Analytical Chemistry

- a branch of chemistry involved with the analysis of chemical substances.

2 Main Divisions

1. Qualitative Analysis

Concerned with the identifying substances by understanding how different

substances react with solvents and with each other. It is possible to deduce their
identity by performing systematic tests on them and the rest might include.

a. Solubility Test to see if a solid dissolves in a solvent

b. Precipitation Test to see if a solid formed when two dissolves substances
are mixed.
c. pH Test to determine the concentration of dissociated [H] atoms.
d. Flame Test to see what color is produced when the substance is burned

2. Quantitative Analysis

Deals with the determination of amounts or concentrations of the constituents

Classification of Quantitative Analysis

1. Complete or Ultimate Analysis the amounts of all the constituents in the sample
were determined.
2. Partial Analysis only same are determined
3. Elemental or molecular analysis refer to the determination of the amounts of
elements and molecules
4. Major Constituents of Macro Analysis implies that the constituents determined
was present in high concentrations
5. Trace Analysis constituents determined was present in low concentrations

Division of Quantitative Analysis

A. Gravimetric Methods the constituent to be determined, w/c is the analyte, is

isolated, either as an element or as a compound of definite composition. This
B. element or compound is weighed, and from its weight and its known chemical
composition, the amount of the design constituents is determined.

1. Chemical Precipitation Methods

2. Electronic Deposition Methods

C. Volumetric Methods a well defined reaction is cause to take place, where in the
reagent is added from an apparatus so designed that the volume of the solution
employed to complete the reaction can completely be measured.
1. Chemical Indicator Methods
2. Electrometric Methods
a. Potentiometric
b. Conductometric
c. Amperometric
d. Coloumetric

D. Colometric Methods the substance to be determined is converted to some

compound which imparts to its solution a distinct color, the intensity of w/c varies
in proportion to the amount of the compound in the solution. Such a solution is
compared to a standard.
E. Other Physiochemical Methods measure properties such as turbidity of
suspension of semi-colloidal precipitates, the degree to w/c the plane is polarized
light is rotated by certain solution, the intensity of spectrum lines, and the degree
of refraction.
F. Gas Volumetric Methods quantitative determination of the components of
mixture gases.

Steps in an analysis
1. Overall Plan or Goal
2. Collecting the sample
3. Measuring the sample
4. dissolving the sample

Solvents
a. water
b. acids
c. organic solvents
d. fusion

5. Dealing with potential inferences

6. Treating the sample and measuring the analyte
7. Calculating the amount and evaluating the result

Review of some basic principles

1. Precipitates downward pointing arrow or underline

2. Gases with symbol (g) or upward pointing arrow
CaCo3 + 2H+ Ca+2 + H2O + CO2

3. Only this constituents actively taking part in a chemical reaction are included in
the reaction
Ba+2 + SO4-2 BaSO4
BaCl2 + NaSO4 BaSO4 + 2NaCl
 4. In cases where the reactant or product exists in equilibrium with its constituents
parts, only that form present in the greatest amount is included in the rxn:

a. Ferric Nitrate Solution + Sodium Hydroxide Solution

Fe+3 + 30H- Fe(OH)3

b. Ferric Nitrate Solution + Ammonium Hydroxide Solution

Fe+3 + 3NH4OH Fe(OH)3 + 3NH+4
Fe+3 + 3NH3 + 3H2O Fe(OH)3 + 3NH+4

c. Zinc Sulfide Suspension + Hydrochloric Acid

ZnS(s) + 2H+ H2S(g) +Zn+

d. Cuppric Ammino Sulfate Solution + Acetic Acid

Cu(NH3)4+2 + 4HC2H3O2 Cu+2 + 4NH+ + 4CH3COO

e. Ferrous Sulfate + Potassium Dichromate (acidic solution)

6Fe+2 + Cr2O7-2 + H+ 6Fe+3 + 2Cr+3 + 7H2O

II. Acids, Bases and Salts

Hydronium Ion - H3O+ or H2O.H+

- solvated proton

Acid - substance w/c in solution gives a hydrogen ion concentration

- solute that increases the anion solvent of the computer

Base - substance w/c gives a hydroxyl ion

- solute that increases the anion concentration of the solvent

Salt substance formed when electron are transferred from one atom to another to form
an ionized particles held together by electrovalents bonds.

Bronsted Lawry Theory

Acid substance that can donate protons

Base substance that can take proton from an acid

Acid .H+ + Base

Conjugate acid-base pair

Methods of Expressing Concentration

 wt of solute
Concentration = unit volume of so ln

A. Grams per unit volume

g solute
Concentration = L So ln

B. Percentage Composition
g solute
Concentration = g So ln

C. Specific Gravity
subs tan ce
Specific gravity = H2O at ref.

D. Volume Ratios
E. Molar and Formal Solution

Molar Solution containing grammolecular weight of solute in a liter

solution or moles of solute per volume (liter) solution

F. Normal Solution
g solute
Normality = molecular weight.

N = fM

Sample Problem ( Preparation of Solution)

1. What is the normality of a solution prepared by dissolving 25.20g oxalic

acid in sufficient water to give 1.2 liters of solution? What is the Molarity
of the solution?
25.20 g 1

Normality = 126.1 1.2 = 0.3330N
2
M = N/f =0.1665

2. What volume of 0.15N reagent is needed for the preparation of 500ml

0.1N solution?

meq
0.1 500ml = 50 meq
ml
 50 meq
Volume required = 0.15 meq = 333.3 ml
ml
By formula of dilution: N1V1 = N2V2

(0.15)V1 = (0.1)(50)

V1 = 333.3ml

3. A sample of impure oxalic acid w/c weighs 0.4750g requires 35.50ml, 0.2
N NaOH. Calculate the percentage oxalic acid in the sample?

Milliequivalent base = milliequivalent acid

meq
0.2 35.60 ml = 7.120 meq
ml

126.1 mg
Milligrams oxalic acid =
mmol 7.120meq = 448.9 mg
2 meq
mmol
0.4489
% Oxalic Acid = 100% = 94.51%
0.4750

4. A sample of impure calcite, w/c weighs 0.4950 is dissolve in 50ml of

standard acid, and excess acid is titrated with 5.25 ml standard base; 1.0ml
of acid is equivalent to 0.0053g sodium carbonate; 1.05ml acid = 1.0ml
base, calculate the percentage of calcium carbonate in the sample.

