.

• To avoid this error, the AgCl precipitate is filtered

off or shaken with nitro-benzene. Nitrobenzene is a
liquid which is immiscible with water and heavier
than water.

• Shaking with nitrobenzene coagulates and coats

the silver chloride precipitate, so that it cannot
react with the aqueous layer of solution during
titration.
• If Volhard method is used for the determination
of bromide or iodide, the back-titration of excess
Ag+ can be carried out without shaking the
precipitate with nitrobenzene because both AgBr
and AgI are less soluble than AgSCN and so
they do not react with the thiocyanate back-
titrant.
VOLHARD METHOD FOR OXALATE
(Same as that for chloride)

• Reactions:
• When oxalate solution is mixed with excess AgNO3
solution:
2Ag+(aq) + C2O4- Ag2C2O4(s) + excess Ag+
• When excess Ag+ is back-titrated with KSCN
solution:
• Ag +
(aq)
+ SCN- (aq)  AgSCN(s)

• At the end point: Fe3+ + SCN-(aq)  Fe(SCN)2+

Example # 03:
• To an aqueous solution of 1.7883g impure
sample of KBr, 75.00 cm3 of 0.2242 M
AgNO3 is added. The excess Ag+ requires
18.02 cm3 of 0.1121 M KSCN for
precipitation of AgSCN.

• Calculate the mass percentage of KBr in the

sample. Formula weight of KBr =119.002.
Answer
• Amount of SCN- used in back-titration to react
with Ag+ excess
= 18.02 x 10-3 dm3 x 0.1121 mol/dm3
= 2.020 x 10-3 mol
• Reaction:
Ag+ excess + SCN-(aq)  AgSCN(s)
(1 mol) (1 mol)

• Moles of Ag+ excess = Moles of SCN- reacting

with it = 2.020 x 10-3 mol
• Moles of Ag+ original
= 75.00 x 10-3 dm3 x 0.2242 mol / dm3
= 16.82 x 10-3 mol
• Moles of Ag+ reacting with Br-
= Ag+ original - Ag+ excess
= 16.82 x 10-3 -2.020 x 10-3
= 14.80 x 10-3 mol of Ag+
Reaction:
Ag+ + Br-  AgBr
(lmol) (1 mol)
• Therefore, Moles of Br-

= Moles of Ag+ reacting with it

= 14.80 X 10-3 mol
= Moles of KBr

• Molar mass of KBr

= 119.002 g / mol
Therefore Mass of 14.80 x 10-3 mol KBr

= 14.80 x 10-3 mol x 119.002g/mol

= 1.761 g Mass percentage of KBr in the

sample

= 1.761 g/ 1,7883 g x 100%

= 98,49%
 REDOX TITRATIONS 1
• Titrants in Redox Titrations

• Potassium dichromate solution and potassium

permanganate solution are two commonly used
titrants in redox titrations.

• These titrants are powerful oxidising agents.

• Potassium Permanganate solution

• Potassium permanganate is not a primary standard.

Usually it contains manganese dioxide as an impurity.
Therefore, a stock solution of approximately known
strength is first prepared and then standardized.

• The manganese dioxide impurity catalyses the auto-

decomposition of permanganate:

4MnO4- + 2H2O + MnO2  4MnO2+ 4OH-+ 3O2

(1)
• MnO2 must be removed from the permanganate
solution to prevent this auto-decomposition.

• Usually a stock solution is allowed to stand

overnight and then filtered before standardizing
the solution. Filter paper readily reduces
permanganate and so a porous glass filter is used
for filtration.

• Sunlight also catalyses the decomposition of

permanganate .Therefore, permanganate solution
should be stored in a brown bottle.
Standardization of Permanganate solution
by Fowler-Bright Method

• Permanganate solution is standardized

using a standard solution of sodium oxalate
in dilute H2SO4.
• Reactions:
[ C2O42-  2CO2 + 2e- ] x 5 (oxidation) (2)

[ MnO4- + 8H+ + 5e-  Mn2+ + 4H2O] x 2

(reduction) (3)
• 2MnO4
-
+ 16H+
+ 5 C2 4 
O 2-

2 Mn2+ + 8 H2O + 10 CO2 (4)

• The reaction between 2MnO 4

-
and C 2 4 is
O 2-

very slow at room temperature and very fast

at higher temperatures and therefore the
titration is carried out at about 65 °C.
• At high temperatures C2O42- decomposes as:

• C2OC2- + 2 H+ ⇄ H2C2O4 heat

H2O + CO2 + CO (5)

• This will cause an error in the titre value. To avoid

this, the bulk of the titration is done at room
temperature.

• Near the end point the solution is heated to about

65°C and the titration is continued until the first pink
colour of MnO2- appears, which shows the end point.
• This method requires an initial titration at a
temperature between 60 – 80 °C to
determine the approximate endpoint, before
proceeding with the accurate titration.

• This method was recommended by two

scientists namely Fowler and Bright and
therefore the method is known as Fowler-
Bright method.