Mass of sample = 0.4950 g

1.0 ml acid = 0.0053g Na2CO3

1.05 ml acid = 1.0 ml base

Equivalent weight of Na2C03 ( complete neutralization)

Weight of mol in grams eq/mol eq wt. in grams

106 2 53.0
 5.30 mg
ml meq
Normality = = 0. 1
53 mg ml
meq

Net Volume Acid required for titration of sample

1.05ml acid
= 50ml ( 1.0 ml base 5.25 ml base )

= 44.49 ml

meq acid = meq CaCo3

meq
meq CaCo3 = 0. 1 (44.49ml) = 4.449 meq
ml

100.1 mg
mass CaCo3 =
mmol x 4.449 meq = 222.7 CaCo
3
2 meq
mmol
222.7 mg
% CaCo3 = 495.00mg x 100% = 44.99%

Equilibrium Constants

A + B C + D

d [ A] d [ B ]
= = k ' [ A][ B ]
dt dt

d [C ] d [ D]
= = k ' [C ][ D ]
dt dt

[C][D] k '
= =k
[ A][B] k"
A + 2B C + D
 [C ][ D ]
=k
[ A][ B ] 2

Generally:
aA + bB cC + dD

[C ]C [ D ] D
=k } Law of mass action
[ A] A [ B ] B

Low Product Constant Water

H2O H+ + 0H-

Mass Action Constant

[H + ][0H - ]
= k constant unity = 1
[ H 2 O] 2

@ 25 o C 1.0 x 10 14
Kw = [H +][0H - ] 0o C 1.2 x 10 15
100 o C 5.8 x 10 13

pH and pOH first process by sorensen

pH = -log [H+] pH + pOH = 14

Ionization Constant

- the ionization of a weak acid or a weak base furnishes an excellent example of

reversible reaction

Consider:

NH3 + H20 (NH4OH) NH4+ 0H-

@ equilibrium
+
[ NH 4 ][OH ]
K NH 4OH = = 1.75 x 10 5 @ 25 o C
[ NH 4 OH ]

Much better as
 +
[ NH 4 ][OH ]
K NH 3 =
[ NH 3 ]

Another

CH3COOH CH3COO- + H+

[CH 3 COO ][ H + ]
K NH 3COOH =
[CH 3 COOH ]

Common Ion Effect on Weak Acids and Bases

Buffered Solution solution of weak acids or weak bases, in w/c the dissociation is cut-
down by the presence of common ion

- change resistant to pH

Example : A solution of formic acid (HCOOH) is prepared by dissolving 1.15g of pure

acid in water and diluting to 250ml. What is the concentration of the acid in mol/l? If tge
acid in this solution is 4.6% ionized, what is the molar concentration of H+, HCOO- , and
undissociated HCOOH in the solution.

MW = HCOOH = 46

1 mol HCOOH
1.15g HCOOH ( 46 g
) = 0.025 mol HCOOH

Getting the concentration

0.025 mol HCOOH
M= ( ) = 0.1 M
0.250 L

HCOOH HCOO- + H+
0.1 - x x x

Since 4.6% has been ionized, then

[H+] = 0.1 M (4.6/100) = 0.0046 M = [HCOO-]

100 4.6
[HCOOH] = 0.1 ( ) = 0.0954M
100

Example 2:
From the fact that acetic acid (CH3COOH) is 1.3 % ionized in 0.1 M aq solution,
calculate the ionization constant of acetic acid and its percentage ionization in 0.2 M
solution. What would be the hydrogen-ion concentration in a solution 0.10 M in acetic
acid and containing sufficient dissolve acetate to give a total acetate-ion concentrated of
1.5M?

Solution:
CH3COOH H+ + CH3COO-

[ H + ][ CH 3 COO ]
K CH 3COOH =
[CH 3 COOH ]

[0.0013][0.0013]
K CH 3COOH = = 1.8 x 10-5
[0.1 0.0013]

In 0.2 M solution

CH3COOH H+ + CH3COO-
0.2 X X X

[ x ][ x ]
K CH 3COOH = 1.8 x 10-5 =
[0.2 x ]

X = 1.9 x 10-3 M

1.9 x 10 3
% ionization = X 100 = 0.95%
0.2
For [CH3COO-] = 1.5 M

[ H + ][1.5]
= 1.8 x 10-5
[0.1]

[H+] = 1.2 x 10-6 M

Dissociation Constant of Complex Ions

An aqueous solution containing 0.1mol (=25g) CuSO4.5H2 is made ammoniacal (Cu+2 +
4Nh Cu (NH3)4+2) and is diluted o 500ml. The concentrated of dissolve NH3 in the
resulting solution is found to be 1.5m. What is the molar concentrated of free cupric ions
(Cu+2)? Dissipates constant Cu (NH3)4+2 = 4.5x10-14)

Solution:
 4
[Cu +2 ][ NH 3 ]
+2
= 4.6 x 10-14 [Cu+2] = 1.8 x 10-15 M
[Cu ( NH 3 ) 4 ]

4
[Cu +2 ][1.5]
= 4.6 x 10-4
[0.2]

Solubility Product (ksp)

The solubility of calcium phosphate, Ca3 (PO4)2, in water is 2.5x10-5 g/ml. How many
moles/liter does a standard solution of Ca3 (PO4)2 contain? How many grams of Ca are
present in 500ml of the standard solution.

Solution:

MW Ca3(PO4)2 = 310

2.5 x 10 5 g 1000 ml 1 mole

x x 310 g = 8.1 x 10-5 mol/L
ml 1L

Ca3 (PO4)2 3Ca+2 + 2 PO4-2 (100% ionized)

Ca3(PO4)2 = 3Ca+2

3(8.1 x 10-5) x (500/1000) = 1.2 x 10-4 mol Ca per 500 ml

= 1.2 x 10-4(40) = 0.0048 g Ca

2. What is the solubility product of lead chloride of its solubility Hg per liter? What is the
solubility of lead iodate of its solubility prod is 9.8x10-14? How many grams of lead can
remain dissolve in 500ml of a solution which is 0.10m in iodate ions?

Solution:
PbCl2 Pb+2 + 2Cl- PbCl2 = 278

[Pb+2][Cl-]2 = Ksp

11 g 11
= = 0.0396 M
L 278

(0.0396)[(2)(0.0396)]2 = 2.5 x 10-4

Pb(IO3)2 Pb+2 + 2IO3-

[Pb+2][ IO3-]2 = 9.8 x 10-14
Let x = solubility of Pb(IO3)2 mol/L
x (2x)2 = 9.8 x 10-14
x = 2.9 x 10-5 M = 1.6 x 10-2 g/L

[Pb+2][ IO3-]2 = 9.8 x 10-14

[Pb+2][ 0.10]2 = 9.8 x 10-14

[Pb+2] = 9.8 x 10-12 mol/L = 1.0 x 10-9 per 500 ml

(Please answer Chapter 6 problems pp.113 114 6.03 6.18)

GNERAL PRINCIPLES OF GRAVIMETRIC ANALYSIS

Principal Steps
1. Weighing of the sample
2. Dissolving the sample
3. Separation of some substance from solution containing
4. Isolation of that substance by filtration
5. determination of weight, by ignition

Sample Problem
1. What is the percentage purity of sample KCIO3 which weighted 0.7440g and yielded
precipitate of AgCl which weighed 0.5600g?

1 KCl KClO3
0.86 g AgCl x 1 ( AgCl ) x
KCl
_____________________________ x 100% = 98.67%
0.7440

2. What volume of 0.12M BaCl2 is required to precipitate the BaSO4 after the
oxidation of sample of 0.1g of ore which is approximately 80% FeS2?

Solution:

FeSO4 + BaCl2 BaSO4 + FeCl2

2FeSO 4 2BaCl 2 1 mol

0.1(0.8g) [ ][ ][ ]
FeS 2 FeSO4 BaCl 2
__________________________________ = 0.011125 L
0.12 mol/L
3. What weight of pyrite (FeS2) must be taken for analysis so that each milligram of
precipitated BaSO4 shall represent 0.1% Sulfur is the sample

Solution:
 Let x = mass of the sample

S
0.1
= BaSO 4
100
x

32
0.1
= 233
100
x

X = 137.3391 mg ore sample

VOLUMERIC ANALYSIS / TRITIMETRIC ANALYSIS

- involves measuring the volume of a solution of known concentration that is needed to
react essentially completely with the analysis.

Standard Solution (standard litrant) is a reagent of known concentrated that is used to

carry out a titrimetric analysis.

Titration a process wherein a standard so in is brought into reaction normally to

neutralize the original solution.
End pt point in titration where a physical change happens
- refers to a experimental simation of equivalence point.
Equivalence Point refers to the point when just enough tyrant has been added
equivalent to the amount of analyze present.
Titration Error the difference in volume of mass between equivalence point and the end
point.
Stoichiometric Reaction one in which definite, reproducible relationship exists between
the reacting substances.
Quantitative Reaction one the goes to completion when an amount of titrant equivalent
to the amount of analyte present is added.
Indicators often added to the analyte solution in order to give an observable physical
change.
Primary Standard a highly purified compound that serve as a reference material in all
volumetric and mass titrimetric methods

Important Requirements for a Primary Standard

1. High Purity
2. Stability towards air
3. Absence of hydrate water
4. Readily available to modest cost
5. Soluble water
6. Reasonable large molar mass

Conditions for a Volumetric Mass

1. The reaction must be rapid and can be represented by a simple balance equation.
2. The reaction must be complete and no side reaction occurs.
3. An appropriate indicator must be available in order to detect the end point of the
reaction.

Types of Titration
1. Direct Titration the analyze reacts with the standard solution directly.
2. Back Titration an access standard solution is added and the excess is determined by
the addition of other standard solution.
3. Replacement Titration the analyte is converted to a product chemically related to it
and the product of such reaction is titrated with a standard solution.

Example:
1. Exactly 50ml of a solution containing 0.04m Cl is being titrated with a 0.05M AgNO3.
Calculate the concentrated of Cl when titration is 70% complete, first neglecting and
then include dilution. Assume that the reaction gos to completion. Repeat the calculations
for a 0.50M AgNO3 titrant.

Solution:

a) Cl- + Ag+ AgCl(s)

The amount of AgNO3 added is 70% of the amount of Cl- present

Amt of AgNO3 added = amt Cl- x 0.7

= 50(0.04) mmol Cl- (0.7)
= 1.40 mmol
Amt of Cl- left = 50(0.04)mmol 1.4mmol = 0.6mmol

Neglecting dilution
0.6 mmol
[Cl-] = 50.00 ml
= 0.012 M
For dilution:
Amt AgNO3 added = 1.40 mmol
1.40 mmol
Vol AgNO3 = 0.05 mmol / ml
= 28.0 ml
0.06 mmol
[Cl-] = 50 +28.0ml
= 0.0077 M
b) Neglecting Dilution; [Cl-] = 0.012 M
1.40 mmol
After Dilution; vol AgNO3 = 0.05 mmol / ml
= 2.8 ml
0.6 mmol
[Cl-] = 50 +2.80 ml
= 0.011M
2. (Direct Titration Method)
A 300g sample containing phosphoric acid and insert was diluted with water and
titrated with 0.05M NaOH according to H3PO4 + 2NaOH Na2PHO4 + 2H2O. The end
point was reached after 29.00ml of titrant was added. Calculate the % H3PO4 in the
sample.

wt H 3 O4
Solution: % H3PO4 = x 100 = 23.68%
wt smple

3. (Replacement or Indirect Titration Method)

A 750mg sample of iron one was dissolve in acid and treated to oxidized all of iron to
ferric ion. After destroying any remaining oxidizing agent, excess KL was added. The
liberated I2 required 20.50ml of 0.07M Na2S2O3 for titration. What is the % Fe in the
sample?

Solution:
2Fe+2 + 2I- 2Fe+3 + I2
I2 + 2S2O3-2 2I- + S4O6-2

+3 -2
I2 2 Fe +3 55.85 mol
Amt. of Fe = 28.50 (0.075) mmol S2O3 [ 2 ][ ][ 1 mol Fe +2 ]
2 S 2 O3 I2
= 119.3794 mg Fe+2
119.3794
%Fe = x 100 = 15.92%
750

3. (Back Titration)
An 500mg sample of chromium ore was dissolve and the chromium oxidized to
chromate ion. The solution was treated with 10.00ml of 0.20M AgNO3. The resulting ppt
of Ag2CrO4 was removed and discarded. The excess AgNO3 required 14.50ml of
0.1200M KSCN for titration. Calculate the % Cr2O3 in the ore.

Solution

CrO4-2 + 2Ag+ Ag2CrO4(s)

Ag+ + SCN- AgSN(s)
2 2
1Ag 1CrO 4 1CrO 4 152 mg
% CrO3 = [ 10(0.2) 14.50(0.12) KSCN [ 1KSCN ][ ][ ][ 1mmol ]
2 Ag 2 Ag
X 100% (mg)

800mg

% CrO3 = 9.88/800 x 100% = 1.24%

Examples: 1.To what volume must 1600ml of a 0.2050N solution be diluted in order that
the resulting solution will be 0.2000N

Solution:

N1V1 = N2V2
(0.250) (1600) = (0.2000) V2
V2 = 1640 ml

2. How many milliliters of 0.3200N HCL must be added to 100ml of 0.1000N H2SO4 in
order that the resulting solution will be 0.1200N as an acid?

HCL + H2SO4 acid

N1V1 + N2V2 = N3V3
(0.32) V1 + (0.1) (100) = 0.12 V3
V3 = 100 + V1
V1 = 10 ml

3. What is the normality of a solution containing 0.002892g of K2CO3 per milliliter? (b)
What is the normality of the solution made by diluting 50.00ml of H2SO4 (spgr = 1.080
containing 11.60% H2SO4 by lit) to 1L with water? (c) how many milliliters of the
carbonate solution will be completely neutralize by 7.00ml of the acid.

Solution:
a) N = fM
g 1000 ml 1 mole
N = 2[ 0.008292 ml
x L
x 138 g
] = 0.12 N
b) N1V1 = N2V2
g 1000 ml 1 mol
N1 = 1.080 ml x L
x 98 g
x 2 = 22.0408 N
g
Mass = 1.080 ml ( 0.1160 ) ( 50 ml ) = 6.624 g/L soln
g 1 mol
N = 6.624 L [ 98 g
] 2 = 0.1278 M

c) N1V1 = N2V2
( 0.1200 ) V1 = ( 0.1278 ) ( 7.00 )
V1 = 7.46 ml

Primary Standards for Bases:

1. Benzoic Acid C6H5COOH
2. Oxatic Acid H2C2O4 * 2H2O
3. Potassium Biiodrate KH(103)2
4. Potassium Hydrogen Phthalate (KHP) C6H4COOKCOOH
5. Sulfannic Acid (HSO3NH2)

Primary Standards Acids

1. Calcium Carbonate, CnCO3
2. Mercuric Oxide, HGO
3. Sodium Carbonate, Na2CO3
4. Trishydroxymethylaminomethane THAM (CH2OH)3 COOH

Exercises: About 10ml of concentrated HCL was transferred to a 1-L bottle and diluted
with water. When this solution was use to titrate a sample of pure Na2CO3 weighing
0.3054g, it look 38.09ml to reach the methyl red end point. Calculate the molarity and
left of the solution.

For pH Calculations
Sample: 1. When 0.02mole of a monoprotic acid is dissolved in 350ml of water, the
pH=3.05. What is the ionization constant of this acid?

Solution:
0.02 2
[acid] = = M HA H+ + A-
0.35 35
1
3.05 = pH = - log [ Ka] X X
3
x2
Ka = 1.4 x 10-5 Ka = x2 = Ka Csa
Csa

pH = -log KaCsa

2. What mass in grams of NaC2H3O2 must be dissolved with 500ml of 0.100M acetic acid
to make a 2L of buffer solution of pH=5? Ka=1.8x10-5

Solution of pH = 5? Ka = 1.8 x 10-5

500 ml 0.1M HAC, Ka = 1.8 x 10-5

[ acid ]
pH = pKa log
[conj.base]

500 (0.1) mmol / 2 L

-5
pH = - log[1.8 x 10 ] log [ (mg Na Ac) ]
82mg ? mmol / 2 L
mg Na Ac = -7380 = 7.38 g

APPLICATION OF ACID-BASE-TITRATION

Kjeldahl Method (Determination of Organic Nitrogen)

1. Step 1 Digestion the sample is oxidized in not, concentrated H2SO4 and turns back.
2. Step 2 Distillation the solution is cabled and then treated with NaOH to liberate
ammonia gas.

3. Step 3 Titration
Calculations:

[1 NH 3 ] [1N ] [14mg ]
%N = VHCl MHCl [ ][ ][ [1 mmol N ] ] x 100%
[1 HCl ] [1 NH 3 ]
____________________________________________
Mass sample , mg

[1 HCL ] [1 NH 3 ] [1N ] [14mg ]

%N = VHCl MHCl - VNaOH MNaOH [ [1 NaOH ] ][ ][ ][ ]x
[1 HCl ] [1 NH 3 ] [1 mmol N ]
100%

___________________________________________________________________
Mass sample , mg

% Protein = %N (f) f = 5.70 ( cereals)

f = 6.25 ( meat products )
f = 6.38 ( dairy products )

2. Double Indicator Method:

Mixture Na2CO3 and NaHCO3

CO3 -2 --------------------------------------------------------------------------

A Vo Ph

HCO3- 1st end pt ----------HCO3- ---------------------------------------------------- Vo MR

A B

CO2 CO2 2nd end pt -----------------------

Ph phenolphthalein MR Methyl/Red / Methyl orange (MO)

Solution

1 mmol Na 2 CO3 106.00 mg Na 2 CO3

Mg Na2CO3 = 2 (Vo ph) ( MHCl ) [ 2 mmol HCl x 1 mmol Na 2 CO3

1 mmol NaHCO3 84.01 mg NaHCO3

Mg NaHCO3 = (Vph MR - Vo ) ( MHCl ) [
ph
1 mmol HCl x ]
1 mmol NaHCO3

1 mmol NaHCO3 84.01 mg NaHCO3

Mg NaHCO3 = (Vph MR - 2Vo ph ) ( MHCl ) [ 1 mmol HCl x
1 mmol Na 2 CO3
]

Mixture of Na2CO3 and NaOH

Solution:

NaOH--------------CO3 -2 -------------------------------

A Vo Ph

H2O HCO3- 1st end pt ---------- Vo MR

A Vph MR

CO2 2nd end pt -----------

1 mmol Na 2 CO3 106.00 mg Na 2 CO3

Mg Na2CO3 = 2 (Vph MR
Mg Na2CO3 = 2 (VMR
) ( MHCl ) [ 2 mmol HCl x 1 mmol Na 2 CO3 ]
1 mmol Na 2 CO3 106.00 mg Na 2 CO3
) ( MHCl ) [
ph
2 mmol HCl x 1 mmol Na 2 CO3

1 mmol NaOH 40.00 mg NaOH

Mg NaOH = (Vo ph - Vph MR ) ( MHCl ) [ 1 mmol HCl x 1 mmol NaOH ]

1 mmol HCl 40.00 mg NaOH

Mg NaOH = (2Vo ph V0 MR ) ( MHCl ) [ 1 mmol HCl x 1 mmol NaOH ]

Relationship Between Sample Composition and Volumes of CHl Titrant to Reach

Phenolphthalein and Methyl Red Point

Sample Composition
PRECIPIMETERY
- also called Argentometric Titration because AgNO3 is employed in such technique.
- method in which a desired consistent is precipitated from solution by means of a
standard solution of precipitating agent.
- titration based on reaction produce sparingly soluble substances.
- among the oldest titrations

Applications:
1. Solubility Product the concentration of a dissolved solute at equilibrium with its
undissolved form.

Solution:

AB aA + bB

Ksp = [A]a [B]b

AgCl Ag+ + Cl

[ Ag + ][Cl ]
Ke =
[ AgCl 5 ]

Ke = Ke [ AgCl(s)] = [ Ag+ ] [ Cl- ]

Example: The solubility of Mg(OH)2 I 9.0x10-4g/100ml

Compute Ksp value:
Solution:
9.0 x 10 4 g 1 mol
= 9.0 x 10-3 [ 58 g ] = 1.55 x 10-4 M
100 ml ml

[Mg+2] = 1.59 x 10-4 M ; [OH-] = 2 (1.55 x 10-4) = 3.10 x 10-4

Ksp = [Mg+2] [OH-]2

= (1.54 x 10-4) ( 3.10 x 10-4)2
= 1.49 x 10-11

2. Effects of Common Ions on Solubility

Example: How many grams of AgCl ml dissolved in a liter of 0.01 MNaCl?

Solution:

NaCl Na + Cl- AgCl Ag+ + Cl-

0.001 0.001 0 0.01
 S S
______________________
S S+0.01

Ksp = [Ag+] [Cl-] = 1 x 10-10

= (S) ( S+0.01)
S = 10-8 M

WAgCl = 143 x 10-8 g/l MWAgcl = 143

Example 2: Will a precipitate of AgCl be obtained when 3mg AgNO3 and 2mg NaCl are
added o 250ml H2O?
Solution:

3 2
mmol AgNO3 + mmol NaCl
170 58.453

[AgNO3] = 7.0588 x 10-5 M : [NaCl] = 1.3686 x 10-5 M

Ksp = [7.0588 x 10-5 M] [1.3686 x 10-5 M] = 9.6607x 10-9

Ksp AgCl- = 1 x 10-10 ; precipitation will occur

COMPLEXIMETRY
- particularly used for the determinations cations
- typical reagents used are organic compounds containing groups which are electron
donors and have the ability to form multiple covalent bonds with th metal ions.

A. Determination of Cyanide by th Liebig Method

2CN-1 + Ag+ Ag(CN)2-1
Ag(CN)2-1 + Ag+ Ag [ Ag(CN)2-1](s) endpt.
Self indicating: ep = formation of permanent faint turbidity

B. Determination of Nickel
Addition of excess cyanide : Ni(NH3)2+6 + 4CN-1 + 6H2O Ni(CN)4-1 + 6N
Back titration w/ Ag+ : 2CN-1 + Ag+1 Ag(CN)2-1
Endpt : Ag(CN)2-1 + Ag+ Ag [Ag(CN)2-1](s)

C. Titration with EDTA (hexadentate) 4carboxyl groupsand 2amine

MIn-1 + HY-3 HIn-2 + MY-2
Red blue

D. Direct Tred Titration with added metal ions

% - detn of Cat2
 - small amount of MgCl2 is added to EDTA
- Ca+2 replaces Mg+2 then bind with EBT to from red complex

Example: A 2.00g sample of impure NaCN requires 24.95ml of 0.0500M AgNO3

solution to form a faint permanent turbidity. What is the % purity of th sampe?
Given: 0.2g sample
24.95ml 0.05M AgNO3

Solution:
Given: 0.2 grams sample
24.95 ml 0.05 M AgNO3

Ag 2CN 1 mmol CN
(24.95)(0.05) mmol AgNO3 [ ][
][ 2 mmol CN ]
AgNO3 Ag
122.255 mg NaCN
= 200 mg
= 61.1275%

2. A 500mg sample containing NaCN required 23.50ml of 0.1255M AgNO3 to obtain a

permanent faint turbidity. Express the result of this analysis as % CN-

Given: 500 mg sample NaCN

23.5 ml, 0.1255M, AgNO3
Ag 2CN 26mg
= (23.5)(0.1255) mmol AgNO3 [ ][ ][ ]
AgNO3 Ag 1CN

153.361 mg
= x 100 = 30.6722%
500

3. A solution is known of contain both KCl and KCN. A volume of 15.50ml of 0.1000M
AgNO3 is required to give a faint permanent turbidity to he solution. A further addition of
25ml pipetful of the AgNO3 is made and the precipitate of the combined AgCl and
Ag[Ag(N)2] is filtered off. The filtrate then requires 12.40ml of 0.05N KSCN to give are
brown color with fern c ions. How many grams of KCl and of KCN were presnt in the
sample.

Solution:

15.50 ml 0.100 M AgNO3

Ag 2CN KCN 65 mgKCN
= (15.5)(0.1) mmol AgNO3 [ ][ ][ ][ ]
AgNO3 Ag 1CN 1mmol
= 201.5 mg KCN

For AgCl
m
(25 ml 15.50 ml)(0.1) (12.4)(0.05) = 143.45
 m KCl
MAgCl = 47.3385 g [ m AgCl ] = 24.5685 mg KCl

Determination of Nickel
Example: A 750.25mg alloy of nickel was dissolved and treated to remove the impurities.
The ammoniacal solution was treated with 50ml of a 0.1075M KSCN and the xss
cyanide required 2.25ml of 0.00925M AgNO3. Det % Ni in the alloy.

Solution:
3
2 KCN 1Ni ( NH 3 ) 6 58.71
= [50 (0.1075) (5.25) (0.00925) [ ][ ][1Ni][ ]
1AgNO3 1Ni
4CN
78.2806mg
= x 100 = 10.43%
750.25

Example 2: A alloy of nickel, free from interfering consistents an weighing 0.100g is

dissolved in acid. The solution is made ammoniacal and is treated with 49.80ml of KCN
solution, Ni(NH3)6+2 + 4CN-+6H2O ---- Ni(CN)4+6NH4OH. The xss cyanide is then
titrated with 5.91ml of standard AgNO3 for a faint turbidiy, using KS as the indicator.
The KCN solutions contains 7.810g KCN per liter, the AgNO3 solution contains
0.01699g AgNO3 per ml Calculate the % Ni in the alloy.

7.810 g 1mol
N of KCN = [ 65 g ] = 0.1202
L
0.0169 g 1000ml 1mol
N of AgNO3 = [ ][ 170 g ] = 0.0999N
ml 1L
3
2CN 1Ni ( NH 3 ) 6 58.71
[(49.80) (0.1202) (5.91) (0.0999) [ ][ ][1N][ ]
AgNO3 4CN 1Ni

70.5275mg
= 100mg
x 100 = 70.53%

TITRATION WITH EDTA AND DIRECT TITRATION W/ ADDED METAL ION

Example

1. An EDTA soln prepared from its disodium salt was standardized using 506.3 mg of
primary standard CaCO3 and consumed 28.50 ml of the soln. The standard soln was
used to determine the hardness of a 2L sample of mineral water, w/c reqd 35.57 ml
EDTA soln. Express the analysis in terms of ppm CaCO3.

506.3mg CaCO3
x 35.57 ml EDTA / 2L = 315.9490
28.50ml EDTA

2. What volume of 0.0305 M EDTA is needed to titrate Ca in 178.56 mg of CaCO3?

 MCaCO3
(vol EDTA) (0.0305) mmol EDTA = = 178.56 mg
100 mg / mmol
Vol EDTA = 58.5543 ml

3. A 100 ml aliquout of only drinking water was treated w/ a small amt. of an ammonia
ammonium chloride buffer to bring the pH to 10. After the addition of (Ca Inagite)
indicator, the solution equation 21.46 ml of 5.140 x 10-3 M EDTA for titration. Calculate
the water hardness in terms of ppm CaCO3.

1CaCO3 100mg
= (21.46)(5.140 x 10-3) mmol EDTA [ ][ ]
1EDTA 1mmol
____________________________________________________ = 110.3044; 110 ppm
1L
100 ml x
1000ml
(Neutralization)
1. Calc. the solution during titration 50 ml of 0.05 M of NaCl w/ 0.1 M AgNO3 after the
addition of the ff. volumes of the reagent
(a) 0.00 ml
(b) 24.5 ml
(c) 25 ml
(d) 25.5 ml

2. The arsenin in a 9.13g sample residue was converted to ASO4-3 and precipitated as
Ag3ASO4 w/ 50 ml of 0.02105 M of AgNO3. The excess Ag+ was titrated w/ a 4.25 ml of
0.04321 M KSCN, Calculate the % AS2O3 in the sample.

(50) (0.02125) (4.75) ( 0.04321) = AS2O3 = 2 AsO4-3 = 6 AgNO3

1AS 2 O3 AS 2 O3 )
(0.8023 AgNO3 )( )(0.1984 g )(
= 6 AgNO3 mmol = 0.2906
9.13 g sample

3. A mixture of LiCl and BaBr2 weighing 0.5g is treated w/ 37.6 ml of AgNO3, and the
excess of the latter requires 18.50 ml of KSCN solution for titration, find the % of Cl in
the mixture.

mLiCl + m BaBr2 = 0.5g m BaBr2 = 0.5 m LiCl

0.2 N, 37.6 ml AgNO3

18.5 ml of 1/9 N KSCN

For Titration
mLiCl mBaBr2 1AgNo3
MW / f
+ = mol AgNO3 mol KSCN [ ]
MW / f 1KSCN

x 0 .5 x
+ = (0.2)(0.0376) (1/9)(0.0185)
42.5 / 1 297 / 2

X = m LiCl = 0.1247g
m BaBr2 = 0.3753g
35.45
% = 0.1247g [ ] / 0.5 x 100% = 20.82%
42.45

What is the normality of a solution of KSCN, and how many grams of KSCN are
contained in each liter of 19.80 ml are required to titrate the silver in a 0.1 g sample of an
alloy w/c contains 90.20% Ag & 9.80% Cu2.

mmol Ag
19.8 ml [ ][ ]
ml 1000 = 0.9020
0.1
NKSCN = 0.0422 N
97 g
0.0422 N [ ] = 4.0934 g
1mol

A sample of iron ore weighing 385.8 mg was dissolved in acid and pass through a Jones
redactor. If the resulting solution requires 52.36 ml of 0.01436 M K2Cr2O7 for titration,
calculate the % Fe3O4 and Fe2O3 in the sample.

52.36 ml, 0.01436 K2Cr2O7

(6)(52.36)(0.01436) m
=
1000 55.81 / 1
mFe = 0.251958205 g
1Fe3 O4
mFe3O4 = 0.251958205 [ ] = 0.3482
3Fe
0.3482
%Fe3O4 = x 100 = 90.30%
0.3856

A mixture of LiCl & BaBr2 weighing 0.6g is treated 45.15 ml of 0.2017 N AgNO3, and the
excess is found to require 25 ml of 0.1 N KSCN solution for the titration using ferric
aluminum as indicator. What is the % of BaBr2 in the sample?

LiCl + BaBr2 = 0.6g

mBaBr2 = 0.6 mLiCl
( 45.15)(0.2017) ( 25)(0.1) mLiCl 0.6 mLiCl
= +
1000 42.45 297 / 2

mLiCl = 0.1525 g
mBaBr2 = 0.4475 g
% BaBr2 = 74.58 %

COMPLEX FORMATION TITRATION

Ligand donor species

Coordination Number the number of covalent bonds that a cation tends to form w/
electron donors

Chelates particular class coordination

- produced when a metal ion coordinates w/ two or more donor groups of a
single ligand to form a five or six membered heterocyclic ring

Problem
Calculate of equilibrium concentrate of Ni+2 in a solution with an analytical NiY2 conc.
Of 0.0150 M at pH (a) 3.0 (b) 8.0

Ni+2 + Y+4 NiY2-

[ NiY 2 ]
KMY = = 4.2 x 1018
[ Ni +2 ][Y 4 ]

[NiY2-] = 0.0150 [Ni+2]

If we assume [Ni+2] <<< 0.0150

NiY-2 = 0.0150

[Ni+2] = CT = [Y-4] + [HY-3] + [H2Y-2] + [H3Y-1] + [H4Y]

[ NiY 2 ] [ NiY 2 ]
KMY = 4 KMY = =
[ Ni +2 ]CT [ Ni +2 ] 2
= 2.5 x 10-11 @ pH 3.0

0.0150
= KMY = 2.5 x 10-11 x 4.2 x 1018 = 1.05 x 108
[ Ni +2 ] 2

0.0150
[Ni+2] = = 1.43 x10 10 = 1.2 x 10-5 M
1.05 x10 8
@ pH 8

KMY = 5.4 x 10-3 (4.2 x 1018) = 2.27 x 1016

0.0150
[Ni+2] = 16
= 8.1 x 10-10 M
2.27 x10

Volumetric analysis

Analysis of samples
All titremetric analysis require the ff. steps
1. Preparation of sample solution.
2. Titration of the sample solution
The solution is titrated by a standard solution of the reagent
The titration may be made either to (a) a dead stop endpoint or (b)
past the end pt, followed by back titration w/ sample soln or another std soln.

3. Computations can be express in

(a) molarity or normality of the solution
(b) weight of the given substance present
(c) percentage of the given constituent sample
Sources of Error in Titremetric Operations

1. Loss of sample or solution by spilling in weighing, spilling solution as it transfers,

leaking burets, faulty piping, etc.
2. Contamination on solution by failure to properly rinse burets, pipets and bottles.
3. Faulty mixing of solutions after they have been diluted.
4. Impurities in the primary standard in w/c the concentration values are based.
5. Errors in weighing
6. Errors in reading burrets.
7. The use of wrong indicators for titrations
8. Poor drainage from buret or pipet because application has not been cleaned.

Neutralization Method
Standard Solution
- usually solutions of strong acids or bases. Bases, however, are not as good as
acids for permanent std because they absorb CO2 whenever they come in
contact in air.
- Also reacts with glass on long storage
- Can be stored in pyrex or plastic bottles

For many purposes it is desirable to remove the carbonate when preparing standard
solutions of bases. The prescence of carbonate ions interferes with some titrations by so
buffering the solution that the endpoint is not sharp.
 The carbonate can be sufficiently removed either by precipitation as BaCO3 or by
initially making a saturated solution of sodium hydroxide, in w/c sodium carbonate has a
fairly ion solubility and filtering out the carbonate before diluting the desired strength

Standardization
KHP phenolphthalein carbonate free strong bases

Gravimetric Standardization if no primary std. reagent is available, acid base soln

may be standardized by determining the chloride ion of a hydrochloric acid solution
gravimetrically.

Other standards
1. Tris ( Hydroxymethyl) aminomethane ( CH2OH)3CNH2
- non hygroscopic ( THAM )
2. Calcite
3. Sulfamic Acid ( HNH2SO3)

Acid Base Indicators

- in all neutralization titrations, result are dependent on the selection of the
proper indicator

Indicators used in Neutralization Titrations

- highly colored organic compounds
- change color when [ H+] of the solution is changed over a certain range.

Most Widely Used

1. Phenolpthalein colorless [H+] > 10-8 pink [H+] < 10-15
2. Methyl Orange
3. Methyl Red
4. Brom cresol green

#22. 265(P) A 9.05 NH3 solution is treated w/ 50 ml 0.4982 N H2SO4 ; 21.64 ml 0.1016 N
NaOH is required for back titration. What is the percentage of NH3 in the solution?

1 meq H 2 SO4 1 meq NH 3

[50(.4982) (21.64)(.1016) meq NaOH x ][ ][
1 meq NaOH 1 meq H 2 SO4
17 mg
] x 100%
1 meq NH 3
9050 mg

= 4.27%

*note: in equivalence : all are equal not to be confused with mmols as units
#23/265 (P) 44.50 ml 0.2020 NaOH is required to neutralized a 0.5g sample of a
crystalline organic acid. What is the equivalent weight of the acid? If the acid is dibasic
and completely neutralized in the titration, how many grams of it are required to prepare
300 ml 0.40 M solution?

45.50 ml 0.2020 N NaOH = 0.50 g organic acid

(a) g equivalent weight

(b) g of acid for preparation of 300ml 0.4M solution if it is treated

g solute
1
N = g eq weight x
L

meq 500 mg 1
0.2020 ml
= g eq weight
x
45.50ml

500
(a) g equivalent weight = = 54.4010 mg/meq
(0.2020)( 45.50)
(b) f =2 MW = ?

MW
g eq wt = MW/f 54.4010 = 2 meq / mmol

MW = 108.802089 mg/mmol

mmol
0.4 (300ml) = 120 mmol
ml

108.802089 mg/mmol (120 mmol) = 13056.25068 mg

= 13.0563 g of organic acid

#23/265 (P) The saponification number of a fat or oil is defined as a number of

milligrams of KOH required to saponify 1g of fat or oil. To a sample of butter weighing
2.010g is added 25ml 0.4900 N KOH solution. After saponification is complete, 8.13 ml
0.5 N HCl is found to required to neutralize the excess alkali. What is the saponification
number of butter.

[25(0.49) 8.13(0.5)] 56 mg
________________________ = 228.04
2.10 g

#28/266(P) To what volume must 50 ml conc. nitric acid, d = 1.4450 g/ml containing
78% HNO3 by weight, be diluted to contain 10g HNO3 per 100 ml (10 W/V %)
 78 g HNO3 1.445 g so ln 10 g
[ ] 50ml = (vol 2 )
100 g solution ml solution 100 ml

V2 = 563.55 ml

TITRATION WITH 2 INDICATORS

The existence of two breaks in the titration curves of polyprotic acids or their salts
permits simultaneous determination of two constituent of sample mixtures, by a single
titration employing two separate indicators to give separate end pt.

Solution containing NaOH & Na2CO3

- titrated by HCl to ph end pt.
- amt of acid used = amt of OH- + amt that reqd to convert CO3-2 to HCO3-
- volume of the acid is noted
- then Mo turning at pH 4 5 is added
- continued to reach the second end pt. is required to convert HCO3- to CO2

Ex. It is found that 15.00 ml 0.100 N HCl titrates a sample containing both NaOH and
Na2CO3 to pH end pt. an additional 10 ml of acid is required to continue the titration to
MO EP. Compute the weights of NaOH of Na2CO3 in the sample.

Total vol of HCl used = 15 + 10 = 25ml

25 (0.100) = 2.5 meq

10 ml @ 1.0 meq HCO-3 CO2 and H2O then

10 ml @ 1.0 meq CO3-2 HCO3-

Total meq used by the carbonate = 2.0 meq

Wt. of Na2CO3 = 2.0 (53 mg/meq) = 106.00 mg Na2CO3

Since 2.0 meq HCl was used to titrate the carbonate, the amount of HCl used for NaOH =
2.5 2.00 = 0.5 meq

0.5 meq (40 mg/meq) = 20 mg NaOH

OXIDATION REDUCTION ANALYSIS

Two types of reactions in aquaeous solution

1. Metathesis or double decomposition (precipitation & neutralization)
2. Oxidation Reduction ( change in oxidation states )

Gaining of electrons reduced

 Losing of Electrons oxidized

Ce+4 + Fe+2 Ce+3 + Fe+3

1e - + Ce+4 Ce+3 O.A
Fe+2 Fe+3 + 1e- R.A

REDOX reaction may be used as a basis for a volumetric analysis if

1. There is only one reaction under given condition
2. This reaction goes essentially to completion at the equivalence pt.
3. Suitable indicator ( or other means ) is available to locate the endpt.

3 Categories in the General Methods of Redox Analysis

1. A solution of a substance that really oxidized is titrated by a std. soln of strong

oxidizing agent (SOA)

Most wildly used strong O.A.

(a) MnO4- in acidic solution
(b) Cr2O7-2 in acidic solution
(c) Ce+4 in acidic solution
(d) I2 in I- solution
(e) MnO4- in basic solution

In titrations of reducing agents by a strong oxidizing agent, it is necessary to pre-treat the

sample before the titration, to ensure that all the sought subs. Is reduced to its lower
oxidation state to insure that no reducing agent other than the sought material is in the
solution. For example, Fe
2Fe+2 + Zn 2 Fe+2 + Zn+2
After reduction, metallic zinc is removed from the solution, then titrated by a standard
solution of KMnO4
: MnO4- + 5e+2 + 8H+ Mn+2 + 5e+2 + 4H20

2. If the sample is SOA, it mat be analyzed by titrating the solution w/in a solution
of a reducing agent.

Most widely used red agents

(a) Ferrous Salt solution

(b) Arsenious Acid

* Samples of Oxidizing Agents that are not water soluble may be analyzed by treating a
known weight of sample w/ a measured volume of standard Reducing Agent, and after
the reaction is complete, back-titrating the excess of the reducing agent in the solution
with a std soln of an oxidizing agent.Thus, the amount of MnO2 in a sample is determined
by treating a weighed portion with a measured volume of standard. FeSO4 solution and
back titrating the xss with a standard KMnO4 solution.
3. An indirect method is frequently used for analysis of oxidizing agents. The sample is
treated with a solution of KI, and liberated iodine is titrated by a solution of Na2S2O3 w/c
reacts rapidly and quantitatively with I2.

I2 + S2O3-2 2I- + S4O6-2

3 Standard Reagents
1. KMnO4 strong OA
2. H3AsO3 strong RA
3. Na2SO3 specific reagent for I2

Indicatots for Redox Titrations

- the indicator must be a substance that is oxidized or reduced at or near the
equivalence point of titration.
For Titrating a Reducing Agent
- indicator must be a substance that is more difficult to oxidized than the sample

Two most widely used

1. Diphenylamine Sulfonic Acid ( normally used as the soluble barium or sodium salt)
- strong RA used for Cr2O7-2
2. Ferrous Complex or Orthophenanthroline ( Ferrom)
- strong OA for KMnO4, CeSO4

More Common Specific Redox Indicators

1. Color of the permanganate ion
- When the reduced MnO4 gives (in acid solution) the colorless Mn+2
- The colored endpt. Appears with the first drop of MnO4- in xss, after all the
sample is oxidized

2. Starch Indicator for I2

- colloidal suspension of starch will, in the prescence of I-, give an intense blue
color with free I2

3. Spot Test Indicator

- made as the equivalent pt is approached
- done by withdrawing a drop of solution after each addition of each reagent
and testing this drop for the constituent that is being oxidized or reduced

4. Potentiometric Endpoint
- voltage difference

Oxidation Reduction Equations

First step in balancing equation is to know the products formed in the reaction.

Common Oxidizing Agents and their products

Reactant Medium Products
MnO4- + H+ Acid Mn+2 + H2O
Cr2O7-2 + H+ Acid ` Cr+3 + H2O
Ce+4 Acid Ce+3
ClO3- + H+ Acid Cl- + H2O
BrO3- + H+ Acid Br- + H2O
IO3+ + H+ Acid I- + H2O
NO3- + H+ Acid NO + H2O
H2O2 + H+ Acid H2O
MnO2(s) + H+ Acid Mn+2 + H2O
PbO2(s) + H+ Acid Pb+2 + H2O
Fe+3 Acid Fe+2

Common Reducing Agents and their Products

Reactant Medium Products
HNO2 +H2O Acid NO3- + H+
I- Acid or neutral I2
C2O4-2 Acid CO2
H2S Acid S(s) + H+
SO2 + H2O Acid SO4-2 + H+
H3ASO3 + H2O Acid or neutral H3ASO4 + H+
S2O3-2 Acid or neutral S4O6-2
+2
Fe Acid Fe+3
Sn+2 Acid Sn+2
Zn(s) Acid Zn+2

Example 1
MnO4- + H+ Mn+2 + H2O
1. Write the half reaction for O.A.
2. Balance half rxn
MnO4- + 8H+ Mn+2 + 4H2O

3. Balance the charge

Mn+7 + 5e- Mn+2
MnO4- + 8H+ + 5e- Mn+2 + 4H2O

4. Write the half reaction for R.A.

Fe+2 Fe+3 + 1e-

5. Balance the electron in two half rxn

(MnO4- + 8H+ + 5e- Mn+2 + 4H2O) 1
(Fe+2 Fe+3 + 1e-) 5

MnO4- + 8H+ + 5e- Mn+2 + 4H2O

5Fe+2 5Fe+3 + 5e-
 6. Add the 2 half rxn
MnO4- + 8H+ + 5Fe+2 Mn+2 + 4H2O + 5Fe+3

In molecular state form

KMnO4- + 4H2SO4 + 5FeSO4 MnSO4 + 4H2O + 2.5Fe2(SO4)3 + 0.5 K2SO4

Or 2KMnO4- + 8H2SO4 + 10FeSO4 2MnSO4 + 8H2O + 5Fe2(SO4)3 + K2SO4

Cr2O7-2 + 14H+ + 6e- 2Cr+3 + H2O

( H2S S + 2H+ 2e- ) 3

Cr2O7-2 + 8H+ + 3e- 2Cr+3 + 7H2O + 3S

K2Cr2O7-2 + 4H2SO4 + 3H2S Cr2(SO4)3 + 7H2O + 3S + K2SO4

Typical Calculations
MW
A. Preparation of reagent g eq wt = # of electron gained + lost

1. What weight of pure K2Cr2O7 is needed for the preparation of 500 ml 0.1 N
solution?

K2Cr2O7
g eq wt = = 294.21/6 = 49.04 g/eq
6e
meq= 49.04 mg

500 (0.1) = 50 meq

50 (49.04) = 2452 mg or 2.452 g

B. Standardization of reagent

1. A solution of KMnO4 is standardized by comparison with Na2C2O4. From the ff.

data, calculate the N of KMnO4.

Wt of MnO4- = 40.41 ml
Wt of Na2C2O4 = 0.2538 g
Purity of oxalate = 99.60%

C2O4-2 2CO2 + 2e-

g eq wt of Na2C2O4 = 0.5 mole f=2

wt of pure Na2C2O4 = 0.996 (0.2538) = 252.8 mg
g eq wt of Na2C2O4 = 134/2 = 67 mg/meq
1 meq
meq of Na2C2O4 = meq KMnO4 =252.8 mg [ 67 mg ] = 3.773 meq
3.773 meq
Normality KMnO4 = = 0.0934 N
40.41ml

C. Analysis of sample

A sample contg iron is dissolve, all iron is reduced to ferrous condition and the
resulting solution is titrated with std KMnO4 solution. From the ff. data, calc the %
iron, as Fe2O3 in the sample.

Wt of the sample = 1.097 mg

Vol KMnO4 = 37.63 ml
N of KMnO4 = 0.1050 N

0.1050meq
meq Fe = meq KMnO4 = 37.63 ml [ ] = 3.951 meq
ml
159.70 mg
g eq wt. Fe2O3 = 2meq
79.85 mg
wt Fe2O3 = [ meq ] (3.951 meq) = 315.4 mg
0.3154
% Fe2O3 = x 100 = 28.75%
1.097

D. Indirect Oxidation Titration

A solution of KMnO4 is 0.10 N; 40ml of this solution is added to an acidified solution

w/c contains excess KI. The I2 liberated is titrated by 35.00 ml Na2S2O3 solution. What is
the normality of Na2S2O3?

2MnO4- + 16H + 10I 2Mn+2 + 5I2 + H2O

I2 + 2S2O3-2 S4O6-2 + 2I-

meq of KMnO4 = 40 (0.1) = 4 meq = meq I2 = meq Na2S2O3

NNa2S203 = 4 meq/ 35 ml = 0.1143 N

Sample Prob.

#8. How many grams of AS2O3 must be dissolved in conc. NaOH to produce 500 ml 0.05
N NaASO2.
 198mg
500 (0.05) meq [ 4meq ] = 1237.5 mg

#11 How many ml of 0.0973 N K2Cr2O7 solution are reqd to titrate a 0.3563 g sample of
an iron ore w/c is 78.33% Fe2O3?

Volumetric Analysis by precipitation

Recall: Determination can be made by volumetric methods if

1. The reaction goes rapidly to completion

2. There is only one reaction
3. There is a marked change in some property of the solution at the equivalence pt.
4. An indicator is available w/c will show the change at the equivalence pt.

most precipitation reaction fulfill three requirements since they are ironic
no indicators are available for most precipitation reactions

Indicators

1. Formation of colored ppt.

- best known example is the use of silverchromate as indicator in the titration of
chloride with silver nitrate solution
- known as the Mohr Method
2. Formation of soluble colored compound

Volhard Method
- solution contg Ag ion are titrated with std soln of KSCN.

Ag + SCN- AgSCN ( white ppt)

When the equivalence is passed, the concentration of thiocyanate increases to

such an extent that the ion may be detected by means of reaction

Fe+3 +6SCN- Fe (SCN)6-3 (colored)

Ferric aluminum is usually employed as indicator

Titration may be made in nitric acid solution

3. Absorption Indicators

Fajans et al. shown that certain organic dyes may be used as indicators for
volumetric precipitations reactions. The action of these indicators is due to fact that
the equivalence pt. the indicator is absorbed by the precipitate.
The theory of the action of the absorption indicators is based on the properties of
colloids. At the surface of the colloidal particle is a layer of that ion of the lattice w/c
predominate in the surrounding solution. This primarily absorbed layer hold by
secondary absorption oppositely charged ions w/c are present in the solution.

The ion w/c is most strongly held by secondary absorption is the ion of the solution
whose compound w/ the primarily absorbed ion in least soluble. Flourescein or
dichlorofluorescein may be used as absorption indicators in titration of chlorides by
silver ion. Before the equivalence pointis reached, the primary absorption is one of
chloride ion, the lattice in excess. Just at the equivalence point silver ion is absorbed,
giving a positively charged particles w/c can hold negatively charged fluorescein ions
by secondary absorption. When this occurs, the structure of the fluorescein ion is
changed to for a colored substance that coats the particle. Succesful use of absorption
indicators requires the following conditions

1. The indicator ion must be of opposite charge to the ion used for titration reagent.
2. The indicator must be specifically absorbed to such extent that the color change
appears immediately after the equivalence point.
3. the indicator must not be strongly absorbed by the precipitation. If this occurs, the
absorption of the indicator may be a primary reverse w/c takes place before the
equivalence point is reached.
4. The ppt formed should remain highly dispersed. Since the color changes occurs
only at the surface precipitated particles, the visibility of the changed depends on
the number of particles.

Partial list of Absorption Indicators for volumetric

Titration Titration ion Indicator Notes

Cl- Ag+ Dichlorofluorescein ph > 4

Br Ag+ Eosin ph > 2
I- Ag+ Eosin
SCN- Ag+ Eosin
CN- Ag+ Diphenyl carbazide
Ag+ Br- Rhodamine In 0.5 N HNO3
OH- Pb+2 Fluorescein Quitesharp in 0.01
and 0.1 N Solutions
BO2- Pb+2 Dichlorofluorescein Accurate in neutral solution
B4O7-2
SO4-2 Pb+2 Dibromofluorescein A better method is based on
fractional precipation

Quiz No.3
Precipitimetry and Compleximetry
Compleximetry
1. What is Compleximetry?
2. Cite instances/examples where compleximetry is being utilized? Choose one
application and explain how the analysis is done.
3. Discuss the theory of complexation of indicators. Explain the mechanism.

Precipitimetry
1. Discuss the precipitimetry. What are the factors to be considered in a
precipitimetric analysis? Explain each.
2. Discuss all the methods in precipitimetry. Cite each process, how it is done
and the advantages and disadvantages. Tabulate your result.
3. How is the equivalence point is achieved in precipitimetry and the factors the
shape of titration curve.

Chem 351 Analytcal Chemistry Laboratory

Comprehensive Examination

Objectives

1. To be able to develop and apply knowledge in analytical chemistry lectures.

2. To be familiar with the principles and procedures in the preparation and
standardization of reagents.
3. To enhance the critical thinking skills of students in the application of principles
and knowledge gained.

General Direction : Answer all the following items using your knowledge gained in Anal
Chem Laboratory. Several principles and theories can be recalled / used from your
general chemistry and engineering sciences.